Development Document for Effluent Limitations Guidelines
 and New Source Performance Standards for the
 PETROLEUM  REFINING
 Point Source Category
               APRIL 1974
S    t       u-s- ENVIRONMENTAL PROTECTION AGENCY
       °             Washington, D.C. 20460

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                   DEVELOPMENT DOCUMENT

                            for

              EFFLUENT LIMITATIONS  GUIDELINES

                            and

             NEW SOURCE PERFORMANCE STANDARDS

                          for the
                    PETROLEUM REFINING
                   POINT SOURCE CATEGORY
                     Russell E. Train
                       Administrator
                       James L. Agee
Assistant Administrator for Water and Hazardous Materials
                        Allen Cywin
          Director, Effluent Guidelines Division
                       Martin Halper
                      Project Officer
                         April  1974

               Effluent Guidelines  Division
          Office of Water and Hazardous Materials
           U.S.  Environmental Protection Agency
                 Washington, D.C.    20460
    For sale by the Superintendent of Documents, U.S. Government Printing Office, Washington, 0.C. 20402 - Price $2.75

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                            ABSTRACT

This development document presents the findings of  an  extensive
study  of  the  Petroleum  Refining  Industry for the purposes of
developing   effluent   limitation   guidelines,   standards   of
performance,  and  pretreatment  standards  for  the  industry to
implement  Sections  304,  306  and  307  of  the  Federal  Water
Pollution  Control  Act  of  1972,  (PL  92-500) .  Guidelines and
standards were  developed  for  the  overall  petroleum  refining
industry, which was divided into five subcategories.

Effluent  limitation  guidelines  contained  herein set forth the
degree of reduction of pollutants in effluents that is attainable
through the application of best  practicable  control  technology
currently   available  (BPCTCA),  and  the  degree  of  reduction
attainable through the application of best  available  technology
economically  achievable   (BATEA)  by  existing point sources for
July 1, 1977, and  July  1,  1983,  respectively.   Standards  of
performance  for new sources are based on the application of best
available demonstrated technology (BADT).

Annual costs for the petroleum refining  industry  for  achieving
BPCTCA  Control  by  1977  are estimated at $244,000,000, and the
additional annual costs for attaining BATEA Control by  198C  are
estimated  at  $250,000,000.  The estimated annual costs for BADT
for new sources is $26,000,000.

Supporting data and rationale for  the  development  of  proposed
effluent  limitation  guidelines and standards of performance are
contained in this development document.
                               iii

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                               CONTENTS


Section

            ABSTRACT

            CONTENTS                                                    v

            FIGURES                                                     x

            TABLES                                                      xi

I           CONCLUSIONS                                                 1

II          RECOMMENDATIONS                                             3

III         INTRODUCTION                                                11

              Purpose and Authority                                     11
              Methods Used for Development of the Effluent              12
                Limitation Guidelines and Standard of
                Performance
              General Description of the Industry                       14
              Storage and Transportation                                19
                Crude Oil and Product Storage                           19
                  Process Description
                  Wastes
                  Trends
                Ballast Water                                           20
                  Process Description
                  Wastes
                  Treands
              Crude Desalting                                           20
                Process Description
                Wastes
                Trends
              Crude Oil Fractionation                                   22
                Process Description
                  Prefractionation and Atmospheric Distillation
                     (Topping or Skimming)
                  Vacuum Fractionation
                  Three Stage Crude Distillation
                Wastes
                Trends
              Cracking                                                  25
                Thermal Cracking                                        25
                  Process Description
                  Wastes

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Section
                    Trends
                Catalytic Cracking                                      26
                  Process Description
                  Wastes
                  Trends
                Hydrocracking                                           og
                  Process Description
                  Wastes
                  Trends
              Hydrocarbon Rebuilding                                    29
                Polymerization                                          29
                  Process Description
                  Wastes
                  Trends
                Alkylation                                              29
                  Process Description
                  Wastes
                  Trends
              Hydrocarbon Rearrangements                                30
                Isomerization                                           30
                  Process Description
                  Wastes
                  Trends
                Reforming                                               3]
                  Process Description
                  Wastes
                  Trends
              Solvent Refining                                          32
                Process Description
                Wastes
                Trends
              Hydrotreating                                             33
                Process Description
                Wastes
                Trends
              Grease Manufacture                                        34
                Process Description
                Wastes
                Trends                                                  ._
              Asphalt Production                                        "*&
                Process Description
                Wastes
              Product Finishing                                         35
                Drying and Sweetening                                   35
                  Process Description
                  Wastes
                  Trends
                                     vi

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Section

                Lube Oil Finishing
                  Process Description
                  Wastes
                  Trends                                                 _
                Blending and Packaging
                  Process Description
                  Wastes
                  Trends
              Auxiliary Activities                                      37
                Hydrogen Manufacture                                    37
                  Process Description
                  Wastes
                  Trends
                Utilities Function                                      39
              Refinery Distribution                                     42
              Anticipated Industry Growth                               48

IV          INDUSTRY SUBCATEGORIZATION                                  55

              Discussion of the Rationale of Subcategorization          55
              Development of the Industry Subcategorization             55
              Subcategorization Results                                 59
              Analysis of the Subcategorization                         5S
                Topping Subcategory
                Low and High Cracking Subcategory
                Petrochemical Subcategory
                Lube Subcategory
                Integrated Subcategory
              Conclusion                                                6
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Section
                Hexane ExCractables - Oil and Grease
                Ammonia as Nitrogen
                Phenolic Compounds
                Sulfides
                Total Chromium
                Hexavalent Chromium
              Other Pollutants                                       81
                Zinc
                IDS
                Cyanides
                pll (Acidity and Alkalinity)
                Temperature
                Other Metallic Ions
                Chlorides
                Fluorides
                Phosphates

VII         CONTROL AND TREATMENT TECHNOLOGY                         91

              In-Plant Control/Treatment Techniques                  91
                Housekeeping
                Process Technology
                Cooling Towers
                  Evaporative Cooling Systems
                  Dry Cooling Systems
                  Wet Cooling Systems
                At-Source Pretreatment                               95
                  Sour Water Stripping
                  Spent Caustic Treatment
                  Sewer System Segregation
                  Storm Water Runoff
                  Gravity Separation of Oil
                  Further Removal of Oil and Solids Clarifiers
                End-of-Pipe Control Technology                      102
                  Equalization
                  Dissolved Air Flotation
                  Oxidation Ponds
                  Aerated Lagoon
                  Trickling Filter
                  Bio-Oxidation Tower
                  Activated Sludge
                  Physical Chemical Treatment
                  Flow Reduction Systems
                  Granular Media Filters
                  Activated Carbon
                                   vill

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Section                                                            Page

                  Sludge Handling and Disposal                      111
                    Digestion
                    Vacuum Filtration
                    Centrifugation
                    Sludge Disposal
                    Landfilling
                    Incineration

VIII        COST, ENERGY, AND NON-WATER QUALITY ASPECTS             113

              BPCTCA Treatment Systems Used For Economic Evaluation
              BATEA Treatment Systems Used For Economic Evaluation
              Estimated Costs of Facilities
              Non-Water Quality Aspects

IX          BEST PRACTICABLE CONTROL TECHNOLOGY CURRENTLY           143
            AVAILABLE—EFFLUENT LIMITATIONS

              Procedure for Development of BPCTCA Limitations
              Application of Oxygen Demand Limitations
              Variability Allowance for Treatment Plant Performance

X           BEST AVAILABLE TECHNOLOGY ECONOMICALLY ACHIEVABLE—     169
            EFFLUENT LIMITATIONS

              Flow
              Procedure for Development for BATEA Effluent Limitations
              Statistical Variability of a Properly Designed and
              Operated Waste Treatment Plant

XI          NEW SOURCE PERFORMANCE STANDARDS                        175

              Procedure for Development of BADT Effluent Limitations
              Variability Allowance for Treatment Plant Performance

XII         ACKNOWLEDGEMENTS                                        179

XIII        BIBLIOGRAPHY                                            :i81

XIV         GLOSSARY AND ABBREVIATIONS                              187
                                    ix

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                              LIST OF FIGURES


Figure No.                         Title                                Pnge No.

   1             Crude Desalting (Electrostatic Desalting)               21

   2             Crude Fractionation (Crude Distillation,                24
                 Three Stages)

   3             Catalytic Cracking (Fluid Catalytic Cracking)           27

   4             Geographical Distribution of Petroleum                  44
                 Refineries in United States

   5             Hypothetical 100,000 Barrel/Stream Day                  45
                 Integrated Refinery

   6             BPCTCA - Wastewater Treatment System                    132

   7             BATEA - Proposed Treatment                              136

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                                   TABLES
Table No.                          Title                         Page No.

    1             Topping Subcategory Effluent Limitations           4
    2             Cracking Subcategory Limitations                   5
    3             Petrochemical Subcategory Effluent
                  Limitations                                        6
    4             Lube Subcategory Effluent Limitations              7
    5             Integrated Subcategory Effluent Limitations        8
    6             Runoff and Ballast Effluent Limitations            9
    7             Intermediates and Finished Products
                  Frequently Found in the Petroleum Refining
                  Industry                                          15
    8             Major Refinery Process Categories                 17
    9             Qualitative Evaluation of Wastewater Flow
                  and Character!'sites by Fundamental Refinery
                  Processes                                         18
   10             Crude Capacity of Petroleum Refineries by
                  States as of January 1, 1974 (3)                  43
   11             Process Employment of Refining Processes as
                  of January 1, 1973 (3)                           446
   12             Trend in Domestic Petroleum Refining from
                  1967 to 1973                                      47
   13             1972 Consumption of Petroleum Feedstocks          49
   14             Sources of Supply for U. S. Petroleum Feed-
                  stocks                                            50
   15             Characteristics of Crude Oils from Major
                  Fields Around the World                           51-53
                               xi

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Table No.                          Title                        Page No.


   16             Subcategorization of the Petroleum                60
                  Refining Industry Reflecting Significant
                  Differences in Waste Water Characteristics

   17             Median Net Raw Waste Loads from Petroleum         61
                   Refining Industry Categories

   18             Topping Subcategory Raw Waste Load                64

   19             Cracking Subcategory Raw Waste Load               65

   20             Petrochemical Subcategory Raw Waste Load          66

   21             Lube Subcategory Raw Waste Load                   67

   22             Integrated Subcategory Raw Waste Load             68

   23             Waste Water Flow from Petroleum Refineries        70
                  Using 3% or Less once-Through Cooling
                  Water for Heat Removal

   24             Significant Pollutant Parameters for the          72
                  Petroleum Refining Industry

   25             Mettalic Ions Commonly Found in Effluents         87
                  from Petroleum Refineries

   26             Observed Refinery Treatment Systems and          104
                  Effluent Loadings

   27             Expected Effluents from Petroleum Treatment      105
                  Processes

   28             Typical Removal Efficiencies for Oil Refinery    106
                  Treatment Processes

   29             Estimated Total Annual Costs for End-of-Pipe     114
                  Treatment Systems for the Petroleum Refining
                  Industry (Existing Refineries)

   30             Summary of End-of-Pipe Waste Water Treatment     115
                  Costs for Representative Plants in the
                  Petroleum Refinery Industry
                               xii

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Table No.                           Title                        Page No.


    31            Water Effluent Treatment Costs Petroleum          117
                  Refining Industry - Topping Subcategory

    32            Water Effluent Treatment Costs Petroleum          118
                  Refining Industry - Topping Subcategory

    33            Water Effluent Treatment Costs Petroleum          119
                  Refining Industry - Topping Subcategory

    34            Water Effluent Treatment Costs Petroleum          120
                  Refining Industry - Cracking Subcategory

    35            Water Effluent Treatment Costs Petroleum          121
                  Refining Industry - Cracking Subcategory

    36            Water Effluent Treatment Costs Petroleum          122
                  Refining Industry - Cracking Subcategory

    37            Water Effluent Treatment Costs Petroleum          123
                  Refining Industry - Petrochemical Sub-
                  category

    38            Water Effluent Treatment Costs Petroleum          124
                  Refining Industry - Petrochemical Sub-
                  category

    39            Water Effluent Treatment Costs Petroleum          125
                  Refining Industry - Petrochemical Sub-
                  category

    40            Water Effluent Treatment Costs Petroleum          126
                  Refining Industry - Lube Subcategory

    41            Water Effluent Treatment Costs Petroleum          127
                  Refining Industry - Lube Subcategory

    42            Water Effluent Treatment Costs Petroleum          128
                  Refining Industry - Lube Subcategory

    43            Water Effluent Treatment Costs Petroleum          129
                  Refining Industry - Integrated Subcategory

    44            Water Effluent Treatment Costs Petroleum          130
                  Refining Industry - Integrated Subcategory
                               xm

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Table No.                            Title                       Page No.
    45           Water Effluent Treatment Costs Petroleum           131
                 Refining Industry - Integrated Subcategory

    46           BPCTCA - End-of-Pipe Treatment System              133-135
                 Design Summary

    47           BATEA - End-of-Pipe Treatment System Design        137
                 Summary

    48           Attainable Concentrations from the Applica-        145
                 tion of Best Practicable Control Technology
                 Currently Available

    49           BPCTCA - Petroleum Refining Industry Effluent      147
                 Limitations (Annual Average Daily Limits)

    50           Variability Factors                                149

    51           Petroleum Refining - Process Breakdown             151-168

    52           Flow Basis for Developing BATEA Effluents          171
                 Limitations

    53           BATEA Reductions in Pollutants Loads Achiev-       172
                 able by Application of Activated Carbon to
                 Media Filtration Effluent (BPCTCA)

    54           BATEA - Petroleum Refining Industry Effluent       173
                 Limitations (Annual Daily Limits)

    55           Variability Factors for BATEA                      174

    56           BADT - New Source Performance Standards for        176
                 the Petroleum Refining Industry (Annual
                 Average Daily Limits)

    57           Metric Units Conversion Table                      178
                               xiv

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                            SECTION I

                           CONCLUSIONS
This  study  covered  the  products  included  in  the  Petroleum
Refining  Industry  (SIC 2911).  The 252 U.S. petroleum refineries
currently process 2.2 million cubic meters  (14  million  barrels)
of  crude oil per stream day.  U.S. refineries vary in complexity
from the very small, with simple  atmospheric  fractionation,  or
topping,  to the very large integrated refineries manufacturing a
multitude of petroleum and petrochemical products from a  variety
of  feedstocks.   The  raw waste water load is dependent upon the
types of processes  employed  by  the  refinery,  justifying  the
utilization  of  production  process  groupings, as delineated by
their  effects  on  raw  waste  water  as  the  basis   for   the
subcategorization.  The subcategories developed for the petroleum
refining  industry  for  the  purpose  of  establishing  effluent
limitations are as follows:
Subcategory

    Topping




    Cracking
Basic Refinery Operations Included

Topping,    catalytic    reforming,    asphalt
production,    or   lube   oil   manufacturing
processes, but  excluding  any  facility  with
cracking or thermal operations.

Topping and cracking.
    Petrochemical  Topping,    cracking
                   operations.*
                        and
    petrochemicals
    Lube
    Integrated
Topping, cracking and lube
processes.
oil  manufacturing
Topping,  cracking,  lube  oil   manufacturing
processes and petrochemicals operations.*
*   The term "petrochemical operations" shall mean the production
of second  generation  petrochemicals   (i.e.  alcohols,  ketones,
cumene,  styrene,  etc.)  or  first generation petrochemicals and
isomerization products  (i.e.  BTX,  olefins,  cyclohexane,  etc.)
when  15%  or  more of refinery production is as first generation
petrochemicals and isomerization products.

All  five  subcategories  generate  waste  waters  which  contain
similar  constituents.  However, the concentration and loading of
these constituents, termed "raw waste  load,"  vary  between  the
subcategories.   Existing  control  and  treatment technology, as
practiced by the industry, includes  both  end-of-pipe  treatment
and  in-plant  reductions.   Many  of  the  individual wastewater
streams, such as  sour  waters,  have  a  deleterious  effect  on
biological   treatment   facilities   and/or   receiving  waters.
Consequently, these individual streams are  pretreateci  in-plant,

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prior to discharge to waste water facilities.   Current technology
for  end-of-pipe  treatment  involves  biological  treatment  and
granular media filtration.   Biological treatment systems employed
include  activitated  sludge  plants  and  aerated  lagoons   and
stabilization pond systems.

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                           SECTION II

                         RECOMMENDATIONS
The  significant  waste  water  constituents  are BOD5, COD, TOC,
total suspended  solids,  oil  and  grease,  phenolic  compounds,
ammonia  (N),  sulfides,  total  and  hexavalent chromium.  These
waste water constituents were selected to be the subject  of  the
effluent limitations.

Effluent limitations commensurate with the best practical control
technology  currently  available  are  proposed for each refinery
subcategory.    These  limitations,  listed  in  Tables  1-6   are
explicit  numerical  values  for  the allowable discharges within
each subcategory.  Implicit in BPCTCA  in-process  technology  is
segregation of non-contact waste waters from process waste water.
BPCTCA  end-of-pipe technology is based on the application of the
existing waste water treatment processes currently  used  in  the
Petroleum  Refining  Industry.  These consist of equilization and
storm diversion; initial oil and solids removal  (API  separators
or  baffle  plate  separators);  further  oil  and solids removal
(clarifiers,  dissolved air flotation, or  filters);  carbonaceous
waste  removal   (activated  sludge,  aerated  lagoons,  oxidation
ponds, trickling filter, activated  carbon,  or  combinations  of
these);  and filters (sand, dual media; or multi-media) following
biological treatment methods.  The variability of performance  of
biological  waste  water treatment systems has been recognized in
the development of the BPCTCA effluent limitations.

Effluent  limitations  commensurate  with  the   best   available
technology   economically   achievable   are  proposed  for  each
subcategory.   These effluent limitations are listed in Tables  1-
6.   The  limitations  are  explicit  numerical  values  for  the
allowable discharges within each subcategory.  The  primary  end-
of-pipe  treatment  proposed  for  BATEA  effluent limitations is
activated carbon adsorption, as further treatment in addition  to
BPCTCA control technology.  Also implicit in BATEA technology are
achievable reductions in waste water flow.

New  source  performance  standards  commensurate  with  the best
available  demonstrated  technology  are  based  on   the   flows
achievable  with  BATEA  technology,  and the end-of-pipe control
technology  achievable  with  BPCTCA  technology.    These   BADT
effluent  limitations are listed in Tables 1-6.  Activated carbon
adsorption has not been included as BADT  technology,  since  the
use of this technology has not been sufficiently demonstrated, at
this  time,  on  petroleum  refining  waste  water  to insure its
applicability and reliability on secondary effluent waste  waters
from refineries.

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                              BPCTCA
                              Effluent
                              limitations
                     Table 1
Petroleum Refining Industry Effluent  Limitations
             Topping Subcategory

                                       (a )
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                                                                        Table  2
                                                   Petroleum  Refining  Industry Effluent Limitations
                                                               Cracking  Subcategory
                               BPCTCA
                               Effluent
                               limitations
                                                    BATEA
                                                    Effluent
                                                    limitations
                                                                          BADT
                                                                          Effluent
                                                                          limitations
                    Maximum for
                    any one day
                  Average of daily
                  values for thirty
                  consecutive days
                  shall not exceed
                   Maximum for
                   any one day
                  Average of daily
                  values for thirty
                  consecutive days
                   shall not exceed
                    Maximum for
                    any one day
                  Average of daily
                  values for thirty
                  consecutive days
                  shall not exceed
      (Metric units)

RODS
1SS
COO*
Oil and grease
Phenolic compounds
Ammonia as N
Sulfide
Total chromium
!!i;xsvalent chromium
oil

      (English units)

MODS
T.SS ~
COD*
Oil and grease
Phenolic compounds
A.MUNonia as  N
.S'llfi.le
T'ltal chromium
licxavalent chromium
pll
   kg/k cu m of feedstock
 28.2
 17.1
 210
 8.4
 0.21
 18.8
 0. 18
 0.43
 0. 0087
15.6
10.2
109
4.5
0.10
8.5
a 082
0.25
0.0040
Within the range 6.0 to 9.0
    Ib/Mbbl of feedstock
 9.9
 6.1
 74
 3.0
 0.074
 6.6
 0.065
 0.15
 0.0031
5.5
3.6
38.4
1.6
0.036
3.0
0.029
0.088
0.0014
                         kg/k cu m of feedstock
3.4
3.2
19.2
0.68
0.016
4.6
0.075
0.16
0.0035
2.7
2.7
15.4
0.54
0.011
3.5
0.048
0.14
0.0022
                      Within the range 6. 0 to 9. 0

                         Ib/Mbbl of feedstock
1.2
1.2
6.8
0.24
0. 0055
1.6
0.026
0.058
0.0013
0.99
0.99
5.4
0.19
0.0039
1.2
0.017
0.049
0. 0008
                                                                                                                    kg/k cu m of feedstock
16.3
9. 9
118
4.8
0.119
18.8
0.105
0.24
0.0050
8. 7
5.8
61
2. 6
0.058
8.6
0.048
0. 14
0.0022
                                                                                          Within the range 6. 0 to 9. 0
                                                                                             Ib/Mbbl of feedstock
5.8
3.5
41.5
1.7
0.042
6. 6
0.037
0.084
  .0018
3.1
2.0
21
0. 93
0.020
3.0
0.017
0.049
0.00081
 Within the range 6. 0 to 9. 0
                      Within the range 6. 0 to 9. 0
                                                                                          Within the range 6. 0 to 9. 0
 (nl The limits H<:t forth above are to be
 ir.utiiplicd by the following factors to
 arrivt: at the maximum for any one day
 atid the maximum average of daily values
 for thirty consecutive days.
                         (1) Size factor

                         Mbbl of feedstock per stream day

                              0 - 34. 9
                              35 - 74.9
                              75 - 109.9
                              110 - 149.9
                              150 or greater
 '•'•i> 'I hi.- a;l(ln 'onnl ;il lo<-a! ions to be applied whore appropiatc for
 storm v.uu.r i-uiioi'f und ballast water are in Table 6.
                                      Size factor

                                         0.89
                                         1.00
                                         1.14
                                         1.31
                                         1.41
                                  (2) Process factor

                                  Process configuration

                                       1. 5 - 3.49
                                       3. 50 - 5.49
                                       5.50 - 7.49
                                       7.50 - 9.49
                                       9. 50 - 1 0. 5 or greater
                                             Process factor

                                                 0.58
                                                 0.81
                                                 1.13
                                                 1.60
                                                 1.87

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        BPCTCA
        Effluent
        limitations
                                                                   Table  3
                                             Petroleum Refining Industry  Effluent Limitations
                                                        Petrochemical Subcategory
                                                                            BATEA
                                                                            Effluent
                                                                            limitations
                                                                          BADT
                                                                          Effluent
                                                                          limitations
                    Maximum for
                    any one day
                  Average of daily
                  values for thirty
                  consecutive days
                   shall not exceed
                   Maximum for
                   any one day
                   Average of daily
                   values for thirty
                   consecutive days
                   shall not exceed
                   Maximum for
                   any one day
                  Average of daily
                  values for thirty
                  consecutive days
                  shall not exceed
       (Metric units)

 BODS
 TSS~
 COD*
 Oil and grease
 Phenolic  compounds
 Ammonia as N
 bull'id e
 Total chromium
 llexavalent chromium
 pH

       (English units)

 BOD5
 TSS~
 COD*
 Oil and grease
 Phenolic  compounds
 Ammonia as  N
 Sulfide
 Total chromium
 Hexavalent chromium
 PH
    kg/k cu m of feedstock
 34.6
 20.6
 210
 11.1
 0.25
 23.4
 0. 22
 0.52
 0.0115
18.4
12.0
109
5.9
0.120
10.6
0.099
0. 30
0.0051
Within the range 6. 0 to 9. 0

    Ib/Mbbl of feedstock
1 2.1
7.3
74
3.9
0.088
8.25
0.078
0.183
0.0040
6.5
4.25
38.4
2.1
0. 0425
3.8
0.035
0.107
0.0018
                         kg/k cu m of feedstock
4.6
4.4
22
0. 90
0.022
5.6
0. 099
0.22
0.0048
3. 7
3.7
17
0. 72
0.015
4.2
0.063
0.19
0.0031
                      Within the range 6. 0 to 9. 0
                         Ib/Mbbl of feedstock
                                             1.7
                                             1.6
                                             7.6
                                             0. 32
                                             0. 0077
                                             2.0
                                             0.035
                                             0. 080
                                             0.0017
                                            1.3
                                            1. 3
                                            6.1
                                            0.26
                                            0. 0054
                                            1.5
                                            0.022
                                            0.068
                                            0.0011
                                                                                                                    kg/k cu m of feedstock
21.8
13.1
133
6. 6
0.158
23.4
0. 140
0.32
0.0062
11.6
7.7
69
3.5
0.077
10.7
0.063
0. 19
0.0031
                                            Within the range 6. 0 to 9. 0

                                               Ib/Mbbl of feedstock
7.7
4. 6
47
2.4
0.056
8.3
0.050
0.116
0. 0024
4.1
2.7
24
1.3
0.027
3.8
0.022
0.068
0. 0011
 W ithin the range 6. 0 to 9.0
                      Within the range 6. 0 to 9. 0
                                                                                         Within the range 6. 0 to 9. 0
 (a) The limits set forth above are to be
"multiplied by the following factors to
 arrive at the maximum for any one day
 and the maximum average of daily values
 for thirty consecutive days.
                       (1) Size factor

                       Mbbl of feedstock per stream day

                           0-49.9
                           50 - 99.9
                           100 - 149. 9
                           150 or greater
                                   Size factor

                                     0.73
                                     0.87
                                     1.04
                                     1.13
                                 (2) Process factor

                                 Process configuration

                                   3.25 - 4.74
                                   4. 75 - 6.74
                                   6. 75 - 8.74
                                   8. 75 - 10.25 or greater
                                           Process factor

                                               0.67
                                               0.91
                                               1.27
                                               1.64
 (b) The additional allocations to be applied where appropiate for
 »torm water runoff and ballast water are in Table 6.

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                               BPCTCA
                               Effluent
                               limitations
                                             Table  4
                       Petroleum Refining Industry  Effluent Limitations
                                       Lube  Subcategory
                                                          (a)(b)
                                                  BATEA
                                                  Effluent
                                                  limitations
                                                                         BADT
                                                                         Effluent
                                                                         limitations
                   Maximum for
                   any one day
                  Average of daily
                  values for thirty
                  consecutive days
                  shall not exceed
                 Maximum for
                 any one day
                   Average of daily
                   values for thirty
                   consecutive days
                   shall not exceed
                   Maximum for
                   any one day
                  Average of daily
                  values for thirty
                  consecutive days
                  shall not exceed
      (Metric units)

BODS
rss~
COD*
Oil and grease
Phenolic compounds
Ammonia as N
bul fide
•fetal chromium
litrxavalent chromium
pll

      (English units)

HODS
TSS
COD*
Oil and grease
Phenolic compounds
Ammon'a as N
Sulfide
Total chromium
Hexavalent chromium
pH
    kg/k cu m of feedstock
 50.6
 31.3
 360
 16.2
 0.38
 23.4
 0.33
 0.77
 0.017
25.8
18.4
187
8.5
0. 184
10.6
0.150
0.45
0.0076
W ithin the range 6. 0 to 9. 0

   Ib/Mbbl of feedstock
17.9
11.0
127
5.7
0.133
8.3
0.118
0.273
0.0059
9.1
6. 5
66
3.0
0.065
3.8
0.053
0.160
0.0027
                       kg/k cu m of feedstock
7.8
7.4
40
1.4
0.034
5.6
0.16
0.36
0.0081
6.3
6.3
32
1. 1
0.024
4.2
0. 10
0.31
0. 0052
                    Within the range 6. 0 to 9. 0

                       Ib/Mbbl of feedstock
                                           2.7
                                           2.6
                                           13.8
                                           0.50
                                           0.012
                                           2.0
                                           0.055-
                                           0. 13
                                           0.0029
                                           2.2
                                           2.2
                                           11.0
                                           0.40
                                           0.0087
                                           1.5
                                           0.035
                                           0.11
                                           0.0018
                                                                                                                   kg/k cvi in of feedstock
34.6
20.6
245
10.5
0.25
23.4
0.22
0.52
0.0115
18.4
12.1
126
5. 6
0. 12
10.7
0.10
0.31
0.0052
                                             W ithin the range 6. 0 to 9. 0

                                                Ib/Mbbl of feedstock
12.2
7.3
87
3.8
0.088
8.3
0. OT8
0.180
0.0056
6.5
4. 3
45
2.0
0.043
3.8
0.035
0.105
0.0018
Within the range 6.0 to 9.0
                    Within the range 6. 0 to 9. 0
                                                                                        W ithin the range 6. 0 to 9. 0
(a) The limits set forth above are to be
multiplied by the following factors to
arrive at  the maximum for any one day
and the maximum average of daily values
for thirty consecutive days.
                        (1) Size factor

                        Mbbl of feedstock per stream day

                              30 - 69.9
                              70 - 109.9
                              110 - 149. 9
                              150 - 199.9
                              200 or greater
 (Ij) The additional allocations to be applied where appropiate for
 storm water runoff and ballast water are in Table 6.
                                     Size factor

                                       0.71
                                       0.81
                                       0.93
                                       1.09
                                       1.19
                                   (2) Process factor

                                   Process configuration

                                    6. 0 or less - 7. 99
                                    8.0-9. 99
                                    10.0 - 11. 99
                                    12.0 - 14. 0 or  greater
                                            Process factor

                                                0.88
                                                1.23
                                                1.74
                                                2.44

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                                                              Table  5
                                         Petroleum Refining  Industry Effluent Limitations
                                                     Integrated Subcategory
                              BPCTCA
                              Effluent
                              limitations
                                                 BATEA
                                                 Effluent
                                                 limitations
                                                       BADT
                                                       Effluent
                                                       limitations
                   Maximum for
                   any one day
                Average of daily
                values for thirty
                consecutive days
                shall not exceed
Maximum for
any one day
Average of daily
values for thirty
consecutive days
shall not exceed
                                                                                                            Maximum for
                                                                                                            any one day
                                                                                                                                  Average of daily
                                                                                                                                  values for thirty
                                                                                                                                  consecutive days
                                                                                                                                  shall not exceed
     (Metric units)
kc/k cu m of feedstock
j;()D5                 54.4
 lASS"                 32.8
COO-                 388
O il and grease         17.1
I'iienolic compounds    0.40
/\;;imonia as N         23.4
.SuH'idt-                0.35
Toial chromium       0.82
I !i-xavalfiit chromium  0.017
I'll

      (English units)
                     W ithin the range 6. 0 to 9. 0
                                              28.9
                                              19.2
                                              198
                                              9.1
                                              0.192
                                              10.6
                                              0.158
                                              0.48
                                              0.0079
                           Ib/Mbbl of feedstock
f!OD5                 19.2
TSS                   11.6
roD*                 136
Oil and grease         6. 0
Phenolic compounds    0.14
Ammonia as N         8. 3
bulfide                0.124
Total chromium       0.29
[I'-xavalent chromium  0.0062
                                             10.2
                                             6.8
                                             70
                                             3.2
                                             0.068
                                             3.8
                                             0.056
                                             0. 17
                                             0.0'028
      kg/k cu m of feedstock
                                                                   8.8
                                                                   8.4
                                                                   47
                                                                   1.7
                                                                   0.041
                                                                   5.6
                                                                   0.19
                                                                   0.44
                                                                   0.0092
                                                                7.1
                                                                7.1
                                                                38
                                                                1.4
                                                                0.029
                                                                4.2
                                                                0.12
                                                                0. 37
                                                                0.0059
                                         W ithin the range 6. 0 to 9. 0

                                            Ib/Mbbl of feedstock
                                         3.2
                                         3.0
                                         16. 8
                                         0. 60
                                         0.015
                                         2.0
                                         0.066
                                         0.15
                                         0.0033
                          2.6
                          2.6
                          13.4
                          0.48
                          0.010
                          1.5
                          0.042
                          0.13
                          0.0021
                            kg/k cu m of feedstock
                                               41.6
                                               24.7
                                               295
                                               12.6
                                               0.30
                                               23.4
                                               0.26
                                               0.64
                                               0.013
                                                22.1
                                                14.5
                                                152
                                                6.7
                                                0.14
                                                10.7
                                                0. 12
                                                0.37
                                                0.0059
                                               Within the range 6. 0 to 9. 0

                                                  Ib/Mbbl of feedstock
                     W ithin the range 6. 0 to 9. 0
                                         Within the range 6.0 to 9.0
                         14. 7
                         8.7
                         104
                         4.5
                         0.105
                         8.3
                         0.093
                         0.220
                         0.0047
                                                                                                                                      7.8
                                                                                                                                      5.1
                                                                                                                                      54
                                                                                                                                      2.4
                                                                                                                                      0.051
                                                                                                                                      3.8
                                                                                                                                      0.042
                                                                                                                                      0.13
                                                                                                                                      0.0021
                                               W ithin the range 6. 0 to 9. 0
(u) The limits set forth above are to be
multiplied by the following factors to
arrive at the maximum for any one day
and the maximum average of daily values
for thirty consecutive days.
                      (1) Size factor

                      Mbbl of feedstock per stream day

                          70 - 144.9
                          150 - 219.9
                          220 or greater
                    Size factor

                       0. 69
                       0.89
                       1.02
               (2) Process factor

               Process configuration

                  6.0 or less  - 7.49
                  7.5-8. 99
                  9.0 - 10. 5 or greater
                                                                                                                                      Process factor

                                                                                                                                         0.78
                                                                                                                                         1.00
                                                                                                                                         1.30
   The additional allocations to be applied where appropiate for
   riii water runoff and ballast water are in Table 6.

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                                                                      Table  6
                                          Petroleum  Refining Industry  Effluent Limitations
                                                Storm  Water  Runoff  and Ballast  Water
 >a) Runoff: The allocation being allowed for storm runoff flow shall be based solely on that
 storm flow  ( process area runoff ) which is treated in the main treatment system. All
 additional storm runoff { from'tankfields and non-process areas ) that has been segregated
 from tlit' main waste stream for discharge,  shall not exceed a concentration of 35 mg/1 of
 TOC or 15 mg/1 of oil and grease when discharged.
                              BPCTCA
                              Affluent
                              limitations
                                                                   BATEA
                                                                   Effluent
                                                                   limitations
                                                                                                                    BADT
                                                                                                                    Effluent
                                                                                                                    limitations
Maximum for
any one day
                                         Average of daily
                                         values for thirty
                                         consecutive days
                                         shall not exceed
                                                         Maximum for
                                                         any one day
                                                                                    Average of daily
                                                                                    values for thirty
                                                                                    consecutive days
                                                                                    shall not exceed
                                                                                   Maximum for
                                                                                   any one day
                                                                                  Average of daily
                                                                                  values for thirty
                                                                                  consecutive days
                                                                                  shall not  exceed
     (Metric units)
                    kg/cu m of flow
roir-
( 5

i x . i)
(,hi i  und gr^ati e
nil
0.40
0.24
3. 1
0. 126
                          0.21
                          0.14
                          1.6
                          0.067
                     V. ithin the range 6.0 to 9.0
                        kg/cu m of flow

                      0.0105                0.0085
                      0.010                 0.0085
                      0.028                 0.022
                      0.0020                0.0016
                     Within the range 6. 0 to 9. 0

                        Ib/Mgal of flow

                      0.088                 0.071
                      0.084                 0.071
                      0.24                  0.19
                      0.018                 0.014
                     Within the range 6.0 to 9.0
 (M P.alla.st: The allocation being allowed for ballast water flow
 ballast waters treated at the refinery.

                              BPCTCA
                              Effluent
                              limitations
                                                          shall be based on those
                                                                          BATEA
                                                                          Effluent
                                                                          limitations
                                                                                                               kg/cu m of flow
                                                                                       0.048
                                                                                       0.029
                                                                                       0.37
                                                                                       0.015
                                                                                                                0.026
                                                                                                                0.017
                                                                                                                0. 10
                                                                                                                0.0080
                                                                                                       Within the range 6. 0 to 9. 0
                                                                                                               Ib/Mgal of flow
                                                                                                             0.40
                                                                                                             0.24
                                                                                                             3. 1
                                                                                                             0. 126
                                                                                                                              0.21
                                                                                                                              0. 14
                                                                                                                              1.6
                                                                                                                              0.067
                                                                                                             Within the range 6.0 to 9.0
                                                                                                                BADT
                                                                                                                Effluent
                                                                                                                limitations
Maximum for
any one day
BGU5_
T56
C-CD*
Cil and grease
pH
                                         Average of daily
                                         values for thirty
                                         consecutive days
                                         shall not exceed
     (Metric units)
                0.048
                0.029
                0.47
                0.015
                                                         Maximum for
                                                         any one day
                                                                                     Average of daily
                                                                                     values for thirty
                                                                                     consecutive days
                                                                                     shall not exceed
                          kg/cu m of flow
                                             0.026
                                             0.017
                                             0.24
                                             0.008
               W ithin the range 6. 0 to 9. 0

(English units)        Ib/Mgal of flow
UGD5
TSi ~
COD*
(A! and grease
I'M
   0.40
   0.24
   3.9
   0.126
0.21
0.14
2.0
0.067
                      Within the range 6.0 to 9.0
                                               kg/cu m of flow

                                             0.0105               0.0085
                                             0.010                0.0085
                                             0.038                0.030
                                             0.0020               0.0016
                                             Within the range 6.0 to 9. 0

                                               Ib/Mgal of flow

                                             0.088                0.071
                                             0.084                0.071
                                             0.32                 0.26
                                             0.018                0.014
                                             Within the range 6.0 to 9.0
                                                                                     Maximum for
                                                                                     any one day
                                                                                    Average of daily
                                                                                    values for thirty
                                                                                    consecutive days
                                                                                    shall not exceed
                                                                                                           kg/cu m of flow
                                                                                           0.048
                                                                                           0.029
                                                                                           0.47
                                                                                           0.015
                                                                                       0.026
                                                                                       0.017
                                                                                       0.24
                                                                                       0.0080
                                                                                                               Within the range 6.0 to 9.0

                                                                                                                 Ib/Mgal of flow
                                                                                                              0.40
                                                                                                              0.24
                                                                                                              3.9
                                                                                                              0. 126
                                                                                                                               0.21
                                                                                                                               0. 14
                                                                                                                               2.0
                                                                                                                               0.067
                                                                                                               Within the range 6. 0 to 9. 0

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                           SECTION III

                          INTRODUCTION
Purpose and Authority

Section  301 (b)  of  the Act requires the achievement by no later
than July 1, 1977, of effluent  limitations  for  point  sources,
other than publicly owned treatment works, which are based on the
application  of the best practicable control technology currently
available as defined by the Administrator,  pursuant  to  section
304 (b)  of the Act.  Section 301 (b) also requires the achievement
by not later than July 1, 1983, of effluent limitations for point
sources, other than publicly owned  treatment  works,  which  are
based  on  the  application  of  the  best  available  technology
economically achievable, which will result in reasonable  further
progress toward the national goal of eliminating discharge of all
pollutants,  as  determined in accordance with requlations issued
by the Administrator, pursuant to  section  304 (b)   of  the  Act.
Section 306 of the Act requires the achievement by new sources of
a  Federal  standard  of performance providing for the control of
the discharge of pollutants which reflects the greatest degree of
effluent reduction  which  the  Administrator  determines  to  be
achievable   through   the  application  of  the  best  available
demonstrated technology, processes, operative  methods  or  other
alternatives,  including, where practicable, a standard permitting
no discharge of pollutants.

Section  304(b)  of the Act requires the Administrator to publish
within one year of enactment of the  Act,  regulations  providing
guidelines  for  effluent limitations setting forth the degree of
effluent reduction attainable through the application of the best
practicable control technology currently available and the degree
of effluent reduction attainable through the application  of  the
best   control   measures   and  practices  achievable  including
treatment  techniques,   process   and   procedure   innovations,
operation   methods  and  other  alternatives.   The  regulations
proposed  herein  set  forth  effluent   limitations   guidelines
pursuant  to section 304 (b)  of the Act for the petroleum refining
industry source category.

Section 306 of the Act requires  the  Administrator,  within  one
year  after a  category of sources is included in a list published
pursuant  to  section  306 (b)   (1)  (A)   of  the  Act,  to  propose
regulations establishing Federal standards of performance for new
sources  within  such categories.   The Administrator published in
the Federal Register of January 16, 1973 (38 F.R. 1624),  a  list
of  27  source  categories.    Publication of the list constituted
announcement of the Administrator's  intention  of  establishing,
under  section  306,  standards  of performance applicable to new
sources within the petroleum refining  industry  source  category
which was included in the list published January 16, 1973.
                                11

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Methods   Used   for  Development  of  the  Effluent  Limitations
Guidelines and Standards of Performance

The Office  of  Air  and  Water  Programs  of  the  Environmental
Protection  Agency  has  been  given  the  responsibility for the
development of effluent  limitation  guidelines  and  new  source
standards  as  required  by  the Act.  In order to promulgate the
required guidelines and standards, the  following  procedure  was
adopted.

The  point  source category was first categorized for the purpose
of determining whether separate  limitations  and  standards  are
appropriate   for   different  segments  within  a  point  source
category.  Such sub-categorization was based upon  raw  materials
used,  products  produced,  manufacturing processes employed, raw
waste loads, and other factors.  This included an analysis of (1)
the source and volume of water used in the plant and the  sources
of  waste and waste waters in the plant; and (2)  the constituents
(including  thermal)  of  all  waste  waters   (including   toxic
constituents and other constituents) which result in taste, odor,
and  color  in  water  or aquatic organisms.  The constituents of
waste waters which should  be  subject  to  effluent  limitations
guidelines and standards of performance were identified.

The  full  range  of  control and treatment technologies existing
within  each  subcategory  was  identified.   This  included   an
identification of each distinct control and treatment technology,
including  both  inplant  and end-of-pipe technologies, which are
existent or capable of being designed for each  subcategory.   It
also  included  an  identification,  in  terms  of  the amount of
constituents  (including thermal) and the chemical, physical,  and
biological  characteristics  of pollutants, of the effluent level
resulting from the application  of  each  of  the  treatment  and
control technologies.  The problems, limitations, and reliability
of  each  treatment  and  control  technology,  and  the required
implementation  time  was  also  identified.   In  addition,  the
nonwater quality environmental impact  (such as the effects cf the
applisubcation   of   such   technologies  upon  other  pollution
problems, including air, solid waste, noise, and  radiation)  was
also  identified.   The energy requirement of each of the control
and treatment technologies was identified, as well as the cost of
the application of such technologies.

The information, as outlined above, was then evaluated  in  order
to  determine methods or other alternatives.  In identifying such
technologies, various factors were  considered.   These  included
the  total  cost  of application of technology in relation to the
effluent reduction benefits to be achieved from such application,
the age of  equipment  and  facilities  involved,  the  processes
employed,  the  engineering aspects of the application of various
types of control techniques, process  changes,  nonwater  quality
environmental  impact   (including  energy requirements) and other
factors.

-------
During the initial phases of the study, an assessment was made of
the availability, adequacy, and usefulness of all  existing  data
sources.   Data  on  the  identity and performance of waste water
treatment systems within the  petroleum  refining  industry  were
known to be included in:

         1.   National Petroleum Refining Waste Water
              Characterization Studies and the
              Petroleum Industry Raw Waste Load Survey of 1972.
              (EPA/API Raw Waste Load Survey).

         2.   Environmental Protection Agency (Refuse Act) Permit
              Application.

         3.   Self-reporting discharge data from various states.

         U.   Monitoring data on individual refineries, collected
              by state agencies and/or regional EPA offices.

A  preliminary  analysis  of these data indicated an obvious need
for   additional   information.    Although   approximately   135
refineries  were  surveyed during the 1972 Raw waste Load Survey,
five  activated  sludge  treatment  plants  were   subjected   to
intensive  sampling  for  identification of waste water treatment
plant effluent  performance.   Identification  of  the  types  of
treatment  facilities  used  by  the  other individual refineries
included no performance data.

Refuse Act Permit Application data are limited to  identification
of   the   treatment   systems   used   and  reporting  of  final
concentrations (which were diluted with cooling  waters  in  many
cases);   consequently,   operating   performance  could  not  be
established.

Self-reporting data  was  available  from  Texas,  Illinois,  and
Washington.    These   reports   show  only  the  final  effluent
concentrations and identify the systems in use;  rarely  is  there
production   information   available   which   would  permit  the
establishment of unit waste loads.

Monitoring data from the individual states  and/or  regional  EPA
offices  again  show  only  the final effluent concentrations and
identify the systems in use.  Rarely  is  production  information
available to permit the establishment of unit waste loads.

Additional  data  in the following areas were therefore required:
1) currently practiced  or  potential  in-process  waste  control
techniques;  2)   identity  and effectiveness of end-of-pipe waste
control techniques;  and  3)  long-term  data  to  establish  the
variability  of  performance  of  the  end-of-pipe  waste control
techniques.  The best source of  information  was  the  petroleum
refineries  themselves.  New information was obtained from direct
interviews  and   inspection   visits   to   petroleum   refinery
facilities.    Verification   of   data   relative  to  long-term
performance of waste control techniques was obtained by  the  use


                                13

-------
of standard EPA reference samples to determine the reliability of
data submitted by the petroleum refineries, and by comparison  of
the  refinery  data  with monitoring data from the state agencies
and/or regional EPA offices.

The selection of petroleum refineries as candidates to be visited
was guided by the trial categorization, which was  based  on  the
1972  Raw  Waste  Load Survey.  The final selection was developed
from identifying information available in the 1972 Raw Waste Load
Survey, EPA Permit Applications, state  self-reporting  discharge
data,  and contacts within regional EPA offices and the industry.
Every effort was  made  to  choose  facilities  where  meaningful
information   on  both  treatment  facilities  and  manufacturing
processes could be obtained.

Survey  teams  composed  of  project  engineers  conducted  plant
visits.   Information  on  the  identity and performance of waste
water treatment systems were obtained through:

    1.   Interviews with plant water pollution control personnel.

    2.   Examinations of treatment plant  design  and  historical
         data  (flow rates and analyses of influent and effluent).

    3.   Inspection of operations and analytical procedures,  in-
         cluding  verification of reported analyses by the use of
         EPA standard reference samples and by comparison of  the
         refinery  data  with monitoring data from state agencies
         and/or regional EPA offices.

Information on process  plant  operations  and  associated  waste
water characteristics were obtained through:

    1.   Interviews with plant operating personnel.

    2.   Examination of plant design and operating data.

    3.   Inspection of in-plant waste water controls.

The data base obtained  in  this  manner  was  then  utilized  to
develop   recommended   effluent  limitations  and  standards  of
performance for the petroleum  refining  industry.   All  of  the
references  utilized are included in Section XIII of this report.
The data obtained during the field data  collection  program  are
included in Supplement B.

General Description of the Industry

The  industrial waste water profile covers the petroleum refining
industry in the United States, as defined by Standard  Industrial
Classification    (SIC)  Code  2911  of  the  U.S.  Department  of
Commerce.  Intermediates and finished products in  this  industry
are  numerous  and varied.  Table 7 is a partial listing of these
products.  The production of crude oil or natural gas from wells,
or the  production  of  natural  gasoline  and  other  operations
                                14

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                 TABLE 7


        Intermediates and Finished Products
Frequently Found in the Petroleum Refining Industry

                    SIC 2911
               Acid Oil
               Alkylates
               Aromatic Chemicals
               Asphalt and Asphaltic Materials:
                 Semi-Solid and Solid
               Benzene
               Benzol
               Butadiene
               Coke  (Petroleum)
               Fuel Oils
               Gas, Refinery or Still Oil
               Gases,  (LPG)
               Gasoline, except natural gasoline
               Greases:  Petroleum, mineral jelly,
                         lubricative, etc.
               Jet Fuels
               Kerosene
               Mineral Oils, natural
               Mineral Waxes, natural
               Naphtha
               Naphthenic Acids
               Oils, partly refined
               Paraffin Wax
               Petroleums, nonmedicinal
               Road Oils
               Solvents
               Tar or  Residuum
                     15

-------
associated  with such production, as covered under SIC Code 1311,
are not within the scope of this study.   This study also does not
include  distribution  activities,  such  as   gasoline   service
stations.   Transportation  of petroleum products is covered only
to the extent that it is part of refinery pollution control, such
as the treatment of ballast water.  Other activities outside  the
scope  of  the  SIC Code 2911 were included in the development of
raw waste load data, and are listed as auxiliary processes  which
are  inherent to an integrated refinery operation.  Some of these
include soap manufacture for the  production  of  greases,  steam
generation, and hydrogen production.

