EPA-450/3-78-109
   Screening  Study on  Feasibility
    of Standards  of Performance
for Hydrofluoric Acid  Manufacture
                         by

                    Vladimir Boscak

             The Research Corporation of New England
                  125 Silas Deane Highway
               Weathersford. Connecticut 06109
                  Contract No. 68-02-2615
                      Task No. 6
              EPA Task Manager: Kenneth R. Woodard

            Emission Standards and Engineering Division



                      Prepared for

            U S. ENVIRONMENTAL PROTECTION AGENCY
                Office cf Air, Noise, and .Radiation
             Office of Air Quality Planning and Standards
            Research Triangle Park. North Carolina 27711

                      October 1373

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This raport has been reviewed by the Emission Standards and Engineering Division of the Office of Air
Quality Planning and Standards, EPA, and approved for publication. Approval does not signify that the
contents necessarily reflect the views and policies of the Environmental Protection Agency, nor does
mention of trade names or commercial products constitute endorsement or recommendation for use.
Copies of this report are available through the Library Services Office (MD-35), U.S. Environmental
Protection Agency, Research Triangle Park, N.C. 27711; or, for a fee, from the National Technical
Information Services, 5285  Port Royal Road. Springfield, Va. 22161.
                             Publication No. EPA-450/3-78-109

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                                TABLE OF CONTENTS
SECTION                                                                    PAGE

1.0            ABSTRACT	1

2.0            EXECUTIVE SIE1MARY	  2

3.0            CONCLUSIONS AND RECOMMENDATIONS  	  6
   3.1           Conclusions	,	6
   3.2           Recommendations	6

4.0            HYDROFLUORIC ACID MANUFACTURING INDUSTRY - ECONOMIC
                PROFILE AND STATISTICS  „  	  7
   4.1           Industry Size and Geographic Location  	  7
   4.2           Capacity Utilization and Consumption 	 10
   4.3           Industry Growth Trends .,	13
   4.4           References	16

5.0            HYDROFLUORIC ACID MANUFACTURING PROCESS	17
   5.1           Hydrofluoric Acid Manufacturing Chemistry  	 17
   5.2           Typical Hydrofluoric Acid Manufacturing Process  	 19
   5.3           Major Variations of Hydrofluoric Acid Manufacturing
                  Processes	25
   5.4           Recovery of Fluoride Value From Phosphate Rock 	 33
   5.5           References	37

6.0            EMISSION SOURCES AND RATES IN HF PRODUCTION AND
                MANUFACTURING  	 38
   6.1           Sources and Nature of Point Source and Fugitive
                  Emissions	38
   6.2           Controlled and Uncontrolled Emission Rates 	 40
   6.3           Annual Emission Rates arid Plant Inventories	44
   6.4           Gypsum Pond Emissions	48
   6.5           References	51

7.0            CONTROL OF EMISSIONS FROM HF MANUFACTURE	52
   7.1           Particulate Emission  Control  	 52
   7.2           Gaseous Emission Control  	 57
   7.3           Fugitive Emission Control   	 68
   7.4           Summary of Best Control Technology	69
   7.5           References	72

8.0            STATE AND LOCAL  EMISSION REGULSTIONS  	 73
   8.1           Summary of Applicable Emission Regulations 	 73
   3.2           List of Regulations Applicable to  the Hydrofluoric
                  Acid Manufacturing Industry  	 74
   8.3           Definition of  Plant Modification  	 94
   8.4           References	96
                                   iii

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                          TABLE OF CONTENTS (Continued)
SECTION                                                                    PAGE

9.0            HP MANUFACTURE EMISSION SOURCE SAMPLING AND ANALYSIS .... 97
   9.1           Particulates	99
   9.2           Total Fluorides	 .	99
      9.2.1        TRC's Experience With Fluoride Sampling and Analysis .  .103
      9.2.2        Remote Sensing of Fluoride Emissions 	108

10.0           ENVIRONMENTAL EFFECTS OF FLUORIDE EMISSIONS	113
   10.1          Vegetation Effects	113
   10.2          Effect on Farm Animals	115
   10.3          Effects in Man	117
   10.4          Other Effects	118
   10.5          References	118

11.0           EMISSION REDUCTION WITH NEW SOURCE PERFORMANCE STANDARDS .  .119
   11.1          Introduction	119
   11.2          Model IV - Background Information	120
   11.3          Industrial Factors	124
   11.4          Emission Factors	127
   11.5          Results of Model IV Calculations	128
   11.6          References	129

12.0           LIST OF CONTACTS	130

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                                 LIST OF FIGURES
FIGURE                                                                  PAGE

 £-1           Location and Relative Capacity of Hydrofluoric
                Acid Manufacturers9 	   8
 5-1           Schematic Flow Diagram for the Manufacture of
                Hydrogen Fluoride-'	24

 5-2           Process Flowsheet for the Manufacture of
                Hydrofluoric Acid3 Using Buss Technology	26

 5-3           Anhydrite Recovery Flowsheet3	28

 5-4           EPA Exemplary Hydrofluoric Acid Process Flow Diagram .  .  32

 5-5           Vertical Hydrolysis System11 	  35

 6-1           Typical Tail Gas Exhaust Stack	41

 6-2           Hydrofluoric Acid Production - Uncontrolled
                Process Model1	42

 6-3           HF Production - Controlled Process Model1	45

 6-4           Effluent Recycle System at an Exemplary Plant5  . 	  49

 7-1           Baghouse for Control of Spar Emission	  54

 7-2           Typical Baghouse with Pulsed Air Cleaning1 	  55

 7-3           Kiln Venturi Scrubber System3	  56

 7-4           Relationship Between Collection Efficiency and
                Particle Size in Venturi Scrubbers	  58

 7-5           Typical Packed Tower3	  .  .  59

 7-6           Power  Consumed in HF Absorption	62

 7-7           Power  Consumed in SiF^. Absorption	63

 7-3           Power  Consumed in Absorbing S0£	64

 7-9           Typical Tank Car Unloading Connections When Using
                Compressed Air for Unloading Anhydrous
                Hvdroflucric Acid'	70
                                    v

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                      LIST OF FIGURES (Continued)
FIGURE                                                                PAGE

 3-1      Ohio Collector Efficiency Curve1*	    80

 8-2      Pennsylvania Allowable Emissions Curve for
           Sources Not Listed in Section 123,136 	    83

 8-3      Texas Allowable Particulate Emission Rates
           for Specific Flow Rates7	    86

 8-4      Texas Allowable Particulate Emission Rates
           for Specific Flow Rates7	    87

 8-5      Texas Fluoride Standards 	    88
            Graph 1	    89
            Graph 2	    90

 9-1      Method 5 Particulate-Sainpling Train	100

 9-2      Method 17 Particulate-Sampling Train, Equipped
           With Iii-Stack Filter	101

 9-3      Schematic of a Ground Upwind-Downwind and
           Vertical Traverse Sampling Station  	   104

 9-4      Experimental Arrangement for Evaluation of
           Hydrogen Fluoride Sampling and Analysis 	   105

 9-5      EPA ROSE Infrared Spectrometer System  	   109

 9-6      Gypsum Pond Spectra	112

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                                 LIST OF TABLES


TABLE                                                                 PAGE

 4-1           Hydrofluoric Acid Manufacturing Plants in the
               United States 	     9

 4-2           Population Statistics .	    12

 4-3           Hydrofluoric Acid Production	    13
 4-4           1976-1977 Producton of Fluorocarbons Fll and F12. .  .    14

 4-5           Aluminum Industry Production 1975-1982	    15

 5-1           The Physical Properties of Anhydrous Hydrogen Fluoride  18
 5-2           The Physical Properties of Fluorspar (CaF2)  	    19

 5-3           Reactions of Fluorides. .	    22

 5-2           Process Flowsheet for the Manufacture of Hydrofluoric
               Acid Using Buss Technology	    26

 6-1           Emission Factor Ranking for Hydrofluoric Acid ....    43

 6-2           Soluble Fluoride Emissions from HF Production ....    46

 6-3           Emission Inventory for HF Manufacturing Plants.  ...    47

 6-4           Waste Products from HF Manfacturing Plants.  .....    50

 7-1           Advantages Si Disadvantages of Wet & Dry Air  & Gas
               Cleaning Devices   	    53
  7-2           Hydrogen Fluoride Absorption Date  	   61

  7-3           Best  Control Technology  in HF Manufacture  	  .   71

  8-1           San Francisco  Bay Area Regulations Applicable  to
               HF Manufacturing	   75

  8-2           Kentucky State Regulations Applicable  to HF
               Manufacturing  	   76

  8-3           Louisiana  State Regulations Applicable to  HF
               Manufacturing  	    77
                                     Vll

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                             LIST OF TABLES (Cont)


TABLE                                                                 PAGE

 8-4           Ohio State Regulation Applicable to HF Manufacturing .    78

 8-5           City of Cleveland Regulations Applicable to HF
               Manufacturing	,	    81

 8-6           Pennsylvania Commonwealth Regulations Applicable to
               HF Manufacturing	    82

 8-7           Texas State Regulations Applicable to Hf Manufacturing   84

 8-8           West Virginia State Regulations Applicable to HF
               Manufacturing	    91

 S-9           New Jersey State Regulations Applicable to HF
               Manufacturing	,	    92

 8-10          Summary of State Regulations on Allowable
               Emissions	    93

 9-1           Sampling and Analysis Techniques for the Emissions
               For HF	    98

10-1           Hydrogen Fluoride Concentrations and Exposures for
               Sensitive and Resistant Plant Species	114

10-2           Safe Level of Fluorine in Livestock Feed	116

11-1           Model IV Input Variables  . .,	122

11-2           Model IV Industrial and Emission Factors -
               Hydrofluoric Acid	128
                                   vni

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                                   DISCLAIMER









     This Final Report was submitted to the U. S. Environmental Protection Agency




by TRC - TdE RESEARCH CORPORATION of New England, Wethersfield, Connecticut in




partial fulfillment of Contract No. 68-02-2615, Task No. 6.  The opinions,




findings, and conclusions expressed are those of the author and not necessarily




those of the Environmental Protection Agency or of cooperating agencies.  Mention




of company or product names is not to be considered as an endorsement by the




Environmental Protection Agency.
                                    ix

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                                ACKNOWLEDGEMENTS









     The author would like to acknowldege helpful discussions with Messrs.




Kenneth Woodard and Kenneth Durkee, Environmental Protection Agency, Office of




Air Quality Planning and Standards, Emission Standards and Engineering Division,




Raleigh - Durham, North Carolina.




     In addition, the author would like to make a collective acknowledgement to




the personnel at each hydrofluoric acid manufacturing plant without whose coopera-




tion this project could not have been completed, and state and local air pollu-




tion control agencies for furnishing information to TRC.  The opportunity to




visit the Allied Chemical plants in Baton Rouge and Geismar, Louisiana, the




DuPont plant in LaPorte, Texas, and the Harshaw Chemical Company office in




Cleveland, Ohio is greatly appreciated.




     The following TRC personnel in addition to the author participated in this




project::  Mr. Bradley Raffle, Ms. Pamela Katz, Ms. Patricia Tyszka, Mr. Reed Cass,




and Ms. Sandv Sholovitz.

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1.0  ABSTRACT




     This report contains background information on the hydrofluoric acid manu-




facturing industry.  This information was obtained in the open technical literature




and through visits to several typical plants.




     The economic profile of the industry indicates there will be no growth in




the next five years.




     General description of manufacturing process emission sources, rates and




controls are the main part of the report.  State and local emission regulations




and emission source sampling and analysis methods are also discussed.




     The background information has been used in a simple emission projection




model (Model IV) to determine the emission reductions that could be achieved by




the application of New Source Performance Standards.
                                       -1-

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2.0  EXECUTIVE SUMMARY




     Industry's Economic Profile




     In the United States at the present time, there are 9 hydrofluoric acic




(HF) plants in operation.  Two are located in Louisiana, 2 in Texas and 1 each




in California, Kentucky, New Jersey, Ohio, and West Virginia.  According to 1977




figures, the industry produced 268,000 tons of hydrofluoric acid, while 1975




data showed the annual capacity to be 369,000 tons.  In recent years almost all




HF produced is in the anhydrous form.  Major HF uses are fluorocarbon production




(39%), aluminum industry production  (27%), and with the remaining being used for




uranium enrichment, petroleum alkylation, stainless steel pickling and miscellaneous,




     The fluorocarbon aerosol ban resulted in a 20% reduction in HF production.




The volume of HF manufacture will be the same for at least the next 5 years.




