PB-243 222
RECYCLING OF WASTE OILS
NATIONAL OIL RECOVERY CORPORATION
PREPARED FOR
ENVIRONMENTAL PROTECTION AGENCY
JUNE 1975
DISTRIBUTED BY:
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4. TITLE AND SUBTITLE
. REPORT NO.
EPA-670/2-75-068
TECHNICAL REPORT DATA .
(Please read Instructions on the reverse before completing}
2.
5. REPORT DATE
June 1975
RECYCLING OF WASTE OILS
6. PERFORMING ORGANIZATION CODE
PB 243 222
- Issuing Date
7. AUTHOR(S)
Solfred Maizus
8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
National Oil Recovery Corporation
P.O. Box 338
Bayonne, New Jersey 07002
10. PROGRAM ELEMENT NO.
1BB041/ROAP 21AVJ;Task 06
11. CONTRACT/XJMWntW-
68-01-0177
Project No. 15680 HLB
12. SPONSORING AGENCY NAME AND ADDRESS
National Environmental Research Center
Office of Resaarch and Development
U.S. Environmental Protection Agency
Cincinnati, Ohio 45268
13. TYPE OF REPORT AND PERIOD COVERED
Final
14. SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
16. ABSTRACT
The objective of the work reported is the development of technology to
recycle waste oils to useful products, without producing undesirable
wastes. Both crankcase and other waste oils were studied in the labo-
ratory and in a 1000 barrel per day vacuum distillation pzxicess oper-
ated by National Oil Recovery Corporation in Bayonne, New Jersey. .Plant
operations demonstrated that vacuum distillation is a suitable process
for producing fuels from a wide variety of waste oils. Laboratory and
engineering studies showed that the distillate side pro^Ct J>*aSuced
from crankcase waste oil could be catalytically hydrotrfeated to produce
a lube with good odor, color, and stability characteristics. .Overall,
the vacuum distillation/hydrogen treatment process for re-refining
wgi'ste oils holds great promise. The distillation bottoms, containing
high concentrations of lead and other metals, can be used as a fuel in
secondary lead smelting. Pretreatment and chemical reduction agents
show promise in refining, but additional laboratory and evaluation work
is required. , Reproduced by
NATIONAL TECHNICAL
\( INFORMATION SERVICE
US Department ol Commerce
Springfield, VA. 22151 " ~ '
17.
KEY WORDS AIMU uuturvitN I
DESCRIPTORS
b.lDENTIFIEHS/OPEN ENDED TERMS c. COS AT I Field/Group
Oil Recovery
Oils
Materials Recovery
Waste Oil
Resource Recovery
Re-refining
Crankcase Oil
Waste Crankcase Oil
Oil Reuse
Oil Recycling
13B
18. DISTRIBUTION STATEMENT
RELEASE TO PUBLIC
19. SECURITY CLASS (ThisReportf
Unclassified
CvjDF PAGES
20. SECURITY CLASS (Thispage)
Unclassified
EPA Form 2220-1 (9-73)
mm SUBJECT
/
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EPA-670/2-75-068
June 1975
RECYCLING OF WASTE OILS
By
Project Director
Solfred Maizus
National Oil Recovery Corporation
Bayonne, New Jersey 07002
Contract No. 68-01-0177
Project No. 15080 HLB
Program Element No. 1BB041
Project Officer
Richard Keppler
Environmental Protection Agency
Region I
Boston, Massachusetts 02203
NATIONAL ENVIRONMENTAL RESEARCH CENTER
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
CINCINNATI, OHIO 45268
-------
REVIEW NOTICE
The National Environmental Research Center — Cincinnati
has reviewed this report and approved its publication.
Approval does not signify that the contents necessarily
reflect the views and policies of the U.S. Environmental
Protection Agency, nor does mention of trade names or
commercial products constitute endorsement or recommenda-
tion for use.
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FOREWORD
Man and his environment must be protected from the adverse
effects of pesticides, radiation, noise and other forms of pol-
lution, and the unwise management of solid waste- Efforts to pro-
tect the environment require a focus that recognizes the inter-
play between the components of our physical environment — air,
water, and land. The National Environmental Research Centers
provide this multidisciplinary focus through programs engaged in
• studies on the effects of environmental
contaminants on man and the biosphere, and
• a search for ways to prevent contamination
and to recycle valuable resources.
This report covers attempts to develop an economical way
of rerefining waste oils that might otherwise be wasted to
usable fuel products, attempts to minimize pollution, and in-
cidentally permits recovery of lead values.
A. W. Breidenbach, Ph.D.
Director
National Environmental
Research Center, Cincinnati
ill
-------
ABSTRACT
The objective of the work reported is the development
of technology to recycle waste oils to useful products/
without producing undesirable wastes. Both crankcase and
other waste oils were studied in the laboratory and in a
1000 barrel per day vacuum distillation process operated
by National Oil Recovery Corporation in Bayonne, New Jersey,
Plant operations demonstrated that vacuum distillation
is a suitable process for producing fuels from a wide
variety of waste oils. Laboratory and engineering studies
showed that the distillate side product produced from
crankcase waste oil could be catalytically hydrotreated
to produce a lube with good odor, color, and stability
characteristics. Overall, the vacuum distillation/hydrogen
treatment process for re-refining waste oils holds great
promise. The distillation bottoms, containing high con-
centrations of lead and other metals, can be used as a fuel
in secondary lead smelting.
Pretreatment and chemical reduction agents show promise
in re-refining, but additional laboratory and evaluation
work is required.
This report was submitted in fulfillment of Contract
Number 68-01-0177, by the National Oil Recovery Corporation,
Bayonne, New Jersey, under the sponsorship of the Environ-
mental Protection Agency.
iv
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TABLE OF CONTENTS
Page
Abstract iv
List of Figures vii
List of Tables viii
Acknowledgments xiv
Sections
I. Conclusions 1
II. Recommendations 3
III. Introduction 4
IV. Plant Operations 5
Description of NORCO Plant 5
Crankcase Waste Oils 11
Other Waste Oils 27
Operability Problems and Solutions 31
Pollution Control 33
V. Research Studies 39
Pretreatment 39
Lead Recovery From Crankcase Waste Oils 49
Catalytic Hydrogen Treatment 71
Chemical Reductions 73
Diesel Tests 111
VI. Design and Economic Studies 112
Process Screening Studies 112
Vacuum Distillation/Hydrotreating Process 119
Wastewater Treatment 122
VII. References 131
v
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TABLE OF CONTENTS (Continued)
Sections
VIII. Appendices I33
A. Summary Log of Operability-Problems
and Solutions
B. Log of Research and Development Work
C. Consultant's Reports on Waste Oil
Filtration 147
D. Commercial Centrifuge Experiments 155
E. Hydrotreating Analyses and Data
F. Diesel Engine Fuel Tests
G. Waste Oil Characterization Data
H. Coalescing Plate Oil/Water Separator 206
I. ASTM vs. Union Color Correlation 213
J. Process Screening Studies 214
K. Waste Oil Run Data 233
L. Manufacturer's Data on Hydrides 266
vi
-------
LIST OF FIGURES
No.
1, Crankcase Waste Oil Processing Flow Sheet
2, Vacuum Distillation Column '
3. Flow Diagram for GE Separator Test 37
4, Treatment of Crankcase Oil with DET-Experimental
Procedure 59
5 Sulfur Content of Overhead Distillate
Fractions of Used Motor Oil 61
6 Nitrogen Content of Overhead Fractions
of Used Motor Oil 62
7 Oxygen Content of Overhead Fractions
of Used Motor Oil 63
8 Acidity of Overhead Fractions of Used
Motor Oil 64
9 Vacuum Distillation/Hydrotreating Process
Hydrotreating Section 120
10 Wastewater Treatment Flow Diagram 123
VI1
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TABLES
No. Page
1 Principal NORCO Tankage 8
2 Log of Feed and Products 9
3 May 1973 Crankcase Waste Oil Run Flow Rates 14
4 May 1973 Crankcase Waste Oil Run Average 15
Conditions
5 Inspections for Crankcase Oil Run - 18
January 1974
6 Laboratory Distillation Data 19
7 January 1974 Crankcase Waste Oil Run - 20
Average Temperatures
8 January 1974 Crankcase Waste Oil Run - 22
Average Pressures
9 January 1974 Crankcase Waste Oil Run - 24
Steam Consumption
10 January 1974 Crankcase Waste Oil Run 25
Major Sources of Power Consumption
11 January 1974 Crankcase Waste Oil Run - Yields 26
12 Water Determination Method for Waste Oils 28
13 (Recommended Temperatures for Drying Waste 29
Fuel Oil
14 Typical Fuel Product in Tankage December 1972 30
15 Waste-water Quality When Processing 35
Miscellaneous Waste Oils
16 Wastewater Oil and Grease Content During 36
Miscellaneous Fuel Oil Runs - June-July 1973
viii
-------
TABLES (Continued)
No. Page
17 Wastewater Analyses - January 1974 38
Crankcase Waste Oil Run
18 Separation of Sludge and Water from 41
Crankcase Oil by Settling
19 Centrifugation of Crankcase Oils 42
20 Separation of Sludge and Water from 44
Crankcase Oil by Centrifugation
21 Consecutive Heating itnd Centrifugation of 45
Crankcase Supernatant Oils
22 Analysis of Solid Sludge From Centrifugation 46
of Raw Crankcase Oil
23 Solvent Miscibility Tests 47
24 Residue Produced by Solvent Treating of 48
Raw Crankcase Waste Oil
25 Butanol Treating Experiment 51
26 Butanol Treating Experiment 51
27 Butanol Treating Experiment 52
28 Distillation of n-Butanol-Crankcase 53
Oil Mixture
29 Solvent Treatment with 2-Amino Ethanol 54
30 Treatment of Supernatant Liquids From 54
Centrifugation with Tetraethylenepentamine
31 Solvent Treatment with 2-Amino-Ethanol 55
32 Treatment of Crankcase Oil with 57
Diethylenetriamine (DET)
33 Lead Recovery From Crankcase Waste Oils 60
IX
-------
TABLES (Continued
No. Pag
34 Centrifugation of Crankcase Oil Bottoms 66
35 "Dry Lead Ore" From Bottoms of Crankcase 67
Oil Bottoms Tank
36 Residue Separation From NORCO Crankcase Oil 67
Tank Bottoms by Naphtha Dilution and Settling
37 Solids Content of Crankcase Oil Bottoms 68
38 Upgrading Berk's Bottoms (from spill) by 69
Naphtha Dilution and Filtration
39 Solvent Treatment of Berk's Bottoms 70
40 Product Quality Improvement by Catalytic 72
Hydr©treatment of Crankcase Oil Distillate
41 Redistillation of Crankcase Oil Distillate 75
With and Without Potassium Borohydride
42 Redistillation of Crankcase Oil Distillate 76
With 0.0016% Potassium Borohydride
43 Redistillation of Crankcase Oil Distillate 77
With 1,25% Potassium Borohydride
44 Double Distillation with Sodixm Borohydride 78
to Improve Color
45 Redistillation of NORCO No. 3 (Light Side- 79
stream) Crankcase Oil Distillate With
0.001% Sodium Borohydride
46 Redistillation of NORCO No. 4 (Heavy 80
Sidestream) Crankcase Oil Distillate With
0.001% Sodium Borohydride
-------
TABLES (Continued)
No. Page
47 Redistillation of Crankcase Oil Distillate 81
with 0.016% Potassium Borohydride and
0.156% Aluminum Chloride
48 Effect of Temperature on Treatment of 84
Crankcase Oil Distillate with 0.12%
Sodium Borohydride
49 Redistillation of Crankcase Oil Distillate 85
With Sodium Borohydride—Effect of Concen-
tration
50 Redistillation of Crankcase Oil Distillate 85
With 0.012% Sodium Borohydride After
Washing With Potassium Hydroxide
51 Pretreatment of Crankcase Oil Distillate 86
With 10% H2S04vPrior to 0.024% Borohydride
Treatment
52 Pretreatment of Crankcase Oil Distillate 87
With 5% KOH Followed by 10% H2S04 Prior
to 0.012% Borohydride Treatment
53 Redistillation of Crankcase Oil Distillate 88
With 0.0012% Sodium Borohydride
54 Redistillation of Crankcase Oil Distillate 89
With 0.012% Sodium Borohydride
55 Redistillation of Crankcase Oil Distillate 90
With an Oil/Sodium Borohydride Mixture
56 Redistillation of Crankcase Oil Distillate 91
With Sodium Borohydride
57 Redistillation of Crankcase Oil Distillate 92
With 0.049% Sodium Borohydride
58 Treatment of Crankcase Oil Distillate With 93
0.01 Wt. % Sodium Borohydride at 600°F
for Six Minutes
xi
-------
TABLES (Continued)
59 Redistillation of Crankcase Oil Distillate 94
With 0.02% Sodium Borohydride After
Washing With Potassium Hydroxide
60 Deodorization of NORCO Blended Distillate 95
With Hot Water
61 Deodorizing Crankcase Oil Distillate 95
62 Deordorization of NORCO Blended Distillate 96
With 10% KOH Prior to Borohydride Treatment
63 Odor Reappearance After Redistillation of 97
Deodorized/Decolorized Crankcase Oil
Distillate
64 Redistillation of Crankcase Oil Distillate 98
With 0.016% Lithium Aluminum Hydride
65 Redistillation of Crankcase Oil Distillate 99
With 0.26% OMH-1
66 Redistillation of Crankcase Oil Distillate LOO
With OMH-1
67 Redistillation of Crankcase Oil Distillate 100
After Pretreatment With OMH-1
68 Redistillation of Crankcase Oil Distillate 101
With 0.13 Weight Percent OMH-1
69 Redistillation of NORCO No. 3 and 4 Blend 102
(50-50 by Volume) From January 23, 1974
Operation With OMH-1
70 Redistillation of Crankease Oil Distillate 103
With Borohydride Plus OMH-1 Treatment
71 Redistillation of Crankcase Distillate 104
Heavy Cuts From Previous Borohydride Plus
OMH-1 Experiments with 0.01% Sodium
Borohydride and 0.13% OMH-1
xxi
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TABLES (Continued)
No. Page
. _^^^^j^^^
72 Distillation of Raw Crankcase Oil With 105
0.005% Sodium Borohydride After Washing
With Potassium Hydroxide
73 Treatment of Raw Crankcase Oil with 10% 106
KOH and Distillation With 0.012% Sodium
Borohydride
74 Distillation of Raw Crankcase Oil Treated 107
With 0.24 and 0.36% Potassium Borohydride
75 Distillation of Raw Crankcase Oil Pretreated 108
With 0.24% Sodium Borohydride
76 Treatment of Raw Crankcase Oil With 0.36% 109
Potassium Borohydride—Effect of Pretreatment
77 Redistillation of Crankcase Oil Bottoms 110
With Potassium Borohydride
78 Screening Study Economics 113
79 Case Descriptions 115
80 Feed and Products 115
81 Profits 116
82 Costs 117
83 Summary of Crankcase Waste Oil Processes 118
84 NORCO Waste Oil Recycling Operations-Upgrading 126
of Wastewater Treating Facilities
85 Sizing of Major Treatment Plant Units 128
86 Projected Water Effluent Quality 130
Xlll
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ACKNOWLEDGMENTS
The work reported here was ably directed by
Mr. Solfred Maizus, with major contributions by
Mr. Seymour Maizus, Mr. Kenneth Urquhart, Mr.
Gerhart Weiss/ Dr. Jerome Geyer, and Dr. Norman
J. Weinstein. Special thanks are due to Mr.
Richard R. Keppler of EPA for his dedication as
Project Officer to the goal of a waste oil
recycling program which does not produce adverse
environmental impact. Mrs. Carol Picker has done
her usual amazing job producing the tables and
the manuscript.
xiv
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SECTION I
CONCLUSIONS
1. Extensive plant operations by NORCO have shown that
vacuum distillation is a suitable process for producing
low water content fuel from a uide variety of waste
oils.
2. NORCO's plant vacuum distillation experience and devel-
opment work on catalytic hydrogen treating have provided
the basis for a profitable process to produce lube
stocks from crankcase waste oils.
3. Lead-containing vacuum distillation bottoms from crank-
case waste oil processing can be considered as a fuel
and a source of lead in the secondary lead smelting
industry, but additional full scale tests are required.
4. Lead in vacuum distillation bottoms from crankcase
waste oil processing can be concentrated by additional
processing to 30% lead/ a material potentially useful
for lead recovery.
5. Commercially available anti-fouling agents are useful
for reducing vacuum distillation fouling problems.
6. Pretreatment of crankcase waste oil with two parts of
butanol to one part of crankcase waste oil to increase
yields and decrease fouling is a potentially attractive
method for improving the vacuum distillation/hydrogen
treating process, but development work is required.
7. Pretreatment of crankcase waste oil with low concentra-
tions of amines, or possibly ammonia, may decrease
vacuum distillation fouling/ but development work is
required.
8. Low concentrations of chemical hydrogenation agents,
e.g./ sodium borohydride, can reduce fouling problems/
and could possibly replace catalytic hydrogen treating,
but development work is required.
-------
9. The use of raw distillate from vacuum distillation of
crankcase waste oil as a diesel fuel without further
refining is questionable at best.
10. An economical wastewater system for a vacuum distilla-
tion process requires that indirect condensers and
mechanical vacuum pumps be used to minimize the
quantity of contaminated water.
-------
SECTION II
RECOMMENDATIONS
1. A large scale demonstration of a vacuum distillation/
hydrotreating process to re-refine crankcase waste
oil to high quality lube oil without producing waste
products.
2. Comprehensive full-scale tests for using lead-con-
taining vacuum distillation bottoms in secondary lead
smelting.
3. Continued research and development on chemical reduc-
tion methods for re-refining crankcase waste oils.
4. Study and demonstration of chemical emulsion breaking
systems to concentrate oil from high water content
oil/water wastes, e.g., ballast and bilge wastes from
oil tankers, oil tank cleaning wastes, oil spill
recovery wastes, etc.
5. Federal support should be considered for these
recommended programs.
-------
SECTION III
INTRODUCTION
Recent estimates show that only 80 million gallons per
year of re-refined lubricating oil is available and sold,
as compared to over one billion gallons per year of waste
lubricating oils generated in the U. S. Most of the re-
mainder is used as a fuel, used for road oiling and dust
control, or disposed of to the environment. This situation
is both wasteful, because of the high cost of producing
virgin lubes from special crude oils; and environmentally
damaging, because of fine metallic particles (including
lead from crankcase waste oils) emitted when burning many
waste oils. Indiscriminate waste oil disposal is harmful
to surface water and can also interfere with the operation
of wastewater treatment plants.
One of the major reasons for this unfortunate lack of
recycling is the absence of adequate technology which can
produce high grade lubricating oils, while minimizing or
eliminating wastes. Acid/clay treating, the most commonly
used re-refining process, produces acid sludge and spent
clay wastes. The acid sludge, a concentrated sulfuric
acid/polymerized hydrocarbon/metal contaminated mixture is
a highly undesirable waste, generally disposed of on land.
Such disposal can lead to water pollution problems. The
spent clay, which is much less hazardous, is also disposed
of on land. The technology used for handling other waste
oils, not suitable for lubricating purposes, is also gen-
erally inadequate.
The work discussed in this report was aimed at improv-
ing the technology of waste oil recycling so as to produce
useful products while eliminating or minimizing wastes. It
is an extension of an earlier program which showed that
vacuum distillation is a promising method for processing
waste oils. Both laboratory and commercial scale tests
(1000 barrels per day and higher) have been conducted to
meet the stated objective.
4
-------
SECTION IV
PLANT OPERATIONS
The National Oil Recovery Corporation (NORCO) facili-
ties in Bayonne, New Jersey accept a wide variety of waste
oils for reclamation and recycle. These range from automo-
tive crankcase waste oils to tank bottoms recovered during
tank cleaning operations, oil recovered from wastewater
treating systems, and oil recovered after spills. Most of
the lubricating type oils, such as crankcase waste oil, is
processed by vacuum distillation to produce cuts suitable
for further processing into lube oils or suitable for fuel
use. Most of the other waste oils received are contaminated
principally by water. These are dried by vacuum distilla-
tion and blended into fuels.
GENERAL PLANT DESCRIPTION
The NORCO plant equipment and operations were described
in an earlier report.1 Although some modifications have
been made, the basic equipment and flows are similar to the
descriptions in that report. An up-to*-date flow sheet and a
drawing of the vacuum distillation column are presented as
Figures 1 and 2.
In addition to the basic equipment shown, NORCO main-
tains about two million gallons of feed and product storage.
on this storage is provided in Table 1. Waste oils
received primarily from private collectors, in trucks
in size from about 1400 gallons to 7000 gallons.
waste oils are purchased in larger quantities and re-
ceived in trucks arranged by contract.
The waste oils are usually pumped directly into a large
holding tank. Samples are taken for BS&W (bottom sediment
and water) determination as necessary, depending on the oil
source and the supplier.
A log of feed and products produced is given in Table 2
Operating data are provided later in this section for crank-
case waste oil runs made in May 1973 and January 1974, and
for thirty other waste oil runs made from November 1972
through May 1973.
-------
tfvr
InocruNno* outHCAO
n> nw«
CRMRCMB HMT8 OIL fHOCKBSltV} HJOH •BDET
1
-------
•* VMVK OUTLET
3KKOMETKIC CONDEHSCR
INLET
~5ID£ FANS UtTH OMCRETE TILL-
i'C//?CU/.AT/W5 REFLUX
JM.ET
REFLUX AND HE*VY CUT
oun£T
3." LfV£L CONTROLLER
¥ BOTTOMS fVHK SUCTIOH
VACUUM DISTILLATION COLUMN
FIGURE 2
-------
Table 1. PRINCIPAL NORCO TANKAGE
(as of April 1, 1974)
DI;
TANK NOS.
1
2
3
100-109 (fien tanks)
110-117 (8 tanks)
129-230 (2 tanks)
205-209 (5 tanks)
FT.
40
40
40
15
10
20
15
16
HEIGHT
FT
30
30
30
42
24
20
42
16
NOMINAL
CAPACITY
OF EACH
GALLONS
NORMAL
SERVICE
280,000
280,000
280,000
551/000
14,000
47,000
55,000
24,000
Feed
Feed
Feed or
Bottoms
Product
Product
Feed
Feed or
Product
Feed or
Product
Total
1,895,000 gallona*
* Excludes miscellaneous small tanks and blending tanks.
-------
Table 2. LOG OF FEED AND PRODUCTS
2/15-3/15/74
1/15-2/15/74
12/15/73-1/15/74
11/15-12/15/73
10/15-11/15/73
9/15-10/15/73
8/15-9/15/73
7/15-8/15/73
6/15-7/15/73
5/15-6/15/73
4/15-5/15/73
3/15-4/15/73
- 150,750 gal. waste fuel oil processed and
103,870 gal. saleable reclaimed fuel oil
produced
- 55,840 gal. waste fuel oil processed and
38,640 gal. saleable reclaimed fuel oil
produced
- 169,130 gal. crankcase waste oil processed
and 161,680 gal. of saleable products pro-
duced including 45,000 gal. of 16.4°API
bottoms for NL Industries test
- No runs
- 236,200 gal. waste fuel oil processed and
161,200 gal. saleable reclaimed fuel oil
produced
- 295,200 gal. waste fuel oil processed and
212,200 gal. saleable reclaimed fuel oil
produced
- 161,040 gal. waste fuel oil processed and
99,960 gal. of saleable reclaimed fuel oil
produced
- 329,386 gal. waste fu^it oil processed and
216,552 gal. saleable reclaimed fuel oil
produced
- 379,048 gal. blended waste fuel oil (in-
cluding 40°API recycled naphtha) process-
ed and 280,839 gal. saleable reclaimed
fuel oil produced
- 485,400 gal. waste fuel oil processed and
386,389 gal. saleable reclaimed fuel oil
produced
- 58,750 gal
44,850 gal
produced
- 60,848 gal. crankcase oil processed to
produce 15,029 gal. bottoms, 37,300 gal.
dark lube oil, and 5,476 gal. fuel oil
- 288,396 gal. waste fuel processed and
226,964 gal. saleable reclaimed fuel oil
produced
- 267,658 gal. waste fuel oil processed and
200,726 gal. saleable recalimed fuel oil
produced
waste fuel oil processed and
saleable reclaimed fuel oil
-------
Table 2. (Continued) LOG OF FEED AND PRODUCTS
2/15-3/15/73
1/15-2/15/73
4/1/72-1/15/73
11/7-12/7/72
10/7-11/7/72
9/7-10/7/72
8/7-9/7/72
7/7-8/7/72
6/7-7/7/72
5/7-6/7/72
4/7-5/7/72
3/7-4/7/72
- 231,877 gal. waste fuel oil processed and
190,914 gal. saleable reclaimed fuel oil
produced
- 346,085 gal. waste fuel oil processed and
280,498 gal. saleable reclaimed fuel oil
produced
- 2,330,00$ gal. waste oil received. Bro-
duced 1,572,000 gal. recycled fuel oil
and 393,000 gal. of recycled crankcase
oil products
- 349,441 gal. waste fuel oil processed and
316,532 gal. saleable reclaimed fuel oil
produced
- 106,500 gal. waste fuel oil and 147,500
gal. waste lube oils processed
- 122,148 gal. waste fuel oil and 83,000
gal. crankcase waste oil processed
- 150,000 gal. waste fuel oil processed.
About 50,000 gal. free water evaporated
from the 250,000 gal. sludge, water, etc.
received from Pottstown (Berks)
- 100,000 gal. fuel oil produced
- 100,000 gal. fuel oil produced from low
sulfur oil (from Butterworthing) and some
shore storage tank bottoms. 90,000 gal.
fuel oil produced from oil from above
sources plus about 30% barge tank bottoms
containing about 40% water (pour point of
130°F reduced by the blending operation).
Both fuel oil and crankcase oil runs were
made
Both fuel oil and crankcase oil runs were
made
Several test runs were conducted
10
-------
CRANKCASE WASTE OILS
When sufficient crankcase waste oil, at least 40,000 to
80,000 gallons, has been received and, stored separately from
other waste oils* a run is conducted. Five products are re-
covered during such a run:
Flash Towar Naphtha
Vacuum Distillation Naphtha (#2)
Light Distillate (#3)
Heavy Distillate (#4)
Vacuum Distillation Bottoms
Referring to Figure 1, the crankcase waste oil is
pumped from a heated storage tank to a vertical coil heater,
where it is heated to about 200-210°F. The heater coil is
composed of 13-5 ft. turns of 3 in. schedule 40 pipe. The
oil leaving the furnace enters a 3 ft. diameter, 20 ft. high
flash column which is designed primarily to dehydrate the
raw oil. The flash column is fitted with a cyclone at the
outlet to minimize particle entrainment, and a % in. screen
at the bottom to prevent coarser;' solids from entering the
bottoms pump .
The flash column vacuum (19-22 in. Hg) is generated by
a single stage steam jet pump after a barometric condenser.
The condensed water and the flash tower naphtha (NORCO #1)
distilled overhead go to an oil/water separation tank from
which the bulk of the naphtha is recovered. The contamin-
ated water is discharged to the wastewater system which will
be described later in this Section.
The bottoms, at about 160 to 200°F, is pumped to the
vacuum fractionator furnace where the oil is heated and
vaporized, reaching a temperature of 600-700°F. The furnace,
fired by a single burner using plant fuel (usually naphtha) ,
is rated at about 8 million BTU/hr. fired, with a duty of
about 4-5 million BTU/hr. The furnace contains 84-12 ft. ,
4 in. O.D. tubes with a 1/8 in. wall thickness.
The oil leaving the furnace enters the vacuum fraction-
ator, where vacuum distillation naphtha (#2), light distil-
late (#3) , heavy distillate (#4) , and vacuum distillation
bottoms cuts are recovered. Both light distillate and heavy
distillate reflux streams are returned to the vacuum frac-
tionator at 150-200°F; the light distillate to the top of
the column, and the heavy distillate to the upper distilla-
tion tray.
11
-------
The fractionator (Figure 1) is maintained at about
27 in. Hg vacuum by a two stage steam jet with barometric
condensers. The oil/water mixtures from the condensers are
drained to a common sump and then to oil/water separators
for recovery of vacuum distillation naphtha and water
purification.
The light and heavy distillates withdrawn from the
vacuum distillation column each pass through stripping col-
umns. The liquid is removed from the bottom of each column
and split into reflux and product streams. The reflux and
distillate product streams, as well as the bottoms product,
are separately cooled in pipe coils submerged in a tank
through which cooling water from the Kill Van Kull is cir-
culated once-thru. The light distillate product cooler con-
tains 12-19 ft. 3 in. sections of 2 inch welded schedule 40
pipe with return bends; each of the other four coolers con-
tains 6 sections. Each of the products, whose temperatures
may vary from about 130°F for the light distillate to about
280°F for the bottoms, is then pumped to an appropriate
storage tank. The reflux streams are returned to the frac-
tionator as previously noted.
May 1973 Run
A crankcase oil run was made primarily to produce an
experimental quantity of 11.0 - 12.0° API bottoms for test-
ing by NL Industries to determine the practicality of using
the bottoms for fuel and as a lead source.
This crankcase oil run was interrupted three times by
mechanical difficulties: to renew the horizontal run of the
4 in. flash tower barometric condenser cooling water drain
pipe; to renew the drive belt on the fractionator heater
burner; and finally to renew the drive shaft of the burner.
Difficulty with the flow of light cut reflux was experienced
during the last part of the run because of tarry accumula-
tion and displacement of concrete filler on the top liquid-
washed side-to-side pan at the top of the fractionator.
None of the above problems was necessarily the result of
running crankcase oil, since all of this equipment is used
also for other waste oils. However, tar accumulation is
expected from crankcase oil distillation.
12
-------
An anti-foulant from Nalco Chemical Co. (D-59C08)was
injected into the crankcase oil charge (ahead of flash tower
furnace) and into the light and heavy dark lube oil cuts at
the rate of 50 ppm by weight at each point. The results
were very similar to those obtained when an anti-foulant
from Exxon was injected in 1969. * Fouling in heater tubes
appeared to be reduced. Also fouling in the light and heavy
lube oil cooling coils was somewhat reduced. The color of
these two products was slightly darkened/ to about L7.5 to
8.0 (ASTM) from a normal L7.0. The tarry material settling
in the bottoms of bottles of samples of the lube distillates
remains fluid and does not solidify and tenaciously adhere
to the bottom of bottles, as occurs without anti-foulant in-
jection. The odor seemed to be somewhat reduced. The Nalco
anti-foulant is considerably less viscous than that from
Exxon. The lubricators satisfactorily injecting the Exxon
anti-foulant are not dependable injecting the less viscous
Nalco anti-foulant.
The yields and operating conditions for this run are
reported in Tables 3 and 4. The bottoms produced had a
gravity of 11.9°API and were found by NL Industries to be
satisfactory for a full scale trial as a fuel in a reverbera-
tory furnace.
13
-------
Table
MAY 1973 CRANKCASE WASTE OIL RUN FLOW RATES
Start: May 17, 1973 Complete: May 25, 1973
(interrupted by mechanical problems)
Onstream Time: 39*2 hours
FEED
Gravity
QAPI
23.4
Total
Gallons
60,864
1554*
Flash Tower
Naphtha (#1)
Vac. Dist.
Naphtha (#2)
Light Distillate(#3) 31.1
Heavy Distillate(#4) 30.3
Bottoms
Water + LOSS +
UTILITIES
Cooling Water
Steam for Stripping
Steam to vacuum pumps
Steam to fractionator
Steam to bottoms pump
Steam to tank heaters
Total steam produced
60,864 1,554.0
_2_00_GPM_
0
700 Ibs/hr
0
50 Ibs/hr
155 Ibs/hr
9-05-
Yield
Vol. %
46.1
33.2
31.1
30.3
11.9
__
913
5,478
37,310
15,027
2,136
23.3
139.9
952.6
383.7
54.5
1.5
9.0
61.3
24.7
3.5
100.0
* 888 barrels/day
+ unaccounted for
14
-------
Table 4. MAY 1973 CRANKCASE WASTE OIL RUN
AVERAGE CONDITIONS
Flash heater inlet
Flash heater outlet
Flash tower vapor outlet
Flash tower bottom
Fractionator heater inlet
Fractionator heater outlet
Fractionator flash zone
Fractionator bottom
Fractionator top
Flash tower
Fractionator bottom
Flash heater inlet
Fractionator heater inlet
Steam boiler
Temperatures, °F
72
200
161
160
158
670
630
610
250
Pressures
20-21 in. Hg. vacuum
27.2 ±n« Hg. vacuum
12 psig.
54 psig.
105 psig.
15
-------
January 1974 Run
A brief but successful crankcase waste oil run was con-
ducted in January 1974 during which special attention was
given to obtaining process data useful for design purposes.
The run started on January 22 and was shut down four days
later on January 26 because of a shortage of feed. Before
the run started, the following vessels were opened , cleaned,
inspected and closed: fractionator; flash tower; light and
heavy product reflux accumulators; and light and heavy pro-
duct stripper.
Feed and product inspections are sumi.-xrized in Table
5 and 6. They show high chlorine values '~>^ all fractions,
and surprisingly high lead contents in the ligltv fractions.
This lead may be due to volatile lead compounds, Xjr to fine
particulate entrainment. A previous analysis of attend of
the two NORCO vacuum sidestream distillates (#3 and f<) show-
ed a lead content of 2 ppm.
Average run conditions are shown in Tables 6-10.
are estimated in Table 11. As can be seen, this particular
run provided a high yield of vacuum distillation bottoms at
the expense of lube stock yield, providing a light, rela-
tively low viscosity, low lead bottoms easier to handle for
the NL Industries combustion tests .
Two anti-fouling additives were used during this run.
Nalco Additive No. D-59C08 was injected into the cold crank-
case oil charge prior to the flash heater, and sodium boro-
hydride was injected into the light and heavy distillate
product reflux accumulators. Additive rates were as follows:
Nalco D-59C08 50 ppm by weight
Sodium Borohydride 275 ppm by weight (total NaBH4)
as a 12 weight % solution in
40% NaOH solution
In order to detect the effect of the sodium borohydride, the
vacuum distillation tower was opened and inspected after the
run. The following observations were made (see Figure 2) :
16
-------
Tower Bottom
In normal runs the deposit is hard. During this run
the deposit was softer and looked like asphalt.
Cyclone Deck
There was very little deposit in this section. The
sodium borohydride appears to have inhibited deposit
formation.
Top of 6 ft.Section
There were fewer deposits than previously noted.
Top of Light Cut Section
A hard rubber like deposit came out of this section
from the top tray. This deposit is considered unusual.
Light End Stripper
The bottoms from the accumulator showed a dark/ heavy
residue. In previous runs the residue had been hard,
but in this run it was soft and greasy.
None of the deposits appeared to be serious, but the run was
too short to draw definite conclusions.
However, simple sodium borohydride injection in this
run did not provide the color improvement found during
research studies reported in Section V.
17
-------
Table I. raspecTxaa TO* CJWSKCASI oil mm - JAHDART 1174
SM9LE DESCXIFTXOH
»I Gravity t 60°r
Carbon. Ht. %
Hydrogen. wt. »
Sulfur. Mt. t
Kitroqen. wt. ft
CMocine. Kt. %
Bromine. Ht. ft
Ash, Ht. %
Water, wt. ft
Lead, ppn
Per.tane Insol., Ht. %
Viscosity | 100°r, sec.
ASTH Color
Flash. °T
Corrosion. 3 hre 1 2i2°F
Con. Carbon. %
Heut. No., 09 KQB/9
Pour Point (ASTM) , °F
IBP, °F
10ft Recovery
Recovery, ft
Cracked, °F
reel Flash !•!)
Kaphtha
1/2S-8AM l/2S-13Pa
24. 4 — 34.?
85.37 85.02
12.81 12.27
0.11
0.11 0.03
0.56 IS. 2
1.57
4.0
6800
7.25
_
—
«
H
—
„
185
0.02
1.1
__
—
H
_ _
~
Vec.Dlet. (I:
Naphtha
1/2S-8A*
35.1
85.78
12.15
0.21
0.63
0.81
...
Trace
35
0.02
2.79
112
_ —
—
..
_ —
—
> Vnasat e
1/25-4PH
11. 60
16.10
11.52
0.19
None
0.61
0.11
O.I
IS
0.28
78
4.2
245
rasies/U
0.06
1.32
416
__
—
'stlllation U«St Distill]
l/2!-12noon 1/25-8UI
a.n —
__
0.097
Traea
0.1)
(0
4.2
240
--
__
_^
'ii.35-
UB
0.010
Trace
0.011
7«
4.1
240
"™"
-
__
*» (13)
1/24-4MI
0.034
Trace
0.041
110
5.0
255
~~
"
~~
~™
__
l-<%3?
8«.»
11.1
0.19
0.02
0.09
0.062
0.2
9
0.019
104
4.5
250
Paeeea/lB
••
0.81
9
*~
~~
~
1/22-8MI
~~
0.151
0.2
0.81
100
4.2
245
— —
II
™
™
* ~
Venn
1/26-4PK
~~
0.15
trac*
0.20
259
8+
410
—
..
~~
~—
"~
UK OlstlllatlOB Heavy Distillate (14)
1/29-4M 1/24-4M 1/23-6PM 1/22-8PM
10.00 29.90 29.73 59. »J
86.61 — 86.58
11.22 — 11.11 —
0.16 — 0.17 —
0.01 — None
0.16 - --
0.084
trace
14
0.11
24C
8.0
420
Posses/IB
0.16
0.11
292
•~
~~
--
0.014
trace
0.081
2(6
7.0
425
™
..
—
~~
"*™
o.oe
0.099
trace
10
0.21
296
6-8
430
Faaaee/lB
0.06
0.22
IS
"
~~
~~
—
0.114
tree*
0.20
250
0*
420
™
—
~-
~~
~
Vac. Diet
Bottoete
1/25-8AM
u.i —
•5.87
12.38
0.61
0.54
0.27
0.21
4.49
16,000
6.01
160 (122*17
440
—
—
~~
~*
~
-------
Table 6. LABORATORY DISTILLATION DATA
(ASTM Distillation D-86)
LIGHT DIST. HVY. DIST.
(#3) (#4)
1/25/74-4 PM 1/25/74-4 PM
Initial Boiling Point, °F 368 414
5% Recovery 535 665
10% 606 678
12% — 680
20% 647 690
30% — 692
40% 678 695
50% 688 698
60% 690
70% 694
80% 707
Final Boiling Point 712 714
% Recovery 86 55
19
-------
Table 7. JANUARY 1974 CRANKCASE WASTE OIL RUN
AVERAGE TEMPERATURES
Flash heater inlet 51
Flash heater outlet 200
Flash tower vapor outlet 152
Flash tower bottom 152
Fractionator heater inlet 121
Fractionator heater outlet 607
Fractionator flash zone 593
Fractionator bottom 588
Fractionator top (wapor outlet) 203
Vapor space above hvy reflux inlet 406
Heavy cut at additive mixer 528
Light cut at additive mixer 238
Heavy cut at stripper inlet 542
Light cut at stripper inlet 243
Bottoms Cooler Inlet 547
Bottoms Cooler Outlet 283
Heavy Reflux Cooler Inlet 506
Heavy Reflux Cooler Outlet 176
Light Reflux Cooler Inlet 230
Light Reflux Cooler Outlet 156
20
-------
Table 7 (Continued) JANUARY 1974 CRANKCASE
WASTE OIL RUN
Op
Light Distillate Cooler Inlet 234
Light Distillate Cooler Outlet 131
Heavy Cooler Outlet 206
Line to 1st Stage Vacuum Pump 42
Line to 2nd Stage Vacuum Pump 135
Cooling Water Intake 41
Cooling Water Discharge 54
Ambient 40
21
-------
Table 8. JANUARY 1974 CRANKCASE WASTE OIL RUN
AVERAGES PRESSURES
Flash Heater Inlet
Flash Heater Outlet
Fractionator Heater Inlet
Fractionator Heater Outlet
Fractionator Flash Zone
Fractionator Bottom
Vacuum Fractionator Barometric
Condenser Outlet 28.4
Light Cut Drawoff 28.9
Heavy Cut Drawoff 28.3
Heavy Stripper Inlet 28.1
Light Stripper Outlet 28.2
Bottoms Cooler Inlet 6
Bottoms Cooler Outlet 3
Heavy Reflux Cooler Inlet 45
Heavy Reflux Cooler Outlet 43
Heavy Distillate Cooler Outlet 43
Light Reflux Cooler Inlet 41
Light Reflux Cooler Outlet 8
Light Distillate Cooler Inlet 31
Light Distillate Cooler Outlet 30
Flash Barometric Condenser Outlet 23.4
1.4 psig
14.2 in. Hg vacuum
32 psig
20.8 in. Hg vacuum
28.1 in. Hg vacuum
28.1 in. Hg vacuum
in. Hg vacuum
in. Hg vacuum
in. Hg vacuum
in. Hg. vacuum
in. Hg vacuum
psig
psig
psig
psig
psig
psig
psig
psig
psig
in. Hg vacuum
22
-------
Table 8. (Continued) JANUARY 1974 CRANKCASE WASTE
OIL RUN
Steam Boiler 103 pgig
Water Pump 25 psig
23
-------
Table 9. JANUARY 1974 CRANKCASE WASTE OIL RUN
STEAM CONSUMPTION
Flash Tower Vacuum Pump
Fractionator Vacuum Pumps
Bottoms Pump
Heavy Cut Stripper
Light Cut Stripper
Fractionator
Control Room
Ibs./hr,
131
456
69
0
0
0
12
668
24
-------
Table 10. JANUARY 1974 CRANKCASE WASTE OIL RUN
MAJOR SOURCES OF POWER CONSUMPTION
220 Volts, 3 Phase
Water pump
Heavy cut pump
Light cut pump(S)
Light cut pump(N)
Flash tower bottoms pump (Viking)
Flash tower bottoms pump (Imo)
Test separator pump (Moyno)
Air compressor
Feed pump
Flash Heater Burner
Fractionator Heater Burner
Fractionator Heater Blower
Compressor - South Boiler
Burner - South Boiler
Fuel Pump - North boiler
Burner - North Boiler
Motor
RPM
1755
3450
1730
1760
1140
3500
1170
1740
1155
3450
1750
1160
3500
1730
1160
3500
Amps
64.8
26.