A  petroleum  refinery is a complex combination of interdependent
operations  engaged  in  the  separation   of   crude   molecular
constituents,   molecular   cracking,  molecular  rebuilding  and
solvent finishing to produce the products listed under  SIC  code
2911.   The  refining  operations may be divided among 12 general
categories, where each  category  defines  a  group  of  refinery
operations.  The categories are listed in Table 8.

The  characteristics  of  the waste water differ considerably for
different processes.  Considerable knowledge  is  available  that
can  be  used  to  make meaningful qualitative interpretations of
pollutant loadings from refinery processes.  Such information  is
presented in Table 9, a semi-graphic outline of the major sources
of  pollutants  within  a  refinery.   In  order to set forth the
character  of  the  waste  derived  from  each  of  the  industry
categories  established  in  Section IV, it is essential to study
the sources and contaminants  within  the  individual  production
processes  and  auxiliary  activities.   Each process is itself a
series of unit operations which causes chemical  and/or  physical
changes   in  the  feedstock  or  products.   In  the  commercial
synthesis of a single product  from  a  single  feedstock,  there
generally  are  sections  of  the  process  associated  with: the
preparation  of  the  feedstock,  the  chemical   reaction,   the
separation  of  reaction  products, and the final purification of
the desired product.  Each unit operation  may  have  drastically
different water usages associated with it.  The type and quantity
of  contact  waste  water  are  therefore directly related to the
nature of the various processes.  This in turn implies  that  the
types  and  quantities  of  waste water generated by each plant's
total production mix are unique.  The  processes  and  activities
along  with  brief  process descriptions, trends in applications,
and a delineation of waste water sources, are as follows:
                             16

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                            TABLE 8
                  Major Refinery Process Categories

 1.   Storage and Transporation
 2.   Crude Processes
 3.   Coking Processes
 4.   Cracking and Thermal  Processes
 5.   Hydrocarbon Processing
 6.   Petrochemical  Operations
 7.   Lube Manufacturing Processes
 8.   Treating and Finishing
 9.   Asphalt Production
10.   Auxiliary Activities  (Not listed under SIC Code 2911)
                                  17

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                                                                     TABLE 9
                                          Qualitative Evaluation of Wastewater Flow and Characteristics
CD
Production
Piocesses
Crude Oil and
Product Storage
Crude Desalting
Crude Distill-
ation
Thermal Cracking
Catalytic Cracking
Hydrocracktng
Polymerization
Alkylatlon
Isomerlzatton
Reforming
Solvent Refining
Asphalt Blowing
Dewaxlng
Hyd retreating
Drying and
Sweete Ing
Flow BOD COD
XX X XXX
XX XX XX
XXX X X
XXX
XXX XX XX
X
X XX
XX X X
X
X 0 0
X X
XXX XXX XXX
X XXX XXX
XXX
XXX XXX X
by Fundamental Refinery Processes
Emulsified Am-
Phenol Sulflde Oil Oil pH Temp. monta Chloride Acldltv Alkalinity SUSP. Solids
X XXX XX 0 0 0 0 XX
X XXX X XXX X XXX XX XXX 0 X 3CXX
XX XXX XX XXX X XX XXX X OX X
XXX XX XX X X 0 XX X
XXX XXX X X XXX XX XXX X 0 XXX X
XX XX XX XX
OX XOXXXX X 0 X
0 XX X 0 XX Z X XX XX 0 XX

XXX OOZXOO 0 0
X 0 X X 0 OX
X XXX
X 0 X 0
XX 0 XX XX 0 0 X 0
XX 00 X XX 0 X 0 X X XX
                   XXX - Major Contribution.     XX - Moderate Contribution,
X - Minor Contribution,
0 - No Problem .
— No Data

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1.  STORAGE AND TRANSPORTATION

A.  CRUDE OIL AND PRODUCT STORAGE

Process Description

Crude oil, intermediate, and  finished  products  are  stored  in
tanks  of varying size to provide adequate supplies of crude oils
for  primary  fractionation  runs  of  economical  duration,   to
equalize  process  flows  and provide feedstocks for intermediate
processing units, and to store final products prior  to  shipment
in  adjustment to market demands.  Generally, operating schedules
permit sufficient  detention  time  for  settling  of  water  and
suspended solids.

Wastes

Waste  waters  associated  with storage of crude oil and products
are mainly in the form of free and emulsified oil  and  suspended
solids.   During storage, water and suspended solids in the crude
oil separate.  The water layer accumulates below the oil, forming
a bottom sludge.  When the water layer is drawn  off,  emulsified
oil  present  at  the  oil-water  interface  is often lost to the
sewers.  This waste is high in COD and contains a  lesser  amount
of  BODS.   Bottom  sludge  is  removed  at infrequent intervals.
Additional quantities of waste result from  leaks,  spills,  salt
"filters" (for product drying), and tank cleaning.

Intermediate  storage  is  frequently  the  source of polysulfide
bearing waste waters and iron sulfide suspended solids.  Finished
product storage can produce high BODS, alkaline waste waters,  as
well  as  tetraethyl  lead.   Tank  cleaning can contribute large
amounts of oil, COD, and suspended solids, and a minor amount  of
BODS.  Leaks, spills and open or poorly ventilated tanks can also
be a source of air pollution, through evaporation of hydrocarbons
into the atmosphere.

Trends

Many  refineries  now have storage tanks equipped to minimize the
release  of  hydrocarbons  to  the  atmosphere.   This  trend  is
expected  to  continue  and  probably  accelerate.   Equipment to
minimize the release of hydrocarbon vapors  includes  tanks  with
floating-roof  covers,  pressurized  tanks, and/or connections to
vapor recovery systems.  Floating-roof covers add  to  the  waste
water  flow  from storage tanks.  Modern refineries impose strict
Bottom Sediment and Water  (BSSW)  specifications  on  crude  oil
supplies,   and   frequently   have  mixed-crude  storage  tanks;
consequently, little or no  waste  water  should  originate  from
modern  crude  storage.   Another  significant  trend  is  toward
increased  use  of  dehydration  or  drying  processes  preceding
product  finishing.    These  processes  significantly  reduce the
water  content  of  finished  product,  thereby  minimizing   the
quantity of waste water from finished product storage.
                                 19

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B.  BALLAST WATER

Process Description

Tankers which are used to ship intermediate  and  final  products
generally  arrive  at  the  refinery in ballast (approximately 30
percent of the cargo capacity is generally required  to  maintain
vessel stability).

Wastes

The ballast waters discharged by product tankers are contaminated
with  product  materials  which are the crude feedstock in use at
the refinery, ranging from  water  soluble  alcohol  to  residual
fuels.   In  addition to the oil products contamination, drackish
water and sediments  are  present,  contributing  high  COD,  and
dissolved solids to the refinery waste water.  These waste waters
are  generally  discharged  to  either  a  ballast  water tank or
holding ponds at the refinery.  In many cases, the ballast  water
is  discharged  directly to the waste water treatment system, and
constitutes a shock load on the system.

Trends

As the size of tankers and refineries increases,  the  amount  of
ballast waters discharged to the refinery waste water system will
also  increase.   The  discharge  of  ballast water to the sea or
estuary without treatment, as had been the previous  practice  by
many  tankers,  is no longer a practical alternative for disposal
of ballast water.  consequently, the ballast water  will  require
treatment  for the removal of pollutants prior to discharge.  The
use of larger ballast water storage tanks or ponds,  for  control
of flow into the waste water treatment system, should increase as
ballast water flow increases.

2.  CRUDE DESALTING

Process Description

Common to all types of desalting are an emulsifier  and  settling
tank.   Salts can be separated from oil by either of two methods.
In the first method, water wash  desalting  in  the  presence  of
chemicals   (specific  to the type of salts present and the nature
of the crude oil) is followed by heating and gravity  separation.
In  the  second  method,  water  wash  desalting  is  followed by
water/oil separation  under  the  influence  of  a  high  voltage
electrostatic field acting to agglomerate dispersed droplets.  In
either case, waste water containing various removed impurities is
discharged  to  the  waste stream, while clean desalted crude oil
flows from the upper portion of the holding tank.  A process flow
schematic of electrostatic desalting is shown in Figure 1.

wastes
                                20

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PROCESS
WATER
              ELECTRICAL
                POWER
                                                                          DESALTED
                                                                              CRUDE
                                                                          EFFLUENT
                                                                             WATER
HEATER
                                      EMULSIFIER
                                    Figure  \

                                 Crude Desalting
                              (Electrostatic Desalting)
                                         21

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Much of the BS&W content in crude oil is caused by the  "Load-on-
Top"  procedure  used on many tankers.  This procedure can result
in one or more cargo tanks containing mixtures of sea waters  and
crude oil, which cannot be separated by decantation while at sea,
and  are  consequently  retained  in the crude oil storage at the
refinery.  While much of the water and sediment are removed  from
the  crude oil by settling during storage, a significant quantity
remains to be removed by desalting prior  to  processing  of  the
crude in the refinery.

The  continuous  waste  water  stream  from  a  desalter contains
emulsified, and occasionally free oil, ammonia, phenol, sulfides,
and suspended solids.  These pollutants produce a relatively high
BOD5 and COD.  This waste water also  contains  enough  chlorides
and  other  dissolved  materials  to  contribute to the dissolved
solids problem in the areas where the waste water  is  discharged
to   fresh  water  bodies.   There  are  also  potential  thermal
pollution problems because the temperature of the desalting waste
water often exceeds 95°C  (200°F).

Trends

Electrical desalting is currently used much  more  than  chemical
desalting.   In  the  future, chemical methods are expected to be
used only as a supplement where the crude has a  very  high  salt
content.   Two  stage  electrical  desalting  will  become a more
prevelant process, as dirtier crude feedstocks are  processed  in
refineries.   The  growth  in  capacity  of  desalting units will
parallel the growth of crude oil capacity.

3.  CRUDE OIL FRACTIONATION

Fractionation serves  as  the  basic  refining  process  for  the
separation  of  crude  petroleum  into  intermediate fractions of
specified  boiling  point  ranges.    The   several   alternative
subprocesses   included   are  prefractionation  and  atmospheric
fractionation, vacuum fractionation, vacuum flashing, and  three-
stage crude distillation.

Process Description

Prefractionation   and   Atmospheric   Distillation   (Topping  or
Skimming)

Prefractionation is an optional distillation process to  separate
economical  quantities  of  very light distillates from the crude
oil.  Lower temperature and higher pressure conditions  are  used
than would be required in atmospheric distillation.  Some process
water  can be carried over to the prefractionation tower from the
desalting process.

Atmospheric Distillation  breaks the heated crude oil as follows:

    1.   Light overhead products  (C5 and  lighter) as in the  case
         of prefractionation.


                                 22

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    2.   Sidestream distillate cuts of kerosene, heating and  gas
         oil can be separated in a single tower or in a series of
         topping  towers,  each  tower  yielding  a  successively
         heavier product stream.

    3.   Residual or reduced crude oil.

Vacuum Fractionation

The asphaltic residuum from the atmospheric distillation  amounts
to  37  percent  (U.S.   average)   of  the  crude  charged.  This
material is sent to vacuum stills, which recover additional heavy
gas oil and deasphalting feedstock from the bottoms residue.

Three Stage Crude Distillation

Three stage crude distillation, representing  only  one  of  many
possible  combinations  of  equipment,  is shown schematically in
Figure 2.  The process consists of:

    1.   An atmospheric fractioning stage which produces  lighter
         oils;

    2.   An initial vacuum stage which produces  well-fractioned,
         lube oil base stocks plus residue for subsequent propane
         deasphalting;

    3.   A  second  vacuum  stage  which   fractionates   surplus
         atmospheric  bottoms not applicable for lube production,
         plus surplus initial vacuum stage residuum not  required
         for  deasphalting.   This  stage  adds the capability of
         removing catalytic cracking stock from  surplus  bottoms
         to the distillation unit.

Crude  oil  is first heated in a simple heat exchanger, then in a
direct-fired crude charge  heater.   Combined  liquid  and  vapor
effluent  flow  from  the heater to the atmospheric fractionating
tower,  where  the  vaporized  distillate  is  fractionated  into
gasoline  overhead product and as many as four liquid sidestreams
products:naphthaf kerosene, light and heavy diesel oil.  Part  of
the  reduced  crude  from  the bottom of the atmospheric tower is
pumped  through  a  direct-fired  heater  to  the   vacuum   lube
fractionator.   Bottoms  are  combined  and  charged  to  a third
direct-fired  heater.   In   the   tower,   the   distillate   is
subsequently condensed and withdrawn as two sidestreams.  The two
sidestreams  are  combined to form catalytic cracking feedstocks,
with an asphalt base stock withdrawn from the tower bottom.

Wastes

The waste water from crude oil fractionation generally comes from
three sources.  The first source is  the  water  drawn  off  from
overhead  accumulators  prior  to  recirculation  or  transfer of
hydrocarbons to other  fractionators.   This  waste  is  a  major
source  of  sulfides and ammonia, especially when sour crudes are


                              23

-------
                            Atmospheric
                           Fr.iet ionator
Stabllizer
 (
Vacuum Lube
Fract ionator
                                                                                                             Propane  Deasphalter Feed
                          Oesalter
                                                                  Figure  2

                                                              CRUDE FRACTIONATI ON
                                                        (CRUDE DISTILLATION,  THREE STAGES)

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being processed.  It also contains significant  amounts  of  oil,
chlorides, mercaptans and phenols.

A  second  waste  source  is  discharged from oil sampling lines.
This should be separable but may form emulsions in the sewer.

A third possible waste source is the very  stable  oil  emulsions
formed  in  the  barometric condensers used to create the reduced
pressures  in  the  vacuum  distillation  units.   However,  when
barometric  condensers  are replaced with surface condensers, oil
vapors do not come in contact with water; consequently, emulsions
do not develop.

Trends

The general industry trend to larger and more complete refineries
has been  reflected  also  in  larger  and  more  complete  crude
fractionation  units.   Thus,  simple atmospheric "topping" units
are being replaced by the atmospheric- vacuum  combinations  with
an  increasing  number  of sidestream products.  Installed vacuum
fractionation capacity  now  totals,  0.8  million  cu  m/day  (5
million  bbl/day).   (3)   Modern refineries are installing surface
condensers to significantly reduce waste water loads from  vacuum
operations.

4.  CRACKING

A.  THERMAL CRACKING

Process Description

This fundamental process is defined  in  this  study  to  include
visbreaking  and coking, as well as regular thermal cracking.  In
each of these operations, heavy gas oil  fractions   (from  vacuum
stills)  are  broken  down  into lower molecular weight fractions
such as domestic heating  oils,  catalytic  cracking  stock,  and
other  fractions  by  heating, but without the use of a catalyst.
Typical thermal cracking conditions are 480°  -  603°C,   (900°
1100°F)  and 41.6 - 69.1 atm  (600-1000 psig).  The high pressures
result from the formation of light hydrocarbons in  the  cracking
reaction  (olefins, or unsaturated compounds, are always formed in
this chemical conversion).  There is also always a certain amount
of   heavy  fuel  oil  and  coke  formed  by  polymerization  and
condensation reactions.

Wastes

The major source of  waste  water  in  thermal  cracking  is  the
overhead   accumulator   on  the  fractionator,  where  water  is
separated from the  hydrocarbon  vapor  and  sent  to  the  sewer
system.   This  water  usually contains various oil and fractions
and may be high in BOD5, COD, ammonia, phenol, and sulfides,  and
may have a high alkalinity.

Trends


                               25

-------
Regular  thermal  cracking, which was an important process before
the development of  catalytic  cracking,  is  being  phased  out.
Visbreaking  and coking units are still installed but, because of
product sulfur restrictions, to  a  lesser  extent  than  before.
With  the  trends  toward  dirtier crudes containing more sulfur,
hydrocracking  and  propane  deasphalting  are   receiving   more
attention  to  recover  salable  products with low sulfur content
from the residuum.

B.  CATALYTIC CRACKING

Process Description

Catalytic  cracking,  like   thermal   cracking,   breaks   heavy
fractions,  principally  gas  oils,  into  lower molecular weight
fractions.  This is probably the key process in the production of
large volumes of high-octane gasoline stocks;  furnace  oils  and
other   useful  middle  molecular  weight  distillates  are  also
produced.  The use of a  catalyst  permits  operations  at  lower
temperatures  and  pressures  than  with  thermal  cracking,  and
inhibits  the  formation  of  undesirable  polymerized  products.
Fluidized  catalytic  processes,  in  which  the  finely powdered
catalyst is handled as a fluid, have largely replaced  the  fixed
bed  and  moving  bed  processes,  which use a beaded or pelleted
catalyst.  A schematic flow diagram of fluid  catalytic  cracking
is shown in Figure 3.

The  process  involves  at  least  four  types  of reactions:  1)
thermal decomposition; 2)   primary  catalytic  reactions  at  the
catalyst  surface;  3)  secondary catalytic reactions between the
primary products, and U)  removal of polymerizable  products  from
further  reactions by absorption onto the surface of the catalyst
as coke.  This last reaction is the  key  to  catalytic  cracking
because  it  permits  decomposition  reactions  to move closer to
completion than is possible in simple thermal cracking.  Cracking
catalysts  include  synthetic  and/or   natural   silica-alumina,
treated  bentonite  clay, Fuller's earth, aluminum hydrosilicates
and bauxite.  These catalysts are in the form of beads,  pellets,
and  powder,  and are used in either a fixed, moving or fluidized
bed.  The catalyst is usually heated,  lifted  into  the  reactor
area  by  the  incoming  oil  feed which, in turn, is immediately
vaporized upon contact.  Vapors from  the  reactors  pass  upward
through  a cyclone separator, which removes most of the entrained
catalyst.  These vapors then enter the  fractionator,  where  the
desired  products  are  removed and heavier fractions recycled to
the reactor.

Wastes

Catalytic cracking units are one of the largest sources  of  sour
and   phenolic   wastewaters  in  a  refinery.   Pollutants  from
catalytic cracking generally come from the  steam  strippers  and
overhead  accumulators  on  fractionators,  used  to  recover and
separate  the  various  hydrocarbon  fractions  produced  in  the
catalytic reactors.
                                26

-------
 PRESSURE
 REDUCING
 ORIFICE
 CHAMBER
  u
      is
FLUE GAS STEAM
   GENERATOR  U

  COMBUSTION AIR11
O
RAW OIL
CHARGE
                       REACTOR
                            CATALYST
                            STRIPPER
                        F. EG EN ERATO R
                      COMBINED  REACTOR
                          CHARGE
                                                  J L
                                          J L
                                              GAS AND GASOLINE TO
                                              GAS CONCENTRATION PLANT
                                                MAIN COLUMN

                                                LIGHT CYCLE GAb OIL
                                                                 »
                                                HEAVY CYCLE GAS OIL.
                                                 A
                                                   HEAVY RECYCLE CHARGE


                                                       CLARIFIED SLURRY^
                                                                   SLURRY
                                                                   SETTLER
                                                                    RAW OIL
                                                                    SLURRY CHARGE
                        Figure  3


                     CATALYTIC CRACKING

                 (FLUID  CATALYTIC CRACKING)
                             27

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The major pollutants resulting from catalytic cracking operations
are   oil,  sulfides,  phenols,  cyanides,  and  ammonia.   These
pollutants produce an alkaline waste water with high BOD5 and COD
concentrations.  Sulfide and phenol concentrations in  the  waste
water  vary  with  the  type of crude oil being processed, but at
times  are  significant.   Regeneration  of  spent  catalyst  may
produce  enough  carbon monoxide and catalyst fines to constitute
an air pollution problem.

Trends

Recycle rates have been declining since 1968, and  the  trend  is
expected  to  continue  due to the development of higher activity
catalysts (molecular sieve catalysts, as opposed to high  surface
area  silica-alumina  catalysts).   The  trend in subprocesses is
toward greater use of large fluid catalytic cracking  in  prefer-
ence  to  moving or fixed-bed cracking.  Catalytic cracking units
are also being  supplanted  by  hydrocracking  and  hydrotreating
processes.   During  1972, a decline of 1.4 percent in fresh feed
catalytic cracking capacity was experienced in the United States.
(3)

C.  HYDROCRACKING

Process Description

This process is basically catalytic cracking in the  presence  of
hydrogen, with lower temperatures and higher pressures than fluid
catalytic cracking.  Hydrocracking temperatures range from 203° -
425°C  (400° - 800°F), while pressures range from 7.8 - 137.0 atm
(100 to 2000 psig).  Actual conditions and  hydrogen  consumption
depend  upon  the  feedstock,  and  the  degree  of hydrogenation
required.  The molecular weight distribution of the  products  is
similar  to catalytic cracking, but with the reduced formation of
olefins.

Wastes

At least one waste water stream from the process should  be  high
in  sulfides,  since  hydrocracking reduces the sulfur content of
the material being cracked.  Most of the sulfides are in the  gas
products  which  are  sent  to a treating unit for removal and/or
recovery of sulfur and ammonia.  However, in  product  separation
and fractionation units following the hydrocracking reactor, some
of the HS will dissolve in the waste water being collected.  This
water  from  the separator and fractionator will probably be high
in sulfides,  and  possibly  contain  significant  quantities  of
phenols and ammonia.

Trends

Hydrocracking  has greater flexibility than catalytic cracking in
adjusting operations to meet changing product demands.   For  the
last  few  years,  it  has  been  one of the most rapidly growing
refining processes.  This trend is expected to continue.
                             28

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5.  HYDROCARBON REBUILDING

A.  POLYMERIZATION

Process Description

Polymerization  units  are  used  to  convert  olefin  feedstocks
(primarily  propylene)  into  higher octane polymer units.  These
units generally consist of a feed  treatment  unit   (remove  H2S,
mercaptans,  nitrogen  compounds),  a  catalytic reactor, an acid
removal section, and a gas stabilizer.  The catalyst  is  usually
phosphoric  acid,  although  sulfuric  acid is used in some older
methods.  The catalytic reaction occurs at 147° - 22U°C   (300°  -
435°F) ,  and  a  pressure  of 11.2 - 137.0 atm (150 - 2000 psig).
The temperature and pressure vary with the individual  subprocess
used.

Wastes

Polymerization  is  a  rather dirty process in terms of pounds of
pollutants per  barrel  of  charge,  but  because  of  the  small
polymerization  capacity  in  most  refineries,  the  total waste
production from the process is small.  Even  though  the  process
makes  use  of  acid  catalysts,  the  waste  stream is alkaline,
because the acid catalyst in most subprocesses is  recycled,  and
any  remaining  acid  is removed by caustic washing.  Most of the
waste material comes from the pretreatment of  feedstock  to  the
reactor.   The  waste  water is high in sulfides, mercaptans, and
ammonia.  These materials  are  removed  from  the  feedstock  in
caustic acid.

Trends

Polymerization is a marginal process, since the product octane is
not significantly higher than that of the basic gasoline blending
stocks,  and  does not provide much help in upgrading the overall
motor fuel pool.  In addition,  alkylation  yields  per  unit  of
olefin   feed   are   much  better  than  polymerization  yields.
Consequently, the current polymerization downtrend is expected to
continue.

B.  ALKYLATION

Process Description

Alkylation is the reaction of an isoparaffin (usually  isobutane)
and  an olefin  (propylene, butylene, amylenes)  in the presence of
a catalyst at carefully controlled temperatures and pressures  to
produce  a  high  octane  alkylate for use as a gasoline blending
component.  Propane and butane are also produced.  Sulfuric  acid
is  the  most widely used catalyst, although hydrofluoric acid is
also used.  The reactor products  are  separated  in  a  catalyst
recovery   unit,  from  which  the  catalyst  is  recycled.   The
hydrocarbon stream is passed through a  caustic  and  water  wash
before going to the fractionation section.
                               29

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Wastes

The  major  discharge from sulfuric acid alkylation are the spent
caustics from the neutralization of hydrocarbon  streams  leaving
the sulfuric acid alkylation reactor.  These waste waters contain
dissolved   and  suspended  solids,  sulfides,  oils,  and  other
contaminants.  Water drawn off  from  the  overhead  accumulators
contains   varying   amounts   of   oil,   sulfides,   and  other
contaminants, but  is  not  a  major  source  of  waste  in  this
subprocess.   Most  refineries  process  the  waste sulfuric acid
stream from the reactor to recover clean acids, use it as if  for
neutralization of other waste streams, or sell it.

Hydrofluoric acid alkylation units have small acid rerun units to
purify  the acid for reuse.  HF units do not have a spent acid or
spent caustic waste stream.  Any leaks  or  spills  that  involve
loss  of  fluorides  constitute a serious and difficult pollution
problem.  Formation of fluosilicates has caused line plugging and
similar problems.  The major sources of waste  material  are  the
overhead accumulators on the fractionator.

Trends

Alkylation  process  capacity  is currently declining slowly, but
this trend may be reversed, as the  demand  for  low  lead,  high
octane gasoline increases.

6.  HYDROCARBON REARRANGEMENTS

A.  ISOMERIZATION

Process Description

Isomerization is a process technique for obtaining higher  octane
motor  fuel by converting light gasoline stocks into their higher
octane isomers.  The greatest application has  been,  indirectly,
in  the  conversion  of isobutane from normal butane, for uses as
feedstock for the alkylation process.  In a  typical  subprocess,
the  desulfurized  feedstock  is  first  fractionated to separate
isoparaffins from normal paraffins.   The  normal  paraffins  are
then   heated,  compressed,  and  passed  through  the  catalytic
hydrogenation reactor which  isomerizes  the  n-paraffin  to  its
respective high octane isomer.  After separation of hydrogen, the
liquids are sent to a stabilizer, where motor fuel blending stock
or synthetic isomers are removed as products.

Wastes

Isomerization  waste  waters present no major pollutant discharge
problems.  Sulfides and ammonia are not likely to be  present  in
the  effluent.   Isomerization waste waters should also be low in
phenolics and oxygen demand.

Trends
                              30

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The requirements for units to  isomerize  n-butane  to  isobutane
will  not  be as great in refineries where hydrocracking is being
installed, as the hydrocracking process yields an off-gas rich in
isobutane.  However, the isomerization capacity of U.S.  refiners
is  not  expected  to  decrease,  but  to continue to grow as the
demand for motor fuel grows.

B.  REFORMING

Process Description

Reforming  converts  low  octane  naphtha,  heavy  gasoline,  and
napthene-rich  stocks,  to  high  octane gasoline blending stock,
aromatics for petro-chemical use, and isobutane.  Hydrogen  is  a
significant  by-product  of  the  process.   Reforming  is a mild
decomposing process, since some  reduction  occurs  in  molecular
size  and boiling range of the feedstock.  Feedstocks are usually
hydrotreated for the removal of  sulfur  and  nitrogen  compounds
prior  to  charging to the reformer, since the platinum catalysts
widely used are readily poisoned.

The predominant reaction during reforming is the  dehydrogenation
of   naphthenes.    Important   secondary   reactions   are   the
isomerization and dehydrocyclization  of  paraffins.   All  three
reactions result in higher octane products.

One  subprocess  may  be  divided  into three parts:  the reactor
heater section, in which the charge plus recycle  gas  is  heated
and  passed  over  the  catalyst  in  a  series of reactions; the
separator drum, in which the reactor effluenr is  separated  into
gas and liquid streams, the gas being compressed for recycle; and
the   stabilizer  section,  in  which  the  separated  liquid  is
stabilized  to  the  desired  vapor  pressure.   There  are  many
variations in subprocesses, but the essential, and frequently the
only, difference is the composition of the catalyst involved.

Wastes

Reforming  is  a  relatively  clean process.  The volume of waste
water flow is small, and none of the waste water streams has high
concentration of significant  pollutants.   The  waste  water  is
alkaline,  and  the  major pollutant is sulfide from the overhead
accumulator on the stripping tower used to  remove  light  hydro-
carbon   fractions  from  the  reactor  effluent.   The  overhead
accumulator catches any  water  that  may  be  contained  in  the
hydrocarbon  vapors.   In  addition  to sulfides, the waste water
contains small amounts of ammonia, mercaptans and oil.

Trends

Reforming capacity in the U.S. is currently growing at about  the
same  rate  as  total  crude  capacity.   This  growth  rate  may
increase, however, as the demand for motor fuel grows.
                             31

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7. SOLVENT REFINING

Refineries employ a wide spectrum of contact  solvent  processes,
which  are  dependent  upon  the differential solubilities of the
desirable and undesirable feedstock  components.   The  principal
steps are:  counter-current extraction, separation of solvent and
product  by  heating  and  fractionation,  and  solvent recovery.
Napthenics, aromatics unsaturated hydrocarbons, sulfur and  other
inorganics  are separated, with the solvent extract yielding high
purity products.  Many  of  the  solvent  processes  may  produce
process  waste waters which contain small amounts of the solvents
employed.  However, these are ususally minimized, because of  the
economic incentives for reuse of the solvents.

Process Description

The major processes include:

Solvent  Deasphalting  -  The  primary  purpose  of  solvent  de-
asphalting is to recover lube or  catalytic  cracking  feedstocks
from  asphaltic residuals, with asphalt as a by-product.  Propane
deasphalting  is   the   predominant   technique.    The   vacuum
fractionation  residual  is  mixed  in  a fixed proportion with a
solvent in which asphalt is not  soluble.   The  solvent  is  re-
covered  from  the oil via steam stripping and fractionation, and
is reused.  The asphalt  produced  by  this  method  is  normally
blended into fuel oil or other asphaltic residuals.

Solvent  Dewaxing - Solvent dewaxing removes wax from lubricating
oil stocks by promoting crystallization  of  the  wax.   Solvents
which  are  used  include:   furfural,  phenol,  cresylic  acid -
propane  (Duo-Sol), liquid sulfur dioxide (Eleleanu process),  B-B
-  dichloroethyl  ether,  methyl  ethyl ketone, nitrobenzene, and
sulfur-benzene.  The  process  yields  de-oiled  waxes,  wax-free
lubricating oils, aromatics, and recovered solvents.

Lube Oil Solvent Refining - This process includes a collection of
subprocesses  for improving the quality of lubricating oil stock.
The raffinate or refined lube oils obtain  improved  temperature,
viscosity,  color  and  oxidation  resistance characteristics.  A
particular solvent is selected  to  obtain  the  desired  quality
raffinate.   The  solvents  include:   furfural,  phenol,  sulfur
dioxide, and propane.

Aromatic Extraction - Benzene,  toluene,  and  xylene   (BTX)  are
formed  as  by-products  in  the reforming process.  The reformed
products are fractionated to give a BTX concentrate cut, which in
turn is extracted from the napthalene and the paraffinics with  a
glycol base solvent.

Butadiene  Extraction  -  Approximately  15  percent  of the U.S.
supply of butadiene is extracted from the C4 cuts from  the  high
temperature  petroleum  cracking  processes.  Furfural or cuprous
ammonia  acetate   (CAA)  are  commonly  used  for   the   solvent
extraction.
                             32

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Wastes

The  major potential pollutants from the various solvent refining
subprocesses are the solvents themselves.  Many of the  solvents,
such  as  phenol,  glycol,  and  amines, can produce a high BODS.
Under ideal conditions the solvents are continually  recirculated
with  no  losses  to  the  sewer.  Unfortunately, some solvent is
always lost through pump seals, flange leaks, and other  sources.
The   main   source   of  waste  water  is  from  the  bottom  of
fractionation towers.  Oil and solvent are the major waste  water
constituents.

Trends

Solvent  extraction capacities can be expected to slowly increase
as quality requirements for all  refinery  products  become  more
stringent,  as  the  demand  for  lube  oils  grows,  and  as the
petrochemicals   industry   continues   to   require   increasing
quantities of aromatics.

8.  HYDROTREATING

Process Descrip-tion

Hydrotreating processes are used  to  saturate  olefins,  and  to
remove sulfur and nitrogen compounds, odor, color and gum-forming
materials,  and  others  by  catalytic  action in the presence of
hydrogen,  from  either   straight-run   or   cracked   petroleum
fractions.   In  most  subprocesses,  the feedstock is mixed with
hydrogen, heated, and charged  to  the  catalytic  reactor.   The
reactor  products  are  cooled,  and the hydrogen, impurities and
high grade product separated.  The principal  difference  between
the  many  subprocesses  is  the  catalyst;  the  process flow is
similar for essentially all subprocesses.

Hydrotreating processes are used to reduce the sulfur content  of
product  streams  from sour crudes by approximately 90 percent or
more.   Nitrogen   removal   requires   more   severe   operating
conditions,  but generally 80 - 90 percent, or better, reductions
are accomplished.

The primary  variables  influencing  hydrotreating  are  hydrogen
partial  pressure,  process  temperature,  and  contact time.  An
increase  in  hydrogen  pressure  gives  a  better   removal   of
undesirable  materials and a better rate of hydrogenation.  Make-
up hydrogen requirements are generally high enough to  require  a
hydrogen  production  unit.   Excessive temperatures increase the
formation of coke, and the contact time is set to  give  adequate
treatment  without  excessive  hydrogen  usage  and/or undue coke
formation.  For the various hydrotreating processes the pressures
range from 7.8 - 205.1 atm   (100  to  3000  psig).   Temperatures
range  from  less than 177°C (350<>F) to as high as 450°C  (850°F) ,
with most processing done in the range of 314°C  (600°F) to  427°C
 (800°F).  Hydrogen consumption is usually less than 5.67 NM3 (200
scf) per barrel of charge.

Principal hydrotreating subprocesses are used as follows:
                              33

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         1.   Pretreatment of catalytic reformer feedstock.
         2.   Naphtha desulfurization.
         3.   Lube oil polishing.
         4.   Pretreatment of catalytic cracking feedstock.
         5.   Heavy gas-oil and residual desulfurization.
         6.   Naphtha saturation.
Wastes
The   strength   and   quantity  of  waste  waters  generated  by
hydrotreating depends upon the  subprocess  used  and  feedstock.
Ammonia  and  sulfides  are the primary contaminants, but phenols
may  also  be  present,  if  the  feedstock  boiling   range   is
sufficiently high.

Trends

The  use  of  hydrotreating  is increasing and should continue to
increase at a greater rate than crude capacity since the  process
can  be  applied  to  almost any sour feedstock, is flexible, and
eliminates contaminants of concern to the refining industry  from
an  operating  standpoint,  and  to  the  general  public from an
aesthetic standpoint.

9.  GREASE MANUFACTURING

Process Description

Grease  manufacturing  processes  require  accurate   weight   or
volumetric  measurements  of  feed  components,  intimate mixing,
rapid heating and cooling, together with milling, dehydration and
polishing in batch reactions.  The feed components  include  soap
and petroleum oils, with inorganic clays and other additives.

Grease  is primarily a soap and lube oil mixture.  The properties
of grease are determined in large part by the properties  of  the
soap  component.   For example, sodium metal base soaps are water
soluble and would then not be suitable for water contact service.
A calcium soap grease can be used in water service.  The soap may
be purchased as a raw material or may be manufactured on site  as
an auxiliary process.

Wastes

Only  very  small  volumes  of  waste water are discharged from a
grease manufacturing process.  A small amount of oil is  lost  to
the waste water system through leaks in pumps.  The largest waste
loading occurs when the batch units are washed, resulting in soap
and oil discharges to the sewer system.

Trends

Because  of  an increase in sealed grease fittings in automobiles
and longer lasting greases, a slight decline in grease production
is expected through 1975.


                                34

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10. ASPHALT PRODUCTION

Process Description

Asphaltic feedstock (flux) is contacted with  hot  air  at  203°C
(400°F)  to  280°C  (550°F)  to obtain desirable asphalt product.
Both batch and continuous processes are in operation at  present,
but   the   batch  process  is  more  prevalent  because  of  its
versatility.  Nonrecoverable catalytic compounds include:  Copper
sulfate,  zinc  chloride,  ferric  chloride,  aluminum  chloride,
phosphorous   pentoxide,  and  others.   The  catalyst  will  not
normally contaminate the process water effluent.

Wastes

Waste waters from asphalt blowing contain high concentrations  of
oils,  and  have high oxygen demand.  Small quantities of phenols
may also be present.

11. PRODUCT FINISHING

A.  DRYING AND SWEETENING

Process Description

Drying and sweetening is  a  relatively  broad  process  category
primarily  used  to  remove  sulfur  compounds,  water  and other
impurities from gasoline, kerosene, jet fuels,  domestic  heating
oils,   and   other  middle  distillate  products.   "Sweetening"
pertains to the  removal  of  hydrogen  sulfide,  mercaptans  and
thiophenes, which impart a foul odor and decrease the tetra-ethyl
lead susceptibility of gasoline.  The major sweetening operations
are oxidation of mercaptans or disulfides, removal of mercaptans,
and  destruction  and removal of all sulfur compounds.  Drying is
accomplished by salt filters or absorptive clay  beds.   Electric
fields  are  sometimes  used  to  facilitate  separation  of  the
product.

Wastes

The  most  common  waste  stream  from  drying   and   sweetening
operations  is spent caustic.  The spent caustic is characterized
as phenolic or sulfidic, depending on which  is  present  in  the
largest  concentration.   Whether  the  spent caustic is actually
phenolic or sulfidic is mainly determined by the  product  stream
being  treated.  Phenolic spent caustics contain phenol, cresols,
xylenols, sulfur compounds,  and  some  neutral  oils.   Sulfidic
spent  caustics  are  rich  in  sulfides,  but do not contain any
phenols.  These spent caustics have very high BOD£ and COD.   The
phenolic  caustic  streams  are  usually sold for the recovery of
phenolic materials.

Other waste streams from the process result from water washing of
the treated product and regeneration  of  the  treating  solution
such  as  sodium plumbite  (No2 PbO2) in doctor sweetening.  These
                             35

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waste streams will contain small amounts of oil and the  treating
material, such as sodium plumbite (or copper from copper chloride
sweetening) .

The treating of sour gases produces a purified gas stream, and an
acid  gas  stream  rich in hydrogen sulfide.  The H2S rich stream
can be flared, burned as  fuel,  or  processed  for  recovery  of
elemental sulfur.

Trends

As  air  pollution  agencies  increase  their  efforts to control
sulfur emissions to the atmosphere, the  restrictions  on  sulfur
content  in fuels can be expected to tighten.  This will generate
a strong trend to replacement of the sweetening processes by more
hydrotreating  (desulfurization),  because  hydrotreating  removes
almost  all  sulfur  compounds  and  not  just  hydrogen sulfide,
mercaptans,  and  elemental  sulfur.   Nevertheless,  on  certain
feedstocks sweetening will continue to be used because it will be
as  effective as, and more economical than, hydrotreating.  Those
processes producing high waste loads  (Doctor  Sweetening,  etc.)
are being replaced by lower waste-producing processes.

B.  LUBE OIL FINISHING

Process Description

Solvent refined and  dewaxed  lube  oil  stocks  can  be  further
refined  by  clay  or  acid treatment to remove color-forming and
other undesirable materials.  Continuous contact  filtration,  in
which  an oil-clay slurry is heated and the oil removed by vacuum
filtration, is the most widely used subprocess.

Wastes

Acid treatment of lubricating oils produces acid  bearing  wastes
occuring  as rinse waters, sludges, and discharges from sampling,
leaks  and  shutdowns.   The  waste  streams  are  also  high  in
dissolved  and suspended solids, sulfates, sulfonates, and stable
oil emulsions.

Handling of acid sludge can  create  additional  problems.   Some
refineries  burn  the  acid  sludge  as fuel.  Burning the sludge
produces large volumes of  sulfur  dioxide  that  can  cause  air
pollution  problems.  Other refineries neutralize the sludge with
alkaline wastes and discharge it to the sewer, resulting in  both
organic  and inorganic pollution.  The best method of disposal is
probably processing to recover the sulfuric acid, but  this  also
produces  a  waste water stream containing acid, sulfur compounds
and emulsified oil.

Clay treatment results in only small quantities  of  waste  water
being  discharged  to  the sewer.  Clay, free oil, and emulsified
oil are the major waste constituents.  However, the operation  of
clay  recovery kilns involves potential air pollution problems of
                                36

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hydrocarbon and particulate emissions.  Spent clays  usually  are
disposed of by landfill.

Trends

Acid  and clay treatment of lube oils is gradually being replaced
by hydrotreating methods.  Acid treatment in particular is  being
phased out rather rapidly.

C.  BLENDING AND PACKAGING

Process Description

Blending is  the  final  step  in  producing  finished  petroleum
products  to meet quality specifications and market demands.  The
largest volume operation is  the  blending  of  various  gasoline
stocks (including alkylates and other high-octane components)  and
anti-knock  (tetra-ethyl  lead) , anti-rust, anti-icing, and other
additives.  Diesel fuels, lube oils, and waxes  involve  blending
of  various components and/or additives.  Packaging at refineries
is generally highly-automated  and  restricted  to  high  volume,
consumer-oriented products such as motor oils.

Wastes

These  are  relatively  clean  processes because care is taken to
avoid loss of product through spillage.  The  primary  source  of
waste  material  is  from  the  washing  of railroad tank cars or
tankers prior to loading finished products.   These  wash  waters
are high in emulsified oil.

Tetra-ethyl  lead is the major additive blended into gasoline and
it must be  carefully  handled  because  of  its  high  toxicity.
Sludges  from  finished  gasoline storage tanks can contain large
amounts of lead and should not  be  washed  into  the  wastewater
system.

Trends

There  will  be  an  increased  use  of  automatic  proportioning
facilities for product blending with a trend  toward  contracting
out  of packaging of lower-volume products that are less suitable
to highly-automated operation.

12. AUXILIARY ACTIVITIES

A.  HYDROGEN MANUFACTURE

Process Description

The rapid growth of hydrotreating and hydrocracking has increased
the demand for hydrogen beyond the level of  by-product  hydrogen
available  from reforming and other refinery processes.  The most
widely used process  for  the  manufacture  of  hydrogen  in  the
refinery  is  steam reforming, which utilizes refinery gases as a


                              37

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charge stock.  The charge is purified to remove sulfur  compounds
that would temporarily deactivate the catalysts.

The  desulfurized  feedstock  is mixed with superheated steam and
charged  to  the  hydrogen  furnace.    On   the   catalyst   the
hydrocarbons  are  converted  to  hydrogen,  carbon monoxide, and
carbon dioxide.  The furnace supplies the heat needed to maintain
the reaction temperature.

The gases  from  the  furnace  are  cooled  by  the  addition  of
condensate  and  steam,  and  then  passed  through  a  converter
containing a high- or low-temperature shift catalyst depending on
the degree of carbon monoxide conversion desired.  Carbon dioxide
and hydrogen are produced by the reaction of  the  monoxide  with
steam.

The  gas  mixture  from  the  converter is cooled and passes to a
hydrogen purifying system where carbon dioxide is  absorbed  into
amine solutions and later driven off to the atmosphere by heating
the rich amine solution into the reactivator.

Since  some refining processes require a minimum of carbon oxides
in the product gas, the oxides are reacted  with  hydrogen  in  a
methanation  step.   This  reaction takes place in the methanator
over a nickel catalyst at elevated temperatures.

Hydrocarbon impurities in the product hydrogen  usually  are  not
detrimental  to  the  processes where this hydrogen will be used.
Thus, a small amount of hydrocarbon is tolerable in the  effluent
gas.

Wastes

Information   concerning   wastes   from  this  process  are  not
available.  However, the process appears to be a relatively clean
one.  In the steam reforming subprocess a potential waste  source
is the desulfurization unit, which is required for feedstock that
has  not  already  been  desulfurized.   This  waste stream would
contain oil,  sulfur  compounds,  and  phenol.   In  the  partial
oxidation  subprocess  free  carbon  is  removed by a water wash.
Carbon dioxide is discharged to the atmosphere at several  points
in the subprocess.

Trends

Hydrogen  requirements  of  the rapidly growing hydrocracking and
hydrotreating processes in many instances exceed  the  by-product
hydrogen   available   from  catalytic  reforming  units.   Since
hydrocracking and hydrotreating are expected to grow more rapidly
than  other  refinery  processes,   the   demand   for   hydrogen
manufacturing units should continue to be strong.
                             38

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B.  UTILITIES FUNCTION

Utility functions such as the supply of steam and  cooling  water
generally  are  set up to service several processes.  Boiler feed
water is prepared and steam  is  generated  in  a  single  boiler
house.   Non-contact steam used for surface heating is circulated
through  a  closed  loop  whereby  varying  quantities  are  made
available   for   the  specific  requirements  of  the  different
processes.  The condensate  is  nearly  always  recycled  to  the
boiler house, where a certain portion is discharged as blowdown.

The  three  major uses of steam generated within a refinery plant
are:

         1.   For   non-contact   process   heating.    In   this
              application,  the  steam  is  normally generated at
              pressures of 9.5 to 45.2 atm  (125 to 650 psig).

         2.   For  power  generation  such  as  in   steam-driven
              turbines,  compressors,  and  pumps associated with
              the process.  In this  application,  the  steam  is
              normally  generated at pressures of 45.2 to 103 atm
              (650 to 1500 psig) and requires superheating.

         3.   For use as a diluent, stripping medium,  or  source
              of  vacuum  through  the use of steam jet ejectors.
              This steam actually contacts  the  hydrocarbons  in
              the  manufacturing  processes  and  is  a source of
              contact process waste water when condensed.  It  is
              used  at  a  substantially  lower pressure than the
              foregoing and frequently is exhaust steam from  one
              of the other uses.

Steam  is  supplied  to  the different users throughout the plant
either  by  natural-  circulation,  vapor-phase  systems,  or  by
forced-circulation  liquid  heat-transfer systems.  Both types of
systems discharge some condensate as  blowdown  and  require  the
addition   of   boiler   make-up   water.    The  main  areas  of
consideration in boiler operation are normally boiler efficiency,
internal deposits, corrosion, and the required steam quality.

Boiler efficiency is dependent  on  many  factors.   One  is  the
elimination of boiler-tube deposition that impedes heat transfer.
The  main contributors to boiler deposits are calcium, magnesium,
silicon, iron, copper, and aluminum.  Any of thase can  occur  in
natural  waters,  and some can result from condensate return-line
corrosion  or  even  from  make-up  water  pretreatment.   Modern
industrial boilers are designed with efficiencies on the order of
80  percent.  A deposit of 0.32 cm  (1/8 inch) in depth will cause
a 2-3 percent drop in this efficiency, depending on the  type  of
deposit.

Internal  boiler  water treatment methods have advanced to such a
stage that corrosion in the steam  generation  equipment  can  be
virtually  eliminated.   The  control of caustic embrittlement in
boiler tubes and drums is accomplished through  the  addition  of
sodium  nitrate  in the correct ratio to boiler water alkalinity.
                                 39

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Caustic corrosion in high  heat  transfer  boilers  can  also  be
controlled  by  the  addition  of chelating agents.  This type of
solubilizing internal boiler water treatment has been shown to be
more  effective  than  previous  precipitation  treatment   using
phosphate.

Other  factors influencing boiler efficiency include reduction of
the  amount  of  boiler  blowdown   by   increasing   cycles   of
concentration of the boiler feedwater, efficiency of the blowdown
heat-recovery equipment, and the type of feed used.

Steam purity is of prime importance if:

    1.   The boilers are equipped with superheaters.

    2.   The boilers supply power-generation equipment.

    3.   The  steam  is  used  directly  in   a   process   where
         contamination  could  affect  product quality or destroy
         some material  (such as  a  catalyst)   essential  to  the
         manufacture of the product.

The minimum purity required for contact steam (or contact process
water)  varies  from  process  to  process.  Limits for suspended
solids, total solids, and  alkalinity  vary  inversely  with  the
steam pressure.  The following tabulation summarizes boiler water
concentration limits for a system providing a steam purity of 0.5
-  1.0  ppm  total solids, which is required for most non-contact
steam uses.  It should be noted that the  boiler  operation  must
incorporate  the  use  of  antifoam  agents  and steam separation
equipment for the concentrations shown to be valid.

                  Boiler Water Concentration Required to
           Maintain Steam Purity at 0.5 - 1.0 ppm Total Solids

                                     Boiler Pressure, atm.