While new plants are not planned two plants are expected to be closed by mid




1979.  The rest of the  industry will increase the utilization of their capacity




to compensate for the difference.









     HF Manufacturing Process




     HF is manufactured  from  fluorspar and sulfuric acid in a rotary kiln according




to  the  endothennic reaction:




     CaF2 + H2SOi+ ->• CaSOv -i- 2 HF




The  product anhydrite is either slurried  and  transferred  to  a gypsum pond,  or




neutralized and recovered in  the solid form.  HF gases  are first scrubbed and




cooled, and almost all  HF is  recovered in  a condenser.  The  remaining HF and




impurities are scrubbed in an acid  scrubber while  fluosilicic acid  can be re-




covered in a  water scrubber.  Almost all  processes  used a  tail  gas  scrubber




before  venting the gas  to the atmosphere.  Crude HF is  distilled  to a high




purity  for a  further  use.

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     Four major variations of HF manufacture are:




     1.   Buss Process




     2.   Typical Process (described by EPA)




     3.   Aluminum Fluoride Manufacture Process




     4.   Patented Process




HF can be recovered from a phosphate rock using silicon tetrafluoride  (a by




product), but the process is in the early stages of development.
     Emission Sources and Rates




     There are few sources of air emissions in a HF manufacture plant.  The major




source of particulate emission is fluorspar drying and handling.  The literature




suggests that the spar emission rate is about 20 Ib/ton and emission data from




typical plants indicate that this emission factor is realistic.  The only point




source of gaseous emission is from the tail gas scrubber.  The emissions consist




of small amounts of HF, SiF^ and S0£.  The HF manufacturing process model shows




that uncontrolled soluble fluoride emission is 52 Ib F/ton of HF.  Controlled




emissions using a gas scrubber with 90% efficiency amount to 4 Ib F/ton HF.




Total annual emission of soluble fluoride from HF manufacture after currently




used control is 700 tons F/year.  The projection for the year 2000 shows 5300




tons ?/year based on 6% yearly growth.  Since this growth is probably unrealistic,




this emission projection appears to be high.




     Fugitive fluoride emissions are expected from process upsets, HF handling




and the gypsum pond (with pH of 1).




     The emission inventory for HF manufacturing plants  is too unreliable  to




develoo actual emission factors.
                                        -3-

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Control of Emissions




     Particulate emissions for spar drying and handling are controlled with




fabric filters and wet scrubbers.  The best control appears to be the use




of a fabric filter with 99% efficiency.  The gaseous emissions are controlled




with wet scrubbers.  The best control technique is the use of a packed




tower with about 5 transfer units using alkaline scrubbing liquid which can




achieve an efficiency of 99% for removal of HF, SiFi+ and S02.  HF fugitive




emissions from a kiln under upset conditions are best controlled with a stand-by




caustic scrubber.  Liming of the gypsum pond to obtain a pH of 6 would prevent




any HF or SiF^ emission.









     State and Local Emission Regulations




     Although hydrofluoric acid manufacturing  is regulated under the permit and




particulate regulations of the states where operations exist, no state has yet




adopted regulations which specifically address HF  production.  Rather, states




treat HF manufacturing as a process  industry for purposes of  air pollution control




regulations.  An analysis of state regulations indicates that process weight




and/or  fluoride emissions standards  apply  to virtually all HF plants.









     Emission Source  Sampling and Analysis




     Sampling and  analysis methods for  criteria  pollutants, particulate,  SC>2,  No




are  covered under  EPA Methods 5,  (17),  6  and  7.  Total  fluoride  is  covered under




EPA  Method 13.  TRC  experience  indicates  that  a  simplified sampling train can  be




used for  gaseous  fluoride emissions  measurement.   Remote Optical  Sensing




of Emissions  (ROSE)  has  been  developed  by EFA's  Environmental Sciences  Research




Laboratory/HTP.  This technique  is well suited for the  measurement  of  ambient




fluoride  concentrations,  and  it  distinguishes  between HF  and  SiFu.

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     Emission Reduction With NSPS




     Results of the Model IV calculation indicate that there would be no reduction




in 1987 emission if NSPS are implemented.  This is due to the projected lack of




increase in production volume.  Review of emissions control on an industry-wide




basis shows that most plants are using best control technology.  Since some




plants have better controls in one area and some in the other NSPS would bring




the plants on an equal level.  It appears that fluoride emission would be reduced




by 20-30% if best control technology was applied to all plants.
                                        -D-

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3.0  CONCLUSIONS AND RECOMMENDATIONS

3.1  Conclusions

     1.    No growth is expected in the HF manufacturing industry in the next 5
          years.  The growth after that is unpredictable but will be probably
          below 6% annually (an average for last 3 decades).

     2.    There are 4 variations in HF manufacture that are described in this
          report.

     3»    HF manufacturing has 2 major sources of emission:  Particulate emis-
          sions from spar drying and tail gas from the HF absorption train.

     4..    The best control for particulate emissions are fabric filters and wet
          scrubbers for tail gas containing HF, SiF^ and S02-

     5.    The quantitative data on gaseous emissions containing fluorides are
          virtually non-existent due to the lack of regulations.

     6.    It is unclear whether the fluorspar should be included in the fluoride
          emissions and what is its effect: on vegetation, animals and man.

     7.    The major problem in HF manufacturing is corrosion which can result in
          HF emissions. Good maintenance is essential for proper operation.

     8..    The major benefit of NSPS for this industry would be to equalize
          emissions controls throughout the industry resulting in overall 20-30%
          reduction in fluoride emission in the existing plants.
3.2  Recommendations

     In order to obtain a better understanding of HF manufacture  environmental

problems the following are recommended:

     1.   Measure fluoride concentrations  in  tail gas  from HF manufacture.

     2..   Quantify fugitive emissions  in HF manufacture.

     3..   Determine fluorspar  effects  and  whether they should be  considered
          fluorides or particulates.
                                       -6-

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4.0  HYDROFLUORIC ACID MANUFACTURING INDUSTRY - ECONOMIC PROFILE AND STATISTICS




4.1  Industry Size and Geographic Location




     Hydrofluoric acid (KF) manufacturing is a segment of the inorganic chemical




industry under the Standard Industrial Classification  (SIC) 2819 - Industrial




Inorganic Chemicals.




     In the United States at the present time, there are 11 hydrofluoric acid




plants in operation.  Three of these are located in Louisiana, three in Texas and




one each in California, New Jersey, Ohio, West Virginia and Kentucky.  Figure 4-1




illustrates the approximate locations and relative size of each plant as deter-




nined by 1975 annual capacity statistics.




     The tern "HF Manufacturing Plant" needs some clarification.  All HF manu-




facturing facilities are a part of large chemical plants and only 20 to 90




employees out of several hundred are involved in HF production.  In several




plants HF is a link in a production chain consisting of ^SOtt - HF - fluoro-




carbons.  In several plants all HF manufactured is used within the plant.




     According to 1977 actual data determined from the industry 268,000 tons of




hydrofluoric acid were produced for internal use and for outside consumption.




In spite of the aerosol controversy, fluorocarbon production consumed about 39%




of the total hydrofluoric acid supply.  The alum-inn^ industry accounted for




about 272%.  The remainder of the hydrofluoric acid supply was utilized for




uranium enrichment  (62T) , stainless steel pickling  (2%), alkylation of olefins




(4%) and miscellaneous application (22%).   [Table 4-1  presents the annual capa-




city for each plant.]
                                         -7-

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O 80-100 thousand tons/year
 O A5-5S  thousand tons/year
 • 10-20  thousand  tons/year

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                                     TABLE 4-1

            HYDROFLUORIC ACID  MANUFACTURING PLANTS IN THE UNITED STATES
Source:  1977 Directory of Chemical Products, U.S.A.   Chemical Information
         Services,  Stanford Research Institute


1.






2.
3.


4.

5.

6.

7.


8.

9.


PRODUCER
Allied Chem. Corp.
Indus t. Chens. Div.




Specialty Chema. Div.
Aluminum Co. of America
Ashland Oil, Inc.
Ashland Chen. Co., dlv.
Lehlgh Valley Chetn. Co. div.
E. I. du Pont de tlemoura 4 Co., Inc.
Biochems. Dept.
Essex Chem. Corp.
Chents. Dtv.
Kaiser Aluminum & Chen. Corp.
Kaiser Cliems. Div.
k'ewanee Indust., Inc.
Harshaw Chemical Co., subs id.
Indust. Chems. Dept.
Pennwalt Corp.
Inorganic Chen. Div.
Stauffer Chem. Co.
Indus t. Chem. Dlv.

LOCATION

1. Baton Rouge La.
2. dayman t Del.
3. Geismar, La.
4. Nitro, W.Va.
5. Pittsburg, Calif.
6. Marcus Hook, Pa.
Point Comfort, Tex.


Clendon, Pa.

La Porte, Tex.

Paulsboro, M.J.

Craoercy. La.


Cleveland, Ohio

Calvert City, Ky.

Greens Bayou, Tex.
ANNUAL CAPACITY
(THOUSANDS OF TONS)

20
25
45
15
12
n.a.
55


5

100

11

50


18

25

18
IN OPERATION
SIHCE

1946

1967
1959
1952

1961




1964






1972

1949


                                                       TOTAL
                                                               399
  Sources: Chemical Marketing Reporter, November 17, 1973 and communication with industry.
 Comments:
1.
       Contacts with the industry  indicate that 3 of above plants  (Allied Chemical's
       Clavmont. and the Ashland' plant)  no longer manufacture HF    ^equei^'
       total annual capacity without these plants is 369  thousand  tons  per year.

       Actual total 1977 production (obtained under confidentiality agreement) is
       268 thousand tons.  The  discrepancy is the result of erroneous  annual
       capacity listing and capacity's under utilization.
                                           -9-

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4.2  Capacity Utilization and Consumption




     The existing hydrofluoric acid plants have been underutilizing their capacity




for the past several years.  In 1977 the annual capacity of the industry totaled




369,000 tons, while total production amounted to 268,000 tons, or 73% of total




capacity.




     The major users of all of the marketed hydrofluoric acid are the aluminum




and fluorocarbon industries.  In aluminum manufacturing, the hydrofluoric acid




is not used directly in the smelting process, but goes into producing aluminum




fluoride and synthetic cryolite from reaction with alumina and caustic soda,




respectively.  These products together with bauxite are then used in the molten




bath which undergoes electrolysis to produce aluminum.2  An estimated 56 pounds




of hydrofluoric acid are  required to produce 1  ton of  aluminum.   Table  4-5  in




Section 4.3 shows  the production/consumption figures for  the  aluminum industry.




     Fluoride production  accounted  for  42%  of  the  total hydrofluoric acid  supply




in 1976.2  Inorganic fluorides are  manufactured for utlization as preservatives,




insecticides, catalysts,  fluxes,  for steel  pickling and  for use in fire extin-




guishers.  Hydrofluoric acid  is used in the manufacture  of elemental  fluorine




gas which  in  turn  is used to  manufacture uranium hexafluoride sulfur  hexafluoride,




halogen  fluorides  and emulsified  perfluorochemicals.   The organic fluorides,




which  utilize the  rest  of the available hydrofluoric  acid, are manufactured for




production of various chlorofluorocarbons.   These  fluorocarbons are widely used




as refrigerants, aerosol  propellants,  resins,  solvents and elastomers.








     The geographic  location  of the hydrofluoric acid  plants  is significant in




determining  the potential effects of atmospheric fluorides on plants and ani-




mals.  Table  4-2 gives  population statistics for 1 and 5  mile circles around
                                        -10-

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each plant.  The farm statistics give an indication of the amount of agricul-




tural activity in the vicinity of each plant which may be subject to fluoride




emissions.




     Based on the number of employees involved in HF manufacture and actual




production data, one can calculate that about 1.5 employees are needed  to




produce one thousand tons/year of anhydrous HF.  This adds up  to a  total of  402




employees  (nationwide) in HF manufacture.
                                       -11-

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PLANT
                                    TABLE 4-2


                              POPULATION STATISTICS
               (based on TELE/SITE and contacts with the industry)
             EMPLOYEES       POPULATION          FARM POPULATION
LOCATION    IN HF MANUF. 0-1 MILES 1-5 MILES  0-1 MILES - 1-5 MILES

Alcoa
DuPont
Stauffer

Allied
Allied
Kaiser

Allied

Pennwalt

Essex

Harshaw

Allied
Texas
Point Comfort 5-1 0 8,386 0
La Porte 90 13 41,335 0
Greens Bayou n.a.* 2,454 105,894 0
Louisana
Geismar 15 0 5,312 0
Baton Rouge 30 1,375 178,292 0
Gramercy n.a. 0 11,851 0
California
Pittsburg 25 28 41,079 0
Kentuckv
Calvert City 41 0 4,145 0
New Jersey
Paulsboro n.a. 8,084 158,884 5
Ohio
Cleveland 20 16,631 479,543 17
W. Virginia
Nitro 25 1,972 39,904 1

21
4
20

64
285
87

56

32

169

216

12
      *n.a.  = not available.
                                       -12-

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4.3  Industry Growth Trends

     The production of industrial inorganic chemicals depends upon a wide range

of economic activities and does not rely on one specific sector of the economy.