13.
27.
15.
8.
22
19
22.
3.
8.
9.
20
2.
5.
25.
294
8
6
0
0
4
4
9
8
8
0
4
_4_
Hp.
25
10
5
10
5
3
7.5
7.5
7.5
1.5
3
3
7.5
h
1.5
10
108
25
-------
Table 11.
JANUARY 1974 CRANKCASE WASTE OIL RUN
Start: January 22, 1974
Onstream Time: 90 hours
Feed
Products
Flash Tower Naphtha (#1)
Vac. Dist. Naphtha (#2)
Light Distillate (#3) \
Heavy Distillate (#4) /
Bottoms
Water (Flash Tower)
Loss (unaccounted for)
Stop: January 26, 1974
Total
Gallons
169,000
Gallons/
hr.
1879*
Vol.
%
1,000
36,800
80,400+
45,000
5,500
400
169,100
11
409
893
500
61
—
0.6
21.8
47.5
26.6
3.3
0.2
lOOTTO"
* 1074 barrels per stream day.
+ Approximately 58% light distillate, 42% heavy distillate.
26
-------
OTHER WASTE OILS
During the period covered by this Report, NORCO accept-
ed waste oils from a multitude of sources. Considerable
plant and laboratory effort was consumed in characterizing
waste oils and in converting them to useful products. Dif-
ficulty in measuring water content of very wet oils was
ocercome as shown in Table 12.
The following represents a few of the oil sources and
characterizations. Additional data are provided in Appendix
G, and in Section V.
- Oil stored in 20x20 South Tank (charge for run
no. 9), 10-15% water, 8.5 to 29.5°API, depending
on sampling point.
- Oil from tank cleaning, 33.8% H^O, 0.9% sediment.
- Oil from an industrial separator, 1.4% t^O,
0.74% sediment.
- Tank bottoms, 50.2% BS&W.
- Oil from a spill cleanup, 47.6% H20, 13.5% ash
- Oil from barge cleaning, 0-90%
The prinicpal methods used for upgrading the wide
variety of waste oils received were settling in tanks ,
drying by distillation, and blending. Drying operations
were conducted in the vacuum distillation column, bypassing
the flash column used in crankcase waste oil operations.
The vacuum column was generally run at about 22-26 in. Hg
vacuum, and at a bottom temperature near that recommended
on Table 13. The throughput was limited primarily by the
water content of the oil being run.
Product characteristics were largely a function of the
feed type . Extensive blending was used to produce saleable
fuel oil. Table 14 provides an example of processed fuel in
storage .
Data for 28 runs using blended waste oils are reported
in Appendix K.
27
-------
Table 12. WATER DETERMINATION METHOD FOR WASTE OILS
Determination of water content in many waste fuel oils
cannot be satisfactorily obtained by the usual centri-
fuging tests, ASTM D1796 and ASTM D2709, because of
formation of a gel which precipitates in the bottom of
the centrifuge tube. Water in the oil apparently com-
bines with various compounds in the oil to form the gel
in a total volume which bears no direct relation to the
volume of water. If the sample is diluted 1:1 with
naphtha or kerosene and distilled in a mariner somewhat
like that described in the test ASTM D-95, the water
content can be accurately and reliably determined.
Modification of apparatus and procedure in distillation
test ASTM D-&S provides rugged inexpensive apparatus
and satisfactory procedure for determining water content
over a very wide precentage range. The sample may be
heated and distilled to the required temperature to
drive over all water much faster than when following the
procedure specified in distillation test ASTM D-86.
Also the dilution with naphtha or kerosene may be varied
according to viscosity and probably water content, judged
from gravity and appearance.
Following are some typical determinations made in
this way using a 50-50 mixture of waste oil and benzene,
Load No.
1
2
*jt
4
S
7
8
27
48
H20
66.0
76.6
73.3
50.0
70
90
66
50
60
% Sediment
3.0
3.0
3.0
3.0
3.0
1.3
3.0
2.0
1.0
Total BS&W
69.0
79.6
76.3
53.0
73.0
91.3
69
62
61
-------
Table 13. RECOMMENDED TEMPERATURES FOR
DRYING WASTE FUEL OIL
Fractionator Boiling Point Recommended
Vacuum of Water Fractionator
in. Hg °F Bottom Temp. , °F*
29 76.5 117
28 100 140
27 114 154
26 124.5 165
25 133 173
24 140 180
23 146 186
22 152 192
21 157 197
20 161 201
18 169 209
16 176 216
14 182 222
12 187 227
10 192 232
8 197 237
6 201 241
4 205 245
2 209 249
Atmospheric 212 252
*40°F over boiling point, °F (heater stack limited to
660°F and heater inlet limited to 62 psig.)
29
-------
Table 14. TYPICAL FUEL PRODUCT IN TANKAGE DECEMBER 1972
Gravity
Flash Point P.M. C.C.
Viscosity, S.U. § 100°F
Viscosity S.F. i 122°F
Pour Point
Sulfur, ASTM D1552
Water & Sediment
BTU/gallon
Ash
25.0°API
206°F
350 sees.
24.9 sees.
minus 25°F
0.37%
0.3%
144,632
0.04%
30
-------
OPERABILITY PROBLEMS AND SOLUTIONS
Operability problems encountered with crankcase waste
oils in a vacuum distillation type process have been dis-
cussed in a previous report.1 Mechanical and other problems
encountered because of the wide variety of waste oils pro-
cessed in recent operations are discussed in Appendix A,
along with discussion of solutions to many of the problems
considered.
The crankcase waste oil problems are related primarily
to oil instability, the tendency of the oil to form poly-
meric materials, especially at elevated temperatures but
also at moderate temperature. This is true for the dis-
tillation products as well as the raw oil. The chemistry
of this problem and methods of pretreatment are considered
in Section V.
As discussed earlier in this section and in the earlier
report,1 anti-fouling additives are hlepful even though, not
totally effective. These may be expected to cost less than.
0.1C per gallon of oil for 50 ppm of the Nalco or similar
types, but the cost of the borohydride used in the January
1974 crankcase oil run would exceed 1C per gallon. Insuf-
ficiant experience was accumulated to determine optimum
concentration or justification for anti-fouling additives.
The importance of careful design to minimize serious
fouling during crankcase waste oil operations cannot be
overemphasized. For example:
1. Tower internals should be simple and should not
allow accumulation of liquids. Mist eliminators
tend to foul and have been replaced by cyclonic
type mist separation in both the flash column
and the vacuum fractionator. Spray decks in the
upper section of the fractionator were filled
with concrete to prevent liquid accumulation
and tar formation.1
2. Furnaces must be designed to minimize extreme
fouling caused by high tube metal temperature,
even at the expense of higher capital cost.
Flue gas recycle practiced by NORCO and internal
furnace modification to prevent excessive radia-
tion have improved operation.
31
-------
3. Furnaces, heat exchangers, and product coolers
must be designed for easy access to allow fast
cleanout when fouling does occur, or spares
must be provided.
4. Product accumulators are useful where settling
of solids can occur without causing serious
fouling problems such as in lines, valves, or
pumps. A screen is used in the bottom of the
flash column to avoid such problems.
These design approaches are useful in improving operability,
but do not contribute to improved lube distillate quality.
This can be accomplished only by treatment, such as with.
clay or with hydrogen.
Other waste oils may cause problems similar to crank-
case oil, but other problems also arise as discussed in
Appendix A. The most serious of these are solids deposition
throughout the system, but especially in furnace tubes, and
erosion due to sand and other foreign materials which con-
taminate many "garbage oils." Here, design solutions such.
as suggested above, are important as is filtration prior to
processing and anti-erosion design. The elimination of
sharp turns, the use of extra-hard materials, and especially
the replacement of elbows which plugged tees have been found
to be helpful. The foreign material tends to accumulate in
the plugged branch of the tee, providing an erosion resis-
tant surface.
32
-------
POLLUTION CONTROL
Because most processing systems are closed and because
the waste oils normally encountered are high boiling and
low in sulfur, air pollution has not been a problem in
NORCO's operations. Very little odor is noted from the
oil/water separator area, from tank vents, or from the
vacuum system. Therefore, it is noL believed to be neces-
sary to provide air pollution controls in the type of oper-
ation conducted to date. As will be discussed in Section
VI, hydrogen treatment will produce small quantities of
gaseous emission which may require some form of control.
On the other hand, wastewater from the processing plant
must be monitored and controlled for oil and possibly other
pollutants. The four primary sources of oil emissions are:
1. Oil vaporized when distilling or drying crankcase
or other waste oils which contaminates steam
condensate from steam jet vacuum pumps and steam
stripping, cooling water used in barometric con-
densers, and water which is also vaporized from
wet oils.
2. Oil remaining in water removed from tanks where
primary oil/water separation takes place.
3. Oil which leaks from coolers into the cooling
water.
4. Spills and leaks in process areas which contam-
inate surface runoff waters.
In the present NORCO operation, the greatest volume of oil
contaminated water arises from the first source, as shown
below:
GPM
Flash tower barometric condenser (normally 7T5
used only for crankcase waste oil)
Vacuum distillation barometric condensers 180
Product co&lers (contaminated only when leading) 50
Boiler blowdown minor
Tank withdrawals and runoff water variable
All wastewater is processed through the oil/wate&r separation
system.
33
-------
Barometric condenser effluents undergo primary oil/
water separation in tanks to recover the bulk of the oil
present. The contaminated water effluent from these tanks,
with other wastewaters, pass through two oil/water separa-
tors in series. These separators each have a holding
capacity of about 7300 gallons, providing a total residence
time of 49 minutes when the flow rate is 300 GPM.
Oil separation from discharged water appears to be
highly variable as shown in Tables 15-17. Oil and phenol
contamination appear to be higher when processing crankcase
waste oil than when other waste oils are processed. At
times, the oil content of the intake water from the Kill
Van Kull appeared to be extraordinarily high, The waste-
water discharge data reported here are consistent with
previously reported information on other waste oil pro-
cessing plants.8
A General Electric Model OPC-50 oil/water separator
was tested during the January 1974 crankcase waste oil run
as to suitability for oil removal from wastewaters. The
separator is a gravity type designed to achieve total
laminar flow of the wastewater from the input manifold,
through baffles, and through a combination of specially
configured coalescing plates and packs. With a flow head
of approximately two feet to maintain capacity flow, the
unit operates at atmospheric pressure with essentially no
pressure drop from inlet to outlet. While the wastewater
flows through the separator horizontally, the oil adheres
to the plates and moves vertically through the specially
configurated plate banks. When the oil reaches the liquid
surface level in the separator, it is automatically skimmed
off by a passive float device that can also control the oil
layer thickness to insure that water-free oil is removed
from the separator. The separator can be run under an inert
gas blanket, and a coalescing media pack can be provided for
final polishing, but these options were not used in this
test. A sketch of the separator and a more detailed des-
cription may be found in Appendix H.
The GE OPC-50 separator provided a nominal residence
time of 14 minutes at 100 GPM (neglecting internals). The
test flow scheme is shown in Figure 3. Data obtained at
60 to 100 GPM flow rate through the GE separator are shown
in Table 17. The separator removed 90-98% of the oil, but
the high inlet loading prevented really effective cleanup.
The GE separator could be considered for final cleanup
after conventional gravity separators.
34
-------
Table 15. WASTEWATER QUALITY WHEN PROCESSING
MISCELLANEOUS WASTE OILS
Sate
(1973)
2/14-15
2/21-23
2/26-27
3/5-6
4/9-10
4/25-26
4/30-5/1
5/31
May Crank -
case Oil
Run
Sample
CW In*
Out+
CW In
Out
CW In
Out
CW In
Out
CW In
Out
CW In
Out
CW In
Out
CW In
Out
CW In
Out
Oil
Ppm
< 20ND
209
-
-
-
-
-
-
-
-
< 1ND
2.4
-
-
-
-
—
-
Phenol
ppm
<0.05ND
5.1, 0.1
0.15
0.8
-
-
-
-
<0.05ND
16
<0.05ND
5
<0.05ND
5
<0.05ND
2
<0.05ND
14, 10
pH
6.8
6ol5
7.72
6.65 1'
7.2
6.75
7.1
6.6
7.25
5.2
6.9
6.15
7.15
6.0
6.85
5.95
7.15, 7.1
5.45, 5.3
TOC
EE2L
350,360
17,425,380
312,575
* From Kill Van Kull- CW = cooling water.
+ Leaving 2nd oil/water separator
35
-------
Table 16. WASTEWATER OIL AND GREASE CONTENT DURING
MISCELLANEOUS FUEL OIL RUNS - JUNE-JULY 1973
Oil & Grease, ppm
In_ Out
June 1973 103 124
<1 ND <1 ND
13 90
38 70
68 31
<1 ND 2
July 1973 6 16
97 54
6 10
5 21
8 35
<1 ND 2
9 14
6 13
-------
U>
-4
SOUTH
SEPARKFOK,
?M/g>-C
QRiFfce PUMP
WCHAR.GE W/VTEK TO
KILL VAN KULL.
FLOW DIAGRAM FOR GE SEPARATOR TEST
FIGURE 3
-------
u>
CO
Table 17. WASTEWATER ANALYSES - JANUARY 1974 CRANKCASE WASTE OIL RUN
mg/1
Sample
Sample Time
Date (All PM) pH
Cooling Water Inlet
GE Separator Inlet
GE Separator Outlet
Discharge to Kill*
Cooling Water Inlet
GE Separator Inlet
GE Separator Outlet
Discharge to Kill*
Cooling Water Inlet
GE Separator Inlet
GE Separator Outlet
Discharge to Kill*
Cooling Water Inlet
GE Separator Inlet
GE Separator Outlet
Discharge to Kill*
1/23/74
1/24/74
1/25/74
1/26/74
2
I!
n
n
6.8
6.4
6.0
6.5
7.2
6.4
6.5
6.5
7.5
6.7
6.5
6.7
7.1
6.6
6.7
6.9
Total
Suspended
Solids
8
11
5
14
23
36
53
47
6
26
20
35
47
81
24
50
Phenols
0
9
10
10
0
10
14
6
0
12
12
6
0
12
12
6
Oil
Content
0
2100
40
1200
0
2500
450
1250
0
2000
200
500
0
2800
100
700
TOG
18
560
430
350
18
420
380
310
17
380
365
425
11
575
377
312
GE Separator Outlet Temperature approximately 44 F
* Kill Van Kull
-------
SECTION V
RESEARCH STUDIES
The research conducted in this program was aimed pri-
marily at improving methods of recycling crankcase waste
oils. They consisted of:
- laboratory and field studies of methods for pre-
treatment, designed to avoid problems in pro-
cessing crankcase waste oils by distillation;
- laboratory studies of bottoms/ and other lead
containing fractions;
- laboratory studies of catalytic hydrogen treat-
ment to improve color, odor/ and other properties
of lube distillates;
- laboratory studies of chemical reductions with
hydrides to improve color, odor/ and other
properties of lube distillates; and
- diesel engin tests^on a distillate fraction.
In addition, considerable laboratory work was done to char-
acterize both crankcase and other waste oils, and water
effluents. These data are covered in Section IV.
PRETREATMENT
Pretreatment experiments were conducted both to try to
separate existing sludge and metals in crankcase waste oil,
and to eliminate precursors to further sludge formation
during processing. These precursors appear to be products
of crankcase oil reactions with blowby gases, such as nitro-
gen oxides. Precursors can be related to nitrogen oxide
compounds present in the used oil.2 Tfefi use of cjwas&ia afid
centrifugation pretreatmeht has been described previously.8
In this work, centrifugation .experiments with and without
solvents succeeded i^u separating me-cals and sludge, and
treatment with amines appeared to improve oil stability.
39
-------
Centrifugation
As shown in Table S6, some separation of sludge and
water does occur from crankcase waste oil by settling
This can be enhanced by dilution with naphtha. However,
the process is slow and incomplete. The difficulties of
filtration, as an alternative, are described in Appendix C.
The centrifugation experiments in Tables • 19-44 clearly
show that, although high speed centrifugation succeeds in
removing sludge and water, the recovered oil remains un-
stable and new sludge is formed at 250°F from precursors
(Table 21). As expected, separated sludge contains a wide
variety of metals as shown by semi-quantitative speeto-
graphic analysis. Quantitative analysis for Pb, Ba» Zn,
and Ca showed 2.4, 1.4, 1.1, and 0.9 weight percent respec-
tively (Table 2(2) . Commercial centrifuge experiments des-
cribed in Appendix D were relatively unsuccessful because
a force of only about €000 x G was obtainable and because
of difficulty in solids discharge. However, -the use of
butanol, which will be described ; under Solvent Hreatweftt*.
did improve solids separation to some extent.
Solvent Treatment
The following solvents were screened to test their
ability to coagulate and precipitate impurities in crankcase
waste oil: methanol, ethanol, n-propanol, -isopropanol,
n~butanol, isobutanol, pentanol, cyclohexanol, tolttene,
methyl ether, methylethylketone , acetone, antyl alcohol,
glycerol, n-heptanol, hexanol, 2-furaldehyde, furfurol,
iclodecanoi, tetraethylenepentamine, phenol, n-oc-fe'anol,
;3So-*octaflol, 2-aminoethanol, hexane and naphtha (Tables
.22 and SS) . Por'.the data in Table 84, solvent U«atios of
1 to 4 volumes per volume of raw crankcase -waste oil were
shaken in a separatory funnel and allowed to Settle for
several days. The light solvents such as •metfia'hol and
ethanol showed little precipitation power. The more pro-
'mising solvents, as -determined by visual observation of
precipitation power, were studied further to Determine the
relative amovlnts of precipitate produced. In t:he 10/000 x
G one hour experiments, the supernatant solve'ht phases
appeared very bright for cyclohexanol/ butanol, and octanol,
as compared to a dark oil supernatant liquid where 'no
solvent was used.
40
-------
Table 18. SEPARATION OF SLUDGE AND WATER FROM CRANRCASE OIL
BY SETTLING
Vol. % Water and Sludge on Standing*
- - - - '
1 Hour 3 Hours 24 Hours 48 Hours Residue"*"
Crankcase
Oil - - 12 -
Crankcase
Oil/Naphtha
(1:1) 8.3 21.7 25.0 - 2.0
Crankcase
Oil/Naphtha
(2:1) 10.0 - 20.0 - 2.2
* Volume % based on oil only
(specific gravity of water layer = 1.016)
+ After 72 hrs. standing, decanting water layer,
1 hr. centrifugation at 10,000 G. Based on
oil only. Oil layer dark-bright.
41
-------
Table 19. CSNflllFUGATIQKt OF CBANKCASE OILS
to
Charge: *
Solvent
Solvent/CCO+
Centrifugation, G
min
Wt. % water
Wt. % residue
Phases
Top Phase
Charge:*
Solvent
Solvent/CCO+
Centrifugation, G
min
Wt. % water
Wt. % residue
Phases
Top Phase
GCO-1
Naphtha
1/1
it, ooo
60
2.00
CCO (E)
0/1
10,000
60
0.5
1.8
~
"™"
CCQ-1
Naphtha
1/1
5,000
6Q
2.02
CCO-2
o/i
10,000
60
1.3
2
Dark
CCO (A)
0/1
10,000
€0
15.0
1,5
CCO-2
Naphtha
1/4
10,000
60
1.5
3
Dark
CCO(B)
0/1
10,000
60
1.5
1.3
CCO-2
Phenol
1/10
10,000
60
1.8
3
Bright
CCO(C)
0/1
10,000
60
1.0
1.4
CCO-2
Phenol
1/5
10,000
60
1.7
3
Bright
CCO(D)
0/1
10,000
60
1.0
1.6
CCO-1
Naphtha
1/1
10,000
30
1.92
—
* CGO-1 = raw crankcase oil from NORCO tankage (batch 1)
CCO-2 = raw crankcase oil from NORCO tankage (batch 2)
CCO(A), CCO(B), §£e. = raw crankcase oil from supplier A, B, etc.
„ wt. ratio
? Preheated to 13QOp prior to centrifuging
-------
Table 19. CENTRIBUGATION OF CRANKCASE OILS (Continued)
to
Charge: *
Solvent
Solvent/CCO+
Centrifugation, G
min
Wt. % water
Wt. % residue
Phases
Top Phase
Charge:*
Solvent
Solvent/CCO+
Centri fugation, G
min
Wt. % water
Wt. % residue
Phases
Top Phase
CCO-1
Naphtha
1/1
5,000
30
1.96
-
CCO-2*
0/1
5,000
60
0.91
~
CCO-2 CCO-2 CCO-2 CCO-2
n-Butanol n-Butanol - Naphtha
1/1 1/4 0/1 1/4
5,000 5,000 5,000 5,000
30
1.54
-
CCO-2*
Naphtha
1/4
5,000
60
1.43
—
~
30
1.27
-
CCO-2*
Naphtha
1/2
5,000
60
1.70
—
«*
60
0.69
2
CCO-2
o/i
3,000
60
0.69
2
Cloudy
60
1.55
3
CCO-2
Naphtha
1/4
3,000
60
1.10
3
Cloudy
CCO-2
Naphtha
1/2
5,000
60
1.93
3
CCO-2
Naphtha
1/2
3,000
60
1.37
3
Slightly
Cloudy
-------
Table 20. SEPARATION OF SLUDGE AND WATER FROM
CRANKCASE OIL BY CENTRIFUGATION
Charge: Oil/Naphtha =1:1
3,000 G 5,000 G
Volume %
Water
Color of
Oil
Residue,
wt. %*
10,OQOG
30 min. 60 min. 30 min. 60 mxn. 30 min. 60 rnigT
1.9
30
30
Dark
Brown
2.0
2.2
1.
30
30
Dark
Bright —
2.3
1.9
* Based on oil only
44
-------
Table 21. CONSECUTIVE HEATING AND CENTRIFUGATION
OF CRANKCASE SUPERNATANT OILS
Original charge—Raw crankcase waste oil
Heating Phase—250°F for 60 minutes (with stirring)
Centrifugation—32,000 G for 60 minutes
Heating -I- Centrifugation + Residue Washing + Decanting
= 1 Cycle
Cycle Wt %
No. Residue"*"
1 1.3 (8 tests/1.26-1.40)
2 0.10 (4 tests/0.08-0.11)
3 0.05 (4 tests/0.048-0.055)
4 0.13 (4 tests/0.12-0.14)
5 0.09 (4 tests/0.09-0.10)
6 0.10 (4 tests/0.09-0.10)
7 0.05 (4 tests/0.04-0.06)
8 0.05 (4 tefets/0.04-0.07)
Based on supernatant liquid charged to cycle indicated.
45
-------
Table 22. ANALYSIS OF SOLID SLUDGE FROM CENTRIFUGATION
OF RAW CRANKCASE OIL
PPM by Semiquantitative Spectrographic Analysis
7000-
70/000
Ca (8,900)
Pb (23,620)
700-
7000
P
Mg
Fe
Si
Al
C«
En (10,600)
' 70-
700
B
Mn
Sn
Cr
Ni
Mo
Ti
1-
70
As
V
Zr
In
Co
Bi
0.7-
1
§1
Ag
<0.7
Be
Ba (13,700) Sr
Not Detected: Sb, Nb, Cd, Na, K, Hg
Procedure: Approximately 40 g. samples of used crankcase
oil were centrifuged in 50 ml. conical tubes
to obtain a sludge that was oil wetted (Sorvall
Model SS-1 high speed centrifuge), The oil
wetted solids were further washed with pentane
to arrive at dry solids which were analyzed
(further drying at 100°C overnight yielded a
30% weight loss). Dry solids approximately
2% of original oil.
46
-------
Table 23. SOLVENT MISCIBILITY TESTS
1 part solvent: 1 part raw crankcase oil
at room temperature
1. Hexane - completely miscible
2. Butanol - 2 phases—dark sediment on bottom,
light red layer on top
3. Pentanol - 1 phase
4. Methyl ether - 2 phases—80% bottom dark,
20% top red
5. Toluene - 1 phase
6. Methyl ethyl ketone - 2 phases—dark deposit on
sides, black oil on top
7. Methanol - 2 phases (very distinct)—top yellow
layer
47
-------
Table 24. RESIDUE PRODUCED BY SOLVENT TREATING
OF RAW CRANKCASE WASTE OIL
Centrifugation at 32,000 G for 1 hr.
wt. % Residue
Solvent/Oil Ratio IT 1;1 2:1 3:1 "TsT
No Solvent* 4.1 -
isopropanol* - 4.1 4.4 5.4
isobutanol* - 3.6 4.2 - 6.5
n-butanol* - 4.4 4.1 - 17.7
2-aminoethanol# - 15.3 16.4 18.5 21.0
cyclohexanol - 8.4 7.5 6.8
Centrifugation at 10,000 G for 1 hr.
wt. % Residue
Solvent/Oil Ratio 0 1:1 2;1 3:1 4:1
No Solvent 3.3
isopropanol - - - - 6.3
isobutanol - - - - 8.3
n-butanol - 3.7 4.4 6.9 7.0
Centrifugation at 10/000 G for 1 hr.+
wt. % Residue
Solvent/Oil Ratio ~0~ 1;1 2:1 371 37T
n-butanol** - ~27T 172" 175" ~TT6~
cyclohexanol# - 2.2 2.2 2.6 3.3
n^heptanol - 2.1 2.1
hexanol - 2.1 2.4
2-furaldehyde - 1.7 1.9
furfurol - 2.2 2.2
Centrifugation at 10,000 G for 30 min.
wt. % Residue
Solvent/Oil Ratio ""0""" 1:1 2;1 3~7I 4TT~
Na Solvent 2.6 - ~ ~^~ —T~~
dodecanol - 2.7 2.7
octanol - 2.9 3.3 2.6
* Residue pentane~washed
+ Residue pentane washed twice followed each time by
10,000 G for 15 min.
f 3 phases present
** 4 phases present
48
-------
The high residue observed with 2-aminoethanol (Tables
24 and 29) could indicate either a high precipitation effi-
ciency or reaction of the solvent itself. Most likely, at
least some reaction occurs.
The alcohol group shows real promise for precipitation.
A process based on isopropanol has been proposed.11 In the
present work, n-butanol was pursued further, including the
engineering feasibility study reported in Section VI, and
some simple treating experiments shown in Tables 25-28.
Treatment with butanol results in an oil with a clear red-
dish cast and a sweet odor. The odor can be eliminated by
treatment with hot water or vacuum evaporation, but subse-
quent high temperature distillation restores a "burnt" odor.
Work with various amines, shown in Tables 29-32, indi-
cates that these can accomplish precipitation similar to
the solvents previously discussed, but with lower concen-
trations. Odor seems to be reduced by amine treatment,
probably by reaction with carbonyls. Color is sometimes
intensified, possibly by reduction of nitrogen oxide com-
pounds forming azo groups. Inexpensive amines or ammonia
could be considered as agents for sludge precipitation, but
further investigative work is required.
LEAD RECOVERY FROM CRANKCASE WASTE OILS
Lead concentrates can be recovered from tank bottoms
and pretreatment precipitates (Table 33), or from vacuum
distillation bottoms. The distillation bottoms, or unvapor-
ized portion of the crankcase waste oil fed to the vacuum
distillation column, contains virtually all of the unpre-
cipitated metals and high boiling polymerized fractions of
the oil, as well as some hydrocarbons which could be con-
sidered potentially valuable as lubricating stock. The oil
serves as a carrier for the impurities, but in actual fact
should be minimized to the extent possible. To minimize
the quantity of bottoms, it is necessary to operate at as
high a vacuum and as high a temperature as possible, limited
by cracking in the preheat furnace and in the distillation
column.
Previous studies have shown that impurities in crank-
case waste oil, such as nitrogen and oxygen, also tend to
concentrate in the bottoms fraction,3 These data are repro-
duced as Figures 5-8. Properties of typical bottoms frac-
tions are provided in Section IV.
49
-------
The crankcase waste oils available at the time this
work was done (most gasoline leaded) contained on the order
of 1% lead, with significant quantities of calcium, zinc,
and barium. Based on taking a 5 to 20 percent bottoms cut
from crankcase waste oil feed, the bottoms lead content
would then be about 5 to 20 weight percent.
50
-------
Table 25. BUTANOL TREATING EXPERIMENT
Charge: 70 ml. raw crankcase waste oil
120 ml. butanol
30 ml. pentane
20 ml. acetone
2~TO~
Results: Immediate dropout of sludge.
Centrifuged for 1 hr.
Distillation: Mixture heated in water bath with vacuum
applied to flask. 50 ml. oil recovered
from flask dark (6+ color) with only a
very faint smell of alcohol. Alcohol
recovered had a yellowish tinge.
Chromatographic
Treatment: 10 ml. of above oil passed over 10 g. of
a 24/40 granular material (Georgia-
Tennessee Mining & Chemical Co., Harrison,
N.J.)_._ No change in color.
Table 26- BUTANOL TREATING EXPERIMENT
Charge: 40 ml. butanol
160 ml. raw crankcase waste oil
Results: Solids separated in centrifuge
Distillation:
Mixture heated in water bath to 65°C water
temperature at 27 in. Hg vacuum. 68 ml.
left in flask after a few hours. Alcohol
remaining in flask as detected by odor.
51
-------
Table 27. BUTANOL TREATING EXPERIMENT
Charge: 160 ml. butanol (80 Vol. %)
40 ml. raw crankcase waste oil (20 Vol. %)
Results: About 2% by weight solids separated in
centrifuge
Distillation: About 130 ml. of solvent came off at 110-
118°C. As temperature rose in the distilla-
tion an acrid smell was noted in the oil.
An IR examination showed acid present which
had been previously absent (butyric) .
52
-------
Table 28. DISTILLATION OF n-BUTANOL-CRANKCASE
OIL MIXTURE
Charge: 250 ml of 1:1 n-butanol/crankcase oil mixture
after centrifuging for 30 min. at 10,000 G
Liquid Still Vapor
Temp, °C Temp, °C Cut, ml.
99 87 1st drop over
102 94 17.5 (5 ml. bottom layer)
105 95 12.5 (3 ml. bottom layer)
109 96 14.5 (2.5 ml. bottom layer)
115 103 17.0 (1.0 ml. bottom layer)
119 110 20.5 (no bottom layer)
120 113 24.6 (no bottom layer)
120 113 30.0 (no bottom layer)
120 113 30.5 (no bottom layer)
120.5 113 30.0 (no bottom layer)
125 115 20.5 (no bottom layer)
217.6
(Some alcohol still in bottoms)
Added 250 ml. of fresh charge to bottoms
103 92 1st drop over
107 94 25
109 98 50
115 105 75
118 110 100
121 111 150
123 111 175
133 110 210
20 end
230" ml.
Recovered 48 ml. of bottoms
Recovery = 217.6 + 230 + 48 = 99%
500
Cumulative
-------
Table 29. SOLVENT TREATMENT WITH 2-AMINO ETHANOL
Residue After Centrifugation
At 10,000 G for 30 min.
Solvent/Oil Ratio 1;1 0.5;1 0.1
Number of Phases 3
Vol. % - Top Phase 62.5
Vol. % - Middle 37.5
Wt. % - Residue 18.1 19.8 9.0 2.6
Table 30. TREATMENT OF SUPERNATANT LIQUIDS FROM
CENTRIFUGATION WITH TETRAETHYLENEPENTAMINE
a. 1 part by wt. of naphtha to 2 parts crankcase oil
centrifuged at 32,000 G for 30 min.
(Top layer = 1.58 ml/g. crankcase oil)
b. Top layer heated to 120°F with 1 part tetraethylene-
pentamine to 10 parts original crankcase oil charge
and centrifuged at 32,000 G for 30 min.
(Top layer = 0.96 ml/g. original crankcase oil charge)
c. Residue washed with pentane twice
(% Residue, based on original crankcase oil charge,
- 1.0)
54
-------
Ui
U1
Table 31. SOLVENT TREATMENT WITH 2-AMINO-ETHANOL
Oil Charge*
Wt. Ratio, Solvent/
Oil Charge
Centrifuge Speed, G
Centrifuge Time, min,
Separation
Top, ml/g oil
Bottom, ml/g oil
Residue Treatment"1"
Wt. % Residue
Distillate Distillate Distillate
1/10
5000
60
1/4
5000
60
1/2
5000
60
CCO
1/10
5000
60
0.65
1.01 1.04 0.99
0.04 0.15 0.25
Washed with 20 ml P/twice with 20 ml M/
twice with 20 ml 3:1 P:M/twice with P
@ 5000 G, 15 min. —
2.13 2.15 2.00 1.95
CC©
0
5000
60
0.70
0.27
1.19
* CCO = raw crankcase waste oil
+ P = pentane; M - methanol; i-P = isopropanol
-------
Table 31. SOLVENT TREATMENT WITH 2-AMINO-ETHANOL (Continued)
Oil Charge*
Wt« Ratio, Solvent
Oil Charge
Centrifuge Speed, G
Centrifuge Time, ndn.
Separation
Top, ml/g oil
Bottom, ml/g oil
Residue Treatment*
Wt. % Residue
CCO
1/10
3&00
30
0.70
CCO
1/10
5000
30
0.75
3 washes with washed with
1:1 i-P:P/once 1:1 i-P:P
with P g 3000 G
1.55 1.98
4:1 CCO/Naphtha
1/4
5000
60
1.40, 0.90
washed 4 times with
1:1 i-P:P/once with P
0.8, 2.0
Ui
o\
-------
Table 32. TREATMENT OF CRANKCASE OIL WITH
DIETHYLENETRIAMINE (DET)
Charge: Raw crankcase oil
Procedure: 1. Centrifugation @ 31,890 G for 30 minutes
to remove the preformed solids.
2. Vacuum distillation of the desludged oil
to remove light ends and water. The ter-
minal temperature at the still was 431°F
and the vapor temperature was 392°F.
3. To obviate reaction of the amine with acids
in the used oil, a 10 weight percent solu-
tion of 30% pottassium hydroxide was added
to each sample that was treated. The mix-
ture was then heated with agitation for 1
hour @ 150°F. (Each experiment involved
two samples.)
4. The oil was again centrifuged @ 10,000 9
for 30 minutes.
5. The residue was carefully washed and the
percentage recorded.
6. Variable amounts of DET were added to the
supernatant oil, and heated for one hour
@ 150°F.
7. The oil was again centrifuged at 31,890
G for 30 minutes.
8. TSe percent residue was determined.
9. An equal percentage of DET was again added
with agitation for one hour at 150°F.
10. The oil was centrifuged at 31,890 G for
30 minutes.
11. The percent residue was determined.
The accompanying Figure 4 illustrates the procedure followed,
57
-------
Table 3|. TREATMENT OF CRANKCASE OIL WITH
DIETHYLENETRIAMINE (DET) (Continued)
Experiment Experiment
No. 1 No. 2
Additive
Residue" affeet
15% DET
Heat Only
No KOH Treat.
KOH Treatment 0.58%, 0.68% .56%,. 59%
(Step 5)
Experiment
No. 3
5% DET
2.2%, 2.1%
Residue after
Additive Treat. 1.11%, 1.27% .346%,. 343% 1.9%, 3.2%
(Step 8)
Residue after
Additive Treat.2 0.15%, 0.16% .22%, .21%
(Step 11)
0.27%, 0.50%
Total Deposits 1.83%, 2.11% 1.13%, 1.15% 4.4%, 5.8%
58
-------
Crankcase Oil
(1) Centrifuge
oil
Deposits
(2) Distill
(3) KOK
A "
Oil
(4) Centrifuge
(5) Deposits
Oil
Oil
(6) Amine
(7) Centrifuge
(8) Deposits
(9) Amine
(10)
TREATMENT OF CRANKCASE
OIL WITH DET-EXPERIMENTAL
PROCEDURE
FIGURE 4
NOTE: See Table
for results
59
-------
Table 33. LEAD RECOVERY FROM CRANKCASE WASTE OILS
1. NORCO tank bottoms (green)+ 42.92% Pb*
2. Sludge obtained by centrifugation
(Centrico bowl type) of crankcase
waste oil 13.52% Pb
3. Sludge obtained by centrifugation
(Centrico bowl type) of crankcase
waste oil treated with 2 parts of
butanol/part oil 15.88% Pb
* By semi-quantitative spectrographic analysis
10-100%—Pb; 1-10%—Ca; 0.1-1.0%—Mg, Fe, Al,
Cw, Si, Zn, Ba? 0.01-0.1%—Cr, Sn, Ni, V, Mo/
Mn, Ti; 0.001-0.01%—B, Bi, Ag, Sr; Not Detected-
P, Sb, As, Nb, Be, Zr, Cd, In, Na, Co, K, Hg
"""Bottoms from tank holding vacuum
distillation bottoms fraction.
60
-------
0.4
Figure 5
SULFUR CONTENT OP OVERHEAD DISTILLATE FRACTIONS
OF USED MOTOR OIL3
0.3 -
Texas (W) Used Oil
Neater/Faust Semi-Worka Spinning Band
Distillation Column Operated with 5/1
Reflux Ratio and 500 ml/hr Boil-up Rate.
•a
0.2 •
3
(/J
0.1 -
10 20 30 40 50 60
Volume Percent Distilled Overhead
70
80
61
-------
0.10 n
Figure 6
NITROGEN CONTENT OF OVERHEAD FRACTIONS OF
USED MOTOR OIL
0.075'
Texas (W) Used Oil
Neater/Faust Semi-Works Spinning
Band Distillation Column Operated with
5/1 Reflux Ratio and 500 nd/hr
Boil-Up Rate.
M
I
0.050-
•H
•z.
0.025-
10 20 30 40 50 60
Volume Percent Dili tilled Overhead
70
80
62
-------
1.0 T
Figure 7
OXYGEN CONTENT OF OVERHEAD FRACTIONS OF USED MOTOR OIL8
0.75-
Texas (W) Used Oil
Nester/Faust Semi-Works Spinning
Band Distillation Column Operated with
5/1 Reflux Ratio and 500 ml/hr
Boil-up Rate.
M 0.50-
S
C
3
0.25-
10 20 30 AO 50 60
Volume Percent Distilled Overhead
70
80
63
-------
1
SB
g
8
OJ
Vi
u
9
41
2
1.4
1.2
i.o •
0.8 -
0.6 •
).4 '
0.2-
Figure _8
ACIDITI OF OVERHEAD FRACTIONS OF USED MOTOR OIL *
Texas (U) Used Oil
Nester/Faust Semi-Works Spinning
Band Distillation Column Operated
with 5/1 Reflux Ratio and 500 ml/hr
Boil-up Rate.