Parameters          21.4     21.5 - 31.6   31.7 -41.8  41.9 - 52.0
Total Solids  (mg/1)    6,000       5,000        4,000       2,500
Suspended Solids(mg/1) 1,000         200          100          50
Total Alkalinity (mg/1) 1,000         900          800         750


Water conditioning or pretreatment systems are normally  part  of
the   utilities  section  of  most  plants.   From  the  previous
discussions, it is obvious that the  required  treatment  may  be
quite  extensive.  Ion-exchange demineralization systems are very
widely employed,  not  only  for  conditioning  water  for  high-
pressure  boilers,  but  also  for  conditioning  various process
waters.  Clarification  is  also  widely  practiced  and  usually
precedes the ion-exchange operation.

Non-contact  cooling  water  also is normally supplied to several
processes from the utilities area.  The system is either  a  loop
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which utilizes one or more evaporative cooling towers, or a once-
through system with direct discharge.

Cooling  towers  accomplish  the cooling of water circulated over
the tower by moving a predetermined flow of ambient  air  through
the  tower with large fans.  The air water contact causes a small
amount of the water to be evaporated by the air.   Thus,  through
latent  heat  transfer,  the remainder of the circulated water is
cooled.

Approximately 252 kg cal  (1,000 BTU) are removed from  the  total
water circulation by the evaporation of O.H5U kg (1 Ib) of water.
Therefore,  if  45.4  kg  (100 Ibs)  of water are introduced at the
tower inlet and O.U54 kg  (1 Ib)  is evaporated to the moving  air,
the remaining 44.9 kg  (99 Ibs) of water are reduced in total heat
content  by  252  kg  cal  (1,000 BTU), of water leaving the tower
have been cooled 3.24°c/kg/kg cal  (l°F/lb/BTU  removed,  and  the
exit temperature is reduced by about 5,500  (1C°F).   This leads to
the  common  rule  of thumb:  1 percent evaporation loss for each
5.5°C  (10°F) cooling.

Since cooling is primarily by transfer of  latent  heat,  cooling
tower selection is based on the total heat content or enthalpy of
the  entering  air.   At any one enthalpy condition, the wet bulb
temperature is constant.  Therefore, cooling towers are  selected
and  guaranteed  to  cool  a specific volume of water from a hot-
water temperature to a cold-water temperature while operating  at
a design wet-bulb temperature.  Design wet-bulb temperatures vary
from   15.6°C   (60°F)  to  35°C (85°F) depending on the geographic
area, and are usually equaled or exceeded only 2.5 percent  to  5
percent of the total summer operating time.

Hot  water  temperature  minus  cold  water temperature is termed
cooling range, and the difference between cold water and wet-bulb
temperature is called approach.

A closed system is  normally  used  when  converting  from  once-
through  river cooling of plant processes.  In the closed system,
a cooling tower is used for cooling all of the hot water from the
processes.  With the closed system, make-up water from the  river
is required to replace evaporation loss at the tower.

Two  other water losses also occur.  The first is drift, which is
droplet carryover in the air as contrasted to  evaporative  loss.
The cooling tower industry has a standarized guarantee that drift
loss  will  not  exceed 0.2 percent of the water circulated.  The
second loss in the closed system is blowdown to sewer  or  river.
Although blowdown is usually taken off the hot water line, it may
be  removed  from  the  cold water stream in order to comply with
regulations that limit the temperature of water returned  to  the
stream.   Blowdown from a tower system will vary depending on the
solids concentration in the make-up water, and on the  occurrence
of  solids that may be harmful to equipment.  Generally, blowdown
will be about 0.3 percent per 5.5°C  (10°F) of cooling,  in  order
                                 41

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to  maintain  a solids concentration in the recirculated water of
three to four times that of the make-up water.

The quantity and quality of the blowdown form boilers and cooling
towers depend on the  design  of  the  particular  plant  utility
system.   The  heat content of these streams is purely a function
of the  heat  recovery  equipment  associated  with  the  utility
system.   The  amounts  of waste brine and sludge produced by ion
exchange and water treatment systems depend  on  both  the  plant
water  use function and the intake source.  None of these utility
waste streams can be related directly to specific process units.

Quantitative limitations on parameters such as dissolved  solids,
hardness,  alkalinity,  and  temperature,  therefore,  cannot  be
allocated  on  a  production  basis.   The  limitations  on  such
parameters  associated  with non-contact utility effluents should
be established on the basis of the water quality criteria of  the
specific  receiving water body or an EPA study of all industries,
to define specific utility effluent limitations.

Refinery Distribution

There are a total of 252 operating petroleum  refineries  in  the
United  States, Puerto Rico and the Virgin Islands, as of January
1, 1973, with a combined capacity of 2.24 million  cu  m/day  (14
million  barrels/day)  of  crude oil processing (see Figure 4 and
Table 10).  The capacity of these plants range from 32  cu  m/day
(200 bbl/day) to 69,000 cu m/day (434,000 bbl/day) of crude oil.

Within the United States, refineries are concentrated in areas of
major  crude  production (California, Texas, Louisiana, Oklahoma,
Kansas), and in major population areas (Illinois, Indiana,  Ohio,
Pennsylvania, Texas, and California).

There  are  an  almost  unlimited  number of process combinations
possible within the process area, or  "Battery  Limits",  of  the
typical  refinery.   Selection  of  the  processing route for the
manufacture of a particular product mix at a particular  location
or  time  is  a decision based on the particular refiner's unique
situation.  In order to illustrate the  diversity  of  operations
which  may  be  included  within  a  refinery, Figure 5 shows the
schematic  flow  diagram  for  a  hypothetical  15,900  cu  m/day
(100,000   bbl/day)   integrated   refinery.   This  hypothetical
refinery includes essentially all production processes previously
outlined; hence the hypothetical refinery shown in  Figure  5  is
completely   integrated   for  current  U.S.  refinery  capacity.
Inspection of Table 11 demonstrates the general  distribution  of
refining processes.

The  trend in the petroleum refining industry is toward fewer and
larger  refineries,  which  are  integrated  with  satellite   or
companion  industries.   This  consolidation trend for a six-year
period   (1967-1973)  is  shown  in  Table  12.   Refineries  with
capacities  over  15,900 cu m/day (100,000 bbl/day)  (11.5 percent
of the total) represented 48 percent  of  the  domestic  refinery
                               42

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                                       TABLE 10

                     CRUDE CAPACITY OF PETROLEUM REFINERIES BY
                        STATES AS OF JANUARY 1, 1974T3T
State

Alabama
Alaska
Arizona
Arkansas
California
Colorado
Delaware
Florida
Georgia
Hawaii
Illinois
Indiana
Kansas
Kentucky
Louisiana
Maryland
Michigan
Minnesota
Mississippi
Missouri
Montana
Nebraska
New Jersey
New Mexico
New York
North Dakota
Ohio
Oklahoma
Oregon
Pennsylvania
Tennessee
Texas
Utah
Virginia
Washington
West Virginia
Wisconsin
Wyoming
Puerto Rico
Virgin Islands
  TOTAL
Number of Plants   Cubic Meters/Day
      4
      4
      1
      4
     34
      3
      1
      1
      2
      2
     11
      7
     11
      3
     18
      2
      6
      3
      5
      1
      8
      T
      5
      6
      2
      2
      7
     12
      1
     11
      1
     40
      6
      1
      7
      3
      1
     10
      3
      1
    251
    5,885
   10,970
    1,590
    9,220
  301,270
    9,210
   23,850
      875
    2,410
   11,720
  191,820
   93,500
   66,470
   26,550
  275,580
    3,930
   23,410
   31,480
   47,440
   17,570
   26,430
      875
  102,735
    9.080
   17,650
    8,790
   96,430
   79,130
    2,340
  115,945
    4,770
  619,550
   22,360
    8,870
   57,400
    3,260
    6,040
   28,810
   46,269
   71.550
2,483,110
Rated Crude Capacity
    Barrels/Day

       37,010
       69,020
       10,000
       58,000
    1,894,800
       57,920
      150,000
        5,500
       15,130
       73,689
    1,206,390
      588,050
      418,050
      167,000
    1,733,180
       24,740
      147,230
      198,000
      298,390
      110,530
      166,200
        5,500
      646,131
       57,130
      111,000
       55,300
      606,500
      497,695
       14,740
      729,215
       30,000
    3,896,560
      140,620
       55,790
      361,100
       20,500
       38,000
      181,210
      291,000
      450.000
   15,617,050
                                            43

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o
                                     Figure      4
                        Geographical  Distribution of Petroleum
                                  Refineries in the
                                    United States

-------
                                                                            FIGURE   5
                                                HYPOTHETICAL 100,000  BARREL/STREAM DAY INTEGRATED REFINERY
wt  mint 11 mimms mmim mms tmtnui
    II IMREL5 HI ITIEIK ttl (I/SD).

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                                                        TABLE 11

                         Process  Employment  Profile of  Refining Processes  as  of  January  1,  1973  (  3 )
   Production  Processes
Number of Refineries
Employing a Production Process
by Crude Capacity Classification
  Storage:  Crude 6 Product
  Crude Desalting
  Atmospheric Distillation
  Vacuum Distillation
jai Thermal Cracking
01 Catalytic Cracking
  Hydrocracking
  Hydrotreating:  Cat Reformer
    and Cat Crack Feed
    Middle Distillates & Naptha
    Lubes
    Heavy Oils and Residuals
    Other Feedstocks
  Alkylation
  Isomerization
  Reforming
  Aromatics
  Lubes
  Asphalt
All
Refineries
247
24?
247
175
87
141
45
129
54
13
5
57
125
30
166
35
44
111
<35
MB/SD
141
141
141
79
27
41
11
42
11
2
2
14
30
4
65
3
16
58
35 to 100
MB/SD
65
65
65
55
32
59
11
52
21
2
3
17
57
19
60
16
10
30
>100
.MB/SD
41
41
41
41
28
41
23
35
22
9
-
26
38
7
41
16
18
23
Percent of Refineries
Employing a Production Process
by Crude Capacity Classification
All
Refineries
100
100
100
70
35
57
18
52
22
5
2
23
51
12
67
14
18
45
<35
MB/SD
100
100
100
56
19
29
8
30
8
1
1
10
21
3
46
2
11
41
35 to 100
MB/SD
100
100
100
85
49
91
17
80
32
3
5
26
88
29
92
25
15
46
>100
MB/SD
100
100
100
100
68
100
56
85
54
22
-
63
93
17
100
39
44
56

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                                   TABLE 12
              Trend in Domestic Petroleum Refining from 1967 to 1973 (3,3a)
Percent
January 1, 1967 January 1, 1973 Change
Crude Capacity, M3/SD(bbl/SD) 1
Total Compnaies
Total Refineries
Refineries with Capacity 	 100
Refineries with Capacity 35
Total Capacity of All 100
,853,618


Mbbl/SD
Mbbl/SD
Mbbl/SD
(11,657,975)
146
269
31
159
5,597,300
2,224,661(13,991,580)
132
247
41
141
8,167,200
+ 20
(- 10)
(- 8)
+ 32
(- ID
+ 46
  Refineries

Average Refinery Capacity, M3/SD (bbl/SD) 6890 (43,338)   9006(55,646)           + 31
                                        47

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crude  capacity  in 1967; in 1972, 16.6 percent of the refineries
had capacities of 15,900 cu m/day (100,000 bbl/day)  or more,  and
represented  58  percent of the domestic refinery crude capacity.
Growth of the large refinery was a result of the annual need  for
increased  fuel capacity, and the imposed load due to the phasing
out of smaller refineries.  Refineries are increasing  capacities
for   reforming,   hydrotreating,   cracking,  and  isomerization
processes to obtain higher octane  gasoline  in  lieu  of  adding
lead.   Desulfurization  of  heavy fuels, longer process catalyst
life requirements, and high quality,  low sulfur, light fuels  and
lubes  are  factors  in the rapid growth of the hydrogen treating
process.  The complexity and size of the typical refinery can  be
expected  to  increase  at  a  rate comparable to the period 1967
through 1972 for the near  future,  and  no  major  technological
breakthroughs are expected that would drastically alter petroleum
processes.

Anticipated Industry Growth

The petroleum refining industry is presently facing a shortage of
crude  oil.  There have been  shortages of gasoline and fuel oil.
Since demand continues to grow  and   little  refinery  expansion
work  is  under  way,  shortages will become more severe over the
next few years.  Consumption  of  petroleum  products  will  keep
growing,  and supplies must be generated to satisfy these growing
demands.   (1972 consumption of petroleum products, shown in Table
13,  was  approximately  2.56  million  cu  m/day  (16.1  million
bbl/day).    The  growth rate in consumption has been 5.2 percent
per year; the projected growth in consumption over the next eight
years is 43 percent, or a compounded growth rate of  4.6  percent
per year.

Supplies  of  refinery  feedstocks and products will show a rapid
increase in imports.  Table 14 indicates  current  and  projected
1980  sources  of  feedstocks  and  products.   In  1972, imports
accounted for 29 percent of the total supply;  in  1980,  imports
are projected at 55 percent of the total supply.

Refinery  runs  of  crude oil are projected to increase from 1.86
million cu m/day  (11.7 million bbl/day) in 1972 to  2.73  million
cu  m/day   (17.2  million bbl/day) in 1980.  Refinery capacity in
1972 was about 2.23 million cu m/day  (14.0 million bbl/day).   By
1980 the national refinery capacity must increase to 3.18 million
cu   m/day   (20.0  million  bbl/day)   to  satisfy  the  projected
requirements.  The need for 0.95 million cu  m/day  (6.0  million
bbl/day)  of new refinery construction for real growth, plus 0.64
million cu m/day  (4.0 million bbl/day) of  new  construction  for
replacement,  indicates  a  total  of 1.59 million cu m/day  (10.0
million bbl/day) of new  refinery  construction  is  required  by
1980.

Because  of  crude supply limitations, most new refinery capacity
will be designed to process higher  sulfur  crudes.    (A  partial
list  of  analyses of crude oils from major oil fields around the
world is given in Table 15.)  The use  of  sour  crude  feedstock
                              48

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                                TABLE 13

            1972 Consumption of Petroleum Products (63)



Products                         1972 Consumption, Million Cubic Meters/Day
                                                   (Million Barrels/Day"
Motor Gasoline                                       1.02 (6.4)

Aviation Fuel                                        0.17 (1.1)

Middle Distillates                                   0.49 (3.1)

Residual Fuels                                       0.40 (2.5)

All Other Products                                   0.49 (3.1)
                                    49

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                             TABLE 14

           Sources of Supply for U.S. Petroleum Feedstocks^
                                   Supply,  Million Barrels/Day
Source                             19721980 (Projected)
Domestic Crude Oil Production       9-5                 8.5

Domestic Natural Gas Liquids        1.7                 1.5

Crude Oil Imports                   2.2                 8.7

Residual Fuel Imports               1.7                 2.5

Other Imports                       0.8                 1.5

Miscellaneous Sources               0.^                 0.5
                                   50

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                            TABLE 15




Characteristics of Crude Oils from Major Fields  Around the World  ( ^0,
Country
Abu Dhabi
Algeria
Brunei
Canada
Alberta
Bonnie Glen
Golden Spike
Judy Creek
Pembina
Swan Hi 11s
Saskatchewan
Midale
Weyburn
Indonesia
1 ran
1 rag
Libya
Mexico
Ebano Panuco
Naranjos-Cerro-Azul
Poza Rica
Peru
Saudi Arabia
United States
Alaska
Cook Inlet
Prudhoe Bay
Swanson River
Arkansas
Smackover
Gravity
39.3
46 -
21 -


41 -
36 -
42 -
35 -
41

28 -
24 -
35
31 -
35 -
37 -

12
20
35
33.5
27 -


36
30.5
29.7

22.2
, API

48
37


42
39
43
42


32
33

38
36
41




- 35.5
38







Sulfur, Percent Nitrogen, Percent

0.15
0.1


0.25
0.23

0.42
0.80

1.89
2.12
0.10
1.12 - 1.66
1.97
0.23 - 0.52

5.38
3.80
1.77
0.12
1.30 - 3-03


0.0

0.16 0.203

2.10 0.080

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                                 TABLE 15
                                  (Continued)


Country                   Gravity,  API          Sulfur,  Percent     Nitrogen,  Percent

 Cali forn ia
    Elk Hills               22.5                    0.68                0.1*72
    Huntington Beach        22.6                    1.57                0.048
    Kern River              12.6                    1.19                0.604
    Midway-Sunset           22.6                    0.94
    San Ardo                11.1                    2.25                0.913
    Wilmington              22.1                    1.44
 Colorado
    Rangely                 34.8                    0.56                0.073
 Kansas
    Bemis Shutts            34.6                    0.57                0.162
 Loui s iana
    Bayou Sale              36.2                    0.16
    Caillou Isl.            35.4                    0.23                0.040
    Golden Meadow           37.6                    0.18
    Grand Bay               35                       0.31
    Lake Barre              40.4                    0.14                0.02
    Lake Washington         28.2                    0.37                0.146
    West Bay                32.1                    0.27                0.071
    Bay Marchand Blk.  2      20.2                    0.46
    Main Pass Blk.  69        30.6                    0.25                0.098
    South Pass Blk, 24      32.3                    0.26                0.068
    South Pass Blk. 27      35.6                    0.18                0.069
    Timbalier Bay           34.4                    0.33                0.081
    West Delta Blk. 30      27                       0.33                0.09
 Mi ss i ss i ppi
    Baxterville             17.1                    2.71                 0.111
 New Mexico
    Vacuum                  35                       0.95                0.075
 Oklahoma
    Golden Trend            42.1                    0.11
 Texas
   Anahuac                 33-2                    0.23                 0.041
    Con roe                  37.6                    0.15
    Diamond M               45.4                    0.20
    East Texas              39-4                    0.32
    Hastings                 31.0                    0.15                 0.02
    Hawkins                 26.8                    2.19                 0.076
    Headlee                 51.1                  <0.10                0.083
    Kelly Snyder            38.6                    0.29                0.066
    Levelland               31.1                    2.12                 0.136
   Midland Farms           39-6                    0.13                 0.080
   Panhandle               40.4                    0.55                 0.067
    Seeliason               41.3                  <0.10                 0.014
                                      52

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                                 TABLE  15
                                   (Continued)
Country

    Tom O'Connor
    Wasson
    Webster
    Yates
 Utah
    Aneth

Venezuela

 Bachaquero
 Boscan
 Laguni1 las
 Mene Grande
 Tia Juana
 Oficina
 Los Claros
Gravity, API

   31.1
   31.9
   29.3
   30.2
                     Sulfur, Percent
21.
10.
18.
20.
21.
2*4.8
                           ,16
                           ,40
                         0.21
                         1.54
                         0.20
 ,62
 ,53
 ,18
 ,65
 ,49
0.59
                 Nitrogen, Percent

                       0.03
                       0.07
                       0.046
                       0.150

                       0.059
10.5
                                         53

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from  outside the United States will require not only a change in
processing equipment, but changes in in-plant waste water control
and treatment operations.  Some  refineries  currently  consuming
sweet  crude stocks are not employing strippers to remove minimal
amounts of ammonia and hydrogen sulfide from their waste  waters.
When  processing  sour  crude within these refineries, sour water
strippers will be required prior to discharge of the waste waters
to  biological  waste  water  treatment  facilities.   Two  stage
desalting  will  become  more  prevalent.   Other changes will be
required within the refinery to minimize  corrosion,  treat  more
sour heavy bottoms, and reduce emissions of sour gases.

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                           SECTION IV

                   INDUSTRY SUBCATEGORIZATION


Discussion of the Rationale of Subcategorization

The goal of this study is the development of effluent limitations
commensurate   with   different   levels   of  pollution  control
technology.  These effluent limitations will specify the quantity
of pollutants which will ultimately be discharged from a specific
manufacturing facility and will be related to the quantity of raw
materials consumed and the production methodology.

The diverse range of products and manufacturing processes  to  be
covered suggests that separate effluent limitations be designated
for  different  segments  within  the  industry.   To this end, a
subcategorization of the Petroleum  Refining  Industry  has  been
developed.   The  subcategorization  is  process oriented, with a
delineation between  subcategories  based  upon  raw  waste  load
characteristics   in  relation  to  the  complexity  of  refinery
operations.

Today's petroleum refinery  is  a  very  complex  combination  of
interdependent  operations  and systems.  In the development of a
pollution profile for this industry, ten major process categories
were listed as fundamental to the  production  of  principal  oil
products  (see listing in Table 8).

The   American   Petroleum   Institute   (API)  has  developed  a
classification system which utilizes this  technology  breakdown.
They   have   tentatively   divided   U.S.     refineries  into  5
classifications, which primarily  recognize  varying  degrees  of
processing  complexity  and  resultant  distribution of products.
The present API classification system is as follows:

    Class          Process Complexity

      A            Crude Topping

      B            Topping and Cracking

      C            Topping, cracking, and petrochemicals

      D            "B" Category, and lube oils processing

      E            "D" Category, and petrochemicals

Development of Industry Subcategorization

Age, size,  and  waste  water  treatability  of  refineries  were
considered during the subcategorization of the refining industry.
However,  subcategorization  by age is not necessarily useful, as
additions to and modifications of refineries are  the  industry's
principal  form  of  expansion.   Since  most  of  the technology
                             55

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employed within the  industry  is  of  an  evoluationary  nature,
refinery    age    was   not   a   major   factor   in   refinery
subcategorization.

While the size of a refinery is important in terms of  economical
waste water treatment, the control technology employed in smaller
refineries  need  not be as sophisticated a technology to achieve
parity with larger refineries within the same subcategory.

Treatability characteristics of refinery  waste  waters  indicate
that  these  waste  waters  are  generally  amenable to excellent
degrees of removal of pollutants.  Since this is an industry-wide
characteristic,   the    proper    place    to    evaluate    the
subcategorization  of  the  industry  is  with the raw waste load
delivered to the refinery waste water treatment plant.  The  1972
National  Petroleum Refining Waste Water Characterization Studies
of 135 refinery API separator effluents, provides  a  major  tool
for  this  evaluation.   Attempts  to  explain  and  justify  the
differences based solely on type and method of  cooling,  inplant
pretreatment,  and  housekeeping  practices  were also fruitless.
However, generally speaking those refineries with good  practices
in all these areas did have the lower waste loadings.

In  an  attempt to determine the effects of process technology, a
further analysis was made  of  the  API  individual  or  combined
categories  to  evaluate  the raw waste load as a function of the
degree of cracking employed within the refinery.  The  operations
included   in  degree  of  cracking  were:   thermal  operations,
catalytic cracking and hydroprocessing.  The degree  of  cracking
was  expressed  as  percentage  capacity  of  the total feedstock
processing capacity within the refinery.  The data for evaluating
the net raw  waste  loads  by  this  criteria  were  obtained  by
analyzing  the  raw  waste  load  surveys supplied by refineries,
literature sources, and analysis of the 1972  National  Petroleum
Refining Waste Water Characterization Studies.

Even  though this new breakdown was a step in the right direction
it did not explain raw  waste  load  differences  caused  by  the
amount of cracking in the other subcategories and did not explain
the  effect  of  other process on the raw waste load.  Therefore,
the effort to further  determine  the  effect  of  each  refining
process on the raw waste load continued.

Since  the  guideline  is  based  on  attainable  flow  rates and
achievable concentrations based on each treatment technology, the
effort  was  directed  toward  determining  the  relative   flows
expected from the many refining processes.

The approach taken, was the use of a multiple regression analysis
using  process  and  flow  data  from the 1972 National Petroleum
Refining  Waste  Water  Characterization   Studies.    The   data
consisted  of waste water flows and individual process capacities
for 94 refineries with less than 3 percent heat removal by  once-
through  cooling.   Those  refineries with greater than 3 percent
                                56

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once-through cooling water were not used in order to eliminate as
much of the non-process flow variation as possible.

The initial regressions carried out were in the form:
               (1) Total Flow = A + B £ Ci Pi
                   Capacity

where A,B,and C are the  constants  to  be  determined  from  the
regressions;  Pi is the capacity of individual process categories
relative to the refinery throughput and for each Pi there is a Ci
which is the relative "weight"  or  importance  of  each  process
category  in  explaining the flow.  The initial process breakdown
used was supplied through the American  Petroleum  Institute  and
broke 126 individual process types into nine process categories.

Since  the  results  of  this  initial  form  were not considered
satisfactory, attempts were made to find out what other  factors,
if any, had explanatory power in predicting refinery flow.  After
many  attempts,  it  was  found  that  in addition to the process
configuration of the refinery, the refinery size was an important
factor in explaining the flow.


The final form of the equation which gave the  best  fit  to  the
data was as follows:
           (2) log Total Flow = A + BT + C £Di Pi
                   Capacity (T)

where T or capacity is equal to the refinery throughput; A, C, Di
and  Pi  are  the  same  as A, B, Ci and Pi, respectively, in the
initial regression form; and B is a constant.

Adjustments were then made to the API breakdown  of  the  process
categories  to  improve  the fit to the data.  The 126 individual
processes were finally put into one of the following nine process
categories:

     1.  crude processes
     2.  cracking processes
     3.  hydrocarbon processing
     4.  lubes and greases
     5.  coking processes
     6.  treating and finishing processes
     7.  first generation petrochemicals
     8.  second generation petrochemicals
     9.  asphalt production

It was found that only crude processes, cracking processes, lubes
and greases, coking processes, second  generation  petrochemicals
and asphalt production showed significance in the regression.  In
addition,  even  though  second  generation petrochemicals showed
significance, the Di or "weighting factor" for it  was  -6.   The
                                 57

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nonsignificant  processes  and  second  generation petrochemicals
were therefore given 0 (zero) weighting factors.

The Di's   or  weighting  factors  for  the  significant  process
categories  are as follows: crude process f-1; cracking and coking
processes -f-6; lubes and greases *13; and asphalt production -H2.
A breakdown of the individual process in each process category is
contained in Table 51.
The values for constants B and C were then obtained by regressing
against flow with equation (2)  with  the  Di  value  defined  as
above.   The  resulting  values  are  B=1.51  and  C=0.0738.  The
magnitude of A has no significance since the analysis  is  to  be
used   only   within   each   subcategory   and  not  across  all
subcategories.  (Fitting the actual flows  with  those  predicted
was  tried both using the analysis across the entire industry and
within each subcategory, with the results being much better using
it only to explain differences within subcategories).

The above results were then put into a usable form by taking  the
anti log of equation (2), which is

                            BT    C  £. DiPi
       (3)  flow(galXbbl)  = AlO  10


The  constant  A is now the 50 percent probability flow (gal/bbl)
which was used  previously  to  calculate  the  limits  for  each
subcategory.  To apply this to each subcategory (to determine the
variance  needed  for each case from the average refinery in each
subcategory) the average   size (Ta)   and  process  configuration
(C £~ DiPi ]a)  for  each subcategory was calculated.  The range of
sizes and process configurations were then divided up into ranges
and the midpoint of each range was then compared to  the  average
for that subcategory to calculate the size and process factor for
that range  (see below).

                  BT    l.Sl(Ti-Ta)
                10  = 10

                C £ DiPi    0.0738[ ( £ DiPi) j-( £DiPi)a]
              10       =  10

where Ti is the midpoint of that particular size range; Ta is the
average  size in the subcategory, with both Ta and Ti in millions
of barrells per day; [<£. DiPi ]i is the midpoint of that particular
process configuration range; and [ ^DiPija is the average process
configuration of the subcategory.

Further analysis of the data showed a break in  the  significance
of  size  in  explaining  flow  for those refineries over 150,000
bbl/day.  This means that over 150,000 bbl/day only  the  process
configuration  has  significance  in  explaining the flows.  As  a
                               58

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result the size ranges where broken off at either 150,000 bbl/day
or the average refinery size  in  a  subcategory,  whichever  was
greater.

An  example of the application of the size and process factors is
in section IX.  The basic data used, regressions run, etc. are in
Supplement B "Refinery Configuration Analysis".

The size and process factors are in Table 1-5, Section II.

Subcategorization Results

Using the procedures outlined above, many trials  were  performed
in  order to obtain a Subcategorization of the petroleum refining
industry which is reflective of  the  net  raw  waste  load  with
respect  to  type  of  refinery  (function) ,  process  technology
employed,   and    severity    of    operations.     The    final
Subcategorization  obtained from this analysis is indicated below
in Table 16.  Detailed probability plots for the  development  of
the Subcategorization are contained in supplement B.

For  each  of  these  new  subcategories  the  parameters for the
selected median values are indicated  in  Table  17.   A  further
enumeration  of  overall  net  raw  waste load characteristics is
given in Section V.


Analysis of the Subcategorization

Topping subcategory

The topping subcategory is similar to the previous API category A
in that it does not  include  any  refineries  with  cracking  or
coking  processes.   That  is  to  say it includes all refineries
which combine all other porcesses except cracking and coking.

Cracking subcategory

API  Category  B  includes  refineries  which  contain   topping,
reforming,  and cracking operations.  Also included are all first
generation   conventional   refinery-associated    products    or
intermediates,  such  as  benzene-toluene-xylene  (BTX), alkanes,
alkenes, alkynes, and other miscellaneous items such  as  sulfur,
hydrogen and coke.


Subcategory  B  as  defined  here  is  the same as API category B
execpt that the  inclusion  of  first  generation  petrochemicals
shall  only be for those whose production amounts to less than 15
percent of the refinery throughput.

Petrochemical subcategory

The petrochemical subcategory is similar to the API  category  C.
Operations   included   within   this  subcategory  are  topping,


                             59

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                               TABLE 16

           Subcategorization of the Petroleum Refining  Industry
        Reflecting Significant Differences  in Waste Water Characteristics
Subcategory               Basic Refinery Operations Included

Topping                   Topping and catalytic reforming whether
                          or not the facility includes any other process
                          in addition to topping and catalytic process.

                          This subcategory is not applicable to facilities
                          which include thermal processes (coking,  visbreaking,
                          etc.) or catalytic cracking.

Cracking                  Topping and cracking, whether or not the  facility
                          includes any processes in addition to topping  and
                          cracking, unless spefified in one of the  subcategories
                          listed below.

Petrochemical             Topping, cracking and petrochemical  operations,  whether
                          or not the facility includes any process  in addition
                          to topping, cracking and petrochemical operations,*
                          except lube oil manufacturing operations.

Lube                      Topping, cracking and lube oil  manufacturing processes,
                          whether or not the facility includes any  process in
                          addition to topping, cracking and lube oil  manu-
                          facturing processes, except petrochemical operations.*

Integrated                Topping, cracking, lube oil manufacturing processes,
                          and petrochemical operations, whether or  not the
                          facility includes any processes in addition to
                          topping, cracking, lube oil manufacturing processes
                          and petrochemical operations.*


* The term "petrochemical operations" shall mean the production of second
  generation petrochemicals (i.e., alcohols, ketones, cumene, styrene, etc.)
  or first generation petrochemicals and isomerization products (i.e., BTX,
  olefins, cyclohexane, etc.) when 15% or more of refinery production is
  as first generation petrochemicals and isomerization products.
                                       60

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                            TABLE 17

             NET RAW WASTE LOADS FROM PETROLEUM REFINING
  INDUSTRY CATEGORIES (50 Percent Probability of Occurrence)
                   KILOGRAMS/10000 M3  (LB/1000 BBLS)
SUBCATEGORY

TOPPING

CRACKING

PETROCHEMICAL

LUBE

INTEGRATED
    BODS
  3.43(1.2)

 72.93(25.5)

171.6(60)

217(76)

197(69)
 OIL/GREASE
  PHENOL
AMMONIA
  8.29(2.9)

 31.17(10.9)

 52.91(18.5)

120.1(42)

 75(26)
0.034(0.012)  1.20(0.42)

4.00(1.4)    28.31(9.9)

7.72(2.7)    34.32(12)

8.3(2.9)     24.1(8.5)

3.8(1.3)     20.5(7.2)
                                   61

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cracking, and petrochemical operations.   Petrochemical operations
include   first   generation   conventional   refinery-associated
production,  as  described  in the cracking subcategory, but only
when it amounts to  greater  than  15  percent  of  the  refinery
throughput.  This takes into consideration the additional cooling
tower   blowdown  from  this  operation.    Intermediate  chemical
production, including such typical products as  cumene,  phthalic
anhydride,  alcohols,  ketones,  trimer,   and  styrene, shall  be
considered  second  generation   petrochemical   operations   and
classify a refinery in this subcategory.


Lube subcategory

The  lube subcategory is the same as the  API category D.

In  the  lube  subcategory,  the  operations  included  under the
cracking  subcategory  are   expanded   to   include   lube   oil
manufacturing    processes.    Lube   oil   processing   excludes
formulating blended oils and additives.


Integrated subcategory

The  integrated subcategory is the same as API category E, except
for the definition of petrochemical operatons  specified  in  the
petrochemical subcategory.

Conclusion

The   subcategorization   of   the  petroleum  refinery  industry
presented above allows for the definition of logical segments  of
the  industry  in  terms  of  factors  which effect generated API
separator effluent waste water  quality.    It  allows  for  rapid
identification  of  the  expected median net raw waste loads as a
basis for developing effluent guidelines for the  discharge  from
the  individual refinery.  The subcategorization determined above
is used throughout this report as the basis  for  development  of
effluent limitations and guidelines.
                                  62

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                            SECTION V

                     WASTE CHARACTERIZATION
General

After  developing  an understanding of the fundamental production
processes and their inter-relationships in  refinery  operations,
determination  of  the  best method of characterizing of refinery
discharges will enhance the interpretation of the industry  water
pollution  profile.   If  unit raw waste loads could be developed
for each production process,  then  the  current  effluent  waste
water  profile could be obtained by simply adding the components,
and  future  profiles  by  projecting  the  types  and  sizes  of
refineries.   However,  the  information  required  for  such  an
approach is not available.  Essentially all of the available data
on refinery waste waters apply to total API  separator  effluent,
rather than to effluents from specific processes.

Another  factor detracting from the application of a summation of
direct subprocess unit raw waste loads, is the frequent  practice
of  combining  specific  waste  water  streams  discharging  from
several units for treatment and/or reuse.  Thus, such streams  as
sour  waters,  caustic  washes,  etc.,  in  actual  practice  are
generally not traceable  to  a  specific  unit,  but  only  to  a
stripping  tower  or  treatment unit handling wastes from several
units.  The  size,  sequence,  and  combination  of  contributing
processes  are  so  involved  that  a breakdown by units would be
extremely difficult to achieve.

In view of the limitations imposed  by  the  summation  of  waste
water  data  from  specific production process, the evaluation of
refinery waste  loads  was  based  on  total  refinery  effluents
discharged  through  the API (Oil)  separator, which is considered
an integral part of refinery process operations  for  product/raw
material recovery prior to final waste water treatment.

Raw Waste Loads

The  information  on raw waste loading was compiled from the 1972
National Petroleum Refining Waste Water Characterization  Studies
and  plant  visits.  The data are considered primary source data,
i.e., they are derived from field sampling and operating records.
The raw waste data for each subcategory of the petroleum refining
industry, as subcategorized in Section IV, have been analyzed  to
determine the probability of occurrence of mass loadings for each
considered   parameter   in  the  subcategory.   These  frequency
distributions are summarized in Tables 18  through  22  for  each
subcategory.

Waste water Flows

As shown in Table 18 through 22, the waste water flows associated
with  raw  waste  loads  can  vary  significantly.   However, the
                                63

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                              TABLE 18

                  TOPPING SUBCATEGORY RAW WASTE LOAD**
                 EFFLUENT FROM REFINERY API SEPARATOR

             NET KILOGRAMS/1000 M3  (LB/1000 BBLS) OF FEEDSTOCK
                               THROUGHPUT
PARAMETER
  PROBABILITY OF OCCURRENCE
PERCENT LESS THAN OR EQUAL TO
BOD.5

COD

TOC

TSS

O&G

PHENOLS

AMMONIA

SULFIDES

CHROMIUM

FLOW*
10%
1.29(0.45)
3.43(1.2)
1.09(0.38)
0.74(0.26)
1.03(0.36)
0.001(0.0004)
0.077(0.027)
0.002(0.00065)
0.0002(0.00007)
8.00(2.8)
50% (MEDIAN)
3.43(1.2)
37.18(13)
8.01(2.8)
11.73(4.1)
8.29(2.9)
0.034(0.012)
1.20(0.42)
0.054(0.019)
0.007(0.0025)
66.64(23.3)
90%
217.36(76)
486.2(170)
65.78(23)
286(100)
88.66(31)
1.06(0.37)
19.45(6.8)
1.52(0.53)
0.29(0.1)
557.7(195)
*  1000 cubic meters/1000 m  Feedstock Throughput (gallons/bbl)
** Probability plots are contained in Supplement B
                                 64

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                              TABLE 19

               CRACKING SUBCATEGORY RAW WASTE LOAD**
                EFFLUENT FROM REFINERY API SEPARATOR

         NET KILOGRAMS/1000 M3 (LB/1000 BBLS) OF FEEDSTOCK
                             THROUGHPUT
PARAMETER



BOD5_

COD

TOC

O&G

PHENOLS

TSS

SULPHUR

CHROMIUM

AMMONIA

FLOW*
  10%
14.3(5.0)

27.74(9.7)

 5.43(1.9)

 2.86(1.0)

 0.19(0.068)

 0.94(0.33)

 0.01(0.0035)
   PROBABILITY OF OCCURRENCE
 PERCENT LESS THAN OR EQUAL TO

	     50%(MEDIAN)
   90%
            72.93(25.5)

           217.36(76.0)

            41.47(14.5)

            31.17(10.9)

             4.00(1.4)

            18.16(6.35)

             0.94(0.33)
 0.0008(0.00028)   0.25(0.088)

 2.35(0.82)       28.31(9.9)

 3.29(1.15)       92.95(32.5)
 466.18(163)

2516.8(880)

 320.32(112)

 364.65(127.5)

  80.08(28.0)

 360.36(126.0)

  39.47(13.8)

   4.15(1.45)

 174.46(61.0)

2745.6(960.0)
*   1000 cubic meters/1000 m3 Feedstock Throughput (gallons/bbl)
**  Probability plots are contained in Supplement B
                                 65

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                               TABLE 20

              PETROCHEMICAL SUBCATEGORY RAW WASTE LOAD**
                 EFFLUENT FROM REFINERY API SEPARATOR

           NET KILOGRAMS/1000 M3 (LB/1000 BBLS) OF FEEDSTOCK
                               THROUGHPUT
                               PROBABILITY OF OCCURRENCE
                             PERCENT LESS THAN OR EQUAL TO
PARAMETER



BOD_5

COD

TOC

TSS

O&G

PHENOLS

AMMONIA

SULFIDES

CHROMIUM

FLOW*
**  Probability plots are contained in Supplement B
10%
40.90(14.3)
200.2(70)
48.62(17)
6.29(2.2)
12.01(4.2)
2.55(0.89)
5.43(1.9)
0.009(0.003)
0.014(0.005)
26.60(9.3)

50% (MEDIAN)
171.6(60)
463.32(162)
148.72(52)
48.62(17)
52.91(18.5)
7.72(2.7)
34.32(12)
0.86(0.3)
0.234(0.085)
108.68(38)

90%
715(250)
1086.8(380)
457.6(160)
371.8(130)
234.52(82)
23.74(8.3)
205.92(72)
91.52(32)
3.86(1.35)
443.3(155)
_—. — /!_!_ 1 \
                                    66

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                               TABLE 21

                   LUBE SUBCATEGORY RAW WASTE LOAD**
                 EFFLUENT FROM REFINERY API SEPARATOR

           NET KILOGRAMS/1000 M3 (LB/1000 BBLS) OF FEEDSTOCK
                               THROUGHPUT
                               PROBABILITY OF OCCURRENCE
PARAMETERS                   PRECENT LESS THAN OR EQUAL TO

BOD5_
COD
TOG
TSS
O&G
PHENOLS
AMMONIA
SULFIDES
CHROMIUM
FLOW*
10%
62.92(22)
165.88(58)
31.46(11)
17.16(6)
23.74(8.3)
4.58(1.6)
6.5(2.3)
0.00001(0
50% (MEDIAN)
217.36(76)
543.4(190)
108.68(38)
71.5(25)
120.12(42)
8.29(2.9)
24.1(8.5)
.000005) 0.014(0.005)
0.002(0.0006) 0.046(0.016)
68.64(24)
117.26(41)
90%
757.9(265)
2288(800)
386.1(135)
311.74(109)
600.6(210)
52.91(18.5)
96.2(34)
20.02(7.0)
1.23(0.43)
772.2(270)
*   1000 cubic meters/1000 m3 Feedstock Throughput (gallons/bbl)
**  Probability plots are contained in Supplement B
                                 67

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                               TABLE 22

                INTEGRATED SUBCATEGORY RAW WASTE LOAD**
                 EFFLUENT FROM REFINERY API SEPARATOR

           NET KILOGRAMS/1000 M3 (LB/1000 BBLS) OF FEEDSTOCK
                               THROUGHPUT
                            PROBABILITY OF OCCURRENCE
PARAMETERS-               PERCENT LESS THAN OR EQUAL TO	

                    10%	      50%(MEDIAN)          90%
BOD_5               63.49(22.2)        197.34(69.0)        614.9(215)

COD                72.93(25.5)        328.9(115)         1487.2(520)

TOC                28.6(10.0)         139.0(48.6)         677.82(237)

O&G                20.88(7.3)          74.93(26.2)        268.84(94.0)

PHENOL              0.61(0.215)         3.78(132)          22.60(7.9)

TSS                15.16(5.3)          58.06(20.3)        225.94(79.0)

SULPHUR             0.52(.182)          2.00(.70)           7.87(2.75)

CHROMIUM            0.12(0.043          0.49(0.17)          1.92(0.67

AMMONIA             3.43(1.20)         20.50(7.15)        121.55(42.5)

FLOW*              40.04(14.0)        234.52(82.0)       1372.8(480)

                            o
*   1000 cubic meters/1000 m  Feedstock Throughput  (gallons/bbl)
**  Probability plots are contained in Supplement B
                                 68

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loadings of pollutants tend to vary within fairly narrow  limits,
independent of flow.

Since  the inter-refinery data suggest that the pollutant loading
to  be  expected  from  a  refinery  is  relatively  constant  in
concentration,  an  examination  of water use practices was made.
The waste water flow frequencies reported in Tables 18 through 22
are dry-weather flows, and in many cases include large amounts of
once-through cooling water.  Refineries with more exemplary waste
water treatment systems are probably making a greater  effort  to
control  waste loads and flows.  Conversely, refineries with very
high water usages and/or raw  waste  loads  either  do  not  have
identifiable  waste  water  treatment  plants, or have them under
construction.

The -primary methods for reduction of the waste water flows to the
API separator are  either  segregation  of  once-through  cooling
waters,  or  by installation of recycle cooling towers and/or air
coolers.   In  order  to  estimate  the  flows  that  should   be
attainable in refineries with good water practices, a statistical
analysis  was made of flows from refineries in which 3 percent or
less of the total heat removal  load  is  accomplished  by  once-
through cooling water.  Data for this analysis were obtained from
the  tabulation  of  refinery  cooling practices contained in the
1972 National Petroleum  Pefining  Waste  Water  Characterization
Studies.   These  frequency distributions are summarized in Table
23.

Basis for Effluent Limitations

The 50 percent probability-of-occurrence raw waste loads outlined
in Tables 18 through 22 are  reflective  of  the  performance  of
median  refineries  within  each  subcategory.  At the same time,
attainable process waste water flows, as reflected by the  median
water  usage  for  refineries  in  which 3 percent or less of the
total heat removal load is accomplished by  once-through  cooling
water,  are  indicative of equitable process waste water loadings
which require waste water treatment.

Consequently, these 50  percent  probability-of-occurrence  waste
water  loadings  and  estimated  process  waste  water flows were
selected as one basis for developing  effluent  limitations,  and
are   used  in  subsequent  sections  to  define  these  effluent
limitations.
                              69

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                               TABLE 23

            WASTE WATER FLOW FROM PETROLEUM REFINERIES USING
        3% OR LESS ONCE-THROUGH COOLING WATER FOR HEAT REMOVAL*

                KILOGRAMS/1000 M3 (LB/1000 BBLS)  OF FEEDSTOCK
                                THROUGHPUT
SUBCATEGORY



TOPPING

CRACKING

PETROCHEMICAL

LUBE

INTEGRATED
    PROBABILITY OF OCCURRENCE
PERCENT LESS THAN OR EQUAL TO
10%
8.01(2.8)
16.59(5.8)
40.04(14)
65.78(23)
91.52(32)
50% (MEDIAN)
57.2(20)
71.5(25)
85.8(30)
128.7(45)
137.28(48)
90%
314.6(110)
148.72(52)
183.04(64)
243.1(85)
1287(450)
*  Probability plots are contained in Supplement B
                                   70

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                           SECTION VI

                SELECTION OF POLLUTANT PARAMETERS
Selected Parameters

The selection of the complete list of pollutant parameters  which
are  discharged  in  significant quantities was based on a review
of:  the Environmental Protection Agency permits for discharge of
waste waters from a number of refineries; reviews with  personnel
in  regional  EPA  offices;  the 1972 National Petroleum Refining
Waste Water characterization Studies; discussions  with  industry
representatives and consultants; and literature survey data.  The
results  of  the above indicated the parameters shown in Table 24
are  significant  in  describing  the  physical,   chemical   and
biological  characteristics  of  waste  waters  discharged by the
petroleum refining industry, as defined in the Act.

The rationale and justification for inclusion of these parameters
are discussed below.  This discussion will provide the basis  for
selection   of   parameters   upon   which  the  actual  effluent
limitations  were  postulated   and   prepared.    In   addition,
particular  parameters  were selected for discussion in the light
of current knowledge as to their limitations from  an  analytical
as well as from an environmental standpoint.

Oxygen Demand Parameters

Three  oxygen  demand parameters are discussed below:  BODS, COD,
and TOC.  It should be noted that  limitations are specified  for
BOD5,   COD,  and  TOC  in  sections  IX,  X,  and  XI  for  each
subcategory.

Almost without exception, waste waters from petroleum  refineries
exert  a  significant  and  sometimes  major  oxygen demand.  The
primary  sources  are  soluble  biodegradable  hydrocarbons   and
inorganic  sulfur  compounds.   Crude distillation, cat cracking,
and the product finishing operations, are the major  contributors
of  BOD5.   In  addition,  the  combination  of  small  leaks and
inadvertent losses that occur almost  continuously  throughout  a
complex refinery can become principal BOD5 pollution sources.

Biochemical  oxygen  demand   (BOD)   is  a  measure  of the oxygen
consuming capabilities of organic matter.  The BOD  does  not  in
itself  cause direct harm to a water system, but it does exert an
indirect effect by depressing the oxygen content  of  the  water.
Sewage  and  other  organic  effluents  during their processes of
decomposition exert a BOD, which can have a  catastrophic  effect
on  the ecosystem by depleting the oxygen supply.  Conditions are
reached frequently where all  of  the  oxygen  is  used  and  the
continuing  decay  process causes the production of noxious gases
such as hydrogen sulfide and methane.   Water  with  a  high  BOD
indicates   the   presence  of  decomposing  organic  matter  and
                                71

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             TABLE 24
Significant Pollutant Parameters for
   the Petroleum Refining Industry
   Biochemical Oxygen Demand  (BOD5)
   Chemical Oxygen Demand  (COD)
   Total Organic Carbon (TOC)
   Oil and Grease (0§G)
   Ammonia as Nitrogen (NH3-N)
   Phenolic Compounds
   Sulfides
   Chromium
             72

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subsequent high bacterial counts that  degrade  its  quality  and
potential uses.

Dissolved  oxygen  (DO)   is  a water quality constituent that, in
appropriate  concentrations,  is  essential  not  only  to   keep
organisms living but also to sustain species reproduction, vigor,
and  the development of populations,  organisms undergo stress at
reduced DO concentrations that make  them  less  competitive  and
able  to  sustain  their  species within the aquatic environment.
For  example,  reduced  DO  concentrations  have  been  shown  to
interfere  with fish population through delayed hatching of eggs,
reduced size and vigor of embryos, production of  deformities  in
young,  interference  with  food digestion, acceleration of blood
clotting, decreased tolerance to certain toxicants, reduced  food
efficiency   and  growth  rate,  and  reduced  maximum  sustained
swimming  speed.   Fish  food  organisms  are  likewise  affected
adversely  in  conditions  with suppressed DO.  Since all aerobic
aquatic  organisms  need  a  certain  amount   of   oxygen,   the
consequences  of total lack of dissolved oxygen due to a high BOD
can kill all inhabitants of the affected area.