Presently, the largest consumers of hydrofluoric acid are the fluorocarbon

and aluminum industries, accounting for 42% and 32% of the total hydrofluoric

acid usage in 1976.2  A good indicator of the hydrofluoric acid production

trend is the consumption of acid-grade fluorspar used in its manufacture.

Table 4-3 illustrates the production trend from 1972 through 1977.
                                    TABLE 4-3
                          HYDROFLUORIC ACID PRODUCTION
                           1972 - 1977
                                       (2,3,4,5,6,7,8)

Acid -Grade
Fluorspar Consumed
(Short Tons)

HF
Produced
(Short
Tons)
Withdrawn
From
System
Not
Withdrawn
From
System
1972

752,728

248,879

93,270
1973

803,999

269,153

96,301
1974

838,211*

281,620

99,385
1975

673,626

229,247

84,138
1976

631,300

202,644

85,518
1977

!
.
560,519

182,690

73,000
           *Derived  by  assuming  2.2  Ib  acid-grade  fluorspar  -  1  Ib hydrogen
            fluoride

      Early in  1975  a controversy  arose concerning the  use of  fluorocarbon aero-

 sols  and  their possible  effect  on the  ozone layer of  the stratosphere.   As  a

 result  of the  controversy,  fluorocarbon aerosol sales  decreased as  did  the  demand

 for  the hydrofluoric acid used  in their manufacture.   In April  of  1977,  the

 Food  Drug Administration (FDA)  and  Consumer Product Safety  Commission (CPSC)

 stated  the need for warning labels  to  be placed on all products containing

 fluorocarbon propellants.   Following this action in May of  1977 the EPA along

                                       -13-

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with the FDA and the CPSC issued a set of rules which would ban fluorocarbon

aerosol propellants for nonessential uses by December 15, 1978 and would prohit

their shipment between states by April 15, 1978. ^  This ruling has had a signifi-

cant effect on hydrofluoric acid production since 1975.  This controversy has

reduced the demand for HF by approximately 20%.  The statistics for production

of the controversial fluorocarbon Fll and F12 for 1976 and 1977 are shown in

Table 4-4.  An illustration of the reduction in fluorocarbon  production  is

the fact that three plants have been closed since 1975 and production at one

has declined 50%.
                                    TABLE 4-4
                           1976 -  1977 PRODUCTION OF
                      FLUOROCARBONS Fll  and F12^j '**' 5> 6 >7>
                                 (MILLION  POUNDS)


Hydrofluoric
Acid Consumed*
Fll & F12
Produced

1976

624

218
1st Qtr.
1977

140

49
2nd Qtr.
1977

158

55
3rd Qtr.
1977

144

50
4th Qtr.
1977

104

36
Total
1977

546

191
           *Derived  by  assuming  .35  Ibs  HF = 1  Ib  fluorocarbon


     Table 4-5  presents  the  production  statistics  for  the  aluminum industry  from

 1975 through  1977 and  estimated  production through 1982.

-------
                                   TABLE 4-5
                         ALUMINUM  INDUSTRY  PRODUCTION
                            1975  -  1982  (2»3»^.StS.7)
                                 (THOUSAND TONS)
Hydrofluoric
Acid Consumed*
Aluminum
Produced
1975
109
3,880
1976
119
4,250
1977
127
4,530
1980T
164
5,857
1982'
195
6,964
                    *Derived by assuming 56 Ib HF » 1 ton aluminum
                     (via cryolite and aluminum fluoride)
                    tAssuaie 97, increase each year
     The economic strength in HF manufacturing is that it will be indispensable to

the aluminum industry for many decades despite the introduction of aluminum

process techniques that avoid HF.'

     The major weakness is the enormous aluminum inventory surplus and the de-

pressed economy.  These factors are expected to keep the aluminum supply loose

and production low for several years.

     In conclusion it appears that HF manufacture will not increase  for at least

5 years.  Contacts with the  industry revealed  that 1982  production will stay

on  the 1977  level with a  total of 254,000  tons.  Two plants  are  expected  to be

closed by mid-1979.   The  rest of  the  industry  will operate at a  higher  capacity

to  compensate  for  the difference.   Contacts with HF manufacturers  also  indicate

that no new  facilities or modifications  are expected  in  the  next 5  years.  The

importation  of HF  is likely to  increase.
                                        -15-

-------
4.4  References

1.   Inorganic Chemicals Industry Profile  (Update), Datagraphics, Inc.
     Pittsburgh, PA for EPA under program  #12020EJ1, July 1971.

2.   Division of Nonmetallic Minerals.  1977.  Fluorspar in 1976.  Bureau of
     Mines Minerals Industry Surveys, U.S. Department of the Interior,
     11 pages.

3.   Singleton, Richard H. and  Shelton, John E. 1975.  Fluorspar.  Preprint
     from the 1975 Bureau of Mines Minerals Yearbook, U.S. Department of
     the Interior, 19 pages.

4.   Division of Nonmetallic Minerals.  1977.  Fluorspar in First Quarter
     1977.  Bureau of Mines Minerals  Industry  Surveys, U.S. Department of the
     Interior, 7 pages.

5.   Division of Nonmetallic Minerals.  1977.  Fluorspar in Second Quarter
     1977.  Bureau of Mines Minerals  Industry  Surveys, U.S. Department of the
     Interior, 8 pages.

6.   Division of Nonmetallic Minerals.  1977.  Fluorspar in Third Quarter
     1977.  Bureau of Mines Minerals  Industry  Surveys, U.S. Department of the
     Interior, 8 pages.

7.   Division of Nonmetallic Minerals.  1977.  Fluorspar in Fourth Quarter
     1977.  Bureau of Mines Minerals  Industry  Surveys, U.S. Department of the
     Interior, 8 pages.

8.   Bureau of the Census.  1978.  Inorganic Chemicals February  1978.  Current
     Industrial Reports, U.S. Department of Commerce, 4 pages.

9.   Chemical Marketing  Report, Vol.  208,  No.  20,  November 17, 1975.
                                     -16-

-------
5.0  HYDROFLUORIC ACID MANUFACTURING PROCESS




5.1  Hydrofluoric Acid Manufacturing Chemistry




H? Properties




     In volume of production, HF is the most important manufactured compound of




fluorine.1  Both the anhydrous and aqueous acids are used directly or as inter-




mediates but anhydrous acid is becoming a principal product.




     Anhydrous HF is a colorless liquid or gas  (bp 19.5°C) , highly water soluble




and fuming strongly in contact with the atmosphere.  The formula weight is 20.006,




but hydrogen bonding between molecules produces extensive polymerization, and




the liquid and gas show large departure from ideal behavior.  As a matter of fact




HF is the most imperfect gas studied.^ The physical properties  of anhydrous HF




are shown in Table 5-1.
Fluorspar Properties




     The preferred  raw materials  for  the manufacture of  HF  in the  United  States




are  acid grade  fluorspar  and  sulfuric acid..   The physical properties  of  fluorspar




are  shown on Table  5-2.3  The  fluorspar is  treated with sulfuric  acid  according




to the  endothermic  reaction:




          Ca F2 + H2SOu * Ca  S0i»  + 2  HF




     The reaction is  believed to  take place  in a sequence of steps3




          Ca F2 + H2  SO,,  -* Ca (HSO^.F.HF)




          Ca  (HSO^.F) + HF -»• Ca SOu + 2 HF




     The ability of the reaction to proceed  to the maximum  degree in commercial




operation  is  influenced by the purity and  fineness of the fluorspar,  the tempera-




ture of the reaction,  the time allowed for completion of the reaction, and the




intimacy of mixing  of the acid and spar.
                                        -17-

-------
                                TABLE  5-1
THE  PHYSICAL PROPERTIES  OF  ANHYDROUS  HYDROGEN  FLUORIDE1
     formula, weight (calculated)
     molecular weight
       saturated vapor, at boiling point
       saturated vapor, at 100°C
     boiling point, at 1 atm
     melting point
     density
       liquid, at 25*C
       vapor, saturated, at 25 °C
     vapor pressure, at 25°C
     heat of vaporization
       boiling point, at 1 atm

     heat of fusion, melting point
     heat capacity, constant pressure
       liquid, boiling point
       vapor, at 25°C, 1  atm
     heat of formation
       ideal gas, at 25*Ce
     free energy of formation
       ideal gas, at 25 °C*
     entropy, ideal gas, at 25 "C*
     critical temperature
     critical pressure
     critical density
     viscosity, at O'C
     surface tension, at boiling point
     refractive index,  5893 A, at 25 "C
     molar refractivity (5893 A, formula wt)
     conductivity, at O'C
     dielectric constant, at 0°C
     dipole moment, EF molecule
20.006

7S.24
49.08
19.51°C
-83.37'C

0.9576 g/cmj
3.553 g/liter
17.S psia

J1609cal/20.01 g
(1785
46.93cal/g

12.2cal/(20.01 g)(°C)
143cal/(20.01 g)(°C)

-64.9kcal/20.01g

-65.0Iccal/20.01 g
41.5cal/(20.01gX°C)
ISS'C
941 psia
0.29 g/cm'
0.26cP
8.6 dyn/cm
1.1574
2.13cm1
<1.6 X 10~« mho/cm
S3.6
1.S3D
     * From vapor pressure vs temperature.
     * From ealorimetry.
     ' The enthalpy change for the reaction HF (ideal gas) — HF (real gas), at 2d°C, 1 atm, i.s
 certain, and may exceed several kilocalories per mole (20).
                                      -18-

-------
                               TABLE 5-2
             THE PHYSICAL PROPERTIES OF FLUORSPAR  (CaF2)
Molecular weight - 78.08

Melting point 1418°C

Boiling point 2513°C

Density - 3.18 g/cm3

Solubility of CaFo in Water

                     Cms. CaF? per liter  sat, sol.

          t°C
t°C
                                                   (flurospar)
                                                   (fluorspar)
                                                   (calcined)

                                                   (fluorspar)
                                                   (ph  -  6.4)
                                                   (fluorspar)
              Cms.   CaF2  dissolved per 3LQO  cc.  in aqueous

              0.5  Normal  CH -£OOH.    1.0 Normal  CH-£OOH.    2.0  Normal  CH;COOH.
0
15
18
18
18
25
25
25
40
Solubility of CaF? ±
0.013
0.015
0.016
0.01S
0.015
0.018
0.016
0.040
0.017
n Acetic Acid
      40	   0.0153
      60	   0.0178
      80	   0.0206
     100	   0.0229
                                    0.0175
                                    0.0203
                                    0.0237
                                    0.0264
   0.0192
   0.0229
   0.0267
   0.0300
 Solubility of  CaF^  in Hydrochloric Acid at 25°C
      Normality
      of  aq.  KC1

       0.01
       0.10
       1.00
                               Gm. moles
                             Dissolved per liter

                                   0.00087
                                   0.0053
                                   0.0280
 Heat of Formation (Solid at 298°K - 290.3 Kcal/g mole)

 Heat of Fusion - 7.10 Kcal/g mole

 Heat of Vaporization - 83.0 Kcal/g niole

 Entropy at 298°K - 16.4 eu.

                                      -19-
 pH of
sat, sol.

  2.02
  1.05
  0.04

-------
5.2  Typical Hydrofluoric Acid Manufacturing Process




     In reviewing the HF manufacturing process, a typical process schematic will




be discussed first, followed by four major variation of  the process.  The  initial




intention was to present a process schematic for each plant and describe its




process.  However, since some companies consider their process description and




schematic confidential, this was not feasible.




     The first step in HF manufacturing is spar drying.  Most of the plants




import acid grade spar from Mexico, North Africa or Italy.  The spar is received




in the particle size needed for reaction and can be wet  (10% moisture) or  dry.




Almost all plants have spar drying facilities.  Spar dryers are usually rotary




kilns internally heated and some employ an independent cooling kiln with a heat




recovery system.




     Sul'furic acid, a second raw material for HF manufacturing, is  frequently




manufactured at the same facility.