10
• • 'i • •
20 30 40 50 60 70
Volme Percent Distillad Overhead
80
64
-------
This fact led to investigation of the possibility of lead
recovery. Two major avenues were investigated. In the
first, the lead was further concentrated into a solid mater-
ial/ in the second the bottoms fraction was prepared for
introduction into secondary lead smelting as a fuel.
Lead Concentration
Lead in the bottoms fraction can be concentrated by
treating with naphtha to precipitate the solids, followed
by evaporation of volatile hydrocarbons from the precipi-
tated solids. Supporting data are shown in Tables 34-^36.
Solid material containing 32.6% lead, prepared as shown
in Table 35, was sent to the American Smelting and Refining
Company for laboratory evaluation. The evaluation showed
that, although lead recovery from this fraction was feasi-
ble, special processing schemes would have to be developed
to handle it because of the hydrocarbons present.
Similar iwork and solvent treating tests were conducted
on other lead-containing fractions, and on heavy bottoms
material recovered from the Schuylkill River following a
hurricane jerk's bottoms). These are reported in Tables
37-39.
Use of Bottoms in Secondary Lead Smelting^
At the end of 1971, there were 23 firms operating
approximately 45 secondary lead smelting plants in the IKS.1*
Reverberatory, blast, and pot furnaces are commonly used in
these plants. Both reverberatory and blast furnaces must
be protected by high efficiency air pollution control equip-
ment to minimize particulate (and lead) emissions to the
atmosphere. In the reverberatory furnace, a large refrac-
tory chamber, lead scrap material is fed and melted by
firing burners directly into the chamber. In the blast
furnace (similar to the blast furnace used in iron making)
lead scrap is mixed with coke, which acts both as a fuel
and as a reductant, and fed to the top of the furnace. Air
is introduced at the furnace tuyeres. Molten slag and lead
are removed from the base of the furnace.
65
-------
Table 34. CENTRIFUGATION OF CRANKCASE OIL BOTTOMS
Charge:*
Oil Layer, ml/g+
Water Layer, ml/g+
Residue, wt. %+
%Pb in Charge
% Pb in Oil Layer
% Pb in Residue
%-C in Residue
Other Metals in
Residue
1-10%
0.1-1%
0.01-0.1%
0.001-0i01%
-------
Table 35.
Procedure:
Product:
"DRY LEAD ORE" FROM BOTTOMS OF CRANKCASE OIL
BOTTOMS TANK
Mixture of 3 parts of naphtha to one part
of bottoms settled for two weeks; supernatant
decanted; solids pentane washed and dried on
a room radiator.
Solids dry to touch
32.6 % Pb
31.5 % C
1-10 % Si, Zn, Ca, Ba
25-40 % volatile at 400°F (avg. 32 %)
Table 36. RESIDUE SEPARATION FROM NORCO CRANKCASE OIL
TANK BOTTOMS BY NAPHTHA DILUTION AND SETTLING
CHARGE: 300 gallons of bottoms from crankcase
oil tank
PROCEDURE: Mixture of 3 parts NORCO naphtha to 1 part
bottoms allowed to settle for 14 days.
Supernatant liquid decanted leaving 180 Ibs,
of solids (approx. 7.2 wt. %)
PRODUCT: Volatiles at 220°F (overnight) - 26.9%
Lead content - 11>7 wt. %
Carbon content - 38 wt. %
67
-------
Table 37. SOLIDS CONTENT OF CRANKCASE OIL BOTTOMS
NORCO Bottoms* Berks Bottoms"1"
Charge:
Result:
Charge:
Result:
10.0495 g. oil
10.4865 g. pentane
10.3864 g. oil
10.4642 g. pentane
After centrifuging 30 rain, at 32,000 G
1.7602 g. solids 2.3390 g. solids
(17.51 % solids) (22.54 % solids)
179.5 g. oil
179.5 g. pentane
After one month settling
50.0 g. residue (wet with pentane)
(27.85% solids)
* NORCO settled bottoms - 0.9725 s.g.
+ Berks aged bottoms - 1.0507 s.g.
68
-------
Table 38. UPGRADING BERK'S BOTTOMS (FROM SPILL) BY
NAPHTHA DILUTION AND FILTRATION
After 1:1 dilution
with 43° API naphtha
As and filtration through
Recovered Buchner Funnel
47.6 2.3
13.5 1.0
80.2 99.
0.060 0.008
1.1 0.13
0.40 0.08
0.004 0.001
0.31 0.01
0.57 0.07
0.06 0.01
0.02 0.002
0.42 0.05
0.006 0.001
0.34 0.09
3.8 0.06
2.3 0.04
0.008 0.002
0.008 0.001
0.21 0.04
Water
Ash on Ignition
Combustibles
Cu
Ba
Ca
Cr
Al
Fe
Mg
Mn
Na
Ni
P
Pb
Si
Sn
Ti
Zn
69
-------
Table 39. SOLVENT TREATMENT OF BERK'S BOTTOMS
Treat
Results
Solvent
Amyl Alcho.i/
10% P
Amyl Alcohol
Amyl Alcohol/
10% P
Amyl Alcohol/
10% P
Methanol/10% P
Methanol/10% P
Methanol/10% P
50% Methanol/
50% P
Isopropanol/
10% P
Isopropanol/
10% 5
Isopropanol/
10% P
Amyl Alcohol/
10% P
Amyl Alcohol/
10% P
50% Butane Diol/
50% MEK
ml oil/
ml Solvent
5/5
5/5
4/8
2/8
5/5
4/8
2/8
2/8
5/5
4/8
2/8
5/5
2/8
5/5
mi
5
5
5
4
-
7
-
-
6
6
5
6
2
01
.5
.0
.4
.4
.5
.5
.5
.5
.5
.5
1 hr
1 Solvent
Cloudy
Good Septn.
Good Septn.
Good Septn .
SI. Cloudy
Cloudy Yellow
Coagulated
Coagulated
SI. Cloudy
SI. Cloudy
SI . Cloudy
Good Septn.
Good Septn.
Coagulated
5 days
ml oil
5.0
5.0
4
4.5
4.2
-
7.5
7.1
6.5
6.5
5.5
6.5
2.2
8.8
Solvent
Clear/
Dark
Yellow
Coagulated
Clear
Coagulated
Coagulated
SI. Yellow
SI. Yellow
Light Yellow
Good Septn.
Good Septn.
Coagulated
P = Pentane
-------
Based on preliminary tests conducted by NL Industries,
and an analysis of lead smelter operations, it is felt that
the most promising method of using the crankcase waste oil
bottoms in secondary lead smelters is to replace or par-
tially replace the fuel normally fired in the reverberatory
furnace. In this way, both fuel and lead values could be
realized, with the lead contained in the bottoms captured
either in the furnace or in the baghouse used for air pol-
lution control. The baghouse material is normally recycled
for lead recovery.
After preliminary tests showed that combustion of the
bottoms was feasible, a decision was made to conduct a full
scale test on a reverberatory furnace in an NL Industries
plant. The work was done under a grant from the U. S.
Environmental Protection Agency. The results will be re-
ported in the near future in a separate document.
CATALYTIC HYDROGEN TREATMENT
Hydrogen is commonly used as a reagent in conventional
petroleum refining to remove sulfur and nitrogen from petro-
leum fractions. The finishing of lube stocks with hydrogen.
has largely replaced acid and clay treatment* Hydrogen
treatment is usually conducted at 300 to 1000 psi and 500
to 700°F over catalysts containing a cobalt/molybdenum or
nickel/molybdenum complex.
In this and other work,3 it has been shown that cataly-
tic hydrogen treatment can be used to upgrade distillate
fractions obtained by vacuum distillation of crankcase waste
oil. Nitrogen and oxygen is removed from the distillate
fraction, forming NHo and H20. Some sulfur may also be re-
moved from the distillate, which is already low in sulfur,
as H2S. These impurities are oxidized or scrubbed from a
purge gas stream. The purification process improves the
stability, color, and odor of lube distillates, as shown
in Table 40.
71
-------
Table 40. PRODUCT QUALITY IMPROVEMENT BY CATALYTIC
HYDROTREATMENT OF CRANKCASE OIL
DISTILLATE
HRI Data*
ASTM Color
Odor
Exxon Data3
ASTM Color
Neutr. No.
Con. Carbon, Wt.%
Sulfur, Wt.%
Nitrogen, Wt.%
Waste
Crankcase
Oil
D8
Offensive
Black
5.87
3.33
0.30
0.08
Untreated
Distillate
L 7.5
Offensive
Black
0.51
0.01
0.12
0.018
Hydro-
Treated
Distillate
L 2.5-L 3.5
Odor Removed
Lt. 1.0-1.5
0
0.001
0.1-0.05
0.002-0.006
See Appendix
72
-------
The results of small scale pilot plant runs on NORCO
distillate are provided in Appendix E. The type of exper-
iment conducted does not answer two other important ques-
tions about hydrogen treatment, namely hydrogen consumption
and catalyst life. Hydrogen consumption was estimated to
be 70 to 160 standard cubic feet per barrel of distillate by
hydrogenation bomb tests and by changes in physical and
chemical properties. The basis for these estimates is
provided in Appendix E.
No tests were made to determineocatalyst life. However/
neither the catalytic hydrogen treatment tests run in this
work (67 hours), or the other work previously mentioned
(about 100 hours) showed any sign of catalyst deactivation.
CHEMICAL REDUCTIONS
The use of hydrides for the reduction of precursors and
color and odor producing compounds in lube distillates may
be a practical alternative to catalytic hydrotreating, Re-
ductants studied in this work were lithium aluminum hydride,
sodium and potassium borohydride, and sodium aluminum di-
ethyl dihydride. Other aluminum hydrides, borohydrides,
and similar compounds might also be considered.
Sodium borohydride rapidly reduces most aldehydes,
peroxides, and hydroperoxides. Most ketones are reduced at
a much slower rate than aldehydes. Carboxylic acids, carb-
oxylic acid esters, amides, nitriles, and nitro compounds
are not normally reduced. Other types of compounds which.
are usually reduced by sodium borohydride are: acid chlor-
ides, aromatic azides, organic disulfides, carbon/carbon
and carbon/nitrogen double bonds, lactones, ozonides, cyclic
quarternary ammonium salts, and Schiff bases. Reductive N-
alkylations, cleavages, cyclizations, deaminations, and deoxy-
genations can occur. Numerous inorganic reductions are also
possible.5'6 Technical information on sodium borohydride
is provided in Appendix 1. Qualitative infrared informa-
tion confirmed that the borohydrides used did reduce nitro-
gen, oxide compounds (6.3 microns), but few carbonyls (5.95
microns).
73
-------
Aldehyde, ketone, organic acid, ester, organic acid
chloride, oxime, amide, nitrile, and nitro compound reduc-
tions by sodium aluminum diethyl dihydride (OMH-1) are
known.7 The ability to reduce organic acids, esters,
amides, nitriles, and nitro compounds distinguishes OMH-1
from sodium borohydride, making it possibly more attractive
for waste oil treatment. However, OMH-1 must be handled
under an inert atmosphere. Technical information is pro-
vided in Appendix L. Qualitative infrared information con-
firmed* the reactivity of OMH-1 for nitrogen oxide and
carbonyl compounds.
Sodium borohydride can in theory generate 4 moles of
H2 per mole by hydrolysis:
NaBH4 + 4 H20 = NaB(OH)4 + 4 H2.
Therefore, one pound of NaBH4 can generate 37.94 standard
cubic feet (32°F? 1 atm) of hydrogen. Correspondingly, one
pound of sodium aluminum diethyl dihydride can t-he<>J?feti*-
cally generate 13.04 standard cubic feet of hydrogen fcjp
hydrolysis:
NaAl(C2H5)2H2 + 4 H20 = NaA102 + 2C2H5OH + 4 H2.
The potential usefulness of chemical reduction reagents
depends upon selectivity for compounds which contribute to
poor lube properties, the cost of the reagent, and addition-
al steps required, for example to eliminate odors arid remove
precdpitated salts. The odor problem will be discussed
further. A base which appeared in treated samples due to
salts, water (where present), and other reaction products
can ba removed by washing (e.g. amines), redistillation,
arid/of filtering.
Redistillation of a blend of NORCO No. 3 and 4 distil-
late yields fractions showing an ASTM color of 2.4 to 4.2,
with itiost of the light cuts at 2.4 (Table 41). Addition of
solid KBH4 or NaBH4 to the distillation flask can improve
the color to as low as 1.1 to 1.75, depending on the con-
centration (Tables 41 to 47). It appears that at least
0.016 weight percent K3H4 was required to make a significant
improvement in color. However, odor was not improved in any
cas^. Some degradation of color after several weeks was
noted in sample bottles containing borohydride treated oils.
74
-------
Table 41. REDISTILLATION OF CRANKCASE OIL DISTILLATE WITH
AND WITHOUT POTASSIUM BOROHYDRIDE
Distillation of NORCO #3 and #4 blend and
.08 weight % KBH4
% Still
Recovered Temp.,(
10
20
30
40
50
60
70
80
90
10
20
30
40
50
60
70
80
90
10
20
30
40
50
60
70
80
90
580
600
612
630
640
658
676
700
730
Vapor
Temp.,°C
260
280
295
304
310
328
332
352
358
Vacuum
(Torr)
49
58
49
49
47
47
47
47
47
ASTM Color
1.75
1.75
1.75
1.75
1.75
1.75
2
2
40
80
4.20
Distillate recovery - 92%
Distillation of NORCO #3 and #4 blend -
no KBHyi added
580 255 48
600 280 48
618 295 48
636 305 49
648 315 49
665 320 49
674 328 47
692 334 47
730 348 47
Recovery - 93.5%
2.4
2.4
2.4
2.4
2.4
2.8
2.8
3.5
4.2
Distillation of NORCO #3 and #4 blend and
0.016 weight % KBH4
405
524
570
590
610
630
677
700
738
190
195
242
268
270
275
278
285
270
57
49
48
48
48
48
48
48
48
1,
1,
1,
1.
75
75
75
75
1.75
2.75
2.75
3.50
7
75
-------
Table 42. REDISTILLATION OF CRAN.KCASE OIL DISTILLATE WITH Q.QQ16%
POTAS SIUM BOROHYDRIDE*
Distillation of NORCO #3 and #4 blend and O.Q016 weight % KBH4
Recovered Still Temp. ,°F Vapor Temp. ,°C Vacuum (Torr) ASTM Color
10
20
30
40
50
60
70
80
90
538 (575)
548 (615)
562 (640)
576 (660)
595 (683)
610 (702)
657 (720)
672 (765)
704
240 (280)
242 (305
248 (318)
250 (330)
254 (343)
257 (350)
260 (360)
280 (375)
270
51
51
51
51
51
51
51
51
51
(86)
(77)
(73)
(73)
(75)
(77)
(92)
(77)
2-3/4
2-3/4
2-3/4
2-3/4
2-3/4
3-1/2
3-1/2
4-1/8
4-3/4
(2-3/8)
(2-3/4)
(2-3/8)
(2-3/8) +
(2-3/8)
(2-3/4)
(3 1/2)
(4-3/4)
* Numbers in parentheses represent a second experiment
+ Original Color as above = 2-3/8
Color after 12 days = 3-1/2
Color after heat treatment with agitation
at 200°F for 45 minutes - 3-1/2
-------
Table 43. REDISTILLATION OF CRANKCASE OIL DISTILLATE
WITH 1.25% POTASSIUM BOROHYDRIDE
Distillation of NORCO 3 and 4 blend* with 1.25\weight % KBH4
Vol. %
Recovered
initial
10
20
30
40
50
60
70
Still
Temp. ,°F
410
560
588
600
614
630
651
673
Vapor
Temp . , °C
75
235
270
278
282
290
298
303
Vacuum
(Torr)
4*
, J^|
43
43
43
43
43
43
ASTM
Color
1.75
1.1
1.1
1.1
1.1
1.1
1.75
A semi-quantitive reduction of the 1st sample was shown
by infra-red analysis.
* 56.2% No. 3 and 43.8% No. 4 by weight
77
-------
Table 44.
TREATMENT:
DOUBLE DISTILLATION HITS SODIUM BOROE^DRIDE
TO IMPROVE COLOR
0.05% NaBH4 added directly to distillation
flask with NORCO No. 3 and 4 blend
Vol. %
Recovered
10
20
30
40
50
60
70
80
85
TREATMENT:
10
20
30
40
50
60
70
30
85
Still
Temp.,°F
575
600
628
638
648
668
695
740
750
Vapor
Temp. /
268
280
295
305
325
335
340
335
Vacuum
(Torr)
55
55
55
55
55
55
55
55
55
ASTM Color
1-3/4
1-3/4
1-3/4
1-3/4
1-3/4
2-3/4
2-3/4
4-3/4
Redistillation of above cuts above 50%
with additional 0.05% NaBH, (mixture color
= 3+)
594
607
618
627
642
660
690
720
260
273
276
278
290
303
310
315
50
55
55
55
55
55
55
55
2-3/8
1-3/4
1-3/4
1-3/4
1-3/4
1-3/4
2-3/4
3-1/2
* About 1/3 of charge was a cut from a previous
run with a 2-7/8 ASTM color
78
-------
Table 45.
TREATMENT:
REDISTILLATION OF NORCO NO. 3 (LIGHT SIDE-
STREAM) CRANKCASE OIL DISTILLATE WITH 0.0"01%
SODIUM BOROHYDRIDE
0.0017 grams of NaBH4 added to 200 ml
NORCO No. 3 followed by distillation
Vol. %
Recovered
Initial
Boiling Point
10
20
30
40
50
60
70
Still
Temp.,°F
370
523
553
576
585
586
605
660
Vapor
Temp.,°C
75
180
205
223
233
240
260
210
Vacuum /
Torr
82
80
80
80
80
80
80
80
ASTM
Color
1 3/4
1 3/4
1 3/4
2 3/8
2 3/4
3 1/2
4 3/4
79
-------
Table 46. REDISTILLATION OF NORCO NO. 4 (HEAVY SIDESTKEAM)
CRANKCASE OIL DISTILLATE WITH 0.001% SODIUM
BOROHYDRIDE
TREATMENT: NONE
Vol. %
Recovered
Initial
Boiling Point
10
20
30
40
50
60
70
Still
Temp.,°F
494
543
558
575
588
613
645
688
Vapor
Temp.,°C
90
220
230
243
250
255
250
230
Vacuum,
Torr
60
65
65
65
65
65
65
65
ASTM
Color
2 3/4
2 3/4
2 3/4
3 1/2
3 1/2
4 1/8
4 3/4
TREATMENT:
0.0017 grams of NaBH4 added to 200 ml.
NORCO No. 4 followed by distillation with
stirrer on and N2 purge
Initial
Boiling Point
10
20
30
40
50
60
70
80
540
559
575
593
645
657
671
690
710
143
236
250
258
267
273
277
281
273
55
55
55
55
55
55
55
55
55
2 3/4
2 3/4
2 3/4
3
3 1/2
4 1/8
4 1/8
5 1/2
80
-------
Table 47. REDISTILLATION OF CRANKCASE OIL DISTILLATE
WITH 0.016% POTASSIUM BOROHYDRIDE AND 0.156%
ALUMINUM CHLORIDE
TREATMENT: 0.0272 grams of KBH'4 and 0.272 grams of
A1C13 added to blend of NORCO No. 3 and 4
followed by distillation with stirrer on
and
purge
Vol. %
Recovered
10
20
30
40
50
60
70
Still
Temp . , °F
510
546
570
590
613
638
650
Vapor
Temp. ,°C
195
220
230
235
247
273
283
Vacuum t
Torr
49
50
50
51
45
43
43
ASTM
Color
1 3/4
1 3/4
1 3/4
2 3/8
2 3/8
2 3/4
2 3/4
81
-------
Results obtained using a soluble water solution of 12
weight percent NaBH4 in 40% NaOH solution were similar, but
substantial color improvement was indicated at treatments
as low as 0.0016 weight percent NaBH4 (Tables 48-54).
Again, no odor improvement was noted.
About 0.01 weight percent NaBH4 seemed to be required
for color improvement when using an agent containing 5
weight percent NaBH4 in oil (Tables 55-59). Odor was not
improved.
It was found that odor improvement was possible by
treating the distillate with hot water or potassium hydr-
oxide solution (Tables 60-63), but color was not improved.
Unfortunately, the odor reappears again after redistilla-
tion (Tables 62 and 63). This occurred even when Solvent
150 Neutral was distilled.
A single experiment with 0.016 weight percent lithium
aluminum hydride treatment showed little or no color or odor
improvement (Table 64), indicating little incentive to
pursue this approach.
The use of sodium aluminum diethyl dihydride (QMH-1)
not only improves color, but reduces odor to some extent,
probably 4>y the elimination of carbonyl as noted by infrared,
(Tables 65-i-JZl) . However, as previously indicated, odor
does return when the oils are reheated for distillation.
When treating distillation cuts with OMH-1 after sodium
borohydride treatment and distillation, all samples got
cloudy with precipitation of some black material (pyridine
odor).
Several experiments with borohydride treatment of raw
crankcase oil indicated some possibility of this approach
being successful, but distillation would probably be neces*
•sary to remove the darker color heavy cuts, even if centri-
•fugation could be used to remove metals and sludge (Tables
72T-76J-.
laboratory prepared bottoms also showed some improve'*
swant in color when treated with potassium borohydride
(Table 11} >
82
-------
The relatively low quantity of hydride reagents re-
quired to improve color and odor, and the mild conditions
used, suggest that the impurities are reactive and that
cayalytic hydrotreating could possibly be improved by the
development of more selective and active catalysts.
83
-------
Table 48.
TREATMENT!
Vol. %
Recovered
10
20
30
40
50
60
70
80
EFFECT OF TEMPERATURE ON TREATMENT 01 CRANKCASE
OIL DISTILLATE WITH Q.12% SODIUM BOROHYDRIDE
Blend of NORCO No. 3 and 4 treated with 1%
SWS Csoluble water solution containing 12%
NaBH, in 40% NaOH water solution) at 180°F
for I hour followed by centrifugation at
32,000 G for 30 minutes. The supernatant
was distilled as follows.
Still
Temp.,°F
550
558
580
606
640
675
688
738
Vapor
Temp . , °C
225
227
237
247
257
265
283
250
Vacuum
(Torr)
56
53
54
55
55
55
55
55
ASTM Color
1-3/4
1-3/4
1-3/4
1-3/4
1-3/4
2-3/8
2-3/4
4-3/4
TREATMENT:
10
20
30
40
50
60
70
80
1% SWS added directly to distillation flask
with No. 3 and 4 blend.
545
550
560
584
615
660
187
232
237
247
255
260
270
260
55
55
55
55
55
55
55
55
1-1/8
1-1/8
1-1/8
1-1/8
1-1/8
1-1/8
1-3/4
2-3/4
84
-------
Tabl« 49.
REDISTILLATION Of CMNRCASB OIL DISTILUVTB WITH SODIUM
BOROHYDRIDE — EFFECT OF CONCENTRATION*
vol. »
Recovered
10
20
30
40
50
60
70
80
90
10
20
30
40
50
60
70
eo
90
Still Temperature ,°F
0
575"
602
615
630
634
660
678
704
765
50
55
55
55
55
55
55
55
55
0.0008
578
590
608
620
639
648
€98
740
-
55
60
60
60
60
60
60
60
60
0.0016
550-
590
610
630
648
665
685
715
760
Vacuum,
60
60
60
60
60
60
60
60
60
0.012
-5ST-
595
608
621
665
675
685
710
770
Torr
55
55
55
55
55
55
55
55
55
0.024
"570"
600
618
630
650
662
688
715
-
55
55
55
55
55
55
55
55
55
0.071
610
615
625
650
660
670
702
733
55
55
55
55
55
55
55
55
55
Vapor Tempo
0
TTT
276
278
280
283
285
287
287
295
0.0008
1 141"
260
265
270
272
275
285
280
-
0.0016
— I5o
260
265
268
270
275
280
283
280
ratur* ,
0.012
-JT7~
267
270
272
282
288
290
292
288
°C
O.OZ4
T5TT
268
275
285
287
290
292
2S2
-
D.071
J57
263
265
270
258
278
284
285
268
ASTM Color
2 3/4
2 3/4
2 3/4
2 3/4
2 3/4
2 3/4
3 1/2
4 1/4
6 1/2
.2 3/4
2 3/8
2 3/8
2 3/8
2 3/8
2 3/4*
2 3/4
3 1/2
1 3/4
1 3/4
1 3/4
1 3/4
2 3/4
2 3/4
2 3/4
3 1/2
6 1/2
1 3/4
1 3/4
1 3/4
1 3/4
1 3/4
2 3/8
2 3/4
3 1/2
1 3/4
1 3/4
1 3/4
1 3/4
1 3/4
2 3/8
2 3/8
3 1/2
--
1 1/8
1 1/8
1 1/8
1 1/8
1 1/8
1 1/8
1 3/4
1 3/4
~
* Blend of NORCO Ho. 3 and 4 treated with 0, 0.0008, 0.0016, 0.012, 0.024, or 6.071
NaBH. as a 12%NaBH./49«NaOH water solution,
+ After thi* cut an additional 0,0008»NaBH, added (vacuum broken).
Table 50.
TREATMENT:
REDISTILLATION OF CRANKCASE OIL DISTILLATE
WITH 0.012% SODIUM BOROHYDRIDE AFTER WASHING
WITH POTASSIUM HYDROXIDE
Wash 200 ml. of NORCO No. 3 and 4 blend
with 5 vol.% of 10 wt.% KOH solution,
centrifuge at 3000 G for 30 min. Add
0.175 grams of 12% NaBH4/40% NaOH water
solution and distill.
Recovered
Initial
Boiling Point
10
20
30
40
50
60
70
80
90
Still
Temp.,°F
430
540
557
565
585
597
610
632
685
760
Vapor
Temp.,°C
60
233
250
260
265
270
275
278
290
250
Vacuum t
Torr
60
60
60
60
60
60
60
60
60
60
ASTM
Color
1
1
1
1
1
1
2
5
3/4
1/8
1/8
1/8
1/8
3/4
3/8
3/4
3/4
85
-------
Table 51,.
TREATMENT:
PRETREATMENT OF CRANKCASE OIL DISTILLATE
WITH 10% H2S04 PRIOR TO 0.024% BORQHYDRIDE
TREATMENT
Wash 200 ml. of blend of NORCO No. 3 and 4 with
5 vol. % of 10 wt. % H2S04/ centrifuge at 3000 G
for 30 min., and repeat. Add 0.024 wt. % NaBH4*
and redistill.
Vol. %
Recovered
Initial
10
20
30
40
50
60
70
80
90
Still
Temp.,°F
456
545
568
585
602
615
630
643
670
710
Vapor
Temp.,°C
58
245
260
270
280
285
288
292
300
313
No improvement in odor noted.
Vacuum
Torr
55
55
55
55
55
55
55
55
55
55
ASTM Color
1 3/4
1 1/8
1 1/8
1 1/8
1 1/8
1 3/4
1 3/4
1 3/4
3 1/2
* As 1.2 wt. %> NaBH4 in 40 wt. % NaOH water solution.
86
-------
Table 52.
TREATMENT:
Vol. %
Recovered
Initial
10
20
30
40
50
60
70
80
90
PRETREATMENT OF CRANKCASE OIL DISTILLATE
WITH 5% KOH FOLLOWED BY 10% HjSO* PRIOR TO
0.012% BOROHYDRIDE TREATMENT
Wash 200 ml. of blend of NORCO No. 3 and 4 twice
with 10 vol. % of 5 wt. % KOH and then twice
with 5 vol. % of 10 wt. % H2S04. Add 0.012 wt.
% NaBH4* and redistill.
Still
Temp.,°F
480
558
576
591
606
620
627
646
660
706
Vapor
Temp.,°C
190
260
275
285
288
290
295
296
298
305
Vacuum
Torr
55
55
55
55
55
55
55
55
55
55
No improvement in odor noted»
ASTM Color
1/8
1/3
1/8
3/4
3/4
3/4
3/4
3/4
3 1/2
* As 12 wt. % NaBH, in 40 wt. % NaOH water solution.
87
-------
GO
00
Table 53. REDISTILLATION OF CRANKCASE OIL DISTILLATE WITH
0.0012% SODIUM BOROHYDRIDE*
Pretreatmant: A. Add 16.5 grams stainless metal sponge to 200 ml oil.
B. None
C.I) Heat oil to 400°F with agitation
2) Add borohydride
3} Hold at 400°F for 6 minutes
4) Quench flask
5) Centrifuge @ 31,000 G for 30 minutes
Vol. %
Recovered
I0~~ ~
20
30
40
50
60
70
80
90
Still
Temp . , °F
A
B
C
571T
552 590 588
570 610 600
590 630 633
618 648 662
643 665 686
674 685 710
705 715
750 760
Vapor
Temp.,°c
ABC
2T7 2~5F 2TJ
238 260 238
243 265 240
250 268 244
255 270 246
262 285 249
.270 280 230
273 283
270 280
Vacuum
Torr
A
F5
65
65
65
65
65
65
65
65
B
615"
60
60
60
60
60
60
60
60
i
C
55
55
55
55
55
55
55
55
55
ASTM
A
1
1
2
2
2
2
2
3
6
3/4
3/4
3/8
3/8
3/8
3/4
3/4
1/2
1/2
Color
B
1
1
1
1
2
2
2
3
6
3/4
3/4
3/4
3/4
3/4
3/4
3/4
1/2
1/2
C
r
i
i
2
2
3
-
-
-
3/4
3/4
3/4
3/8
3/4
1/2
-
-
-
* Blend of NORCO No. 3 and 4 treated with 0.01%
12%NaBH4/40%NaOH water solution.
-------
Off
UD
Table 54. REDISTILLATION OF CRANKCASE OIL DISTILLATE WITH 0.012%
SODIUM BOROHYDRIDE*
Pretreatment: A. None
B. Digestion at 150°F for 1 hour.
C.
Digestion at 300°F for 1 hour followed by
centrifugation at 32,000 G for 30 minutes.
Vol. %
Recovered
1C
20
30
40
50
60
70
80
90
Still
Temp.,°F
A B C
565 565 590
595 590 608
608 603 615
621 618 630
665 635 660
675 665 686
685 690 704
710 730 734
770 - 760
Vapor
Temp.,°C
A B C
24T ~2l5~ ^50"
267 265 2tO
£70 270 265
272 280 270
282 285 280
288 287 290
290 290 294
292 305 298
288 - 290
Vacuum ,
Torr
A
55
55
55
55
55
55
55
55
55
B
5T
55
55
55
55
55
55
55
—
C
85
80
80
80
80
80
80
80
80
ASTM Color
A
IT
1
i.
1
1
2
2
3
__
3/4
3/4
3/4
3/4
3/4
3/8
3/4
1/2
1
1
1
2
2
2
3
4
—
B
3/4
3/4
3/4
3/8
3/8
3/4
1/2
1/8
—
C
—
1
1
1
1
2
2
3
—
3/4
3/4
3/4
3/4
3/4
3/4
1/2
* Blend of NORCO No. 3 and 4 treated with 0.1%
12%NaBH4/40%NaOH water solution.
-------
Table 55.
TREATMENT
REDISTILLATION OF CRANKCASE OIL DISTILLATE WITH AN OIL/SODIUM
BOROHYDRIDE MIXTURE*
Blend of NORCO No. 3 and 4 charged to vacuum distillation
with Borex.* Three tests equivalent to 0.005, 0.01, and
0,03 weight precent NaBH*.
Still Temp., °F
Vapor Temp . , °C
Recovered
10
20
30
40
50
60
70
80
90
%
Recovered
10
20
30
40
50
60
70
8.0
90
0.001 0
504,
558
580
607
646
660
690
715
-
Vacuum
Torr
60
60
60
60
60
60
60
60
60
.005
538""
564
580
595
610
637
660
690
747
t
0.01
~553~
580
600
615
632
652
700
740
-
0.001
3 1/2
2 3/4
2 3/4
2 3/4
2 3/4
2 3/4
3 1/2
4 1/8
. —
0.02 0.03 0.001 0.005 0.01
584 582 19? 137 ~2~30~
602 600 235 262 255
618 614 253 270 2672
625 628 260 273 275
646 638 267 280 278
667 663 275 282 282
686 685 288 285 288
716 715 292 287 285
760 760+ - 270
ASTM Color
0.005 0.01 0.02 0.03
2 3/8 I~3~74 2~378 r~3/4
1 3/4 1 3/4 2 3/8 1 3/4
1 3/4 1 3/4 2 3/8 1 3/4
2 3/8 2 3/8 2 3/8 1 3/4
2 3/8 2 3/4 2 3/8 1 3/4
2 3/4 2 3/4 2 3/4 1 3/4
3 1/2 3 1/2 2 3/4 2 3/4
3 1/2 4 3/4 2 3/4 3 1/2
5 3/4 — — 4 3/4
0.02
~2~6Tf
270
275
280
283
285
287
297
270
0.03
"255"
270
275
280
285
287
290
295
270
* Blend of NORCO No. 3 and 4 treated with 0.001, 0.005, 0.01, 0.02, and
0.03 wt.% NaBH4 approximately 5 wt.% NaBH4 in "Bayol 385" oil known
as Borex (Ventron Corporation).
-------
Table 56. REDISTILLATION OF CRANKCASE OIL DISTILLATE WITH SODIUM
BOROHYDRIDE*
Vol. %
Still Temp,,0^1
Recovered Q.Q11
Initial
10
20
30
40
50
60
70
80
90
440
510
532
555
570
590
607
645
668
750 +
0.02^
450
545
560
570
580
600
618
657
700
-
0 ,D24
425
535
560
570
583
590
598
605
650
~
Vapor Temp. ,°C
0.011
150
215
250
257
265
270
275
280
285
175
OVQ2+-
58
235
260
265
268
270
274
273
268
-
Q «Q24
40
225
253
258
260
262
264
268
255
-
Vacuum ASTM Color
Torr
55
55
55
55
55
55
55
55
55
55
0.011
^
1-3/4
1-3/4
2-3/8
2-3/8
2-3/8
2-3/8
3-1/2
3-1/2
5-3/4
Q.Q2T
_
1-3/4
1-3/4
1-3/4
1-3/4
1-3/4
2-3/8
3-1/2
4-3/4
—
u «u^«
_
1-3/4
1-3/4
1-3/4
1-3/4
1-3/4
1-3/4
2-3/4
3-1/2
—
* Borex - 5 wt. % NaBH4 in oil. Subheadings represent percent by
weight NaBH^ treatment.
+ 0.01% added initially and 0.01% added after the 40% cut was taken.
-------
Table 57. REDISTILLATION OF CRANKCASE OIL DISTILLATE
WITH 0.049% SODIUM BOROHYDRIDE*
Vol.% Still Vapor Vacuum
Recovered Temp.,°F Temp./ C Torr A8TM Color
Initial 500 135 55
10 553 255 55 2 3/4
20 570 275 55 1 3/4
30 587 280 55 1 3/4
40 600 290 55 1 3/4
50 608 295 55 1 3/4
60 618 297 55 1 3/4
70 642 299 55 2 3/4
80 676 290 55 3 1/2
* Borex-5 wt. % NaBH4 in oil
92
-------
Table 58.
TREATMENT:
Vol. %
Recovered
10
20
30
40
50
60
70 +
TREATMENT OF CRANKCASE OIL DISTILLATE
WITH 0.01 WT. % SODIUM BOROHYDRIDE AT
600°F FOR SIX MINUTES
Mixture of NORCO No. 3 and 4 distillate heated
to 600°F, 0.01 wt. % NaBH4 added,* mixture
held at 600°F for 6 minutes, mixture quenched
and then centrifuged at 31,000 G for 30 minutes
to remove NaBH4 from further reaction. Mixture
then distilled.
Still
Temp.,°F
570
580
600
633
662
686
710
Vapor
Temp.,°C
222
238
240
244
246
249
230
Vacuum
Torr
55
55
55
55
55
55
55
ASTM Color
1 3/4
1 3/4
1 3/4
2 3/4
2 3/8
2 3/4
3 1/2
* As Borex (5% NaBH4 in oil).
+ Another 17% recovered in cold trap.
93
-------
Table 59.
TREATMENT:
REDISTILLATION OF CRANKCASE OIL DISTILLATE. "V
WITH 0.02% S^J&IUM BOROHYDRIDE AFTER WASHING
WITH POTASSIUM HYDROXIDE
Wash 200 ml. blend of NORCO No. 3 and 4 with
200 ml. of 50% KOH solution and centrifuge,
at 3000 G for 30 minutes. Add 0.7 grams of
Borex (5% NaBH4 in oil).
Recovered
Initial
Boiling Point
10
20
30
40
50
60
70
80
90
Still
Temp.,°F
450
560
580
598
610
625
614
678
700
720
Vapor
Temp. /
70
230
245
255
257
260
262
263
275
260
Vacuum,
Torr
60
60
60
60
60
60
60
60
60
60
ASTM -
Color
1 3/4
1 3/4
1 3/4
1 3/4
3/4
3/4
3/4
2 3/4
4 1/4
94
-------
Table 60.
TREATMENT:
RESULT:
DEODORIZATION OF NORCO BLENDED DISTILLATE
WITH HOT WATER
150 ml. of NORCO No. 3 and 4 sidestream blend
treated with 150 ml. of water at 200°F for
10 min.
The odor in the oil phase was diminished,
but not altogether gone. An odor appeared
in the water phase. Phenol in water phase
about 10 ppm.
Table 61. DEODORIZING CRANKCASE OIL DISTILLATE
Charge: 2nd 20 ml. cut (out of 200 ml. total)
after 0,08% KBH.4 treat with distillation
Charcoal
150°F treatment -- some improvement but basic
odor still present.
30% KOH
3 washes with 1 volume oil/volume KOH solution
odor disappeared but oil cloudy after 20 hours
standing.
10% NaHC03
1 wash with 1 volume oil/volume NaHC03solution —
no odor improvement (cresylic-phenol type odor
picked up)
95
-------
Table 62. DEQRDORIZATION OF NQRCO BLENDED DISTILLATE
WITH 10% KOH PRIOR TQ BOROHYDRIDE TREATMENT
TREATMENT: Blend of NORCO No. 3 and 4 sidestream blend
treated twice with 5 vol. % of a 10 wt. % KOH
solution followed by centrifugation at
3000 G for 30 min.
RESULT: Odor removed. Water fraction contained o<|or.
TREATMENT: Redistillation of oil after KOH treatment with
0.012 % sodium borohydride (0.1 wt. % of
12 wt. % NaBH, in 40 wt. % aqueous sodium
hydroxide solution).
Vol. %
Recovered
initial
10
20
30
40
50
60
70
80
90
Still
Temp.,°F
430
540
557
565
585
597
610
632
685
760
Vapor
Temp.f°C
60
233
250
260
265
270
275
278
290
250
Vacuum
Torr
60
60
60
60
60
60
60
60
60
60
ASTM Color
1 3/4
1
1
1
1
1
2
2
5
1/8
1/8
1/8
1/8
3/4
3/8
3/4
3/4
Odor reappears after distillation.
96
-------
Table 63. ODOR REAPPEARANCE AFTER REDISTILLATION OF
DEODORIZED/DECOLORIZED CRANKCASE OIL DISTILLATE
Charge: 30, 40, and 50% fractions of NORCO No. 3 and 4
blend redistilled with 0.016 wt.% sodium boro-
hydride (ASTM color of 2 3/8 for each fraction).
Typical crankcase oil distillate odor.
Treatment: Wash oil twice with 5 vol.% of 10 Wt.% KOHf
centrifuge at 3000 G for 30 minutes, and
distill.*
% Still Vapor Vacuum, ASTM
Recovered Temp.,°F Temp.,°C Torr Color
Initial
Boiling Point 450 80 60
10 525 225 60 1 1/8
20 538 247 60 1 1/8
30 548 255 60 1 1/8
4C 558 260 60 1 1/8
50 574 265 60 1 1/8
60 592 270 60 1 1/8
70 622 273 60 1 3/4
80 640 278 60 2 3/8
90 710 220 60 4 1/4
* Odor removed by KOH treatment, but reappears after
distillation.
97
-------
Table 64. REDISTILLATION OF CRANKCASE OIL DISTILLATE
WITH 0.016% LITHIUM ALUMINUM HYDRIDE
TREATMENT: 0.0272 grams of U_A1H4 stirred with 20$ ml.