If a high BOD is present, the quality of  the  water  is  usually
visually  degraded  by  the presence of decomposing materials and
algae blooms due to the uptake of degraded  materials  that  form
the foodstuffs of the algal populations.

Historically,  the  BOD^  test has also been used to evaluate the
performance of biological waste water  treatment  plants  and  to
establish effluent limitation values.  However, objections to the
use of the BODS test have been raised.
The major objections are as follows:

    1.   The standard  BOD5  test  takes  five  days  before  the
         results  are  available,  thereby  negating its use as a
         day-to-day treatment plant operational indicator.

    2.   At  the  start  of   the   BODjj   test,   seed   culture
         (microorganisms)  is  added  to the BOD5 bottle.  If the
         seed culture was not  acclimated,  i.e.,  exposed  to  a
         similar  waste  water in the past, it may not readily be
         able to biologically degrade the waste.  This results in
         the reporting of a low BOD5 value.   This  situation  is
         very   likely   to   occur  when  dealing  with  complex
         industrial wastes, for which acclimation is required  in
         most   cases.    The   necessity  of  using  "acclimated
         bacteria" makes it very important to take  a  seed  from
         the biological plant treating the waste or downstream of
         the discharge in the receiving waterbody.

    3.   The BOD.5 test is sensitive to toxic  materials,  as  are
         all biological processes.  Therefore, if toxic materials
         are  present  in  a particular waste water, the reported
         BODJ5 value may very well be erroneous.   This  situation


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         can  be  remedied  by  running  a  toxicity  test, i.e.,
         subsequently diluting the sample until  the  BOD5  value
         reaches  a  plateau indicating that the material is at a
         concentration  which  no  longer   inhibits   biological
         oxidation.

There  has  been much controversy concerning the use of BOD5 as a
measure of pollution, and  there  have  been  recommendations  to
substitute  some  other  parameter,  e.g.,  COD  or TOC.  EPA has
recently pointed out that some or all  of  the  previously  cited
reasons  make  the  BOD5  test  a  non-standard  test, and ASTM's
Subcommittee D-19 has also recommended  withdrawal  of  the  BOD5_
test as a standard test.

However, some of the previously cited weaknesses of the BOD5 test
also  make  it uniquely applicable.  It is the only parameter now
available which measures the amount of oxygen  used  by  selected
microorganisms  in metabolizing a waste water.  The use of COD or
TOC to monitor the  efficiency  Of  BOD5  removal  in  biological
treatment is possible only if there is a good correlation between
COD  or  TOC  and  BOD.   After  consideration of the advantages,
disadvantages and constraints, BODjj will continue to be used as a
pollutional indicator for the petroleum refining industry.

Typical raw waste load concentrations for  each  subcategory  are
listed below:

          Subcategory         BOD5 RWL Range, mg/1

             Topping             10 - 50
             Cracking            30 - 600
             Petrochemical       50-800
             Lube               100 - 700
             Integrated         100 - 800
As  a  matter of reference, typical BOD5. values for raw municipal
waste waters range between 100 and 300 mg/L.

COD

Chemical oxygen demand  (COD)  provides a measure of the equivalent
oxygen required to oxidize the materials present in a waste water
sample, under acid conditions with the aid of a  strong  chemical
oxidant,  such  as  potassium dischromate, and a catalyst  (silver
sulfate).  One major advantage  of  the  COD  test  is  that  the
results  are  available normally in less than three hours.  Thus,
the COD test is a faster test by which to  estimate  the  maximum
oxygen  exertion  demand  a waste can make on a stream.  However,
one  major  disadvantage  is  that  the   COD   test   does   not
differentiate between biodegradable and non-biodegradable organic
material.   In  addition,  the  presence  of  inorganic  reducing
chemicals (sulfides, reducible metallic ions, etc.) and chlorides
may interfere with the COD test.

The slow accumulation  of  refractory  (resistant  to  biological
decomposition)  compounds in watercourses has caused concern among


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various  environmentalists  and  regulatory  agencies.   However,
until  these  compounds  are  identified,  analytical  procedures
developed  to  quantify them, and their effects on aquatic plants
and animals are documented, it  may  be  premature   (as  well  as
economically  questionable)  to  require their removal from waste
water sources.         •  , ,'

Typical raw waste load concentrations for  each  subcategory  are
listed below:

           Subcategory           COD RWL Range, mg/1

             Topping                50 - 150
             Cracking              150 - 400
             Petrochemical         300 - 600
             Lube                  400 - 700
             Integrated            300 - 600
Typical COD values for raw municipal waste waters are
between 200 mg/1 and 400 mg/1.

TOC

Total  organic  carbon (TOC) is a measure of the amount of carbon
in the organic  material  in  a  waste  water  sample.   The  TOC
analyzer  withdraws  a  small  volume  of  sample  and  thermally
oxidizes it at 150°C.  The water vapor and  carbon  dioxide  from
the  combustion  chamber   (where  the  water vapor is removed)  is
condensed and sent to an  infrared  analyzer,  where  the  carbon
dioxide  is  monitored.  This carbon dioxide value corresponds to
the total inorganic value.   Another portion of the same sample is
thermally oxidized at 950°C, which converts all the  carbonaceous
material to carbon dioxide; this carbon dioxide value corresponds
to  the total carbon value.  TOC is determined by subtracting the
inorganic carbon (carbonates and  water  vapor)  from  the  total
carbon value.

The  recently  developed automated carbon analyzer has provided a
rapid and simple means of determining organic  carbon  levels  in
waste  water  samples,  enhancing  the  popularity  of  TOC  as a
fundamental   measure   of   pollution.    The   organic   carbon
determination  is  free of many of the variables which plague the
COD and BOD analyses, yielding  more  reliable  and  reproducible
data.   However,  meaningful  correlations  between the three are
sometimes hard to develop.

Typical  raw  waste  concentrations  for  each  subcategory   are
presented below:

          Subcategory           TOC RWL Range, mg/1

            Topping                 10-50
            Cracking                50 - 500
            Petrochemical          100 - 250
            Lube                   100 - 400
            Integrated              50 - 500


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Typical  values  for  raw municipal waste waters range between 50
and 250 mg/L.

TSS

In refineries, major sources of suspended matter are  contributed
by  crude  storage,  alkylation,  crude  desalting  and finishing
operations.  Quenching and removal operations in  the  production
of  coke can contribute significant amounts of suspended fines to
the refinery effluent.

Suspended solids include both organic  and  inorganic  materials.
The  inorganic  components  include  sand,  silt,  and clay.  The
organic fraction includes such materials  as  grease,  oil,  tar,
animal  and  vegetable  fats,  various fibers, sawdust, hair, and
various materials from  sewers.   These  solids  may  settle  out
rapidly  and  bottom deposits are often a mixture of both organic
and  inorganic  solids.   They  adversely  affect  fisheries   by
covering  the  bottom  of  the  stream  or lake with a blanket of
material that destroys the fish-food bottom fauna or the spawning
ground  of  fish.   Deposits  containing  organic  materials  may
deplete  bottom  oxygen  supplies  and  produce hydrogen sulfide,
carbon dioxide, methane, and other noxious gases.

In raw  water  sources  for  domestic  use,  state  and  regional
agencies generally specify that suspended solids in streams shall
not be present in sufficient concentration to be objectionable or
to  interfere  with normal treatment processes.  Suspended solids
in water may interfere with many industrial processes, and  cause
foaming  in  boilers,  or  encrustations  on equipment exposed to
water, especially as the temperature rises.  Suspended solids are
undesirable in water for  textile  industries;  paper  and  pulp;
beverages;   dairy   products;  laundries;  dyeing;  photography;
cooling systems, and  power  plants.   Suspended  particles  also
serve   as   a  transport  mechanism  for  pesticides  and  other
substances  which  are  readily  adsorbed  into  or   onto   clay
particles.

Solids  may  be suspended in water for a time, and then settle to
the  bed  of  the  stream  or  lake.   These  settleable   solids
discharged  with  man's wastes may be inert, slowly biodegradable
materials,  or  rapidly  decomposable   substances.    While   in
suspension,  they  increase  the  turbidity  of the water, reduce
light penetration  and  impair  the  photosynthetic  activity  of
aquatic plants.

Solids  in  suspension  are aesthetically displeasing,  when they
settle to form sludge deposits on the stream or  lake  bed,  they
are  often  much  more  damaging  to  the life in water, and they
retain the  capacity  to  displease  the  senses.   Solids,  when
transformed  to  sludge  deposits,  may  do a variety of damaging
things, including blanketing the stream or lake bed  and  thereby
destroying  the  living  spaces  for those benthic organisms that
would otherwise occupy the  habitat.   When  of  an  organic  and
therefore decomposable nature, solids use a portion or all of the


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dissolved  oxygen  available in the area.   Organic materials also
serve as a seemingly inexhaustible food  source  for  sludgeworms
and associated organisms.

Typical  total suspended solids raw waste concentrations for each
subcategory are listed below:

            Subcategory          TSS RWL Range, mg/1

              Topping                 10 - 40
              Cracking                10 - 100
              Petrochemical           50 - 200
              Lube                    80 - 300
              Integrated              20 - 200

Total suspended solids concentrations for typical  raw  municipal
waste waters range from 100 to 300 mg/1.

Freon Extractables - Oil and Grease

No  solvent  is  known  which  will directly dissolve only oil or
grease, thus the manual "Methods for  the  Chemical  Analysis  of
Water   and   Wastes   1971"  distributed  by  the  Environmental
Protection Agency states that their method  for  oil  and  grease
determinations includes the freon extractable matter from waters.

In  the petroleum refining industry, oils, greases, various other
hydrocarbons and some inorganic compounds will be included in the
freon extraction procedure.  The majority of material removed  by
the  procedure in a refinery waste water will, in most instances,
be of a hydrocarbon nature.   These  hydrocarbons,  predominately
oil  and  grease type compounds, will make their presence felt in
the COD, TOC, TOD, and usually the  BOD  tests  where  high  test
values  will  result.  The oxygen demand potential of these freon
extractables is only one of the detrimental  effects  exerted  on
water  bodies  by  this  class  of  compounds.  Oil emulsions may
adhere to the gills of fish or coat and destroy  algae  or  other
plankton.  Deposition of oil in the bottom sediments can serve to
exhibit  normal  benthic  growths,  thus interrupting the aquatic
food chain.  Soluble and emulsified materials  ingested  by  fish
may taint the flavor of the fish flesh.  Water soluble components
may exert toxic action on fish.  The water insoluble hydrocarbons
and  free  floating  emulsified oils in a waste water will affect
stream ecology by interfering with oxygen transfer,  by  damaging
the  plumage  and  coats  of water animals and fowls, and by con-
tributing taste and toxicity problems.  The effect of oil  spills
upon  boats and shorelines and their production of oil slicks and
iridescence upon the  surface  of  waters  is  well  known.   The
average  freon extractable material recorded by a refinery survey
for effluent waters from the refineries ranged from a maximum  of
37 mg/1 to a minimum of 4. mg/1.

Grease   is   defined   in  "Webster's  Third  New  International
Dictionary" as a thick lubricant.  The class of refinery products
known as greases are usually included in  the  freon  extractable


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portions  of  a  water  analysis.   Some  thick  heavy  petroleum
products coat the silt and sediment of a  stream  bottom  samples
which have been contaminated by oily products over a long period.
An infrared scan of such an extract done on bottom sediments from
the  New  York  Harbor  area  compares  closely to a typical 90 w
automative grease.  Such bottom  contamination  can,  of  course,
exert  influence  upon the aquatic life of a stream, estuary, bay
or other water body.  Typical oil and grease  concentrations  for
each sutcategory are listed below:

                         Freon Extractables as Oil and Grease
           Subcategory           RWL Range, mg/1

           Topping                  10-50
           Cracking                 15 - 300
           Petrochemical            20 - 25C
           Lube                     UO - 400
           Integrated               20 - 500

    Ammonia as Nitrogen

Ammonia   is   commonly   found   in  overhead  condensates  from
distillation and cracking and  from  desalting.   It  is  usually
found combined with sulfide as an ammonium sulfide salt.  Ammonia
is a common product of the decomposition of organic matter.  Dead
and  decaying animals and plants along with human and animal body
wastes account for much  of  the  ammonia  entering  the  aquatic
ecosystem.  Ammonia exists in its non-ionized form only at higher
pH levels and is the most toxic in this state.  The lower the pH,
the  more  ionized  ammonia is formed and its toxicity decreases.
Ammonia, in the presence of dissolved  oxygen,  is  converted  to
nitrate  (NO3) by nitrifying bacteria.  Nitrite  (t)O2) , which is an
intermediate  product  between  ammonia  and  nitrate,  sometimes
occurs in  quantity  when  depressed  oxygen  conditions  permit.
Ammonia   can   exist  in  several  other  chemical  combinations
including ammonium chloride and other salts.

Nitrates are considered to be among the poisonous ingredients  of
mineralized  waters,  with potassium nitrate being more poisonous
than sodium nitrate.  Excess nitrates  cause  irritation  of  the
mucous linings of the gastrointestinal tract and the bladder; the
symptoms  are  diarrhea  and  diuresis, and drinking one liter of
water containing 500 mg/1 of nitrate can cause such symptoms.

Infant methemoglobinemia,  a  disease  characterized  by  certain
specific  blood  changes  and  cyanosis,  may  be  caused by high
nitrate concentrations in the water used  for  preparing  feeding
formulae.    While  it  is  still  impossible  to  state  precise
concentration limits, it has been widely recommended  that  water
containing  more  than 10 mg/1 of nitrate nitrogen  (N03-N) should
not  be  used  for  infants.   Nitrates  are  also   harmful   in
fermentation processes and can cause disagreeable tastes in beer.
In  most  natural  water  the pH range is such that ammonium ions
 (NHJ4+)  predominate.    In   alkaline   waters,   however,   high
concentrations  of  un-ionized  ammonia in undissociated ammonium


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hydroxide increase the toxicity of ammonia solutions.  In streams
polluted with sewage, up to one  half  of  the  nitrogen  in  the
sewage  may  be in the form of free ammonia, and sewage may carry
up to 35 mg/1 of total nitrogen.  It has been  shown  that  at  a
level  of  1.0 mg/1 un-ionized ammonia, the ability of hemoglobin
to combine with  oxygen  is  impaired  and  fish  may  suffocate.
Evidence  indicates  that  ammonia  exerts  a  considerable toxic
effect on all aquatic life within a range of less than  1.0  mg/1
to  25  mg/1,  depending  on  the  pH  and dissolved oxygen level
present.

Ammonia can add to the problem  of  eutrophication  by  supplying
nitrogen  through  its  breakdown products.  Some lakes in warmer
climates, and others that are aging quickly are sometimes limited
by the nitrogen available.  Any increase will speed up the  plant
growth and decay process.

Typical  ammonia  as  nitrogen  raw waste concentrations for each
subcategory are listed below:

                     Subcategory         NH3 - N RWL Range, mg/1

                       Topping              0.05 - 20
                       Cracking             0.5  - 200
                       Petrochemical           4-300
                       Lube                    1-120
                       Integrated              1-250

Phenolic Compounds

Catalytic cracking, crude distillation, and product finishing and
treating, are the major sources of phenolic compounds.  Catalytic
cracking  produces  phenols  by  the  decomposition   of   multi-
cyclicaromatics,  such  as  anthracene  and  phenanthrene.   Some
solvent refining processes use phenol as a solvent  and  although
it is salvaged by recovery processes, losses are inevitable.

Many  phenolic  compounds  are more toxic than pure phenol; their
toxicity varies with the combinations and general nature of total
wastes.   The  effect  of  combinations  of  different   phenolic
compounds is cumulative.

Phenols  and  phenolic compounds are both acutely and chronically
toxic to fish and other  aquatic  animals.   Also,  chlorophenols
produce  an  unpleasant  taste  in fish flesh that destroys their
recreational and commercial value.

It is necessary to limit phenolic compounds in raw water used for
drinking water supplies, as conventional treatment  methods  used
by  water supply facilities do not remove phenols.  The ingestion
of concentrated solutions of phenols will result in severe  pain,
renal irritation, shock and possibly death.
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Phenols  also  reduce the utility of water for certain industrial
uses, notably food  and  beverage  processing,  where  it  causes
unpleasant tastes and odors in the product.
Typical  phenolic
are listed below:
raw  waste concentrations for each subcategory
            Subcategory

            Topping
            Cracking
            Petroleum
            Lube
            Integrated
            Phenolics,  RWL Range,  rag/1

                    0-200
                    0-100
                    0.5-50
                    0.1-25
                    0.5-50
Sulfides
In the petroleum refining  industry,  major  sources  of  sulfide
wastes  are  crude  desalting,  crude  distillation  and cracking
processes.  Sulfides cause corrosion, impair product quality,  and
shorten the useful catlyst life.   They are  removed  by  caustic,
diethanciamine,  water  or  steam,  or  appear as sour condensate
waters in these  initial  processing  operations.   Hydrotreating
processes  can be used to remove sulfides in the feedstock.   Most
removed and recovered sulfide is burned to produce sulfuric  acid
or elemental sulfur.

When present in water, soluble sulfide salts can reduce pH;  react
with  iron  and  other  metals to cause black precipitates;  cause
odor problems; and can be toxic to aquatic life.  The toxicity of
solutions of sulfides to  fish  increases  as  the  pH  value  is
lowered.   Sulfides  also  chemically react with dissolved oxygen
present in water, thereby lowering dissolved oxygen levels.


Typical sulfide raw waste concentrations for each subcategory are
listed below:
      Subcategory

      Topping
      Cracking
      Petroleum
      Lube
      Integrated

    Total Chromium
            Sulfide, RWL Range, mg/1

                      0-5
                      0-400
                      0-200
                      0-40
                      0-60
Chromium may exist in water supplies in both the  hexavalent  and
trivalent   state.    Chromium  salts  are  used  extensively  in
industrial processes and chromate compounds are frequently  added
to cooling water for corrosion control.  The toxicity of chromium
salts  toward  aquatic  life  varies  widely  with  the  species,
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temperature, pH, concentration, and synergistic  or  antagonisitc
effects of other water constituents, especially hardness.

Chromium, in its various valence states, is hazardous to man.  It
can   produce   lung   tumors   when  inhaled  and  induces  skin
sensitizations.  Large doses of chromates have corrosive  effects
on  the  intestinal  tract  and  can  cause  inflammation  of the
kidneys.  Levels of chromate ions that  have  no  effect  on  man
appear to be so low as to prohibit determination to date.

The  toxicity of chromium salts toward aquatic life varies widely
with the species, temperature, pH, valence of the  chromium,  and
synergistic or antagonistic effects, especially that of hardness.
Fish  are  relatively  tolerant  of chromium salts, but fish food
organisms and other lower forms of  aquatic  life  are  extremely
sensitive.  Chromium also inhibits the growth of algae.

In  some agricultural crops, chromium can cause reduced growth or
death of the crop.  Adverse  effects  of  low  concentrations  of
chromium on corn, tobacco and sugar beets have been documented.

Typical  total  chromium  raw  waste load concentrations for each
subcategory are listed below:

     Subcategory                Total Chromium, RWL Range, mg/1

     Topping                          0-3
     Cracking                         0-6
     Petrochemical                    0-5
     Lube                             0-2
     Integrated                       0-2

Hexavalent Chromium

The hexavalent chromium content of potable water supplies  within
the U.S. has been reported to vary between 3 to UO micrograms per
liter.   In  the +6 oxidation state; chromium is usually combined
with oxygen in the form of the oxide, chromium trioxide  cr03  or
the  Oxyanions  chromate  Cr04=  and dichrornate Cr207.  Chromates
will generally be present in a refinery waste  stream  when  they
are used as corrosion inhibitors in cooling water.

Other Pollutants

Other  pollutants  which  were examined in this study of refining
waste water practices included:  total dissolved solids, cyanide,
zinc, temperature, various metallic ions, chloride, fluoride  and
phosphates.

It  was  determined  that these parameters are generally found in
refineries in small enough amounts as not to warrant accross  the
board   treatment.   Restrictions  on  these  parameters  may  be
required as a result of water quality requirements.

Zinc


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Zinc is an essential and beneficial element in  human  metabolism
when  its  intake  to  an organism is limited.  At higher amounts
zinc can lead to gastrointestinal irritation and large amounts of
the metal have  been  reported  to  upset  trickling  filter  and
activated sludge waste treatment processes.

Concentrations  of zinc in excess of 5 mg/1 in raw water used for
drinking water supplies cause an undesirable taste which persists
through conventional treatment.  Zinc can have an adverse  effect
on man and animals at high concentrations.

In  soft  water,  concentrations  of zinc ranging from 0.1 to 1.0
mg/1 have been reported to be lethal to fish.  Zinc is thought to
exert its toxic action by forming insoluble  compounds  with  the
mucous  that  covers the gills, by damage to the gill epithelium,
or possibly by acting as an internal poison.  The sensitivity  of
fish  to  zinc varies with species, age and condition, as well as
with the physical and  chemical  characteristics  of  the  water.
Some acclimatization to the presence of zinc is possible.  It has
also  been  observed  that  the effects of zinc poisoning may not
become apparent immediately, so  that  fish  removed  from  zinc-
contaminated  to  zinc-free water  (after 4-6 hours of exposure to
zinc)  may die 48 hours later.  The presence of  copper  in  water
may  increase  the toxicity of zinc to aquatic organisms, but the
presence  of  calcium  or  hardness  may  decrease  the  relative
toxicity.

Observed values for the distribution of zinc in ocean waters vary
widely.   The  major concern with zinc compounds in marine waters
is not one of acute toxicity, but rather of  the  long-term  sub-
lethal  effects of the metallic compounds and complexes.  From an
acute toxicity point of view, invertebrate marine animals seem to
be the most sensitive organisms tested.  The growth  of  the  sea
urchin, for example, has been retarded by as little as 30 ug/1 of
zinc.

Zinc sulfate has also been found to be lethal to many plants, and
it could impair agricultural uses.

Zinc  compounds  can  be used as corrosion inhibitors for cooling
water.  In addition, zinc is produced in the combustion of fossil
fuels and may find its  way  into  refining  waters  by  leaching
processes.

A  survey  of effluents from petroleum refineries across the U.S.
reports zinc concentrations of .04 to 1.84 mg/1 in  the  effluent
waters.   The median concentration of zinc found in the effluents
was .16 mg/1.
TDS

Dissolved solids in  refinery  waste  waters  consist  mainly  of
carbonates,  chlorides, and sulfates.  U.S. Public Health Service
Drinking Water Standards for total dissolved solids  are  set  at
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500  mg/L  on the basis of taste thresholds.  Many communities in
the United States use water containing from 2,000 to  4,000  mg/1
of  dissolved solids.  Such waters are not palatable and may have
a laxative effect on certain  people.   However,  the  geographic
location   and   availability   of  potable  water  will  dictate
acceptable standards.  The following is a summary of a literature
survey indicating the levels of dissolved solids which should not
interfere with the indicated beneficial use:

        Domestic Water Supply                 1,000 mg/1
        Irrigation                              700 mg/1
        Livestock Watering                    2,500 mg/1
        Freshwater Fish and Aquatic Life      2,000 mg/1

Median  total  dissolved  solids  concentrations   for   refinery
effluents  are  400-700  mg/L.   The  extensive amount of process
water recycle and reuse is primarily responsible for  these  high
concentrations.

Because  dissolved  solids  concentrations are intimately tied to
process recycle and the quality of the process raw water  source;
it  is recommended that this parameter be dictated by local water
quality requirements.

Cyanides


Cyanides  in  water  derive   their   toxicity   primarily   from
undissolved  hydrogen  cyanide  (HCN)  rather than from the cyanide
ion (CN~).  HCN dissociates in water into H+ and  CN~  in  a  pH-
dependent  reaction.   At a pH of 7 or below, less than 1 percent
of the cyanide is present as CN-; at a pH of 8, 6.7 percent; at a
pH of 9, U2 percent; and at a pH of 10, 87 percent of the cyanide
is dissociated.  The toxicity of cyanides is  also  increased  by
increases  in  temperature  and reductions in oxygen tensions.  A
temperature rise of 10°C produced a two- to threefold increase in
the rate of the lethal action of cyanide.

Cyanide has been shown to be poisonous  to  humans,  and  amounts
over  18 ppm can have adverse effects.  A single dose of 6, about
50-60 mg,  is reported to be fatal.

Trout and other aquatic  organisms  are  extremely  sensitive  to
cyanide.   Amounts as small as .1 part per million can kill them.
Certain metals, such as  nickel,  may  complex  with  cyanide  to
reduce  lethality  especially  at  higher pH values, but zinc and
cadmium cyanide complexes are exceedingly toxic.

When fish are poisoned by cyanide, the gills become  considerably
brighter  in  color  than  those  of  normal  fish,  owing to the
inhibition by cyanide  of  the  oxidase  responsible  for  oxygen
transfer from the blood to the tissues.

Cyanide raw waste load data for the refining industry show median
values  of  0.0  -  0.18  mg/L  for the five subcategories.  Only
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occasionally are any values  found  above  1.0  mg/1.   At  these
concentration  ranges,  no  inhibition  is expected in biological
waste  facilities.   Consequently,  the  values  are  such   that
specific  limitations  are not required.  Cyanides are on the EPA
toxic materials list and limitations based on health effects will
be made available at a later date.

pH (Acidity and Alkalinity)

The acidity of a waste is a measure of the quantity of  compounds
contained therein which will dissociate in an aqueous solution to
produce  hydrogen  ions.   Acidity  in  petroleum  refining waste
waters can be contributed by both organic and inorganic  compound
dissociation.  Most mineral acids found in waste waters (sulfuric
acid,  hydrochloric  acid,  nitric  acid,  phosphoric  acid)  are
typically strong acids.   The  most  common  weaker  acids  found
include the organic acids such as carboxyl and carbonic.

Compounds  which  contribute  to  alkalinity  in waste waters are
those which dissociate in aqueous solutions to  produce  hydroxyl
ions.   Alkalinity is often defined as the acid-consuming ability
of the waste water and is measured by titrating a given volume of
waste with standard acid until all of the alkaline  material  has
reacted  to  form  salts.   In  effect,  alkalinity  is the exact
opposite of acidity; high alkalinities  lower  the  hydrogen  ion
concentration of a solution and raise its pH.

Most  refinery  waste  waters are alkaline due to the presence of
ammonia and the use of  caustic  for  sulfur  removal.   Cracking
(both  thermal  and  catalytic)  and  crude  distillation are the
principal  sources  of  alkaline  discharges.    Alkylation   and
polymerization  utilize  acids  as  catalysts  and produce severe
acidity problems.

Extreme pH values  are  to  be  avoided  because  of  effects  on
emulsification  of  oil, corrosion, precipitation, volatilization
of sulfides and other gases, etc.  In streams and water  courses,
extreme  pH  levels  accentuates  the  adverse  effects  of other
pollutants as well as causing toxicity itself.

The  hydrogen  ion  concentration  in  an  aqueous  solution   is
represented by the pH of that solution.  The pH is defined as the
negative  logarithm  of  the  hydrogen  ion  concentration  in  a
solution.  The pH scale ranges from zero to fourteen, with  a  pH
of   seven,   representing   neutral   conditions,   i.e.,  equal
concentrations of hydrogen and hydroxyl ions.  Values of pH  less
than  seven  indicate  increasing  hydrogen  ion concentration or
acidity;  pH  values  greater  than  seven  indicate   increasing
alkaline  conditions.  The pH value is an effective parameter for
predicting  chemical  and  biological   properties   of   aqueous
solutions.   It   should  be  emphasized that pH cannot be used to
predict the quantities of  alkaline or acidic materials in a water
sample.  However, most effluent and stream standards are based on
maximum and minimum allowable pH values rather than on alkalinity
and acidity.


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Since pH RWL values are not additive, it is not  always  possible
to  predict  the  final  pH  of  a process waste water made up of
multiple discharges.   In  addition,  the  individual  refinery's
discharge characteristics will dictate final pH ranges, which may
be  kept  within  the acceptable range merely by equalization, or
which may require more sophisticated  neutralization  facilities.
However,  it  is  recommended  that  a  pH range of 6.0 to 9.0 be
established as the .effluent limitation.

Temperature

Crude   desalting,   distillation,   and   cracking    contribute
substantial thermal wasteloads.
Temperature  is  one  of the most important and influential water
quality characteristics.  Temperature  determines  those  species
that  may  be  present;  it  activates  the  hatching  of  young,
regulates their activity,  and  stimulates  or  suppresses  their
growth  and development; it attracts, and may kill when the water
becomes too hot or becomes chilled too  suddenly.   Colder  water
generally   suppresses   development.    Warmer  water  generally
accelerates activity and may be a primary cause of aquatic  plant
nuisances when other environmental factors are suitable.

Temperature  is a prime regulator of natural processes within the
water  environment.   It  governs  physiological   functions   in
organisms  and, acting directly or indirectly in combination with
other water quality constituents, it affects  aquatic  life  with
each  change.   These  effects  include  chemical reaction rates,
enzymatic functions, molecular movements, and molecular exchanges
between membranes within and between  the  physiological  systems
and the organs of an animal.

Chemical  reaction  rates  vary  with  temperature  and generally
increase as the temperature  is  increased.   The  solubility  of
gases  in  water  varies  with  temperature.  Dissolved oxygen is
decreased by the decay  or  decomposition  of  dissolved  organic
substances and the decay rate increases as the temperature of the
water  increases  reaching  a  maximum at about 30°C (86°F).  The
temperature of stream water, even during  summer,  is  below  the
optimum  for pollution-associated bacteria.  Increasing the water
temperature increases the bacterial multiplication rate when  the
environment is favorable and the food supply is abundant.

Reproduction  cycles  may  be  changed significantly by increased
temperature because this function takes  place  under  restricted
temperature  ranges.   Spawning  may  not  occur  at  all because
temperatures are too high.  Thus, a fish population may exist  in
a  heated  area  only by continued immigration.  Disregarding the
decreased reproductive potential,  water  temperatures  need  not
reach  lethal  levels  to  decimate a species.  Temperatures that
favor competitors, predators, parasites, and disease can  destroy
a species at levels far below those that are lethal.
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Fish  food  organisms  are  altered  severely  when  temperatures
approach or  exceed  90°F.   Predominant  algal  species  change,
primary  production is decreased, and bottom associated organisms
may  be  depleted  or  altered   drastically   in   numbers   and
distribution.   Increased  water  temperatures  may cause aquatic
plant nuisances when other environmental factors are favorable.

Synergistic actions of pollutants are more severe at higher water
temperatures.  Given amounts of domestic sewage, refinery wastes,
oils,  tars,  insecticides,  detergents,  and  fertilizers   more
rapidly  deplete  oxygen in water at higher temperatures, and the
respective toxicities are likewise increased.

When water temperatures increase, the predominant  algal  species
may  change  from  diatoms  to  green  algae, and finally at high
temperatures to blue-green algae, because of species  temperature
preferentials.  Blue-green algae can cause serious odor problems.
The  number  and  distribution  of benthic organisms decreases as
water temperatures increase above 90°F, which  is  close  to  the
tolerance  limit for the population.  This could seriously affect
certain fish that depend on benthic organisms as a food source.

The cost of fish being attracted to heated water in winter months
may be considerable, due to fish mortalities that may result when
the fish return to the cooler water.

Rising  temperatures  stimulate  the  decomposition  of   sludge,
formation  of  sludge gas, multiplication of saprophytic bacteria
and fungi  (particularly in the presence of organic  wastes),  and
the   consumption  of  oxygen  by  putrefactive  processes,  thus
affecting the esthetic value of a water course.

In general, marine water temperatures do not change as rapidly or
range as widely as those of freshwaters.   Marine  and  estuarine
fishes,  therefore,  are  less tolerant of temperature variation.
Although this limited tolerance is greater in estuarine  than  in
open water marine species, temperature changes are more important
to  those  fishes  in  estuaries  and  bays than to those in open
marine areas, because of the nursery and replenishment  functions
of  the  estuary  that  can  be  adversely  affected  by  extreme
temperature changes.


Other Metallic Ions

Several metallic ions in addition to chormium  and  zinc  may  be
found  in  refinery  effluents.   The  major  sources  for  their
presence in waste water are from the crude itself  and  corrosion
products.  The concentration of metallic ions varies considerably
dependent   upon   the  effectiveness  of  catalyst  recovery  in
production process.  Table 25 lists those  metals  which  may  be
commonly   found  in  petroleum  refinery  effluents.   Dissolved
metallic ions create turbidity and discoloration, can precipitate
to form bottom sludges, and can impart taste to water.
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                             TABLE 25

Metallic Ions Commonly Found in Effluents from Petroleum Refineries

                             Aluminum
                             Arsenic
                             Cadmium
                             Chromium
                             Cobalt
                             Copper
                             Iron
                             Lead
                             Mercury
                             Niche1
                             Vanadium
                             Zinc
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Metallic  ions  such  as  copper,  and  cadmium  are   toxic   to
microorganisms because of their ability to tie up the proteins in
the key enzyme systems of the microogranisms.

Chlorides:

Chloride  ion  is  one  of  the  major  anions found in water and
produces a salty taste at a  concentration  of  about  250  mg/1.
Concentrations  of 1000 mg/1 may be undetectable in waters which
contain appreciable amounts of calcium and magnesium ions.

Water is invariably associated with  naturally  occurring  hydro-
carbons  underground and much of this water contains high amounts
of sodium chloride.  The saltiest oil field waters are located in
the  mid-continent  region  of  the  country  where  the  average
dissolved  solids  content  is  174,000  ppm;   therefore,  waters
containing high levels of salt may be expected.

Copper chloride may be used in a sweetening process and  aluminum
chloride  in  catalytic  isomerization.   These products may also
find their ways to waste streams.

The toxicity of chloride salts will depend upon  the  metal  with
which   they   are   combined.    Because   of  the  rather  high
concentration of the  anion  necessary  to  initiate  detrimental
biological  effects,  the limit set upon the concentration of the
metallic ion with which it may be tied, will automatically govern
its concentration in effluents, in practically all  forms  except
potassium, calcium, mganesium, and sodium.

Since  sodium  is  by  far  the  most  common  (sodium 75 percent,
magnesium 15 percent, and calcium 10 percent)   the  concentration
of  this  salt  will  probably  govern the amount of chlorides in
waste streams from petroleum refineries.

It is extremely difficult to pinpoint the exact amount of  sodium
chloride  salt  necessary to result in toxicity in waters.  Large
concentrations have been proven toxic to sheep, swine, cattle  or
poultry.

In  swine  fed  diets  of  swill  containing   1.5 to 2.0% salt by
weight, poisoning symptoms can be  induced  if  water  intake  is
limited  and  other factors are met.  The time interval necessary
to accomplish this is still about one full day of feeding ar this
level.

Since problems of corrosion, taste and quality of water necessary
for industrial or agricultural purposes occur at sodium  chloride
concentration  levels  below  those  at  which  toxic effects are
experienced, these factors will undoubtedly determine the  amount
of  chlorides  allowed  to  escape in waste streams from refining
operations.   The  study   of   refinery   effluents   previously
mentioned,  placed  net chloride levels at values ranging from 57
to 712 mg/1.  The median value was 176 mg/1.
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Fluoride:  HF

Alkalation units (when hydrofluoric acid is used) can  contribute
fluoride  ion  to  the plant's waste effluent.  Since calcium and
barium fluoride are insoluble in  water  the  fluorides  will  by
necessity be associated with other cations.

In  concentrations  of  approximately  1  mg/1  in  potable water
supplies fluorides have been found to be an  effective  preventor
of  dental cavities.  In concentrations greater than this amount,
fluorides  can  cause  molting  of  tooth  enamel  and   may   be
incorporated into the bones.

Natural  waters can contain levels of fluorides up to 10 ppm.  If
these waters are to be used for potable supplies or  for  certain
industrial  or  agricultural purposes the fluoride levels must be
reduced.   Since   many   municipal   waters   are   artificially
fluoridated  as  a  dental  health  aid,  the  U.S. Public Health
Service has placed limits on the total  amounts  of  fluorides  a
water  supply  may  contain.   Their  recommended  control levels
depend upon temperature and are expressed as lower, optimum,  and
upper  limits.   Optimum  limits  range  from .7 to 1.2 mg/1.  If
values exceed two times the optimum value,  the  supply  must  be
rejected  or  the  fluoride  content  lowered.   Because refinery
effluents may empty into water ways which may  eventually  become
public  supplies,  the  maximum  permissible  limits of fluorides
present in an effluent will probably be derived  from  the  USPHS
control limits for drinking water.

Phosphate - Total

Various   forms  of  phosphates  find  their  way  into  refinery
effluents.  They range  through  several  organic  and  inorganic
species   and   are  usually  contributed  by  corrosion  control
chemicals.  Plant cooling systems may contain 20 to  50  mg/1  of
phosphate ion.

Phosphorus  is  an  element  which  is  essential to growth of an
organism.  It may at times become a growth limiting  nutrient  in
the  biological  system  of  a water body.  In these instances an
over abundance of the element contributed from an outside  source
may  stimulate  the  growth  of  photosynthetic aquatic macro and
micro-organisms resulting in nuisance problems.  Since the  forms
of  phosphorus  in waters or industrial wastes are so varied, the
term total phosphate has been used to indicate all the  phosphate
present  in  an  analyzed sample regardless of the chemical form.
Also, many phosphorus compounds tend to degrade  rather  readily,
and in these less complex forms phosphate may be readily utilized
in  the aquatic life cycle.  It is therefore reasonable to direct
concern toward the total amount of phosphorus present rather than
chemical structure it may assume, for in only very unusual  cases
may  the  form or concentration of the element present in a waste
stream be toxic.  Total phosphate values noted  on  a  nationwide
refinery  survey were 9.49 mg/1 maximum and .096 mg/1 minimum for
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effluents.   The  median  value  was  .68   mg/1   expressed   as
phosphorus.
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                           SECTION VII

                CONTROL AND TREATMENT TECHNOLOGY
Petroleum refinery waste waters vary in quantity and quality from
refinery to refinery.  However, the wastes are readily treatable.
The  results  of  the  industry  survey  indicate,  as  would  be
expected, that techniques  for  in-process  control  are  general
across  the  industry  and  the  specific  application  of  these
techniques at individual plants determines their success.   Local
factors  such  as  climate,  discharge  criteria, availability of
land, or other considerations may dictate the  use  of  different
waste  water treatment processes to reach an acceptable effluent.
The survey has shown that although the  end-of-pipe  waste  water
treatment  technologies  used  throughout  the petroleum refining
industry  have  a  marked  similarity  in  operational  steps,  a
considerable variation in treatment results exist.  The processes
used  for  treating refinery waste water, however, are similar in
purpose;  namely—maximizing  oil  recovery  and  minimizing  the
discharge   of   other   pollutants.   The  wastewater  treatment
technology described below is  generally  applicable  across  all
industry sutcategories.

In-Plant Control/Treatment Techniques

In-plant  practices  are  the  sole  determinant of the amount of
waste water to be treated.   There  are  two  types  of  in-plant
practices  that reduce flow to the treatment plant.  First, reuse
practices involving the use of water from one process in  another
process.   Examples  of  this  are:   using  stripper bottoms for
makeup to crude desalters;  using  blowdown  from  high  pressure
boilers  as  feed  to  low  pressure  boilers;  and using treated
effluent as makeup water  whereever  possible.   Second,  recycle
systems  that  use  water  more  than  once for the same purpose.
Examples of recycle systems are:  the use of steam condensate  as
boiler   feedwater;   and   cooling  towers.   The  reduction  or
elimination of a waste stream allows the end-of-pipe processes to
be smaller, provide better  treatment,  and  be  less  expensive.
Since  no  treatment  process  can  achieve 100 percent pollutant
removal from the individual stream, reduction in flow allows  for
a smaller pollutant discharge.

Housekeeping

In  addition  to  reuse/recycle of water streams and reduction in
flows by other in-plant techniques,  another  effective  in-plant
control  is  good  housekeeping.   Examples  of good housekeeping
practices are:  minimizing waste  when  sampling  product  lines;
using  vacuum  trucks or dry cleaning methods to clean up any oil
spills; using a good maintenance program to keep the refinery  as
leakproof  as  possible;  and individually treating waste streams
with special characteristics, such as spent cleaning solutions.
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The use of dry cleaning,  without  chemicals,  aids  in  reducing
water  discharges  to the sewer.  Using vacuum trucks to clean up
spills and charging of this recovered material to slop oil tanks,
reduces the discharge of both oil and water to  the  waste  water
system.  The oil can also be recovered for reprocessing.  Process
units  should  be  curbed  to  prevent the contamination of clean
areas with oily storm runoff and to prevent spills from spreading
widely.  Prompt cleanup of  spills  will  also  aid  in  reducing
discharges  to the sewer systems.  Additionally, sewers should be
flushed regularly to prevent  the  buildup  of  material  in  the
sewer,  eliminating  sudden  surges  of  pollutants  during heavy
rains.  Collection  vessels  should  also  be  provided  whenever
maintenance  is  performed on liquid processing units, to prevent
accidental discharges to the sewers.

Operations during turnaround present  special  problems.   Wastes
generated  by  cleaning  tanks and equipment should be collected,
rather than draining directly to  the  sewer.   The  wastes  from
these  holding tanks should be gradually bled to the sewer, after
first pretreating as necessary to eliminate  deleterious  effects
on  the  waste  water treatment system.  An alternative method of
disposal is through the use of contract carriers.

While these  are  not  all  the  examples  of  good  housekeeping
practices  which  can  be  cited  for  refinery operations, it is
evident that housekeeping practices within a  refinery  can  have
substantial  impact on the loads discharge to the waste treatment
facilities.  The application of good  housekeeping  practices  to
reduce  waste loads requires judicious planning, organization and
operational philosophy.

Process Technology

Many of the newer petroleum refining processes are being designed
or  modified  with  reduction  of  water   use   and   subsequent
minimization  of  contamination  as  design criteria; although no
major innovations in basic refining technology  are  anticipated.
Improvements  which can be expected to be implemented in existing
refineries are: primarily dedicated to better control of refinery
processes  and  other   operations;   elimination   of   marginal
processing  operations,  and  specific  substitution of processes
and/or cooling techniques to  reduce  discharge  loads  to  waste
treatment facilities.  Examples of the possible changes which may
be implemented include:

    1.   Substitution of improved  catalysts  which  have  higher
         activity  and  longer  life, consequently requiring less
         regeneration and resulting in lower waste water loads.

    2.   Replacement  of  barometric  condensers   with   surface
         condensers  or  air  fan  coolers, reducing a major oil-
         water  emulsion  source.   As  an  alternative,  several
         refineries  are  using oily water cooling tower systems,
         with  the  barometric  condensers,  equipped  with   oil
         separation/emulsion breaking auxiliary equipment.
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    3.   Substitution of air fan coolers to relieve water cooling
         duties simultaneously reduces blowdown discharges.

    U.   Installation   of   hydrocracking   and    hydrotreating
         processes  will allow generation of lower waste loadings
         than the units they replace.  The rapid  pace  at  which
         such  units  are  being  installed  is exerting and will
         continue to exert a strong influence on the reduction of
         waste  loadings,   particularly   sulfides   and   spent
         caustics.

    5.   Installation of  automatic  monitoring  instrumentation,
         such  as  TOC  monitors,  will  allow early detection of
         process upsets which result in excessive  discharges  to
         sewers.

    6.   Increased  use  of  improved  drying,  sweetening,   and
         finishing  procedures  will  minimize spent caustics and
         acids,  water  washes,  and  filter   solids   requiring
         disposal.

Cooling Towers

Cooling  towers  eliminate  large volumes of once through cooling
water by passing heated water through  heat  exchange  equipment.
By  recycling  the  cooling water many times, the amount of water
used is greatly reduced.  The number of times cooling  water  can
be  reused  is  determined  by  the  total dissolved solids (TDS)
content of the water, and the effects high dissolved solids  have
on  process  equipment.   When  the TDS becomes too high, scaling
occurs and heat transfer efficiency decreases.  The TDS level  in
the  circulating  water is controlled by discharging a portion of
the steam  (blowdown) from the system.  The higher  the  allowable
TDS  level, the greater number of cycles of concentration and the
less make-up water is required   (87).   Installation  of  cooling
towers  will  reduce the amount of water used within the refinery
by at least 90 percent  (87).

There  are  three  types  of  cooling  towers   (106);   wet   or
evaporative, dry, and combined "wet-dry."

Evaporative Cooling Systems

Evaporative  cooling  systems  transport  heat by transfer of the
latent heat of  vaporization.   This  results  in  a  temperature
decrease  of  circulating  water  and  a temperature and humidity
increase of cooling air.

Spray ponds are an evaporative cooling system using  natural  air
currents   and   forced   water   movement.    Because  of  their
inefficiency, spray ponds are used less in industry than  cooling
towers.   Cooling  towers  have  a higher efficiency because they
provide more intimate contact between the air and water.  As  the
water  falls over the packing, it exposes a large contact surface
area.  As the water heats up the air, the  air  can  absorb  more
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water.   The  more water evaporated, the more heat is transferred
 (106).  Because an evaporative  cooling  tower  is  dependent  on
ambient  temperatures  and  humidity, its performance is variable
throughout the  year.   There  are  three  types  of  evaporative
cooling  towers:   mechanical  draft  towers; atmospheric towers,
which use wind or natural air currents; and natural draft towers,
which use  tall  stacks  to  move  air  by  stack  effect.   Most
refineries  use  mechanical  draft  towers,  which  have baffles,
called drift eliminators, to separate entrained  water  from  the
air  stream,  thus  reducing the amount of water carried into the
air.  The evaporative system is the least costly of  all  cooling
towers.

Dry Cooling Systems

There  are  two  types of dry air cooling systems.  Either system
can be used with  either  mechanical  or  natural  draft  cooling
towers.   Most refineries use mechanical draft towers on indirect
condensing systems.  The tubes used in dry cooling equipment have
circumferential fins to increase the heat  transfer  area.   Most
tube  designs  have  an  outside  to inside surface area ratio of
20:1.  (106) The advantage of  the  dry  air  system  is  that  it
requires  no makeup water and there is no water entrainment.  Dry
air cooling systems are being increasingly  used  to  reduce  the
amount of water discharged to the waste water treatment plant.  A
disadvantage  of the dry cooling process is that it has low rates
of heat transfer requiring large amounts of land  and  uses  more
power  than other cooling systems.  The dry cooling tower is also
more expensive to install than evaporative systems.

Wet-Dry Systems

The  wet-dry  systems  use  an  evaporative  and  non-evaporative
cooling  tower in either series or parallel, each of which can be
operated with a mechanical or natural draft  tower.   The  series
design  has  the  evaporative  cooling process preceeding the dry
process  with  respect  to  the  air  flow.   This   lowers   the
temperature  of the air entering the dry process which would mean
a smaller unit could be used.  The problem with  this  method  is
that  solids are deposited in the dry tower due to drift from the
wet section.  The parallel  process  uses  a  dry  cooling  tower
upstream  of  the  wet  section,  each  of  which has its own air
supply.  The two air streams are mixed and  discharged,  reducing
the vapor plume.

Recycle/Reuse Practices

Recycle/reuse  can  be accomplished either by return of the waste
water to its original use, or by using  it  to  satisfy  a  lower
quality  demand.  The recycle/reuse practices within the refining
industry are  extremely  varied  and  only  a  few  examples  are
described briefly below:

     1.   Reduction  of  once-through  cooling  water  results  in
         tremendously decreased total effluents.
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    2.    Sour water stripper bottoms are being  used  in  several
         refineries   as   make-up   water   for  crude  desalter
         operations.  These  sour  water  bottoms  are  initially
         recovered  from  overhead  accumulators on the catalytic
         cracking units.

    3.    Regeneration of contact process steam from  contaminated
         condensate  will  reduce the contact process waste water
         to a small amount of blowdown.  This scheme can be  used
         to  regenerate  steam in distillation towers or dilution
         steam stripping in pyrolysis furnaces.

    H.    Reuse of waste water treatment plant effluent as cooling
         water, as scrubber water, or  as  plant  make-up  water,
         reduces total make-up requirements.