     The schematic of a typical•HF manufacturing process is shown in Figure 5-1.




This process schematic applies  in general to most HF manufacturing  facilities.




In recent years almost all HF is manufactured,  in anhydrous form; 70% acid  is




manufactured by dilution of anhydrous  HF with water.  The process schematics 6.2




showing  the manufacture of 80%  acid in strong  acid  absorbers and 50% H? in weak




acid absorbers are becoming obsolete.




     The reaction between  spar  and  sulfuric  acid  in the  kiln is endothermic and




in most  cases heat is  supplied  to  speed up  the  reaction. To effect a  release  of




over 98% of  fluorine  in  the  spar  the  reaction  time  is  normally  30-60 minutes  at




200-250°C with HF  leaving  the reactor  at  100-150°C.
                                         -20-

-------
     Since fluorine values dominate raw material costs, these factors are




optimized to give the T-aximum yield of hydrogen fluoride.




     Acid-grade fluorspar is a finely ground flotation product having the




following typical specifications:




Screen analysis:  325 mesh.  1% on 100 mesh, 12% on 200 mesh, 30% on 250




niesh, 45% through



                    Car2           minimum 97.5-98%




                    Si02           maximum 1.0%




                    S              maximum 0.05%




                    H20            maximum 0.1%




                    CaC03          principal remainder





Silica is a highly objectionable  contaminant,  since each pound consumes 2.6 Ib.




of fluorspar and 3.3 Ib. of sulfuric acid by the reaction:




          Si02 + 2 CaF2 +  2 H2S01+ -  SiF^ +  2 CaSOi+ +  2 H20




When hydrogen fluoride containing SiF^ is absorbed in water,  a further loss




of fluorine values occurs  by the  reaction:




                     SiFt, -f 2 HF  (aq) -* H2SiF6(aq)




Carbonates are harmful in  consuming  sulfuric acid, in producing  foaming  in




the  generator, and in  contributing  carbon dioxide  to  the  gas  stream where




it acts  as a noncondensible  dilutent to  the hydrogen  fluoride.   Sulfur-bearing




minerals in fluorspar  (e.g.,  galena, pyrites)  may generate hydrogen sulfide




or sulfur dioxide, contaminating the hydrogen  fluoride,  and sometimes




causing  deposits of  sulfur in  the gas-handling equipment.
                                      -21-

-------
Table  5-3  gives  an  extensive  list of fluoride  reactions  many of  which  can take

place  in HF manufacturing.
                                              TABLE  5-3"


                                         Reactions of  Fluorides
                               Formation of Silicon Tetrariuoride In An Acid Medium
I.
2.
3.
4.

5.
6.
7.
8.

CaF: 4- HrSO, = CaSO, 4- 2 HF
4 HF 4- SiO: = SiF, 4- 2 H,0
6 HF 4- SiO, - H,5iF« 4- 2 H,0
H,SiF. = Sir. 4- 2 HF
Formation of Silicon Tetrafluoride in Thermal
Processes
Na-SiF. = 2 NaF 4- SiF,
CaF, 4- 1/2 Si03 = CaO 4- 1/2 SiF.
CaF: 4- 3/2 5:0: = CaSiO, 4- 1/2 SiF.
CaF: 4-1/2 CaSiO, = 3/2 CaO 4- 1/2 SiF.
Reactions of Silicon Tetrairluoride With Water
                      3 SiF, •+• 2 H,0 = 2 H,SiF. +  SiO,
                      SiF. (g) 4-  2 H;0 (g)  = SiO,  <»)  4- 4 HF (g)
                                        Formation of Boron Trifluoride
               11.
6 CaF,
          B-0, = 4 BF, 4- 3 Ca, B, 0,
                                 Formation o-f Hydrogen Fluoride By Hydrolysis
               12.
               13.
               H.
               15.
               16.
               17.
CaF, 4- H=0 = CaO 4- 2 HF
2 .NaF 4- H,0  = Na=0 4- 2 HF
2/3 A1F, 4- H,0 = 1/3 Al.O. 4- 2 HF
CaF, 4- H;0 4- SiO, = CaSiO, 4- 2 HF
CaF, 4- H;0 4- Al.O, =  Ca (A10,)s 4- 2 HF
.\a>AlF. 4- 2 H;0 = Na A10, 4- 2 .NaF 4-4 HF
                                     Formation of Volatile Metal Fluorides
               18.
               19.
               20.
CaFr 4- Na.-SiO, = CaSiO, 4- 2 NaF
CaF, 4- K;SiO. = CaSiO, 4- 2 KF
CaF, 4- Na, CO, 4 SiO.. = CaSiO, 4- CO, 4- 2 NaF
CaF, 4- 4/3 A1;O, =  Ca(A10j, 4- 2/3 AlF,
                                                   -22-

-------
      The ratio of ^SO^ to CaF2 is seldom stoichiometric, since, depending upon




.the relative cost of the two, one is used in slight excess.  Recent practice has




 been to use excess acid.  Almost all plants use externally heated horizontal




 kilns with spar fed continuously at the forward end by a screw conveyor.  Acid is




 also added at the forward end of the kiln, and anhydrite is removed through an




 air lock at the opposite end.  The anhydrite is then either slurred and transferred




 to system pond or recovered in the solid form.  The gases emanating from the kiln




 are removed at the front end of the kiln.  The gases consisting of HF, H20, SC>2,




 SiFi,, S02» H2S01+ and particulate are'first, treated in a precondenser or scrubber.




 The purpose of the precondenser is to remove particulate, water and sulfuric acid




 and to cool down the gas stream.  The HF vapors are subsequently condensed in two




 refrigerant-chilled shell and tube condensers.  The crude condensed HF represents




 almost 98% of production.  It flows to intermediate storage tanks and is later




 distilled.  The uncondensed gases from condensers enter a fresh l^SOi^ absorption




 tower.  The gas stream leaving the acid absorber contains most of the SiF4 and




 enters two water scrubbers where fluosilicic acid is recovered.  The gases are




 then vented into the atmosphere or are introduced into a caustic scrubber.  The




 driving force for gas movement through the absorption train is provided by an




 ejector.




      The  total pressure drop across the HF absorption train is 15-20 inches W.G.




 The kiln  is kept under negative pressure  of 1/2 in W. G.




      The  crude HF obtained from the two condensers is distilled in  two  distillation




 columns to a purity of  99.98% making it the purest chemical in regular  commercial




 distribution.
                                        -23-

-------
HF, S02. SiF4, C02
SiF«. S02, C02. HF
    j. S02



Oleum

Sulfuric ac



r

,
Ui

Makeup
id i


Pfeconoense
+
J






c?
in
04
X.
8*
u?
0*
O
x~
u.

Kiln
L
u
c
d>
§
K
-M




1





s
c
u
TO

-------
5.3  Major Variations of Hydrofluoric Acid Manufacturing Processes




     Since it is not possible to present a specific HF manufacturing process




schematic and description for each individual plant, four major process variations




will be described.  Only open literature information was used to describe these




variations.  Three plants were visited in the course of this screening study:




Allied Chemical plants in Baton Rouge and Geismar, Lousiana and DuPont plant in




La Porte, Texas.  Reports of trips to these plants contain some confidential




information and are not present in this report.  The visit reports are a part of




the EPA's confidential files.








     a.  Buss Process"




     Figure 5-2 shows the process flow sheet for HF manufacturing using Buss




technology.  Since the process is almost identical to a typical HF process described




in paragraph 5.2, only specifics of  the process will be discussed.




     One of the special features of  this process is the use of a premixer called




Ko-Kneader developed by the  Buss Co. of Basle, Switzerland.
                                          -25-

-------
Figure 5-2 Process Flowsheet for the Manufacture of Hydrofluoric Acid3
           Using Buss Technology
1.   Premixer (Ko-kneader)
2.   Rotary kiln
3.   Precondenser
4.   Primary scrubber
5.   1st condenser
6.   2nd condenser
7.   Storage tank
8.   Absorption tower
 9.   1st weak acid scrubber
10.   2nd weak acid scrubber
11.   Storage tank
12.   Exhaust fan
13.   Rectifying column
14.   Distillation column
15.   Storage tank
                                     -26-

-------
The incorporation of the Ko-Kneader provides a series of important advantages over




conventional HF processes, namely:




     1.    3y zo.iducting the first, most corrosive portion of the reaction




          in a relatively  small piece  of equipment  (about  6-ft.  long  by




          1 ft.  in diameter as compared with the 55 by 8 ft. reaction




          kiln),  the initial investment and replacement cost of corrosion-




          resistant-alloy parts is kept low and the parts are physically




          easy to replace.




     2.    The thorough mixing of sulfuric acid and spar accelerates the




          subsequent reaction in the kiln, increasing plant capacity as




          .much as 30% for a given kiln size.




     3.    A much smaller excess (or even stoichiometric amounts) of




          sulfuric acid can be used, 'since separation of the two components




          is no longer possible after  leaving the Ko-kneader and a local




          shortage of sulfuric acid is avoided.  This results in better




          quality HF and in an anhydrite quality suitable  for further




          processing.




     4.    Due to the perfectly homogeneous mixture of sulfuric acid and




          spar substantially lower temperature can be employed in the




          kiln, whereby:  (a) the  sulfuric acid has a lower vapor pressure




          and contaminates the HF stream to a lesser extent and  (b) the




          kiln is subjected to much less chemical attack.




     The  other specific  feature of the Buss process  is  that it  results  in  a by-




product anhydrite and  not  in  the  gypsum pond  slurry  used  in most other  processes.




Figure 5-3  shows an anhydrate  recovery flowsheet.3
                                     -27-

-------
w
ACCELERATOR
'DRITE-
?OM K1LN~
LIME
r 1
j
L
' r
L

_^ MILL ID—* CU
OVERSIZE

^SSIFIER
T r
                                      SILO
                       ANHYDRITE TO
                          BAGGING
Figure 5-3 Anhydrite Recovery Flowsheet3
               -28-

-------
     The anhydrite leaves the kiln through a seal screw.  It contains a




small amount of unreacted sulfuric acid which is neutralized with lime.




An accelerator is added and anhydrite is ground to the standard commercial




fineness.  The anhydrite can be marketed as a high strength building material




or a soil conditioner.




     Three plants are believed to use the Buss process.
                                     -29-

-------
b.   Typical Process7




     Figure 5-4 shows a schematic of an Exemplary Process used by EPA in the




     study for effluent limitation guidelines and New Source Performance




     Standards.  It is believed that four or five plants use this process.




     The flow diagram is similar to that for the Buss Process, major differences




     being that no premixer is used and that anhydrite is slurried and  transported




     to the gypsum pond.  Another difference is that fluosilicic acid is not




     recovered in this process so lower SiC>2 content can be tolerated in




     spar.  It might also result in SiF^ emissions.  All HF is recovered as




     anhydrous in both the Exemplary and Buss Process.  The tail gas emission




     volume from this process is considerably lower  than that from the  Buss




     Process.




c.   Aluminum Fluoride Manufacturing Process




     Aluminum fluoride is one of the major  products  in which HF  is used as a




     raw material.  In a typical A1F3  process gaseous HF emanating from the




     kiln is contacted directly with hydrated aluminum  in a fluidized bed




     reactor.  Some plants use all HF  together with  impurities for A1F3




     production, while other  isolate a portion of  gaseous HF as  anhydrous




     using an absorption train similar to  that used  in  a  typical process.




     In the case when all HF  is used in gaseous  form for A1F3 production,  it




     is questionable  if  it can be  considered  an  HF manufacturing plant.  In




     such case only  two  steps used  in  a typical  HF manufacturing plant,




     namely spar drying  and  its reaction with H2S01+  in  the  kiln, are utilized.