NORCO No. 3 and 4 blend for 1 hour followed
by distillation with stirrer on and purge,
Vol. %
Recovered
10
20
30
40
50
60
70
Still
Temp . , °F
507
535
548
563
567
590
615
Vapor
Temp. /°C
200
215
230
237
238
240
215
Vacuum,
Tprr
57
57
57
57
57
57
57
ASTM
Color
2 3/4
2 3/8
2 3/8
2 3/8
2 3/4
2 3/4
3 1/2
98
-------
Table 65. REDISTILLATION OF CRANKCASE OIL
DISTILLATE WITH 0.26% OMH-1*
Vol. % Still Vapor Vacuum
Recovered Temp.,°F Temp.,°C Torr ASTM Color
Initial 490 65 55
10 558 247 55 1-1/8
20 575 265 55 1-1/8
30 593 270 55 1-1/8
40 605 273 55 1-1/8
5C 618 277 55 1-3/4
60 635 280 55 1-3/4
70 650 282 55 1-3/4
80 655 284 55 2-3/4
90 695 280 55 4-3/4
* 0.26 wt.% OMH-1 as 26.3 wt.% OMH-1 (sodium aluminum
diethyl dihydride) in toluene (containing 3-4%
tetrahydrofuran).
99
-------
Table 66. REDISTILLATION OF CRANKCASE OIL
DISTILLATE WITH OMH-1*
Vol. % Still Vapor Vacuum
Recovered Temp.,0? Temp.,°C Torr ASTM Color
Initial 480 160 55
10 522 210 55
20 550 235 55 1-3/4
30* 573 243 55 1-3/4
40 605 253 55 1-3/4
50* 620 258 55 1-3/4
60 638 259 55 1-3/4
70* 648 268 55 1-3/4
80 665 270 55 3-1/2
90 700 265 55
* 0.065 wt.T OMH-1 as 26.3 wt.% OMH-1 (sodium aluminum
diethyl dihydride) in tolisene (containing 3-4%
tetrahydrofuran) added after each of the indicated cuts,
T«b!» «7. RBDISTILtATZCH OP CMNKCME Oil DISTILLATE AFTBR
PKETREMHEOT WITH OMH-l*
• Je.5 vf.. % OMH-1 (aotfiun nlostriui. dlathyl dihydcite) ia toluon*
(eoxtainincj }-«» catrchydrofuKact). nubiwUlng* rcpniwnt pcronnt
by uvlcjht OMH-1 tra*tn«ntt
100
-------
Table 68.
Vol, %
Recovered
REDISTILLATION OF CRANKCASE OIL DISTILLATE WITH
0.13 WEIGHT PERCENT OMH-1*
Initial
10
20
30
40
50
60
70
80
90
490
546
575
580
590
598
600
615
620
680
Still Temp.,°F
~~¥3 #4
555
572
598
602
606
633
635
650
680
700 +
Vapor Temp.,°C
~!3#4
140
225
255
265
268
278
278
278
280
290
120
235
254
258
262
270
280
280
283
275
Vacuum
Torr
11
95
95
95
95
95
95
95
95
95
95
il
55
55
55
55
55
55
55
55
55
55
ASTM Color
HT
2-3/4
2-3/8
2-3/8
2-3/8
2-3/8
2-3/8
2-3/8
2-3/8
-
11
1-3/4
1-3/4
1-3/4
2-3/8
2-3/8
2-3/4
3-1/2
3-1/2
6-1/2
* As 26.3 wt.% OMH-1 (sodium aluminum diethyl dihydride) in tolvene
(containing 3-4% tetrahydrofuran). NORCO No. 3 and 4 distillates
from run on Jan. 23, 1974.
-------
Table 69u REDISTILLATION OF NORCO NO. 3 AND 4 BLEND (50-50 BY VOLUME)
PROM JANUARY 23, 1974 OPERATION WITH OMH-1
Vacuum
Vol. % Still Temp.,°F Vapor Temp.,°C Torr . ASTM Color
Recovered A B ^H^IL £.5.
Initial 480 500 130 120 75 55
10
20
30
40
50
60
70
80
90
A = 0.13 weight % OMH-1
added to blend before distillation.
B = Cuts from A reblended (ASTM Color = 2-3/4) and then
redistilled (no added OMH-1)
548
560
566
575
584
595
596
630
670
540
558
570
588
595
613
634
690
225
247
255
257
257
260
260
262
265
243
255
260
270
272
278
282
288
-
75
55
55
55
55
55
55
55
55
55
55
55
55
55
55
55
55
55
1-3/4
1-3/4
1-3/4
1-3/4
1-3/4
3-3/4
2-3/4
3-1/2
5-3/4
1-3/4
1-3/4
1-3/4
1-3/4
1-3/4
1-3/4
2-3/8
3-1/2
-
-------
o
oo
Table 70. REDISTILLATION OF CRANKCASE OIL DISTILLATE WITH BOROHYDRIDE
PLUS OMH-1 TREATMENT -0.01 wt. % NaBH4 (as 12 wt. % NaBH4 in
40 wt. % NaOH water solution) added prior to distillation
in each case
Vol. %
Recovered
% OMH-1
Initial
% OMH-1
10
% OMH-1
20
% OMH-1
30
% OMH-1
40
% OMH-1
50
% OMH-1
60
% OMH-1
70
% OMH-1
80
Still Temp. ,°F
440
-
538
-
562
-
572
~
578
0.052
570
-
580
-
615
-
685
430
-
530
-
543
0.078
560
-
562
-
571
-
588
-
625
-
687
420
-
540
-
562
-
572
-
585
-
600
0,078
627
-
660
-
718
Vapor Temp. ,°C
0.13* -
540 105
-
588
-
610
-
614
-
626
-
635
-
644
-
660
-
700
—
218
-
232
-
240
-
235
0.052
230
-
233
-
227
-
240
90
-
210
-
248
0.078
247
-
248
-
247
-
246
-
245
-
247
90
-
235
-
247
-
247
-
250
-
255
0.078
260
-
270
-
260
ASTM Color
0.13*
60 -
-
215
-
267
-
280
-
275
-
280
-
282
-
284
-
285
-
1-3/4
-
1-3/4
-
1-3/4
-
1-3/4
0.052
1-3/4
-
1-3/4
-
2-3/4
-
3-1/2
-
1-3/4
-
1-3/4
0.078
1-3/4
-
1-3/4
-
1-3/4
-
2-3/8
-
3-1/2
-
5-3/4
-
1-3/4
-
1-3/4
-
1-3/4
-
1-3/4
-
1-3/4
0.078
1-3/4
-
3-1/2
-
4-3/4
0.13
-
-
-
1-3/4
-
1-3/4
-
1-3/4
-
1-3/4
-
1-3/4
-
2-3/4
-
3-1/2
* Vacuum = 85 Torr. 55 Torr in other experiments
-------
Table ^U REDISTILLATION OF CRANKCASE DISTILLATE
HEAVY CUTS FROM PREVIOUS BOROHYDRIDE PLUS
OMH-1 EXPERIMENTS WITH 0.01% SODIUM
BOROHYDRIDE AND 0.13% OMH-1
FEED: 60, 70, and 80 volume percent cuts from previous
experiments. ASTM color of cuts ranged from
2-1/2 to 4-1/2.
REAGENTS: 0.01 wt.% NaBH4 as 12 wt.% NaBH4 in 40 wt.%
NaOH water solution plus 0.13 wt.% OMH-'l as
26.3 wt.% OMH-1 (sodium aluminum diethyl
dihydride) in toluene (containing 3-4%
tetrahydrofuran).
Vol. % Still Vapor Vacuum
Recovered Temp. ,OF Temp. ,°C Torr ASTM Color
Initial 510 90 55
10 565 235 55 1-3/4
20 575 245 55 1-1/8
30 580 250 55 1-1/8
40 588 252 55 1-1/8
50 600 257 55 1-1/8
60 615 260 55 1-^1/8
70 638 278 55 1-1/8
80 662 283 55 3-3/4
90 700 250 55 3-1/2
104
-------
Table li» PXSMLLATION OF RAW CRANKCASE OIL WITH 0.005%
I- SQPtin* BOROHYDRIDE AFTER WASHING WITH SQfSfcSiiittM
HYDROXIDE
TREATMENT; Wash 200 ml. of raw crankcase oil with 10 vol. %
of 5 wt, % KOH solution twice,
and centrifuge at 3000 G for 30 minutes.
Add 0.175 grams of Borex (5% NaBH4 in oil).
% Still
Recovered Temp.,°F
Initial
Boiling Point 420
10 546
20 618
30 622
40 638
50 655
60 680
70 712
80 745
Vapor
Temp.,°C
45
130
255
260
270
275
277
282
273
Vacuum,
Torr
70
70
60
60
60
60
60
60
60
ASTM
Color
2 3/4
2 3/8
2 3/4
3 1/2
* First cut - lOcc oil + lOcc water
105
-------
Table 73,
TREATMENT
Vol. %
Recovered
Initial
10
20
30
40
50
60
70
80
0? RAW CRANKCASE OIL WITH 1Q% KOH AND DISTILLATION
WITH Q.Q12
-------
Table 74, DISTILLATION OF RAW CRANKCASE OIL TREATED
WITH 0.24 AND 0.36% POTASSIUM BOROHYDRIDE*
Recovered
10
20
30
40
50
60
70
80
Still
Temp
0.24
5T8~~
585
605
630
655
677
670
695
Op
• / £
0.36
56T~
590
600
618
663
695
710
-
Vapor
Temp
0.24
2T4~~
240
247
253
256
258
255
240
°C
• i *-
0.36
2~2Tr~
245
260
255
255
260
280
275
Vacuum ,
Torr
0.24
~§F"
50
50
50
50
50
50
50
0.36
53
58
58
58
57
57
57
57
0
2
2
2
4
4
-
-
-
ASTM
Color
.24
3/4
3/4
3/4
1/4
3/4
0
2
1
1
1
2
4
5
-
.36
3/4
3/4
3/4
3/4
3/4
1/4
5/8
* In 12% KBH4/40% KOH water solution,
107
-------
Table 75'. DISTILLATION OF RAW CRANKCASE OIL PRETREATED WITH Q.24%
SODIUM BQRQHYDRIDE*
Pretreatment: 2 wt. % soluble water solution of NaBH,* at 2QO°F for 1 hour
fo3.1owed by centrifugation at 32,000 G for 30 minutes
Vol. %
Re cove red 3ti3,l Temp. , °F Vapor Temp.,°C Vacuum (Torr} ASTM Color
o
00
10
20
30
40
50
60
70
75
80
550 (558)
566 (585)
600 (605)
620 (630)
652 (655)
673 (677)
698 (670)
720 -
- (695)
225 (214)
235 (240)
243 (247)
245 (253)
264 (256)
270 (258)
275 (255)
270 -
240
50
50
50
50
50
50
50
50
50
1-3/4 (2-3/4)
1-3/4 (2-3/4)
1-3/4 (2-3/4)
2-3/8 (4-1/4)
3-1/2 (4-3/4)
3-1/2 -
4-3/4 -
12% NaBH, in 40% aqueous sodium hydroxide solution
First 5% recovered was water
Numbers in parentheses are for duplicate run with
no preheating and no centrifugation
-------
Table 76.
TREATMENT OF RAW CRANKCASE OIL WITH 0.36% POTASSIUM BOROHVDRIDE*—
EFFECT OF PRETREATMENT
Pretreatment Methods A. None (KBH4 added to still).
B. Centrifuged 15 minu4.es at 32,000 G. Then added KBHj.
C. Centrifuged 15 minutes at 10,0000. Then added KBH4.
D. Heat treatment at 200°F for 1 hour. Centrifuged at
32,000 G for 30 minutes. Decanted oil and added 0.18%
KEH.. Additional 0.18% KBH4 added gradually during
distillation.
Distillation Resalts
%
Still
Recovered Temperature ,°F
10
20
30
40
50
6n
70
80
. A
5TQ-
590
600
618
663
695
710
B
5TO-
540
550
604
648
683
695
760
C
55TT
563
575
610
650
705
730
-
D
57T
600
615
645
666
695
718
Vapor
Temperature L
A
2~2TT
245
260
255
260
280
275
-
B
rsir
170
194
200
243
250
254
210
C
20TT
220
228
235
240
260
258
°C
D
2T5-
223
235
240
240
240
235
-
Vacuum,
A
57
58
58
57
57
57
57
-
B
57
55
55
55
55
55
55
55
Torr
C
57
55
58
58
58
58
58
-
D
5T
55
55
55
55
55
55
-
ASTM Color
B C D
1 3/4 1 3/4 1 3/4
1 3/4 1 3/4 1 3/4 1 1/8
1 3/4 1 3/4 1 3/4 --
1 3/4 1 3/4 1 3/4 —
2 3/4 1 3/4 2 3/B --
4 1/4 2 3/4 4 1/4 --
5 5/8 3 1/2 6 1/2 —
6 3/4 ~
* In 12% KBH /40% KOH water solution.
109
-------
Table 77; REDISTILLATION OF CRANKCASE OIL BOTTOMS
WITH POTASSIUM BOROHYDRIDE
Charge: 600 ml. of raw crankcase oil after
centrifugation at 32,000 G for 30 minutes
Still Vapor
Vol. Recovered Teinp, °F Tempy°C
initial boiling point 2~50~5T
5 ml. 359 67
10 410 88
20 443 106
30 476 144
40 486 144
50 518 194
60 530 224
70 end of distillation
Bottoms recovered and 200 ml plus 4.40 grams
of potassium borohydride charged to vacuum
distillation
Vacuum ASTM
mm Hg Color
initial boiling point 420 60 11.2
20 ml 572 180 11.0 4 7/8
40 666 210 11.0 4 1/8
60 640* 175* 9.0 4 7/8
80 660 217 5.7 4 7/8
100 690 275 5.3 4 1/8
120 725 253 5.7 4 7/8
140 750 285 5.7 53/4
Restarted after problems with vacuum pump
110
-------
DIESEL FUEL TESTS
The following results were obtained from a diesel
engine truck test using NORCO No. 3 distillate:
Ratio NORCO #3 Total Gals. Miles Per
Test to Reg. Diesel Used Gallon
1 50/50 137 4.0
2 75/25 103 6.0
3 100/0 134 6.2
No foreign matter or varnish was detected in the fuel filter
system. However, traces of black smoke were emitted from
the exhaust pipe and a very objectionable odor was noted.
In a test with a second trucking company, 3 diesel
trucks used NORCO #3 as a fuel for distances up to 500 miles,
Engine inspections after the tests showed some tar deposi-
tion. Black smoke was noted intermittently in these tests/
especially on very short runs.
It was concluded that light distillate recovered from
crankcase waste oil can be used as a diesel fuel, but that
further treatment of the distillate is necessary. A lengthy
laboratory and field testing program would be necessary to
develop this market. A diesel test report is provided in
Appendix F.
It should be noted that there is apparently no tax
incentive for converting waste lubricating oil to diesel
fuel, based on the following quotation from the Internal
Revenue Regulations, Regulation Section 48.4091-2 (b) (2) :
"For purposes of the tax imposed under Sec. 4091,
the term "manufacturer" does not include: (i) any
person who merely blends or mixes two or more
taxable oils, (ii) any person who merely cleans,
renovates, or refines used or waste lubricating oil,
or (iii) any person who merely blends or mixes one
or more taxable oils with used or waste lubricating
oil which has been cleaned, renovated, or refined,...."
Ill
-------
SECTION VI
DESIGN AND ECONOMIC STUDIES
The design and economic studies reported here were
undertaken to help guide research and planning aimed at
the development of a process or processes for conversion
of waste oils to useful prodtftpts, while eliminating or
minimizing waste products wh^ch contribute to environ-
mental pollution. In NORCG'sf' previous work, it had been
shown that vacuum distillation could be used to convert
crankcase waste oil to naphtha, useful as a fuel; to dis-
tillates, potentially useful as lube stock, but suffering
from stability, color, and odor problems? and a bottoms
fraction with questionable application.1
In the present work reported in Sections IV and V,
it was shown that the distillates could be upgraded by
catalytic hydrogen treatment and that the bottoms could be
used in secondary lead smelting, thus technically meeting
the objective of producing useful products without simul-
taneously producing wastes. At the same time,it was
shown that vacuum distillation could be used to upgrade a
broad spectrum of waste oils, especially those contaminated
with water. The following information verifies that these
technical innovations are economically feasible.
PROCESS SCREENING STUDIES
The analysis of process options open to NORCO was com-
plicated by the availability to NORCO of used vacuum dis-
tillation and catalytic hydrotreating equipment from Exxon's
Bayonne facilities. This equipment, which had been used in
wax processing service, has a nominal capacity of about 3500
barrels per stream day. Therefore, the screening studies,
provided in Appendix J, consider both relocating the Exxon
equipment and building a grass roots plant. The results
can be summarized as shown on Table 78.
It was concluded from this study that:
1» There is a strong economic incentive to develop
processes for refining crankcase oil to produce
saleable lube oils, when there is a spread on
the order of 13C/gal. between crankcase oil and
lube oil.
112
-------
Table 78^ SCREENING STUDY ECONOMICS
Pre-Treat.
Post-Treat.
Equip.
Feed, 106
gals/yr.
Invest„
$106
Profit
$/yr.
Return, %/yr.
before tax
-wone
Exxon Exxon
9 29
0.49 1.12
0.129 1.57
26 140
New
29
3.05
1.49
49
- - ooxvent
Exxon
34.8
1,77
2.19
124
Notes: 1. Crankcase waste oil at 3C/gal.
2. Lube product at 16
-------
2. Investments and operating costs projected for
vacuum distillation and hydrotreating can easily
be justified if they can produce 60% or greater
yield of lube oil.
3. Additional investment for solvent pretreatment
can be justified, if yield of lube oil is
improved,
4. Based on knowhow available from the petroleum
refining industry, the prognosis for technical
and economic success of a vacuum distillation/
catalytic hydrotreating process is' highly
favorable.
Later studies (June 1973) showed that either relocation
of the Exxon equipment or a grass roots (new) plant pro-
cessing about 29 million gallons per year of crankcase waste
oil and/or other waste oils is a potentially profitable ven-
ture (Tables 79482)-*
A subsequent study showed that the vacuum distillation/
catalytic hydrogen treatment process compared favorably with
other re-refining processes in a 5 million gallon per year
plant producing lube blending stocks.8'9 Of the processes
available, only the hydrotreating approach produces no waste
products (Table 83).
The principal economic problem encountered today in any
re-refining operation is competition for feedstock with in-
discriminate use as a fuel or for road oiling, both of which
contribute to environmental pollution. One solution to this
problem is governmental regulations to control the burning
of waste oils which have high metals contents (including all
automotive crankcase waste oils, many of which contain more
than 1% lead). Another important aid is the development of
superior re-refining technology (e.g., hydrotreating) in
large plants/which is sufficiently attractive at current
(1975) lube stock prices (40-60 cents per gallon) to allow
at least 10-13 cents per gallon payment to collectors for
the waste oil (or which provides an incentive for collection
by the re-refiner).
114
-------
Table 79.
CASE DESCRIPTIONS
CASE
Feed, MMGPY
Crankcase Oil
Fuel Oil -
10% BS&W
Vac. Fract.
B/SD
Hrs/Yr.
Hydrotreat.
B/SD
Hrs/Yr .
Incremental
Investment, $M
Exxon Equip.
New Vac. Dist.
New Hydrotreating
New H2 Plant
Other
PURCHASE
VACUUM
1
9.0
20.0
EXXON
MONOPHINER +
FRACT±ONATOR
2
14.5
14.5
29.0 29.0
3314 3314
5000 5000
2117 2li7
15=2 • aibo
889-
:
3
29.0
29.0
3314
5000
2117
5000
~-
611
1500 -
• - — —
4
9.0
20.0
29.0
3314
5000
657
5000
850
530
240
1480
3100
GRASS
S
14.5
14.5
29.0
3314
5000
1059
sobo
e£o
740
320
1480
3390
ROOTS
6
29.0
29.0
3314
5000
2117
5000
850
1200
470
1480
4000
PLANTS
7
14.5
14.5
29.0
4000
4l43
1497
3537
940
930
380
1700
3950
8
20.5
14.5
35.0
4000
5000
1497
5000
940
930
380
1700
3950
CASE
Feed, MMGPY
Crankcase Oil
Fuel Oil
Kat Products, MMGPY
tuba Oil
Light Cuts
Pb Eiudgo
1
9.0
20.3
29.0
5.75
1.96
17.60
SS.31
2 3
14.5 2».0
14.5
29.0 29.0
9.2« 18.52
3.17 6.34
12.90
25.33 25.68
4
9.0
20.0'
29.0
5.75
1.96'
17.60
2f.31
_L_
14.5
14.5.
29.0
9.26.
3.17
12.90
15.33
6
29.0
*"*^~
29.0
18.52
3,34
„
25.68
_?_
14.5
14.5.
29.0
9.26
3.17
12.90
25.33
8
20.5
Hi!
35.0
13.09
4.48
12.92
30.49
115
-------
CASE
% Hydrotreat.
Cap. Used.
Feed, MMGPY
Crankcase Oil
Fuel Oil
10% BS&W
Feed Costs,
SM/Yr.
Crankcase Oil
@ 50/G*
Fuel Oil @
1«/G*
Oper. Costs, $M/Yr.
To^al Costs, $M/Yr.
Revenues , $M/Yr .
Lube Oil 3 20«/G
Light Cuts
e IO«/G.
Pb Sludge 6 2«/G
Fuel Oil $ 10«/3
Profi'c B.T. ,Sl4/tte.
Profit After 50 t
Tax, $M/Yr.
Return A. T. , %/^r,
Table
1 2
— Relocate Exxon
31.0
9.0
20.0
257TT
4SO
200
T50"
851
1501
1150
_«. —
39
1760
5579"
1448
724
48.3
50.0
14.5
£4.5
ZTHJ"
725
145
TTTr
925
1795
1852
«__
€3
1290
350T
1410
705
47.0
81. PROFITS
3
Equip.—
100
29.0
•_•••_..
ZSTTJ"
1450
..
T4To"
1090
2540
3704
82
127
— — «
35TT
1373
£86.5
45.8
— _=rr-
100
9.0
20.0
277TT
450
200
"BTB"
768
1418
1150
____
39
1760
2T4T
1531
765. 5
24.7
5 6
— — Grass Roots
100
14.5
14.5
2§TF
725
145
870
820
1690
1852
____
63
1290
3JoT
1515
757.5
22,3
100
29.0
H»_^
&rv
145Q
„_»_
IT5T
920
2370
3704
82
127
•-._—
'am
1543
771.5
19.3
7
70.7
14.5
14.5
29.0
725
145
~m
875
1745
1852
____
63
1290
35oT
1460
730
18.5
8
100
20.5
14.5
157TT
1025
145
TT70"
902
2072
2618
____
90
1292
I5oT
1928
964
24.4
"Includes transportation costs, if any
116
-------
Table 82.
COSTS
CASE
Feed, KMGPY
CranXcase Oil
Fuel Oil
% Hydrotreat.
Cap. Used
Dir. Op. Costs i
?.M/Yr .
Op. Labor
Labor O.H.
Ins. + Taxea
Catalyst
Antifoulant
Hydrogen
Maint .
Deprec.
Power
City Water
Nat. Gas
«/Gal. Feed
Indir. Op. Coats,
$M/Yr.
Salaries
Salary O.H.
R £, D
Lab. & Office
Exp.
Consultants «
Other
«/Gal. Feed
1
— Relocate
9.0
20.0
5J75"
31.0
110.0
16.5
60.5
14.7
2.3
an c
ou . 3
78.2
233.5
23.1
2.0
__-._
621.3
2.14
143.0
22.0
25.0
15.0
25.0
2 3d. 0
0.79
2
3
Exxon Equipment —
14.5
14.5
2THT
50.0
110.0
16.5
60.5
23.7
3.7
1 9Q 7
2,£y a f
78.2
233.5
• 35.0
4.0
__-* —
694.8
2.40
230.0
0.79
29.0
____
5THT
100
100.0
15.0
60.5
47.3
7.3
o CQ -a •
Z37 • J
78.2
233.5
53.6
5.2
___u
859.9
2.97
230.0
0.79
4
«—•'•"
9.0
20.0
Tsmr
100
110.0
16.5
60.5
14.7
2.3
93.0.
206.7
20.0
3.0
10.9
537. 6
1.85
230.0
0.79
5
— - Grass
14.5
14.5
Z371T
100
110.0
16.5
60.5
23.7
3.7
101.7
226.0
25.0
5.0
17.5
589.6 .
2.03
230.0
0.79
6
29.0
— —
Z5TTT
100
100.0
15.0
60.5
47.3
7.3
120.0
266.7
31.0
7.0
35.1
£69.9
2.38
230.0
0.79
7
14.5
14.5
5T7o"
70.7
110.0
16.5
60.5
23.7
3.7
118.5
263.3
25.0
5.0
17.5
mrr
2.22
230.0
0.79
8
20.5
14.5
3370-
100
110.0
16.5
60.5
33.4
5.2
118.5
263.3
32.0
8.0
24.8
27271
1.92
236. (5
0.66
117
-------
Table S3), SUMMARY OF CRANKCASE WASTE OIL PROCESSES
oo
Process
Acid/Clay
Extraction/
Acid/Clay
Distillation/
Clay
Distillation/
H2 Treating
Primary Product
Lube blending
stock
Lube blending
stock
Lube blending
stock
Lube blending
stock
Primary Wastes
& Byproducts
Acid sludge,
spent clay
Grass Roots Econ.-
5 Million Gal/Yr.
Investment Op. Cost*
$1,153,000 21.94/Gal.
Lube
Acid sludge, $1,363,000
spent clay? high
ash fuel byproduct
Spent clay;
high ash fuel
byproduct
High ash fuel
byproduct
$1,173,000
$1,342,000
18.4$/Gal.
Lube
17.3«/Gal.
Lube
19.0«/Gal.
Lube
Comments
Widely used
in U. S.
One operating
plant in Italy.
At least two
plants in U.S.
Under
development.
Distillation
Fuel oil (diesel
fraction could
possibly be re-
covered)
High ash fuel
byproduct
$ 930,000 14.6
-------
VACUUM DISTILLATION/HYDROTREATING PROCESS
The basic scheme for the distillation section of the
process was provided in Figure 1; the hydrotreating section
is shown in Figure 9. The raw crankcase oil is first run
through a flash column where water and some of the gaioline
contamination is taken overhead. The flash bottoms are then
processed through a vacuum distillation column separating
the following components: gasoline contamination overhead;
a vacuum distillation bottoms product, containing high boil-
ing hydrocarbons and non-volatiles including metallic com-
ponents; and one or two distillate fractions. The distil-
late is dark in color and otherwise unsuitable for use as a
high quality lubricant.
The distillate is then catalytically hydrogen treated
to meet specifications as a lubricating oil blending stock.
Work reported by Esso Research and Engineering Co. shows
that hydrogen treated distillate can match typical proper-
ties of 150 vis neutral lube base stock.3 Other approaches
to hydrogen treatment have been reported in patent litera-
ture .l °
The gasoline fraction can be used internally as a fuel,
and the balance sold. The vacuum distillation bottoms,
which may contain more than 10% lead, can be used as fuel in
secondary lead smelting furnaces, as reported in Section V.
The principal problems in catalytic hydrogen treating
left unanswered by previous work are the questions of
catalyst life and hydrogen consumption. In Esso's work,
about 100 hours of continuous hydrogen treating of the used
motor oil distillate was loqged_with no noticeable jsatalyst,,
deactivation. In the experiments reported in Apperidix E,
no problems were noted after 67 hours of operation*- At a
lead content of 2 ppm in the distillate and 1.0 V/^/hr»
space velocity, the catalyst bed would contain about 1.5%
lead after one year of operation, if breakthrough did not
occur. Actually breakthrough would be expected, and, in
any case, this lead level would not be expected to seriously
affect the catalyst.
119
-------
NJ
O
IU3E
OlStlUATE
1 ^
CODIES
HYORQTREATEO LUBE DISTILLATE
COOLER, , ,
. ^j »| | » TO fUEL
z I A *
JL WATER TO
/" N WASTEWATER TREATMENT
n CATALYTIC
f—yV— — HYOROTREATIHG STEA|, „ . SUAM
I/ J J 1 B"CTOB STRIPPER
f S ° """ >*>
FU8«ACE L^
i i_jn ___ ^^ *\. -. .-,.._
IM3 — ""J. t
f~" ^- FLASH HA/
?„ PRUMS \ PISTILLATE
1 y/ LUBE STOCK
1 TO STORAGE
TO BIOWOOWM p]^ J
| VACUUM TO VACUUM
1
PURGE
VACUUM DISTILLATION/HyDSPTBEATJflG PROCESS
HYDEOTREAf UJG SECTION
FIGURE 9
-------
Hydrogen consumption is a serious matter, since hydro-
gen costs for the relatively small quantities required are
on the order of $4 per 1000 standard cubic feet. Accurate
measurement of hydrogen consumption in small pilot units is
very difficult and expensive. Therefore, two different
approaches have been used to estimate the hydrogen which
will be consumed. (Sea Appendix E for details).
In one approach a static hydroganation bomb test for
distillate was compared to a bomb test for Nujol at the
required temperature and pressure. This data, after being
subjected to corrections involving catalyst reduction,
ammonia, hydrogen sulfide, and water formation, and sorp-
tion phenomena, gave a maximum hydrogen consumption of 70
to 160 SCF/B.
In an alternative approach, hydrogen consumption was
calculated from changes in the characteristics of distil-
lates during catalytic hydrogen treating. The characteris-
tics examined include sulfur, nitrogen, and oxygen contents,
hydrogen content as predicted from specific gravity changes,
and Iodine Number (unsaturation). This approach led to a
predicted hydrogen consumption of 153 SCF/B, in reasonable
agreement with the values cited above. Hydrogen makeup
cost at the 150 SCF/B level is about IC/gal. of raw waste
oil ($4 per 1000 standard cubic feet for hydrogen).
121
-------
WASTEWATER TREATMENT
The existing wastewater treatment system consists of a
primary oil separator drum, and two oil/water gravity separator
tanks arranged in series for treatment of all process and cool-
ing warers prior to discharge to the Kill Van Kull. Oil is
recovered by the use of vacuum hoses, and solids are removed
by periodic cleaning of ,the oil/water separators. The planned
addition of a new process unit will increase plant capacity by
approximately 3500 bbls. per day from the current capacity of
1000 bbls. per day and will necessitate upgrading of the present
waste water treatment system.
The improved treatment facility will include holding areas
for process water and rainwater runoff, and the addition of a
dissolved air flotation unit downstream of the existing separa-
tors. The quality of effluent is expected to be significantly
improved by (1) the additions to the physical facilities of the
treatment plant referred to above and (2) reduction in the
quantity of wastewater requiring treatment by a factor of 9
(43.8 gpm vs. 420 gpm). Figure 10 is a flow plan of the upgraded
treatment facility.
Holding Areas
The holding ponds and contaminated water storage tanks pro-
vide a reliable method for maintaining a constant flow rate to
the treatment plant, and permit the collection and treatment.of
storm water. In addition, some oil and suspended solids removal
can be achieved in the holding ponds and tanks before the im-
pounded water is fed to the treatment plant.
No. 1 Pond has a holding capacity of 27,000 gallons. The No. 1
Pond is the main collection basin used to feed the treatment
plant, and is located for easy access to all processing units,
truck loading facilities and tankage. Contaminated water will
flow by gravity from the storage tanks to the pond. A pump is
provided to pump water from the pond to the contaminated water
storage tanks during heavy precipitation.
No. 2 Pond has a holding capacity of 6,000 gallons. The No. 1
Fond~Ti~i secondary collection basin used for control of storm
watsr collected at the South end of the property.- and for storm
water in the No. 1 Tank Area. Water from the No. 2 Pond is
pumped to the No. 1 Pond or to the contaminated water storage
tanks prior to being fed to the treatment plant.
122
-------
ro
u>
Ij
», a-BA^r
4 UWfT
t
^
\ *
1
1
WASTEWATER TREATMENT FLOW DIAGRAM
FIGURE 10
-------
Contaminated Water Storage Tanks (2) are provided for stor-
age o£ process and runoff waters.Each tank is 20 ft, in
diameter and 20 ft. high with a capacity of 47,000 gal.
Oil/Water Separators
The two oil/water separators are arranged in series for
treatment of wastewater and storm water from the No. 1 Pond.
The two separators are of identical design, each having a
water holding capacity of approximately 7300 gallons. They
consist of a hemispherical section of a cylindrical tank 29
feet in length and 10'3" in diameter. The liquid at the
center of the tank is approximately 52 inches deep. Each of
the two tanks are gravity fed and are baffled at the down-
stream (South) end for retention of oil for removal by
skimming.
Air Flotation Unit
After leaving the two separators the wastewater rer-
ceives additional treatment in an air flotation unit which
consists of a central treatment chamber equipped with a
mechanical scraper for removing oily froth from the surface,
an entrance section, a discharge section and auxiliary
equipment for the introduction of compressed air with the
feed water. The air flotation unit is approximately 13
feet long x 3.5 feet wide x 3.5 feet liquid depth. The
auxiliary equipment consists of a recirculation pump and a
tank for the introduction of compressed air. As very small
air bubbles are released in the central chamber, they carry
oil droplets and solid particles to the surface. These are
removed by the mechanical scraper and transferred to a froth
drum where addition of heat or chemicals eliminates air be-
fore transferring to the slop tank. Coagulant chemicals and
coagulant aids are added as necessary to the feed in order
to achieve maximum efficiency in removal of oil and solid
particles. It is expected that the hydrocarbons reaching
the air flotation unit will have a low vapor pressure and
will not cause significant hydrocarbon emissions to the air.
If this should prove to be a problem.a controlled vent sys-
tem might be required.
124
-------
Continuous Oil Skimmers
j
Skimmers utilizing continuous floating collector .fsubes
(Brill oil skimmers—Model T-6) are installed at the eff-
luent weirs of the No. 1 Holding Pond, and in each of the
two separators. Continuous skimming will prevent the build-
up of significant quantities of "oil. on: the> wafeer saii^^ee
and will thus prevent reentrainment and carry-over to down-
stream treatment units. Recovered oil from the skimmers is
directed to the slop tank for reprocessing.
Run-Off Water
The entire system is designed to prevent inadvertent
draining of run-off waters to the Kill. This is accomr
plished by the use of curbing and drainage ditches around
the NORCO site. Run-off waters due to precipitation or
washing operations are collected in (1) one of two holding
ponds, (2) process area sumps, (3) behind tank area curbing,
and (4) the loading area sump. The ultimate destination of
all these waters, either by drainage or pumping, is the No. 1
Holding Pond, The water from the No. 1 Holding Pond is
pumped at a controlled rate through the wastewater treating
system described in the previous section, and finally the
clean effluent is discharged to the Kill.
The system designed handles all rainfalls up to approx-
imately 1 1/3 inches over a one hour period. In the event
of an extremely heavy rainfall in excess of this figure,
means are provided for diverting clean water run-off dir-
ectly to the Kill, bypassing the wastewater treatment sys-
tem. This operation is done by closing gates which serve
as inlets to the two holding ponds, preventing additional
water from overflowing into or out of the full ponds.
Flow Measurement and Sampling
A flow measurement and sampling box will be provided
at the effluent outflow to monitor discharges.
Additional Information
The design basis, sizing of major equipment, and pro-
jected water effluent quality are provided in Tables 84-86.
125
-------
Table 84, NORCO WASTE OIL RECYCLING OPERATIONS
UPGRADING OF WASTEWATER TREATING FACILITIES
DBS 1C-:; BAFIg
1. The steam jets and barometric condenser for the existing
10CC B/D vacuum flash tcwer will be replaced with ar.
indirect condenser and mechanical vacuum pump.
2. The steam jet condensers and barometric condenser for
the existing 1000 B/D vacuum distillation tower will be
replaced with an indirect condenser and mechanical
vacuum pump.
3. The steara jets and barometric condenser for the relocated
3500 B/D vacuum distillation tower will be replaced with
ar. indirect conderser and mechanical vacuum pump.
4. The steam jets and barometric condenser for the relocated
vacuum stripper will be replaced with an indirect condenser
and mechanical vacuum pump.
5. All cooling services in the plant will be by indirect heat
exchange with air or cooling water. The coolinc water
will be punped from the Kill Van Kull, and used'once-thru.
An oil detector will be used at the discharge to detect
leaks. Leak detection will result in diversion of the
water to retention ponds or shutdown of the leaking
equipment. A higher pressure on cooling water than
on oil will cause leakage of water into oil rather
than oil into water.
6. All process water (water contained in and recovered from
waste Oils) will be directed to the oil/water separation
system,
?. All normal runoff water will be directed to the oilA'ater
separation system, up to 1 1/3 inches rainfall in a one hour
period. Excess runoff in very heavy storms will bvpass
the separation system.
Sc Basic calculations -
Runoff
3.5 acres** 43,560 fV/acre x 12 = 12,750 ft3/inch rainfall
*Note total site area is approximately 3.5 acres. About 25%
of total area covered by diked or curbed process and tank
areas. Therefore, one inch of precipitation over 3.5 acres
is equivalent to ^. = 1 1/3 inches over free area.
126
-------
Table 844 (Continued).
Waste Water Holding Areas
Holding Pond No. 1 - 3,600 ft3 ( 27,000 gal.)
Holding Pond No. 2 - 800 ft3 ( 6,000 gal.)
4,400 ft3 ( 33,000 gal.)
3.
Contaminated Water Storage (2 Tanks) - 94,000 gal. (12,600 ft )
Run-off Treatment Rate (Based on 1 inch over 7 days)
3
12,750 ft over 7 day period
12,750 ft x 7.48 gal/ft3 = g>5
7 day x 1440 min./day
Process Water - Maximum
3500 B/D Crankcase Oil @ 57= water = 5.1 G?M
2000 B/D Other Waste Oils
-------
Table 85. SIZING OF MAJOR TREATMENT PLANT UNITS
National Oil Recovery Corporation
Bayonne, New Jersey 07002
No. 1 Holding Pond (27/000 gal.)
This pond was designed to contain the process water re-
sulting from normal operations and, with the contaminated
water storage tanks, to have sufficient capacity for con-
taining the first 1 inch of rainfall collected from the 3.5
acre site. Since approximately 25% of the site contains
separate enclosures, capacity is about 1.33 inches of rain-
fall. The capacity provided will handle normal daily rain-
fall, with bypassing required only occasionally (usually
not more than once in a given month).
No. 2 Holding Pond (6,000 gal.)
This pond was designed to collect storm water run-off
from the South portion (approximately 3/4 acre) of the
property which is too low in elevation to drain into the
No. 1 Holding Pond. Pond 2 therefore is used for pumping
to Pond 1. In addition, storm water from the No. 1 Tank
Area can be manually discharged to Pond 2 for pumping to
the No. 1 Holding Pond. A 500 GPM pump will be provided.
Oil/Water Separators
At the design treatment rate of 43.8 GPM, and the
liquid holding capacity of 7300 gallons, each separator has
a detention time of 166 minutes (2.75 hours). The detention
time for both separators is therefore 5.5 hours. Accepted
design practice for gravity separators utilizes detention
time of approximately 4 hours to achieve maximum oil-water
separation efficiency.
Air Flotation Unit
Based on the design treatment rate of 43.8 GPM ,and the
liquid holding capacity of 1200 gallons, the detention time
in the flotation unit is approximately 27 minutes. Recom-
mended detention times ranging from 4 minutes up to the time
U3ed were obtained from various manufacturers of flotation
equipment. A second parameter used to size flotation equip-
ment is the overflow rate which is defined as the throughput
128
-------
Table 8$. (Continued)
rate (GPM) divided by the liquid surface area of the cen-
tral flotation chamber (sq.ft.). The overflow rate of the
unit described is 43.8/25 or 1.75 which is more conservative
than the accepted value of 2 used for design of most re-
finery units in service today. Proprietary information
based on pilot plant studies in a refinery show that a
flotation unit designed using these criteria and using
chemical additions will remove 80 to 90 percent of the sus-
pended solids present in the feed and will reduce oil con-
tent to the range of 10-40 mg/1. The oil content of the
combined outflow (with cooling water) is expected to be less
than 6 ppm,
Continuous jDil^ Skimmers
The capacity of the Brill Model T-6 oil skimmer is
rated by the manufacturer approximately as follows:
heavy residual oil 2500 gallons/day
lubricating oil (SAE 20) 500 gallons/day
fuel oil (No. 2) 250 gallons/day
At the design wastewater flow of 43.8 GPM, and assuming
as a liberal estimate that the water entering the pond con-
tains 0.5% oil, the daily removal requirement approximates
400 gallons of oil. The three skimmers provided can easily
remove that amount of oil.