    5.    Cooling tower blowdowns are frequently  reused  as  seal
         water on high temperature pump service, where mechanical
         seals are not practicable.

    6.    Storm water retention ponds are  frequently  used  as  a
         source  of  fire  water  or  other  low  quality service
         waters.

Many other conservation methods can be implemented, such  as  the
use  of  stripped sour water as low pressure (LP) boiler make-up,
and LP boiler blowdown as  make-up  water  for  crude  desalting.
However,  these,  and  the  other  possible  recycle/reuse  cases
outlined above must be examined by  the  individual  refinery  in
light   of  its  possible  advantages/disadvantages,  insofar  as
product quality or refining process  capabilities  are  affected.
For  example,  one refinery has reported that reuse of sour water
stripper bottoms for desalting resulted in a desalted crude which
was difficult to process downstream.

At-Source Pretreatment

Major at-source pretreatment processes which  are  applicable  to
individual  process  effluents  or  groups  of effluents within a
refinery  are  stripping  of  sour  waters,  neutralization   and
oxidation  of  spent caustics, ballast water separation, and slop
oil recovery.  The  particular  areas  of  application  of  these
processes are discussed below.

Sour Water Stripping

Sour or acid waters are produced in a refinery when steam is used
as  a  stripping  medium  in the various cracking processes.  The
hydrogen  sulfide,  ammonia  and  phenols  distribute  themselves
between  the water and hydrocarbon phases in the condensate.  The
concentrations of these  pollutants  in  the  water  vary  widely
depending on crude sources and processing involved.

The 1 purpose of the treatment of sour water is to remove sulfides
(as hydrogen sulfide, ammonium sulfide, and polysulfides)  before
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the  waste  enters  the sewer.  The sour water can be treated by:
stripping with steam  or  flue  gas;  air  oxidation  to  convert
hydrogen   sulfide   to   thiosulfates;   or   vaporization   and
incineration.

Sour water strippers are designed primarily for  the  removal  of
sulfides  and  can  be expected to achieve 85-99 percent removal.
If acid is not required to  enhance  sulfide  stripping,  ammonia
will  also  be  stripped  with the percentage varying widely with
stripping temperature and pH.  If acid  is  added  to  the  waste
water,  essentially  none  of the ammonia will be removed.  Thus,
ammonia removals in sour  water  strippers  vary  from  0  to  99
percent.   Depending  upon  such  conditions  as  waste water pH,
temperature,  and  contaminant  partial  pressure;  phenols   and
cyanides can also be stripped with removal as high as 30 percent.
The  bottoms  from  the stripper usually go to the desalter where
most of the phenols are extracted and the waste water can be sent
to the regular process water treating plant.  COD  and  BODJ5  are
reduced  because  of  the  stripping out of phenol and oxidizable
sulfur compounds.

The heated sour water is stripped with steam or  flue  gas  in  a
single  stage  packed  or plate-type column.  Two-stage units are
also being installed to enhance the separate recovery of  sulfide
streams  and ammonia streams.  Hydrogen sulfide released from the
waste water can be recovered as sulfuric acid or sulfur,  or  may
be  burned  in  a furnace.  The bottoms have a low enough sulfide
concentration to permit discharge into the  general  waste  water
system  for biological treatment.  If the waste contains ammonia,
it is neutralized with acid before steam  stripping.   The  waste
liquid  passes  down the stripping column while the stripping gas
passes upward.   Most  refiners  now  incinerate  th  sour  water
stripper   acid  gases  without  refluxing  the  stripper.   This
converts the ammonia to nitrogen with possibly traces of nitrogen
oxides.   Due  to  the  high  concentrations  of  sulfur  dioxide
produced more complex processing will probably be required in the
future.

Several   stripping  processes  are  available.   These  include:
Chevron WWT; ammonium sulfate production;  a  dual  burner  Claus
sulfur  plant;  and  the  Howe-Baker  ammonex process.  Deep well
injection and oxidation to the thiosulfate are also  being  used,
but in the future probably won't do a good enough job.

The  Chevron  WWT  process   (37) is basically two stage stripping
with ammonia pruification,  so  that  the  hydrogen  sulfide  and
ammonia  are  separated.   The  hydrogen  sulfide  would  go to a
conventional Claus sulfur plant and the ammonia can  be  used  as
fertilizer.

Ammonium  sulfate  can be produced by treating with sulfuric acid
but a very dilute solution is produced and concentrating  it  for
sale as fertilizer is expensive.  Again the hydrogen sulfide goes
to a conventional Claus sulfur plant.
                              96

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A dual burner Glaus sulfur process is generally the answer in new
plants,  but adding the second burner to an existing sulfur plant
is difficult.  The  second  burner  is  required  to  handle  the
ammonia.   A  refluxed  stripper  is required to reduce the water
vapor in  the  hydrogen  sulfide-ammonia  mixture  and  the  line
between  the  stripper  and  the Glaus Unit must be kept at about
150°F to prevent precipitation of ammonium sulfide complexes.

Howe-Baker Engineers Inc. of Tyler, Texas have developed  to  the
pilot plant stage a process they call "Ammonex".  It is a solvent
extraction  process  that  basically is intended to complete with
the Chevron WWT process.  No commercial units have been built.

Another way of treating sour water is  to  oxidize  by  aeration.
Compressed  air is injected into the waste followed by sufficient
steam to raise  the  reaction  temperature  to  at  least  190°F.
Reaction pressure of 50-1 CO psig is required.  Oxidation proceeds
rapidly and converts practically all the sulfides to thiosulfates
and  about  10  percent  of  the  thiosulfates  to sulfates.  Air
oxidation, however, is much  less  effective  than  stripping  in
regard  to  reduction  of the oxygen demand of sour waters, since
the remaining thiosulfates can later be oxidized to  sulfates  by
aquatic microorganisms.


The  stripping  of  sour  water is normally carried out to remove
sulfides and hence,  the  effluent  may  contain  50-100  ppm  of
ammonia,  or  even considerably higher, depending on the influent
ammonia concentration.  Values of ammonia have been  reported  as
low as  1 ppm, but generally the effluent ammonia concentration is
held to approximately 50 ppm to provide nutrient nitrogen for the
refinery biological waste treatment system (2,14,33,58).

Spent Caustic Treatment

Caustic  solutions  are widely used in refining. Typical uses are
to neutralize and extract:

    a.   Acidic materials that may occur naturally in crude oil.
    b.   Acidic reaction products that may be produced by various
         chemical treating processes.
    c.   Acidic materials formed  during  thermal  and  catalytic
         cracking   such  as  hydrogen  sulfide,  phenolics,  and
         organic acids.

Spent  caustic  solutions   may   therefore   contain   sulfides,
mercaptides  sulfates,  sulfonates, phenolates, naphthenates, and
other similar organic and inorganic compounds.

At least four companies process these spent  caustics  to  market
the phenolics and the sodium hyposulfide.  However, the market is
limited  and  most  of  the spent caustics are very dilute so the
cost of shipping the water makes this operation uneconomical.
                              97

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Seme refiners neutralize the caustic  with  spent  sulfuric  from
other  refining  processes,  and  charge  it  to  the  sour water
stripper.  This removes the hydrogen sulfide.   The  bottoms  from
the  sour  water  stripper go to the desalter  where the phenolics
are extracted by the crude oil.

Spent caustics usually originate as batch dumps, and the  batches
may  be  combined  and  equalized  before  being  treated  and/or
discharged to the general refinery waste waters.   Spent  caustic
solutions  can  also  be treated by neutralization with flue gas.
In  the  treatment  of  spent  caustic  solutions  by  flue  gas,
hydroxides  are  converted to carbonates.  Sulfides, mercaptides,
pbenolates, and other basic salts are converted by the  flue  gas
stripping.   Phenols  can be removed and used  as a fuel or can be
sold.  Hydrogen sulfide and mercaptans are usually  stripped  and
burned  in  a  heater.   Some  sulfur  is recovered from stripper
gases.  The treated solution will contain mixtures of carbonates,
sulfates, sulfites, thiosulfates  and  some  phenolic  compounds.
Reaction  time  of 16-24 hours is required for the neutralization
of caustic solution with flue gas.

The oxidation phase of spent caustic treatment is  aimed  at  the
sulfide  content  of  these  wastes  and  achieves  85-99 percent
sulfide  removal.   In  this  process,  sulfides   are   oxidized
primarily  to  thiosulfates  although in some  variations there is
partial oxidation of the sulfur compounds to sulfate.   Oxidation
processes  are  not  applied  to  phenolic  caustics,  as phenols
inhibit oxidation.  It should be noted that those processes which
oxidize the sulfide only to  thiosulfate,  satisfy  half  of  the
oxygen  demand  of  the  sulfur,  as  thiosulfate can be oxidized
biologically to sulfate.  Neutralization  of  spent  caustics  is
applied  to  both  phenolic  and  sulfidic  caustic  streams; the
sulfidic caustics are also steam stripped, after  neutralization,
to  remove  the  sulfides.   When  phenolic  spent  caustics  are
neutralized, crude acid oils or "crude carbolates" are sprung and
thus removed from the waste water.  The major  part of the phenols
will appear in the oil  fraction,  but  a  significant  part  may
remain in the waste water as phenolates.

Fluid  bed incineration is also now being used.  This process was
developed under an EPA demonstration grant  (26) and at least  two
large  units  are  under  construction.   Once the incinerator is
started up, the sludge should provide the necessary heating value
to keep the system operating.  Oxidizing fuels  may  be  required
when  the  sludge  is  burnt,  as  ash  remains in the bed of the
incinerator.  A constant bed level is maintained, so the sand bed
originally in the incinerator is gradually replaced by the  inert
sludge ash  (5).  The gasses pass through a scrubber, so the fines
and  particulate  matter can be recovered.  The ash and fines can
be landfilled.  This landfill is cleaner than  a sludge  landfill,
because  there  are  no  organic materials present to contaminate
ground water or run-off.
                               98

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In the past  ocean  dumping,  deep  well  injection,  evaporative
lagoons,  and  simple dilution have all been used.  These methods
will no longer be acceptable.

Sewer System Segregation

Waste water quantity is one of the major factors that affect  the
cost of waste treatment facilities most directly.  Water usage in
the  petroleum  refining industry varies from less than 5 gallons
of water per barrel of crude charge in the  newer  refineries  to
higher  than  1000 gallons of water per barrel of crude charge in
the older refineries.  In order to provide efficient treatment to
the wastes originating within a refinery, it  is  very  important
that  segregation  of  concentrated  waste streams be considered.
Segregation of waste streams frequently simplifies waste treating
problems as well as  reduces  treatment  facility  costs.   Thus,
treatment  of  highly  polluted  waste  streams at the source can
prevent gross pollution of  large  volumes  of  relatively  clean
waste  water.  Such treatment is often a more economical solution
of a problem than would be  possible  if  wastes  are  discharged
directly to the refinery sewers.  Treatment at the source is also
helpful in recovering by-products from the wastes which otherwise
could not be economically recovered when the wastes are combined.

In   areas   where   water   supply  is  limited,  reduced  water
requirements  have  been  incorporated  into   the   design   and
operation, thereby reducing total water usage.

To minimize the size of the waste water treatment processes it is
imperative   polluted   water  only  be  treated.   This  can  be
guaranteed by  segregating  the  various  sewer  systems.   There
should  be  a sewer carrying process and blowdown waters that are
treated continuously.  A polluted storm water sewer should go  to
a  storage  area from which it can be gradually discharged to the
treatment facilities.  A  sewer  system  containing  clean  storm
water  can  be  discharged  directly to the receiving water.  The
sanitary system should be treated  separately  from  the  process
water  because  of  the  bacteria  present  in this stream.  Once
through cooling water should be  kept  separate  because  of  the
large  volumes  of  water  involved  and  the  low waste loadings
encountered.  A connection  to  the  treatment  plant  should  be
provided in case of oil leaks into the system.

Storm Water Runoff

An  additional source of pollution from a petroleum refinery area
is caused by rainfall runoff.  Size and  age  of  refinery  site,
housekeeping,  drainage  areas,  and  frequency  and intensity of
rainfall are seyeral of the factors which compound the assignment
of allowable pollutional values.

There are several measures that refiners can provide to  minimize
storm  water  loads to their treatment system after diverting all
extraneous  drainage  around  the  refinery  area.    The   major
consideration is a separate storm water sewer and holding system.
                             99

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By  providing  separate  collection  facilities  for  storm water
runoff, protection is afforded the operation of the separator and
ancillary treatment systems by controlling the hydraulic load  to
be  treated.   Comingling  of inorganic particles with oily waste
water often times produces an  emulsion  which  is  difficult  to
break in the oil-water separator.

Design  of this facility should be based on the maximum ten-year,
twenty-four-hour rainfall runoff of the refinery  drainage  area.
Diversion  of  the  collected storm water runoff to the oil-water
separator facilities can be provided when hydraulic flows  return
to  normal  operations.  In the event of excessive collection due
to  a  high  intensity  storm,  diversion  facilities  should  be
provided  to  allow for emergency bypass capability to divert the
trailing edge of the runoff hydrograph (the leading edge normally
contained the mass of pollutants in urban runoff investigations).
An oil retention baffle and an API type overflow weir  should  be
provided to prevent the discharge of free and floating oil.

An  alternate to the separate sewer system would be the provision
of a storm surge pond that would receive the polluted waters when
the flow to the oil-water separator exceeded 15  percent  of  the
normal  hydraulic  flow.   During  normal  periods, the collected
storm water-refinery water could then be  diverted  to  the  oil-
water  separator   (provided  process flow did not equal or exceed
the units hydraulic capacity).

The major cause of pollution by storm water runoff is the lack of
housekeeping within  the  refinery  confine.   Proper  procedures
should  be  encouraged  to  prevent the accumulation of materials
which contribute to pollution due to rainfall  runoff.   Some  of
the  more  common  preventive  measures are:   (1) Provide curbing
around process unit pads;  (2) Prevent product sample drainage  to
sewers;   (3) Repair pumps and pipes to prevent oily losses to the
surface areas;  (4) Contain spilled oil from turnarounds;  (5) Dike
crude and product tank areas and valve precipitation to the storm
water sewer.

In the event the collected water needs to be  released  from  the
storm  water detention pond due to overflow, samples of the water
should be monitored for;  (1) Oil and Grease,  (2) Organic analysis
such as TOC.

Ballast Water Separation

Ballast water normally is not discharged directly to the refinery
sewer system because  the  intermittent  high-volume  discharges.
The potentially high oil concentrations, would upset the refinery
waste  water  treatment  facilities.   Ballast waters may also be
treated   separately,  with  heating,  settling,  and   at   times
filtration  as  the  major  steps.  The settling tank can also be
provided  with a steam coil for heating the tank contents to  help
break  emulsions,  and  an  air  coil  to provide agitation.  The
recovered oil, which may be considerable, is  generally  sent  to
the slop  oil system.
                              TOO

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Slop Oil Treatment

separator skimmings, which are generally referred to as slop oil,
require treatment before they can be reused, because they contain
an  excess amount of solids and water.  Solids and water contents
in excess of about 1 percent generally interfere with processing.

In most cases slop oils are easily treated by  heating  to  190°F
for  12  to  m  hours.   At  the end of settling, three definite
layers exist:  a top layer  of  clean  oil;  a  middle  layer  of
secondary  emulsion;  and  a  bottom  layer  of  water containing
soluble components, suspended solids, and oil.  In some cases, it
is advantageous  or  even  necessary  to  use  acid  or  specific
chemical  demulsifiers  to  break  slop oil emulsions.  The water
layer resulting from acid and heat treatment  has  high  BOD  and
COD,  but  also  low  pH,  and  must  be treated before it can be
discharged.

Slop oil can also be successfully treated by centrifugation or by
precoat filtration using diatcmaceous earth as the precoat.


Gravity Separation of Oil

Gravity separators remove a majority of the  free  oil  found  in
refinery   waste   waters.   Because  of  the  large  amounts  of
reprocessable  oils  which  can  be  recovered  in  the   gravity
separators,  these  units  must be considered an integral part of
the refinery processing operation and not a waste water treatment
process.  The functioning of gravity-type separators depends upon
the difference  in  specific  gravity  of  oil  and  water.   The
gravity-type  separator will not separate substances in solution,
nor will it break emulsions.  The effectiveness  of  a  separator
depends  upon  the temperature of the water, the density and size
of the oil globules, and the amounts of  characteristics  of  the
suspended matter present in the waste water.  The "susceptibility
to  separation"  (STS)   test  is  normally  used  as  a  guide to
determine what portion of the influent to a separator is amenable
to gravity separation.

The API separator is the most widely used gravity separator.  The
basic design is a long rectangular basin, with  enough  detention
time  for most of the oil to float to the surface and be removed.
Most API separators  are  divided  into  more  than  one  bay  to
maintain  laminar flow within the separator, making the separator
more  effective.   API  separators  are  usually  equipped   with
scrapers  to  move the oil to the downstream end of the separator
where the oil is collected in a slotted pipe or on  a  drum.   On
their  return  to the upstream end, the scrapers travel along the
bottom moving the solids to  a  collection  trough.   Any  sludge
which settles can be dewatered and either incinerated or disposed
of as landfill.

The  gravity  separator usually consists of a pre-separator (grit
chamber) and a main  separator,  usually  rectangular  in  shape,
                             101

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provided   with  influent  and  effluent  flow  distribution  and
stilling devices and with  oil  skimming  and  sludge  collection
equipment.  It is essential that the velocity distribution of the
approach flow be as uniform as possible before reaching the inlet
distribution baffle.

Another  type  of  separator  finding  increasing  employment  in
refineries  is  the  parallel  plate  separator.    The  separator
chamber is subdivided by parallel plates set at a 45° angle, less
than  6  inches  apart.  This increases the collection area while
decreasing the overall size of the  unit.   As  the  water  flows
through  the separator the oil droplets coalesce on the underside
of the plates and travel upwards where the oil is collected.  The
parallel plate separator can  be  used  as  the  primary  gravity
separator, or following an API separator.

Further Removal of Oil and Solids

If  the effluent from the gravity separators is not of sufficient
quality  to  insure  effective  treatment  before  entering   the
biological or physical-chemical treatment system, it must undergo
another  process  to remove oils and solids.  Most refineries use
either clarifiers, dissolved air flotation units  or  filters  to
reduce the oil and solids concentration.  Each of these processes
has  also  been  used  to  treat  the  effluent from a biological
system.

Clarifiers

Clarifiers use gravitational  sedimentation  to  remove  oil  and
solids  from  a waste water stream.  Often it is necessary to use
chemical coagulants such as alum or lime to aid the sedimentation
process.  These clarifiers are usually equipped with a skimmer to
remove any floating oil.   clarifiers  used  after  a  biological
system  normally  do  not  have  skimmers  as  there should be no
floating oils at that point.  The sludge from the  clarifiers  is
usually treated before final disposal.

End-of-Pipe Control Technology

End-of-pipe control technology in the petroleum refining industry
relies  heavily  upon  the  use  of biological treatment methods.
These are supplemented by appropriate pretreatment to insure that
proper conditions,  especially  sufficient  oil  removal  and  pH
adjustment,  are  present  in  the feed to the biological system.
When   used,   initial   treatment   most   often   consists   of
neutralization  for  control  of  pH  or  equalization  basins to
minimize  shock   loads   on   the   biological   systems.    The
incorporation  of solids removal ahead of biological treatment is
not as important as it is in treating municipal waste waters.

One of the initial criteria used to  screen  refineries  for  the
field  survey,  was  degree  of treatment provided by their waste
water treatment facilities.  Therefore, the selection  of  plants
was  not  based  on  a  cross-section of the entire industry, but
                             102

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rather was biased in favor of those segments of the industry that
had the more efficient waste water treatment  facilities.   Table
26  indicates  the  types of treatment technology and performance
characteristics which were observed during the survey.   In  most
of  the  plants  analyzed,  some type of biological treatment was
utilized  to  remove  dissolved  organic  material.    Table   27
summarizes  the  expected  effluents  from  waste water treatment
processes throughout the petroleum  refining  industry.   Typical
efficiencies for these processes are shown in Table 28.

During   the   survey   program,   waste  water  treatment  plant
performance history was obtained when possible.  This  historical
data  were  analyzed  statistically  and  the  individual plant's
performance evaluated in comparison to the original design basis.
After this evaluation, a group of plants was  selected  as  being
exemplary  and  these  plants  were  presented  in Table 26.  The
treatment data in Table 28 represent  the  annual  daily  average
performance  (50 percent probability-of-occurrence).

There  were  enough plants involving only one subcategory to make
the interpretation meaningful.  In preparing  the  economic  data
base,  however,  all  the  waste  water treatment plant data were
analyzed to develop a basis for subsequent capital and  operating
costs.

The   treatment  data  from  the  exemplary  plants  referred  to
previoulsy were analyzed to formulate the  basis  for  developing
BPCTCA effluent criteria.  The effluent limitations were based on
both  these  treatment data, other data included in Supplement B,
and other sources as discussed in  Section  IX.   These  effluent
limitations  were developed for each subcategory individually and
thus no common treatment efficiency was selected as being typical
of the petroleum refining industry for use in the BPCTCA effluent
limitations.  A brief description  of  the  various  elements  of
end-of-pipe treatment follows.

Equalization

The  purpose of equalization is to dampen out surges in flows and
loadings.   This  is  especially  necessary  for   a   biological
treatment plant, as high concentrations of certain materials will
upset or completely kill the bacteria in the treatment plant.  By
evening  out  the  loading on a treatment plant, the equalization
step enables the treatment plant to operate more effectively  and
with  fewer  maintenance  problems.   Where  equalization  is not
present, an accident or spill within  the  refinery  can  greatly
affect the effluent quality or kill the biomass (R7, R20).

The  equalization  step usually consists of a large pond that may
contain mixers to provide better mixing of the wastes.   in  some
refineries  the  equalization  is  done in a tank  (55, R29).  The
equalization step can be before or after  the  gravity  separator
but  is  more  effective  before  as  it  increases  the  overall
efficiency of the separator.  However,  care  must  be  taken  to
prevent anaerobic decomposition in the equalization facilities.
                               103

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SL'BCATEGORT
                                   Observed Refinery Treatment System and Effluent Loadings
                                                                TABLE 26
Type of OP AL-PP
Treatment
Refinery R32 R18
Observed Average
Effluent Loadings
Met-kg/1000 m3 of
feedstock
(lb/1000 bbl of
feedstock)
BODS 8(2.8)
COD 	 39(13.8)
TCC _» —_. _,__,.,„
JL3O _»•-•-_-__ —_._.— «.
Ac/* 4 A/ A 7\ 41 /rt B\
O&G Z . 0\0. 7) Z.j(O.o)

Phenolic
Compounds 0.14(0.05) 0.003(0.001)

Sulflde 0.03(0.009) 	

AL-F E-DAF-A

R27






8.0(4.4) 5.9(2.1)
68(24) 96(34)
25(8.7) 34(12)
A/I t\ t. n/i A
9(3*2) 4*0(1*4


0.4(0.145) 0.37(0.

0.2(0.07) 0(0)

S OP I

R26






10(3.6)
71(25.0)
8.5(3.0)
4Q/1 7\
• O^X* / /

13) 0.05(0.018)

0.03(0.010)

)AF,AL,PP

R7






3.7(1.3)
39(13.8)
4.2(1.5)
2 ft/1 f\\
*0\1 t\JJ
0 14(0 05^


0.0006
(0.002)
0.014
(0.005)
DAK. AS

R20






13(4.6)
67(23.5)
13.6(4.8)
6*5(2 • 3)
Ac /i f\
* J VX >O/

0.06
(0.023)
0.05
(0.018)
DAF.AS DAF.AL.FP E,TF,AS E.AS DAF.AS.PP

R8 R23 R24 R28 R25






2.7(0.95) 2.6(0.91) 7.4(2.6) 14(5.0) 17.5(6.2)
	 54(19, 57(20) 136(48) 320(113)
8.5(3.0) 7(2.5) 12(4.3) 38(13.5) 36(12.7)
A /I A\ 79/9R^^ 91 n *1\
•»•»••••-- *t \X • *t y ***V**^'^ ** \ / • / /
—— — _ 9^n 7\ i 9 fn AA^ -.. _ o ^/A n\
-"••"•— ^ \,u* if x* _; vu**my _._-— » *• j ^u, o/

	 	 0.17(0.06) 	 0.017(0.005)

	 	 	 	 0.20 (.07)

Footnotes!  AL-aerated lagoon
           AS-actlvated sludge
          DAF-dlssolved air flotation
            E-equallzatlon
 F-flltratlon
OP-oxldatlon pond
PP-pollshing pond
TF-trlckling filter
A-Topplng          D-Lube
B-Cracking      B-lntegr«t«d
C-Petrochemicals

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                                                                TABLE  27



                                            Expected Effluents from Petroleum Treatment Processes
EFFLUENT CONCENTRATION
PROCESS
1
2
3
It
5
6
T.
8,
9.
10.
IX.
12.
. API Separator
. Clarlfler
. Dissolved Air
Flotation
. Granular Media
Filter
. Oxidation Fond
. Aerated Lagoon
Activated Sludge
Trickling Filter
Cooling Tower
Activated Carbon
Granular Media Filter
Activated Carbon
PROCESS
INFLUENT
Raw Waste
1
1
1
1
2,3,1*
2,3,1*
1
2,3.1.
2.3.U
5-9
5-9 and 11
BOD5
250-350
1*5-200
1*5-200
1*0-170
10-60
10-50
5-50
25-50
25-50
5-100 .
NA
3-10
COD
260-700
130-1*50
• 130-1*50
100-1*00
50-300
50-200
30-200
80-350
1*7-350
j. 30-200
NA
30-100
TOC
NA
NA
NA
NA
NA
NA
20-80
NA
70-150
NA
25-61
1-17
ss
50-200
25-60
25-60
-5-25
20-100
10-80
5-50
20-70
U. 5-100
10-20
3-20
1-15
, WS/L
OIL
20-100
5-35
5-20
6-20
1.6-50
5-20
1-15
10-80
20-75
2-20
3-17
0.8-2.5

PHENOL
6-100
10-1*0
10-1*0
3-35
0.01-12
0.1-25
0.01-2.0
0.5-10
.1-2.0
41
0.35-10
0-0.1

AMMOHIA
15-150
NA
SA
NA
3-50
lt-25
1-100
25-100
1-30
10-lUo
NA
1-100

SULF1DE
HA
NA
HA
HA
0-20
0-0.2
0-0.2
0.5-2
HA
NA
NA
0-0.2

Ktmuaiuiss
7, 13, 30, ill, It9 ,59
3U.UBa.l0
13,29,32,l*8a,l<9
17»ltl,l*8a,l*8
18 ,22 ,23,31, 1*2 ,U8»,
!*9,55,75,R18
31,39,l*2a,l*8a,li9,
55,59,R7,R23,R26
13,2l*,27,30,3l*,35,
1*2, l*8a, 1*9 ,60 ,69 ,72
R8,R20,R2l*,R25,R27
R28.R29
18,30,1*2,1* 8a,l*9>
33,1*1
17,2l,27,l*8,l*8a,l*9,
53,62a
17,1*8,51*
17,21,27,l*8,1.8a,l*9,
C-3 ^O_
                                                                                                                                    53,6
- Data lot Available

-------
                                                                        TABLE  28



                                            Typical Removal Efficiencies for Oil Refinery Treatment  Processes
PROCESS
1.
2.
3.
It.
5.
6.
T.
8.
9.
10.
11.
12.
API Separator
Clarifler
Dissolved Air
Flotation
Filter
Oxidation Pond
Aerated Lagoon
Activated Sludge
Trickling
Filter
Cooling Tower
Activated
Carbon
Filter
Granular Media
Activated
Carbon
PROCESS
INFLUENT
Raw Waste
1
1
1
1
2.3.U
2.3.U
1
2,3,1*
2,3,U
5-9
5-9- plus 11
REMOVAL EFFICIENCY, %
BODs
5-1*0
30-60
20-70
1*0-70
1*0-95
• 75-95
80-99
60-85
50-90
70-95
NA
91-98
COD
5-30
20-50
10-60
20-55
30^65
60-85
50-95
30-70
1*0-90
70-90
NA
86-9U
TOC
HA
HA
HA
HA
60
HA
1*0-90
HA
10-70
50-80
50-65
50-80
SS
10-50
50-80
50-85
75-95
2"0-70
1.0-65
60-85
60-85
50-85
60-90
75-95
60-90
OIL
60-99
60-95
JO-85
65-90
50-90
70-90
80-99
50-80
60-75
75-95
65-95
70-95
PHENOL
0-50
0-50
10-75
5-20
60-99
90-99
95-99+
70-98
75-99+
90-100
5-20
90-99
AMMONIA
NA
NA
HA ,
HA
0-15
10-1*5
33-99
15-90
60-95
7-33
NA
33-87
SULFIDE
NA
NA
NA
NA
70-100
95-ioo
97-100
70-100
NA
NA
NA
NA
REFERENCES
7, 13, 30, Ul ,1*9 ',59
3lt,l*8a,l*9
13,29,32,l*8a,U9
17,l*l,l*8a,l*9
18,22,23,31,1*2,1*8
!*9,55,75,Rl8
31, 39 ,!t2, 1*811,1*9,
55,59,R7,R23,R26
13,2l»,R7,30,3l*,35
1*2,1* 8a, 1)9 ,60,69,72
R8,B20,?2l*,R25,R2
R28.R29
18,30, 1*2, l*8a,l*9
33,1*1
17 ,21 ,27 ,1*8', l*8a, 1*9
l*9,53,62a
17,1*8,51*
rr^i^.w.usa,
>*9,53,62a
HA - Data lot Available

-------
Dissolved Air Flotation

Dissolved  air  flotation consists of saturating a portion of the
waste water feed, or a portion of the feed or  recycled  effluent
from  the flotation unit with air at a pressure of 40 to 60 psig.
The waste water or effluent recycle is held at this pressure  for
1-5  minutes in a retention tank and then released at atmospheric
pressure to the  flotation  chamber.   The  sudden  reduction  in
pressure  results in the release of microscopic air bubbles which
attach themselves to oil and suspended  particles  in  the  waste
water  in  the  flotation  chamber.  This results in agglomerates
which, due to the entrained air, have greatly-increased  vertical
rise  rates  of  about  0.5  to  1.0  feet/minute.   The  floated
materials rise to the surface to form a froth  layer.   Specially
designed  flight  scrapers or other skimming devices continuously
remove the froth.  The retention time in the  flotation  chambers
is  usually  about 10-30 minutes.  The effectiveness of dissolved
air flotation depends upon  the  attachment  of  bubbles  to  the
suspended  oil  and  other particles which are to be removed from
the waste stream.  The attraction  between  the  air  bubble  and
particle  is  a  result  of  the particle surface and bubble-size
distribution.

Chemical flocculating agents, such as salts of iron and aluminum,
with or without organic polyelectrolytes, are  often  helpful  in
improving  the  effectiveness of the air flotation process and in
obtaining a high degree of clarification.

Dissolved air flotation is used by  a  number  of  refineries  to
treat  the  effluent  from  the  oil  separator.   Dissolved  air
flotation using flocculating agents is also  used  to  treat  oil
emulsions.   The  froth  skimmed  from  the flotation tank can be
combined with  other  sludges   (such  as  those  from  a  gravity
separator) for disposal.  The clarified effluent from a flotation
unit  generally  receives further treatment in a biological unit,
prior to discharge.  In two refineries, dissolved  air  flotation
is used for clarification of biologically treated effluents (29).

Oxidation Ponds

The  oxidation  pond  is  practical  where  land is plentiful and
cheap.  An oxidation pond has a large surface area and a  shallow
depth,  usually  not  exceeding  6  feet.   These ponds have long
detention periods from 11 to 110 days.

The shallow depth  allows  the  oxidation  pond  to  be  operated
aerobically  without  mechanical aerators.  The algae in the pond
produce oxygen through photosynthesis.  This oxygen is then  used
by  the  bacteria  to  oxidize  the  wastes.   Because of the low
loadings, little biological sludge is produced and  the  pond  is
fairly resistant to uspsets due to shock loadings.

Oxidation  ponds are usually used as the major treatment process.
Some refineries use ponds as  a  polishing  process  after  other
treatment processes.
                             107

-------
Aerated Lagoon

The  aerated  lagoon is a smaller, deeper oxidation pond equipped
with mechanical aerators or diffused air units.  The addition  of
oxygen  enables the aerated lagoon to have a higher concentration
of microbes than the  oxidation  pond.   The  retention  time  in
aerated  lagoons is usually shorter, between 3 and 10 days.  Most
aerated lagoons are operated without final clarification.   As  a
result, biota is discharged in the effluent., causing the effluent
to  have  high  BODJ>  and solids concentrations.  As the effluent
standards  become  more  strict,  final  clarification  will   be
increasing in use.

Trickling Filter

A  trickling filter is an aerobic biological process.  It differs
from other processes in that the biomass is attached to  the  bed
media, which may be rock, slag, or plastic.  The filter works by:
1) adsorption of organics by the biological slime 2)  diffusion of
air into the biomass; and 3) oxidation of the dissolved organics.
When  the biomass reaches a certain thickness, part of it sloughs
off.  When the filter is used as the major treatment  process,  a
clarifier is used to remove the sloughed biomass.

The trickling filter can be used either as the complete treatment
system  or  as  a  roughing  filter.   Most  applications  in the
petroleum industry use it as a  roughing  device  to  reduce  the
loading on an activated sludge system.

Bio-Oxidation Tower

The  bio-oxidation  tower uses a cooling tower to transfer oxygen
-to a waste water.  API (112) has called the bio-oxidation  towers
a  modified  activated  sludge process, as most of the biomass is
suspended in the wastewater.  Results from refineries indicate it
is a successful process to treat portions or all  of  a  refinery
waste water  (80, 81, 92).

Activated Sludge

Activated  sludge  is  an aerobic biological treatment process in
which high concentrations  (1500-3000  mg/L)  of  newly-grown  and
recycled  microorganisms  are  suspended  uniformly  throughout a
holding tank to which raw waste  waters  are  added.   Oxygen  is
introduced by mechanical aerators, diffused air systems, or other
means.   The  organic materials in the waste are removed from the
aqueous phase by the microbiological growths  and  stabilized  by
biochemical   synthesis   and  oxidation  reactions.   The  basic
activated sludge process consists of an aeration tank followed by
a sedimentation tank.  The flocculant microbial  growths  removed
in  the  sedimentation  tank are recycled to the aeration tank to
maintain a high concentration of active microorganisms.  Although
the microorganisms remove almost all of the organic  matter  from
the  waste  being  treated,  much of the converted organic matter
remains in the system in the  form  of  microbial  cells.   These


                                108

-------
cells  have  a  relatively high rate of oxygen demand and must be
removed from the treated waste  water  before  discharge.   Thus,
final  sedimentation  and  recirculation of biological solids are
important elements in an activated sludge system.

Sludge is wasted on a continuous basis at a relatively  low  rate
to  prevent  build-up  of excess activated sludge in the aeration
tank.  Shock organic loads usually result in an overloaded system
and poor sludge settling characteristics.  Effective  performance
of activated sludge facilities requires pretreatment to remove or
substantially  reduce  oil,  sulfides  (which  causes toxicity to
microorganisms), and  phenol  concentrations.   The  pretreatment
units  most  frequently  used  are:   gravity  separators and air
flotation units to remove oil; and sour water strippers to remove
sulfides, mercaptans,  and  phenol.   Equalization  also  appears
necessary  to  prevent shock loadings from upsetting the aeration
basin.   Because  of  the  high  rate  and  degree   of   organic
stabilization possible with activated sludge, application of this
process  to  the  treatment  of  refinery  waste  waters has been
increasing rapidly in recent years.

Many variations of the activated sludge process are currently  in
use.   Examples  include: the tapered aeration process, which has
greater air addition at the influent where the oxygen  demand  is
the  highest;  step aeration, which introduces the influent waste
water  along  the  length  of  the  aeration  tank;  and  contact
stabilization, in which the return sludge to the aeration tank is
aerated  for  1-5  hours.   The  contact stabilization process is
useful where the oxygen demand is in the suspended  or  colloidal
form.   The  completely  mixed  activated sludge plant uses large
mechanical mixers to mix the influent with the  contents  of  the
aeration basin,  decreasing the possibility of upsets due to shock
loadings.   The  Pasveer  ditch  is a variation of the completely
mixed activated sludge process that is  widely  used  in  Europe.
Here  brushes are used to provide aeration and mixing in a narrow
oval  ditch.   The  advantage  of  this  process  is   that   the
concentration  of  the  biota  is higher than in the conventional
activated sludge process,  and  the  wasted  sludge  is  easy  to
dewater.   There is at least one refinery using the Pasveer ditch
type system.

The activated sludge process has several disadvantages.   Because
of the amount of mechanical equipment involved, its operating and
maintenance  costs are higher than other biological systems.  The
small volume of the aeration basin makes the process more subject
to upsets than either oxidation ponds or aerated lagoons.

As indicated in Table 25, the activated sludge process is capable
of achieving very low concentrations of BODS, COD, TSS, and  oil,
dependent  upon  the  influent  waste  loading and the particular
design basis.  Reported efficiencies for BODS removal are in  the
range of 80 to 99 percent.

Physical-chemical Treatment
                               109

-------
Physical-chemical  treatment  refers  to treatment processes that
are non-biological in nature.  There are two types  of  physical-
chemical  processes;  those that reduce the volume of water to be
treated (vapor compression evaporators, reverse  osmosis,  etc.),
and  those  that  reduce  the  concentration  of  the  pollutants
(activated carbon).

Physical-chemical   (P-C)   processes  require   less   land   than
biological  processes.   P-C  processes are not as susceptible to
upset due to shock loading as are biological processes.   Another
advantage  of  P-C  is  that  much  smaller amounts of sludge are
produced.

Flow Reduction Systems

Flow reduction systems produce two effluents, one  of  relatively
pure  water  and one a concentrated brine.  The pure water stream
can be reused within the refinery resulting in a smaller effluent
flow.  The brine is easier to treat as it is highly concentrated.
Both of the processes described herein have been demonstrated  on
small  flows only and at present the costs involved are extremely
high (45,  52, 93).

In the vapor compression evaporator the waste  water  flows  over
heat  transfer surfaces.   The steam generated enters a compressor
where the temperature is  raised  to  a  few  degrees  above  the
boiling  point  of the waste water.  The compressed steam is used
to  evaporate  more  waste  water  while  being  condensed.   The
condensed  steam  is  low in dissolved solids.  The major process
costs are the costs of electrical power, which  is  approximately
$1.0/1000 gallons of clean water  (93).

The reverse osmosis process uses high pressures  (400-800 psig) to
force  water  through  a  semi-permeable  membrane.  The membrane
allows the water to pass through, but  contains  the  other  con-
stituents in the waste water.  Currently available membranes tend
to  foul  and blind, requiring frequent cleaning and replacement.
Until this  problem  is  corrected,  reverse  osmosis  is  not  a
practicable  process.   The  operating cost for a reverse osmosis
unit is approximately 20-300/1000 gallons  (U5, 95).

Granular Media Filters

There are several types of granular media  filters:   sand,  dual
media,  and  multimedia.    These filters operate in basically the
same way, the only difference being the filter media.   The  sand
filter uses relatively uniform grade of sand resting on a coarser
material.   The dual media filter has a course layer of coal above
a  fine layer of sand.  Both types of filters have the problem of
keeping the fine particles on the bottom.  This problem is solved
by using a third very heavy, very fine material,  (usually garnet)
beneath the coal and sand.

As the water passes down through a filter, the  suspended  matter
is  caught  in  the  pores.   When  the pressure drop through the
                               110

-------
filter becomes excessive, the flow through the filter is reversed
for removal of the collected solids loading.  The backwash  cycle
occurs  approximately  once  a day, depending on the loading, and
usually lasts for 5-8 minutes.  Most uses of  sand  filters  have
been  for  removing  oil  and solids prior to an activated carbon
unit.  There is one refinery that uses a mixed  media  filter  on
the  effluent  from  a biological system.  Granular media filters
are shown to be capable of consistently operated  with  extremely
low TSS and oil effluent discharges, on the order of 5-10 mg/L.

Activated Carbon

The  activated  carbon   (AC)   process utilizes granular activated
carbon to adsorb pollutants from waste water.  The adsorption  is
a  function  of  the  molecular size and polarity of the adsorbed
substance.  Activated carbon preferentially adsorbs large organic
molecules that are non-polar.

An AC unit follows a  solids  removal  process,  usually  a  sand
filter  which  prevents  plugging  of the carbon pores.  From the
filter the water flows to a bank of carbon  columns  arranged  in
series  or  parallel.  As the water flows through the columns the
pollutants are adsorbed by  the  carbon,  gradually  filling  the
pores.   At  intervals,  portions  of the carbon are removed to a
furnace  where  the  adsorbed  substances  are  burnt  off.   The
regenerated  carbon  is  reused  in the columns, with some makeup
added, because of handling and efficiency losses.

Activated carbon processes currently have only limited  usage  in
the  refining  industry.  However, there are new installations in
the  planning  construction  stages.   The  increasing   use   of
activated  carbon has occured because activated carbon can remove
organic materials  on  an  economically  competitive  basis  with
biological  treatment.   Activated  carbon  regeneration furnaces
have high energy requirements.

Sludge Handling and Disposal

Digestion

Digestion  is   usually   used   preceding   the   other   sludge
concentration  and disposal methods.  The purpose of digestion is
to improve the dewatering of the  sludge.   Digestion  can  occur
aerobically   or   anaerobically.    During  digestion,  bacteria
decompose the organic material in the sludge  producing  methane,
carbon  dioxide  and water.  At the end of the digestion process,
the sludge is stable and non-decomposable.

Vacuum Filtration

The various vacuum filters,  usually  a  revolving  drum,  use  a
vacuum  to  dewater  the  sludge.   The revolving drum type has a
vacuum applied against a cloth.  The  water  passes  through  the
cloth  and  returns  to the influent of the treatment plant.  The
sludge remains on the drum until it is scraped off with a knife.
                               Ill

-------
Centrifugation

Centrifugal!on uses high speed rotation to  separate  sludge  and
water.   The  heavier sludge moves to the outside and is conveyed
to one end, where it is collected for final disposal.  The  water
flows  out  the  opposite  end  and  is returned to the treatment
plant.

Sludge Disposal

From any waste water treatment plant, the sludge must be disposed
of.  The methods used are landfilling,  landfarming,  barging  to
sea, and incineration.

Landfilling

A  landfill  operation  requires  a large amount of land.  Before
landfilling,  the  sludge  should  be  digested  to  avoid   odor
problems.   The  sludge  is  disposed  of  in an excavation site.
After each batch is disposed of, it is covered with  a  layer  of
earth.   When the site is filled to capacity it is covered with a
thick layer of earth.

The largest problem of industrial landfills is the  pollution  to
ground  and  surface  waters  by  leaching.  Leaching occurs when
water percolates through the landfill.  As it drains through  the
landfill  site, the water carries with it dissolved and suspended
solids and organic  matter.   This  water  can  then  contaminate
underground or surface streams it comes in contact with.

Incineration

Incineration  is gradually complementing landfills as a method of
sludge  disposal.    The   principal   process   is   fluid   bed
incineration.   In  this process, a bed of sand is preheated with
hot air to U82-538°C  (900 - 1000°F).  Torch oil is then  used  to
raise  the  bed  temperature  to 649 - 705°C  (1200 - 1300°F).  At
this point waste water sludge and/or sludge is introduced and the
torch oil is stopped.  The solid products of combustion remain in
the bed which is a gradually withdrawn to maintain a constant bed
height.  Eventually, the bed will be composed of only ash.

The sludge fed to the incinerator usually contains  inorganic  as
well  as  organic  material.   However, the sludge must contain a
minimum amount of organics to maintain  the  combustion  process.
One  refinery  (26)  suggests  a  minimum  of  1,930,000 cal/cu m
(29,000 Btu/gal)  of sludge heating value is necessary to maintain
the combustion process.
                                112

-------
                          SECTION VIII

           COST, ENERGY, AND NON-WATER QUALITY ASPECTS
The first part of this section summarizes the costs   (necessarily
generalized)  and effectiveness of end-of-pipe control technology
for BPCTCA and BATEA and BADT-NSPS effluent limitations.   Treat-
ment  costs  for  small,  medium,  and  large  refineries in each
subcategory have been estimated for the technologies  considered.
The  expected  annual  costs for existing plants in the petroleum
refining  industry  in  1977  consistent  with  BPCTCA   effluent
limitations  are estimated at $225 million (end-of-pipe treatment
only).  For 1983, consistent with EATEA effluent limitations, the
estimated additional annual costs are estimated at  $250  million
(end-of-pipe  treatment  only).  For BADT-NSPS the annual cost is
estimated  at  $26  million.   These  costs  are  summarized   by
subcategory in Table 29.

The  effect of plant size relative to annual costs can be seen in
Table 30 where the annual costs are summarized for application of
BPCTCA and BATEA to small, medium, and large refineries  in  each
subcategory.   The  cost, energy, and nonwater quality aspects of
in-plant  controls  are  intimately  related  to   the   specific
processes  for  which  they  are  developed.    Although there are
general cost and energy requirements for  equipment  items   (e.g.
surface air coolers), these correlations are usually expressed in
terms  of  specific  design parameters, such as the required heat
transfer area.  Such parameters are  related  to  the  production
rate   and   specific  situations  that  exist  at  a  particular
production site.

There is a wide variation in refinery  sizes.   When  these  size
ranges  are  superimposed on the large number of processes within
each subcategory, it is apparent that many detailed designs would
be required to develop a meaningful understanding of the economic
impact of process modifications.   The  decision  to  attain  the
limitations through in-plant controls or by end-of-pipe treatment
should  be  left  up  to  individual manufacturers.  Therefore, a
series of possible designs for the end-of-pipe  treatment  models
is provided.

Alternative Treatment Technologies

The   range   of  components  used  or  needed  for  either  best
practicable or best available technology have been combined  into
five  alternative  end-of-pipe  treatment  steps,  which  are  as
follows:

    A. Initial treatment, consisting of dissolved air  flotation,
    equalization,  neutralization, and nutrient  (phosphoric acid)
    feed facilities.
                                113

-------
                                   TABLE 29


            Estimated Total Annual Costs for End-of-Pipe Treatment
      Systems for the Petroleum Refining Industry (Existing Refineries)


Subcategory                                     Total Annual Cost, $ Million
                                                1977               1983

Topping                                        $14.2               $16.5

Cracking                                        81.3                92.5

Petrochemical                                   53.9                50.0

Lube                                            70.1                66.2

Integrated                                      55.5                24.8
                             Industry Total   $255.0              $250.0
                                       114

-------
                                   TABLE 30

                 Summary of End-of-Pipe Waste Water Treatment Costs
           for Representative Plants 1n the Petroleum Refining Industry
Subcategory
Topping
Cracking
Petrochemical
Lube
Integrated
                 Representative
                 Refinery Size
              1000 m3/day   1000 BBL/day
                                Annual
                             Level 1 Costs
                           $/1000 m3  $/1000 gal
                                    Annual  Additional
                                   Level 11 Costs
                                    $/10QO m3  $/1000  gal
 0.318
 1.11
 2.4

 2.4
11.9
23.8

 4.0
15.9
31.8

 4.0
17.5
39.8

 9.8
23.0
49.0
  2
  7
 15

 15
 75
150

 25
100
200

 25
110
250

 65
152
326
0.066
0.030
0.018
0.014
0.007
0.006
0.009
0.007
0.005
0.009
0.006
0.005
0.006
0.005
0.005
17.31
7.86
4.87
3.78
1.84
1.62
2.32
1.78
1.35
2.33
1.50
1.25
1.67
1.28
1.13
0.070
0.034
0.023
0.019
0.008
0.006
0.010
0.006
0.005
0.010
0.006
0.004
0.006
0.005
0.003
18.41
9.06
5.97
4.90
2.20
1.47
2.65
1.63
1.20
2.57
1.51
0.93
1.53
1.05
0.65
                                       115

-------
    B.  Biological  treatment,  consisting  of  acitvated  sludqe
    units, thickness, digesters, and dewatering facilities.