     It is believed  that at  least  three plants utlize this  process.
                                   -30-

-------
d.   Patented Process




     In the patented process fluorspar is reacted with a mixture of sulfuric




     acid, sulfur trioxide, and water vapor at a temperature low enough




     to allow liquid 11230!+ to condense on and to react with CaF2 but high




     enough so that CaF2 particles do not become sticky.  The temperature




     of reaction can be closely controlled and the resulting anhydrite can




     be readily withdrawn from the reactor.  The heat for reaction  (between




     spar and I^SO^) is provided through reaction of steam and 863.  An




     additional benefit of this process is that the use of heat transfer




     surfaces and attendant problems! has been eliminated.
                                  -31-

-------
I
U)
NJ
FLUORSPAR
                             GAS FUEL
                             AND AIR
         THREE

       ,""7"
        PARALLEL
         RESIDUE
         CaSQ4 TO
       TRENCH AND
         RECYCLE
                                                FIGURE  5-4

                          EPA EXEMPLARY HYDROFLUORIC ACID PROCESS  FLOW DIAGRAM
                                                                                                      CONDENSER
                                                                                         DISTILLATION
                                                                                           COLUMN
                                                                                              TO PURE
                                                                                              PRODUCT
                                                                                                                    COOLING
                                                                                                                     -o.
                                                                                                                    SEWER

-------
5.4  Recovery of Fluoride Value From Phosphate Rock

     Most phosphate rock used in the manufacture of phosphate fertilizer con-

tains 3-5% fluorine in the form of the mineral fluorapatite  (Ca3 (POI+) sF) .  When

this rock is treated by either acid or thermal processes, fluorine is released

as SiFu.  Many studies to produce HF from this source have been made9 but  two

hurdles exist:


     1.   SiFi+ cannot be conveniently converted into HF.

     2.   Collection of SiF^ for an economic capacity is  expensive.   A proposed
          process10 starts by reacting silicon tetrafluoride with recycled
          ammonium fluoride solution to  form ammonium flousilicate.

                    SiFt, + ZNH^F -»•  (NHt+)2SiF6

     When this solution is neutralized with ammonia, silica precipitates and

more ammonium fluoride is formed.

               (NHtt)2SiFs + 2 H20 + 4 NH3 •->• Si02 + 6 NH^F

     The ammonium fluoride solution  (except that recycled) is evaporated to a

salt concentration of 94-95%, when some  conversion to ammonium bifluoride,

NH1+HF2, takes place by vaporization of ammonia.  The evaporation continues until

a salt concentration of 98% is reached,  when  the mixture  solidifies  at about

100°C.  The solid mixture of ammonium fluoride and bifluoride, containing  60%  of

fluorine, is decomposed with 93-95% sulfuric  acid  at 180-190°C.  Ammonium  bisul-

fate is the principal component  of  the residue;  this can  be  converted to ammonium

sulfate by neutralizing with ammonia.

     The economics cf this process  depend  on  a low-cost supply of  silicon  tetra-

fluoride, a premium market for precipitated silica (proposed,  for  example, as

reinforcing pigment for rubber),  and a local  market  for ammonium sulfate.   The

process is handicapped by a  large filtration  and evaporation load.
                                       -33-

-------
     The alternative way to recover the fluoride value from phosphate  rock  is  to




use waste fluosilicic acid.  H2SiF,5 is formed in the phosphate fertilizer




plants' scrubber towers in which SiF^ hydrolyzes:




          3 SiF^ + 2 H20 -> Si02 + 2 H2 SiF5




     Two procedures to recover HF from H2 SiFg can be used.11 The first




procedure is direct hydrolysis of H2 SiF$ according to the following reactions:




          H2 SiF5 + 2 H20 ->• SiOp + 6 HF




     The reaction is carried out when H2 SiFg is volatilized in a flash




vaporizer and the vapors are passed through a quartz tube externally heated




to 1000°C.  A water cooled copper condenser is used to recover HF.




     The results of a laboratory study showed that direct hydrolysis at




elevated temperatures  was subject to many mechanical difficulties, and




that corrosion of construction materials was a serious problem.   Elimination




of Si02 from the HF product was generally poor.




     The  second  procedure,  showing more  promise,  is  hydrolysis  of lime -




neutralized H2 SiF5.  Neutralization proceeds in two  steps:




          H2 SiF6 + Ca  (OH)2 * Ca SiF6 + 2 H20




          Ca SiF6 -t- 2 Ca  (OH)2 - 3 CaF2  +  Si02 + 2 H20




     More Si02 is needed  to  satisfy  the  following  reaction:




          CaF2 + Si02 4- H20 -* Ca Si03 +  2  HF




     The  apparatus used for  hydrolysis of  lime - neutralized  H2  SiFs  is




shown  in  Figure  5-5.il




     To operate  the system,  a charge  of  2  1/2  to  3 kilograms  of  pellets




is placed  in  the reactor  tube,  forming a bed  about 16 to 20  inches  deep




in  the zone of maximum heat.  The  reactor  and  flash  vaporizer are brought




up  ro  temperature;  the vaporizer  is  heated to  450°C  and  the  reactor heated,
                                     -34-

-------
                                    Condenser
                                   Cooling
                                   water


                                    Product
                                    receiver
                          Cooling  water
             0000
            Plenum
            heater
FIGURE 5-5 - Vertical Hydrolysis  System

-------
for aost of the tests,  to 1,000°C, measured at the outside surface of the reactor

tube.  When operating temperatures are attained, the flow of water was started to

the vaporizer at the desired rate.  This causes a temporary drop in the vaporizer

temperature, but recovery is usually complete within 15 minutes.  The condensed

HP product is collected in a polyethylene container.  Samples are taken periodically

and analyzed for fluorine and SiC>2 content.  The test is usually terminated when

80 to 90 percent of the available fluorine lias been removed from the reactor

charge and the solution becomes increasingly dilute.

     Reaction characteristics of steam-hydrolysis of lime-neutralized H£ SiFg are

as follows:


     1.   Addition of 70 to 100 percent of the calculated Si02  requirement has
          little effect on hydrolysis rate or HF concentration.

     2.   The HF concentration increases with increasing reaction temperature
          over the investigated range 950° to 1,100°C.

     3.   The HF concentration increases with decreasing water  feed rate.

     4.   The Si02 content of the condensed HF product  does not exceed 1.8 per-
          cent of the fluoride content, and is usually  much lower.


     The conclusion of  the survey of processes  for  HF  production  from phosphate

rock is that they are still in the  early stages  of  development.  It will probably

take decades before such processes  can  be  developed into  a  full scale production.

HF manufacturing e from spar will probably remain  the  most  economical process

for  years  to come.
                                        -36-

-------
5.5  References
      1.  Hydrofluoric Acid, Kirk-Othmer Encyclopedia of Chemical Technology 2nd
          Ed. p:610-625, 1964.

      2,  Simons J.H., Fluorine Chemistry Volume 1, p. 230, Academic Press
          Inc., Publishers, New York, N.Y. 1950.

      3,  R.ogers, W.R., Muller, K., Hydrofluoric Acid Manufacture Chem. Eng.
          Prog. Volume 59, No. 5, p. 85, May 1963.

      4.,  Semrau, K.T., Emission of Fluorides From Industrial Process  - A
          Review.  JAPCA, Volume 7, No. 2, August 1957, p. 92-108.

      5.,  Faith, W.L. etal., Industrial Chemicals, Third Edition, John Wiley &
          Sons, Inc., 1965, p. 428.

      6.  Helier A.N., etal.,  Inorganic Chemical Industry, (In: Air Pollution,
          Volume 111, 2nd Ed., Stern A.C./ed.), New York, Academic Press, Inc.,
          1968, p. 197-198.

      7.  Development Document for Effluent Limitations Guidelines & New Source
          Performance Standards for the Major Inorganic Products  Segment of
          Inorganic Chemical Manufacturing Point Source, EPA Report No. 440/1-74-
          007a; NTIS PB-238 611.

      8.  U.S. Patent No. 3,  102,  787, Preparation of Hydrogen Fluoride.

      9.  Tarbutton, W.R.,  etal.,  Ind. Eng. Chem. 50, 1525-1528  (1958).

     10.  Boguslavskiy,  S.N.,  etal, Khim  Prom,  1961  (7), 6-8.

     11.  Good, P.C., Tress,  J.E., Recovery of  Hydrofluoric Acid  for Waste
          Fluosilicic Acid, Bureau of  Mines Report  of  Inv. 7213,  1968, 14  p.
                                          -37-

-------
6.0  EMISSION SOURCES AND RATES IN HF PRODUCTION AND MANUFACTURING

6.1  Sources and Nature of Point Source and Fugitive Emissions

     There are very few sources of air emissions in a HF manufacturing plant.

The major sources and pollutants can be divided into three categories:


     1.   Spar drying and handling

          Spar is received by barges and tank cars and is unloaded into stor-
          age areas or silos.  In addition to the main storage silo(s), most
          plants have a separate spar use silo which normally contains one
          day's supply.  Spar unloading results in fugitive emissions which can
          be substantial under windy conditions.  If spar is stored outdoors
          in a stack, this is a potential source of fugitive emissions.

          The main emission of spar occurs during the spar drying.  The gas
          volumetric flow rate from the dryer is in the order of 2,000-13,000
          ACFM.  The emission consists of spar as a fine particulate and com-
          bustion gases since the rotary kiln dryers are most frequently inter-
          nally fired.  Both natural gas and No. 2 fuel oil are used for firing
          so that SOo, NO , and CO can be present in the emission stream.  The
          emissions from the dryer are controlled with bag filters; only one
          plant uses a high energy Venturi scrubber.  Dry spar is stored in
          silo(s) which are, as a rule, also controlled with a bag filter,
          frequently the same one used for control of the dryer.

     2.   HF manufacturing

          Almost all HF-producing facilities have only one point source from
          HF manufacturing  (consisting of kiln and absorption train).  Since
          the potential pollutant HF is the desired product, it is in  the best
          interest of the plant to recover all HF.  Consequently, HF gas is
          precooled, removed in refrigerant cooler, treated with sulfuric acid,
          and finally scrubbed with water.  The emissions in the tail  gas (after
          the final scrubber) contain small quantities of HF, SiF^, and S02.
          The amounts of these compounds depends on the process and its varia-
          tion.

          a.   Buss Process

               In this process, a caustic scrubber is usually employed as a
               final control step.  Since fluosilicic acid is recovered in
               this process, most of  the SiFu is removed before entering the
               final scrubber.  Caustic should  have 99% efficiency in  remov-
               ing HF.
                                       -38-

-------
          b.    EPA  Exemplary  Process

               The  process  described  as  the EPA Exemplary Process  uses  different
               scrubbing  media  in a final scrubber.   Depending on  whether  the
               scrubber liquid  is acidic gypsum pond  water,  plain  water or
               caustic solution,  the  efficiency can vary from 70%  to  99%.   Since
               fluosilicic  acid is not,  as a rule, recovered in this  process,
               SiFu may be  a  major pollutant.   The emissions might be parti-
               cularly high when acid scrubbing is used and  when spar contains
               high percentages of SiC>2  (over 0.5%)   The tail gas  volumetric
               flow rate  in this process is smaller  than in  the Buss  Process
               and  runs in  the  order  of  hundreds of ACFM. A typical  tail  gas
               exhaust stack  is shown in Ilgure 6-1.   There  is a possibility
               of HF emissions  from acidic pond water;  this  will be discussed
               under water  pollution  in  Section 6.4.   The emissions from spar
               handling and drying are similar to those trom tne auss Process.

          c.    A1F3 Manufacturing Process

               There is no  tail gas in this process  if all HF is used for  A1F3
               production in  a  fluidized bed reactor.  When  HF isolation is
               used, emissions  are similar to those  from the Exemplary  Process.
               Spar handling  and drying  emissions are similar to those  described
               for  the other  processes.

          d.    Patented Process

               In  this process  the tail  gas is scrubbed with limed water,  so
               low  HF emissions are expected.  SiF^  emissions could be  high
               since fluosilicic acid is not recovered.  S02 content  in the
               tail gas could be high because of S02  evolution in  the reactor.
               Spar handling  and drying  emissions do  not vary from the  other
               processes.


     In addition to tail  gases, reaction kilns are potential sources  of HF

emissions.  Normally the  kiln operates under negative pressure but, under upset

conditions caused  by a  plugged  absorption train or incorrect spar-^SO^ ratio,

it can emit HF.  Many plants have an emergency scrubber or a bypass to  the final

scrubber which is  operated under upset conditions.


     3.   HF Handling and Other Fugitive Sources

          Almost all HF isolated in manufacturing is in  the anhydrous  form.  If
          70% is Che desired product, it is obtained by mixing anhydrous HF with
          water.  The HF  emissions from  this source are  frequently controlled by
          a wet scrubber  using pure water as a scrubbing  liquid.
                                      -39-

-------
          Anhydrous and aqueous HF is stored in the storage vessels and trans-
          ferred to tank cars or trucks for transportation.  If not properly
          controlled,  the loading process is a possible source of fugitive
          emissions.  At least one plant was found where this was a major source
          of intermittent HF emissions causing complaints from the neighbors.

          Leaks throughout the HF plant can be another source of fugitive
          emissions caused by the corrosive nature of HF.  HF plants have an
          unusually high ratio of maintenance to operating personnel and good
          maintenance  was pointed out as a key to successful HF manufacturing.