129
-------
Table 86. .
PROJECTED WATER EFFLUENT QUALITY
Present
Limitation'1'
Required Effluent
Discharge'2'
pH
TOC
M °*G
U)
0 TSS
Temp.
Zn - Total
Cr - Total
Avq. (Max.)
6-9
1200 Ibs/day
3300 Ibs/day
54 Ibs/day
100°F (110)
(1 mg/1)
(1 mg/1)
Av^. (Max.)
6-9
72 Ibs/day (140)
36 Ibs/day (49)
54 Ibs/day (140)
100°F (110)
(1 mg/1)
(1 mg/1)
TargetJEf f liient_Di scharge^3^
[•__{rf«l_X . T Bl'n/l _' nH|j/l_'
6-9
68 Ibs/day 130 19
21 Ibs/day 40 6
32 Ibs/day 60 9
100°F (110)
(1) Initial Effluent Limitation, Aug. 31, 1974 - Aug. 31, 1976,
NPDES Permit No. NJ0003565
(2) Required Effluent Discharge, Aug. 31, 1976 - Aug. 31, 1979
(3) For Phase I plant modifications, about May 1976
(4) Based on discharge from air flotation unit - 43.8 GPM
(5) Based on total discharge to Kill (including cooling water) - 300 OPM
-------
SECTION VII
REFERENCES
Conversion of Crankcase Waste Oil Into Useful Products.
U.S. EPA, Contractor - National Oil Recovery Corpora-
tion. EPCR Series 15080 DBO, March 1971. 87 pages.
Geyer, J. The Mechanism of Deposit Formation and Con-
trol in Gasoline Engines. Esso Research and Engineering
Co. Symposium on Deposit, Wear, and Emission Control By
Lubricant and Fuel Additives. (Presented before the
Division of Petroleum Chemistry. American Chemical
Society- New York City Meeting. Sept. 7-12, 1969.)
pages A15-A23.
Bethea, S. R., D. S. Bosniak, B. E. Claybaugh, and E. L.
Mohundro. To Hydrotreat Waste Lube Oil. Hydrocarbon
Processing: 134-136. September 1973.
Background Information for Proposed New Source Perfor-
mance Standards. Vol. 1. APTD-1352a. U.S. EPA,
Research Triangle Park, North Carolina. June 1973.
62 pages.
Sodium Borohydride-Handling/Uses/Properties/Analytical
Procedures. Ventron Corp. Beverly, Mass. Jan. 1973.
37 pages.
Inorganic Reduction with Sodium Borohydride—Principles
and Practices. Ventron Corp. Beverly, Mass. Jan. 1974.
20 pages.
Private Communication* Ethyl Corp. Baton Rouge, La.
Feb. 6, 1974.
Weinstein, N. J. Waste Oil Recycling and Disposal.
PB-236 148. National Technical Informa-cion Service»
Springfield, Va. Aug. 1974. 328 pages.
Weinstein, N. J. Re-Refining Schemes Compared. Hydro-
carbon Processing: 74-76. Dec. 1974.
131
-------
10. Weinstein, N. J., S. Maizus, and R. R. Keppler. A
Non-Polluting Oil Re-Refining Process. Industrial
Process Design For Pollution Control. AIChE Workshop
f:24-30. American Institute of Chemical Engineers.
New York City. 1975.
11. Automotive Crankcase Drainings Can Yield the Base
Lubricating Oil. Chemical Engineering :51, May 13,
1974.
132
-------
APPENDIX A
SUMMARY LOG OF OPERABILITY - PROBLEMS AND SOLUTIONS
2/15 - 3/15/74
1/15 - 2/15/74
The oil processed contained a high per-
centage of water (30.1% average), consid-
erable very abrasive gritty material, and
troublesome fibrous trash. The high wa-
ter content required excessive recircula-
tion of partially dewatered oil back to
the feed tanks to produce dry oil. The
fibrous trash passed through relatively
fine strainers fitted with cylindrical
basket sheet metal elements with 1/8 inch
diameter holes. The fibrous trash plugged
inlets of channels in the closed impellers
of the two stage centrifugal pump. The
single stage open impeller centrifuggal
pump remained clear. Erosion on the im-
pellers was not severe. The high grit
content of the oil cut the sliding vanes"
in a rotary positive displacement in a-
bout 3 hours. Elements of rotary screw
and rotary gear positive displacement
pumps were out in about five hours.
Heater erosion which occurs due to grit
can be reduced by reducing velocity, e.g.
operating at less vacuum or even under
pressure.
A procedure was worked out whereby waste
oil feed is first pumped from a wanned up
feed tank through cold suction lines with
a rotary positive displacement pump
through a centrifugal pump until the suc-
tion lines and the centrifugal pump are
adequately wanned up and filled with rela-
tively low viscosity feed going into the
fractionatar heater. After about 10-15
minutes, the rotary pump is shut down and
the centrifugal pump takes over. This
procedure eases startup problems and re-
duces the erosion and abrasion wear on
the rotary pump which has been experienced
due to the grit content of the feed (the
centrifugal pump with a priming vacuum
pump is an alternative).
133
-------
12/15/73-1/15/74
11/15 - 12/15/73
10/15 - 11/15/74
With the intake of a greater variety of
waste oils from more sources* including
vacuum tank trucks used for cleaning out
tank bottoms, cleaning up spills, etc., a
great increase in trash, debris, grit,
metal particles, sand, plastic, and other
foreign material have been noted. Swing
strainers with strainer baskets ace pre-
sently being employed. Slant bottom re-
ceiving tanks and strainers operating
with continuous discharge should be con-
sidered for future operations.
The dismantled 2 inch pipe coil coolers
for fractionator bottoms, light cut, light
reflux, heavy cut, and heavy reflux were
inspected after steam and air blowing to
remove oil and tar. All coolers were
found to be relatively clean inside, with
very little tar or signs of fouling. The
outside of pipe coils close to the bottom
of the cooling tub was rather heavily
coated with deposit from the salt cooling
water. All coils were corroded rather
evenly on the outside, with the 180° bends
corroded more severely than the straight
pipe. Corrosion varied from about 3/32
inch to 1/16 inch, with 1/8 inch on outer
curve of bends and some areas corroded
even deeper, accountina for leaks. Sharp
localized pitting did not occur.
Bronze veins tried on a rotary sliding
vane pump, instead of the recommended
plastic vanes, lasted somewhat longer but
the wear on the surfaces of the vane con-
taining slots in the eccentrically posi-
tioned rotor was much more rapid. The ro-
tor had to be replaced. The wear and cost
la excessive when the sliding vane rotary
pump ia used for pumping gritty oil.
Tube ends in the fractionator heater were
sweating (leaking very slightly at ends
where they are rolled into headers). In-
spection showed end of 6 tubes required
re-rolling. Tub,es tend to leak at rolls
when running waste fuel oil as heat input,
pressure, erosion, and fouling rates are
all increased over corresponding rates
when processing waste crankcase oil.
134
-------
10/15 - 11/15/74
(continued)
9/15 - 10/15/74
8/15 - 9/15/73
7/15 - 8/15/73
S/15 - 7/15/13
One leak developed when the flash heater
3 inch pip» coil was tested. In the pro-
cess of patching 'the leak, heavy fouling
of the coil and. thinning of metal by out-
»i
-------
5/15 - 6/15/73
is cleaned out periodically to avoid
carryover of solids to the bottoms pump.
The procedure reduces cleaning time and
coat.
An anti-foulant from Nalco Chemical Co.
was injected into the crankcase oil charge
and into the light and heavy lube oil cuts
at the rate of 50 ppm, with results very
similar to those obtained when an anti-
foulant from Exxon was injected in 1969.
Fouling in the heater tubes and in the
light and heavy lube oil cooling coils
appeared to be reduced. The color of
these two products was slightly darkened
from about L 7.0 to L 7.5 or L 8.0 on the
ASTH color scale. Tarry material which
settles to the bottom of sample bottles
did not solidify and tenaciously adhere as
occurs without anti-foulant injecting.
Odor seemed somewhat reduced. The Nalco
anti-foulant is considerably less viscous
than that from Exxon and required a dif-
ferent injector.
Both bronze and composition vanes have
been tried in rotary displacement sliding
vane pumps. With bronze vanes, the wear
on the vanes is slower than with composi-
tion vanes, but the wear on the slots in
the cast iron rotor is greater. Overall
economics favor composition vanes, but
temperature must be limited to 120°F.
4/15 - 5/15/73 Si
high water (50-55%) fuel oil was re-
ceived. Haste oil containing over about
35-40% water cannot be economically -and
satisfactorily processed in a single pass
through the existing equipment because of
pressure drop and excessive erosion at
high velocities in heater tubes and head-
ers. Therefore, about 20 hours during the
month was spent recycling the high water
content fuel through the fractionator to
bring the oil to dryness. Some recycling
of feedstock is required to start up and
shut down. This is being done in a manner
to get the most evaporation of water pos-
sible , -before going on stream to produce.
136
-------
dry products. A substantial portion of
the water content of the oils is evapor-
ated at relatively low temperature, but,
since the solubility of water in oil in-
creases with temperature, to achieve ade-
quate drying of finished oil, the bottom
of the fractionator must be maintained at
a temperature above the boiling point of
water, usually 4D-50°F, at the absolute
pressure existing at the liquid level.
3/15 - 4/15/73 Waste fuel oils from Butterworthing (wash-
ing of barge and ship tanks) processed
from Nov. 1971 to Dec. 1972 did not con-
tain much abrasive solids. Positive dis-
placement rotary gear pumps and rotary
sliding vane pumps were reasonably satis-
factory for pumping this material. Since
accepting tank bottoms and miscellaneous
waste oils from various sources, the con-
tent of abrasive solids has increased and
the wear on the pumps has been excessive.
The vanes in a feed pump had to be re-
placed after 50 1/2 hours operation. The
steam simplex pump used for pumping dried
processed fuel oil from the bottom of the
vacuum fractionator runs <&t a piston
speed of 30-50 feat per minute. Wear on
the piston, piston rings, and cylinder
appears to be reasonably low, but the ini-
tial and operating costs for such a pump
is high.
The pressure drop from feed tanks to pump
suctions is often so high as to cause very
low auction pressures resulting in erratic
pump operation. Tank heating to lower
viscosity is expensive, so that other sol-
utions such as the use of positive dis-
placement pumps and locating pumps immed-
iately adjacent to tanks are being tried.
Six tubes in the fractionator heater were
replaced because of local overheating and
actual failure of four tubes.
137
-------
2/15 - 3/15/73
i/15 - 2/1S/T3
The stainless steel thermowell in the 4
inch section of the transfer line eroded
through and leaked. It was replaced with
a hard-faced hardened steel thermowell.
The 4 inch x 4 inch x 6 inch steel tee in-
stalled to replace a 4 inch elbow in the
fractionator heater transfer line was in-
spected after 190 hours of service. Lit-
tle erosion was noted, certainly consider-
ably less than previously noted.
Severe erosion of the fractionator heater
tubes and of pumps, which began shortly
after NORCO began accepting waste fuel oil
from vacuum tank trucks and tank cleaning
operators, continued. A rotary twin screw
pump formerly regarded as reasonably sat-
isfactory became excessively worn after 60
hours of operation (about 100,000 gal.).
The vanes in a rotary positive displace-
ment pump lasted about BO hours at the
recommended speed of 500-420 RPM. The
erosion in tubes appears to be most severe
when the waste oil contains a high per-
centage of water. Resultant high veloci-
ties due to high steam formation cause
severe erosion, especially when solids are
present. Demu.Vaification prior to pro-
cessing to separate the bulk of the water
pceaant is very desirable.
The fractionator heater, transfer line,
and fractionator were inspected. A leak
at the>west.header of the first tube in
the bottom radiant row was stopped by re-
roiling the tube end. A small leak re-
Mlting from erosion in the 4 inch by 6
Inch elbow in the transfer line was found
and repaired by welding a 3/8 inch thick
steel patch over the heel of the elbow. A
small amount of fine grit and coke was ob-
served in the bottom of the fractionator,
which probably accounts for the relatively
quick erosion of the elbow in the transfer
line.
138
-------
12/7/72-1/15/73 The fractionator heater tubes and frac-
tionator were thoroughly cleaned and re-
paired during December 1st to 15th, for
the first time since March 20, 1972. Only
four short crankcase oil runs have been
made since that date. Two short drying
runs were made drying part of the water
out of the Berk's bottoms recovered from
the lagoons at the Berk's plant. All
other runs were made charging waste fuel
oil. The fouling rate is probably one
fifth as fast on waste fuel oil charged
during this period as on crankcase waste
oil. But very accurate determinations of
fouling rates on waste fuel oil is diffi-
cult when runs on waste crankcase and
Berk's bottoms are made between waste fuel
oil runs.
One tube in the fractionator heater was re-
placed because of thinning from excessive
metal temperature with resultant formation
of iron oxide and sulfide scale on the out-
side of the tube. Allowable operating
stack temperatures have been lowered to
reduce the tube metal temperatures. The
above will somewhat reduce the feed rate
when processing oil. Seventy-two (72)
stud bolts were re-welded on the heater
tube headers. One tube was re-rolled in
the headers. The 6" diameter section of
the fractionator heater transfer line
'eroded through at a point of high turbu-
lence just beyond the 6" x 4" steel elbow.
A thick fateel patch was welded over the
eroded area. The fire brick of the com-
bustion zone wall at the south side of the
heater fell when high temperature refrac-
tory insulation moulded over supporting
steel cracked and felly exposing support-
ing steel to high temperatures and buckl-
ing. A new steel tee beam was installed
and insulation replaced. The plastic re-
fractory around the burner opening was re-
placed. The burner was cleaned.
139
-------
11/7 - 12/7/72
10/7 - 11/7/72
NORCO's plant was designed primarily for
crankcase waste oil, requiring no tank
heating. However, with the onaet ot win-
ter and increased acceptance of a wider
range of all conceivable varieties of
waste oils, which can be processed and
blended to make saleable fuel oils, the
need for extensive preheating is becoming
apparent. This situation has been aggra-
vated by the increased processing rate,
starting with one 30 gpm feed pump then
two 30 gpm feed;pumps, and now with 50 and
30 gpm feed pumps installed. During the
summer, piping was installed for using two
48,000 gallon tanks equipped with heaters
as preheating means - also both tanks were
equipped with air sparger piping arrange-
ments for quickly and forcible agitating
tank contents with short, large volume
bursts of compressed air. Mixing results
have been quick and effeptive. However,
additional preheating will be required for
handling of quantities of high pour and
viscous oils at economic feed rates.
Since water does net settle rapidly free
the more viscous oils, most of the water
is removed in the fractionator. The lim-
iting factor in processing wet oils has
been the allowable pressure on the oil
heater tubes and headers, and the heating
capacity of the heater.
Determination of water content in many
waste fuel oils cannot be satisfactorily
obtained by the usual centrifuging tests,
ASTM D1796 and ASTM D2709, because of for-
mation of a gel which precipitates in the
bottom of the centrifuge tube. Hater in
the oil apparently combines with various
compounds in the oil to form the gel in a
total volume which bears no direct rela-
tion to the volume of water. If the sam-
ple is diluted 1:1 with naphtha or kero-
sene and distilled in a manner somewhat
like that described in the test ASTM D-95,
the water content can be accurately and
reliably determined. Modification of
140
-------
apparatus and procedure in distillation
teat ASTM D-95 provides a rugged inexpen-
sive apparatus and satisfactory procedure
for determining water content over a very
wide percentage range. The sample may be
heated and distilled to the required temp-
erature to drive over all water much
faster than when following the procedure
specified in distillation test ASTM D-86.
Also the dilution with naphtha or kerosene
may be varied according to viscosity and
probable water content, judged from grav-
ity and appearance.
9/7 - 10/7/72 The oil heating coil in the flash tower
fired heater ruptured during a crankcase
oil run. It was patched for short time
further service. This coil cannot be
readily cleaned by the usual methods:
steam-air decoking; chemical cleaning; or
mechanical cleaning because of the nature
of the deposits. A straight tube heater
would be much preferred for this service.
8/7 - 9/7/72 During the month, sludge oil received
from Pottstown (Berks) waa processed pri-
marily to remove water and trash. As re-
ceived the oil contained considerable free
water not combined as sludge or emulsion.
It also contained considerable trash:
leaves, twigs, sticks, dirt, grit, etc.
She fluid, to the unit varied abruptly from
ncn-viscous practically 100% dirty water
to 100% thick viscous emulsion. Control
of flow and heating in the flow control
instrumentation and tubular heater was
erratic and difficult. Pressure, flow and
temperature varied widely. The positive
displacement charge pump wore rapidly.
After about 100 hours of operation it was
replaced with a Moyno pump, previously
used for pumping oil and water mixtures
from oil water separators. This pump suc-
cessfully pumped the feed from the tank
through about 250 ft. of 4" pipe and hose.
The pipe was made up in 55'-60' sections
connected with hoses. From NORCO's exper-
ience, general purpose waste oil plant
141
-------
operators would do well to develop a trans-
portmble and quickly connected 'system of
pipa Motions and ttpse section's for pumping
«ll tfef various kiiid* of waste oils to be
encountered. Readily transportable and
quickly connected pumps with very short
suction lines would complete the picture.
For cold weather operation portable steam
suction heaters and steam supply would be
necessary. In some instances permanent
equipment might be justified.
7/7 - 8/7/72 Wet waste oils from tank bottoms often are
very high in specific gravity and pour
point. When the water is evaporated from
the oil the pour point of the dried fuel
oil becomes "normal," that is low. This
phenomenon may be associated with a "water-
soluble waxy material" in these oils.
6/7 - 7/7/72 Steam piping size to the flash tower and
fractionator heaters was increased from 1
inch to 1 1/2" to increase steam flow.
The steam is important to the operation
fori injection into the oil charge to
maintain adequate velocity in the colder
convection tubes of the fractionator heat-
art blowing oil out' of the tubes at the'
and of runs; drying out of deposits in
the inside of tubes before tube cleaning;
•nd for injection into the heater fire box
for snuffing out fires in case of tube
failures. The deposit encountered from
waste lubricating oil has quite different
characteristics from that encountered in
usual petroleum refining practice, tending
to be much less brittle and frangible to
impact of tube cleaner cutters. Flushing
and drying increases frangibility and
makes for faster satisfactory cleaning.
A 2 inch air line and hose were rigged up,
to replace the existing one inch line, for
blowing broken up deposits from the frac-
tionator tube heater transfer line. Clean-
ing time was halved from 16 hours to 8
hours.
142
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APPENDIX B
LOG OF RESEARCH AND DEVELOPMENT WORK
3/7-4/7/72
4/7-5/7/72
5/7-6/7/72
6/7-7/7/72
7/7-8/7/72
a.
b,
a.
HRI laboratory report on hydrotreating.
I-R spectrophotometry showed that the
major portion of oxidized impurities
in crankcase waste oil distillate cut
had been reduced by hydrotreating.
Ageing for 2 weeks at room temperature
showed some additional deposit forma-
tion .
Solvent extraction of HRI hydrotreated
oil improved color, haze, and odor to
considerable degree.
a. Solvent extraction program continuing.
a. Examination of crankcase waste oil
bottoms and sludge for Pb, Sin, Ba, S,
Br, V showed Pb, an, Br in major
quantities.
b. Analysis of solids from filtration of
tanker washdown effluent showed %i, Cu,
Fe, Mn, Pb, Br present in major quan-
tities.
c. Analysis showed low metals content in
NORCO sidestreams #3 and #4.
d. Laboratory centrifugation tests showed
most metals showed up in recovered
solids.
e. Contacts made with organizations with
possible interest in sludge.
f. Solvents found which cause settling of
aggregated polymer and solids.
g. Wax and water contents determined for
a waste oil.
a.
b.
c.
Naphtha dilution followed by filtration
upgraded Berk's bottoms (obtained as a
result of hurricane* igaused~spill_in
Schuykill Valley).
Centrifugation of Berk's bottoms.
Breaxit (Exxon)
bottoms.
treatment of Berk's
143
-------
APPENDIX (continued)
7/7-8/7/72
(continued)
8/7-9/7/72
9/7-10/7/72
10/7-11/7/72
11/7-12/7/72
d.
e.
a.
a,
b,
a,
b,
c.
d.
b,
12/7/72-1/15/73 a.
Further solvent treating experiments.
Voges filter trial gave 3.5 gals/ft2/hr.
filtration rate.
Bird and Centrico centrifuges were
tried for solids recoveries from
various waste oils and waste/oil
mixtures.
The possibility of effective filtration
of waste oils was reviewed.
A bowl type Westphalia centrifuge was
used to produce high lead solids.
Solvent dilution produced a greater
yield of solids.
Modification of ASTM method for water
determination for use with waste oils.
Further work on filtration of waste
oils.
Determination of solids content of
bottoms.
Solvent treatment of crankcase waste
oils with methanol, ethanol, n-*propanol,
iso-propanol, n-butanol, iso-butanol,
cyclohexanol, toluene, methyl ethyl
ketone, acetone, amyl alcohol, aJ^iunino
ethanol, glycerol.
Further solvent treatment experiments
using butanol, cyclohexanol, n-heptanol,
hexanol, 2-furaldehyde, furfurol, dode-
canol, tetraethylene pentamine, phenol,
n-octanol, iso-octanol.
Solvent treating of Berk's bottoms with
amyl alcohol with 10% pentane, methanol
with 10% pentane, 50% methanol with 50%
pentane, isopropanol with 10% pentane,
amyl alcohol with 10% pentane, 50%
butane diol with 50% methylethyl ketone.
Further solvent treatment experiments
on 2-amino ethanol, hexanolf heptanol,
butanol.
144
-------
APPENDIX (continued)
12/7/72-1/15/73 b.
(continued)
c.
d.
a.
b.
1/15-2/15/73
2/15-3/15/73
3/15-4/15/73
4/15-5/15/73
5/15-6/15/73
6/15-7/15/73
c.
a.
b.
c.
d.
3o
b.
c.
d.
a.
b.
a.
b.
c.
d.
Distillation of n-butanol/crankcase
oil mixture.
Separation of residue from NORCO
bottoms.
Iodine Number' measurements made.
Separation of residue from NORCO
bottoms and lead analysis.
Separation of sludge and water
from raw crankcase oil.
Treatment of raw crankcase oil with
2-amino ethanol.
Preparation of high lead solids from
crankcase oil tank bottoms.
Crankcase and waste oil characteriza-
tion.
Phenol and n-butanol treatment of
crankcase oil.
Plant wastewater pH measurements.
Distillate bomb hydrogenation test.
Crankcase and other waste oil
characterization.
Centrifugation tests on crankcase oil.
Heat soaking/centrifugation cycle tests.
Crankcase and other waste oil
characterization.
Acetone and methanol treatment of
crankcase oil.
Treatment of crankcase oil with
tetraethyl ammonium hydroxide, diethy-
lenetiriamine, potassium hydroxide.
Plant wastewater phenol and pH
measurements.
Tests of Nalco demulsifying agents
for fuel oil dewatering.
Total acid number of raw crankcase
oil and centrifuged crankcase oil.
Chemical hydrogenation with borohydrides
Waste oil distillations.
145
-------
APPENDIX (continued)
7/15-8/15/73
8/15-9/15/73
9/15-10/15/73
10/15-11/15/73
a,
b,
a,
b.
c.
a
b
b
c
11/15/73-3/15/74 a.
b.
Chemical hydrogenation with borohydrides
and lithium aluminum hydride.
Waste oil characterization.
Chemical hydrogenation with borohydrides.
Waste oil characterization.
Ammonium hydroxide and heat treating of
raw crankcase oil.
Chemical hydrogenation with borohydrides.
Deodorization with KOH solution.
Chemical hydrogenation with borohydrides
and sodium aluminum diethyldihydride.
Deodorization with KOH solution.
H2S04 solution pretreatment.
Characterization of wastewaters
Characterization of oil feeds and
products.
146
-------
APPENDIX C
CONSULTANT'S REPORTS ON WASTE OIL FILTRATION
147
-------
Worn
74-70 I72ND ST., FLUSHING. N. Y. 11366 .2H| 969-9794
Sopteaber 29, 1972
Hr. Sol Halnse
Project Director
National oil Boeorery Corporation
P. 0. BO* 338
Bayonae, New Jersey 07002
Bai Contract No. 68-01-017?
Subjecti Spaol&l Beport on Filtration
Procedures
Dear Hr, Mairasi
AO per your request, X hare prepared for yon e>
oeaprehensiTe presentation of our efforts relating to this
Botnod of separating solid waste oontaainonta froa oil.
We are emitting the obrious and obviously discarded
nothods such as plate and frasa presses, intermittent paper
filtraticn aad organic ocabrones (for the filtration of sub*
•icron particles), Th« latter, because they are nalnly &c*d
for biologlcala, are far toofexpeasive and the flow rate is
toefelow.
Our snrvoy, therefore, extended over industrially
typos including cdc« typs filters which ere capable
of SCBOV&R3 particles of five eicrcna and op. Sen* of these
f.jmftenis remlre the replaconont of the filter oadia vmca use.
Sflrai are calf olooulng by reverse blowing upon deposition
«f ft tiVSQT CClfCS.
ozcsple of the fcraer is offorod by the Billiard
la Eislra, Near yoc'it. The ocapaay maufaotu^ss
a uur'.bisr of aios typa filters coins papor, rcyca, fi^ar^laaa
tad ssT)33tc3 cc^Mtatlcaa and stack aountcd into tabular
(Bhapgl elencnto. ffho latter aolf oloanjn^ typs la oxo=?lifle<
by Vc^eo Plltsr Civic lea of the Cardweill Hacbluo Ccspany la
Klchacad, Virginia whloh is the American liconaee of a
Brlt&olv ocapuoy.
i farther group of filters is represented by
end Cn&o, both ooapaniec located la New Jersey.
148
-------
Sol Mftieua - 2 . September 29, 1972
The former oonpany manufactures a wire wound filter element
of cylindrical shape which can be cleaned (Intermittently
or continually by hand or automatically) by a peripherally
attached ecraping edge. In addition, Purolator manufactures
a line of oiorcnio rosin Impregnated paper filters as well
a* a thread wound filter cartridge known AB niero-pao for
every known fluid,
Th@> latter company, namely, Cuno Dl viol on 6KP, Inc.,
fabricates a netallto ®dg* type filter composed of * Stack
of stationary discs interleaved by corresponding rotating
wipers or eleaning blades.
In addition to the manual AS well as the. automatic
vereloa of this oleanable or self cleaning device, the
ooapany, Cuno, offers sintered metal filter elements, micro
screen cartridges, asbestos and cellulose discs as well as
pleated paper filter elements.
Both types of eelf cleaning filters described above
exhibit element spacings of the disc stack er wire windings
in the order of .001 to .003, thus setting a practical lower
limit of 25 to 30 Microns as the filter capability.
It aasms clear from our Investigations that the
filtration of gelatinous media carrying sub-mloronlo
occlusions presents a formidable probloa to the separation
effort. ThiB Is highlighted by the ultirato breakthrough
of sub-mioronlo particles into a highly ocapnsBoed paper
filter disc after initial clear oil flow had been obtained.
Thle was our experience with the Voices filter which in all
other respects is a superbly serviceable device. Once
started, the sub-oioronio contamination of .the interior of
a filter madia will oortainly preclude any further cleaning
and continued plugging end mloro-merltlo bridging in the
filter pores lends to ultimate clogging. It is, therefore*
obvious that contamination must be held at the filter edge
and it is clear that prior aggregation of the colloids as
well as peptlzatlon of the gels is of utmost Importance for
the feasibility and economy of this separation procedure.
A further effort derived from the above considerations
as well as our success in convincing EPA that the waste oil
r«sld«o should- not b» burned; but reclaimed and sold as a useful,
valuable constituent containing lead and other metallic
compounds. This residue i> probably best produced in a
continual process whloh precludes the necessity of batching
and scraping of the putty-like substance (which is not readily
ejected automatically from a centrifuge or filtration
equipment),
149
-------
Kr. Sol lUUus - 3 - September 29, 1972
Consequently, wo evolve the notion of discarding the filter
medium (paper) with the retained residue. Such a device
known as the Trcaael Vaouum Filter Is made by Technical
Fabricators In Mew Jersey. In It • newsprint type web
Is led over • drum which is connected to a vaouun pump.
The drun is inatnii* is the fluid to be filtered *nd deposition
Is continuous oad would permit ths ensuing sandwich of filter
paper and putty-like residue to be rolled up like 1030. a
very convenient fora of packaging and transport Indeed.
Our previous two progress reports recommended that
we proceed to exaalne filtration as a practical means of
separating our collected waste constituents.
Since the above mentioned Trommel Filter is solely
operable by vacuum, we nay Incur some difficulty if we
Intend to use alcohol or other relatively low boiling
diluents. One would have to resort to some fora of cooling
of the feed stock or preferably achieve a modification of
this filtration method to allow for pressure rather than
vacuum operation. Suoh a devise would have to avail Itself
of a sealed chamber and we would be obliged to study the
pata&t structure of the Troaael filter to insure that no
infringement exists.
Additionally, «• hoy* recommended that the use of
filter Aids or polyeleatrolltes such as Heroufloo be
considered. The latter is organic and thus auto-degrodeable
in the following processing steps. Olatonaoeoua earth as
well as clay could easily be used ia. small quantities and
may even take the place of the more expensive chemical
coagulants now being considered. The addition of a small
amount of Dlcalit* or Piltros should add*little of
significance to the 26 elements already fresent in the
lube stock In their various phoxphate and calcium compound
combinations. The subsequent reclamation steps conducted
by tha suiting eoopanies must certainly include leaching,
roasting or reduction steps capable of digesting such filter
alas, It ee>-;BD obvious that their use would oaterially
influence fchn ease of deposition and filtration rates as
wall AS ooets. Ona might envision this as an adsorption*
aggregation -filtration affect in a single step.
B«yand the above presentations, we have researched
the efforts of separators for the treatment of industrial
and eenUery waste. These include the Cata-Sep Oil/Hater
150
-------
Kr. Sol HalEue - 4 - September 29, 1972
Separators offered by the Pollution Control DlYlsi.cn of FWI
In Tulsfc, Oklahoma, in addition to the 80S System produced
In Santa Ana, California and waste water treetaent station*
utilizing tilted plate separator* a« manufactured by Cabinet
F. Gulguos in France,
The Cata«Sep process utilise* IB addition to a
gravity separation system a unique catalytic coll to recover
gasoline, fnal oil wad ether lube stocks frca water. The
catalytic cell is raelesneble and 18 capable of separating
varying oaounts of oil frca 20ppm to several percent froa
large volunea of rater. This process will effootively broak
all oll/arator eauleions but It Is cot clear frca the literature
submitted to us fthat affeot oil vetted aollds would hare on
the aotlvltj of this equipment.
Howeveri Vhin e:ff«ct is not In doubt with the 3ES
Systea which utilises what 10 essentially a fibrous resin
bonded coagulating cartridge which Is good for one half
million to one million gallons at a flow rate of approximately
ten gallons per DimrU. These cartridges are used in parallel
mltiples thu* poraittlu^ tJie tuili up to sny flew ra*«
required. Their dimensions are as followsi 22" long by
6™ In diameter and ocetiag $27.50 per cartridge. A similarly
dinensloned pr«-fliter cartridge which i« reeoxaendod for use
with waste containing Ifirge amonntM «f d«torg*nta or oil
wetted solids 8«lls for |1<>.50.
151
-------
iabvwi&im
tltm St. fCUSNtNS. N. Y. 113*4 HIJi 96V-W4
Nov«Bber 30. 1972
Kr. Solfred Haleus
Project Director
National Oil Beoovory Corporation
P. 0. Box 33»
Bayonne, Rev Jersey 07002
Bet Contrast No. 68-01-0177
Subject* Konthly Progress aeport 1*9
11/3/7* -* 14/3/72
Dear Mr. Mains*
This will appriKe yea of our progress during the
preceding couth to datei
.' 1. The fellovlns represents an exhaustive
• trefttlient 6t filtration efforts to date
' ' '- and X thtnX4t: siea represents the state
. - ef the art as applied to ear speoif ie
. -'• frobleos. To recap briefly e we were
•rifiaallir giten a BaxUOM flow rate of
, . ,- ", Zgpfi per square foot of filter surface
:/'*' by teetoieal ?a*rtcator». This eztreaely
' ' • ' ' ' tow -tbfa«f%»-»»ft; fS>eBpd us to contact
Talhorst, a Otrt«t«a «t Anetek. regardihg
• perforated bask«% AtBtrifnges. The thinking
' MttioA thi* Bore «se jn JBft lly -to provide
anah «2«*ter PI*«*SMMS than could be
f
by vamjua filtration and coablned
.aa»mtaeM of a dUQpoaabl* liner.
rMvita with this equipment indicated
« tefflSMSttlo iaprcnrenent whieli could, hewerar,
»©t be uaixttalaed for any length of tloe due
t» t'wrly blinding of the filter aedlua. The
addition of dlatoaaeeoua earth resulted in a
rate of Ogpm. per square foot of filter
surface end up to 6 gollono through-put
.before blinding occurred. The proooee, as
oeatenplated, rcaorcn a 5 to 10 nil layer of
the preooat per revolution. However, deeplte
the eatiefaotory filtration rate, the
Alopoaal problea^of over 10,000 Iba. of
4iatonae«ious earth per day for full refinery
152
-------
Rr. Solfred Halzwi - 2 - Noreaber 30, 1972
operation la considered unacceptable.
2. Since It was not ol«ar whether the thlokn«aa
of preooat whloh had to be "shared off* was
due to the difficulty of controlling a finer
out or because of sludge penetration depth,
we once nore swung over to Technical
Fabricators with a request to preooat the
newsprint filter medium used on the raowa
• drum. By this device, we were able to
increase the flow rate from the previous
2gph to iO-14gpm. In this effort the
diatoaaaeooa earth precoat was sprayed
on the paper, but again filter aid use was
considered to be excesslye.
3. Dp to this point all tests had been conducted
with dilutions of Butanol In ratios of 2 to 1.
In an effort to get rid of tha filter aid, we
decided to test some 4 to 1 dilution ratios
and found that a batch, uhich had been prepared
•cae weeks ago, now yielded considerably
reduced filtration rates than had been obtained
wtoen this aixture was freshly prepared. We,
therefore, made up another quantity of 5
gallons consisting of ^ parts Eutcaol and 1
pa?t lube oil stock. To one-half of this
quantity (2*1/2 gallons) was added 300c.c. of
•Paatane la an effort to produce a "drier*,
I.e., less gelatinous deposit. This freshly
prepared naterlal was filtered without filter
al& at tba rate of l?gph for the part containing
Fentano and SOgph for the pure Bntanol aixture.
r
4. Cooiildarlng' all factors such as equipment coats,
based oa processing speeds as well as material
expense and disposal problems, this represents
probably the opti&um result to date. At the
AniH Telocity of lrpE« we would consume
ftpproximately J40.00 worth of paper per hour
when processIng ^00,000 gallons per day. The
paper is, of course, ooneuaed in the reclamation
of the Kietalfl froa the sediment and presents no
.disposal problem whatsoever*
5. too additional alternative is contained in the
proposal b? Aaatek to conduct further tests at
153
-------
Kr. 8elfred Kalrue - 3 - Woreajber 30, 1972
EMt Holtm, Illlnoie laboratory
Mine Solkfl-Floo in place of inorganle
filter fids. this substitution would
alro elfBlmte th« dttpowil problem and
quit* ppoiwbly retult to further
inere««ad throagh-p»t r*tea.
C!OMH£HTABY
»
This work ma conducted with •peolflo emph»aie
en oontlnuottfl operotlon ••* aonporod to the In t emit tent
reaerml of eentrlftsg* sludge. As we pointed out previoualy,
our filtrate Is «n unusnelly difficult coablnatlen of small
and aub-Bloron pnrtlolea In gelatinous nedla and la thus
eztreeely hard to separate. Additionally, the material
exhibits a taekjr oenalateney thus ooaplloatlng its renor«a
froa eqalpoent aurfaoea eren further. For these reaeons,
we have oonoentrated on th« ablative techniques described
above and feel that alsilar techclques night be loTestlgated
In eonneotloa With the diftlllatlou equipment uaed.
Very truly yours,
tABCBATOBZES
/6SBE4BT
Gtf/sJ ; f
154
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RESULTS OF CENTRIFUGATION TESTS USING A
BOWL TYPE CENTRIFUGE
Crankcase oil
The feed sample of crankcase oil when analyzed by the high
speed "Sorvall" centrifuge gave a sludge value of 3.8% by
weight. The effluent of the chamber type clarifier, when
run under a flow rate of 100 gal./hr., gave a value of
2.7% sludge. The efficiency of the clarifier was there-
fore an approximate 29% when running at 8100 G '&&6T"~"~'~
residence time of approximately 10 minutes.
The accumulation of solids product varied from 19 Ibs./
1000 gal. run to 13.3 Ibs./lOOO gal. run. Analysis showed
13.5% lead content.
Crankcase oil treated with solvent (n-butanol)
The crankcase oil was treated with solvents at the ratio
of 1:1 and 1:2. Since agglomeration occurs with solvent,
the analysis of input feed is critically dependent on
sample taken. Because of the time delay in workup and
transmission of proper samples, a great variability was
found in the sample workupa A typical effluent using an
oil/solvent ratio of 1:2 yielded a 0.07% solids content.
The actual run using a 1:2 ratio gave 10 Ibs., of sludge
per 100 gal. of oil, and with a ratio of 1:1 yielded 7
Ibs. of sludge per 100 gals, of oil. The efficiency of
agglomeration is evident with the solvent as compared
with straight crankcase oil (1.9 to 1.3 Ibs. of sludge
per 100 gals, oil) and with crankcase oil diluted 1:1
with naphtha.
Analysis of the solids obtained from a 1:2 centrifugation
run yielded 15.9% lead.
Berks Oil
100 gals, of Berks waste oil bottoms were centrifuged as
obtained and 23 Ibs. of solids were collected. Analysis
of this solid for lead showed an 18.2% content, a value
which is of interest to metals re-refiners.
Coal Tar Oil
100 gals, of coal tar oil pumped from #105 tank was fed to
the centrifuge. Solids buildup was somewhere between 20
and 25 Ibs.
Preceding page blank
156
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CENTRICO, INC.
Q Nottnwjfe G ftaunont. CtM Q Chicago, m. Q wt-n*» H.w«n. fii »v
G*Urt-w QFMUTm Cl Pf oo*M M or i * HI * £59 Os» ,
ComputT NATTp^aL O^T. R^QV^Y C£??P. fMO!tCQ>
**]'«• P.O. Box 388
B«yonn»
, __New._JerBjay^
PROCESS nnPORT
_Mi.i
_9-16-77,
j, Dr. .T. Cnynr
•^«.' 137-7300
taM/r
KG-10006
Clarification on
1611 «97
oil
UACMIM SPiCmCMIDNt
n—oi-jn^ Carbon steel lini*dKMih ^1"S
M, H«*« «ia» — w.'
DM. M 0* D NtXflHl C SlMCM " MM. — MM fcttaf. Ruing CMmM: O knr O C O CU» D Slon.a Q B" ••
2 chanber bowl
PHYSICAL DATA OF PAOOUCT
ii> 80 cja pu^..
Solids diocharg* % • Trace
Feedrata 100 gal/br for 10 hour*.
Open opening tin bowl, kthere was found'^5 gal. of water, and
18 lb». of solids Kludge.
dutoacr requests SO Ibs. of solids sludge (47 Ibs.)
~ ~ pun* vill be Bade with solvent added to the orankcasa oil.
UttChfflAtt
Houtino
ITS
AcW"
Info.
Copy
In.:..
O.K toFitr
157
-------
CENTRtCO. INC.
Q Irtiwi. C*. n OMKOL M. n »M« Hmm, M Br
PROCESS REPORT
QIM-W D *•«*«< Cl*roc«>M«L# -- PB» _i£B - Ojtt .
. OVUM ». -BE*. J ij.'yft1?
P.O. BOX 3JJ
IW Kr.-10006
AMKOUI Clarification of mixed prod. 200 gal.,butvl" and 100 gal. Tkcoil
KM MM* P.H.O. » IMlfUn* .