    C.  Granular  media  filtration, consisting of filter systems
    and associated equipment.

    D.  Physical-chemical  treatment  facilities  consisting   of
    activated carbon adsorption.

    E.  Alternative  Biological  treatment, consisting of aerated
    lagoon facilities.

Tables 31  through  45  are  summaries  of  the  costs  of  major
treatment   steps   required   to  achieve  different  levels  of
technology for  small,  medium,  and  large  refineries  in  each
subcategory;  using median raw waste loads and median "good water
use" flow rates, for the end-of-pipe treatment models.

BPCTCA Treatment Systems Used for the Economic Evaluation

A general flow schematic for the  BPCTCA  waste  water  treatment
facilities is shown in Figure 6.  A summary of the general design
basis  is  presented  in  Table 46 and a summary of the treatment
system effluent limitations for each subcategory is presented  in
Tables 1-6.

BATEA treatment Systems Used for the Economic Evaluation

BATEA   treatment  facilities  are  basically  added  on  to  the
discharge pipe from BPCTCA facilities.  It is expected that flows
will be reduced slightly by the  application  of  BATEA  in-plant
technology, so that the activated carbon treatment unit may treat
a  smaller  hydraulic load.  However, the activated carbon system
was sized for the same flow basis  as  in  BPCTCA  technology  in
order  to  establish a conservative basis for economic evaluation
of proposed effluent limitations.

A general flow  schematic  diagram  for  the  BATEA  waste  water
treatment  facilities  is  shown  in  Figure 7.  A summary of the
general design basis is presented in Table 47.  and a summary  of
the treatment system effluent limitations for each subcategory is
presented in Tables 1-6.
                              116

-------
                               TABLE 31

                 WATER EFFLUENT TREATMENT COSTS

                    PETROLEUM REFINING INDUSTRY

                        TOPPING SUBCATEGORY
Refinery Capacity
     1000 cubic meters/day (1000 bbl/day)

Wastewater Flow
     cubic meters/cubic meter of feedstock (gal/bbl)

Treatment Plant Size
     1000 cubic meters/day (MGD)
                                  0.318 (2)


                                  0.477 (20)


                                  0.146  (0.040)
Costs in $1000



Initial Investment

ANNUAL COSTS:

    Capital Costs (10%)
    Depreciation (20%)
    Operating Costs
    Energy

        Total Annual Costs
           A

          210
          21.0
          42.0
          14.6
           1.0

          78.6
                 Alternative Treatment Steps

                  B_          C          D

                  174         60         390
                 17.4
                 34.8
                 12.4
                   7.8

                 72.4
            6.0
           12.0
            4.2
            1.0
           23.2
          39
          78
          72.5
           6.5

          196.0
Effluent Quality
                   Raw Waste
                      Load
            kg/1000 cu m (lb/1000 bbl)
BOD5
COD
Oil & Grease
Phenolics
Sulfide
Ammonia
Suspended Solids
Total Chromium
13
36
 8
 0
 0
 3
11
3 (4.7)
8 (13)
2 (2.9)
034 (0.012)
054 (0.019)
7 (1.3)
6 (4.1)
                         Resulting Effluent Levels
                      (Design Average kg/1000 cu m)
 0.20 (0.07)
 7. 1
37.6
 3.3
 0.048
 0.048
 0.85
 9.6
 0.24
2.3
4.8
0. 119
 £

1.2
5.0
0.25
0.0051
0.025
0.34
1.2
0.062
                             117

-------
                              TABLE 32

                 WATER EFFLUENT TREATMENT COSTS

                   PETROLEUM REFINING INDUSTRY

                        TOPPING SUBCATEGORY
Refinery Capacity
     1000 cubic meters/day (1000 bbl/day)

Wastewater Flow
     cubic meters /cubic meter of feedstock  (gal/bbl)

Treatment Plant Size
     1000 cubic meters/day (MGD)
Costs in $1000



Initial Investment

ANNUAL COSTS:

    Capital Costs (10%)
    Depreciation (20%)
    Operating Costs
    Energy
 A

320
                        1.11 (7)


                        0.47 (20)


                        0.51  (0.140)
Alternative Treatment Steps

 B          C_         D

290        102        815
32.0
64.0
23.0
2.0
29.0
58.0
19.0
12.0
10.2
20.4
6.0
2.0
81.5
163.0
89.0
9.0
        Total Annual Costs   121.0
           118.0
            38.6
342.5
Effluent Quality
                   Raw Waste
                      Load
            kg/1000 cu m (lb/1000 bbl)
BOD5
COD"
Oil & Grease
Phenolic s
Sulfide
Ammonia
Suspended Solids
Total Chromium
13. 3 (4. 7)
36.8 (13)
8.2 (2.9)
0.034 (0.012)
0.054 (0.019)
3. 7 (1.3)
11.6 (4. 1)
0.20 (0.07)
               Resulting Effluent Levels
            (Design Average kg/1000 cu m)
B
7. 1
37.6
3.3
0.048
0.048
0.85
9.6
0.24
£
_
-
2. 3
-
-
-
4.8
0. 119
D
1.2
5.0
0.25
0.0051
0.025
0.34
1.2
0.062
                               118

-------
                              TABLE 33

                WATER EFFLUENT TREATMENT COSTS

                   PETROLEUM REFINING INDUSTRY

                        TOPPING  SUBCATEGORY
Refinery Capacity
     1000 cubic meters/day (1000 bbl/day)             2.4  (15)

Wastewater Flow
     cubic meters /cubic meter of feedstock  (gal/bbl)   0.47  (20)

Treatment Plant Size
     1000 cubic meters/day (MGD)                     1.1  (0.30)
Costs in $1000



Initial Investment

ANNUAL COSTS:

    Capital Costs (10%)
    Depreciation (20%)
    Operating Costs
    Energy

        Total Annual Costs
          A

          378
           37.8
           75.6
           28.0
            3.0

          144.4
                 Alternative Treatment Steps

                  B_          £          D

                 400       150        1257
                  40.0
                  80.0
                  26.0
                  19.0

                  165.0
          15.0
          30.0
          17.0
           2.0

          64.0
         126.0
         252.0
         101.0
          10.0

         489.0
Effluent Quality
                   Raw Waste
                      Load
            kg/1000 cu m (lb/1000 bbl)
BODS
COD"
Oil & Grease
Phenolics
Sulfide
Ammonia
Suspended Solids
Total Chromium
13
36
 8
 0
 0
 3
11
3 (4.7)
8 (13)
2 (2.9)
034 (0.012)
054 (0.019)
7 (1.3)
6 (4.1)
                         Resulting Effluent Levels
                      (Design Average kg/1000 cu m)
 0.20 (0.07)
 7. 1
37.6
 3.3
 0.048
 0.048
 0.85
 9.6
 0.24
2.3
4.8
0. 119
 D

1.2
5.0
0.25
0.0051
0.025
0.34
1.2
0.062
                             119

-------
                              TABLE 34

                 WATER EFFLUENT TREATMENT COSTS

                   PETROLEUM REFINING INDUSTRY

                       CRACKING SUBCATEGORY
Refinery Capacity
     1000 cubic meters/day (1000 bbl/day)

Wastewater Flow
     cubic meters/cubic meter of feedstock  (gal/bbl)

Treatment Plant Size
     1000 cubic meters/day (MGD)
                                   2.4  (15)


                                   0.596  (25)


                                   1. 37 (0.375)
Costs in $1000



Initial Investment

ANNUAL COSTS:

    Capital Costs (10%)
    Depreciation (20%)
    Operating Costs
    Energy

        Total Annual Costs
           A

           405
            40.5
            81.0
            29.0
             2.0

           152. 5
Alternative Treatment Steps

 13          £          D

 455      158        1458
  45.5
  91.0
  30.0
  21.0

 187.5
15.
31.
11.
 3.
61.4
146.0
292.0
106.0
 10.0

554.0
Effluent Quality
                   Raw Waste
                      Load
            kg/1000 cu m (lb/1000 bbl)
BODS
COD
Oil & Grease
Phenolic s
Sulfide
Ammonia
Suspended Solids
Total Chromium
 72.5 (25)
216.0 (76)
 31.0 (10.9)
  3.95 (1.4)
  1.0 (0.35)
 28.0 (9.9)
 17.8 (6.3)
  0.25 (0.09)
                          Resulting Effluent Levels
                       (Design Average kg/1000 cu m)
   B

  8.8
 67.9
  3.9
  0.059
  0.059
  5. 7
 11.8
  0.3
 2.8
 5.9
 0. 147
 D

1.6
9.6
0.34
0.0065
0.045
2.8
1.6
0.05
                              120

-------
                              TABLE 35

                WATER EFFLUENT TREATMENT COSTS

                   PETROLEUM REFINING INDUSTRY

                       CRACKING SUBCATEGORY
Refinery Capacity
     1000 cubic meters/day (1000 bbl/day)
                                 11.9  (75)
Wastewater Flow
     cubic meters/cubic meter of feedstock  (gal/bbl)    0.596  (25)
Treatment Plant Size
     1000 cubic meters/day (MGD)
                                   6.8 (1.875)
Costs in $1000



Initial Investment

ANNUAL COSTS:

    Capital Costs (10%)
    Depreciation (20%)
    Operating Costs
    Energy

        Total Annual Costs
            A

           950
            95.0
           190.0
            64.0
             8.0

           357.0
                 Alternative Treatment Steps

                  B          £          D

                 1760       290        3600
                  176.0
                  352.0
                   86.0
                   59.0

                  63.0
          29.0
          58.0
          20.0
           7.0

         114.0
          360.0
          720.0
          152.0
           25.0
        125.0
Effluent Quality
                   Raw Waste
                      Load
            kg/1000 cu m (Ib/lOOO bbl)
BODS
COD
Oil & Grease
Phenolic s
Sulfide
Ammonia
Suspended Solids
Total Chromium
 72,
216
 31
  3
  1
 28
 17
5 (25)
0 (76)
0 (10.9)
95 (1.4)
0 (0.35)
0 (9.9)
8 (6.3)
                          Resulting Effluent Levels
                       (Design Average kg/1000 cu m)
  0.25 (0.09)
  &

 8.8
67.9
 3.9
 0.059
 0.059
 5.7
11.8
 0.3
2.8
5.9
0. 147
 D

1.6
9.6
0.34
0.0065
0.045
2.8
1.6
0.05
                              121

-------
                              TABLE 36

                WATER EFFLUENT TREATMENT COSTS

                   PETROLEUM REFINING INDUSTRY

                       CRACKING SUBCATEGORY
Refinery Capacity
     1000 cubic meters/day (1000 bbl/day)
                                 23.8  (150)
Wastewater Flow
     cubic meters/cubic meter of feedstock  (gal/bbl)    0.596  (25)
Treatment Plant Size
     1000 cubic meters/day  (MGD)
                                  13.7 (3.75)
Costs in $1000



Initial Investment

ANNUAL COSTS:

   Capital Costs (10%)
   Depreciation (20%)
   Operating Costs
   Energy

        Total Annual Costs
           A

          1460
           146.0
           292.0
           119.0
            17.0

           574.0
                 Alternative Treatment Steps

                  B          C_          D

                 3080       415        5370
                 308.0
                 616.0
                 236.0
                 113.0

                 123.0
          41.5
          83.0
          31.0
          15.0

         180.5
          537.0
         1074.0
          211.0
           44.0

        1866.0
Effluent Quality
                   Raw Waste
                      Load
            kg/1000 cu m (lb/1000 bbl)
BODS
COD
Oil & Grease
Phenolics
Sulfide
Ammonia
Suspended Solids
Total Chromium
 72,
216,
 31
  3
  1
 28
 17
5 (25)
0 (76)
0 (10.9)
95 (1.4)
0 (0.35)
0 (9.9)
8 (6.3)
                         Resulting Effluent Levels
                      (Design Average kg/1000 cu m)
  0.25 (0.09)
  13

 8.8
67.9
 3.9
 0.059
 0.059
 5.7
11.8
 0.3
2.8
5.9
0.147
 D

1.6
9.6
0.34
0.0065
0.045
2.8
1.6
0.05
                              122

-------
                              TABLE 37

                WATER EFFLUENT TREATMENT COSTS

                   PETROLEUM REFINING INDUSTRY

                   PETROCHEMICAL SUBCATEGORY
Refinery Capacity
     1000 cubic meters/day (1000 bbl/day)

Wastewater Flow
     cubic meters/cubic meter of feedstock  (gal/bbl)

Treatment Plant Size
     1000 cubic meters/day (MGD)
Costs in $1000



Initial Investment

ANNUAL COSTS:

    Capital Costs (10%)
    Depreciation (20%)
    Operating Costs
    Energy

        Total Annual Costs
 A

530
                       4.0  (25)


                        0.715 (30)


                        2.7 (0.75)
Alternative Treatment Steps

 B          £          D

720       195        2050
53.0
106.0
39.0
5.0
72.0
144.0
48.0
34.0
19.5
39.0
15.0
4.0
205.0
410.0
125.0
16.0
203.0
298.0
7.5
56.0
Effluent Quality
                   Raw Waste
                      Load
            kg/1000 cu m (lb/1000 bbl)
BOD5
COD
Oil & Grease
Phenolics
Sulfide
Ammonia
Suspended Solids
Total Chromium
173.0 (60)
460.0 (162)
52.6 (18.5)
7.6 (2.7)
0.9 (0.3)
35.0 (12.4)
47.7 (17)
0.30 (0. 107)
               Resulting Effluent Levels
            (Design Average kg/1000 cu m)
B
10.8
67.9
5.1
0.071
0.071
7. 1
14.2
0.35
£ D
2.2
10.8
3.7 0.45
0.0091
0.045
2.8
7.1 2.2
0.178 0.11
                              123

-------
                              TABLE 38

                WATER EFFLUENT TREATMENT COSTS

                   PETROLEUM REFINING INDUSTRY

                   PETROCHEMICAL SUBCATEGORY
Refinery Capacity
     1000 cubic meters/day (1000 bbl/day)

Wastewater Flow
     cubic meters /cubic meter of feedstock  (gal/bbl)

Treatment Plant Size
     1000 cubic meters/day (MGD)
                                 15.9 (100)


                                  0.715  (30)


                                 10.9 (3.0)
Costs in $1000



Initial Investment

ANNUAL COSTS:

    Capital Costs (10%)
    Depreciation (20%)
    Operating Costs
    Energy

        Total Annual Costs
           A

          1260
           126.0
           252.0
            98.0
            15.0

           491.0
 Alternative Treatment Steps

  1.         £          P.

2700       360        4700
 270.0
 540.0
 203.0
  93.0

1106.0
 36.0
 72.0
 29.0
 12.0

149.0
 470.0
 940.0
 192.0
  38.0

1640.0
Effluent Quality
                   Raw Waste
                      Load
            kg/1000 cu m (lb/1000 bbl)
BODS
COD
Oil & Grease
Phenolics
Sulfide
Ammonia
Suspended Solids
Total Chromium
173.0 (60)
460.0 (162)
 52.6 (18.5)
  7.6 (2.7)
  0.9 (0.3)
 35.0 (12.4)
 47. 7 (17)
  0.30 (0. 107)
                          Resulting Effluent Levels
                       (Design Average kg/1000 cu m)
    B

  10.8
  67.9
   5. 1
   0.071
   0.071
   7. 1
  14.2
   0.35
                                                     C
  3.7
  7. 1
  0. 178
  D_

 2.2
 10.8
 0.45
 0.0091
 0.045
    8
   .2
2.
2.
  0.11
                              124

-------
                              TABLE 39

                 WATER EFFLUENT TREATMENT COSTS

                   PETROLEUM REFINING INDUSTRY

                   PETROCHEMICAL SUBCATEGORY
Refinery Capacity
     1000 cubic meters/day (1000 bbl/day)

Wastewater Flow
     cubic meters/cubic meter of feedstock (gal/bbl)

Treatment Plant Size
     1000 cubic meters/day (MGD)
Costs in $1000



Initial Investment

ANNUAL COSTS:

   Capital Costs (10%)
   Depreciation (20%)
   Operating Costs
   Energy

        Total Annual Costs
                       31.8  (200)


                         0.715 (30)


                        21.9  (6.0)
           Alternative Treatment Steps

  A         13          £          D

1830      4070       430        6650
183.0
366.0
145.0
25.0
407.0
814.0
329.0
155.0
43.0
86.0
37.0
20.0
665.0
1330.0
270.0
60.0
 719.0
1648.0
186.0
2325.0
Effluent Quality
                   Raw Waste
                      Load
            kg/1000 cu m (lb/1000 bbl)
BODS
COD
Oil &. Grease
Phenolics
Sulfide
Ammonia
Suspended Solids
Total Chromium
173.0 (60)
460.0 (162)
52.6 (18.5)
7.6 (2.7)
0.9 (0. 3)
35.0 (12.4)
47.7 (17)
0. 30 (0. 107)
                Resulting Effluent Levels
             (Design Average kg/1000 cu m)
B_
10.8
67.9
5. 1
0.071
0.071
7. 1
14.2
0.35
C D
2.2
10.8
3.7 0.45
0.0091
0.045
2.8
7.1 2.2
0.178 0.11
                             125

-------
                              TABLE 40

                WATER EFFLUENT TREATMENT COSTS

                   PETROLEUM REFINING INDUSTRY

                         LUBE  SUBCATEGORY
Refinery Capacity
     1000 cubic meters/day (1000 bbl/day)

Wastewater Flow
     cubic meters/cubic meter of feedstock  (gal/bbl)

Treatment Plant Size
     1000 cubic meters/day (MGD)
                                  4.0  (25)


                                  1.07  (45)


                                  4. 1 (1.125)
Costs in $1000



Initial Investment

ANNUAL COSTS:

    Capital Costs (10%)
    Depreciation (20%)
    Operating Costs
    Energy

        Total Annual Costs
           A

           690
            69.0
           138.0
            62.0
             6.0

           275.0
                 Alternative Treatment Steps

                  B          C_          D

                1120       220         2700
                 112.0
                 224.0
                  72.0
                  47.0

                 455.0
           22.0
           44.0
           20.0
            5.0

           91.0
          270.0
          540.0
          139.0
           20.0

          969.0
Effluent Quality
                   Raw Waste
                      Load
            kg/1000 cu m (lb/1000 bbl)
BOD5>
COD
Oil & Grease
Phenolics
Sulfide
Ammonia
Suspended Solids
Total Chromium
215
538,
119
  8
  0
 35
 71
0 (76)
0 (190)
0 (42)
2 (2.9)
014 (0.005)
0 (12.4)
0 (25)
                          Resulting Effluent Levels
                       (Design Average kg/1000 cu m)
  0.45 (0. 16)
 15.8
116.0
  7 5
  o!ios
  0. 108
  7.1
 22.0
  0.50
 5.4
10.8
 0.266
  D

 3.7
20.0
 0.71
 0.014
 0.071
 2.8
 3.7
 0. 18
                              126

-------
                              TABLE 41

                WATER EFFLUENT TREATMENT COSTS

                   PETROLEUM REFINING INDUSTRY

                         LUBE SUBCATEGORY
Refinery Capacity
     1000 cubic meters/day (1000 bbl/day)
                                  17.5  (45)
Wastewater Flow
     cubic  meters/cubic meter of feedstock  (gal/bbl)   1.07  (45)
Treatment Plant Size
     1000 cubic meters/day (MGD)
                                  18.0 (4.95)
Costs in $1000



Initial Investment

ANNUAL COSTS:

    Capital Costs (10%)
    Depreciation (20%)
    Operating Costs
    Energy

        Total Annual Costs
            A

          1650
           165.0
           330.0
           129.0
            20.0

           644.0
                 Alternative Treatment Steps

                  B          £          D

                3720       420        6100
                 372.0
                 744.0
                 285.0
                 135.0

                1536.0
           42.0
           84.0
           35.0
           17.0

          178.0
          610.0
          1220.0
          236.0
           52.0

          2118.0
Effluent Quality
                   Raw Waste
                      Load
            kg/1000 cu m (Ib/1000 bbl)
BODS
COD"
Oil & Grease
Phenolics
Sulfide
Ammonia
Suspended Solids
Total Chromium
215.
538.
119.
  8.
  0.
 35,
 71,
0 (76)
0 (190)
0 (42)
2 (2.9)
014 (0.005)
0 (12.4)
0 (25)
                          Resulting Effluent Levels
                       (Design Average kg/1000 cu m)
  0.45 (0. 16)
 15.8
116.0
  7.5
  0.108
  0.108
  7.1
 22.0
  0.50
 5.4
10.8
 0.266
  D_

 3.7
20.0
 0.71
 0.014
 0.071
 2.8
 3.7
 0.18
                          127

-------
                              TABLE 42

                 WATER EFFLUENT TREATMENT COSTS

                   PETROLEUM REFINING INDUSTRY

                          LUBE SUBCATEGORY
Refinery Capacity
     1000 cubic meters/day (1000 bbl/day)

Wastewater Flow
     cubic meters/cubic meter of feedstock (gal/bbl)

Treatment Plant Size
     1000 cubic meters/day (MGD)
                                  39.8 (250)


                                   1.07 (45)


                                  41.0 (11.25)
Costs in $1000



Initial Investment

ANNUAL COSTS:

    Capital Costs (10%)
    Depreciation (20%)
    Operating Costs
    Energy
                     Alternative Treatment Steps

            A         B_          £          D

          3220      7720       600        9500
322.0
644.0
256.0
45.0
772.0
1544.0
595.0
245.0
60.0
120.0
48.0
35.0
950.0
1900.0
370.0
95.0
        Total Annual Costs   1267. 0
                     3156.0
263.0
3315.0
Effluent Quality
                   Raw Waste
                      Load
            kg/1000 cu m (lb/1000 bbl)
BODS
COD
Oil & Grease
Phenolics
Sulfide
Ammonia
Suspended Solids
Total Chromium
215.0 (76)
538.0 (190)
119.0 (42)
  8.2 (2.9)
  0.014 (0.005)
 35.0 (12.4)
 71.0 (25)
  0.45 (0.16)
                          Resulting Effluent Levels
                       (Design Average kg/1000 cu m)
B
15.8
116.0
7.5
0. 108
0. 108
7. 1
22.0
0.50
£
_
-
5.4
-
-
-
10.8
0.266
D
3.7
20.0
0. 71
0.014
0.071
2.8
3.7
0.18
                             128

-------
                              TABLE 43

                WATER EFFLUENT TREATMENT COSTS

                   PETROLEUM REFINING INDUSTRY

                     INTEGRATED SUBCATEGORY
Refinery Capacity
     1000 cubic meters/day (1000 bbl/day)             9.8  (65)

Wastewater Flow
     cubic meters/cubic meter of feedstock  (gal/bbl)    1.14  (48)

Treatment Plant Size
     1000 cubic meters/day (MGD)                    11.4 (3. 12)
Costs in $1000



Initial Investment

ANNUAL COSTS:

    Capital Costs (10%)
    Depreciation (20%)
    Operating Costs
    Energy

        Total Annual Costs
           A

          1270
           127.0
           254.0
           103.0
            20.0

           504.0
                 Alternative Treatment Steps

                  B          C_         D

                 3040       242        4900
                  304.0
                  608.0
                  243.0
                  106.0

                 1261.0
           24.0
           48.0
           21.0
           15.0

          108.0
          490.0
          980.0
          206.0
           43.0

          1719.0
Effluent Quality
                   Raw Waste
                      Load
            kg/1000 cu m (lb/1000 bbl)
BODS
COD"
Oil & Grease
Phenolics
Sulfide
Ammonia
Suspended Solids
Total Chromium
195.
325.
 74.
  3.
  2.
 35
 57
0 (69)
0 (115)
0 (26)
7 (1.32)
0 (0.7)
,0 (12.4)
, 0 (20.3)
                          Resulting Effluent Levels
                       (Design Average kg/I OOP cu m)
  0.48 (0. 17)
   B_

 17.0
125.0
  8.4
  0. 113
  0. 113
  7.1
 22.0
  0.57
 5.7
11.3
 0.283
  D

 4.2
23.7
 0.85
 0.017
 0.085
 2.8
 4.2
 0.22
                              129

-------
                              TABLE 44

                 WATER EFFLUENT TREATMENT COSTS

                   PETROLEUM REFINING INDUSTRY

                     INTEGRATED SUBCATEGORY
Refinery Capacity
     1000 cubic meters/day  (1000 bbl/day)            23.0  (152)

Wastewater Flow
     cubic meters /cubic meter of feedstock  (gal/bbl)    1.14  (48)

Treatment Plant Size
     1000 cubic meters/day  (MGD)                    26.6(7.3)
Costs in $1000



Initial Investment

ANNUAL COSTS:

   Capital Costs (10%)
   Depreciation (20%)
   Operating Costs
   Energy

        Total Annual Costs
           A

          2340
           234.0
           468.0
           203.0
            36.0

           941.0
                 Alternative Treatment Steps

                  B_         £          D_

                5440       434        7860
                 544.0
                 1088.0
                 470.0
                 188.0

                 2290.0
           43.0
           86.0
           38.0
           21.0

          188.0
           786.0
          1572.0
           329.0
            68.0

          2755.0
Effluent Quality
                   Raw Waste
                      Load
            kg/1000 cu m (lb/1000 bbl)
BODS
COD
Oil & Grease
Phenolics
Sulfide
Ammonia
Suspended Solids
Total Chromium
195.
325.
 74.
  3.
  2.
 35
 57
0 (69)
0 (115)
0 (26)
7 (1.32)
0 (0.7)
.0 (12.4)
. 0 (20.3)
                         Resulting Effluent Levels
                      (Design Average kg/1000 cu m)
  0.48 (0. 17)
   Ei

 17.0
125.0
  8.4
  0. 113
  0.113
  7.1
 22.0
  0.57
 5.7
11.3
 0.283
  D

 4.2
23.7
 0.85
 0.017
 0.085
 2.8
 4.2
 0.22
                               130

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                              TABLE 45

                 WATER EFFLUENT TREATMENT COSTS

                   PETROLEUM REFINING INDUSTRY

                     INTEGRATED SUBCATEGORY
Refinery Capacity
     1000 cubic meters/day (1000 bbl/day)             49.0  (326)

Wastewater Flow
     cubic meters/cubic meter of feedstock  (gal/bbl)   1.14  (48)

Treatment Plant Size
     1000 cubic meters/day (MGD)                    56.8 (15.6)
Costs in $1000



Initial Investment

ANNUAL COSTS:

    Capital Costs (10%)
    Depreciation (20%)
    Operating Costs
    Energy
            A

          4410
           441.0
           882.0
           381.0
            69.0
                 Alternative Treatment Steps

                  B          C_         D

                10100       820        10500
                 1010.0
                 2020.0
                  885.0
                  354.0
        Total Annual Costs   1773.0     4269.0
           82.0
          164.0
           71.0
           52.0

          369.0
          1050.0
          2100.0
           439.0
           107.0

          3696.0
Effluent Quality
                   Raw Waste
                      Load
            kg/1000 cu m (lb/1000 bbl)
BODS
COD"
Oil & Grease
Phenolics
Sulfide
Ammonia
Suspended Solids
Total Chromium
195.
325.
 74.
  3.
  2.
 35
 57
0 (69)
0 (115)
0 (26)
7 (1.32)
0 (0.7)
, 0 (12.4)
,0 (20.3)
                          Resulting Effluent Levels
                       (Design Average kg/1000 cu m)
  0.48 (0.17)
   B_

 17.0
125.0
  8.4
  0.113
  0.113
  7.1
 22.0
  0.57
 5.7
11.3
 0.283
  D

 4.2
23.7
 0.85
 0.017
 0.085
 2.8
 4.2
 0.22
                              131

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                     FIGURE 6
           BPCTCA - Wastewater Treatment System

MODEL SYSTEM USED FOR THE ECONOMIC EVALUATION

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                            TABLE 46

              BPCTCA - END OF PIPE TREATMENT SYSTEM
              MODEL USE FOR THE ECONOMIC EVALUATION
                         DESIGN SUMMARY

Treatment System Hydraulic Loading

    Treatment  system  hydraulic  loadings are sized to represent
    the projected waste water  flows  from  small,  average,  and
    large refineries in each subcategory.  The flow range used in
    these  estimates  ranges from 95 to 38,000 m^/day  (25,000 gpd
    to 10,000,000 gpd) .

Dissolved Air Flotation

    The flotation units are sized for an  overflow  rate  of  570
    m3/day/m2 (1400 gpd/sq.ft)

Pump Station

    Capacity to handle 200 percent of the average hydraulic flow.

Equalization

    One  day  detention  time  is  provided.  Floating mixers are I
    provided to keep the contents completely mixed.               I

Neutralization

    The two-stage neutralization basin is sized on the  basis  of
    an  average  detention  time  of  twenty  minutes.  The lime-
    handling facilities are sized to add 1,000 Ibs.  of  hydrated
    lime  per mgd of waste water, to adjust the pH.  Bulk-storage
    facilities (based  on  15  days  usage)   or  bag  storage  is
    provided,   depending   on  plant  size.   Lime  addition  is
    controlled by two pH probes, one in  each  basin.   The  lime
    slurry  is  added  to  the  neutralization  basin from a lime
    slurry recirculation loop.  The lime-handling facilities  are
    enclosed in a building.

Nutrient Addition

    Facilities  are  provided for the addition of phosphoric acid
    to the biological system in order to maintain  the  ratio  of
    BOD:P at 100:1.

Aeration Basin

    Platform-mounted  mechanical  aerators  are  provided  in the
    aeration basin.  In addition, walkways are  provided  to  all
    aerators  for fan access and maintenance.  The following data
    were used in sizing the aerators.

    Oxygen utilization            1.5 kg O2/kg BOD
                               133

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    L
    B
    Waste water temperature
    Oxygen transfer

    Motor Efficiency
    Minimum Basin D.O.
(1.5 Ibs 02/lb. BOD) removed
0.8
0.9
 20°C
1.6 kg (3.5 Ibs.)  O|/hr./shaft HP at
20°c and zero D.O. in tap water
85 percent
1 mg/1
    Oxygen is monitored in the basins using D.O. probes.

Secondary Clarifiers

    All secondary clarifiers are circular units.  The side  water
    depth  is  3.0  meters  (10 ft.) and the overflow rate is 500
    gpd/sq. ft.).  Sludge recycle pumps are sized to  deliver  50
    percent of the average flow.

Sludge Holding Tank-Thickener

    For  the  smaller  plants, a sludge-holding tank is provided,
    with sufficient capacity to hold 5 days flow from the aerobic
    digester.  The thickener provided for the larger  plants  was
    designed  on  the  basis of 29 kg/m2/day  (6 Ibs./sq. ft./day)
    and a side water depth of 3.0 meters (10 ft.)

Aerobic Digester

    The aerobic digester is sized on the  basis  of  a  hydraulic
    detention  time of 20 days.  The sizing of the aerator-mixers
    was based on O.OUUHP/m3 (1.25 HP/1,000  cu.ft.)  of  digester
    volume.

Vacuum Filtration

    The vacuum filters were sized on cake yield of 9.75 kg/m2/hr.
     (2 lbs,/sq.ft./hr) and a maximum running time of 18 hrs./day.
    The  polymer  system  was  sized  to deliver up to  0.005kg of
    polymer/kg of day solids  (10 Ibs. of polymer/ton dry solids).

Granular Media Filters

    The filters are sized on the basis of  an  average  hydraulic
    loading of 9.12m3/mz/min,   (3 gpm/sq.ft.) Backwash  facilities
    are   sized   to  provide  rate  up  to  0.82m3/m2/min.    (20
    gpm/sq.ft.)  and  a  backwash  cycle  of  up  to  20  minutes
    duration.

Final Sludge Disposal

    Sludge  is disposed of at a sanitary landfill assumed to be  5
    miles from the waste water treatment facility.

Design Philosophy
                              134

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The plant's forward flow  units  are  designed  for  parallel
flow,   i.e.  either  half  of  the  plant  can  be  operated
independently.  The sludge facilities  are  designed  on  the
basis  of  series  flow.   All  outside tankage is reinforced
concrete.  The tops of all outside tankage are assumed to  be
12 ft above grade.
                           135

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                                   REGENERATED  CARBON
                                   STORAGE  TANK
FILTER WATER
HOLDING TANK
            CARBON COLUMN
            FEED PUMPS
                                              PLANT
                                              EFFLUENT
                                              CARBON
                                              COLUMNS)
                                                 A
                                        TRANSFER
                                        TANK
DRYING TANK
           AIR
           BLOWER
DRY STORAGE TANK
                                                                         M>»>fr»-,H) SCREW
                                                                                 FEEDER
                                                                          REGENERATION
                                                                          FURNACE
                                                                          QUENCH TANK
             VIRGIN
             CARBON
             STORAGE
                              FIGURE 7

                          BATEA - PROPOSED TREATMENT

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                            TABLE 47

              BATEA - END OF PIPE TREATMENT SYSTEM
                         DESIGN SUMMARY

Granular Carbon Columns

The  carbon  columns  are sized on a hydraulic loading of 0.4-0.8
m3/m2/min. (10-20 gpm/sq. ft.) and a column detention time of  40
minutes.   A backwash rate of  (50 gpm/sq. ft.) was assumed for 40
percent bed expansion at 70°F.

Filter-Column Decant Sump

Tankage is provided to hold the backwash water and decant it back
to  the  treatment  plant  over  a  24-hour  period.   This  will
eliminate hydraulic surging of the treatment units.

Regeneration Furnace

An  exhaustion rate of 1 kg of COD/kg carbon  (1 Ib COD/lb carbon)
was used for sizing the regeneration facilities.

Regenerated Exhausted Carbon Storage

Tankage is provided  to  handle  the  regenerated  and  exhausted
carbon both before and after regeneration.
                               137

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Estimated costs of Facilities

As  discussed previously, designs for the model treatment systems
were costed out in order to evaluate the economic impact  of  the
proposed   effluent   limitations.    The  design  considerations
resulted  in  the  generation  of  cost  data  which   would   be
conservative.   However, relatively conservative cost numbers are
preferred for this type of general, economic analysis.

Activated sludge followed by granular media filtration  was  used
as the BPCTCA treatment system.  The plant designs were varied to
generate cost effectiveness data within each category.  Activated
carbon adsorption was used as the BATEA treatment.

Capital  and  annual  cost  data  were  prepared  for each of the
proposed treatment systems.

The capital costs were generated on a unit  process  basis,  e.g.
equalization, neutralization, etc. for all the proposed treatment
systems.   The following "percent add on" figures were applied to
the total unit process  costs  in  order  to  develop  the  total
capital cost requirements:

                                  Percent of Unit
           Item                     Process Capital cost

    Electrical                         12
    Piping                             15
    Instrumentation                     8
    Site work                           3
    Engineering Design and Construction
      Supervision Fees                 15
    Construction Contingency           15

Land  costs were computed independently and added directly to the
total capital costs.

Annual costs were computed using the following cost basis:

    Item                     Cost Allocation

    Amortization        10 percent of investment.
    Depreciation        5 year-straight line with zero salvage
    Operations and      value.  Includes labor and supervision.
    Maintenance         chemicals sludge, hauling and disposal,
                        insurance and taxes  (computed at 2 per-
                        cent of the capital cost), and maintenance
                         (computed at U percent of the capital cost)
    Power               Based on $1.50/100 KWH for electrical
                        power.

The short term capitalization and depreciation  write-off  period
is  that  which  is  presently  acceptable under current Internal
Revenue Service Regulations pertaining  to  industrial  pollution
control equipment.


                               138

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All  cost  data  were  computed in terms of August, 1971 dollars,
which corresponds to an Engineering News Records  (ENR)  value  of
1580.

The  following  is  a  qualitative  as  well  as  a  quantitative
discussion of the possible effects that variations  in  treatment
technology  or  design  criteria  could have on the total capital
costs and annual costs.
    Technology or Design Criteria

1.  Use aerated lagoons and sludge de-
   watering lagoons in place of the
   proposed treatment system.

2.  Use earthern basins with a plastic
   liner in place of reinforced concrete
   construction, and floating aerators
   versus platform-mounted aerators
   with permanent-access walkways.

3.  Place all treatment tankage above
   grade to minimize excavation,
   espcaially if a pumping station is
   required in any case.  Use all-steel
   tankage to minize capital cost.

4.  Minimize flow and maximize concen-
   trations through extensive in-plant
   recovery and water conservation, so
   that other treatment technologies
   (e.g. incineration)  may be economi-
   cally competitive.
     Capital
    Cost Differential

 1.  The cost reduction
 could be to 70 percent
 of the proposed figures.

 2.  Cost reduction could
 be 10 to 15 percent of
 the total cost.
 3. Cost savings would
 depend on the individual
 situation.
 4. Cost differential
would depend on a number
of items, e.g. age of
 plant, accessibility to
 process piping, local air
 pollution standards, etc.
The following table  summarizes  the  general  ranges  of  sludge
quantities  generated  by  small, medium, and large refineries in
each subcategory.
                               139

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    Subcategory       cu m/vr *        cu yd/yr *

    Topping           2.3-15          3-20
    Low Cracking      76-380        100 - 500
    High Cracking     380-2300      500 - 3000
    Petrochemical     460-3800      600 - 5000
    Lube              610-6900      800 - 9000
    Integrated        760-9200     1000 - 12000

              iWet-weight basis

Particular plants within the petrochemical,  lube, and  integrated
subcategories   may be amenable to sludge incineration because of
the large quantities of sludge  involved.   For  example,  sludge
incineration  would  reduce  the  previous quantities by about 90
percent.  Sludge cake is 80 percent water,  which  is  evaporated
during  incineration,  and  more  than  half of the remaining (20
percent)  solids  are  thermally  oxidized  during  incineration.
Sludge  incineration  costs were not evaluated for those specific
cases, because the particular economics depend to a large  degree
on  the  accessibility  of  a  sanitary landfill and the relative
associated hauling costs.

The following discussion  is  presented  to  help  visualize  the
complexities  involved  in  evaluating  cost  effectiveness data.
Every treatment system is composed of units whose design basis is
primarily hydraulically dependent, organically  dependent,  or  a
combination  of  the  two.   The  following is a list of the unit
processes employed, and a breakdown of the design basis.


    Hydraulically       Organically         Hydraulically and
      Dependent          Dependent        Organically Dependent

    Pump station       Thickener          Aeration basin
    API separator      Aerobic Digestor   Oxygen transfer equipment
    Equalization       Vacuum filter      Air flotation Unit
    Neutralization
    Nutrient addition
    Sludge recycle pump
    Clarifier

The annual cost associated with the hydraulically dependent  unit
processes  is  not  a  function  of effluent level.  On the other
hand, the  sizing  of  the  organically  dependent  units  should
theoretically  vary  in  direct proportion to the effluent level:
e.g. reducing the BOD5 removal  from  95  to  85  percent  should
reduce   the   sizes   of   the   sludge  handling  equipment  by
approximately 10 percent.  However, there  are  two  complicating
factors: 1) only a relatively few sizes of commercially available
equipment;  and  2)  broad  capacity  ranges.  These two factors,
especially  in  regard  to  vacuum  filters,   tend   to   negate
differentials in capital cost with decreasing treatment levels.
                               140

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The  relationship  between  design varying contaminant levels and
the design of aeration basins and oxygen  transfer  equipment  is
somewhat more complex.  The levels are dependent on the hydraulic
flow,   organic  concentration,  sludge  settleability,  and  the
relationship  between  mixing  and  oxygen   requirements.    For
example,  to reach a particular effluent level, the waste water's
organic removal kinetics will require a particular detention time
at a  given  mixed-liquor  concentration.   The  oxygen  transfer
capacity of the aerators may or may not be sufficient to keep the
mixed  liquor  suspended solids in suspension within the aeration
basin.  Therefore, the required  horsepower  would  be  increased
merely  to  fulfill  a solids mixing requirement.  Alternatively,
the oxygen requirements  may  be  such  that  the  manufacturer's
recommended  minimum  spacing  and water depth requirements would
require that the basin volume be increased to accommodate  oxygen
transfer requirements.

Non-water Quality Aspects

The  major nonwater quality consideration which may be associated
with in-process control measures is the use  of  and  alternative
means  of ultimate disposal of either liquid or solid wastes.  As
the process Raw  Waste  Load  is  reduced  in  volume,  alternate
disposal  techniques  such  as incineration, ocean discharge, and
deep-well injection are feasible.  Recent regulations are tending
to limit the  applicability  of  ocean  discharge  and  deep-well
injection  because of the potential long-term detrimental effects
associated with these disposal procedures.  Incineration may be a
viable  alternative  for  highly  concentrated   waste   streams.
However,  associated  air  pollution  and  the need for auxiliary
fuel,  depending  on  the  heating  value  of  the   waste,   are
considerations which must be evaluated on an individual basis for
each  use.  Other nonwater quality aspects, such as noise levels,
will not  be  perceptibly  affected.   Most  refineries  generate
fairly  high noise levels (85-95 dB(A))  within the battery limits
because of equipment such  as  pumps,  compressors,  steam  jets,
flare  stacks, etc.  Equipment associated with in-process or end-
of-pipe control systems would  not  add  significantly  to  these
levels.   In some cases, substituting vacuum pumps for steam jets
would  in  fact  reduce  plant  noise  levels.   There   are   no
radioactive   nuclides  used  in  the  industry,  other  than  in
instrumentation.  Thus no radiation problems  will  be  expected.
Compared  to  the  odor  emissions  possible  from other refinery
sources, odors from the waste  water  treatment  plants  are  not
expected  to  create  a  significant problem.  However, odors are
possible from the waste water  facilities,  especially  from  the
possible  stripping  of ammonia and sulfides in the air flotation
units, and from accidental  anaerobic  conditions  in  biological
facilities during upsets.

The  extra  power  required for waste water treatment and control
systems is negligible compared to the total power requirements of
the petroleum refining equipment.
                             141

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                           SECTION IX

          BEST PRACTICABLE CONTROL TECHNOLOGY CURRENTLY
                 AVAILABLE—EFFLUENT LIMITATIONS
Based on the information contained in Sections III  through  VIII
of  this  report, effluent limitations commensurate with the best
practicable control  technology  currently  available  have  been
established   for   each  petroleum  refining  subcategory.   The
limitations,  which  explicitly  set  numerical  values  for  the
allowable  pollutant  discharges  within  each  subcategory,  are
presented  in  Tables  1-6.   The  effluent  limitations  specify
allowable  discharges  of BODS, COD, TOC, total suspended solids,
oil and grease, phenolic compounds, ammonia (N), sulfides,  total
and hexavalent chromium; based upon removals which are capable of
being  attained  through  the  application  of  BPCTCA  pollution
control technology.

The best practicable control technology  currently  available  is
based  on  both  in-plant and end-of-pipe technology.  BPCTCA in-
plant technology is based on control practices widely used within
the petroleum refining industry, and include the following:

    1. Installation of sour water strippers to reduce the sulfide
    and ammonia concentrations entering the treatment plant.

    2. Elimination of once-through barometric condenser water  by
    using  surface  condensers or recycle systems with oily water
    cooling towers.

    3. Segregation of sewers, so that unpolluted storm runoff and
    once-through cooling waters are not treated normally with the
    process and other polluted waters.

    4. Elimination of polluted  once-through  cooling  water,  by
    monitoring  and repair of surface condensers or by use of wet
    and dry recycle systems.

BPCTCA end-of-pipe treatment technology is based on the  existing
waste  water  treatment processes currently used in the Petroleum
Refining Industry.   These  consist  of  equalization  and  storm
diversion;  initial  oil  and  solids  removal (API separators or
baffle  plate  separators);  further  oil  and   solids   removal
(clarifiers,  dissolved  air flotation, or filters); carbonaceous
waste  removal   (activated  sludge,  aerated  lagoons,  oxidation
ponds,  trickling  filter,   activated  carbon, or combinations of
these); and filters (sand,  dual media; or multi-media)  following
biological   treatment  methods.   It  must  be  recognized  that
specific  treatability  studies  are  required   prior   to   the
application  of  a  specific  treatment  system to the individual
refinery.

Granular media filtration  or  polishing  ponds  prior  to  final
discharge are included so that the total suspended solids and oil
                              143

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concentrations  in the final effluent can be generally maintained
at approximately 10 mg/1 and 5  mg/1,  respectively.   The  final
polishing  step  is  considered BPCTCA for the petroleum refining
industry since several refineries are now using polishing  ponds,
and  granular media filters are becoming accepted technology with
a few installations operating  currently  and  several  more  now
under construction.

In a petroleum refinery the waste water treatment plant should be
used  to  treat  only  polluted waters.  All once-through cooling
water or storm runoff which is unpolluted should be segregated as
it dilutes the  polluted  waters  and  requires  treatment  of  a
greater  flow.   Flows  for  BPCTCA  were based on the 50 percent
probability of occurance flows for plants practicing recycle with
less than 3 percent heat removal by  once-through  cooling  water
(on  a  dry weather basis).  Recognizing the additional flows and
waste loads associated  with  rain  runoff  and  ballast  waters,
allocations  for  these added flows must be given based on strict
segregation of runoff and ballast waters treated.

PROCEDURE FOR DEVELOPMENT OF BPCTCA EFFLUENT LIMITATIONS

The effluent guideline limitations were determined using effluent
data from refineries visited during this  project  or  attainable
effluent   concentrations  and  the  50  percent  probability  of
occurance flow from the refineries with 3 percent or less of  the
heat  removed  by  once-through cooling water.  In some cases the
available data from the refineries visited was considered  to  be
too  stringent  to  be  met by the industry in general.  In these
cases the flow and concentration procedure was used.  The  median
flows  are  presented  in  Table  23,  Section V.  The attainable
concentrations for BPCTCA are presented in  Table  48.   Refinery
data are presented in Tables 26-28, Section VII.

Several  exceptions  to this procedure were required to establish
meaningful effluent limitations in specific cases.  These are  as
follows:

    Topping,    Cracking,  Petrochemical,  Lube,  and  Integrated
Subcategories - Ammonia as Nitrogen

The ammonia as  nitrogen  effluent  limitations  were  calculated
using  an 80 percent reduction from the 50 percent probability of
occurance raw waste loads in each subcategory.

    Topping,   Cracking,  Petrochemial,   Lube   and   Integrated
Subcategories - TOC

Little  data  is  available  on  the reduction of TOC.  Available
effluent data indicate an effluent TOC/BOD  ratio  of  less  than
2.2.  Using this factor, effluent limitations for TOC, were based
on  BODJ3 limitations.  It is recognized that this ratio  (TOC/BOD)
is variable between the refineries, and prior to use,  an  agreed
upon correlation should be developed for the individual refinery.
                             144

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                              TABLE 48
          Attainable Concentrations from the Application of
       Best Practicable Control  Technology Currently Available
Parameter
   BODS
   COD
   TOC
   SS
   0 & G
   Phenol
   NH3-N
   Sulfide
   CrT
   Cr6
Concentration mg/1
       15
        *
        *(2.2 x BODS)
       10
        5
        0.1
        *(80% removal)
        0.1
         .25
         .005
*See Text
                               145

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    Topping,   Cracking,   Petrochemical,   Lube  and  Integrated
Subcategories - COD

The COD effluent concentrations  were  determined  from  refinery
effluent  data  and are as follows: topping - 80 mg/1; cracking -
115  mg/1;  petrochemical  -  96  mg/1;  lube  -  110  mg/1;  and
integrated - 110 mg/1.


The  long  term  (annual  or design)  average effluent limitations
determined are contained in Table U9.

Statistical Variability of a Properly Designed and Operated Waste
Treatment Plant

The effluent from a  properly  designed  and  operated  treatment
plant  changes  continually due to a variety of factors.  Changes
in  production  mix,  production  rate  and  reaction   chemistry
influence  the  composition  of raw wasteload and, therefore, its
treatability.   Changes  in  biological  factors  influence   the
efficiency  of  the treatment process.  A common indicator of the
pollution characteristics of the discharge from a  plant  is  the
long-term  average  of  the effluent load, however, the long-term
(e.g., design or yearly) average is not a suitable  parameter  on
which to base an enforcement standard.  However, using data which
show  the  variability in the effluent load, statistical analyses
can be used to compute  short-term  limits  (30  day  average  or
daily) which should never be exceeded, provided that the plant is
designed  and  run in the proper way to achieve the desired long-
term average load.   It is these short-term limits on  which  make
up the effluent guidelines.

In  order  to  reflect the variabilities associated with properly
designed and operated treatment plants for each of the parameters
as discussed above, a statistical analysis  was  made  of  plants
where  sufficient data was available to determine these variances
for day-to-day and month-to-month operations.