          A significant unknown in HF plant ?ir emissions is the gypsum pond.
          In cases when pond liquid is acidic, it could be a source of fugitive
          HF and SiF^  emissions.
6.2  Controlled and Uncontrolled Emission Sates

     As a first step in the determination of emission rates from HF manufactur-

ing, TRC obtained printouts for all eleven HF manufacturing facilities in the

National Emission Data System (NEDS) and the Compliance Data System (CDS).   Both

computerized data bases were of little help in this project.  NEDS contains

little quantitative data most of which is out of date and unreliable.  Most

quantitative information is listed as confidential and cannot be presented in

this report.  CDS contained no quantitative information.

     Figure 6-2  shows a schematic of HF manufacturing indicating major emission

streams and emission rates.  This process model assumes that the only HF fluoride

emission stream is tail gas.  No spar emissions from the dryers have been esti-

mated in this model but another study5 indicates that maximum emissions after

control would not exceed 20 Ib/ton.  The emission factor ranking shown in

Table 6-1 is relatively low indicating that these factors must be considered

Questionable.
                                       -40-

-------
te&JSSJF'&r^&l-'-'-i.'*' '—.""' •'•-  •"- '• : ••--. '...•-.
                                       :

                                                   •••-;^v%^"\>j-i^>--^r ••'•
                                                  _-• -\:i,^.:-,x.v?i-Si.-:..^...".-...7>. -.
          Figure 6-1:   Typical  Tail Gas  Exhausc Stac
                                        -41-

-------
                    SIHMIKK'
                    ACIU(»4X.V

AHIIMI i »0%  AIIIIYDIOtii IIF,
Jj'j. tACH Of 50% ANli »0»,i llf

• hit AUiulHlGll iYSItM IliUAtlY
  COHlAlin / lOV/fIS, 5 Wl'/K ACIU
  AMO V SI«ONl'> ACID AOSOkltKS.
                                                        II,M>4 HtlYLH
                                                                IJO'f
  COMVmlK)fMI KtlllE-IYrt
  lit ill! II OClllAIlNG AI
              J40-I-.
 •  lYfll'AI fA«llClf SIU;
   iv on i oo /.if si i
  u* on iooMisii
  30% ON 2iOMfSM
  4}% IIKU iiSMlSII
                  ACID C-IAlt
                  riuoiscAf
                                     " 1 30 10 tO
                                       J MIN AI 400-1
                                    '"" in mm
                   iiiisi m AIM.  UIHING             CAICUIM
                   MOVtMtMl OfrOWDCHtO           SUlfAIE
                                                  IfSILllIt
IIYDIIOflUOIdC
AClu  (liO'X.1
                                                                               OA'.li  - 2!i 10N1/DAI llf CHOUUtllON  (AiiUKS WI AJIIKUWIUS IIF. Zil tACII Of Ult Mill UOl HI)

                                                                                                  -LUS/IIH


III
sit,
lot.) lluorld.!
luUI .> 1
C.CO
j
Slllj
Ii^io4 (itJ)
t^o4
^
'\'"
liix-l
A(>|iio«. lot*!
UPC--.
~^~ -•--•-" - ' * ---' •- L n *•
1
4KW(i»|l)
4100
tiaa
40(A)
40<*>


.(AI
'

4i'uO

:





b400




i.400

3
„,>,""
20
III







211

,,„,„„,
4








I,
7»Ut Kill
.-

i""
w
40
M

M

7100



;luo

»
41-1 (II
blO
*M _




111)


640

/
SID |l|
bill
41X1




'.,111


101 III

8







4UII


4UO

K
/.. (,>""
» (,)""
1.0
10



•M9>
J(ij)


un


lu
hilo(t)
lulu
VIII







linn

                                                                           •Cjseoui effluent itream

                                                                           (A)  Impurities in the fluorspar feeJ.

                                                                           (B)  Ihtf calcium sulfdte residue itreara uny liberate  fluorides.   Literature
                                                                                search revealed nu data.

                                                                           (C)  References 2,  3

                                                                           (0)  Reference 4

                                                                           Soluble fluoride evolution  fatlor. •= 52 Ib r/lon llf

                                                                           (s)  Solid

                                                                           (g)  Caseous
                                         Figure  6-2:    Uydrof luorit:  Acid  Production  -  Uucont roJ 1 tul Process Model1

-------
                          TABLE 6-1




       EMISSION FACTOR RANKING FOR HYDROFLUORIC ACID1*
Emission Data   Process Data   Engineering Analysis   Total




   0-20            0-10               0-10




    35                  3                11
                             -43-

-------
     The soluble fluoride emission evaluation factor is 52 Ib F/ton HF.  It




must be mentioned here that there are problems in evaluating fluoride emissions




by available sampling methods.  If Method 13 is used as a means of determining




fluoride emissions, both gaseous and solid fluorides would be measured.  It




appears that any evaluation of fluoride emissions should also include the spar




stream.




     Figure 6-3 shows the controlled process model in which the tail gas is




scrubbed.  The soluble fluoride emission is estimated to be 4.1 Ib F/ton HF.




     Fugitive emissions have not been estimated but indications are they might




be high.  The State of Louisiana regulatory agency Emission Inventory Question-




naire shows that fluoride fugitive emissions are of the same order of magnitude




as controlled ones.  One indication of fugitive emissions is ambient fluoride




concentration.  The Texas Air Control Board sampled HF property line ground




levels at one location and discovered that plant downwind HF concentration is




2-10 ppb higher than upwind.








6.3  Annual Emission Rates and Plant Inventories




     Table 6-2 shows the annual estimated soluble fluoride emissions from HF




production.  The basis for calculations  is available emission factors and an




expected annual growth rate of 6%.  This projected growth rate is undoubtedly




much too high since the production capacity for 1977 is about the same as it




was in 1970.  The  projected production for the year 1982 obtained from industry




shows  that no growth is expected.




     Table 6-3 shows the emission inventory for HF manufacturing plants.  An




attempt was made to develop emission factors based on a plant's emission inven-




tory but data are  too scarce, variable,  and are too unreliable to draw valuable




conclusions.

-------
                         WATER-
                            ISO'F
                                                 -TO STACK
                                              SPRAY SC3UB3ER
                                              EFr.  * 90% GASEOUS
                             TO NEUTRALISATION
                               AND DISPOSAL
                                      BASIS - 25 TONS/DAY HF  PROCl'CTION
                     (ASSUMES 1/2 ANHYDROUS HP. 1/4 30? HF AND  1/4 301 HF PRODUCED)

                                          PROCESS STREAMS - U3/HR
Mate rid Is
HF
Sir",
Total rluoric!es
Total as F
coz
H2a
Accra*. Total
Strgira
Stream Muroer
9
2S(g)
34(g)
SO
SO
16(g)
3(9)
ao
n
Z«(9)
JHg)
55
46
z.s un(A)
60!A)
12«
2(3) (Est.)
3(g) (cst.)
S
4
'S(g)
Q.S(g)
20
'Gaseous effluent Stream

(A)  Plus scrjbbing water.

(3)  Ajjunes 100; usage of scrubbers an all  facilities.
Source
Scruoaer
Assuned Fugitive
*_
Total Emission
Saluole Fluoride Emission
Factor - lb F/ton HF
4.5
0.0
4.1
1
Overait soluole
                    se amssion . 4.]  :b F/ton  HF
(3)
  Figure  6-3:    HF  Production -  Controlled Process  Model1

-------
                                   TABLE 6-2

                SOLUBLE FLUORIDE EMISSIONS FROM HF PRODUCTION1
                     (Based upon a 6% annual growth factor)
HF Production
(105 tons/year)

Soluble Fluoride
Evolution Factor
(Ib F/ton HF)

Soluble Fluoride
Emission Faccor
with Current Practice
(Ib F/ton HF)

Soluble Fluoride
Emission Factor with
99% Control
(Ib F/ton HF)

Soluble Fluoride
Evolution
(103 tons F/year)

Soluble Fluoride
Emission with
Current Practice
(103 ton F/year)

Soluble Fluoride
Emission with
99% Control
102 ton F/year)
1970


0.34


 52



4.1
8.84
0.70
2000


2.60


 52



4.1
                    0.52
67.6
5.33
                    0.68
                                      -46-

-------
                                               TABLE G-J




                         EMISSION INVENTORY  FOR  IIP MANUFACTURING IM-ANTS
  I11.ml
Allle.l
Alcoa






Sl.lllf fOIO
N.I

Clcvolnnil
Oil
i;,i|i.i< lly
1975 O.itL-
Tlinilti.iml Toil!)
15

12

'.5



2(1



100


55

18

50








25

II


IB

Km lea Ion Source
:i|i.if ill yi>r
in II K.MI
Ijp.ll Illl III. Ill
Soil.i auli iiiilunil
Sp;ir H! In
Til II P..1H

S|>ar inn* ullo
j|i«r Uryor
S|>.it si In
Tall ii''s

Spur nllo
T.I 11 I'.'IH

Spur diyi;i
S|>.il alia
-

Spiir lonillnK
Sp;ir fugitive
111 own r fugitive
4 gencr.itorti
fugitive
S|>ar Jiyoi


Spiit allu
Sp.ii unlo.iil Ing

Spur ilrycr
Hall mill
UK kiln
S|i»r ilryor
T.il 1 (',,iu
('out ml
N.'iftlioii'ic
Wi-t in rnl>lier
Hll|*llOII!IO
Wui uciulil>or
ll.lgllOIISO
Sriul>liil">llnlioii.'ie
Wot lii-ruliber

Hni'.liniiNe
Si:rublior

Bngli(iii!ie
BlIgllDIISl'
-






n.'ii'jiouHK


n.iglintiso
-

Bnghii'ini'
Haglioiuif
-
Oni'liiiiific
Srnililii-r
ACIH
5,000

160
-
l.fiOO
170

l.f.OO
fl.900
85
750

-


J.787
1.8)6
-






11,220


1 . 260
-

9,OOO
-
-
J , OOO
'../ SO
Finjfluloii
Kiilc
Ili/lir
It
-
o.ot
120
21
0.6
0.8
21
6.5
0.1
0.8
1.8
!5
6.9
0.1


-

2.8
7.5
2.6
3.6

5.J
0.8

o.a
-

0.8
0.5
0.5
10

Pollutant
S|uir

S|i.n
Soila ash
Spur
S(»2
UK
Spur
Spnr
Spin
SIKS
SO;
Sj-.ijr
soa
F


-

Spnr
S|inr
IIF
F

Spur
NO

Spar
-

S|>nr
S|inr
UK
Spur
F
Kfl Irli-ncy
Z
')')
9')
99. ')
4(,
«)9

96-99
%-99
9'>
99
~

99




-






99


99
-

99
99

9'».5
95

-------
     In conclusion, an emission of 20 Ib/ton of spar is realistic and in line




with findings during plant visits and contacts with the industry.  An emission




of 4 Ib/ton of soluble fluorides also appears to be realistic.









6.4  Gypsum Pond Emissions




     Most HF manufacturers slurry anhydrite and transfer it to gypsum ponds.  The




gypsum ponds have been investigated in the phosphate fertilizer industry and




were found to be a significant source of fluoride emissions and a source of radio-




active isotopes which can be leached into aquifers.  Figure 6-4 shows the waste-




water recycling used in an EPA Exemplary Plant6 where all process and scrubber




wastewaters are recycled.  The waters used to slurry and remove anhydrite and




scrubber water are fed to a pond system after being treated with caustic or soda




ash and lime to precipitate fluorides and adjust the pH.  In  the pond system,




the insolubles are settled out and waters are then reused.




     Table 6-4 shows waste products from HF manufacturing at  the Exemplary Plant.