Carbon steel lined with 316SS
A UOM nww —lAlf MM, Hmy n*M -
>.•« a*. D **•«* t3'*P"eW -
btwl
.MM RrngOmUgMn»M__Zr - "" u— ,.».-. " uu
. HW IPK«. I
-------
M»numvawaew«T.»«.o M*iT»*iw*rmv*a,rMM Mii«o«f*4i*Tt., tortcm
, INC.
January 11, 1973
Kr. H. J. WaliMtain
RICOH SYSTEMS, INC.
Cherry Valley Rood
Princeton, Haw Jersey 08S10
Deer Mr. Ueinsteini
Enolosad pleaae find a copy of our general catalog as well aa
the separata sheet severing tha KO-10006 which is basically the
•ana machine which was run at National Oil Recovery on your pro-
ducts. Tha 2 basic types of machines which would be applicable
for this project would be tha desludger type and the chamber
bowl typ«, both of which are described in the bulletin. It is
in our opinion doubtful If tha desludger type would be able to
consistently discharge tha hard packing solids completely and
therefore at the prasant time wa would not recoiamend such a
machine.
The chamber type bowl-KG-10606 has a maximum G f&rce of 6.UOO*
Tha approximate priea for such a machine would be $18,000, in->
eluding tha notor. Strictly for comparison1• sake, a deeludger
of approximately the saae size would have a price of roughly
»U0,(IOO.
Ha hope the enclosed information will aid you in determining
tha faaAib&lity of applying centrifugal neans toward a solution
of yoor problem. It is CENTRICO'S feeling that this is not an
Ideal application and unless tha economic side of it looks ax-
tramaly good, wa do not feal that our equipment is applicable.
If you should have any further question* or if you would like
to visit with us and discuss tha project we would be happy to
do our Swat to assist you at any tima.
»ary truly yours,
cnmuco, INC.
Our Kef.- PR* S«8 V. Lindensun
Process Engineer
159
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Chamber-type Bowl Clarifier Model K010006
(Supplementary leaflet to KO Pamphlet 3545/687)
Since 1969 \VESTFALIA SEPARATOR AC has extended the KO range of clarifiers to include model KO 10006
in addition to models KO 2006 and KO 8006. The (devious type KG W006 has thus been replaced by a wore
modern version of the same capacity. Particularly the fittings of the KO «Wg* are arranged in a clearer fashion
than those of the old KG type clariftert. Tht fitting* tan be eattty removfd together with the hood permitting
quick access to the bowl.
Technical data end eapacl'Jee
Mods)
Two-chsmb*. bowl total capacity
sludge folding capacity
Sl'*-chamber bowl total capacity
sludge holding capeclty
j Motor power
Bow! ^.oeed"
Capbcitles"*','or beer wort up to
Fruit juice up to
Red wine up to
Capacities" Molasses up So
Hot clear varnishes up lo
Liquors up to
KO 10008
litres
litres
litres
lltrat
MV
IP
cpnt
tttree/h
bop.
lKra»/i)
tap. gola./h
US. pals./h
lltre«/h
imp. gela./h
US. gals./h
kg/h
Ibs/h
ks/tt
Ibs/h
IHreVh
Imp. g«!s./h
US.
76.5
89
75
60
11
15
4500
10000
2200
2640
3000
660
790
5600
1230
1480
3000
6600
5600
12300
11000
2400
2900
Weight of complete machine with motor net kg 1130
net Ibs 2500
gross kg 1370
gross Ibs 3000
Pecking case dimensions frame with motor length In cm 166
In Inches 65
width in cm 96
In Inches 38
height In cm 125
In Inches 50
length In cm 71
in Inches 26
width In cm 71
In Inches 28
height In cm 70
In inches 27
net kg 400
net Ibs 1000
gross kg 460
gross Ibs 1010
Clarifier models KO 2006. KO 8006. and KO 10006 meet the
requirements of the Federal German Physical and Technical
Institute (PTB) and may be used wherever explosion hazards
exist.
Packing case dimensions bowl
Weight of bcwi
* TIM opne depends on the -pscllic gravity ol the feedstock ana on the bowl malarial used. It may therefore diner from the normal speed gltnn above.
** The hourly capacities depend on viscosity, tv/nparature. difference in specific gravities ot feedstock and solid matter, character of the solids to be removed.
and the desired degree ol purlly of th« clarified liquid. If the particle site of trie solids is very small and there Is little difference between the specific
grsvltfes of solids and liquid, the hourly capacity must be reduced to extend the retention time In the bowl. The maximum throughput capacity ot the bowl
Is, however, considerably higher than Indicated.
160
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APPENDIX E
HYDROTREATING ANALYSES AND DATA
Catalytic Hydro1;reating Experiments 162
Hydrotreating Feasibility Analysis 163
Hydrogen Consumption Botnfo Tests 183
161
-------
CATALYTIC HYDROTREATING EXPERIMENTS
SUMMARY
A sample of combined sidestreams obtained from the
Vacuum distillation in the National Oil Recovery Corpora-
tion's plant was hydrotreated by Hydrocarbon Research, Inc.
The color improved from 8 ASTM to 3 ASTM, and the API
gravity increased by two points. The color and odor were
excellent and it was indicated that, even after two days
standing at room temperature, the color was maintained at
this high level.
In addition, the Hydrocarbon Research Laboratory per-
formed a vacuum distillation on a full waste crankcase oil
sample and then charged this sample immediately to their
hydrotreating facilities in the pilot plant laboratory.
The vacuum distillation was operated so as to cut into the
waste crankcase to the extent of allowing the production of
only ten percent bottoms. This sample was indicated to be
darker in color as feed to the hydrotreater than the pre-
vious NORCO distilled sample? however, the product after
hydrotreating was of higher color quality than the previous
sample, and the odor was identical.
There were no operability limitations or any indication
of undue plugging of the catalyst. The pressure was 600
pounds per square inch at 700°P.
162
-------
PRELIMINARY NORCO WASTE LUBE OIL
HYDROTREATING STUDY
Report By
W. C. Rovesti
R. H. Wolk
Hydrocarbon Research, Inc,
Laboratory Report Number L-1236-501
April 18, 1972
163
-------
<>:;*,V''#/:-'.V;TiVf -:••! ' •• •-' . : .,
'l:/'.:*^; i INTRODUCTION
*• *.,- •
'f,-,.
The succ'eissful^ reclamation of waste crankcase ofl Is .Important
both for*the conservation of our natural resources and for eco-
•r* '. •'>•••?.*' • ;','[• '...•'
logical considerations. In order to reduce a suspected tendency
to dispose of the waste oil In a manner which Is detrimental to
the environment; e.g., dumping on the ground, Into sewers or a
convenient waterway, It Is desirable to be able to convert this
(' i
material Into saleable products. Simply burning the waste ofl,
In addition to heavy fouling of combustion equipment, results
lr» the release of >Its heavy metal contaminants Into the atmo-
sphere where they could become a serious air pollution problem.
r
•'•.•} , • ; ••
The National Oil Recovery Corporation (NORCO) waste oil re-re-
»
finery In Bayonne, New Jersey recovers three side streams from
a vacyun''distil Tat fon tower: a light fraction, dlesel blending
components, and fuel oil. All of these are dark In color and
.{.' ' • /••
contain varying amounts of tarry components. A blend of light
and heavy side streams from the vacuum distillation was found
to contain small amounts of a solid residue which Is thought
to fom upon standing. These polymeric solids form a rather
l-
stable "floe", thereby causing the product to have an undesir-
able color. The persistence of an offensive odor also detracts
164
-------
from the salablllty of this product.
f , ' ' l!"''! '"'.' •'
:>. ' •.;:'. ' ' , •.•''•' "' • '
In ordef to study means by which the qualfty of this blend of
i' - ' ' ' ' ' . " •'' ! • , ' '.'
the light and heavy side streams may be Improved, NORCO has
i ''"'• '' '.'•,.; ' ''•• " ' /i'1'1' ' •
comnfss|oned HRI to carry out a short term study to determine
V ' ' ' j
the-effect of hydrotreat ing on the product quality. The Intent
of this study Ss to provide preliminary data rather than to es-
tablish optimum operating conditions and catalyst or provide
data on catalyst deactlvatlon, etc.
165
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SUMMARY AND CONCLUSIONS
'•'y^'^^k-^-^'^jv''-^^^1,' ,.
• - ^'fj'1 . :^Vf'v?:;f,;•-:., j -•i.:;V;" ^:';li:f; •:.:' •"•
, . .- , ,.-. . . •,.,
A preliminary fixed-bed hydrogenatlon study was performed on a
", "' ' ^ ••''"", '
—Wend of side streams from the vacuum distillation of waste
"', » • : •' ' - ,
•• .,•;••',• V -•/' ..' ^-"J- j • • • . •.'<•.,>:,.••
crankca^e of) carried out at NORCO's Bayonne, New Jersey re-
refinery. Freshly distilled heavy vacuum overhead prepared at
HRJ was .also hydrotreated as part of the study. The laboratory
,'~'j • " ; • ^
distillation was carried to a higher end point, and this yielded
i ' .! ' ' ; •
J
a higher proportion of distillate and a substantially lower
"0
,'
quantity of vacuum bottoms. The object of this work was to de-
_,-,:• i
termine the effect of hydrotreatlng on product quality, especially
color, color stability, odor and metals contaminants.
i
Based on the results obtained during the course of the study,
the following can be concluded about the effect of hydrotreatlng
on product quality,
1} A substantial Improvement in color and colon stabtl!ty for
', *
the side stream bland provided by NORCO.
2) An even greater Improvement in color, which was stable, was
obtained for freshly distilled feed.
3) Removal of offensive odor found for both feeds.
166
-------
k) Apparent reduction ?n lead (the major contaminant) content
by well over an order of magnitude for both feeds.
In addition, no problems with the operablllty of the fixed bed
hydrotreater were encountered after a total of 6? hours on
stream using both the NORCO blend and the freshly distilled
* .
feed.
In summary,'the results of this study Indicate that hydrotreat-
fng may be a very effective way of Improving the product quality
and salablllty of products from the reclamation of waste crank-
case oil. The positive results achieved during this test program
Indicate that additional laboratory and engineering work Is justi-
fied In order to arrive at an optimum processing scheme.
167
-------
• '"•' H' "Ji; •':::" .';>*J' ' V;\ EXPERIMENTAL
Feed Materials ;
Three liquid samples from NORCO were received on March 21, 1972.
These were labeled waste crankcase oil (HRI 33^3), light side
stream (HR! 33^0, and heavy side stream (HRI 33^5). A repre-
sentative sample of the waste crankcase oil was taken for analy-
ses. However, no analyses" of the light or heavy side streams
were made. All analytical results are presented In Table 1.
A blend (L-322) of three volumes of the light cut (HRI
and two volumes of the heavy cut (HRI 33^5) was prepared. This
preparation was reported to be the same as that produced In the
NORCO vacuum distillation and constltured 65-volume percent of
' i
the distilled product. Approximately 20-volume percent bottoms
and 15-'volume percent->Hght overhead were produced In the plant
distillation. Analysis of the blend Is also presented !n Table
1.
L1
* NOftCO reports a gravity of 31 to 31.5°API for the light cut
and 29.5 to 29.7SAPI for the heavy cut.
168
-------
and ttie 99 V 5 end point,: was 940°F.
-,>•"**" M' ' - -'I-'' ' '
Fixed Sisd Operation
The MOR0 side stream blend (L-322), and subsequently, freshly
•'•''' ^ * 1. ' : '
prepared heavy vacuum overhead from the distillation of the
waste crankcase oil, were hydrotreated in a continuous bench-
scale, fixed bed pilot unit.; A once-through operation with no
recycling of either liquid or gas was employed. The catalyst
used was a commercially available 1/16" extrudate hydrotreating
catalyst. The catalyst was presulflded prior to use. Operating
conditions employed were:
Hydrogen Pressure - 600 pslg
Temperature - 700°F
•Hydrogen Gas Rate ; - 1500 SCFB
Liquid Volume Space Velocity - 1.0 Vo/hr/Vc
Catalyst* ' -
The hydrotreating operation (Run 184-130 was begun with'the
NORCO side stream blend and after a total of 44 hours of con-
7
tlnuous operation, the heavy vacuum overhead from the first
-batch dJstt Hatton was fed to the unit. Subsequent distillations
i' '• k
f- >.
were carried out to provide sufficient feed. The heavy vacuum
overhead was hydrotreated for 23 hours before a voluntary shut-
down of the unit was made.
*Americ£«i Cynamid .HDS-3A Nickel/Moly 1/16* extrudate
169
-------
. • . • .
Vacuum Distillation of Waste Crankcase Oil
. ,, ;. . . ., ] , ,.
Vacuum Distill at ton of the total waste crankcase oil (HRI
' ' i.>X:JV<... ; • • " ••"-; ' "';"' !i^-v ••*.< i'1'' >;vv-.v..
was farjrlid "out In order to study the effect of hydrptreatlng
' i :*.--' :.'.' ' :;v - . - '• • ".:• -'•!•'••'-.-• ••• '.;-;
prepared- Intermediate fraction distil led under
' '
''•f ' . 'f.' - 1''. •. ;:•": • ''' l ' . , • ' .: '! ''~- ' ' •'••...
conditions where a minimum of 10-volume percent bottoms are
produced. The distillation was carried out In a batch still
(Unft 200)1^ A charge to the still was approximately 3500 grams.
Several distillations were made In order to provide sufficient
feeds for the hydrotreatfng run, described later In this section.
< , fi - '. '< /:'' (
'•< -• - „ ' ' , ' i' '"' ' y .
A sample of the heavy vacuum gas oil (L-3?3)_.wh|ch was fed to
'"',""' 4 . > . ' 'J
the fixed bed unlf during the 8-hour test period (184-131-
Pertod 3D) was analyzed. The analytical results are presented
•4 • '•'< '•' ' ',..'. •.;
In Table I; The vacuum distillation employed In the preparation
of L-323 was carried out to give the following cuts:
Weight %
Knock Outs Plus Light Vacuum Overhead 18.3
Heavy Vacuum Overhead (L-323) ' 76.6
Vacuum Still Bottoms 5.1
The charge (L-323) to the fixed bed hydrotreater (Unit 184) during
Period 3D had gravity of 29.8°API compared to 30.5°API for the
MORCO side stream blend (L-322). The IBP of L-323 was 492°F
170
-------
8,
RESULTS
Qperabtljtv
• ' " ' * ''• '
A total.of 67 hours of trouble-free operation were carried out
using thft two feeds. There was no apparent difference between
the NORCO blend (L-322) and the freshly distilled heavy vacuum
•i
overhead;(L-323) from the standpoint of operablllty over the
short-term, ..fixed bed hydrogenatton run.
Analytical Results
i '
The analyses carried out on the total waste crankcase oil (HRI
33*»3), the blend of NORCO side streams (L-322), Its hydrotreated
product (18VI31-1B) , the freshly distilled heavy vacuum over-
head (L-323), and Its Jfydrotreated product (I8M31-30) are sum-
'„ . i
roar!zed In Table 1.
The metal analyses were run using atomic absorption spectroscopy.
Both hydrotreated products contained a small amount of dark par-
ticuJate natter which readily settled to the bottom of their con-
1-7 i
-------
irs.f^Thp samples were decanted to avoid possible blockage
of the atomic absorption unit burner. Therefore, ^the metal !;
analyses of the products do not reflect any metals'which may :
:-;, "";;> ''•'' '•'•' :;;-.;"£ .•••'"-<.':..;••.• • ' • '. ' .--^n , .-'.{.•••;''.:.'''•.'",
be Tn the.settled part I culates. M i^ - i ;
—Jhe ASTM, color was run according to the ASTM standard D1500-64.
>.•' Hydrotreated products were purged with nitrogen In order to re-
>. wove the dissolved H£S prior to running the determination.
Product Odor
- . .
Both products; wereU'sniffed" after being purged with N2 to re-
jnovfi dissolved 828. The odor characteristic of the feeds
appeared to be absent.
172
-------
SUWAHY OF ANALYSES FROM PRELIMINARY MORCO HYDROTREATING STUDY
10.
1
V % S
•API
V 'A (IBP-400°F)
-V-%- (IBP-600°F)
N, ppm
Pb, ppn **
Ca. ppm --*
Na, ppm **
Fe, ppn **
, Ash
Total Waste
Crankcase
on
HRI 3343
0.22
25.2
-~, —
' 804
._•..
, _ — ,_
«»««
___.
NORCO
Side Streams
Blend
L-322
<0.07
" 30.5
• ....
256
2
0.25
M.b.
0.37
Hy
-------
March 7, 1973
Kr. Solfred Maizus
President,
NATIONAL OIL RECOVERY CORPOWtfTIOH
P. O. &ox 338
Bayonne, ttaw Jersey 07002
Dear Sol:
I have drawn the following observaj
fron my inspection and analysis of the p:
data available on distillate hydro£csA£JU
ons and conclusions
ixon data and other
vezy.
174
-------
Mr. S. Maizus -2- March 7,
In order to fferra up the technical basis for completing
the development of%he vacuum distillation/hydrogen treat-
ing precast, i reconHwsndr
1. Batch bo»b tests in NORCO's laboratory for pre-
liminary hydrogen consumption c-.casuronents. Or.
Oeyer end I are already arranging such teats.
2. Flow experiments to be conducted in an outside
laboratory to firm up hydrogen consumption. I
have discussed such experiments with Sua Oil Co.
This should involve about two weake or leoa work,
if hydrogen consumption is reasonable. The
experimental period nay be lengthened if a para-
meter study is required to minimize hydrogen con-
sumption while making satisfactory product. It
is also proposed that the_£un_vork include certain
performance capability teats, .fiJvputlined in their
letter of February 16.^1473. H»ryill also be
contacted to aacerta^tjyti^r interest and ability
to carry out this
3. A life test on the cafealyat of choice. In view of
the favorable/da£^%0S^^te. X consider this test
to be non-orl'tfcai^od *$£aa to delay initiation
until the ab^y« wortf JLs complete.
to provide a basis for
f oultnrfproblesns. This should be started
" re to Bteet our previous schedule.
ss this with you within the next
S. Continuing research on metaiv recovery from the
distillation bottoms product.
£ have attached some of ».y moat pertinent calculations
and data suaeftaries for your use.
Sincerely,
llorman J. Heinetein
President
NJW/gtf
Enclosures
cc: Messrs. R.
J.
E. Urquhart
175
-------
HqU>ICTIOH OF HYDROGEN CONSUMPTION
Basis: Exxon Data
650°r., (SO peig., 1 v/v/Hr-, 800 scry
HYDROGEN
CONSUMPTION
SCP/B DISTIIJATE
Aromatic Saturation
Desulfurization
DanitroQenation
Deoxygenation
11C
Olefin Saturation
For Q.ffc
153 SCF/B
or 3.64 SCP/Gal.
- 1.4«
-------
Gravity, °API
Sulfur, Wt. %
Nitrogen, wt. %
Oxygen, Wt. I
Hydrogen, Wt. %
I CM! in* NO.
Dlftillat«
29.8
0.31
0.04
0.35
13.03 (frosj gravity
correlation)
871.0 (Based on 2
942.8 SCF/B - 22.5
For 0,4*/SCP H2* nax. Cost » 9.0«/Gal. Distillate Peed
or 0.64 x 9.0 * 5. ?f 6/0*1. R«v »*««
-------
COM SUMPTION
"
Teap. , °F.
Sravit¥, ®APX
ProUuet
Feed
Product
-J B. Wt. 1 S
00 ~~Peed
Product
C. Wt. » H
Peed
Product
o._wt._% o
Product
C«lc i!a Cqpauiaptioo,
~A~
B
C
D
Olttfln Sat.
Total
Reported
1% & • *O////*v5T*
9.03C^/?t|l2N
V \ j
\> y
0.018 OTWi
0.005 0.002
Tro"f3" "57518*
7 7
7 7
>3.9 109.8
3.2 3.9
1.6 2.0
7 7
7 7
fr.TpP ll5..Tf.
URI (7)
1 y/v/^i
700
30.5
32.3
13.20
13.52
\ <0.07
A iP^.51
CTx
fN 0^001
V Vj^in
7
7
219
2.2
7
7
221.24-
- 600 PSZG
700
29.8
31.9
13.07
13.46
0.31
<0.07
6 ' 0.0327
9 0.0022
j
255
i!a
7
7 .
571*70-+
IPP-Lub
Piniahinq
7
27.0
28.5
12.50
12.80
0.30
1.5
0.6
0.9
7
«>«
194.4
33.1
f
227^7
140
e
(1U
7
24.7
25.6
12.04
12.23
-oTIF
2.0
0.8
7
7
*«*•
137.7
45.1
182.8
185
-------
Gravity, "API
Vice. 9 100ey.,SS3
Vise. * 210eF. ,SStJ
Viscosity Index
Ma»h Point, °r.
-J Pour Point, °F.
vo
Natjtx. NO.
ecu, wt. «
Copper Strip Cor?.
A«fe, Wt. %
Sol fated Ash, Wt.t
Hater, vol. »
astw, vol. *
Sapoa. tto.
RAW
M&STR
on. ISSPEX^IOMS
RAHffi3^KW«5UHT"EREO
vacucs H?OSO-
TOMER tREATEO
Loaz on. S>s^I.I.y«*'fEj_3j B^IikA?£
22,0-27.9 (2,4,«J 29.8-30.7 (4,7) 31. 3-31. S (4J
137-54$ C2.4.6) 1
44-1S7.9 (4) 1SS-162 (4)
5S.4-9S.8 C4,*J 43.1-4^.3 (4) 43.8-44.1 (4)
12?-196 (4) ^--— -^
175-400 (2.4«,« S
(-30)-(-45) (4) l^
4.3-7.3 (4) 0
3.3-12.6 (2,4)
-
1.0-J.78 (2.6,7$
1.02-2.41
0.05-11.0 (1,4,6)
Approx. 2.4-15 (6)
11.3-35.4
riOS (4) 131-104 (4)
410-430 (4)
Sf~\\S) «*15)-(*20) C4)
.2^.p/m-_^^ 0-0.005 (4)
\/yV V\o.ooi (4)
\V_-y/i-2»)
— Ts^\\
v^—^y
V_x
TYPICM. 150
VIS trEOTRAI,
LOBE STOCK
31.fi (4)
157 (4)
43.9 (4)
104 (4)
415 (4)
+15 (4)
0.01 (4)
0.01 (4)
1 (4)
RB-EEFISEi
24.6-29.0
271-930
53.5-75.9
£8-105
0-0.19
0.23 (9)
Trace (9)
Pentana Inmoi.,
wt. %
Sulfur, Kt. «
Hltrogea, tft. %
Oxygen, wt., %
1.5-7.3 (1,6)
0.21-0.34 (4,6,7) 0.07-0.31 (4,7)
0.08-0.21 (4,7) 0.02-0.04 (4,7)
1.36-2.25 (4) 0.16-0.35 (4)
0.012-0.07 (4,7) 0.08 (4)
0.002-0.008 (4,7)
-------
OJgt INSPECTIONS (Continued)
saw
WAStfl
VXCOTIN
Mt.t
Color „ ASfH
Oslo* Stability
Metal*.
00
o
bead
Sine
8ari«w
Calcitse
Iron
Fluoride
Other
C.05S-0.il
Bi*ek (4)
350-9S9 (4.C,10)
100-1000 (C,10)'
700-2100 (6,10)
53-2000 («,10J
3$ (10)
Kg,V,B,Cd,Cr,
Cu,Mn,u*l.,Sn.
K,5l,x*,Sr,Mo,
Ti. (6,10)
3.5*8.0 (4,7)
arono-
IREATED
DISTIZJATB
TTPICAI. ISO
VIS HBAOTRAI.
LUliE STOCK
0.5-3.5 (4,7)
16-18 (4,5)j
1,2.9-3.5 (7,12)
0.05-0.4 (7,10)
B,SB,Si
1.5 (4)
RE-US RRED
OltS
0.001
3%-7
1 (*>
O.S (9)
«.S (»)
1 (9)
RECOH SYSTEMS, IMC.
Princeton, H. J.
fi. J. I'oiaateio
March 7, 1973
-------
1. linvironraental Quality Systems, Inc. (KQSX), "Waste
Oil Recovery Practices - State-of-the-Art," December
1972, Table 83.
2. 2QSI, op.cit., Table 8C.
3. Approximately 400-1050°F. boiliny range.
4. Bethea, S. R., et al.,r * A Modern Technique for Automotive
Waste Oil Re-Refiningt Distillation * Hyarofininy,"
Letter free G. R. L. Shepherd, Bsso Research and Enyineer-
imj Co. to P. a. Ledeman, 0. S. Environmental Protection
Agency, March 1, 1973. >j|
5. Ta^-Robinson color after 16 hours lal^ 212°F.
S.
7.
9.
9.
10.
11.
12.
API, "Final Report of the T
Publication Mo. 4036, 1969
Roves ti, M, C. and Wo Ik.
Lube Oil
L-1236-501, April
Armour Research I/O
Disposal,- Report
Refiners, 1960-6
'orce. on Used Oil Di«po«al,'
"Prelitainary NORCO Wast*
URI Lab. Report Mo.
tudy of p«-Reflninq Haste
Nation of Petroleum Re-
3onnif«y,
Spent Lubicatin
and
W. V.
Information obtained frbn tha 0. S.
Protection A'jency. ,
IFF, "Luh« Hydrofinishing,
September 1972, P. 167.
ASttf color aft«r 9€ hours.
) , "A Me%? Process for Reclaiming
ila,' presented et the Mational Fuels
, September 14-15, 1972, .'lew York,
Environmental
RECOM SYSTEMS, INC.
Princeton, «. J.
H. J. Wsinsteln
March 7, 1973
181
-------
ll-O
CONTENT
VS
LUBE OILS
*A/*r
182
-------
HYDROGEN CONSUMPTION
BOMB TESTS
Hydrogen consumption bomb tests were conducted for
NORCO by Merck & Co. Two tests were made; one control test
with Nujol, and the other with a blend of NORCO lube dis-
tillates. The oil recovered from the NORCO oil hydrogena-
tion was remarkably clear in appearance and odorless.
The interpretation of hydrogen consumption from boinb
test pressures is very difficult because a number of simul-
taneous processes can occur, and apparently did occur in
this work. These are catalyst reduction, hydrogen adsorp-
tion and chemisorption, ^O formation and condensation,
physical absorption of hydrogen into the oil, formation of
NH-j and ^S (and possible absorption and adsorption) , and
saturation of aromatic and olefin compounds. As shown in
Tables E-l to E-5, and the attached figure, separation of
these effects was attempted.
The maximum hydrogen consumption projected from the
data for the NORCO blend was 70 to 160 SCF/B. It is believed
that hydrogen consumption can be kept at a reasonable level
as long as no aromatic oils are allowed to enter the lube
distillate boiling range.
The principle uncertainty in the range of hydrogen
consumption is lack of information on the eatent of chemi-
sorption. This and other uncertainties pertaining to ad-
sorption, hydrogen solubility, and especially the effect of
oil composition could be eliminated by a series of bomb
tests. As can be seen from Table E-2, obtaining hydrogen
consumption information from oil compositions is highly
unreliable.
183
-------
TDROGEN
BOMB TEST
300 cc Bomb
1. ftr«s«4»e tee* Mafe-wlth K}.
2. Cha*9« csid boefe with 50 grams oil a»d 50 grans of
3. Chsroa toeob *t *aara «e*p*ratac» (approicimataly 70°P.)
vith J03 t»i9. I^flrogen. IWKicd reon
4. RMt bomb to CSO°«. (343. 3°C.) •• quickly a* possible
without xocfclng. Record t«nperatur« and pressure as
•• poMibl*.
5. Start benb rookimj and hold temperature at 650°F. Record
tecipcratur*. and pr«s»urs as frequently as possible until
preseoro c tarts to line out. Keep system closed for at
lecst 24 hours, lon^ar if pressure has not lined out.
6. Allow bonb to oool to room temperature. Record pressure
and temper atiw« •* feeotiently »» pos*lbl«.
7. Carefully release hydrogen pressure.
a. Keoovsr oil wtst oatalyet for analysis.
10. Ma control with hydrogen and a parafflnio oil (Hvr)ol,e.g.) .
184
-------
TABLE B-2
KORCO OIL HYDROCBNATIOH TB8.T
Oil. ANALYSIS
% c
% H
« N
% S
» O
86.30 t 0.30
13.52 t 0.30
0.03
0.27 t St
0 i 0.2
8«.«7 i 0.30
13. C7 i 0.30
<0.02
0.036 t St
0.2 i 0.2
BOMB CHARGE
50 g. Barahaw No. BT-100 E 1/16* catalyst
SO g. Oil
Hydrogan (saa Table* 4 and S)
CATALYST ARALY8IS (3ar»hii* Brochure)
BiO, vt.« 3,8
MbO3cvt.% IS.8
Si03>»t.« 2.0
Ns20,wt.% 0.02
Pa, wt.t
0.03
Lo»» en Ignition 8 «80°C., wt. % 1.4
Charga Oanslty, Ibs./CF 38
Surf*fl* Ar««, M2/g. 191
Pora Volona to 10,000 A°, co/g. 0.54
Avarage Pora Radiua, A° 63
185
-------
Period I Bomfr filled
at roon temper atari I. Hj under preireve in vapor
to 320-320
a.; HI .edcocbed onto eatalyit
3. Hj diMolved in oil.
Period II Heetup of boafe 1. Additional Hj dissolve* in
oil.
2. .82 deaorptien
3. te»je hydrogenation
Period XXI Agitation at otttttcol 1.
teotporature t*j(V\ 4 HlO * H2O(V) + Hi)
2 • ttyw«TO99tt dWBlBOJC Pt toil *
Period IT Cooldem «t lm*V 1, Bs
• mMtenitation end
186
-------
1. H, v*p«» in. bonk «*»<•»& o* P»r£0* 1 » 634,0
Z> 704.6
III • 615. 1
XV • 460.1
2. Hj adsorbed and dissolved at end of Period
.e-$3.4.0 - 70.6
I lainus fehae at end of j»»rlod II » 7»4.
(70.fi SC?A = 1.7 X J.O 3lbs. HWlb. cat
70.15 ECF/B >« i«.,wU * 83 in oil) tb«r«
effect i« preihsW.y adsorptionfe
3. H-> cl,«misorbe<5 - .mMNHC&a °> 89.5
(§9o5 St?/B • 3.« a«W«* m/trtion « - maxlaura
usually cjoasi«S«r&iS too 'Ira 1.0).
4. Hj adsosrptiois + Hj diesoltstion •*• H;0 condans*-
cion and adsorption • «15. 1-460.1 - 155.0
5. HiO ccndeneAtioD and ad«orpt.ion » H20 used in
catalyst r«*K!ttiea • 15S.O-7G.6 - 84.4
T@4.4 SCF/R » V',,43- w.l«« Ha/mele NiOr
sen* MiBOj My »Mttr al«o) .
1, n • PV/BT
3. No hydrogenation.
3. Cb«mi>orptlon i> Irreversible
under conditionB uead.
4. Hj «
-------
TABLE E-B
NSgto.T» Ot NORCO OIL HYPROGEMATIOM TE3T
NORCO OILi Blend of No. 3 (1.2857) and No. 4 (1.000)
1.
2.
3.
Hj vapor in bank «t end of Period I
II
HZ
IV
Hj adsorption * B« ^1"solution •*> HjO
condensation and Mgorption * 600.6-397.0
Subtract HJ0. u«*d in oatklyat reduction
Subtract Hj itdeorption * BJ dissolution
is
0.671 vs.'O to 0.2% analysed)
Bj adi
tiona
Then additional BjO • H,L
(48.6 SCT/n '" 0.671 vs. -
iroa deoxygenatlon
Apparent 8* consumption « 630.0-600.6
Add H) available from 82 desorption minus
H2 dissolved
Add HjO fron d*oxy«enation
Sobtraot ehestisorbed 8}
Add 8] cscsoraed ia denitrogenatlon (1.3
M& S ctjntrataa in devulfurisatioa (8j
Bae Table* and *„
630.0
877.2
600.6
397.0
• 203.6
_
119. i
70.6
"IB7T
29.
188
-------
h-
00
H, " t
^
SM&H
0*1
14
,1\
-fan** ferae
(fstA/'K)
t,13'?W.
TJ-*H-
aar
*< I
*»i!.
-ET
^
~c-
p /e »s -
r«o/zt-*'
p.n.
-------
-"- »-"<-"«"• l_s_/A_
-------
HYDROGENAT1QN OR HIGH PRESSURE REACTION
PQ NOt VVHITI IN iHtS b
REQUESTED BY__
PROJECT NO
.XT..
.;PaOJECT_
STARTING MATERIAL
NOTE BOOK OR LNO.-
""-. /•!'! f. MOLES.
G. MOLES
MOLES OF HYDROGEN REQUIRED..
OTHER MATERIALS
"F_,;/. ._' r!~ : I,
. ML. OF
REACTION CONDITIONS. E
.\*,~ " ;/Y. .•--IV
STRUCTURAL FORMULA:
EMPIRICAL FORMULA:
TO BE FILLED IN BY HVDROGENATIOh LABORATORY
CATALYST_
SOLVENT_
i! Q. MOLES
--T, 1 U- OF
-ML OP _! __
OTHER MATERIALS
CONTROLLER un . - •" g*
CONTAINER/LINER
CALC'O H, PRESSURE CHOP •
CONDITIONS
. i L.P. SHAKER NO.
HSATER NO. ^-ZiteLl Liic^-BOMB SO. _L^
, SHAKER TANK AUX. TANK SYSTEM VOLUME .
LBS./MOLE . . MOLES •
C. MISC. DATA:.
/» "15
HJ/')^
/OS'S
/;> -v
to •/•_>"
/O ^>"0
A;-7
//>'d
an
11 if
n>^
( % JO
/I? I
.
"V ^/
3' '
C" j •
4,7?
'..77 <
.Iff
.fff-
/.fto
I. it
J.I77
//O
5/6
3V3
5V.
/.;/?
' /.//V
6- ?'>'/'
rr> K>:.L
PRESSURE.,_
191
-------
Mr/ Sol f z-«d';j Maiircsis, • • 'Pro 5edt
National oil iteeovc&y • Co:
P. O. Bc«/3S8
Bayonro*
n
Di««el Engine Fuel Tests
Of
Deer Sirs
As our
ing program
are • produced
a dieeel
._
is desirous1 .of "' p»rt,i»ri|iatlng'-. in"; your Rest
de'^ordstrat® that your epecial falls Vhich.
orankeese w»et®
« the f ol lowing
• ' ••';• • • -^-'i- '-.:: ':-- ' • ,i-
.Test Report op Various %^®l.® IJeed .-for Piaeel .ffiaet.1'
Truck H-5 l@Se Diaraspfl T_JM? CuBittrtinqs C-1BO
5/18/70,
'''"-totalling -'Wrgallon* of
r .f '-1- ., •' t,1- -
••i-*! •••., A '•-•> V,.;,f . V -,-,^;:
S/1%/70 pqlt in ®««n® ^ixtMJ?« totalling 20
. ' .: K; milaage 135,520:^-:. ;,;• ' v •'.
•, • ' ;, - • f / * .• i v .
..-':' " ' : *!•*• -^'V --'-
,.3/20/70'-_pi^tin saffl^'rai^ur® total" 14
5/21/70 Put'vln awtt»\ aaixtiars total' 18 gail
J^*;;/. •r^''jt£i,X ''
Lloria';^^. v-|,''?8i':
5/22/70 *»ut Isa
5/23/70' wis
-------
5/23/70
5/25/70
5/26/70
5/27/70
5/28/70
5/29/70
5/30/70
.Varnish,.•''rft^v«dj|uel filler and took^artv'il
No varnish> no foreign matter on steel;.
,ij i, ' , J i' ' -. -." • ; ''.••>'$'*i/>< • i L< ' . p| ' ',' \ .11 '
-. '.;••.•$„• ; ' . • .•" ;1;;: v
Based on a mixture of 75% LDA
regular diesel, 24 gallons was put in of the
mixture specified> mileage 135,923. -^ r .^,
Put in same mixture totalling 20 gallons,,
mileage 136,043. ; - •
Put in same mixture totalling 18 gallons, ;
mileage 136,151. .-./' V' '^!""',". ^
Put in same mixture totalling 19 gallons,
mileage 136,265. •>. ' .',fV %-;';;
•,.,1.;.^, '' :; ' .-rC *.•?..: ,•;
Put in same mixture totalling 22 gaXldns,
mileage 136,-397«,,;- .' ./.^ '.'"J :^'. t
.Removed fuel filter and check out, all
-------
./. .• .,. • -•. ; /'
The smoking out of the exhaust stack seemed to
,>.-•: turn .to a lightly-'white, but ±heV^odor''
objectionable. The power as claimed
driver seemed to^ be' very 'good-in'
Fuel filter was^diffassenibled/and
clean. A c«rbon!;;SBMB 11 prevailed. ;'':j;'i|^'^>''xi;^^ ---'
:' "^ ';-;:-'T|v ' •^'••'•ifei1. "! '.•;$$£• -&/',;-
we will continue'to test ypur produeitfl dn our i;diesel ,trucks
until instructed otherwise. Let ue again re-state our
willingness to conttibute supplies andK-serVicei'^oj' yo«irr: _
worthwhile • program - ,whiqh Demonstrates e re.' of"1--
_a_wasted natural 3e@®0«irce Into useful
•-'.' • 'v$« • : '* ' >'•',- •
relist
-fff •'" */4',, •: , *'
yi^U'^'ta. J'ii. Vi'';; '"' :'
1 'j&'ii. '• - T • ^ '
w*
-------
Table G-l. CHARACTERIZATION OF WASTE ffUEk OIL
IN 20 X 20 SOUTH TANK
(Charge for Run No. 9)
Tank: 20 ft. diameter x 20 ft. high
API % %
SAMPLE LOCATION GRAVITY WATER* OIL*
1 Top 29.5 - 100
2 18 ft. from 26.0 10 90
top
3 18 ft. from 26.4 10 90
top
4 17 ft. from 25.1 10-15 87-95
top
5 12% in. from 3.5 - 100
bottom
* By centrifugation at 32,000 G for 30 minutes,
ng page blank
197
-------
Table G-2
From
Tank
Top
22.5 ml,
13.0 ml,
1. ml,
CENTRIFUGATION OF A WASTE OIL SAMPLE
(Northern New Jersey Oil Co.)
From
Tank
Middle
20
1155x12
2
From
Tank
Bottom
11-13
5-7
12
Centrifuge
Results
Liquid Oil
Heavy oil or wax
Water
Table G-3. AROMATIC DISTILLATION BOTTOMS WASTE OIL
Specific Gravity 6 60°F 1.136
API Gravity, °F <0
Flash, COC, °F 420
Pour Point, °F +55
Sulfur, % 0.4
Saybolt Furol Viscosity @ 122°F 130
B.T.U./lb. 17,000
Distillation
Initial, °F 630
5% 642
50% 674
Not. mlscible in NORCO #3 sidestream
198
-------
Table G-4. COAL TAR OIL
Hydrogen, wt, % 6.24
Nitrogen 0.18
Sulfur 0.36
Carbon 85.9
Ash 0.028
Distillation (100 ml)
initial, °C 50-59
3 ml. overhead 150 (slight yellow color)
97 ml. liquid - (dark color)
199
-------
Table G-5. WASTE OIL INSPECTIONS
Sundry samples from suppliers and NORCO tanks were analyzed
as follows:
Sample Identification
S - 20 x 20 Tank
S - 20 x 20 - 18'
S - 20 x 20 - 18'
S - 20 x 20 - 17'
Bottoms of S 20 x 20
16 x 16 Tank
J. Noonan B Tank
#6 Oil Sample (NBR-86-2)
J. Trainor (NBR-94-1)
Howard Fuel Corp. (loan 41)
(NBR-94-2)
J. Trainor #3
R & H
J. Trainor (NBR-94-5)
Solar Chemical (Tank 209)
B. Ogust
Ryan (Citgo)
Howard Fuel (loan 14)(NBR-99)
Trainor, Jr,
Trainor, Sr.
Smerdon
Lenza
Smerdon
Trainor, Jr.