This data was acquired during the initial field investigation  or
submitted by API or other industry sources.

The  variability  data have been treated in the following manner:
    a.   The form of the statistical distribution
         which most generally describes the data for  all  plants
         was determined;

    b.   For each plant the statistical parameter which best  fit
         the   plants'   data  to  the  above  distribution  were
         calculated;

    c.   Values  of  "daily  maximum"  and   "30   day   maximum"
         variabilities  were  then  determined  using  the values
         calculated above.  The daily maximum variability was set
         embracing 99% of the expected variation and the  30  day
         average was set embracing 98% of the expected variation.

                                146

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                                                                     TABLE 49
                                                                      BPCTCA

                                                 PETROLEUM REFINING INDUSTRY EFFLUENT LIMITATIONS

                               Annual  Daily Kilograms of Pollutants/lOOOCubic Meters Feedstock (1) Per Stream Day
                                (Annual  Average  Daily Pounds of Pollutant/1000 BBL of Feedstock Per Stream Day)
Ref i nery
Subcategory
Topping
Cracking
Petrochemical
Lube
Integrated
Runoff(2) 0
8allast(3) 0,
8005
7.1(2.5)
8.8(3.1)
10.8(3.8)
15.8(5.6)
17.0(6.0)
.015(0.125
.015(0.125
Total
Suspended
Solids
4.8(1.7)
5.9(2.1)
7.1(2.5)
0.8(3.8)
1.3(4.0)
Oil &
Grease
2.3(0.
2.8(1.
3.7(1.
5.4(1.
5.7(2.
83)
0)
3)
9)
0)
Phenolic
Compounds
0.048(0.017)
0.059(0.
0.071(0.
0.108(0.
0.113(0.
021)
025)
038)
040
Ammonia(N)
0.85(0.30)
5.7 (2.0)
7.1 (2.5)
7.1 (2.5)
7.1 (2.5)
Sulfide
0.
0.
0.
0.
0.
048(0.
059(0.
071(0.
108(0.
113(0.
017)
021)
025)
038)
040)
Total
Chromium
0.119(0,
0.147(0.
0.178(0,
). 266(0,
0.283(0,
.042)
.052)
.063)
.094)
.10)
Hexavalent
Chromium
0.0023(0.0008)
0.0028(0'. 0010)
0.0037(0.0013)
0.0054(0.0019)
0.0056(0.0020)
                            COD         TOC

                            37.6(13.3)   15.6(5.5)

                            67.9(24.0)   19.2(6.8)

                            67.9(24.0)   23.5(8.3)

                           116  (41.0)   35.1(12.4)  10.8(3.8)

                           125  (44.0)   37.4(13.2)  11.3(4.0)

             0.015(0.125)  0.12(1.0)  0.033(0.275)0.010(0.083)0.0050(0.042)

             0.015(0.125)  0.15(1.250)0.033(0.275)0.010(0.083)0.0050(0.042)

(1)   Feedstock - Crude oil  and/or natural  gas  liquids.
(2)   The additional  allocation being allowed for  contaminated storm runoff flow, kg/cubic meter  (lb/1000 gallons), shall be based solely on that storm
     flow which passes through the treatment system.   All additional  storm runoff, that has been segregated from the main waste stream, shall not
     exceed a TOC concentration of 35 mg/1  or  Oil and  Grease concentration of 15 mg/1 when discharged.
(3)   This is an additional  allocation,  based on ballast water intake  -  kilograms per  1000 liters (pounds per  1000 gallons).

-------
Results of -the Data analysis:

The  data from each refinery were determined to be eiter normally
or log normally distributed.

The daily maximums, when the data is  normally  distributed,  the
variability is equal to x +  2.321 Q; where x is the mean or
                            x
design average and Q is the standard deviation for the data.

When the data was log normally distributed, the variability is
           (4.65-2.30R)R/2
equal to 10               : where R is the standard deviation
of the logarithm of the data points.

The  variability  factors  used are contained in Table 50.  These
factors for each parameter except total and  hexavalent  chromium
were  calculated  from  long-term  refinery data.  The factor for
total chromium  is the same as that  used  for  suspended  solids
since   metallic  ion  is  removed  as  an  insoluble  salt.  The
variability factor for  hexavalent  chromium  was  based  on  the
sulfide  variability.   The  guidelines  for  BPCTCA presented in
Tables 1-6 have taken into consideration  the  above  variability
factors.

Process and Size Factor

A  complete  process  breakdown of many of the U.S. refineries is
contained in Table 51.  This table was  prepared  from  the  best
published  data  available   (Oil  and  Gas Journal, International
Petroluem Encyclopedia, and the EPA/API Raw Waste Load Survey  of
1972) ,  but  should  only be used as a guide.  The values used to
determined the process  and  size  factors  for  permit  issuance
should be documented by the individual refineries.

An  example  calculation  of the process and size factors follows
below.  It should be noted that only  crude  processes,  cracking
processes,  lube  processes, and asphalt processes enter into the
calculation of process configuration.

Process                   Processes included    Weighting
category                                        factor

Crude                Atm. crude distillation       1
                     Vacuum crude distillation.
                     Desalting

Cracking and         Fluid cat. cracking           6
  coking             Vis-breaking.
                     Thermal cracking
                     Moving bed cat. cracking
                     Hydrocracking
                     Fluid coking
                     Delayed coking
                            148

-------
                                                TABLE  50

                             VARIABILITY  FACTORS BASED  ON  PROPERLY  DESIGNED
                                  AND OPERATED  WASTE  TREATMENT  FACILITIES


                            BODS       COD.    TOC_    TSS,     0  &  G     Phenol    Ammonia    Sulfide   CrT     Cr6

   Daily                      3.2       3.1     3.1     2.9     3.0       3.5       3.3         3.1     2.9     3.1
   Variability


   30 Day Average             1.7       1.6     1.6     1.7     1.6       1.7       1.5         1.4     1.7     1.4
   Variability
VO

-------
Lube
Asphalt
      Further  defined  in
      Table  51.

      Asphalt  production
      Asphalt  oxidation
      Asphalt  emulsifying
                  13
                  12
Example:  Lube Refinery - 125,000 bbl/day stream day

Process
Crude - ATM
Vacuum
Desalting
   Total

Cracking - FCC
Hydrocracking

    Total

Lubes
  Lube Hydro-
   fining
  Furfural
   Extraction
  Phenol
   Extraction
    Total

Asphalt
   Capacity
(1,000  bbl per
 stream day)

   125
    60
   125
    41
    20
   5.3

   4.0

   4.0
  Capacity     Weighting Process
 relative to    factor   configu-
 throughput

   1
   .48
	1	
   2.48  X

    .328
 	..,160	

    .488 X
    .042

    .032

    .030	

    .113 X
                                 1  =
                                 6  =
                                                        ration
            2.48
            2.48
   4.0              0.032 X
  Refinery process configuration

               NOTES
13

12
1.47

 .38
7.26
See Table 4 for process factor. Process factor =  0.88.   See  Table
4 for.,.,size factor for 125,000 bbl per stream day   lube   refinery.
Size  factor = 0.93.  To calculate the limits for each  parameter,
multiply the limit Table 4 by both the process  factor   and   size
factor.   BODS  limit   (maximum  for  any  1 day)  =  17.9 x 0.88  x
0.93=14.6 Ib.  per 1,000 bbl of feedstock.
                              IbO

-------
                            TABLE 51

               PETROLEUM REFINING - PROCESS BREAKDOWN
Legend:

  A.  Crude Processes

      D - desalting
      A - atmospheric distillation
      V - vacuum distillation

  B.  Cracking Processes

      FCC        - fluid catalytic cracking
      Thermo.    - thermofor
      Houdri.     - houdriflow
      Gas-Oil Cr.- gas-oil cracking
      Visbreak.  - visbreaking
      Fl. Coke   - fluid coking
      Delay.Coke - delayed coking

C.  Lube Processes

      A  - lube hydrofining                  0 - S02 extraction
      B  - white oil  manufacturing           k - wax pressing
      C  - propane - dewaxing, deasphalting  L - wax plant (with neutral  separ.)
      D  - duo sol, solvent dewaxing         M - furfural  extraction
      E  - lube vac.  tower, wax fract.       N - clay contacting - percolation
      F  - centrifuging and chilling         0 - wax sweating
      G  - MEK dewaxing                      P - acid treating
      H  - deoiling (wax)                    Q - phenol  extraction
      I  - naphthenic lubes
                                  151

-------
           TABLE 51  cont'd
PETROLEUM REFINERY - PROCESS BREAKDOWN
COMPANY
Amerada Mess
Corporation
Chevron Oil
Company
Exxon Co., USA


Mobil 011
Corporation
Texaco Inc.


Ashland Petro.
^i Company
Ui
N>
Amerada-Hess
Corporation
Caribbean
Gulf Ref.
Company
Commonweal th
Oil Refining Co.
Inc.
Yabocoa Sun
Oil Company
REGION
2

2

2


2

2


2


2

2


2


2

LOCATION
Port
Reading
Perth
Amboy
Linden


Paulsboro

Westvllle


Tonawanda


St. Croix

Bayamon


Penuelas


Yabocoa

TATE
N.J.

N.J.

N.J.


N.J.

N.J.


N.Y.


V.I.

P.R.


P.R.


P.R.

SUBCAT.
B

B

C


D

C


C


A

B'


C


A

REFINERY
CAPACITY
1000 bbl
day
75.0

92.0

286.0


100.5

88.0


67.0


418.0

40.0


100.0


66.0 *

CRUDE F
Process
D
A .
V
D
A
V
D
A
V
D
A
V
D
A
V
D
A
V

D
A
V
D
A
V
D
A
V
D
A
V
'ROCESSES
Capacity
1000 bbl
day
75.0
75.0
30.0
92.0
92.0
50.0
286.0
286.0
143.0
100.5
100.5
62.6
88.0
88.0
29.5
67.0
67.0
25.0

418.0
418.0
20.0
40.0
40.0
9.0
100.0
100.0
50.0
66.0
66.0
30.0
CRACKING
•Process
FCC

Houdrl .

FCC
Visbreak.

Thermo.
Delay. Cok.
FCC
Visbreak.

FCC




FCC


FCC
Visbreak,



PROCESSES
Capacity
1000 bbl
day
45.0

38.0

140.0
2.2»

25.0
23.7
40.0
13.0

20.0




8.5


40.0
22.0


•'•"
LUBE P
Process







Unk.















E
G
M
ROCESSES
Capacity
1000 bbl
day







13.0















5.0
8.5
6.0
ASPHALT
PRODUCTION
Capacity
1000 bbl /day


25.0

46.0







10.0












PROCESS
CONFIG-
URATION
6.00

8.28

7.41


7.21

5.95


5.96


2.0

3.50


6.22


6.30


-------
           TABLE  51 cont'd
PETROLEUM  REFINERY - PROCESS  BREAKDOWN
COMPANY
Getty Oil Co.
Inc.

Amoco Oil Company
Chevron
Asphalt Company

Atlantic
Richfield Company

BP Oil
Corporation

Bradford Pet.
K(Witco)
00
Gulf Oil
Company

Pennzoil Company


Quaker State Oil
Ref. Corporation

Quaker State Oil
Ref. Corporation

Sun Oil Company




United Refining
Company

REGION
3


3
3


3


3


3


3


3


3


3


3




3


LOCATION
Delaware
City

Baltimore
Bal timore


Phila.


Marcus
Hook

Bradford


Phila.


Rouseville


Emlenton


Farmers
Valley

Marcus
Hook



Warren


STATE
Del.


MD.
MD.


PA.


PA.


PA.


PA.


PA.


PA.


PA.


PA.




PA.


SUBCAT.
C


A
A


B


B


A


B


A


A


A


E




B


REFINERY
CAPACITY
1000 bbl
day
150.0


10.0
13.8


195.0


105.0


7.8


174.0


10.4


3.5


6.8


180.0
*3



38.0


CRUDE
Process
D
A
V
A
D
A
V
D
- A
. V
D
A
V
D
A

D
A
V
D
A
V
D
A
V
D
A
V
D
A
V


D
A
V
PROCESSE
Capacit
1000 bb
day
150.0
150.0
90.7
10.0
13.8
13.8
13.8
195.0
195.0
57.0
105.0
105.0
60.0
7.8
7.8

174.0
174.0
. 65.0
10.4
10.4
3.3
3.5
3.5
1.7
6.8
6.8
2.75
180.0
180.0
48.0


38.0
38.0
8.0
CRACKING
Process
FCC
Hydro.
FT. Coke




Hydro.


FCC
Visbreak.




FCC











FCC




FCC


PROCESSES
Capacity
1000 bbl
day
77.0
17.0
44.0




30.0


41.9
12.0




80.5











85.0




10.2


LUBE P
Process













Unk.





C
D

Unk.


C
G
M
D
E
G
I
M



ROCESSES
Capacity
1000 bbl
day













3.1





0.7
3.0

3.0


1.0
2.5
2.0
5.8
11.7
13.4
10.7
4.0



ASPHALT
PRODUCTION
Capacity
1000 bbl /day



8.0
11.0


19.5




















12.0




4.0


PROCESS
CONFIG-
URATION
8.12 .


10.6
12.6


4.42


5.65


7.17


5.15


6.94


13.63


12.92


9.19




5.08



-------
           TABLE  51  cont'd
PETROLEUM REFINERY - PROCESS BREAKDOWN
COMPANY
Valvoline Oil
Company

Wolf's Head
Oil (Pennzoil)
Amoco Oil
Company

Pennzoil Company


Quaker State Oil
Ref. Corporation

•> Quaker State Oil
I Ref. Corporation


Hunt Oil Co.


Marion Corp.

Vulcan Asphalt
Refining Co.
Warrior Asphalt
Corp.
Seminole Asphalt
Refining, Inc.


Amoco Oil Co.
Young Refining
Corp.
REGION
3


3

3


3


3


3



4


4

4

4

4



4
4

LOCATION
Freedom


Reno

Yorktown


Falling
Rock

Newel 1


St. Mary's



Tuscaloosa


Mobile

Cordova

Holt

St. Mark's



Savannah
Douglasville

STATE
PA.


PA.

VA.


W.V.


W.V.


W.V.



ALA.


ALA.

ALA.

ALA.

FLA.



GA.
6A.

SUBCAT.
A


A

C


A


A


A



A


A

A

A

A



A
A

REFINERY
CAPACITY
1000 bbl.
day
6.5


2.22

53.0


5.5


10.0


5.0



15.75


15.5

3.0

2.6

5.5 •»



12.0
2.5

CRUDE
Proces
D
A
V
A .

D
A
V
D
A
V
D
A
V
D
A
V

D
A
V
D
A
A

A

D
A
V

A
A

PROCESSE
Capacity
1000 bb
day
6.5
6.5
2.0
2.22

53.0
53.0
28.0
5.5
5.5
2.5
10.0
10.0
4.0
5.0
5.0
2.2

15.75
15.75
8.66
15.5
15.5
3.0

2.6

5.5
5.5
2.4

12.0
CRACKING
Process





FCC
Delay. Coke

























PROCESSES
Capacity
1000 bbl
day .





30.5
14.0

























LUBE P
Process
Unk.


F
K



F
K

Unk.


C
F
K
M













ROCESSES
Capacity
1000 bbl
1.3


0.95
0.6



2.4
1.0

7-0


0.7
1.85
1.25
0.8













ASPHALT
PRODUCTION
Capacity
1000 bbl/da


















5.2




1.8

1.73

2.5



i <; *
PROCESS
CONFIG-
URATION
4.91


10.08

7.57


10.49


11.50


14.40



6.51


2.0

'8.20

8.98

7.89



6.5
2.5 |


-------
           TABLE  51 cont'd
PETROLEUM REFINERY - PROCESS BREAKDOWN
COMPANY
Ashland Oil, Inc.


Ashland Oil, Inc.


Somerset Refining
Inc.
Amerada Hess
Corporation

Southland Oil
Company
^Southland Oil
£j Company
Southland Oil
Company

STD. Oil of
Kentucky

Delta Refining
Company
Amoco Oil
Company

Clark Oil and
Refining Corp.

REGION
4


4


4

4


4

4

4


4


4

5


5


i
Clark Oil and j _ 5
Refining Corp. j
i
Marathon Oil \ 5
Company !
!
LOCATION
Catlettsburg


Louisville


Somerset

Purvis


Crupp

Lumberton

Sandersville


Pascagoula


Memphis

WoodRiver


Blue Island


Hartford
i

Robinson


STATE
KY.


KY.


KY.

MISS.


MISS.

MISS.

MISS.


KY.


TENN.

ILL.


ILL.


ILL.


ILL.


SUBCAT.
C


B


A

B


A

A

A


C


B

C


C


3


B


REFINERY
CAPACITY
1000 bbl
day
138.0


26.0


3.0

30.0


3.2

4.26

8.3


240.0


30.0

107.0


70. 0'3


38.0


205.0


CRUDE
Proces
D
A
V
D
A
V
A

D
A

D
A
D
A
D
A
V
D
A
V
D
A
D
A
V
D
A
V
D
A
V
D

A
PROCESSES
Capacity
1000 bbl
day
138.0
138.0
55.0
26.0
26.0
10.0
3.0

30.0
30.0

3.2
3.2
4.26
4.26
8.3
8.3
4.6
240.0
240.0
148.0
30.0
30.0
107.0
107.0
40.0
70.0
70.0
27.0
38.0
38.0
15.0
205.0

205.0
J CRACKING
Process
FCC
Visbreak.

FCC




Thermo.
Delay coke
- Hydro.
"






FCC
Hydro.

Thermo .

FCC


FCC
Hydro .

FCC
Delay.
coke
Gas-Oil
Cr.
Delay.
PROCESSES
Capacity
1000 bbl
day
55.0
4.0

9.0




30.5
6.7
3.0







58.0
59.0

12.0

42.0


25.0
11.0

27.0
13.0

2.8

19.0
LUBE P
Proces



































ROCESSES
Capacity
1000 bbl
day



































ASPHALT
PRODUCTION
Capacity
1000 bbl /day
10.0


3.5


2.5




1.44

2.35

3.5





3.0

10.8


4.5








PROCESS
CONFIG-
URATION
5.83


6.08


11.00

10.04


7.40

8.62

7.61


5.54


5.60

5.94


6.24


8.71


4.89



-------
           TABLE  51  cont'd
PETROLEUM REFINERY - PROCESS BREAKDOWN
COMPANY

Mobil 011
Corporation


Shell 01V
Company

Texaco Inc.


Texaco Inc.


Union 011 Co.
of California

Swireback 011
"^Company
Yetter 011
Company

Amoco 011






Atlantic Rich-
field Company


Gladleux
Refinery Inc.
Ind. Farm
Bureau Coop.
Assoc. Inc.
Laketon Asphalt
Refinery Inc.

REGION

5



5


5


5


5


< 5

5


5






5



5

5


5


LOCATION

Jo! let



Wood River


Lawrencevllle


Lockport


Lemont


Plymouth

Col mar


Whiting






East Chicago



Fort Wayne

Mt. Vernon


Laketon


STATE
ILL.



ILL.


ILL.


ILL.


ILL.


ILL.

ILL.


IND.






IND.



IND.

IND.
.

. IND.


SUBCAT.
B^



D


B


B


B


A

A


D






B



A

B


A


REFINERY
CAPACITY
LQOO bbl
.. .""day
186.0



268.0


84.0


72.0


152.0


1.5

1.0


315.0






140.0


4
10.0

15.2


8.5


CRUDE
Process
D

A
V
D
A
V
D
A
V
D
A
V
D
A
V
A

D
A
V
D
A
V




D
A
V

D
A
D
A
V
D
A
V
PROCESSES
Capacity
1000 bbl
186.0

186.0
82.0
268.0
268.0
91.5
84.0
84.0
24.0
72.0
72.0
14.0
152.0
152.0
55.0
1.5

1.0
1.0
1.0
315.0
315.0
,140.0




140.0
140.0
7.0
'
' 10.0
10.0
15.2
: 15.2
6.0
8.5
8.5
5.0
CRACKING
Process
Delay.
coke
FCC

Vlsbreak.
FCC
Hydro.
Gas-Oil Cr.
Fi,C

Del ay. Coke
FCC

Del ay. Coke
FCC






Del ay. Coke
FCC





FCC





FCC





PROCESSES
Capacity
1000 bbl
day
28.0

66.0

21.0
98.0
33.5
9.0
31.0

27.0
30.0

19.5
60.0






14.5
146.0





50.0





5.8
\

V


LUBE P
Process




A
C
Q














A
B
C
E
G
N
Q




'





'

ACCESSES
Capacity
1000 bbl
day




5.6
11.2
5.6












-

2.5
1.0
3.6
19.1
2.0
0.7
12.2












ASPHALT
PRODUCTION
Capacity
1000 bbl/day




22.5


2.7





2.0







31.0



*


10.4








2.6


PROCESS
CONFIG-
URATION
5.47



7.85


5.53


6.94


5.66


1.0

3.0


8.38






. 5.68



2.0

4.68


! 6.26



-------
           TABLE  51  cont'd
PETROLEUM REFINERY - PROCESS  BREAKDOWN
COMPANY
Gulf Oil
Company

Gulf Oil
Company

STD. Oil
Company of Ohio

STD. Oio
Company of Ohio

Sun Oil

M
Murphy Oil
Corporation

Berry
Petroleum Co.

Cross Oil and
Refining Company

Lion Oil
Company

MacMillian Ring-
Free Oil Co.,
Inc.
Atlas Processing
Company

REGION
5


5


5


5


5


5


6


6


6


6


6


LOCATION
Cleves


Toledo


Lima


Toledo


Toledo


Superior


Stephens

A
Smackover


El Dorado


Norphlet


Shreveport


STATE
OH.


OH.


OH.


OH.


OH.


WIS.


ARK.


ARK.


ARK.


ARK.


LA.


SUBCAT.
B


B


D


B


C


B


A


A


D


A


A


REFINERY
CAPACITY
1000 bbl
day
43.5


51.0


175.0


125.0


130.0


38.0


3.5


5.0


45.0

•3
4.5


29.0


CRUDE
Process
D
A
V
D
A
V
D
A
V
D
A
V
D
A
V
D
A
V
D
A
V
D
A
V
D
A
V
D
A
V
D
A
V
ACCESSES
Capacity
1000 bbl
day
43.5
43.5
13.0
51.0
51.0
12.5
175.0
175.0
51.0 '
125.0
125.0
43.0
130.0
130.0
22.0
38.0
38.0
15.5
3.5
3.5
1.0
5.0
5.0
2.0
45.0
45.0
18.0
4.5
4.5
2.8
29.0
29.0
0.6
CRACKINC
Process
FCC


FCC


Del ay. Coke
FCC
Hydro.
Delay. Coke
FCC
Hydro.
FCC
Hydro .

FCC




,



Solvent
FCC
Therno.






PROCESSES
Capacity
1000 bbl
day
27.0


22.0


15.0
45.5
20.0
12.8
71.5
36.0
57.5
26.0

10.7








5.0
12.5
7.7






LUBE P
Process






G
M













A


unknown








ROCESSES
Capacity
1000 bbl
day






1.7
5.2













1.3


0.8








ASPHALT
PRODUCTION
Capacity
1000 bbl /day
2.9


2.0


- •


7.0





12.0


1.0


1.4


6.0


1.25 •





PROCESS
CONFIG-
URATION
6.82

*
5.30


5.56


8.79


6.02


7.89


5.71


9.14


7.58


5.96


2.02



-------
           TABLE 51  COnt'd
PETROLEUM REFINERY - PROCESS BREAKDOWN
COMPANY
Gulf Oil
Company
Gulf Oil
Company
Kerr McGee
Corporation
La Jet Inc.
Murphy Oil
Corporation
Shell Oil
Company
Tenneco Oil
* Company
i
Texaco Inc.

Caribou Four
Corners Inc.
Famariss Oil
Corporation
Navajo Ref.
Company
Plateau Inc.
Shell Oil
Company
Thriftway
Company
Allied Materials
•Corporation
REGION
6
6

6

6
6

6
6
6

6

6

6
6
6

6

6

LOCATION
Belle
Chase
Venice

Cotton Valley

St. James
Meraux

Norco
Chalmette
Convent

Kirtland

Monument

Artesia
Bl cornfield
Ciniza

Bl cornfield

Stroud

STATE
LA.
LA.

LA.

LA.
LA.

LA.
LA.
LA.

N.M.

N.M.

N.M.
N.M.
N.M.

N.M.

Okla.

SUBCAT.
B
B

A

A
B

B
B
B

A

'A

B
A
B

A

A

REFINERY
CAPACITY
1000 bbl
186.0
29.1

8.0

11.0
95.4

250.0
97.0
140.0

1.4

5.0

20.93
5.2
21.0

2.13

5.8
C • " 11!
CRUDE
Process
D
A
V
D
A
D
A
D
A
D
V
D
A
V
D
A
V
D
A
V
A

A

D
A
V
A
D
A
V
A

D
A,
V
PROCESSES
Capacity
1000 bbl
day
186.0-
186.0
55.0
29.1
29.1
8.0
8.0
11.0
11.0
95.4
14!5
250.0
250.0
90.0
97.0
97.0
23.0
140.0
140.0
35.0
1.4

5.0

20.93
20.93
4.5
5.2
21.0
21.0
8.0
2.13

5.8
5.8
2.8
CRACKINC
Process
Delay. Cok.
FCC
Hydro.




FCC

Delay. Cok.
FCC
Hydro.
Delay. Cok.
FCC
Hydro .
Visbreak.
FCC





Gas-Oil Cr.
Thermo.

FCC





. PROCESSES
Capacity
1000 bbl
day
16.0
78.0
11.5




11.0

18.0
97.0
28.0
9.0
22.0
18.0
12.0
70.0





1.25
5.2

. ./I0.5





LUBE P
Process^




t

















Unk.

ROCESSES
Capacity
1000 bbl
day






















0.9

ASPHALT
PRODUCTION
Capacity
1000 bbl/day


. .





6.0







1.4

0.84 ••



1.21

PROCESS
CONFIG-
URATION
5.33
4.37

2.0

2.0
2.84

6.08
5.27
5.76

1.0

1.0

4.87
1.6
5.86

1.0

7.00


-------
Ul
VO
                                                                  TABLE  51  cont'd
                                                       PETROLEUM REFINERY - PROCESS BREAKDOWN
COMPANY
Apco Oil
Corporation

Champlin
Petroleum Company

Continental Oil
Comapny

Kerr-McGee
Corporation

Midland Coop.
Inc.

Okc Refining
Inc.

Sun Oil
Company

Sun Oil
Company

Texaco Inc.


Tonkawa Ref.
Company
Vickers Petro.
Corporation

-
Adobe Ref.
Company
American
Petrofina Inc.

REGION
6


6


6


6


6


6


6


6


6


6


6


6

6


LOCATION
Cyril


Enid


Ponca


Wynnewood


Gushing


Okmul gee


Duncan


Tulsa


West Tulsa


Tonkawa


Ardmore


LaBlanca

Nt. Pleasant


STATE
Okla.


Okla.


Okla.


Okla.


Okla


Okla


Okla.


Okla.


Okla.


Okla.


Okla.


Tex.

Tex.


SUBCAT.
B


D '


D


B


B


B


B


D


B


4
A


B


A

B


REFINERY
CAPACITY
1000 bbl
day
12.5


52.0


120.0


34.0


19.8


21.5


50.0


90.0


50.0


6.0

4
32.0


5.0

26.0


CRUDE 1
Process
D
A
V
D
A
V
D
A
V
D
A
V
D
A
V
D
A
V
D
A
V
D
A
V
D
A
V
D
A

D
A
V
D
A
D
A
V
'ROCESSES
Capacity
1000 bbl
day
12.5
12.5
5.0
52.0
52.0
18.0
120.0
120.0
34.5 -
34.0
34.0
10.0
19.8
19.8
7.0
21.5
21.5
3.2
50.0
50.0
17.0
90.0
90.0
31.5
50.0
50.0
14.5
6.0
6.0

32.0
32.0
11.0
5.0
5.0
26.0
26.0
15.0
CRACKING
Process
FCC


Delay. Cok.
FCC

Gas-Oil Cr.
Delay. Cok.
FCC
FCC
Hydro.

Delay. Cok.
FCC

Thermo .


Delay. Cok.
FCC

Delay. Cok.
FCC

Gas -Oil Cr.
FCC




Pitch
FCC



Thermo.


PROCESSES
Capacity
1000 bbl
day
7.5


3.7
21.45

13.5
18.5
44.6
13.5
4.5

4.0
10.0

10.0


12.0
35.5

8.2
31.4

6.0
18.0




2.5
13.0



11.8


LUBE P
Process



D
E '
F
D
G
M












C
G
M














ROCESSES
Capacity
1000 bbl
day
'""


- 3.1
1.0
1.6
2.1
2.2
1.9












8.2
8.0
13.6














ASPHALT
PRODUCTION
Capacity
1000 bbl /day
1.3


1.4


3.0


3.5





1.4





4.2








5.0




8.0


PROCESS
CONFIG-
URATION
7.25


7.02


7.09


6.71


6.60


5.72


8.04


9.85


5.17

•
2.0


7.13


2.0

8.99



-------
           TABLE  51 cont'd
PETROLEUM REFINERY - PROCESS BREAKDOWN
o
COMPANY
American
Petroflna Inc.


Amoco Oil
Company

Atlantic
Richfield Company



Champlin Petro.
Company
Charter Inter.
Oil Company

Coastal States
Petrochemical
Company
Cosden Oil &
Chemical Company

Crown Central
Petro. Corp.

Diamond Shamrock
Oil & Gas -Company

Eddy Ref . Company
Exxon Company,
USA

Flint Chemical
Company
Gulf Oil Company

REGION

6


6


6




6

6


6


6


6


6


6
6


6

6

LOCATION

Port
Arthur

Texas City


Houston




Corpus Christl

Houston


Corpus Christi


Big Spring


Houston


Sunray


Houston
Bay town


San Antonio

Port Arthur

STATE

Tex.


Tex.


Tex.




Tex

Tex.


.Tex.


Tex.


Tex.


Tex.


Tex.
Tex.


Tex.

Tex.

SUBCAT.

B


C


E




B

B


C


C


B


B


A
E


A

E

REFINERY
CAPACITY
1000 bbl
day

84.0


333.0


233.5




63.0

66.0


135.0


65.0


103.0


49.0


3.25
420.0


0.75

319.0

CRUDE 1
Process

D
A
V
D
A
V
D
A
V


A
V
D
A
V
D
A
V
D
A
V
D
A
V
D
A
V ,
A
D
A
V
A

D
A
V
'ROCESSES
Capacity
1000 bbl
day

84.0
84.0
28.0
333.6
333.0
131.0
233.5
233.5
70.0


63.0
9.2
66.0
66.0
22.0
135.0
135.0
33.0
65.0
65.0
25.0
103.0
103.0
38.0
49.0
49.0
14.5
3.25
420.0
420.0
180.0
0.75

319.0
319.0
147.4
CRACKING
Process

Visbreak
FCC

Delay. Cok.
FCC
Hydro.
Delay. Cok.
FCC
Hydro.


FCC

Visbreak.
FCC

Delay. Cok.
FCC

Gas-Oil Cr.
FCC

Delay, Cok.
FCC

Gas-Oil Cr.
Thermo .
Houdri .

FCC
Hydro.



Delay. Cok.
FCC
Hydro.
PROCESSES
Capacity
1000 bbl
day

10.0

28.0
22.5
185.0
38.0
27.0
74.0
4.5


10.1

10.0
29.0

12.0
19.3

10.0
25.0

9.5
52.0

2.5
13.5
13.5

145.0
20.0



30.0
126.0
15.0
LUBE P
Process







A
C
D
G
Q


















C
G
Q


A
C
D
u
ROCESSES
Capacity
1000 bbl
day







5.2
3.4
0.6
4.0
6.2 .















"


13.0
9.0
24.0


14.2
4.9
25.9
i i
ASPHALT
PRODUCTION
Capacity
1000 bbl /day




5.3








!•
4.0


0.5


8.0



• •

2.5



12.0






PROCESS
CONFIG-
URATION

5.05
*

7.01


6.09




2.11

6.61


3.63


7.09


5.95


6.52


1.0
6.55


1.0

7.56


-------
           TABLE  51  cont'd
PETROLEUM  REFINERY - PROCESS  BREAKDOWN
COMPANY
Howel 1
Hydrocarbon
La Gloria
Oil and Gas Co.

Longview
Refining Company
Marathon Oil
Company

Mobil Oil
Corporation


Phillips
Petroleum
Company
Phillips
Petroleum Company


Pride Ref. Inc.

Quintana -
Howel 1
Shell Oil Companj

,
Shell Oil Companj

Southwestern Oil
& Ref. Company
REGION
6

6


6

6


6



6


6


6

6

6


6

6

LOCATION
San Antonio

Tyler


Longview

Texas City


Beaumont



Borger


Sweeny


Abilene

Corpus Chrlstl

Deer Park


Odessa

Corpus Christi

STATE
.'TEX.

TEX.


TEX.

TEX.


TEX.



TEX.


Tex.


Tex.

Tex.

Tex.


Tex.

Tex.

SUBCAT.
A

B


A

C


D



C


C


A

A

D


B

B

REFINERY
CAPACITY
1000 bbl
day
3.1

29.0


7.5

63.0


335.0



95.0


85.0


14.69

10.0

293.0
4


34.0

150.0

CRUDE
Process
D
*.«
D
A

A

D
A
V
D
A
V

D
A

D
A
V
D
A
D
A
0
A
V

D
•A
V
D
A
V
'ROCESSES
Capacity
1000 bbl
day
3.1
3.1
29.0
29.0

7.5

63.0
63.0
20.0
335.0
335.0
103.0

95.0
95.0

85.0
85.0
17.0
14.69
14.69
10.0
10.0
293.0
293.0
106.4

34.0
34.0
10.0
150.0
; 150.0
24.0
CRACKING
Process


Gas-Oil Cr.
Del ay. Coke
FCC


FCC


Del ay. Coke
FCC
Thermo.
Hydro.
FCC


FCC






Thermal
Gas-Oil Cr.
FCC
Hydro.
FCC

FCC

PROCESSES
Capacity
1000 bbl
day


3.0
12.0
15.0


33.0


33.0
55.0
•52.0
29.0
70.0


35.0






20.0
65.0
70.0
25.0
15.5

12.0

LUBE P
Process










D
G
M







,



A
C
G
Q




ROCESSES
Capacity
1000 bbl
day










2.5
15.7
13.2











"8.0
3.3
7.9
6.8




ASPHALT
PRODUCTION
Capacity
1000 bbl /day










0.1












-•
3.8






PROCESS
CONFIG-
URATION
2.0

8.21


1.0

5.46


6.55



6.42


4.67


2.0

2.0

7.36 '


5.03

2.64


-------
           TABLE  51  cont'd
PETROLEUM REFINERY - PROCESS BREAKDOWN
COMPANY
Suntlde Refining
Company

Tesoro Petro.
Company
Texaco, Inc.

Texaco, Inc.

Texaco, Inc.



H"
cr>
ro
.Texaco, Inc.


Texas Asphalt
and Refining Co.
Texas City
Refining, Inc.

Three Rivers
Refinery

Union 011
Company of
California
Union Texas
Petro. (Allied)
Winston Refining


REGION
6


6

6

6

6






6


6

6

6


6


6

6


LOCATION
Corpus Chr1st1


CarrUo Springs

Amarlllo

El Paso

Port Arthur






Port Neches


Fort Worth

Texas City

Three Rivers


Nederland


Winnie

Fort Worth


STATE
TEX.


TEX.

TEX.

TEX.

TEX.






TEX.


TEX.'

TEX.

TEX.


TEX.


TEX.

TEX.


SUBCAT.
C


A

B

B

D






A


A

B

A
•

E


B

B


REFINERY
CAPACITY
1000 bbl
day
60.0


13.5

20.0

17.0

406.0






47.0


3.5

63.0

1.5

4
116.0


10.0

15.5


CRUDE I
Process
D
A
V
D
A
D
A
D
A
D
A
V




D
A
V
A

D
A
V
A
V

D
A
V
A

D
A
V
'ROCESSES
Capacity
1000 bbl
day
60.0
60.0
10.0
13.5
13.5
ZO.O
20.0
17.0
17.0
106.0
106.0
142.0




28.0
47.0
26.0
3.5

63.0
63.0
14.5
1.5
0.8

116.0
116.0
44.0
10.0

15.5
15.5
3.5
CRACKING
Process
Delay. Coke
FCC



Del ay. Coke
FCC
Delay. Coke
FCC
Gas-Oil Cr.
FCC
Hydro.

'







Vlsbreak.
Houdrl .




FCC


Hydro.

FCC


PROCESSES
Capacity
1000 bbl
day
7.7
26.5



4.0
8.0
4.0
7.0
51.0
135.0
15.0









5.0
23.0




40.7


3.0

6.0


LUBE P
Process









C
G
J
M
P









inknown


unknown







ROCESSES
Capacity
1000 bbl








.
4.2
17.2
0.6
21.5
3.8









0.8


3.5







ASPHALT
PRODUCTION
Capacity
1000 bbl /day
















9.0






0.12


5.4







PROCESS
CONFIG-
URATION
5.59
•

2.0

5.60
. -
5.88

6.84






4.45


1.0

4.90

9.43


5.44


2.8

4.55



-------
           TABLE  51 cont'd
PETROLEUM REFINERY - PROCESS BREAKDOWN
COMPANY
American
Petroflna, Inc.

Apco Oil
Corporation
CRA Inc.



CRA Inc.


Derby Ref.
Company
£

Mid America
Ref. Company Inc.
Mobil 011
Corporation
National Coop.
Ref. Assoc.
North American
Petro. Corp. •:

Phillips
Petroleum Co.

Skelly 011
Company

Amoco Oil


Gary Western
Co. (Gllsontte)
REGION
7


7
7



7



7


7

7

7

7


7


7


7


8

LOCATION
El Dorado


Arkansas City
Cof fey vllle



PhilHpsburg



Wichita


Chanute

Augusta

McPherson

Shallow
Water

Kansas City


El Dorado


Sugar Creek


Grand Junction

STATE
KAN.


KAN.
Kan.



Kan.



Kan.


Kan.

Kan.

Kan.

Kan.


KAN.


KAN.


KAN.


COLO.

SUBCAT.
B


B
D



B



B


A

B

B

•* B


E


C


B


B

REFINERY
CAPACITY
1000 bbl
25.0


26.0
36.0



21.0



27.0


3.3

52.0

57.0

5.0


85.0


75.0
4

105.0


; 8.5

CRUDE 1
Process
D
A
V
D
A
-V
D
A
V

D
A
V

D
A
V
A
V
A
V
D
A
0
A
V
D
A
V
D
A
V-
0
A
V
D
A
'ROCESSES
Capacity
1000 bbl
day
25.0
25.0
9.0
26.0
26.0
5.0
36.0
36.0
12.5

21.0
21.0
7.5

27.0 '
27.0
8.8
3.3
1.8
52.0
17.7
57.0
57.0
5.0
5.0
2.5
85.0
85.0
15.0
75.0
75.0
23.0
105.0
105..0
40.0
8.5
8.5
CRACKING
Process
FCC


FCC
Hydro.
Delay. Cok.
FCC

•
FCC



Delay. Cok.
Thermo.



Gas-Oil Cr.
Thermo.
Delay. Cok.
FCC
Thermo.


FCC


Delay. Coke
FCC

Del ay. Coke
FCC

Fluid. Coke

PROCESSES
Capacity
1000 bbl
day
11.5


12.0
2.95
8.5
14.2


7.35



3.8
12.55



4.1
23.5
i;:o
21t'o.
4.5


48.0


9.8
48.0

11.0
50.0

8.5

LUBE P
Process




G
K
M
N
















C
E
Q








ROCESSES
Capacity
1000 bbl
day




1.66
0.15
2.76
0.85
















5.2
6.8
2.4








ASPHALT
PRODUCTION
Capacity
1000 bbl /day
2.0


1.4




.2.0








8.0






3.0





6.5



PROCESS
CONFIG-
URATION
6.08


6.29
8.09



5.60



5.96


1.55

6.37

6.0

7.9


8.19


6.93


6.61


8.00


-------
           TABLE  51  cont'd
PETROLEUM REFINERY - PROCESS BREAKDOWN
COMPANY
Continental
011 Company

The Refinery
Corporation

B1g West 011
Company

Cenex

Continental Oil
Company
Exxon' Company
USA

Jet Fuel
Refinery
Phillips Petro.
Company
Tesoro Petro.
Corporation
Westco Ref.
Company
Amoco Oil
Company
Hestland Oil
Company
Amoco Oil
Company
Arizona Fuels
Corporation
Caribou Four
Corners Inc.

REGION
8


8


8


8

8

8

8

8

8

8

8

8

8

8

8

LOCATION
Commerce City


Commerce City

'
Kevin*


Laurel

Billings

Billings

Mosby

Great Falls

Wolf Point

Cut Bank

Handan

W11 listen

Salt Lake City

Roosevelt

Woods Cross

STATE
COLO.


COLO.

*
MONT.


Mont.

Mont.

Mont.

Mont.

Mont.

Mont.

Mont.

N.D.

N.D.

Utah

Utah

Utah

SUBCAT.
B


B


B


B

B

B

A

B

A

B

B

B

B

B

B

REFINERY
CAPACITY
1000 bbl
~3ay
31.0


17.5 •


5.5


44.0

56.0

46.0

1.0

5.7

2.65

5.0

48.0

5.0 *

39.0

11.0

5.0

CRUDE
Process
D
A
V
D
A
V
D
A
V
D
A
V
D
A
V
D
A
V
A

• D
A
V
A

D
A
D
A
D
A
D
A
D
A
D
A
V
PROCESSES
Capacity
1000 bbl
day
26.0
31.0
7.0
17.5
17.5
3.5
5.5
5.5
0.75
44.0
44.0
15.4
38.0
C£ A
56.0
12.2
46.0
46.0
18.0
1.0

5.7
5.7
2.0
2.65

5.0
5.0
48.0
48.0
5.0
5.0
39.0
39.0
11.0
11 .0
5.0
5.0
1.0
CRACKINC
Process
FCC


Vlsbreak.
FCC •

Gas-Oil Cr.


FCC

FCC

Fluid. Cok.
• FCC
Hydro.


FCC



Gas-011 Cr.

FCC

Gas-Oil Cr.

FCC

FCC
\
Hydro.

• PROCESSES
Capacity
1000 bbl
•lay
14.5


6.0
6.5

1.2


18.0

21.0

5.2
34.0
4.9


3.0



2.2

34.0

1-1

22.0

6.0

1.0

LUBE F
Process





















-











ROCESSES
Capacity
1000 bbl
day

































ASPHALT
PRODUCTION
Capacity
1000 bbl /day
3.3





0.325




3.5

13.0



0.8









2.5





PROCESS
CONFIG-
URATION
6.15


6.49


4.15


4.81

4.90

11.54

1.0

7.19

1.0

4.64

6.25

3.32

6.15
i

5.27

3.4


-------
           TABLE   51  cont'd
PETROLEUM REFINERY - PROCESS BREAKDOWN
COMPANY
Chevron 011
Company

Husky Oil
•Company



Phillips Petro.
Company

Amoco Oil
Company


Husky 'Oil
Company
l«i
SI Husky Oil
Company


Little America
Ref. .Company

Mountaineer. Ref.
Company Inc.*
Pasco Inc.


Sage Creek Ref.
Company
Southwestern Ref.
Company
Tesoro Petro.
Corporation
Texaco Inc.


REGION
8


8



8


8



8



8


8


8

8


8

8

8

8


LOCATION
Salt Lake
city


North Salt
Lake


Moods Cross


Casper



Cheyenne



Cody


Casper


LaBarge

Sinclair


Cowley

LaBarge

Newcastle

Casper


STATE
Utah

\

Utah


Utah


Wyn.



Wym.



Wym.


Wym.


Wym.

Wym.


Wym.

Vtfro.

Wym.

Hym.


SUBCAT.
B



B


B


0



8



B


B


A

B


A

A

B

B


REFINERY
CAPACITY
1000 bbl
45.0



12.0


23.0


43.0



24.6



11.2


23.0


O.SO

42.0

«
1.2

0.33

11.0

21.0


CRUDE 1
Process
D
A
V


D
A
V
D
A
V
A
V


0
A
V

D
A
V
D
A
V
A

D
A
V
A

A

D
A
0
A
V
'ROCESSES
Capacity
1000 bbl
day
45.0
45.0
27.0


12.0
12.0
3.8
23.0
23.0
3.0
43.0
13.5


24.6
24.6
14-0

11.2
11.2
6.5
23.0
23.0
5.8
0.5

42.0
42.0
14.2
1.2

0.33

11.0
11.0
21.0
21.0
10.0
CRACKING
Process
FCC
Houdrl .



Thermo.


Thermo


FCC



FCC
t


FCC


Thermo.




FCC






Thermo.

Press. Coke
FCC

PROCESSES
Capacity
1000 bbl
day
12.0
13.0



6.9


10.5


11.0



12.5



4.3


10.5




12.8






8.0

4.0
7.0

LUBE P
Process










F
M
N
0
























ROCESSES
Capacity
1000 bbl
day










1.8
2.6
1.0
0.3











-












ASPHALT
PRODUCTION
Capacity
1000 bbl /day







2.2


1.55



3.0



4.0


2.0




2.3








1.5


PROCESS
CONFIG-
URATION
5.93



5.77


6.02


5.00



7.08

'

9.17


6.03


1.0

4.82


1.0

1.0

6.36

6.48



-------
           TABLE  51  cont'd
PETROLEUM REFINERY - PROCESS BREAKDOWN
COMPANY
Atlanta, Rlchfielc
Company'


1
Beacon 011
'.Company
Exxon Company
USA

Fletcher Oil £
Ref. Company
Golden Bear
Div. (Witco)

Gulf 011 .
Company

Mobil 011 .
Corporation


Mohawk Petro.
Corporation Inc.
Newhall Ref.
Company Inc.
Phillips Petro.
Company

Power line
Oil Company

Sequoia Ref.
Company

Shell Oil
Company

Shell Oil
Company



REGION
9




9

9


9

9


9


9



9

9

9


9


9


9


9




LOCATION
Carson




Hanford

Benlcia


Carson

Oildale


Santa Fe
Springs

Torrence



Bakers-
field •
Newhall

Avon


Santa Fe
Springs

Hercules


Martinez


Wilmington




STATE
Cal.




Cal.

Cal.


Cal.

Cal.


Cal.


Cal.



Cal.

Cal.

Cal.


Cal.


Cal.


Cal.


Cal.




SUBCAT.
C




B

B


A

A


B


B



A

A

D


B


B


E


D




REFINERY
CAPACITY
1000 bbl
day
173.0




12.1

95.0


16.2

vi.o


53.8


130.0



22.8

8.0

110.0


30.0

4
28.3


103.0


101.0




CRUDE
Process
A
V



A

D
A
V
D
A
D
A
V
D
A
V
D
A
V

A

A
V
D
A
V
D
A
V
D
A
V
D
A
V
D
A
V


PROCESSES
Capacity
1000 bbl
day
173.0
93.0



12.1

95.0
95.0.
53.0
16.2
16.2
11.0
11.0
9.5
53.8
53.8
25.0
100.0
130.0
95.0

22.8

8.0
5.0
90.0
110.0
74.5
30.0
30.0
15.0
28.3
28.3
5.9
85.0
103.0
55.3
101.0
101.0
60.0


CRACKING
Process
Gas-Oil Cr.
Visbreak.
Delay. Cok.
FCC
Hydro.
Gas-Oil Cr.
Visbreak.
Fluid. Cok.
FCC
Hydro.

.



Visbreak.
FCC
Hydro.
Visbreak
Delay. Cok.
FCC
Hydro.




Fluid. Cok.
FCC
Hydro.
FCC


Hydro.


FCC
Hydro.

Delay. Cok.
FCC



PROCESSES
Capacity
1000 bbl
day
12.5
42.0
30.0
65.0
19.7
0.5
2.75
21.6
57.0
22.0





13.8
13.8
11.0
16.0
46.64
56.0
18.0




42.0
47.0
22.0
12.0


2.9


86.0
19.0

30.0
40.0



LUBE P
Proces;












Unk.













Unk.