Only cooling water is discharged from this facility.  Neutralization of sulfuric




and hydrofluoric acid wastes with lime, followed by removal of precipitated




CaSO(+ and CaF2 in  settling ponds, reduces fluorides to  18 mg/1 and calcium sul-




fate to approximately 2,000 mg/1 in treated water streams.  Lime treatment of




the isolated wastes and settling pond removal of precipitate  reduces the fluor-




ine content of this small stream to approximately 10 mg/1.  No fluoride emission




is  expected from the gypsum ponds which are neutralized to pH 6-7.  However,




contacts with HF manufacturing plants indicates  that some ponds  have a pH of




1.  In  that case,  HF and  SiF^  emission  is  possible.  Measurement of  fluoride




emission rate is recommended.
                                       -48-

-------
SETTLING
  POND
   A
            SETTLING
             POND
               A
CLEAR
WATER
 POND
RECYCLE
 WATER
 PUMP
                                   ^NEUTRALIZED  RESIDUE SLURRY
                                                                   FURNACE
                                                                   FURNACE
                                  FURNACE
                                                                             UIX-
                                                                             D*
NEUTRALIZING
     PIT
                    Figure 6-4:  Effluent Recycle System at  an Exemplary  Plant6

-------
                   TABLE 6-4

  WASTE  PRODUCTS  FROM HF MANUFACTURING PLANTS6
(Based on Estimates for the  EPA  Exemplary Plant)
Waste Product
Product
Process Source
                              Avg. kg/kkg  (Ib/ton)
2.
3.
4.
5.
6.
7.
8.
CaSO;
CaF2
HF
H2SiF5
Si02
S02
HF '
      Kiln (reactor)
      Kiln (reactor)
      Kiln (reactor)
      Kiln (reactor)
      Scrubber
      Kiln (reactor)
      Scrubber
      Scrubber
                             3,620  (7,240)
                               110  (220)
                                63  (126)
                               1.5  (3)
                              12.5  (25)
                              12.5  (25)
                                  5  (10)
                                  1  (2)
               Total Quantity
     Type

Cooling
  (river water)

Slurry and
  Scrubber
                    cu in/day  (gpd)
                    3,270  (864,000)
                    3,270  (864,000)
                     l/kk%(gal/ton)
                    90,140  (21,600)
                    90,140  (21,600)
                                                   Recycled
                                                    0 percent
                                                  100 percent
                       -50-

-------
6.5  References

     1.   Robinson, J.M., et al., Engineering and Cost Effectiveness Study of
          Fluoride Emissions Control, p. 3-297, Vol. 1.  February 1972, NTIS
          No. PB 207 506.

     2.   Kirk-Othmer, Encyclopedia of Chemical Technology, Interscient Pub-
          lishers, New York 1965, Vol. 9.

     3.   Gaith, W.L., Industrial Chemicals, J. Wiley and Sons, Inc., 3rd Ed.,
          1965.

     4.   TRW Systems Group, Air Pollutant Emission Factors, Dept. of HEW,
          Contract No. 22-69-119, NTIS No. PB 206-924, April 1970.

     5.   Rogers, W.R., Muller, K., Hydrofluoric Acid Manufacture, Chemical
          Engineering Program 59:85-88, May 1963.

     6.   Martin, E.E., Development Document for Effluent Limitations Guide-
          lines and New Source Performance Standards for the Major Inorganic
          Products Segment of the Inorganic Chemicals Manufacturing Point
          Source, EPA Report 440/l-74-007a, NTIS No. PB 238-611.
                                       -51-

-------
7.0  CONTROL OF EMISSIONS FROM HF MANUFACTURE

     Emissions from HF manufacture can be divided into three categories:


     1.   Particulate emissions from spar 'handling and drying

     2.   Gaseous emissions from the HF absorption train (tail gas)

     3.   Fugitive emissions from process, HF loading, and gypsum pond.
7.1  Particulate Emission Control

     The largest source of particulate emission in HF manufacture is the spar

dryer.  The secondary sources of spar are storage silos and transport of solid

materials.  These emissions can be controlled with wet or dry gas cleaning

devices.  Table 7-1 shows the advantages and disadvantages of both methods as

applied to a broad range of particulate matter.

     Out of 9 plants, 8 are using the dry method applying cyclones and bag-

houses.  A typical baghouse used in a HF manufacturing plant is shown in Fig-

gure 7-1.

     Figure 7-2 shows a typical baghouse with pulsed air cleaning frequently

used in spar emission control.

     In selecting the baghouse for spar control, the major parameter is air to

cloth  ratio.

     Figure 7-3 shows a kiln venturi scrubber system similar to one that can be

used on a spar dryer.  In the selection of  the wet  scrubber for particulate

control, one should consider the following  factors1*:


     1.   Particulate characteristics:  physico-chemical properties

     2.   Carrier gas characteristics:  temperature, pressure, humidity, etc.

     3.   Process factors:  gas  flow rate,  particulate  concentration, pressure
          drop, etc.

     4.   Operational factors:   floor space, materials  of construction.
                                       -52-

-------
TABLE 7-1

ADVANTAGES & DISADVANTAGES OF WET  &  DRY  AIR  & GAS CLEANING DEVICES1


ADVANTAGES:
                DRY

      1.  Recover product dry

      2.  Freedom from corrosion

      3.  Less storage capacity
          required for waste

      4.  Insoluble materials > 0.05 ym
          may be collected with high
          efficiency

      5.  Recirculation of treated gas
          may be possible if the gas
          is resoirable.
            WET

1.  Gases & particles col-
    lected together

2.  Soluble materials may
    be readily collected

3.  High temperature gases
    cooled

4.  Corrosive gases and mists
    may be neutralized

5.  Eliminate fire or explo-
    sion hazard.
DISADVANTAGES:
                DRY


      1.  Hygroscopic materials may
          cake

      2.  Dust exposure to mainten-
          ance personnel

      3.  High temperature; costly
          construction

      4.  Not tolerate acids or cor-
          rosive mists

      5.  Secondary dust disposal
          problem
            WET
1.  May require recrystalli-
    zation for soluble parti-
    cles

2.  Easily pumped but may need
    sludge pond

3.  Dissoluble particle recovery
    requires liquid filter

4.  Particles < 1pm not easily
    collected

5.  Freezing problems

6.  Liquid entrainment in efflu-
    ent frequent problem

7.  Cleaned air may not be
    suitable for recirculation,
    high dewpoint causes condi-
    tion.

-------

Figure 7-1:  Baghouse for Control of Spar Emission
                         -54-

-------
                                 rgFIM. DSC^ASGE
Figure 7-2:   Typical Baghousa vita Pulsed  Air Cleaning1

-------
Ch
I
                                                                                CYCLONIC
                                                                                SEPARATOR
FWCSH WATER OR
KILN  COOLING
WATER
                                                                                                          /RECYCLE
                                              7-'3:  Kiln Venturl  Scrubber System3

-------
     Figure 7-4 shows the relationship between collection efficiency and

particle size in Venturi scrubber.

     Only one HF manufacturing plant uses a high energy Venturi scrubber for

spar control.

     The review of control technology for spar emission shows that best control

technology is the use of fabric filters.  The efficiency of fabric filters used in

spar control is about 99%.  A high energy Venturi with a pressure drop of 20-40

in WG would have a comparable efficiency.  The drawback of scrubbers is that they

do not recover spar in usable form and create wastewater problems.



7.2  Gaseous Emission Control

     The major source of gaseous emission from HF manufacture is tail gas from

the absorption train.  The major pollutants are HF, SiF^ and S02.  The best

technique for control of these gaseous pollutants is absorption.

     The absorption of tail gas is usually accomplished in a packed tower

shown in Figure 7-5.  The tail gas is contacted with scrubbing liquid in a

counter current fashion..  To increase the mass transfer the tower is filled

with packing.  The gas on its way from bulk gas to bulk liquid and to final

elimination has to overcome three resistances^:


     1.   Diffusion through gas phase film
     2.   Diffusion through liquid phase film
     3.   Chemical reaction rate.


Any one or a combination of the three resistances can be the rate controlling

step.  Because of the great solubility of HF and SiF^ in water,  the gas film

resistance would be expected to be controlling.
                                       -57-

-------
         0.2  aj a.4 a« a* j
                 ••MTXU sar-
                               3 4 4 •  • O
Figure 7-4:
Relationship  Between Collection
Efficiency and  Particle Size in Venturi  Scrubbers
                      -58-

-------
                                 Discharge
Liquid Inlet

Liquid
Spray Distributor
Gu
Initt
                              Drain
     Figure  7-5:   Typical Packed Tower-
                        -59-

-------
     In such cases  and with packed towers,  it is usually found that5:






     Kg  ^  G0.8




     Where Kga =  mass transfer coefficient, Ib moles/(hr) (cu ft) (atn)




             G =  gas mass flow rate, Ib moles/ (hr) (sq ft)




     Therefore,
     where N_  = number of transfer units




            Z  = tower height, ft






Thus, the number of transfer units obtainable would be controlled by the height




of the tower.  However, the number of transfer units usually increases as the




liquid mass flow rate is increased.




     Table 7-2 shows HF absorption data in various wet scrubbers.6  An import-




ant consideration in pollutant removal is the performance of equipment.  It




is sometimes difficult to compare the performance of two basically different




types of equipment in terms of mass flow rates, height of transfer unit or




mass transfer coefficients.  The performance of equipment has been studied in




terms of the number of transfer units.  The effect of liquid and gas flow rates




is expressed in terms of theoretical power consumed per unit of gas flow rate,




as power consumption as such is usually of more economic concern than liquid or




gas mass flow rate.  Such relations are mainly a matter of convenience and do




not necessarily have a theoretical basis.  Figure 7-6, 7-7 and 7-85 show the




relationship between number of transfer units and power consumption in absorp-




tion of HF, SiF^, and S02.
                                       -60-

-------

Install*-
tion
A




B
C
D
E
r
G








Typ« of Equipment
Cross flow (pray




Cross flow spray
Couoterflow spray
Parallel flow spray
Counlcrflotf spray
Veoturi
Vrotnri







Absorbing
Liquor
Water




Lime water
Water
Lime watar
Water
Water
Water







G, Lb./(Hr.)
(Sq. Ft.)
2,110
1.8BO
2,080
1,830
1,400
2,050
2,000
13,800
2,000
76,000*
-70,000*







L. Lb./(Hr.)

-------
  100 rr
   10
Ul

-------
IUU




V)
t-
1 10
IT
LU
U.
v>
z
<
X.

u.
o
IE
IJ 1
CO '
Z
Z


0 1
— * 1 i t 1 1 1 i
. . . , rr
HYOffOGEN FLUOfflOe
- 9 Vtry* - n.m.lo..«t A
r— 3^ S{Kay* — rt4lnfluti0A 8
_ ^3 ^**«r« — «*ioil«io«i C
£j Sprqr* — ftfttallniioA 0
T^- Saror% • •t»tal!«fi«* E
~ (^) Veniyri * ittiallartM F
— O ^ •***«« - AYtolloftWI C

"" (5t "ti Call — RcfcrvncB 1
. J-J
HLI ««« Cell (HF * M<«t) . 3cf. 2
•• *•"*

HB


B
^
-
][
_
i : • i i i 1 1


*
a

O

u
o
i i 1 1 1 1 it
i I » 1 I J 1 I
SILICON TC
i i i i i 1 1 ^.
TR4FLUORIDE I
• C» ^. f^ /S^
£}t^*±s ~
/^*O O
^^ -™


v
-
-
~
_
i 1 1 1 1 1 1 1
O.OOI .0.01 0.1 1.0 1C
            TOTAL POWER INTRODUCED - Hp/MCFM'
Figure 7-7:  Power  Consumed in SiFi+ Absorption
                      -63-

-------
IOO
   _   1   t-  I 1 * t I I    J   I  I i  I 1 I    i  I  t I I I I I     I  1111(1
        i  t  i 1  i > 11     I  1  t 1 ! I 11     i  i  i 1  i i i r     !  i  > i  i • i i
  0.001           0.01            0.1            1.0            10
       POWER INTRODUCED IN GAS OR "LIQUID PHASE Hp/MCFM
       Figure  7-8:   Power Consumed in Absorbing S02

-------
     The absorption of sulfur dioxide is analogous in many respects to the




absorption of gaseous fluorides, and the relative performance of equipment




should be similar.  It was shown that the number of transfer units obtainable




on grid towers is controlled principally by tower height and is only slight-




ly affected by power expended on the liquid and gas phases.  The performance




of cyclone spray scrubbers is primarily a function of power expended in the




liquid phase and is essentially independent of the power expenditure in the




gas phase.  Performance of Venturi scrubbers, on the other hand, depends




largely on the power expended in the gas phase but is slightly affected by




liquid power expenditure.  These results are useful in characterizing the




dominant factors in the performance of equipment used in the absorption of




gaseous fluorides.




     Nearly all usable data from the absorption of hydrogen fluoride are based




upon application of spray towers.  The performance of this equipment appears




to be dominated by the power expended on the liquid phase, as was the case with




the cyclone scrubber.  Significant differences in performance among the various




spray towers in use were found.  Wet-cell washers require a higher power con-




sumption  than simple  spray towers with the  same performance.




     The  performance  of spray towers absorbing silicon tetrafluoride is not




consistent with simple gas absorption.  One possible explanation is that




mists are formed  in the tower,  which are collected primarily in the entrain-




ment separators just  prior to emergence from the tower.  The mist is probably




rather coarse, however, because high-power  consuming devices such as jet




scrubbers do not  exhibit substantially better performance  than  the low-




power-consuming spray towers.
                                     -65-

-------
In an HF manufacturing plant, the packed tower is most frequently used for

emission control.