Admiral
National - 1
National - 2
OiJ. Tank Cleaning
Industrial Separator
29.5 API gravity 100% oil
26.0
26.4
25.1
90% oil,
10% H20
90% oil,
10% H20
85% oil,
10% H20
100% oil
8.5" "
6.84% Ash
20% H20, 0.215% Ash
100% oil, 0.005% Ash
85% oil
No water
Trace H20
Trace H2O
Trace H2O
60% oil, 10% sediment,
30% water
85% oil, 5% sediment,
10% water}' 0.127%rAsh
1.1% BS&W
50.2% BS&W
15.0% BS&W
3.0% BS&W
4.0% BS&W
6.0% BS&W
5.0% BS&W
5.0% BS&W
20.0% H2O, Gravity 21.6
2.1% BS&W
54% BS&W
33.8% H20, 0.90% Sediment
1.4% H20, 0.74% Sediment
200
-------
Table G-6. WATER CONTENT OF OILS RECOVERED FROM
BARGE CLEANING
VALVE 1 90% H20
VALVE 2 56.6% H
VALVE 3 0 % H20
VALVE 4 0 % HO
201
-------
Table G-7. WASTE OFF-SPEC PETROLEUM PRODUCTS
An inspection and sampling trip was made to the Citgo
terminal at Linden, N.J. where 13 samples were taken.
Eight tanks were gauged and average or top middle and
bottoms samples were taken. Notes were made on existing
terminal pumps and lines. Data was accumulated on lead-
ing hoses and equipment required to economically load
tank trucks with oil from the subject tanks.
The Citgo terminal was formerly the site of a relatively
large asphalt production and also a terminal operation.
The asphalt operation and associated tankage has been
eliminated. The terminal operation with dock and tanks
continues. Eight scattered tanks contained varying
quantities of mixed and contaminated oils which do not
meet standard product specifications covering: flash,
gravity, distillation range, etc. The scattered tanks
and limited access pose transportation problems. Truck
filling from the various tanks will require from 50 to
300 feet of loading hose with fittings depending on
location and pump pressures available.
202
-------
Table G-8. WASTE TAR OIL FROM AN OBSOLETE COAL GAS PLANT
The gas holder at the Long Branch, New Jersey plant was of
the conventional liquid sealed telescoping type. The bot-
tom section, about 147' - 150' in diameter by 35' high, was
almost completely filled with liquid, as is the case during
normal holder operation. It contained about 24' of water
and 10'7" of dark viscous sticky fluid slightly heavier
than water. This dark fluid settled to the bottom of the
bottom section. There seemed to be about 6" semi-solid
ooze on the bottom. The line of demarcation between rela-
tively clear water and dark sticky material was not sharp.
Even at 1' above the floor of the bottom section, turbid
water interpenetrated globs of the dark sticky viscous
material.
Samples of dark viscous fluid taken about 16" above the
bottom ooze contained pockets of turbid water. The water
tasted almost like rain water, felt the same, and on smooth
plane surfaces spread out and behaved like tap water. It
had little odor. Other material from a small tank being
dismantled had the same characteristics.
The plant was provided with what looked like a shell still
with condensing coil and fractionating tower.
From the absence of volatile material, in samples taken,
it was concluded that lower boiling aromatic materials
were promptly removed from coal tar and disposed of when
the plant was operating.
203
-------
Table G-9. CHEMICAL PLANT WASTE OILS ~ ANALYZED AT POINT OF GENERATION
E L EMENTA1. ANALYSIS (%)
Heating
Value ViBcoaity
Nature t
Mo
Solvent
Wastes
1
2
3
4
5
Heavy
Residues
6
7
8
9
10
11
12*
13
14
15
C
65.92
89.46
36.70
37.24
21.15
81.50
68.87
80.93
67.37
71.18
79.87
55.5
62.02
70.56
36.16
H
15.50
9.18
12.20
6.94
10.07
5.10
6.55
10.57
3.82
9.23
5.48
4.75
4.18
8.52
2.00
O
16.15
1.87
47.0
37.11
22.50
8.76
15. 1«
8.90
15.22
15.16
8.76
7.65
1.20
9.32
2.20
N
-
-
3.37
8.86
0.68
_
—
6.70
0.21
9.07
9.30
10.55
7.85
5.81
Sulf Alkali Metals
.') ated Na K Ca
ASH
0.41
0.42
0.23
0.38
0.96
7.94
5.03
0.53
0.23
2.50
Oi37
-
19.74
-
53.71
0
-
-
14
7
0
13
2
2
11
0
14
2
0
_
.9 - -
_ -
- _
.14 - 3.5 -
.69 1.47
.46 - - -
.78 2.66
.4 0.46
.69 0.47
.65 2.24
.19 -
.10 - - -
.43 0.44
.78 -
— « —
Chlorine
2
0
0
1
36
-
-
0
0
-
15
_
0
_
Cl
.04
.33
.13
.51
.8
.77
.75
.72
.15
BTU,
14,650
17,000
10,250
6,100
4,570
13,500
13,125
15,650
11,810
13,280
13,500
10,740
11,770
15,480
8,400
«*?C>
4.2"
2.5"
9.0"
40.0"
20"
270'"
d??1"
625"
'WOO ' ° *
50*1
110'"
150**
1100irr
300-
500"
* Contains 5.7% Zn
Table G-10.CHEMICAL PLANT HASTE OILS
Identification
Wt. * Sulfur
Wt. % Ash
Semi-Quantitative
Spectographic Analysis
of Ash, wt, »
Principal 10-100
Major 1-10
Strong 0.1-1.0
Medium 0.01-0.1
Weak 0. 001-0. ol
Trace 0.0001-0.001
Faint Trace f*. r*inl &•*$•«» **rtf-o.
EN Pitch Bti Pitch
No. 1 l|0. 2
0.002
4.3 4.4
-
Fe,Na Ha
Al,Si,Cu Fe.Cu
Nl,Mq,Pb, Al,Ni,Si,
M.n/ri,c.a Mn.Ca
Cu,Cd,B,£>, C«J.My-Pt'«
Mo.Ba Ti
In,V,£r,Co B,Mo
Ag Ag
SJi „ 0-Mg,Pb,
Mn,Cta,Ti
Cd,Sn,B,Mo,
V,,Ba
Ag ,Zr ,Co
.
Bi,Ge,In,Ga,
AB,Sb,H,P,Au,
Hg , Be , Zn , K
,
'
-
-
SBE Tars
No. 4
3.57
0.4
None
None
Slioht
Good-Excellent*
Good-Excellent*
-
—
Fair
2 ml of (1
Tar t 3 ml
gram
MEK)
+ 3 ml NOKCO 16
Good Mix
prior to miscibility tests.
204
-------
Table G-ll.IODINE NUMBER OF NORCO CRANKCASE OILS
IODINE NUMBER, g./lOOg. oil
Centrifuged Oil 0.73
NORCO No. 3 0.91
NORCO No. 4 1.03
205
-------
APPENDIX H
COALESCING PLATE OIL/WABER SEPARATOR
The attached figures illustrate the separator design.
It consists of three principle sections—an influent region,
the coalescing section itself, and an effluent region. Each
is described below.
The oil/water mixture enterstthe separator through an
"H" shaped inlet manifold. A series of holes drilled in the
vertical members of this manifold (a) helps distribute the
water uniformly over the entire water cross-section of the
tank (b) degasses the influent and (c) dampens pulsating
flows. A vertical slot flow straightener located immediate-
ly downstream of the inlet manifold completes flow distribu-
tion and insures uniform conditions into the coalescing
section.
The coalescing region begins with the first group of
corrugated plates. Eight individual plate stacks, arranged
in two rows of four each, are used in the OPC-50. Each
stack consists of a series of plates stacked vertically,
three plates to the inch, with the convolutions running
horizontally at right angles to the flow. Spacing between
the plates is maintained by tabs molded into each plate.
The entire stack assembly is held together with two tie rods
running between a tubular lower support and a channel at the
top. Stack dimensions are 1 foot by 2 feet by 5 feet high.
The dry weight of each stack is approximately 100 pounds.
Short stainless steel shims arc placed between plate stacks
to lock the entire assembly together.
As the oil/water mixture passes through the plates, oil
particles coalesce and. tend to collect at the crest of each
corrugation. Bleed holes are provided along the crests so
that, as the water passes through the plates, the oil rises
progressively upward through the holes in the plates to
collect and form an oil blanket on the water surface.
206
-------
Two plastic foam coalescing packs can be installed
after the corrugated plate section described above. These
packs are designed to improve the coalescence of finely
emulsified oil droplets or oil coated particles. Both
packs are identical, consisting of a foam pad mounted in a
split frame. This arrangement allows for easy removal of
the flioam for cleaning or replacement. In addition, the
foam is extended beyond the frame to provide a seal with
the tank walls, preventing any water bypass flow.
A second corrugated plate coalescing section consist-
ing of one row of four plate stacks is located downstream
of the packs to complete the separating action. The indiv-
idual stacks are identical to those previously described.
The water outlet is an inverted "U" shape pipe with a
series of holes to admit the water without disturbing the
oil film. The holes are located so that the upper portion
of the manifold acts as an oil dam, preventing the oil
from mixing with the effluent water.
Oil is removed from the unit by a float-type oil skim-
mer. Two ball type floats are used to balance the unit.
The oil flows through a slotted tube between these floats,
then through a flexible hose to the discharge fitting. The
vertical position of the hose on the slotted tube may be
changed to vary the length of the slot and hence the thick-
ness of the oil film. With this exception, operation of
the skimmer is completely automatic.
The entire unit is fitted with a gasketed cover and may
be operated with a low pressure gas blanket. Access ports
for removal of the coalescing pack and access to the skimmer
are included in the cover.
The unit is contained within a rectangular, skid mount-
ed tank. A continuous drip pan is located beneath the tank.
Overall dimensions of the unit are 127" long by 62" wide by
68" high. The dry weight of the assembly is approximately
4700 pounds.
207
-------
The tank is fitted with all necessary flange connec-
tions. These flanges are fiberglass, with a standard ASA
150 pound flange bolt circle configuration. Location, size>
and intended purpose for each flange is shown on the fig-
ures. The intended purpose is self-explanatory with the
exception of the instrument port flange, which is used
primarily for a high level shutdowniif installed. The size
and location of the removable cover sections and the view
ports are also shown. Note clearance requirements for
coalescing pack removal. Four lifting lugs are provided on
the skid for use in handling the unit.
208
-------
• -,.
j
-
209
-------
10
M
o
•
PLATE BANKS
FLOW
"STRAJGHTENER
OIL/WATER
MIXTURE
INFLUENT
91
CLEAN
WATER S
DRAIN
-------
Dimensions
MODEL.
OPC-10
OPC-30
OPC-SO
OPC-100
APPROX. DRY
WEIGHT (lb*.»
850
1350
4700
8500
LENGTH
(InehM)
88
80
127
180
HEIGHT
(Inch**)
44
56
88
70
WIDTH
(HtCnVk)
32
48
63
72
INFLUENT
FLANGE
(IPS)
2"
4"
4"
8"
EFFLUENT
FLANGE
(IPS)
4"
8"
8"
V
EFFLUENT WATER
OIL OUTLET FLANQE
VIEW FORT
4 LIFTING POINTS NOT SHOWN
OAS INLET < SAFETY VENTS
INSTRUMENT MRT
INFLUENT
DRAIN FLANOE
211
-------
KJ
coaiescent nates
increase capacity
01 Tanks or Pits
The unique coalescent plates which are the heart of
the General Electric Oil/Water Separation system
can be added to any existing gravity settling tank or
pit to considerably increase capacity without modi-
fication or enlargement of the existing system.
The coalescent plates are available in any size banks
or modules, each individual plate being 1 ft. x 2 ft.
These can be stacked in virtually any configuration
to permit flexibility of installation and to accommo-
date the desired flow rate.
Gravity separation is increased by the use of these
plates, without the addition of chemicals. Fabricated
with non-corrosive materials and with no moving
parts or filters, operation is virtually maintenance free.
Cost is $80.00 per foot of height of the stacked coa-
lescent plates.
-------
APPENDIX I
ASTM VS. UNION COLOR CORRELATION
t.O
" »/,
— *K / i»
.H-- 2>
213
-------
APPENDIX J
PROCESS SCREENING STUDIES
214
-------
REPORT TO NORCO ON THE
POTENTIAL PROFITABILITY OF SEVERAL
APPROACHES TO RE-REFINING
CRANKCASE WASTE OIL
FOR: NATIONAL OIL RECOVERY CORPORATION
P. 0. BOX 338
BAYONNE, NEW JERSEY 07002
Date
: January 22, 1973
Work By : Dr. N. J. Weinstein
Dr. A. Boyum
Report Bys Dr. N. J. Weinstein
RECON SYSTEMS, INC.
Cherry Valley Road
Princeton, N. J. 08540
215
-------
REPORT TO NORCO ON THE POTENTIAL
PROFITABILITY OF SEVERAL APPROACHES
TO RE-REFINING CRANKCASE WASTE OIL
Summary
Based on NORCO's projections of 3C/gal. or less to
be paid for crankcase waste oil, and 16$/gal. or more
realization for recovered lubricating oils, re-refining
is potentially very profitable. For example:
Pre-treatment None Solvent
Post-treatment Hydrogen Hydrogen
Purchase of
Exxon Equipment Yes Yes No yes
Feed,
gals/yr. 9,000,000 29,000,000 29,000,000 34,800,000
Total
Investment, $ 492,000 1,123,000 3,050,000 1,773,000
Profit, $/yr. 129,000 1,573,000 1,488,000 2,194,000
Return, %/yr.B.T. 26 140 49 124
The most critical factors to be resolved before such
profitability can be realized are:
-assuring a supply of crankcase waste oil, pre-
ferably in excess of 20 million gallons per year
at a cost of 3£/gal. or less.
-assuring a comparable market for re-refined lu-
bricating oils at 16$/gal. or more.
-the development of technology which will convert
the crankcase waste oils to lubricating oils meet-
ing specifications necessary to command the above
price.
^s to the question of technology, we feel that
vacuum distillation followed by hydrogen treating has a
high probability of early success. The availability
216
-------
- 2 -
of most of the necessary equipment from Exxon's
Bayonne Refinery makes this possibility particularly
attractive, if sufficient land area can be assembled.
Chemical treatment is also promising as an independent
method of re-refining, or as an adjunct to vacuum distil-
lation plus hydrogen treating, but this approach will
require a more extensive development program.
The development of vacuum distillation plus
hydrogen treating technology requires solutions to two
major problems: (1) assured operability of the heating
and distillation equipment to avoid premature shutdowns
due to coking and fouling; and (2) upgrading lubricating
oil cuts to meet color, odor, and other specifications.
We feel that the operability problem can be al-
leviated sufficiently by furnace redesign and the use
of anti-fouling additives to obtain the modest 5000
hour per year operation assumed in the economic study.
We recommend an engineering design study to determine
the furnace parameters required for future operations.
Hydrogen treating is widely used for upgrading
virgin lubricating oil and petroleum fuels to meet odor,
color, nitrogen, sulfur, stability and other important
specifications. The brief experimental hydrogen testing
program which NORCO sponsored in April 1972 supports the
possibility that lubricating oil cuts from crankcase
waste oil distillation can be similarly upgraded. Further
experimental work is recommended prior to a commitment
for purchase of Exxon's equipment and erection at a site
assembled by NORCO.
217
-------
- 3 -
Description of Alternatives
Four basic alternatives, shown diagrammatically in
Figures 1 and 2, were studied as possible approaches to
re-refining crankcase waste oil. These are:
CASE A - BASE CASE
Essentially present operation at full capability
of 1030 B/SD for 5000 hrs/yr. using vacuum distil-
lation (including vacuum flashing) alone. This oper-
ation produces lubricating oil with unsatisfactory
color.
CASE B.I.I.
Envisions purchase of Exxon's Monophiner (catalytic
hydrogen treating unit) to upgrade lube oil quality.
Proposed operation shown in Figure 3. Existing vacuum
distillation equipment operates. 5000 hrs./yr.; hydrogen
treating is oversized and required only 1550 hrs./yr.
operation. Anti-foulant is used to ease operability
problem on vacuum distillation equipment, but frequent
shutdowns would still be required for cleaning.
CASE B.I.2.
Envisions purchase of both Exxon's Monophiner and
vacuum distillation equipment. Lube oil is run 1550
hrs./yr. on both vacuum distillation equipment and
hydrotreating. Excess capacity on vacuum distillation
equipment is used to upgrade fuel oil by drying (3450
hrs./yr. at 3322 B/SD). Operability problems with lube
oil on vacuum distillation equipment is expected to be
eased by both anti-foulant and improved furnace design,
but the extent of improvement requires further engineer-
ing design and/or experimental verification.
218
-------
- 4 -
CASE B.2.2.
Envisions purchase of both Exxon's Monophiner and
vacuum distillation equipment to be operated at full
capacity, limited by heat exchanger and furnace
considerations (3322 B/SD for 5000 hrs./yr.; 2115 B/SD
limitation calculated for hydrogen treating at 700°F).
Operatility limitations as in Case B.I.2.
CASE C.I.
1030 B/SD crankcase waste oil is treated at
ambient conditions with n-butanol at a volumetric
ratio of 2/1, as shown in Figure 4. The n-butanol is
recovered by distillation and recycled. A semi-dry
solid product high in lead is recovered from the oil
by centrifugation. Lube oil is recovered from the
treated crankcase oil by existing vacuum distillation
equipment. Operability, product quality, and solids
recovery are questionable, requiring further develop-
ment work. However, 6000 hrs./yr. operation was as-
sumed for this case, as well as improved lube oil yield
(71.8% vs 63.9%).
CASE C.2.
Envisions purchase of Exxon's vacuum distillation
equipment to increase Case C.I. operation from 1030
to 3322 B/SD for 6000 hrs./yr.
CASE C.'1.
Same as Case C.I. except that Exxon's Monophiner
would be purchased to upgrade lube oil quality (2120
hrs./yr.).
219
-------
- 5 -
CASE C.'2.
Same as Case C.2. except that Exxon's Monqphiner
would be purchased to upgrade lube oil quality (6750
hrs./yr.).
CASE D.
Same as Case B.2. except that all equipment is
purchased new on a grass roots basis, including in-
vestment for offices and laboratory.
In the above cases where refinery expansion beyond the
present 1030 B/SD was not contemplated, no pollution con-
trol facilities were added, except for a scrubber on the
hydrogen treating purge gas. Where expansion to 3322 B/SD
was contemplated an air flotation unit was added to handle
oil-water separation problems.
220
-------
- 6 -
Results
A summary of the case descriptions and the required
investments are shown in Table 1. The investments for
removing and relocating Exxon equipment were estimated
to be about 53% of the required investment for new equip-
ment, excluding new equipment to be purchased. All in-
vestments were based on indices for the 4th quarter of
1972.
The potential profitability of each case studied is
shown in Table 2. The calculated return for all cases
was attractive, but returns were especially attractive
for larger operations. Some direct comparisons which can
be made are:
Profit Before Tax Return, %/yr.
Case <=/gal. feed$/yr. before Tax
Purchase of Exxon
equipment B.2. 5.43 1,573,000 140
Grass roots plant D. 5.13 1,488,000 49
9,000,000
gal/yr. feed B.I.I. 1.44 129,000 26
29,000,000
gal/yr. feed B.2. 5.43 1,573,000 140
No pre-treat. B.2. 5.43 1,573,000 140
Solvent pre-treat. C'.2. 6.30 2,194,000 124
to improve yields
and operability
A sensitivity analysis was carried out on Case C'.2.,
since this operation contained most of the major elements
studied. The results of this analysis are shown in Table 3,
221
-------
- 7 -
Doubling process investment, decreasing yields/ doubling
operating labor costs, doubling indirect costs, increasing
feed cost from 3 to SC/gal., increasing hydrogen con-^,1
sumption by a factor of ten, and increasing solvent lo£t
by a factor of five, all had significant effects on: prd-.
fitability, but none of these changed the basic attractive-
ness of the operation. On the other hand increasing lube
oil realization from 16
-------
- 8 -
Conclusions
1. .There appear to be strong economic incentives for
refining crankcase oil to produce saleable lube oils.
2. A spread of 13C/G between crankcase oil and lube oil
easily justifies re-refining in a 29MMGAL/yr. (1900 B/CD)
refinery-
3. Investments and operating costs projected for vacuum
distillation, hydrofining, and solvent treating, or
combinations of these processes, can easily be justified
if they could produce 60% or greater yields of lube oil
(13£/G spread).
4. Insufficient data is available to be assured that any
of the schemes studied can produce these saleable lube
oils.
5. The prognosis for technical and economic success of
R f D in this field is highly favorable.
6. The availability of monophining and vacuum distillation
equipment from Exxon's Bayonne Refinery may provide
NORCO with an unusually favorable position in this field,
if technical feasibility can be quickly demonstrated in
the laboratory.
223
-------
- 9 -
Recommendations
1.
3.
NORCO should immediately undertake or preferably sponsor
hydrofining experimentation to demonstrate the basic
feasibility of this approach. Data is needed on H^
consumption, catalyst life, bed fouling, reactor con-
ditions, etc.
At the same time, NORCO should exhaustively examine the
financial and engineering feasibility of adapting
Exxon's equipment (monophiner + vacuum distillation),
and of obtaining sufficient assured supplies of crank-
case oil and other materials to provide about 25MMgal/yr<
or more refined products.
If (1) and (2) above are favorable, NORCO should proceed
with this project.
NORCO and EPA should formulate a long term R +• D program
designed to provide the data needed to assure the
technical success of modern approaches to re-refining.
Vacuum distillation and hydrofining may be coupled with
chemical methods to provide reasonable lube oil yields.
224
-------
*- LVBC OIL. (POOR
CHIOH ncrm.tr>
CASE A -6ASF
. »»- WfCTCR
y N APHTHA
CRANKCASS
Oft- VACUUM Wt>KO-
^ DISTILL. TKCATIV6
KNTI/WLAMT BoTTom (MICH »tr/\Ls') _ .
CA5£ 6
J-l
I T Y 50i/*3
we (cue* r )
CAS£ C
WATTftT Y Spi(0
C
225
-------
CASES c.i
226
-------
TABLE J-l
CASK DESCRIPTIONS
to
to
CASE
FEED, MMGPY
Crar.X Oil
Fuel Oil
SOI.V. T»£«r
B/SD
Hri. Ar.
VAC. TRACT.
B/SO
Hr»./Yr.
HYDROTIM.
E /So
Kr«./Yr.
Teed.T
IKCREMENTJO,
IKVESTI1ZNT, SM
Exxon Equip
New Equip.
Util.
Waste
Tankage
Royalty
Of£»ite«
A
9.0
-
••
-
1030
5000
_
-
-
Present
Ojwr.-
Opef . Pffefe.
-Poor Qoal.
Lube
•
_
_
..
_
_
B.I.I.
f.O
-
-
-
1030
5000
2115
1550
50
Buy Exxon
Monophin.
332
135
-
~
~
25
49?
B.I. 2.
9.0
30.0
-
-
5322
5000
2115
1550
450
Buy Exxon
Monophin. +
Vac. Tract.
Run Fuel
Oil With
Spare Cap.
889
54
30
30
95
25
imrr
B.2.
29.0
-
-
-
3322
$000
2115
5000
450
C.I.
10.*
-
1030
6000
1030
6000
_
_
-
Buy Exxon Add
Sonophin.
Solvent
4 Vac. Acavb
Tract-Run
Crank Oil
Only
899
54
30
30
95
25
1,123
-
224
46
-
28
.-
T58~
C.2.
34.*
-
3322
6000
3322
6000
_
f
-
Add
Solvent
Exxon Vao.
Fract.
557
494
141
30
140
_
1, 362
C'.l.
10.8
-
1030
6000
1030
6000
2115
2120
50
Add
Solvent
Exxon
Monophin.
332
359
46
~
28
25
1 746
C'.2.
34.1
-
3322
6000
3322
6000
2115
6750
450
Add
Solvent
Exxon
Vac. Tract*
Monophin.
869
549
141
30
140
25
1,773
D
29.0
-
-
-
3322
5000
2115
5000
450
Gra«» Koot*
Vac. Tract. 4-
Hydro' In .
-
1,684
90
30
746
-
2,550
500
TTffSS —
-------
TABLE J-2
to
N>
CO
A.
CASE Vac.
T«
F££D GtV G/G
Crank Oil fTT 3TB~9
fu siuioe i.9«
« .I/Tear.
yafOM
t/year I.T.(2)
7.»3
10.32
o.Si
0.3*
1B75T
1.1*
M5
_
a. 1.1. u.l.2.
—Vac. Bt»t. + ByirofiBJ
MM
CPT C/0
*.2«
9.2*
5.75 10.22
.c» o.lo
1.9* 0.38
7TW 1DT7I
1.44
129
2C.2
f% ^0
20.0 2.00
2.24
4.55
5.75 1.86
.M .02
1.9* 0.12
15. 77 m?
1.80
522
46.3
1.2. ca,
ing— Solr.
MI m
en «/o GPT
2fro" ?7o"o IoT*
2. 45
5.45
18.52 10.22 7.78
.82 .2* -
.59
C.3.4 0.31 .32
aSTSo" lo~7iT i7?T
5.43
1,573
140.1
C.2.
, Treat* Vac.
ft i.
4.84
7.14
11.51 25.00
.31 2.03
0.31 1.04
1I7JT 2575T
4.«3-
47*
1(0.3
Diat
2.22
5.22
11.51
0.41
0.38
15730"
7.08
2,4(2
180.7
C'.l. C'.J. D
Solvent Treating + Graaa
Vac. Dist.+Kvdrofin. Roots (3)
MM
SX !/°
157* 3TffO
(.22
9.22
7.7( 11.51
.23 0.15
.32 0.38
<73T"iJ75T
2.12
303
3*. 4
Ml KM
2.90
5.90
25.00 11.51 11.52
.82
1.52 0.31
1.04 0.38 (.34
27. 5 t 12.20 25.68
(.30
2.1*4
123.1
ft
2.75
5.75
10.22
.2*
.38
10.61
5.13
4*. «
(1) ExelaOw eat* «Md w f
-------
10
TABLE J-3
AHALZSXS
CASK C'.2. (SOLVENT TREAT. + VAC. BIST. »
CASK
COSTS, «/C
FEED
OPER.
CREDITS,
PROFIT
C/G
SMJVY-.-.
INCR, IBf.
ttw
RETURN
»/yr. BT
i. a, 3, 4, 5. e.
BASE DOUBLS DBCR, VOL. DECK. YISLD DECK, DOUBLE DOOBSS
(C*.2) PROCESS YIELD OF AS ID (2) YIBLOjIlO OP. IABOB nTOISEC!
INVEST. LOBE FROM AND MO BOTTOMS COST COSTS
71. Bt TO BOTTOMS CREDIT!
63.9* CREDIT WOO TO
5000 HOT.
3.00
2.90
STTO
12.20
6.3«
2.194
1.773
123.)
3.00
In!
12.20
5.74
2.000
3.322
(0.2
3.00
2.86
57W
11.48
S.82
1.957
1.773
110.2
3.00
ItH
10. «1
4.75
1.533
1.773
93.4
3.00
S.0.41
4.18
1.213
1.77J
«».4
3.00
12.20
5.79
1.010
1.77J
113.2
3.00
ft»
12.20
5.12
2.023
••
1.77S
114.1
7. ». 9.
IBCHZASB aicitetms raoBEAs:
E PEE? COM VOtaTwUX 9-iVt
mm 3 FROM is FXCIOR
TO 5«/C TO 20«/G OF 10
5.00
12.20
4.30
1.498
1.773
(4.4
3.00
15.65
9.75
3.395
1.77S
191.3
3.00
T7W
12.20
5.14
1.792
1.773
101.0
10,
r rtcxzMi
sowitrt
LOSt >Y
FACTOR
OF f
3.00
T^lf
12.20
4.43
1.61*
1.773
91.3
Nomenclature > ••»
-------
TABLE J-4
BMM - tuuw am nmsaext
to
u>
0
r MJ4UPV
crank ruel
ru«l oil
tma. »MS»»
£ua« •*
Z.C. Cuts
Bat.
Ft, Sludge
Fuel Oil
K*ST VALUE
SM (2)
rroeaaa
Ctil * Ha*ta
?anjcage
IKCR. IKV.
*.1 (2)
A
%C.
BXS9.
*.9
S.7S
».>«
l.f«
friy
$00
79
lift
•
3.1.1. 1.1.1.
» Eydzof .
»A ft A
•• *«0
20.0
J-»9 S.M
«•»« 0.»4
!•»« l.»
- J.g HA
y •• r***T
••«» 3J.(J
12C4 1731
•SI "°
I5W JCTT
449 11^*
».*.
x».o
it.sa
3.02
f.34
37. H
1731
120
TS5T
C.i.
telv. <
+ VM.
10.0
7.7*
1.13
1.11
0.32
IB. 35
724
11«
ISTf
c.a.
fr»«t»»i-- •-
Diat.
34.1
as. oo
3. (2
3.11
1.04
537TT
1541
231
»S»
CM.
»»1».
OUt.
10. t
T.7«
1.13
l.il
.32
10.13
1411
11*
ifn
af atOJ
C.'l. B
traat «• v«e. Ciau
+ Hydroit. Root. (it
34. i 3».0
~ •
"'« *M1
siJ? »•?'
1.04, «.M
13^7 TTW
"» 1«|4
231 1M
ml 41
33Jff »]BJ
1123
298
1362
790
1773
3050
(1) Vicuna dliUllMlaa pl« hydroflalB«
(2) Exclude* land and operating capital; Incr. In*. •> Uicrroental Invvitmnt
-------
TABLE J-5
U)
CASE
DESCRIPTIOB
FETD. MMGPt
Crank Oil
Fuel Oil
PV.SMJI
Iner. Inv. (KM
D«pr. Base, SUM
DIR. OP. COSTS,*
Oo. Labor
labor O.H.
Ins. + Taxe»
Catalyst
N-Batanol
Antifoulant
Hydrogen
Haint.
Depree.
Power
City Mater
«/G Feed
A.
Vac.
Diet.
9.0
-
1.221
-
1.221
Iftc.
90.0
36.0
36,6
-
-
-
~
36. 6
81. S
10.6
1.2
292,5
3.25
».!.!. B.l.l. •»«.
-— v«a. but. + ayd»nff.i««f •
9.6
-
1.985
0.492
1.713
100. 0
40.0
S9.6
14.7
-
2.)
lf.1
si. s
114.3
19.0
1.7
"I:..
9.0
20.0
2.604
1.123
1.144
110.0
44.0
78.2
14.7
-
2.3
10.3
78.2
123.1
23.1
2.0
48?:l7
IN31H. OP. COSTS 5MJ»/lfr.
Salaries
Salary O.H.
Lab + Office Exp
Other
«/G Teed
BO.O
32.0
.10.0
20.0
142.0
1.53
80.0
32.0
10.0
20.0
1.58
90.0
36.0
15.0
25.0
166.0
0.57
99.*
2.604
1.133
100.0
40.0
71.
47.
_
7.
26.
78.
123.1
53.6
nH-
1.93
80.0
32.0
15.0
25.0
I5"57o"
0.52
0.1.
telv. Sr«
U.9
-
Hit
t.nt
LSI*
100.0
40.0
"45.6
—
19.7
>
.
45.6
iOl.3
25.8
2.0
80.0
32.0
10.0
20.0
1.32
•ti«*B. MM
14. »
•1.C17
1.34V
2.083
i
110.0
44.0
79.1
63.9
—
79.7
139.2
83.3
6.2
805.4
1.74
90.0
36.0
1S.O
25.0
o!48
««.».
t »*1». (I
Bt»t *
10. i
a.ati
•.?*«
e.oii
120.0
48.0
68. S
19.9
19.7
D-9
68. S
134.1
34.0
2.4
<:»o
80.0
32.0
10.0
20.0
T4TTT5
1.32
CM.
BMtk. » «M
•ydrcCUilBf
34. »
I.JJ4J
1.77J
2.494
130.0
52.0
6
-------
TABLE JV6
BASES FOR OPERATING COSTS
Operating Labor
Labor Overhead
Insurance & taxes
Catalyst
n-Butanol
Anti-foulant
Hydrogen
Maintenance
Depreciation
Power
City water
- $10,000 wages per man per , year.
- direct overhead @ 40% of operat-
ing labor.
- insurance and local property
taxes at 3% of plant value. (See
table 4.)
- $1.10 per pound; one year life
for cases B.2. and D. J other
cases prorated on the basis of
feed thruput*
$2.50
100 ppm (volume basis)
per gallon.
-'$4.00 per 1000 SCF delivered;
15 SCF/B of actual throughput
used. *
- 3% of plant value per year (assum-
ing routine maintenance done by
operating personnel,)
- 6.67%/year of capital invested
in usable equipment.
- 3.5 to 4.0 C/KWH depending upon
usage.
- 70$ per thousand gallons.
*Later information indicated that hydrogen consumption
was probably closer to 150 SCF/B. See Appendix E.
232
-------
Table K-l. NOVEMBER 1972 WASTE FUEL OIL RUN
Run Length = 51 hrs.
Total gallons
Yield, %
Gals./hr.
Gravity, °API
lbs./hr.
BTU/lb. furnace
input (calculated) -- 1,118 137 73
Fired Heater Duty,
BTU/hr.
(Total = 4,055,100) — 2,247,000 128,100 1,680,000
Feed
176,283
—
3,455
25.2
25,960
Water
12,299
6.95
241
10.0
2,014
Overhead
7,000
3.95
137
41.0
935
Bottoms
156,984
89.1
3,077
26.0
23,020
Preceding page blank
234
-------
Table K-2. DECEMBER 1972 WASTE FUEL OIL RUNS
(Averages for two runs)
Heater inlet temperature 110°F
"eater transfer line 215°F
Fractionator bottom 182°F
Fractionator top 175°F
Beater stack 625°F
iieater flue gas recirculated 520°F
Bottom of fractionator vacuum 25.2 in. Hg.
Feater inlet pressure 46 psig
Feed gravity 23.2°API
3cttoms product gravity 25.3°API
Feed to heater 2714 gal./hr.
Bottoms product 2235 gal./hr. (82.42%)
Overhead 81 gal./hr. ( 2.99%)
water 374 gal./hr (13.71%)
Loss 24 gal./hr ( 0.88%)
235
-------
Table K-3. JANUARY 1973 WASTE FUEL OIL RUN
Start: V4/73, 11:30 AM stop: 1/5/73, 2:45 AM
On Stream: 15 hrs. , 15 min*
Feedstock type: Tank bottoms, tank washings, fuel oil
containing water, solids, gasoline
Flow
Rate
Streams Gal/hr.
Feed 2705
Bttms 2533
Overhead 3^
Water &
Loss 133
Volume Sold Gravity Water
Gallons As °API %
41125 23.8
38628 No. 6 Fuel Oil 25.7
595 40.2
1902
3.62
Trace
Trace
STREAMS
Cooling Water
Steam Produced
Steam for Stripping
Steam to Vacuum Jets
Steam to Tower
Steam Bttms Pump
Steam to Tanks
& Line Loss
FLOW
350 GPM
960 LBS/HR
None " "
456 " "
None " "
320 " "
184 " "
TEMPERATURES :
LOCATION WF
Oil H't'r Inlet
Oil H't'r Outlet
Fractionator :
Bottom
Top
Flash Zone
115
218
180
175
180
EQUIPMENT LOCATION
Furnace Coil Inlet
Furnace Coil Outlet
Fractionator Flash Zone
Steam Boilers
UNITS
49 PSIG
- PSIG
24.1 IN..HG Vacuum
236
-------
Table K-4. JANUARY 1973 WASTE FUEL OIL RUN
Start: 1/8/73, 12:10 PM Stop: 1/9/73, 3:15 PM
On Stream: 27 hrs., 5 min.
Feedstock type: Tank bottoms, tank washings, fuel oil
containing water, solids, gasoline
Flow
Rate
Streams Gal/hr.
Feed 2266
Bttms 2092
Overhead 20
Water &
Loss 154
STREAMS
Cooling Water
Steam Produced
Steam for Stripping
Volume
Gallons
61400
Sold Gravity Water
As °API %
23.0 6.61
56650 No. 6 Fuel Oil 25.5 Trace
542
4208
FLOW
350 GPM
960 LBS/HR
None " °
Steam to Vacuum Jets 456 "
Steam to Tower
Steam Bttms Pump
Steam to Tanks
& Line Loss
None " "
320 " "
184 " "
EQUIPMENT LOCATION
Furnace Coil Inlet
UNITS
47 PSIG
41.0 Trace
TEMPERATURES
LOCATION WP
Oil H't'r Inlet 116
Oil H't'r Outlet 217
Fractionator:
Bottom 183
Top 175
Flash Zone 185
Furnace Coil Outlet - PSIG
Fractionator Flash
Zone 24.3 IN
. HG Vacuum
Steam Boilers
237
-------
Table K-5.. JANUARY 1973 WASTE FUEL OIL RUN
Start: Stop:
On Stream: 16 hrs., 30 min.
Feedstock type: Tank bottoms, tank washings, fuel oil
containing water, solids, gasoline
Streams
Feed
Bttms
Overhead
Water &
Flow
Rate
GalAr.
2242
1795
45
402
Volume Sold
Gallons As
37060
29640 No. 6 Fuel Oil
743
6677
Gravity Water
OAPI %
Loss
STREAMS
Cooling Water
Steam Produced
Steam for Stripping
Steam to Vacuum Jets
Steam to Tower
Steam Bttms Pump
Steam to Tanks
& Line Loss
FLOW
350 GPM
960 LBS/HR
None " "
456 " "
None " "
320 " "
184 " "
TEMPERATURES
LOCATION WF
Oil H't'r Inlet
Oil H't'r Outlet
Fractionator :
Bottom
Top
Flash Zone
120
219
181
173
185
EQUIPMENT LOCATION
Furnace Coil Inlet
Furnace Coil Outlet
Fractionator Flash Zone
Steam Boilers
UNITS
53 PSIG
- PSIG
24.7 IN. HG Vacuum
238
-------
Table K-<6. JANUARY 1973 WASTE FUEL OIL RUN
Start: 1/15/73, 1:45 PM Stop: 1/16/73, 8:30 AM
On Stream: 18 hrs., 15 min.
Feedstock type: Tank bottoms/ tank washings, fuel oil
containing water, solids/ gasoline
Streams
Feed
Bttms
Overhead
Water &
Loss
Flow
Rate
Gal/hr
2017
1593
62
362
Volume Sold Gravity V$ner
Gallons As °API %
37818
29961
1162
6695
19.7 17.45
No. 6 Fuel Oil 25.6 Trace
14.0 Trace
STREAMS
Cooling Water
Steam Produced
Steam for Stripping
Steam to Vacuum Jets
Steam to Tower
Steam Bttms Pump
Steam to Tanks
& Line Loss
FLOW
350 GPM
960 LBS/HR
None " "
456 " "
None " "
320 " "
184 " "
TEMPERATURES
LOCATION "F
Oil H't'r Inlet
Oil H't'r Outlet
Fractionator :
Bottom
Top
Flash Zone
117
213
180
176
180
EQUIPMENT LOCATION
UNITS
Furnace Coil Inlet
Furnace Coil Outlet
Fractionator Flash Zone
Steam Boilers
57 PSIG
- PSIG
25.7 IN.HG Vacuum
239
-------
Table K-7. JANUARY 1973 WASTE FUEL OIL RUN
Start: 1/17/73, 12:40 PM stop! 1/18/73, 3:45 AM
On Stream: 15 hrs" 5 min'
Feedstock type: Tank bottoms, tank washings, fuel oil
containing water, solids, gasoline
Streams
Feed
Bttms
Overhead
Water &
Flow
Rate
Gal/hr.
2530
1854
383
293
Volume Sold
Gallons As
38197
27993 No. 6 Fuel Oil
5780
4424
Gravity
°API
21.5
25.9
41.5
Water
%
10.74
Trace
Trace
Loss
STREAMS
Cooling Water
Steam Produced
Steam for Stripping
Steam to Vacuum Jets
Steam to Tower
Steam Bttms Punip
Steam to Tanks
& Line Loss
FLOW
350 GPM
960 LBS/HR
None " "
456 " "
None " "
ii n
n n
TEMPERATURES
LOCATION WF
Oil H't'r Inlet
Oil H't'r Outlet
Fractionator :
Bottom
Top
Flash Zone
120
217
182
176
183
EQUIPMENT LOCATION
UNITS
Furnace Coil Inlet
Furnace Coil Outlet
Fractionator Flash Zone
Steam Boilers
51 PSIG
- PSIG
25.1 IN.HG Vacuum
240
-------
Table K-8. JANUARY 1973 WASTE FUEL GIL RUN
Stop: 1/26/73, 7;00 AM
Start: 1/24/73, 8:55 AM
On Stream: 46 hrs., 5 min.