A
M
P
C
D
E
G
N
ROCESSES
Capacity
1000 bbl
day












4.0













1.67








3.5
4.8
1.8
7.8
24.3
1.8
18.6
7.8
ASPHALT
PRODUCTION
Capacity
1000 bbl /day












3.2


4.0








3.0




5.0





10.4







PROCESS
CONFIG-
URATION
7.41




2.60

8.91


2.0

11.09


7.66


8.81



1.0

6.13

8.75


6.90
• -

2.82


10.96


14.51





-------
           TABLE  51  cont'd
PETROLEUM REFINERY - PROCESS  BREAKDOWN
COMPANY
STD. Oil Company
of Calif.
STD. Oil Company
of Calif.


STD. Oil Company
of Calif.




Texaco Inc.


Union Oil
Company of Calif

Union Oil Company
of Calif.


STD. Oil Company
of Calif.

STD. Oil Company
of Calif.
Atlantic Rich-
field Company

Mobil Oil
Corporation

Shell Oil
Company


REGION
9


9


9





9


9


9



9


10

10


10


10



LOCATION
Bakers-
Field

El Segundo
'

Richmond





Wilmington


Los Angeles


San Francisco



Barber's Point


Portland

Fernadale


Ferndale


Anacortes •



STATE
Cal.


Cal.


Cal.





Cal.


Cal.


Cal.



Haw.


Ore.

Wash.


Wash.


Wash.



SUBCAT.
A


C


E





B


B


D



B


A

B


B


B



REFINERY
CAPACITY
1000 bbl
day
26.0


230.0


190.0





75.0


111.0


115.0



40.0


15.0

100.0


74.5 *


94.0



CRUDE 1
Process
A


D
A
V
D
A
V



D
A

D
A
V
D
A
V

0
A
V
A
V
D
A
V
0
A
V
D
A
V

'ROCESSES
Capacity
1000 bbj
26.0


120.0
230.0
103.0
190.0
190.0
150.0



22.0
75.0

86.0
111.0
83.0
115.0
115.0
38.5

40.0
40.0
15.0
15.0
15.0
100.0
100.0
55.0
74.5
74.5
7.0
94.0
94.0
33.0

CRACKING
Process



Delay. Cok.
FCC
Hydro.
FCC
Hydro.




Delay. Cok.
• FCC
Hydro.
Visbreak.
FCC
Hydro.
Delay. Cok.
Hydro.


FCC




Delay. Cok.
Hydro.

Visbreak.
Thermo.

FCC



PROCESSES
Capacity
1000 bbl
day



54.0
54.5
49.0
54.5
67.5




48.0
28.0
20.0
20.0
52.0
21.0
42.5
30.0


23.0




29.0
35.0

7.0
27/5

53.0



LUBE P
Process






A
C
G
H
J
Q






D
E
G
H















ROCESSES
Capacity
1000 bbl
day






3.1
62.4
7.3
6.2
2.9
4.0






11.2
5.1
6.1
0.8















ASPHALT
PRODUCTION
Capacity
1000 bbl /day
1.1


8.3


n.o








10.0


6.15



•1.3


8.6











PROCESS
CONFIG-
URATION
1.51
•

6.51


13.21





8.97


8.63


9.34



6.19


8.88

6.39


4.87


5.73




-------
           TABLE  51  cont'd
PETROLEUM REFINERY - PROCESS BREAKDOWN
COMPANY
Sound Ref. Inc.


STD. Oil Company
of Calif.
Texaco Inc.


U.S. Oil & Ref.
Company


STD. Oil Company
of Calif.

Tesoro-Alaskan
Petro. Corp.

M
CO


REGION
10


10

10



10



10


10




LOCATION
Tacoma


Richmond
Beach
Anacortes



Tacoma



Kenal


Kenal




STATE
Wash.


Wash.

Wash.



Wash.



Alka.


Alka.




SUBCAT.
A


A

B '



A



A


A




REFINERY
CAPACITY
1000 bbl
day
4.7


. 5.0

63.0



16.0



22.0


39.5


«
4
CRUDE I
Process
D
A
V
A
V
D
A
V

D
A
V

D
A

0
A



'ROCESSES
Capacity
1000 bbl
day
4.7
4.7
4.5
5.0
5.0
63.0
63.0
22.5

16.0
16.0
3.2

22.0
22.0

39.5 '
39.5



CRACKING
Process





FCC


-












PROCESSES
Capacity
1000 bbl





25.0















LUBE P
Process
Unk.




















ROCESSES
Capacity
1000 bbl
d.ay
1.9


-


*"












,.

ASPHALT
PRODUCTION
Capacity
1000 bbl /day
2.6


4.0





3.0



0.3







PROCESS
CONFIG-
URATION
14.85


11.6

4.74



4.45



2.16


2.0





-------
                            SECTION X

             BEST AVAILABLE TECHNOLOGY ECONOMICALLY
               ACHIEVABLE — EFFLUENT LIMITATIONS


The  application  of  best  available   technology   economically
achievable  is being defined as further reductions of water flows
in-plant and the addition of a physical - chemical treatment step
(activated carbon),  end-of-pipe.   The  limitations,  which  set
numerical  values  for  the allowable pollutant discharges within
each subcategory for BATEA are presented in Tables 1-6.  Although
there are specific systems which can effectively reduce the water
usage from a particular  process  to  nearly  zero,  these  "zero
discharge"  systems  cannot  be  uniformly applied throughout the
refinery to develop "zero  discharge"  criteria  for  the  entire
refinery.

BATEA  in-plant  technology  is  based  on  control practices now
practiced by some plants in the petroleum refining industry,  and
include the following:

     (1)  Use of air cooling equipment.
     (2)  Reuse of sour water stripper bottoms in crude desalters.
     (3)  Reuse of once-through cooling water as make-up to the
        water treatment plant.
     (4)  Using waste water treatment plant effluent as cooling water,
        scrubber water, and influent to the water treatment plant.
     (5)  Reuse of boiler condensate as boiler feedwater.
     (6)  Recycle of water from coking operations.
     (7)  Recycle of waste acids from alkylation units.
     (8)  Recycle of overhead water in water washes.
     (9)  Reuse overhead accumulator water in desalters.
     (10)Use of closed compressor and pump cooling
        water system.
     (11)Reuse of heated water from the vacuum overhead condensers
        to heat the crude.  This reduces the amount of cooling water
        needed.
     (12)Use of rain runoff as cooling tower make-up or
        water treatment plant feed.
     (13)Other methods.

Flow

Flow  reductions  proposed  for  BATEA  effluent limitations were
derived from further analysis  of  the  1972  National  Petroleum
Waste  Water Characterization Studies.  The flows from refineries
in each subcategory meeting the BPCTCA flow basis  were  averaged
to  determine  the flow basis for establishment of BATEA effluent
limitations.  That these average flows are achievable within  the
petroleum   refining   industry   is   readily  demonstrable,  by
determining  the  number   and   geographical   distribution   of
refineries  in the United States currently at, or lower than, the
proposed BATEA flows.  There are 3 to 5 refineries in each of the
five subcategories which have flows less than  or  equal  to  the


                               169

-------
proposed  BATEA  effluent limitations.  These refineries range in
size from 827,000 to  69,000,000  cubic  meters  per  stream  day
(5,200  to 434,000 barrels per stream day) ,  and range in cracking
capacity from 0 to 106 percent.  The geographical distribution of
these  refineries  indicates  that  good  water  practices,   and
consequently  low  waste water flows, are not confined to water -
short areas or cool climates,  but  are  located  throughout  the
United  States.   Within  this group of refineries with low-water
usage, there are refineries located in both  high rainfall and dry
areas  (Washington  and  New  Mexico)  and   areas   of   extreme
temperatures (New Mexico and Texas to Alaska and Minnesota).

Consequently,  these  flows,  shown in Table 52, were used as the
basis for  establishment  of  BATEA  effluent  limitations.   The
objective of this basis for flow is to provide inducement for in-
plant  reduction  of  both flow and contaminant loadings prior to
end-of-pipe treatment.  However, it is not the  intent  of  these
effluent  limitations to specify either the  unit waste water flow
which must be achieved or the  waste  water   treatment  practices
which must be employed at the individual petroleum refinery.

The  end-of-pipe system proposed for BATEA technology is based on
the addition of activated carbon adsorption  in fixed bed columns,
to the treatment system proposed as BPCTCA technology.

Procedure for Development of BATEA Effluent  Limitations

The effluent limitations proposed for BATEA technology are  based
on  refinery  pilot  plant  data,  which  indicate the percentage
reductions achievable or concentrations achievable for  effluents
from   activated  carbon  adsorption  systems.   These  data  are
presented in Table 53.

These concentrations were then used in conjunction with the BATEA
flows from Table 53 or the percentage reductions were applied  to
the  BPCTCA  effluent  limit.   The daily annual average effluent
limitations determined are contained in Table 54.

Since these effluent limitations are based upon pilot plant data,
which  have   not   been   fully   demonstrated   in   full-scale
installations  as  actual performance data becomes available, the
effluent  limitations  presented  in  Tables  1-6   may   require
revision.

Variability Allowance for Treatment Plant Performance

The  effluent limitations presented in Tables 1-6 have taken into
consideration the variability factors, as in BPCTCA.  Since there
is not enough performance data from physical - chemical treatment
systems available at this  time  to  determine  variability,  the
ratios  established  for  BPCTCA at the 98% confidence level have
been used.   (See Table 55).
                             170

-------
Subcategory

Topping
Cracking
Petrochemical
Lube
Integrated
                                  TABLE 52
                         FLOW BASIS FOR DEVELOPING
                        BATEA EFFLUENT LIMITATIONS
Flow, per unit throughout
M3/M3               Gallons/BBL
0.255
0.33
0.46
0.73
0.88
10.5
14
19
30.5
36.5
                                 171

-------
                                                TABLE 53


                               BATEA REDUCTIONS  IN  POLLUTANT  LOADS ACHIEVABLE  BY

                                     APPLICATION OF ACTIVATED CARBON TO

                               MEDIA FILTRATION EFFLUENT BPCTCA
Parameter
Type of Data
Achievable
Refinery Effluent

BOD
COD
TOC
TSS
Of!
Phenols
Ammonia
Sulftdes

Pilot Plant
Pilot Plant
Pilot Plant
Pilot Plant
Pilot Plant
Pilot Plant
Pilot Plant
No data
mg/L
5
-
15
5
1-1.7
0.02
-
_
% Reduction
-
75
-
-
80
99
60
-
References



21,27,31A,U8,62A

21,27,31AfU7,53,62A

17,31A,U8,62A

31A>8,53,62A

31A,1*8,62A

31A,lt8,62A

 27,31A,62A

-------
                                                                      TABLE 54
                                                                       BATEA

                            Annual Average Daily Kilograms  of Pollutants/1000 Cubic  Meters  of  Feedstock  (1)  Per Stream Day
                             (Annual Average Daily Pounds of Pollutants/1000 BBL of  Feedstock  Per  Stream Day)
Refinery
Subcategory
BODS
            COD
                1.2(0.44)   5.0(1.75)

                1.6(0.58)   9.6(3.4)

                2.2(0.79)  10.8(3.8)

                3.7(1.3)   20.0(6.9)

                4.2(1.5)   23.7(8.4)
TOC
3.7(1.3)
5.0(1.75)
6.8(2.4)
10.8(3.8)
13.0(4.6)
Total
Suspended
Solids
1.2(0.44)
1.6(0.58)
2.2(0.79)
•3.7(1.3)
4.2(1.5)
Oil &
Grease
0.25(0.088)
0.34(0.12)
0.45(0.16)
0.71(0.25)
0.85(0.30)
Phenolic
Compounds
0.0051(0.0018)
0.0065(0.0023)
0.0091(0.0032)
0.014 (0.0051)
0.017 (0.0061)
Ammonia(N]
0.34(0,12;
2.3 (0.8)
2.8 (1.0)
2.8 (1.0)
2.8 (1.0)
                                                                                                                           Total
                                                                                                                           Chromium
Hexavalent
Chromi urn
                                                                                0.34(0,12)   0.025(0.0087)  0.062(0.022)  0.0012(0.00044)

                                                                                2.3  (0.8)    0.034(0.012)   0.082(0.029)  0.0016(0.00058)

                                                                                            0.045(0.016)   0.11  (0.040)  0.0022(0.00079)

                                                                                            0.071(0.025)   0.18  (0.063)  0.0037(0.0013)

                                                                                            0.085(0.030)   0.22(0.076)   0.0042(0.0015)
  Topping

^jCracking

  Petrochemical

  Lube

  Integrated

  Runoff(Z)    0.0050(0.042) 0.014(0.12) 0.016(0.13) 0.0050(0.042)  0.0010(0.009)

  Ballast (3)  0.0050(0.042) 0.019(0.16) 0.016(0.13) 0.0050(0.042)  0.0010(0.009)


    (1) " Feedstock - Crude oil and/or natural gas liquids.
    (2)  The additional allocation being allowed for contaminated storm runoff flow,  kg/1000 (lb/1000 gallons),  shall  be  based  solely  on  that  storm
         flow which passes through the treatment system.   All  additional  storm runoff,  that has  been  segregated  from the  main waste  stream,  shall  not
         exceed a TOC concentration.of 35 mg/1 or Oil & Grease concentration of 15 mg/1  when discharged.
    (3)  This is an additional allocation, based on ballast water intake -  kilograms  per 1000 liters  (pounds  per 1000 gallons).        »

-------
                                       TABLE 55

                  VARIABILITY FACTORS  BASED ON PROPERLY DESIGNED
                   AND OPERATED WASTE  TREATMENT FACILITIES-BATEA
               BOD,.    COD   TOG   TSS    0  & G   Phenol   Ammonia   Sulfide   CrT    Cr6
Daily
Variability    2.1     2.0   1.6   2.0     2.0      2.4      2.0         2.2     2.0   2.2


30-day
Variability    1.7     1.6   1.3   1.7     1.6      1.7      1.5         1.4     1.7   1.4

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                           SECTION XI

                NEW SOURCE PERFORMANCE STANDARDS


Recommended  effluent  limitations  for  new  source  performance
standards  are  based  upon  the  application  of  BPCTCA control
technology to the waste water flows used as the basis  for  BATEA
effluent limitations.  The proposed BADT effluent limitations are
shown in Tables 1-6.

The  refining  technology available today does not call for major
innovations in  refining  processes.   Basically,  BADT  refining
technology  consists  of tiae same fundamental processes which are
already  in  practice,  with  few  modifications  and  additions.
However,  a  major  design criterion for new refinery capacity is
reuse/ recycle of water streams to the greatest extent  possible,
in   order  to  minimize  discharges  to  waste  water  treatment
facilities.  Consequently, the water flow  on  which  new  source
performance  standards  were  based  is  identical  to  the  best
available technology economically achievable flow, which reflects
the best water usage as demonstrated in  the  petroleum  refining
industry.  These flows are shown in Table 52.

It should be clearly understood that no recommendations have been
made,   nor  are  any  implied,  regarding  the  substitution  of
processes which produce a lower raw waste load  for  others  with
higher raw waste load.

This  is  based  on  the  consideration  that  the  choice  of  a
particular  commercial  route  is   governed   largely   by   the
availability  of  feedstocks and on the conditions in the product
markets.  Companies produce a given  mix  of  products  based  on
their  particular  marketing  and  feedstock  position within the
industry.  The substitution of a cleaner process may be  possible
for  new producers from a technical point of view, but completely
impossible based on limited availability of the required alterna-
tive feedstocks or on the lack of  viable  markets  for  new  .co-
products.

The   waste  water  treatment  technology  recommended  for  BADT
effluent limitations is the same as called for by BPCTCA and does
not  include  physical  -  chemical   treatment,   because   that
technology   has   not  been  sufficiently  demonstrated  by  the
petroleum refining industry.

Procedure for Development of BADT Effluent Limitations

The effluent limitations proposed for BADT technology  are  based
on  the  concentrations  considered  achievable by BPCTCA and the
flows from BATEA.  The daily annual average effluent  limitations
thus determined are contained in Table 56.
                              175

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                                                                      TABLE. 56
                                                                        BADT
  Refinery,
  Subcategory

  Topping

  Cracking

^Petrochemical

-------
Variability Allowance for Treatment Plant Performance

The  guideline  numbers  presented  in Tables 1-6 have taken into
consideration the variability factors, as in BPCTCA.   Since  the
treatment technology and process technology for BADT are the same
as  BPCTCA,  the  ratios established for BPCTCA have been used in
BADT.
                             177

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                                     TABLE 57

                                   METRIC UNITS

                                 CONVERSION TABLE
MULTIPLY (ENGLISH UNITS)

    ENGLISH UNIT      ABBREVIATION
acre
acre - feet
British Thermal
  Unit
British Thermal
  Unit/pound
cubic feet/minute
cubic feet/second „
cubic feet
cubic feet
cubic inches
degree Fahrenheit
feet
gallon'
gallon/minute
horsepower
inches
inches of mercury
pounds
million gallons/day
mile
pound/square
  inch (gauge)
square feet
square inches
tons (short)
yard
* Actual conversion, not a multiplier
     by                TO OBTAIN (METRIC UNITS)

CONVERSION   ABBREVIATION   METRIC UNIT
                            hectares
                            cubic meters

                            kilogram - calories

                            kilogram calories/kilogram
                            cubic meters/minute
                            cubic meters/minute
                            cubic meters
                            liters
                            cubic centimeters
                            degree Centigrade
                            meters
                            liters
                            liters/second
                            killowatts
                            centimeters
                            atmospheres
                            kilograms
                            cubic meters/day
                            kilometer

                            atmospheres (absolute)
                            square meters
                            square centimeters
                            metric tons (1000 kilograms)
                            meters
ac
ac ft
BTU
BTU/lb
cfm
cfs
cu ft
cu ft
cu in
F°
ft
gal
gpm
hp
in
in Hg
Ib
mgd
mi
psig
sq ft
sq in
t
y
0.405
1233.5
0.252
0.555
0.028
1.7
0.028
28.32
16.39
0.555(°F-32)*
0.3048
3.785
0.0631
0.7457
2.54
0.03342
0.454
3,785
1.609
(0.06805 psig +1)*
0.0929
6.452
0.907
0.9144
ha
cu m
kg cal
kg cal/kg
cu m/min
cu m/min
cu m
1
cu cm
°C
m
1
I/sec
kw
cm
atm
kg
cu m/day
km
atm
sq m
sq cm
kkg
m
                                       178

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                           SECTION XII

                         ACKNOWLEDGEMENT

The preparation of the  initial  draft  report  was  accomplished
through  a contract with Roy F. Weston, Inc., under the direction
of Clem Vath, Project Director.  The following individuals of the
staff of Roy F. Weston, Inc.  made significant  contributions  to
this effort:
    David Baker, Project Manager
    Michael Smith, Project Engineer
    M. Jotwani, Project Engineer


Martin  Halper,  Project  Officer  and  David L. Becker, Chemical
Engineer,  Effluent  Guidelines  Division,  contributed  to   the
overall  supervision  of  this  study,  preparation  of the draft
report and  preparation  of  this  Development  Document.   Allen
Cywin,  Director,  Effluent  Guidelines  Division, Ernst P. Hall,
Deputy Director, Effluent  Guidelines  Division  and   Walter  J.
Hunt,  Chief,  Effluent  Guidelines  Development  Branch, offered
guidance and suggestions during this program.

Special appreciation is given to Charles Cook and Gary  Liberson.
Water Program Operations, for their contributions to this effort.

The   members   of   the  working  group/steering  committee  who
coordinated the internal EPA review are:

    Allen Cywin, Effluent Guidelines Division
    Walter J. Hunt, Effluent Guidelines Division
    David Becker, Effluent Guidelines Division
    Martin Halper, Effluent Guidelines Division
    Leon Myers, Office of Research and Monitoring,  (Ada)
    William Bye, Region VIII
    Robert Twitchell, Region III
    Wayne Smith, National Field Investigation Center,  (Denver)
    Thomas Belk, Office of Permit Programs
    John Savage, Office of Planning and Evaluation
    Alan Eckert, Office of General Counsel
    Phillip Bobel, Region IX
    Benigna Carroll, Office of Hazardous Materials Control
    Ned Burleson, Region VI
    Srini Vasan, Region V

Acknowledgement and appreciation is also given to the secretarial
staff of both the Effluent Guidelines Division and Roy F. Weston,
Inc., for their effort in the typing of the drafts and  necessary
revisions,  and  the final preparation of the effluent guidelines
document.  The following individuals are acknowledged  for  their
contributions:

    Kit Krickenberger, Effluent Guidelines Division
    Kay Starr, Effluent Guidelines Division
    Brenda Holmone, Effluent Guidelines Division
                              179

-------
    Chris Miller, Effluent Guidelines Division
    Sharon Ashe, Effluent Guidelines Division
    Susan Gillmann, Roy F. Weston, Inc.
    Judith Cohen, Roy F. Weston, Inc.

Appreciation  is  extended  to staff members of EPA's Regions II,
III, V, VI, IX, and X offices and the Robert S.  Kerr  Laboratory
for their assistance and cooperation.

Appreciation is extended to the following State organizations for
assistance and cooperation given to this program.

    California, State Water Resources Control Board
    Illinois, Environmental Protection Agency
    Michigan, Water Resources Commission
    Texas, Water Control Board
    Virginia, State Water Control Board
    Washington, Department of Ecology

Appreciation  is extended to the following trade associations and
corporations for their assistance and cooperation given  to  this
program.

    American Petroleum Institute
    Amerada Hess Corporation
    American Oil Company
    Ashland Oil Inc.
    Atlantic Richfield Company
    Beacon Oil Company
    BP Oil Corporation
    Champlin Petroleum Company
    Coastal States Petrochemical Company
    Commonwealth Oil & Refining company. Inc.
    Exxon, USA
    Gulf Oil Company
    Kerr - McGee Corporation
    Laketon Asphalt Refining, Inc.
    Leonard Inc.
    Lion Oil Company
    Marathon Oil Company
    OKC Refining Inc.
    Phillips Petroleum Company
    Shell Oil Company
    Sun Oil Company of Pennsylvania
    Texaco Inc.
    Union Oil Company of California
    United Refining Company
    U.S. Oil and Refining Company
                                180

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                          SECTION XIII

                          BIBLIOGRAPHY
1.  American Petroleum Institute, "Petroleum Industry  Raw  Waste
    Load Survey," December, 1972.

2.  Annessen, R. J. , and Gould, G.  D.,  "Sour  Water  Processing
    Turns  Problem  Into Payout," Chemical Engineering, March 22,
    1971.

3.  Annual Refining Surveys, "Survey of Operating  Refineries  in
    the U.S.," The Oil and Gas Journal, April 1, 1973.

3a.  Annual  Refining Surveys, "Survey of Operating Refineries in
    the U.S.", The Oil and Gas Journal 1967.

4.  Armstrong, T. A., "There's Profit in Processing Foul  Water,"
    The Oil and Gas Journal, pp. 96-98, June 17, 1968.

5.  Beavon, David  K.,  "Add-On  Process  Slashes  Claus  Tailgas
    Pollution,"  Chemical  Engineering,  pp.  71-73, December 13,
    1971.

6.  "The Beavon Sulfur Removal Process for  the  Purification  of
    Sulfur Plant Tailgas," Ralph M. Parsons Company Publication.

7.  Benger, M., "Disposal of Liquid and Solid Effluents from  Oil
    Refineries,"  21st  Purdue  Industrial  Waste Conference, pp.
    759-767, 1966.

8.  Beychok,  M.  R.,   Aqueous   Wastes   from   Petroleum   and
    Petrochemical Plants, John Wiley & Sons, London, 1967.

9.  Beychok,  M.  R.,  "Waste  water  Treatment  of  Skelly   Oil
    Company's El Dorado, Kansas Refinery," 16th Purdue Industrial
    Waste Conference, pp. 292-303, 1961.

10. Brown, K. M., "Some Treating and  Pollution  Control  Process
    for  Petroleum  Refineries," The Second INTERPETROL Congress,
    Rome, Italy, June 22-27, 1971.

11. Brownstein, Arthur M.,  U.S.  Petrochemicals,  The  Petroleum
    Publishing Co., Tulsa, Oklahoma, 1972.

12. Brunner, D. R., and Keller, D. J., "Sanitary Landfill  Design
    and   Operation,"   U.S.   Environmental  Protection  Agency,
    Washington, D.C., 1972.

13. Campbell, G. C., and  Scoullar,  G.  R.,  "How  Shell  Treats
    Oakville   Effluent,"   Hydrocarbon  Processing  &  Petroleum
    Refiner, 13 (5):  137-140, May, 1964.
                               181

-------
14.  "Chevron Waste  Water  Treating  Process,"  Chevron  Eesearch
    Company Publication,  September, 1968.

15.  Cohen,  J. M.,  "Demineralization of  Waste  waters,"  Advanced
    Waste Treatment and Water Reuse Symposium, Volume 2,  February
    23-24,  1971.

16.  Conser, R. E., "The Environmental Fuels Processing Facility,"
    SNG  Symposium,  Institute  of   Gas   Technology,   Chicago,
    Illinois, March 12-16,  1973.

17.  Gulp, R. L.,  and Gulp,  G. L., Advanced Waste water Treatment,
    Van Nostrand  Reinhold Company, New York, 1971.

18.  Davis,  R. W.,  Biehl,  V. A.,   and  Smith,  R.  M.,  "Pollution
    Control  and   Waste  Treatment  at  an Inland Refinery," 19th
    Purdue Industrial Waste Conference, pp. 128-138,  1964.

19.  Daniels, E. K., Latz,  J.  R.,  Castler,  L.  A.,  "Pollution
    Control at Ferndale,  Washington," 23rd Midyear Meeting of the
    American  Petroleum  Institute's  Division  of Refining, May,
    1958.

20.  Denbo,  R. T.,  and Gowdy, F.   W.,  "Baton  Rouge  Waste  Water
    Control  Program Nears End," The Oil and Gas Journal, pp. 62-
    65, May 29, 1972.

21.  Diehl,  D. S.,  Denbo,  R. T.,  Bhatta, M. N., and Sitman, W. D.,
    "Effluent Quality Control at a Large  Refinery,"   Journal  of
    the  Water  Pollution  Control Federation, 43 (11), November,
    1971.

22.  Dorris, T. C., Patterson, D., Copeland, B. J., "Oil  Refinery
    Effluent  Treatment  in  Ponds,"  35th  Meeting  of the Water
    Pollution Control Federation, pp. 932-939,  #  October  7-11,
    1962.

23.  Easthagen,  J.  H.,  Skrylov,  V.,   and   Purvis,   A.   L. ,
    •Development  of  Refinery Waste water control at Pascagowle,
    Mississippi," Journal of Water Pollution Control   Federation,
    37 (12):   1621-1628,  December, 1965.

24.  Elkin,  H.  F.,  "Activated  Sludge  Process  Application  to
    Refinery Effluent Waters," Journal of Water Pollution Control
    Federation, 28  (9):  1122-1129, September, 1956.

25.  Fair, G. M.,  Geyer, J.  C., and Okum, D. A., Water  and  Waste
    water  Engineering,  Volume  2,  John Wiley & Sons, Inc., New
    York, 1968.

26.  Fluid Bed  Incineration of Petroleum Refinery Wastes  for  the
    Environmental  Protection  Agency,  Washington,  D.C., March,
    1971.  12050KET
                                182

-------
27.  Ford, D. L., and Buercklin, M. A.,  "The Interrelationship  of
    Biological-Carbon  Adsorption  Systems  for  the Treatment of
    Refinery and Petrochemical Waste waters,"  6th  International
    Water Pollution Research Conference, Session 11, Hall C, June
    18-23, 1972.

28.  Fosberg, T.  M., "Industrial Waste  Water  Reclamation,"  7Uth
    National  Meeting  American  Institute of Chemical Engineers,
    March 11-15, 1973.


29.  Franzen,  A.  E. ,  Skogan,  V.  G.,  and  Grutsch,   J.   F.,
    "Successful  Tertiary Treatment at American," The Oil and Gas
    Journal, April 3, 1972.

30.  Gillian, A.  S., and Anderegg, F. C., "Biological Disposal  of
    Refinery  Wastes,"  14th  Purdue Industrial Waste Conference,
    pp. 145-154, 1959.

31.  Gloyna, E. G., Brady, S. O., and Lyles, H., "Use  of  Aerated
    Lagoons  and Ponds in Refinery and Chemical Waste Treatment,"
    41st Conference of the Water  Pollution  Control  Federation,
    September 22-27, 1968.

31a. Hale, J.H., and Myers, L.H., "The Agencies Removed by Carbon
    Treatment of Refinery Waste waters".

32.  Hart, J. A., "Air Flotation Treatment and Reuse  of  Refinery
    Waste water," 25th Annual Purdue Industrial Waste Conference,
    May, 1970.

33.  Hart, J. A., "On Improving Waste water  Quality,"  Water  and
    Sewage Works, IW 20-26, September-October, 1970.

34.  Hentschel, M. L., and Cox, T. L., "Effluent Water Treating at
    Charter International Oil Company's Houston  Refinery,"  74th
    National  Meeting  American  Institute of Chemical Engineers,
    March, 1973.

35.  Horne, W. R., and Hurse,  J.  E.,  "Biological  Reduction  of
    Phenolic   Type  Industrial  Wastes,"  Southern  Engineering,
    January, 1965.

35a. Ingols, R.S.,  "The  Toxicity  of  Chromium,"  $  percentSth
    Purdue Industrial Waste Conference,$ percent pp. 86-95, 1953.

36.  Kaup, E. C., "Design Factors in  Reverse  Osmosis,"  Chemical
    Engineering, April 2, 1973.

37.  Klett, Robert J., "Treat Sour Water for Profit,"  Hydrocarbon
    Processing, October, 1972.

38.  Klipple,  R.  W.,  "Pollution  Control  Built  into   Guayama
    Petrochemical  Complex," Water and Sewage works, 116  (3):  IW
    2-6, March, 1969.

                                 183

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39. Lankin, J. C., and Sord,  L.  V. ,   "American  Oil  Cleans  up
    Wastes   in   Aerated   Lagoons,"   Hydrocarbon  Processing  &
    Petroleum Refiner, 43 (5):  133-136, May, 1964.

40. "Major Oil Fields Around the World," International  Petroleum
    Encyclopedia,   1967,   Petroleum    Publishing   Co.,  Tulsa,
    Oklahoma.

41. Mohler, E. F. Jr., Clere,  L. T.,   "Development  of  Extensive
    Water  Reuse  and  Bio-oxidation  in  a  Large Oil Refinery,"
    National Conference on Complete Water Reuse, April, 1973.

42. McKinney, R. E., "Biological Treatment Systems  for  Refinery
    Wastes,"  39th  Annual  Conference  of  the  Water  Pollution
    Control Federation, pp.  346-359,  September 24-30, 1966.

43. McKinney, G. M., Ferrero,  E. P.,  and Wenger, W.  J., "Analysis
    of Crude Oils from 546 Important Oil  Fields  in  the  United
    States,"   Report   of  Investigations  6819,  United  States
    Department of the Interior.

44. McPhee, W. T., and Smith,  A. R.,  "From Refinery Waste to Pure
    Water," 16th Purdue Industrial Wastes  Conference,  pp.  440-
    448, May, 1961.

45. McWilliams, F. G., and Schuller,  R. P., "SNG, Naptha and Low-
    Sulfur Fuel Oils from Crude Oils  Using  Commercially  Proven
    Technology,"  American  Institute   of Chemical Engineers, New
    York, November 26-December 2, 1972.

46. Patterson, J. W., and Minear, R.  A.,  Waste  water  Treatment
    Technology, for state of Illinois  Institute for Environmental
    Quality, 2nd, January, 1973.

47. "P.  C.  Treatment  Gets  Industrial  Trial,"   Environmental
    Science  and Technology, Vol. 7,  No. 3, March, 1973, pp. 200-
    202.

48. Peoples,  R.  F.,  Krishnan,  P.,   and  Simonsery,   R.   N.,
    "Nonbiological Treatment of Refinery Waste water," Journal of
    the  Water  Pollution Control Federation, 44  (11): 2120-2128,
    November, 1972.

48a.  "Petroleum   Refining   Effluent   Guidelines",   for   the
    Environmental Protection Agency,  Office of Water Programs.

49. "Petroleum Refining Industry Waste  water  Profile"  for  the
    Federal Water Pollution Control Association.

50. Porges, R., "Industrial  Waste  Stabilization  Ponds  in  the
    United  States,"  Journal  of  the  Water  Pollution  Control
    Federation, 35  (4):  456-468, April, 1963.

51. Prather, B. V., "Effects of Aeration on Refinery Waste  Water
    Effluents,"    Western    Petroleum    Refiners   Association

                               184

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    Proceedings  of  the  Waste  Disposal  and  Stream  Pollution
    Conference, October 7-8, 1959.

52.  "Pretreatment  of  Discharges  to  Publicly  Owned  Treatment
    Works," Federal Guidelines, E.P.A., 1973.

53.  Process Design Manual for  Carbon  Adsorption,  Environmental
    Protection Agency, Washington, D.C., October, 1971.

54.  Process  Design  Manual   for   Suspended   Solids   Removal,
    Environmental Protection Agency, Washington, D.C., 1971.

55.  Purcell, W. L., and Miller, R. B., "Waste Treatment of Skelly
    Oil  Company's  El  Dorado,  Kansas  Refinery,"  16th  Purdue
    Industrial Waste Conference, pp. 292-303, 1961.

56.  Rambow, C. A., "Industrial  Waste  water  Reclamation,"  23rd
    Purdue Industrial Waste Conference, pp. 1-9, May, 1968.

57.  Reid, G. W., and Streebin, L. E., "Evaluation of Waste Waters
    from Petroleum and Coal Processing," Prepared for  Office  of
    Reserach and Monitoring U.S. Environmental Protection Agency,
    Washington,  D.C.,  (Contract  no.  EPA-R2-72-001.  December,
    1972).

58.  Rodriguez, D.  G.,  "Sour  Water  Strippers,"  74th  National
    Meeting  American  Institute of Chemical Engineers, March 11-
    15, 1973.

59.  Rose, B. A., "Water  Conservation  Reduces  Load  on  Sohio's
    Waste  Treatment Plant," Water and Sewage Works, 116  (9):  IW
    4-8, September, 1969.

60.  Rose, W. L., and Gorringe, G.  E.,  "Activated  Sludge  Plant
    Handles Loading Variations," The Oil and Gas Journal, pp. 62-
    65, October, 1972.

61.  Sebald, J. F., "A Survey of Evaporative  and  Non-Evaporative
    Cooling Systems," 74th National Meeting American Institute of
    Chemical Engineers, March 11-15, 1973.

62.  Selvidge, C. W., Conway, J. E.,  and  Jensen,  R.  H.,  "Deep
    Desulfurization of Atmospheric Reduced Crudes by RCD Isomax,"
    Japan Petroleum Institute Meeting, Tokyo, Japan, November 29,
    1972.

62a.  Short,  E.,  and Myers, L.H., "Pilot-Plant Activated Carbon
    Treatment of Petroleum Refinery Waste water".

63.  Skamser, Robert 0., "The U.S. Refining Outlook to 1980," 74th
    National Meeting American Institute  of  Chemical  Engineers,
    March 11-15, 1973.
                              185

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64. Solid Waste Disposal Study, Technical Report Genesee  County,
    Michigan,  U.S.  Department of Health, Education and Welfare,
    Bureau of Solid Waste Management, Cincinnati, 1969.

65. Standard Industrial Classification  Manual,  1967,  Executive
    Office of the President, Bureau of the Budget.

66. Standard Methods for Examination of Water  and  Waste  water,
    American   Public  Health  Association,  American  Waterworks
    Association,  Water  Pollution   Control   Federation,   13th
    Edition.

67. Stern, Arthur C., Air Pollution,  Vol.  Ill,  Academic  Press
    Inc., 1968.

68. Stramberg, J. B., "EPA Research  and  Development  Activities
    with Oxygen Aeration," Technology Transfer Design Seminar for
    Municipal  Waste  water Treatment Facilities, February 29 and
    March 1-2, 1972.

69. Strong, E. R., and Hatfield, R., "Treatment of  Petrochemical
    Wastes  by  Superactivated  Sludge  Process,"  Industrial and
    Engineering Chemistry, 46  (2): 308-315, February, 1954.

70. Strother, C. W., Vermilion, W. L., and Conner,   A.  J.,  "UOP
    Innovations  in  Design  of  Fluid catalytic Cracking Units,"
    Division of Refining, 37th Midyear Meeting, New York, May  8-
    12, 1972.

71. Stroud, P. W., Sorg, L. V., and Lamkin,  J.  C.,  "The  First
    Large  Scale Industrial Waste Treatment Plant on the Missouri
    River," 18th Purdue Industrial Waste conference, pp. 460-475,
    1963.


72. Thompson, C. S., Stock, J.,  and  Mehta,  P.  L.,  "Cost  and
    Operating  Factors for Treatment of Oil waste Water," The Oil
    and Gas Journal, pp. 53-56, November 20, 1972.

72a. U.S. Department of Health, Education  and  welfare,  "Public
    Health Service Drinking Water Standards", PHS Publication No.
    956,1962.

73. Walker, G.  J.,  "A  Design  Method  for  Sour  Water  Stream
    Strippers,"  National  Petroleum  Refiners Association, March
    23-26, 1969.

74. Watkins, C. H., and Czajkowski, G. J.,  "Hydrodesulfurization
    of  Atmospheric  and  Vacuum Gas Oils," 68th National Meeting
    American Institute of  Chemical  Engineers,  Houston,  Texas,
    February 28-March 4, 1971.

75. Wigren, A. A., and  Burton,  F.  L.,  "Refinery  Waste  water
    control,"  Journal of the Water Pollution Control Federation,
    44  (1):  117-128, January, 1972.

                                186

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                           SECTION XIV

                        GLOSSARY AND ABBREVIATIONS


Glossary


Acid Oil

Straight chain and  cyclic  hydrocarbon  with  carboxyl  group(s)
attached.

Act

The Federal Water Pollution Act Amendments of  1972.

Aerobic

In the presence of oxygen.

Alkylates

Branched paraffin hydrocarbons.

Anaerobic

Living or active in absence of free oxygen.

Aquatic Life

All  living  forms  in  natural  waters,  including  plants,  fish,
shellfish, and lower forms of animal life.

Aromatics

Hydrogen compounds involving a 6-carbon, benzene ring  structure.

Best Available Technology Economically Achievable  (BATEA)

Treatment required by July 1, 1983 for  industrial   discharge  to
surface waters as defined by section 310  (b)  (2)  (A) of the  Act.

Best Practicable Control Technology Currently  Achievable  (BPCTCA)

Treatment  required  by  July 1, 1977 for industrial discharge to
surface waters as defined by section 301  (b)  (1)  (A) of the  Act.



Best Available Demonstrated Technology  (BADT)

Treatment required for new sources as defined  by section  306  of
the Act.


                              187

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Biochemical Oxygen Demand

Oxygen used by bacteria in consuming a waste substance.

Slowdown

A  discharge from a system, designed to prevent a buildup of some
material, as in boiler and cooling  tower  to  control  dissolved
solids.

Butadiene

Synthetic hydrocarbon having two unsaturated carbon bonds.

By-Product

Material which, if recovered, would accrue some economic benefit,
but not necessarily enough to cover the cost of recovery.

Capital Costs

Financial charges which are computed as the cost of capital times
the  capital  expenditures  for  pollution  control.  The cost of
capital is based upon a weighted average of the separate costs of
debt and equity.

Catalyst

A substance which can change the rate of a chemical reaction, but
which is not itself involved in the reaction.

Category and Subcategory

Divisions of a  particular  industry  which  processed  different
traits which affect water quality and treatability.

Chemical Oxygen Demand

Oxygen consumed through chemical oxidation of a waste.

Clarification

The  process  of  removing  undissolved  materials from a liquid.
Specifically, removal of solids either by settling or filtration.
Coke Petroleum

Solid residue of 90 to 95 percent fixed carbon.

Cycles of Concentration

The  ratio  of  the  dissolved  solids   concentration   of   the
recirculating water to make-up water.

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Depletion or Loss

The  volume of water which is evaporated, embodied in product, or
otherwise disposed of  in  such  a  way  that  it  is  no  longer
available for reuse in the plant or available for reuse by others
outside the plant.

Depreciation

The cost reflecting the deterioration of a capital asset over its
useful life.

Direct-Fired Heater

A   heater   in   which   heat  is  supplied  by  combustion,  as
distinguished from a heat exchanger where heat is supplied  by  a
hot liquid or gas.

Emulsion

A  liquid  system  in  which  one  liquid  is finely dispersed in
another liquid in such a manner that the two  will  not  separate
through the action of gravity alone.

End-of-Pipe Treatment

Treatment  of  overall  refinery  wastes,  as  distinguished from
treatment at individual processing units.

Filtration

Removal of solid particles or liquids from other liquids  or  gas
streams  by  passing  the  liquid  or gas stream through a filter
media.

Fractionator

A generally cylindrical  tower  in  which  a  mixture  of  liquid
components is vaporized and the components separated by carefully
varying  the  temperature and sometimes pressure along the length
of the tower.

Gasoline

A mixture of hydrocarbon compounds with a boiling  range  between
100o and UOOo F.

Grease

A solid or semi-solid composition made up of animal fats, alkali,
water, oil and various additives.

Hydrocarbon

A compound consisting of carbon and hydrogen.
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Hydrogenation

The   contacting  of  unsaturated  or  impure  hydrocarbons  with
hydrogen gas at controlled temperatures  and  pressures  for  the
purpose  of  obtaining  saturated  hydrocarbons  and/or  removing
various impurities such as sulfur and nitrogen.

Industrial Waste

All wastes streams within a plant.  Included are contact and non-
contact waters.  Not included are wastes typically considered  to
be sanitary wastes.

Investment Costs

The  capital  expenditures  required  to  bring  the treatment or
control technology into operation.  These include the traditional
expenditures such as design; purchase of land and materials; site
preparation;  construction  and  installation;  etc.,  plus   any
additional   expenses  required  to  bring  the  technology  into
operation including expenditures to establish  related  necessary
solid waste disposal.

Isomer

A  chemical compound that has the same number, and kinds of atoms
as another compound, but a different  structural  arrangement  of
the atoms.

Mercaptan

An  organic  compound  containing  hydrogen,  carbon,  and sulfur
 (RSH) .

Microcrystalline Wax

A non-crystalline solid hydrogen with a melting  point  of  about
 106o to 195o F.  Also known as petrolatum.

Motor Octane Number

An expression of the antiknock value of gasoline.


Naphtha

A  petroleum  fraction,  including  parts of the boiling range of
 gasoline and kerosene, from which solvents are obtained.

 Naphthenic Acids

 Partially oxidized naphthalenes.

 New source

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Any building, structure, facility,  or  installation  from  which
there   is  or  may  be  a  discharge  of  pollutants  and  whose
construction is commenced after the publication of  the  proposed
regulations.

No Discharge of Pollutants

No  net  increase   (or  detectable  gross  concentration  if  the
situation dictates) of any parameter designated as a pollutant to
the  accuracy  that  can  be  determined  from   the   designated
analytical method.

Octane

The numerical rating of a gasoline's resistance to engine knock.

Olefins

Unsaturated  straight-chain  hydrocarbon compounds seldom present
in crude oil, but frequently in cracking processes.

Operation and Maintenance

Costs  required  to  operate  and  maintain  pollution  abatement
equipment.  They include labor, material, insurance, taxes, solid
waste disposal, etc.

Overhead Accumulator

A  tank  in  which  the  condensed  vapors  from  the tops of the
fractionators, steam strippers, or stabilizers are collected.

Paraffin Wax

A crystalline solid hydrocarbon with a melting point of  105o  to
155o F.

Petroleum

A  complex liquid mixture of hydrocarbons and small quantities of
nitrogen, sulfur, and oxygen.

PH

A measure of the relative acidity or alkalinity of water.   A  pH
of  7.0  indicates  a  neutral condition.  A greater pH indicates
alkalinity and a lower pH indicates acidity.  A one  unit  change
in pH indicates 10 fold change in acidity and alkalinity.

Phenol

Class of cyclic organic derivatives with basic formula C6HOH.

Pretreatment
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Treatment proved prior to discharge to a publicly owned treatment
works.

Process Effluent or Discharge

The volume of water emerging from a particular use in the plant.

Plant Effluent or Discharge After Treatment

The  volume  of  waste water discharge from the industrial plant.
In this definition, any waste treatment device is considered part
of the industrial plant.

Raffinate

The portion of the oil  which  remains  undissolved  and  is  not
removed by solvent extraction.

Raw

Untreated or unprocessed.

Reduced Crude

The  thick,  dark, high-boiling residue remaining after crude oil
has undergone atmospheric and/or vacuum fractionation.

Secondary Treatment

Biological treatment provided beyond primary clarification.

Sludge

The settled solids from a  thickener  or  clarifier.   Generally,
almost any flocculated settled mass.

Sour

Denotes  the  presence  of sulfur compounds, such as sulfides and
mercaptans, that cause bad odors.


Spent Caustic

Aqueous solution of sodium hydroxide that has been used to remove
sulfides, mercaptans, and organic acids from petroleum fractions.

Stabilizer

A  type  of  fractionator  used  to  remove   dissolved   gaseous
hydrocarbons from liquid hydrocarbon products.

Standard Raw Waste Loads  (SRWL)
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Net  pollution  loading  produced  per unit of production  (or raw
material)  by  a  refining  process  after  separation   of   the
separables (STS).

Stripper

A  unit  in  which  certain  components are removed from a liquid
hydrocarbon mixture by passing a gas, usually steam, through  the
mixture.

Supernatant

The layer floating above the surface of a layer of solids.

Surface Waters

Navigable waters.  The waters of the United States, including the
territorial seas.

Sweet

Denotes  the  absence  of  odor-causing sulfur compounds, such as
sulfides and mercaptans.

Topping Plant

A refinery whose processing is largely confined to oil  into  raw
products by simple atmospheric distillation.

Total Suspended Solids  (TSS)

Any  solids  found  in waste water or in the stream which in most
cases can be removed by  filtration.   The  origin  of  suspended
matter  may  be  man-made  wastes or natural sources such as silt
from erosion.

Waste Discharged

The  amount  (usually  expressed  as  weight)  of  some  residual
substance  which  is suspected or dissolved in the plant effluent
after treatment if any.

Waste Generated

The  amount  (usually  expressed  as  weight)  of  some  residual
substance  generated by a plant process or the plant as whole and
which is suspended or  dissolved  in  water.   This  quantity  is
measured before treatment.

Waste Loading

Total  amount  of  pollutant  substance,  generally  expressed as
pounds per day.


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Abbreviations






AL - Aerated Lagoon



AS - Activated Sludge



API - American Petroleum Institute



BADT - Best Available Demonstrated Technology



BATEA - Best Available Technology Economically Achievable



BPCTCA - Best Practicable Control Technology Currently Available



bbl - Barrel



BOD - Biochemical Oxygen Demand



bpcd - Barrels per calendar day



bpsd - Barrels per stream day  (operating day)



BS and w - Bottom Sediment and Water



ETX - Eenzene-Toluene-Xylene mixture



COD - Chemical Oxygen Demand



cu m - cubic meter(s)



DAF - Dissolved Air Flotation



DO - Dissolved Oxygen



gpm - Gallons per minute



k - thousand(e.g., thousand cubic meters)



kg - kilogram(s)



1 - liter



Ib - pound(s)




LPG - Liquified Petroleum Gas



M - Thousand  (e.g., thousand barrels)




MBCD - Thousand Barrels per calendar day



MBSD - Thousand Barrels per stream day



mgd - Million gallons per day




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 mg/L  -  Milligrams per liter  (parts  per  million)



 MM -  Million (e.g., million pounds)



 PP -  Polishing pond



 psig  -  pounds  per square inch, gauge  (above  14.7 psig)



 RSH - Mercaptan



 sec - second-unit of time



 scf - standard cubic feet of gas at 60o F and 14.7 psig



 SIC - standard Industrial Classification



 SRWL  -  standard Raw Waste Load



 SS -  Suspended Solids



 STS - Susceptible to Separation



 TOG - Total  Organic Carbon



 TSS - Total  Suspended Solids



 VSS - volatile Suspended Solids
ftU.S. GOVERNMENT PRINTING OFFICEU974 58Z-414/81 1-3      195

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