Feedstock type: Tank bottoms, tank washings, fu«_-l i^'
containing water, solids, gaso.l..ne
Streams
Feed
Bttms
Overhead
Water &
Flow
Rate
Gal/hr.
2215
1580
215
420
Volume
Gallons
102100
72806
9900
19394
Sold Gra'-itv
AS °AI-I *
20.0
23.0
39.9
Water
%
18.15
Trace
Trace
Loss
STREAMS
Cooling Water
Steam Produced
Ste._;a for Stripping
Steam to Vacuum Jets
Steam to Tower
Steam Bttms Pump
Steam to Tanks
& Line Loss
FLOW
350 GPM
960 LBS/HR
TEMPERATURES
LOCATION WF
Oil H't'r Inlet
Oil H't'r Outlet
None " " Fractionator:
456 " "
None " "
200 " "
314 " "
Bottom
Top
Flash Zone
115
230
190
179
190
EQUIPMENT LOCATION
Furnace Coil Inlet
Furnace Coil Outlet
Fractionator Flash Zone
Steam Boilers
UNITS
62 PSIG
- PSIG
24.0 IN.HG Vacuum
241
-------
Table K-9. JANUARY/FEBRUARY WASTE FUEL OIL RUN
Start: 1/31/73, 11:00 AM Stop: 2/1/73, 12:30 PM
On Stream: 25 hrs. , 30 Min.
Feedstock type: Tank bottoms, tank washings, fuel oil
containing water/ solids, gasoline
Flow
Rate
Str^£.:r.s Gal/hr.
Feed 1503
Bttms 973
Overhead .343
Water * 187
Loss
STREAMS
Volume Sold Gravity
Gallons As °API
38385 17.5
24820 No. 6 Fuel Oil 19.8
8650 39.5
4915
FLOW
Cooling Water 35° GPM
Steam Produced 87° LB,S/^}R
Steam for Stripping None ^ ^
Steam to Vacuum Jets *4D „ „
Steam to Tower ^one „ „
Steam Bttms Pump ^7° „ „
Steam to Tanks
& Line Loss
Water
11.37
Trace
Trace
TEMPERATURES
LOCATION
Oil H't'r Inlet
Oil K't'r Outlet
Fractionator :
Bottom
Top
Flash Zone
i
"F
118
220
195
180
190
EG JI »y.3NT LOCATION
UNITS
Furnace Coil Inlet
Furnace Coil Outlet
Fraetionator Flash Zone
St.ii«u4 Boilers
35 PSIG
-—PSIG
24.7 IN.HG Vacuum
242
-------
Table K-10.FEBRUARY 1973 WASTE FUEL OIL RUN
Start: 2/7/73, 3:15 PM Stop: 2/8/73, 9:OOPM
pn Stream: I7hrs, 45 min.
Feedstock type: Tank bottoms, tank washings, fuel oil
containing water, solids, gasoline
Flow
Rate Volume Volume Sold Gravity
Streams Gal/hr. Per Cent Gallons AS °API
Feed 2116
Bttms 1662
Overhead 133
Water & 321
Loss
STREAMS
Cooling Water
Steam Produced
Steam for Stripping
Steam to Vacuum Jets
Steam to Tower
Steam Bttms Pump
Steam to Tanks
& Line Loss
EQUIPMENT LOCATION
100.0 37596 ,-No<6 14.1
78.4 29500 /Fuel 22.8
(Oil
6.3 2360 44.3
15.3 5736
FLOW
180 GPM
946 LBS/HR
None " "
456 " "
None " "
320 " "
170 " "
Water
15.1
Trace
Trace
TEMPERATURES
LOCATION UF
Oil H't'r Inlet
Oil H't'r Outlet
Fractionator :
Bottom
Top
Flash Zone
UNITS
117
195
184
178
180
Furnace Coil Inlet 59 PSIG
Furnace Coil Outlet ~ PSIG
Fractionator Flash Zone 22.4 In. HG Vacuum
Steam Boilers
243
-------
Table K-ll.FEBRUARY 1973 WASTE FUEL OIL RUN
Start: 2/14/73, 11:30 AM Stop: 2/15/73, 10 :00 AM,
On Stream: 22 hrs., 30 min. *
Feedstock type: Tank bottoms, tank washings, fuel, Toil:
containing water, solids, gasoline
Flow
Rate Volume Volume Sold Gravity Water
Streams Gal/hr. Per Cent Gallons As OAPI *
Feed J.636
Bttms 1265
Overhead 26
Water & 345
Loss
STREAMS
Cooling Water
Steam Produced
Steam for Stripping
Steam to Vacuum Jets
Steam to Tower
Steam Bttms Pump
Steam to Tanks
& Line Loss
100.0 36818 18-3 26-°
77.3 28464 22.8 Trace
1.6 584 42.1 Trace
21.1 7770
FLOW
180 GPM
906 LBS/HR
None " "
456 " "
None " "
280 " "
170 " "
TEMPERATURES
LOCATION VF
Oil H't'r Inlet 118
Oil H't'r Outlet 205
Fractionator:
Bottom 178
Top 175
Flash Zone 18°
EQUIPMENT LOCATION
UNITS
Furnace Coil Inlet 53 PSIG
Furnace Coil Outlet ~ PSIG
Fractionator Flash Zone 25"° In- HG Vacuum
Steam Boilers
244
-------
Table K-13*. FEBRUARY 1973 WASEE FUEL OIL RUN (Continued)
Start; 2/14/73, 11:30 AM Stop: 2/15/73, 10:00 AM
1
MATERIAL
°API
Distillation
IBP °F
5% Recovered
10%
20
30
40
50
60
70
80
90
H20 Gontent%
Recovery , %
FEED
18.3
Still
212
_
440
600
652
678
697*
712
Vapor
100
-
205
358
454
462
457*
458
26.0
— • |
BOTTOMS
22.8
264
455
539
635
650
651
652
655
657
658*
Trace
PQ
O -7
OVERHEAD
42.1
Trace
* Cracked
245
-------
Table K-12.
FEBRUARY 1973 WASTE FUEL OIL RUN
Start: 2/21/73, 10:30 AM Stop: 2/23/73, 6:00 PM
On Stream: 55 hrs., 30 Min.
Feedstock type: Tank bottoms, tank washings, fuel oil
containing water, solids, gasoline
Flow *
Rate Volume Volume Sold Gravity Wajfer
Streams Gal/hr. Per Cent Gallons As A?1 *
Feed 2084 100.0 115725 , 21.3 13*6
(No. 6
Bttms 1761 84.5 97800 } Fuel 24.7 Trace
\ Oil
Overhead 39 1.9 2162 40.0 Trace
Water & 284 13.6 15763
Loss
STREAMS
Cooling Water
Steam Produced
Steam for Stripping
Steam to Vacuum Jets
Steam to Tower
Steam Bttms Pump
Steam to Tanks
& Line Loss
FLOW
180 GPM
931 LBS/HR
None " "
456 " "
None " "
310 " "
165 " ''
TEMPERATURES
LOCATION WF
Oil H't'r Inlet JJ^
Oil H't'r Outlet ^°5
Fractionator :
Bottom 187
Top 183
Flash Zone I84
EQUIPMENT LOCATION
UNITS
Furnace Coil Inlet 54 PSIG
Furnace Coil Outlet - PSIG
Fractionator Flash Zone 25.7 In. HG Vacuum
Steam Boilers
246
-------
Table K-13.
FEBRUARY 1973 WASTE FUEL OIL RUN
Stop:2/27/73, 8:10 PM
Start: 2/26/73, 3:35 PM
On Stream: 28 hrs., 35 Min.
Feedstock type: Tank bottoms, tank washings, fuel oil
containing water, solids, gasoline
FIOW
Rate Volume Volume s°ld Gravity
Streams Gal/hr. Per Cent Gallons As OAPI
Feed 1461
Bttms y9 6
Overhead 12 3
Water & 342
Loss
STREAMS
Cooling Water
Steam Produced
Steam for Stripping
Steam to Vacuum Jets
Steam to Tower
Steam Bttms Pump
Steam to Tanks
& Line Loss
EQUIPMENT LOCATION
100.0 41738 24.1
(No. 6
68.2 28464 > Fuel 24.9
V Oil
8.4 3518 40.4
23.4 9756
FLOW
170 GPM
836 LBS/HR
None " "
456 " "
None " "
220 " "
160 " "
Water
%
7.4
Trace
Trace
TEMPERATURES
LOCATION
Oil H't'r Inlet
Oil H't'r Outlet
Fractionator :
Bottom
Top
Flash Zone
UNITS
ft up
116
220
185
180
183
Furnace C.ni 1 Tnlet 18 PSIG
Furnace Coil Outlet
Fractionator Flash Zone
Steam Boilers
26.8 IN.HG Vacuum
247
-------
Table K-14.
MARCH 1973 WASTE FUEL OIL RUN
Stop: 3/6/73, 8:30 AM
Start: 3/5/73, 1:30 PM
On Stream: 19 hrs.
Feedstock type: Tank bottoms, tank washings, fuel oil
containing water, solids> gasoline
Flow
Rate
Streams Gal/hr*
Feed .1906
Bttms 1117
Overhead 139
Water 6 65°
Loss
STREAMS
I; , < ;.. '•.
Volume Sold Gravity Watf^r
Gallons AS °API t 'Sl
36224 20.2 30*^)
21244 No. 6 Fuel Oil 24.4 -1;";,,,
2641 41.4 —•.>.;
12,339
FLOW
Cooling Water 18° GPM
Steam Produced 806 LBS/HR
Steam for Stripping None jj "
Steam to Vacuum Jets ^56 " '|
Steam to Tower None " "
Steam Bttms Pump 18^ "
Steam to Tanks 17°
& Line Loss
TEMPERATURES
LOCATION WF;
Oil H't'r Inlet •i??'"''''
Oil H't'r Outlet 21°
Fractionator :
Bottom "i
T°P 182
Flash Zone
EQUIPMENT LOCATION
UNITS
Furnace Coil Inlet 63 PSIG
Furnace Coil Outlet ~ PSIG
Fractionator Flash Zone 25-3 IN.HG Vacuum
Steam Boilers
248
-------
Table K-14.
MARCH 1973 WASTE FUEL OIL RUN (Continued)
Start: 3/5/73, 1:30 PM
Stop: 3/6/73, 8:30 AM
MATERIAL
°API
Distillation
IBP
5% Recovered
10%
20
30
40
50
60
70
80
90
FBP
% Recovery
Water Content
FEED
20. 2
F
20EH
208 /
2T /~\ 1 TA! £? "i~ /*"*• T*
I (j '--_-' 1 9 d L- C- JL
211 j 30.0%
213 J
426
608
689
714
724
716 (87%)
716
87.0
% 30.0
BOTTOMS
24.4
OF
460
500
560
657
660
677
678
690
696
693
85,0
Trace
OVERHEAD
4^.4
°F
190
240
264
290
308
328
344
358
376
396
461
526
99%
Trace
249
-------
Table K-15. MARCH 1973 WASTE FUEL OIL RUN
Start: 3/7/73, 5:45 PM Stop: 3/8/73, 6:00 AM
On Stream: 12 hrs., 15 min.
Feedstock type: Tank bottoms, tank washings, fuel oil
containing water, solids, gasoline
Flow
Rate Volume
Streams Gal/hr. Gallons
Sold
AS
Gravity Water
°API %
Feed
Bttms
Overhead
2880
1860
139
Water & 881
Loss
35320
22780
2628
9912
No. 6 Fuel Oil
21.4 28.1
25.9 Trace
41.7 Trace
STREAMS
Cooling Water
Steam Produced
Steam for Stripping
Steam to Vacuum Jets
Steam to Tower
Steam Bttms Pump
Steam to Tanks
& Line Loss
FLOW
180 GPM
836 LBS/HR
None " "
456 " "
None " "
210 " "
170 • "
TEMPERATURES
LOCATION
Oil H't'r Inlet
Oil H't'r Outlet
Fractionator :
Bottom
Top
Flash Zone
wp
118
212
200
195
197
EQUIPMENT LOCATION
Furnace Coil Inlet
Furnace Coil Outlet
Fractionator Flash Zone
Steam Boilers
UNITS
56 PSIG
- PSIG
25.5 IN.HG vacuum
250
-------
* -.-16. MARCH 1973 WASTE FUEL OIL RUN
fit..i-ts 3/15/73, 11:15 PM Stop: 3/16/73, 5:30 PM
Oft acreams 18 hrs., 45 min.
Feic.stock type: Tank bottoms, tank washings, fuel oil
containing water, solids, gasoline
Streams
Feed
Bttos
i"^,5>r-h*»A
-------
Table K~17. MARCH 1973 WASTE FUEL OIL RUN
Start: 3/21/73, 11:50 AM stops 3/22/73, 2:00 PM
On Stream: 26 hrs., 10 mm.
Feedstock type: Tank bottoms, tank washings, fuel oil
containing water, solids, gasoline
Flow
Rate Volume Sold Gravity
Streams Gal/hr. Gallons As °API
Feed 382°
Bttms 2158
Overhead 205
Water & 1457
Loss
STREAMS
Cooling Water
Steam Produced
Steam for Stripping
Steam to Vacuum Jets
Steam to Tower
Steam Bttms Pump
Steam to Tanks
& Line Loss
EQUIPMENT LOCATION
69505 23.0
56400 No. 6 Fuel Oil 26.4
5250 41.5
7855
FLOW
130 GPM
876 LBS/HR
None " "
456 " "
None " "
260 " "
160 " "
Water
%
11.3
Trace
Trace
TEMPERATURES
LOCATION
Oil H't'r Inlet
Oil H't'r Outlet
Fractionator :
Bottom
Top
Flash Zone
UNITS
vp
119
214
182
178
185
Furnace Coil Inlet
Furnace Coil Outlet
Practionator Flash Zone
Steam Boilers
51 PSIG
- PSIG
23.0 IN. HG Vacuum
252
-------
'x-iB. MARCH 1973 WASTE FUEL OIL RUN
Start* 3/26/13, 10:40 AM Stop: 3/27/73, 6:30 AM
Oft Streami 19 hrs., 50 min.
Feedstock type: Tank bottoms, tank washings, fuel oil
containing water* solids, gasoline
Streams
Peed
Bttras
Overhead
Water &
Flow
Rate
Gal/hr.
2509
2213
121.3
175
Volume
Gallons
50633
44600
2446
3587
Sold Gravity
AS °API
22.3
No. 6 Fuel Oil 26.4
41.6
Water
%
7.1
Trace
Trace
Loss
STREAMS
Celling Water
Steam Produced
St. jam for Stripping
Strain to Vacuum Jets
Steam to Tower
Stiam Bttms Pump
>team to Tanks
S Line Loss
FLOW
120 GPM
876 LBS/HR
None " "
456 " "
None " "
260 " "
160
TEMPERATURES
LOCATION
Oil H't'r Inlet
Oil H't'r Outlet
Fractionator :
Bottom
Top
Flash Zone
vp
120
210
182
178
185
FOUIPMENT LOCATION
' i* :uace Coil Inlet
/ :/oace Coil Outlet
Fractionator Flash Zone
»
St&san Boilers
UNITS
52 PSIG
- PSIG
21.9 IN.HG Vacuum
253
-------
Table K-19.
MARCH 1973 WASTE FUEL OIL RUN
Stop: 3/29/73, 3:00 AM
Start: 3/28/73, 10:30 AM
On Stream: 16 hrs., 30 min.
Feedstock type: Tank bottoms, tank washings, fuel oil
containing water, solids, gasoline
Flow
Rate Volume Sold Gravity
Streams Gal/hr. Gallons AS? °API
Peed 2435 40146 22.8
CNo . 6
„„„„«, Fuel 26.3
( Oil
Overhead 121.0 1996 V 41-7
Water &
Loss
Total
STREAMS
Cooling Water
Steam Produced
Steam for Stripping
Steam to Vacuum Jets
Steam to Tower
Steam Bttms Pump
Steam to Tanks
& Line Loss
SQU I PMENT LOG AT I ON
Furnace Coil Inlet
Furnace Coil Outlet
7?v TJ /*i 4- 4 r\r» a +-/-\v" 1? 1 r.i eV* #
FLOW
120 GPM
886 LBS/HR
None " "
456 " "
None " "
260 " "
170 " "
Water
7.3
Trace
Trace
TEMPERATURES
LOCATION ^F
Oil H't'r Inlet
Oil H't'r Outlet
Fractionator :
Bottom
Top
Flash Zone
UNITS
54 PSIG
- PSIG
24.6 IN.HG Vacuum
117
212
180
175
176
Steam Boilers
254
-------
* K-20. APRIL 1973 WASTZ FUEL OIL RUN
irti 4/2/73, 10:25 AM stc--. 4/2/73, 11:45 PM
Ou Stream: 13 hrs., 10 min.
Feedstock type: Tank bottoms, \iank washings, fuel oil
containing water, solids, gasoline
Flow
Rate Volume Volume Sold Gravity
Sui. earns Gal/hr. Per Cen-c Galio.is As °/J?I
V7c.-i:(.r
S
Feed 3225 100.0 42400 24.3
/No. 6
Bttms 2785
Overhead 175
Water & 265
Loss
STREAMS
Cooling Water
Steam Produced
Steam for Stripping
3 team to Vacuum Jets
CL.aam to Tower
St^am Bttms Pump
o__:ani to Tanks
& Line Loss
i'X-PMENT LOCATION
/.. .,/iace Coil Inlet
86.7 36720 /Fuel 26.3
t Oil
5.2 2220 41.2
8.1 3460
TIL-."1 Z RAT U LIZ 3
FLOW LOCATION
130 GPM oil H't'r li^let
896 LBS/HR oil H't'r Outlet
None " " Fractionator :
456 " " Bottom
None " " Top
280 " " Flash Zone
160 " "
UNITS
57 PSIG
>^p
116
219
193
190
191
'L^^-ace Coil Outlet
. «^oc.ionator Flash Zone
Steam "Boilers
- PSIG
26/3 IN.HG Vacuum
110 PSIG
255
-------
Table K-21. APRIL 1973 WASTE FUEL OIL RUN
Stop: 4/10/73, 1:55
AM
Start: 4/9/73, 10:25 AM
On Stream: 13 hrs., 55 min.
Feedstock type: Tank bottoms, tank washings/ fuel oil
containing water, solids, gasoline
Flow
Rate Volume Volume Sold Gravity Water
Streams Gal/hr. Per Cent Gallons As OAPI *
Feed 2704 100.0 37600
Bttms 2235 82.6 31046
Overhead 195 7.2 2710
22.0,18.2
(No. 6
fFuel 26.0,22.9
( Oil
40.2,43.0
Water & 274 10.2 3844
Loss
STREAMS
Cooling Water
Steam Produced
FLOW
125 GPM
816 LBS/HR
Steam for Stripping None " "
Steam to Vacuum Jets 456 " "
Steam to Tower
None " "
Ste'am Bttms Pump 190 " "
Steam to Tanks
& Line Loss
170 " "
TEMPERATURES
LOCATION WF
Oil H't'r inlet I16
Oil H't'r Outlet 210
Fractionator :
Bottom 180
Top 175
Flash Zone 176
EQUIPMENT LOCATION UNITS
Furnace Coil
Furnace Coil
Fractionator
Steam Boilers
Inlet 60 PSIG
Outlet - PSIG
Flash Zone 23.7 IN.
110 PSIG
HG Vacuum
256
-------
TaL'le K-r-22. APRIL 1973 WASTE 2U13L OIL RUN
Start: 4/10/73, 4:50 PM Stop: 4/11/73, 9:30 AM
On Stream: 14 hrs., 30 min.
Feedstock type: Tank bottoms, tank washing, f.sai oil
containing w^c^r, solids,
Flow
Rate Volume Volume Sold Gravity W«te.r
Streams Gal/hr. Per Cerrc Gallons As °AP4 *
Feed 2877 100.0 41660
Bttms 2527
Overhead 138
Water & 212
Loss
STREAMS
Cooling Water
Steam Produced
Pt-eam for Stripping
Stear.. to Vacuum Jets
Steam to Tower
Ft- earn Bttms Pump
Bteam to Tanks
& Line Loss
LQiJI?.-I3NT LOCATION
87.9 36620
4.8 2000
7.3 3040
FLOW
125 GPM
816 LBS/HR
None " "
456 " "
None " "
200 " "
i f n ii n
160
UNITS
21.6
(No. 6
/Fuel 25.5
1 Oil
41.0
TEK?ERA-_URSS
' LOCATION
1 Oil H't'r Inlet
:0il H't'r Outlet
Zractionator :
Bottom
Top
Flash Zone
!
&'?
118
225
180
175
175
furnace Coil Inlet
]''urriacs Coil Outlet
Tractionator Flash Zone
Steam Boilers
61 PSIG
- PSIG
23.5 IN.HG Vacuum
110 PSIG
257
-------
Table K-23. APRIL 1973 WASTE FUEL OIL RUN
Start: 4/16/73, 11:45 AM Stop: 4/17/73, 9:00 AM
On Stream:21 hrs., 15 min.
Feedstock type: Tank bottoms, tank washings, fuel oil
containing water, solids, gasoline
Flow
Rate Volume Volume Sold Gravity
Streams
Feed
Bttms
Overhead
Water &
Loss
STREAMS
Water
Gal/hr. Per Cent Gallons As °API %
1670
1012 60
51 3
609 36
Cooling Water
Steam Produced
Steam for
Steam to
Stripping
Vacuum Jets
Steam to Tower
Steam Bttms Pump
Steam to
& Line
EQUIPMENT
Tanks
Loss
LOCATION
35250
.63 21379
.05 1076
.32 12795
FLOW
150 GPM
766 LBS/HR
None " "
None " "
150 " "
i /- n ii it
J-OU
UNITS
19.3
/fro. 6
fFuel 24.5^
V Oil
39.4
TEMPERATURES
LOCATION
Oil H't'r Inlet
Oil H't'r Outlet
Fractionator :
Bottom
Top
Flash Zone
°F
117
210
182
180
Furnace Coil Inlet
Furnace Coil Outlet
Fractionator Flash Zone
Steaxn Boilers
58 PSIG
- PSIG
24.4 IN.HG Vacuum
110 PSIG
258
-------
>.Uu-.U> K-24. APRIL 1973 WASTE FUEL OIL RUN
Start: 4/18/73, 1:30 PM Stop: 4/19/73, 3 PM
On Stream: 25 hrs., 30 min.
Feedstock type: Tank bottoms, tank washings, fuel oil
-containing water, solids, gasoline
St-.r earns
Feed
Ettms
overhead
Water &
Loss
STREAMS
Flow
Rate Volume Volume , Sold Gravity Water
Gal/hr. Per Cent Gallons As OAPI %
1491 100.00 38014
1316 88.24 33561
67 4.50 1706
108 7.26 2747
FLOW
Cooling Water 1" GPM
Steam Produced 746 L?S/«R
Steam for Stripping None ^ . ^
Steam to Vacuum Jets 45° „ „
Steam to Tower N°ne „ „
Steam Bttms Pump r4!? „ „
Steam to Tanks 15°
& Line Loss
18.9
(tto.6
JFuel 23.3
( Oil
41.0
TEMPERATURES
LOCATION WF
Oil H't'r Inlet Hg
Oil H't'r Outlet
Fractionator : ,ge
Bottom
TOP l?g|
Flash Zone
EQUIPMENT
LOCATION UNITS
Furnace Coil Inlet
> jrmiciB Coil Outlet
J'ractionator Flash Zone
Steam Boilers
42 PSIG
- PSIG
26.3 IN.HG Vacuum
110 PSIG
259
-------
Table K-25. APRIL 1973 WASTE FUEL OIL RUN
Start: 4/25/73, 1:20 PM stop: 4/26/73, 1:00 PM
On Stream: 23 hrs., 40 min.
Feedstock type: Tank bottoms, tank washings, fuel oil
containing water, solids, gasoline
Flow
Rate
Streams Gal/hr.
Volume
Per Cent
Volume
Gallons
Sold
As
Water
Feed 2153
Bttms 1898
Overhead 95
Water &
Loss
160
100.00 48622
88.15 42864 No. 6 Fuel Oil
4.40 2138
7.45 3620
STREAMS FLOW
Cooling Water 110 GPM
Steam Produced 791 LBS/HR
TEMPERATURES
LOCATION
Oil H't'r Inlet
Oil H't'r Outlet
Steam for Stripping *?°.ne „ „ j Fractionator :
Steam to Vacuum Jets456 „ „ Bottom
Steam to Tower None ^ ^ Top
Steam Bttms Pump \^ „ „ Flash Zone
UF
118
215
182
175
182
Steam to Tanks
& Line Loss
ECUIPMENT LOCATI ON
UNITS
Furnace Coil Inlet 59 PSIG
Furnace Coil Outlet - PSIG
Fractionator Flash Zone 24.4 IN.HG Vacuum
Steam .Boilers 110 PSIG
260
-------
Table K-25.
APRIL 1973 WASTE FUEL OIL RUN (Continued)
Start: 4/25/73, 1:20 PM
Stop: 4/26/73, 1:00 PM
MATERIAL FEED
°API 19.9
Distillation °F
IBP 268
5% Recovered 318
10% 385
20 556
30 570
40 614
45 606
50
60
70
80
90
FBP 606
% Recovery 45
BOTTOMS
24.5
°JL
290
500
545
610
654
668
654
654
50.0
OVERHEAD
36.8
OF
210
278
290
221
360
380
395
412
432
457
490
528
96.0
261
-------
Table K-26.
APRIL/MAY 1973 WASTE FUEL OIL RUN
Start!4/30/73, 1:40 PM Stop: 5/1/73, 12:00 Noon
On Stream: 22 hrs., 20 min.
Feedstock type: Tank bottoms/ tank washings/ fuel oil
containing water/ solids/ gasoline
Flow
Rate Volume Volume s°l* Gravity Water
Streams Gal/hr. Per Cent Gallons As KPI *
Feed 2006 100
Bttms H07 55
Overhead 144 7
Water & 755 37
Loss
STREAMS
Cooling Water
Steam Produced
Steam for Stripping
Steam to Vacuum Jets
Steam to Tower
Steam Bttms Pump
Steam to Tanks
& Line Loss
.00 44850 17.4
.24 24774 22.6
.21 3236 39.8
.55 16840
FLOW
210 GPM
751 LBS/HR
None " "
456 " "
None " "
150 " "
145 " "
TEMPERATURES
LOCATION WF
Oil H't'r Inlet ^°
Oil H't'r Outlet 212
Fractionator :
Bottom t°i
T°p ill
Flash Zone lbu
EQUIPMENT LOCATION
UNITS
Furnace Coil Inlet
Furnace Coil Outlet
Fractionator Flash Zone
Steam Boilers
60 PSIG
- PSIG
24.0 IN.HG Vacuum
110 PSIG
262
-------
K-27.
7 3 WAST2
Sto'i- 5/30/73, 10:20 AM
" '
S-^-t: 5/24/73, 1:30 PM
Oi. Stream; 20.833
feedstock type: -'ank bot'covias , -oar.k ./things, fusi oil
containing wa-cor,, solids, gasoline
Flow
Rate
..-reams Gal/hr.
Volume Volume
Per Cent G^lor
Sold Gravity 77c.-cer
As °API %
Feed
Ettnis
overhead
Water &
Loss
1673
1118.4
54.0
560.6
100.00
66.85
3.23
29.92
34848
23303
1126
10419
("NO. 6
} Fuel
V^ Oil
STREAMS
Cooling VJater
Steam Produced
rteaia for Stripping
•:team to Vacuum Jets
i-c^am to Tower
Ctearr. Bttms Pump
Sveam to Tanks
& Line Loss
PLOW
160 GPM
746 LBS/HR
None " "
456 " "
None " "
150 " "
140 " "
Tz:-;:-2SATUR^s
' LOCATION
Oil H't'r Inlet
Oil H't'r Outlet
Fractionator :
Bottom
Top
Flash Zone
WJ,
116
216
181
178
184
LQUI2M.HKT LOCATION
UXITS
H -rr;ace Coil Inlet
."• -rr.acii Coil Outlet
Fractionator Flash Zone
Steam Boilers
56 PSIG
- PSIG
24.7 IN.HG Vacuum
105 PSIG
263
-------
Table K-27.
MAY 1973 WASTE FUEL OIL RUN (Continued)
Start: 5/24/73, 1:30 PM Stop: 5/30/73, 10;20 AM
MATERIAL FEED BOTTOMS OVERHEAD
°API 19.3 23.5
Distillation °F °F
IBP 269 291
5% Recovered 399 364
10% 500 414
20 566 506
30 589 554
40 602 584
50 615 601 (64%)
60 620
70 612 (65%)
80
90
FBP 620 601
% Recovery 65 46
264
-------
-le K-28.
MAty 1973 WASTE FUEL OIL RUN
Sv.art: 5/31/73, 10:30 AM Stop: 5/31/73, 6:30 PM
On Stream: 8.00 hrs.
Feedstock type: Tank bottoms, tank washings, fuel oil
containing water, solids, gasoline
Plow
Rate Volume Volume Sold Gravity Water
Streams Gal/hr. Per Cent Gallons As °API %
Peed 2986.5 100.0 23892 23.9
(No. 6
Bttms 2692 90.18 21540 fFuel 25.8
V Oil
Overhead 98 3.1 744 37.7
Water & 201 6.72 1608
Loss
STREAMS
Cooling Water
Steam Produced
Steam for Stripping
Steam to Vacuum Jets
it earn to Tower
Steam Bttms Pump
Steam to Tanks
& Line Loss
FLOW
125 GPM
806 LBS/HR
None " "
456 " "
None " "
205 " "
145 " "
TEMPERATURES
LOCATION UF
Oil H't'r Inlet JJJ
Oil H't'r Outlet *"
Fractionator :
?£tom "»°
•^ i an
Flash Zone 1BS
EQUIPMENT LOCATION
UNITS
.Furnace Coil Inlet
Furnace Coil Outlet
Fractionator Flash Zone
Steam Boilers
56 PSIG
- PSIG
24.1. IN.HG Vacuum
K55PSIG
265
-------
APPENDIX L
MANUFACTURER'S DATA ON HYDRIDES
266
-------
BULLETIN H'j. i-,"
BOROHYDRIDE
Formula: NaERj
Molecular Weight: 37.85
Specific gravity: 1.074 g./cc. at 25 °C.
Color: White
Functional Groups Reduced by NaBH.t:
Sodium borohydride rapidly reduces most aldehydes, ketones, peroxides and
hydroperoxides. It reduces, at a slower rate, Schiff bases and cyclic quaternary
iodides. Under special conditions, e.g., through the use of Lewis acids such as
aluminum chloride, its reducing power can be enhanced so that it is almost com-
parable to lithium aluminum hydride.
See brochure on Sodium Borohydride for additional data.
Suggested Uses:
Sodium borohydride has been used extensively in the pharmaceutical and fine
flavor fields for many years, for the conversion of aldehydes and ketones to the
corresponding alcohols. It has found use as a polymerization catalyst,1 as a blow-
ing agent for various plastic and rubber foams,.2 for removal of trace impurities in
many different process impurities in many different process streams, 8 and for
hydrogen generation.4 Ventron technical bulletins are available in each specific
area. Other uses include metal plating and catalyst preparation.
Availability: /—
Sodium borohydride may be purchased as a dry powder or as pellets in 10/32" and f
24/32" sizes, A third form, a stabilized water solution (SWS), is also available. i
Sodium borohydride powder and pellets can be supplied in quantities varying from /
100 grams to car loads, while SWS is available in one gallon to tank car lots.
i
Thermal Stability:
Decomposition starts without melting at above 400°C. in dry air.
Solubility at 25°C.: r
Solvea! g./100 g. solvent [
liquid ammonia 104.0
water 85-°
ethanol 4.0 (reacts slowly)
dimethyl ether of diethylene glycol 5.5
dimethyl formamide 18.0
isopropylamine 6-0
For additional solubility data see Sodium Borohydride brochure (available on
request). \
Typical Assay: r
NaBH4 98.0% L
267
-------
Packaging and Shipping:
Sodium borohydride is shipped in polyethylene bags in metal containers. Shipment
is governed by I.C.C. regulations 73:133, 73:154 and 73:206. Unlimited quantities
can be shipped by Railway Express or Motor Freight.
Handling and Stung*:
Sodium borohydride may be handled in air according to safe practice for inflam-
mable hygroscopic powders (comparable to calcium carbide). The unconfined
powder does not ignite on contact with moisture, but forms a dihydrate which
slowly hydrolyzes. It is stable to shock.
Safety:
Both dry borohydrides and their aqueous solutions are relatively safe materials to
handle. Certain precautions must be taken, however. Borohydride solutions, if
overheated, subjected to acid conditions, or in the presence of the metal salts or
finely divided metallic precipitates of nickel, cobalt, or iron, will decompose
rapidly, evolving large amounts of hydrogen. Other than this, treat as flake caustic
or a 50% caustic solution.
Toxicity:
Sodium borohydride is considered toxic if ingested primarily due to possible gas
embolism resulting from reaction with stomach acids. All precautions should be
taken against ingeation, inhalation of dust, or contact with skin.
First Aid:
In case of accidental contact with the skin, the particles should be brushed off
and the affected area flooded with water.
References:
Ventron Corporation Technical Bulletins;
1. Borohydrides in Polymerization Processes.
2. Sodium Borohydride for Flexible Polyvinyl Chloride Sponge.
3. Process Stream Purification Through Hydride Chemistry.
4. Metal Hydrides for Hydrogen Generation.
The Information contained in this bulletin is, lo our best knowledge, true and accurate.
Since the conditions al n*e s»* beyond our control, we assume no obligation or liability
in connection therewith. Nothing in this bulletin shall be construed as permission or
recommendation to practice a patented Invention without a licenie.
Vejttron Corporation /Chemicals; Division
Congress Street. Beverlv. P-te*achu*e«i Ol91S/Tel: 5617) 922-T87S
268
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('Stabilized Water Solution)
Sodium Borohydride-SWS is a itable, alkaline aqueous solution of sodium
borohvdride, which greatly facilitates the aOplication of sodium borohydride in
chemical processing, particularly to water-based systems. Its handling character-
istics closely resemble those of 30*/« liquid caustic.
For information on uses, see brochure on Sodium Borohydride.
Composition:
NaBH4
NaOH
H20
12 ±0.5%
42 ±2%
Balance
Specific Gravity:
Color and Form:
Viscosity.
Stability:
1.4 s/ml. or 11.7 Ibs./gal.
Off-white Liquid
79.0 centipoise at 23°C.
NaBH4-SWS is remarkably stable under normal storage and
shipping conditions. It decomposes very slowly according to
the equation:
NaBH4+ 2H2O -» NaBO2+ 4H2
The rate varies slightly with temperature . Typical rates are:
•/» decomp. per day
0.000005
0.0002
0.008
21
54
100
Solubility:
Sodium Borohydride-SWS can be diluted for use with water or methanol. Many
organic solvents.normally misclble with water are not suitable because of the
caustic present.
Handling and Storage:
Sodium Borohydride-SWS is similar to the 50% liquid caustic which is an article of
commerce. Accepted storage and handling procedures for 50% liquid caustic apply
also for Sodium Borohydride-SWS. On long standing, a pressure may build up over
the solution. Containers should be periodically checked. There should be at least
10% free volume in all closed containers. If this rule is followed, pressure build-up
will be less than 1 psi per year at ambient room temperature. Some suitable
container materials are stainless steels, mild steel, and polyethylene. Glass Is
attacked by the strong caustic. Sodium Borohydride-SWS should be stored at
temperatures above 65°F. Sodium Borohydrlde-SWS becomes more viscous below
60°F. and can crystallize at temperatures below 55°. To liquefy, warm slowly to 70°
to 90°F. making sure the drum is vented. Do not use live steam.
r
Bulletin No. 26-A
269
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Shipping:
Sodium Borohydrlde-SWS has been classed as a corrosive liquid under DOT
regulations. Laboratory quantities are shipped in one-gallon, sealed, polyethylene
"cubitainers" in a cardboard outer container, which to in turn packaged in an
DOT-approved wooden box. Development and production quantities are shipped in
55-gallon druiM, whtofe have at laaat 14% fn* space. Larger quantities can be
shipped by tank track OK tank car.
Safety:
Due to the presence of water, NaBH(-SWS to considered non-flammable. Certain
precautions must be taken, however. Borohydride solutions will decompose rapidly,
evolving large amounts of hydrogen .gas if •objected to -acid conditions, excessive
temperature, or the presence of metal salts or finely divided metallic precipitates
such as nickel, cobalt or copper.
Toriclty:
Due mainly to the presence of caustic, NaOH, Sodium Borohydride-SWS is
considered toxic if ingested. Borohydride solutions are also toxic if ingested
primarily due to possible gas embolism resulting from reaction with stomach acids.
All precautions should be taken to avoid direct contact or ingestion.
First Aid:
In case of accidental contact, flood with copious amounts of water. Wash skin with
soap and water. Flush eyes with water. Seek medical attention promptly.
References:
VENTRON CORPORATION TECHNICAL BULLETINS:
1. Sodium Borbhydrtde/Handllng/Uses/Properties.
2. Inorganic Reductions with Sodium Borohydride.
3. Hydride Chamtoals for Process Stream Purification.
i, ....
The information contained In this bulletin to, to our best knowledge, true and
accurate. Since the conditions of uw an bayond our control, we" assume no
obligation or liability in connection therewith. Nothing in this bulletin shall be
construod as permission or recommendation to practice1 a. patented invention
without a license. "',•'">'•' • ' •"•""
Ventron Corporatton/Gkemicals Division ' -./ ;(;"''^i,^'' H'iy/'
Congress Street. Beverly, Massachusetts 01915/Tel: (017) 922-1875 <'
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DEVELOPMENT
DKTHYl DiHYDRIDE
OMH-1 (suduun aiamimim diethyl dihydride) is an excellent reducing agent which is soluble
in aror.iatic hydrocarbons. It is similar in action to LiAlH. and NaAlH4 and reduces a wide variety
of runctiooal groups in high yield without participation by the -C.H, groups present. Most reductions
occur readily at 25° C, although temperatures above 100° C can he used with non-reactive solvents
OMH-1 should be useful for pharmaceutical, flavor and fragrance, and fine chemical applications
requiring an active hydrogen reducing agent.
AVAILABILITY
Development quantities from one pint
i-o 355 gallon portable tanks are available
as a 25% solution in toluene containing
3-4% THF.
SOLUBILITY
OMH-1 is soluble to aromatic hydro-
carbons and ethers. It is insoluble in paraffin
hydrocarbons and reacts with faydroxylic or
active hydrogen solvents.
PHYSICAL DATA
Form
Appearance
Typical Analysis
Al, wt%
Active Hydride, rr.eq:/s coin
Total Gas Evolution, mmols/g soln
Density, g/ml at 20° C
Ib/gal at 20° C
Viscosity, cp at 20° C
* Containing 3-4% THF.
25 wt% solution in Toluene'.
slightly colored solution
5.9
4.4
8.8
0.879
7.35
2.08-
HANDLING PEgCAUTIONS .
OMH-1 should be kept from contact with air (Oj and moisture to prevent loss of reducing
capacity through oxidation or hydrolysis. Solutions of greater than 10% by weight concentration
are clashed as pyrophoric for shipping purposes. However, concentrations of 10-25% by weight can
be handled easily and safely if ordinary precautions are observed. Handling under an inert aimos-
phere is recommended. Rags, towels, or other combustible absorbent materials should not be used on
large spills since ignition of the solvent may result under certain conditions. Dry chemical extin-
guishers art recommended for use on fires. Solid OMH-1 or its solutions are corrosive to human
tissue, and adequate protection against contact with the skin and eyes should be employed during
handling and use. The toxicological properties of solutions of OMH-1 have not been fully investi-
gated. In case of accidental spills, inhalation of vapors or fumes should be avoided.
To* Information presented herein le believed to b* accurate and reliable, but 10 presented without guarantee or respon-
sibility on the part of Ethyl Corporation. Further, nothlnr contained herein shall b* taken na an Inducement or
recommendation to tnanufiirture or use any of the bereta dcacrtbed materlala or procea**a In violation ot exletlac or
future patsoti.
ETHYL CORPORATION • Commercial Development Division
Erhyt TOWEI, 451 Flonda. Baton Rouge, la. 70801
FOKM CDH-1
December,
271
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