     One important factor in packed tower design is the type and size of pack-

ing since it determines the efficiency, pressure drop, and flow rates at which

the flooding will occur.  In the air pollution control application of the

packed tower, rather low concentration of gajes in the air stream are usually

encountered.  Therefore, there is generally no need for a higher liquid flow

rate than that required for complete irrigation.

     The quantities which are ordinarily fixed before a packed tower is de-

signed are:


     1.  Volumetric air flow rate, composition and temperature of
         entering gas.

     2.  Composition and temperature of entering liquid (but not
         flow rate).

     3.  Pressure.

     4.  Heat gain  or loss.


     Under  these circumstances,  it can be shown  that  the principal variables

still  remaining are:


     1.  The liquid flaw rate  (or liquid/gas  ratio).

     2.  Height of  packing  (retention  time).

     3.  The fractional absorption of any one component.


     Any two of  these last,  but  not all  three, may be arbitrarily fixed by

a given design.  The  fractional  absorption of HF, SiF^, and  S02  depends on

the liquid  used  in  the  packed  tower.   Three types of  liquid  are  used  in the
                                       -66-

-------
KF industry:  acidic gypsum pond water, neutral plant water, and an alkaline




liquor containing lime or caustic.  The efficiency of the equipment depends on




the choice of scrubbing liquid.  There are no reliable data on fluoride removal




efficiency but it appears that acidic liquid would have an efficiency of 60 to




90%, neutral water about 90%, and caustic up to 99%.  Consequently, a packed




tower with about 5 transfer units and an alkaline scrubbing liquid with a pH




of about 10-11 presents the best available control technology.

-------
7.3  Fugitive Emission Control




     The major source of fugitive spar emission is usually the spar pile.  Under




windy conditions, spar can become airborne and drift beyond the plant property




line especially when the pile is being worked.  The best control for spar emis-




sion is to keep it in a storage building or silos.  Less effective techniques




are to cover the pile with a tarp or use dust suppressing chemicals.  Fugitive




emissions of spar in plant transport are best-controlled by baghouses.  The




conveyor lines should be kept under negative pressure to prevent emission.




     The reactor kiln is under 1/2 to 1 in. wg negative pressure under normal




operating conditions.  Under upset conditions, the kiln can become a source




of concentrated HF emissions.  Most plants practice one of twc control alter-




natives.  The first is to have a standby scrubber connected to a kiln.  The




scrubber is usually a packed bed with caustic as a scrubbing liquid.  The gas




stream is separated from the scrubber by a rupture disc which is ruptured man-




ually in case of emergency.  Some plants ha:ve a provision to short-circuit the




absorption train and go directly to the final scrubber in case of emergency.




The standby scrubber is a better concept and represents the best available




technology.  Only 2 or 3 plants have no provision to control kiln fugitive




emissions.  Most of the gypsum ponds used  in HF manufacture are either




neutralized with lime or have an excess of lime resulting in a pond  pH of




10-11.  A few plants have acidic ponds with a pH of 1 which can be a source




of HF and SiFit emission.  The best method  for control of acidic ponds is  liming.




Once  the pH of pond water is brought to 5-7, no fluoride emissions are expected.




The second alternative is to use dry anhydrite  treatment similar  to  the  Buss




Process..
                                       -68-

-------
     Another source of HF fugitive emissions is tank car loading and unloading.




Figure 7-9 shows the emission control during tank car unloading.  At least one




plant is known to have HF fugitive emission problems during tank car loading/




unloading.








7.4  Summary of Best Control Technology




     There is no one single plant that uses the best control technology on all




emission sources.  Some plants have better control on one source; some on another,




It appears that implementation of New Source Performance Standards would result




in equalizing control efforts throughout industry.  Table 7-3 summarizes the




best available control technology for HF manufacturing plants.  Since fluoride




is not a criteria pollutant NSPS would make it a designate pollutant and




regulation would apply to existing facilities.  If the best control technology




were practiced in all plants the overall fluoride emissions would be reduced




by 20-30%.
                                       -69-

-------
o
I
                                               ^TfO

                                               Plf£
                                       .1.3
                       A-2'
                      A I
                            ^Hfj"-'
                                fci
        GAUGE

h**4*;.f  V:
                                        l-l
                            TANK  ;  CAR
             4 • 4.
                toucnoN
                              PRESSURE REGUIATOR


                                           AIR
                                               IHIEJ
                   'Oi
                     *4*l>
                         for.
                                                                4Cf
                                                                    ^A/A
                                                                                 ( 5
                                                        A.5
                                                         X
                                                          -ixi
                                                          3/«" P»PE  t.4
                                                                                     -txj-
                                                                                                TO PROCESS
                                                A- 7.
                   SAfEFir  RUPTURE DISC
                         WITH
                    VACUUM  PROTECTOR
                                                                        ^x
                         CHECK
                         VAIVE
      ^
                                                     -txh
                                                                             GAUGF
                                                                               G- 3
             MH*J
V
 -
-------
                                  TABLE 7-3

                  BEST CONTROL TECHNOLOGY IN HF MANUFACTURE
Source
   Pollutant
Control Equipment
Efficiency
     7,
Spar dryer
Spar handling
  and storage
Tail gas
Kiln upset
Gypsum pond
  if acidic
HF loading/
  unloading
HF dilution
Spar
particulate
Spar
fugitive
HF, SiF^, S02
HF, SiF^, S02
HF,
HF
HF
Fabric filter
Storage building or silo
  plus fabric filter
Caustic scrubber
Caustic scrubber
Liming
                       MCA* Procedure
Caustic scrubber
    99



    99



    99


    90


    99+



    99+



    99
     *MCA - Manufacturing Chemists Association
                                       -71-

-------
7.5  References
1.   Billings, C.E.,  Fabric Filter Manual, The Mcllvaine Co., Northbrook, Illi-
    nois, 1975.

2.   Strauss, W.,  Industrial Gas Cleaning, p. 214, Pergamon Press, 1966

3.   The Mcllvaine Scrubber Manual, The Mcllvaine Co., 1974.

4.   Air Pollution Engineering Manual, Danielson, J.A., Ed., EPA, OAQPS, May
    1973.

5.   Boscak, V.,  Tendon, J., Odor Abatement: in Animal Food Manufacturing Plants,
    Proceedings  of the First Conference on Energy and Environment, College Cor-
    ner, Ohio, 1973.

6.   Lunde, K.E.,  Performance of Equipment for Control of Fluoride Emissions,
    p. 293-293,  Ind. Eng. Chem., Vol. 50, No. 3, March 1958.

7.   Hydrofluoric Acid, Chemical Safety Data Sheet SD-25, Manufacturing Chemists
    Association,  Washington, DC, 1970 (Rev.).
                                       -72-

-------
8.0  STATE AND LOCAL EMISSION REGULATIONS

     The following sections discuss the state and local regulations

applicable to HF manufacturing and summarize these regulations.  The

values in this section are given in the units that appear in the regulations.



8.1  Summary Of Applicable Emission Regulations

     Although hydrofluoric acid manufacturing is regulated under the

permit: and particulate regulations of the states where operations exist,

no states have adopted regulations which specifically address HF production.

Rather, states treat HF manufacturing as a process industry for purposes

of air pollution control regulations. As such, eight types of control

requirements apply depending upon the particular jurisdiction:

     1.   General process weight limitations, typically using the following
          equation:

          E = 4.10  (P)0'67 where P < 30  tons/hr

          E =  [55.0  (P)0'11] - 40 where  P >_  30 tons/hr

          Where
               •
          E represents allowable emission rate (Ib/hr) and P  represents
          process weight rate  (tons/hr)

     2.   Hass particulate emissions limitations.  These  are  generally
          expressed  in terms of allowable grains or  pounds of  particu-
          late per  standard cubic foot.

     3,.   Control efficiency limitations.  The States of  Ohio  and New
          Jersey use this approach.

     4.   Control based upon the stack gas flow  rate.  Texas  uses  this
          type of regulation.

     5.   Visible emissions limitations.  These  are  applicable  in
          virtually  all states studied.
                                       -73-

-------
     6.    Fugitive emissions  limitations.   These apply in most states
          studied.

     7.    Ambient and  emissions limitations for fluorides.  These apply
          in three of  the states covered by this study:   Kentucky,
          Louisiana, and Texas.

     8.    "Catch-all"  provisions.   A number of states have such provi-
          sions which  are intended to control toxic or hazardous emis-
          sions on a case-by-case basis.
     The conclusion drawn from this analysis of State regulations is that

process weight and/or fluoride emissions standards apply to HF manufacturing

in virtually all states where operations exist.  The level of enforcement of

these regulations is moderate and no State agency indicated that emissions

from this industry was a top agency priority.



8.2   List of Regulations Applicable to the Hydrofluoric Acid
      Manufacturing Industry

      Tables 8-1 through 8-9 present the State and local regulations on parti-

 culate emissions, process weights, visible: emissions, fugitive emissions,

 fluoride standards, and other related areas.  Table 8-10 summaries the state

 regulations on allowable fluoride emission.
                                        -74-

-------
        =  •  T — a — c.
        i.  •  -- — a  -as

          •  i^ J: . S 2
            Tiaris j
            1J >  ^ > ^ 3
            .. -r f ^ - r 1 - ? i- 5 = f "
     r I
t   ! =1= .  - -?-5 'f j v- *  ' r s.» :

^  =  zt:| ;  j:-^|j :jii:|l^£3^
                              -75-

-------
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-------
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 r.iameiiy ale    weight  erufnlutil.                              i.n'lillvv 60 mlnillnd.    liutiie.   Sevun  uui li    ill.itliMin |)lu-     laetlirliiK In      tli-ntale emls:;li>n
 all giiveini-d    llii'lei  Section                                                           precaul luliu nil:       lilhll:l  eiuhi-      In  l.olll s l.ili.l,      HI ,1ndal UM  fm pi>-
 by I he l.iMilii-   I'J.H,  ||ie  SI,ill!                                                          i;|>ei_ 1 f I td,  lluliullng  fll-jim wliluli       HIT t Ions  11.2,      lenrlally  loxle
 I .in.i Stale All  may  tighten                                                              I lie line ul •! lul       will  . .Mi.il- "nil-  9.2-1, Kml tl,    pollutants  ubleli
 I'olliillon        llnvie  I lull Is  lor                                                        i;ol IcctorH.            dc-ilrilile lev-    111  prohibit       are «,.,re Hlrln-
 lli'iilrol          tuHli  iiaillcu-                                                                                   i'l»"  (I.e.,       i-mlH-ilnnn         i;i'"l  Ilini wnnld
 Ke^n lal IOIIH.    late I:IH|M[|OII:|.                                                                                  tiaimfnl  to Itn-    whli'li wuclil       olhi'iulse .ipplv.
                                                                                                                    wans, an I ma I H     runse "tinjc-
                                                                                                                    plwnlH  or |>ro|i-  ulrablf  lev-
                                                                                                                    i.'riy) ol  any      el*j"  uf any
                                                                                                                    air jM.'i Ivii.nii .    pi>! iiiiaiit .
                                                                                                                    ThlM  lias direct   Tin Lunlnl-
                                                                                                                    appt I eat lini Ln    aim Air Cun-
                                                                                                                    fluorldeti and     Ll i>l  CiHHinlK^
                                                                                                                    arid ml MI s        sloii  lias
                                                                                                                    emitted by        aduilnl stra-
 l'HtlCl,SS WKIiaiT  KQIIATfliHS                                                                                         liyrti of linn li-      tlvrly lui-
                                                                                                                    II. Id  plants.      pi em, I, ted
 K'>:                                                                                                                                   Ilil.,  a,i-
                         0 67                                                                                                          "llir "V I'X
      (A)    li - 4.10 (!•) '      (Rcgardlpso  ot p  Valnu)                                                                            et.i al.l IN!,-
                         0 hJ                                                                                                          Inf. ;1 24-hr
      (B)    I: •  4.10 (I') '      (I- <  lun.i/lir)                                                                                       P.|.ilvalr.it
                          /i  li                                                                                                         ambient
            K - I Vj.lt II') '   I  -  40.0 (I1  J  JO lonM/lir)                                                                            flnorlile
                                                                                                                                       Htan.laril  of
W1"'lo!                                                                                                                                 1/20  T.I..V.
                                                                                                                                       ..I  the prop-
            l< - Allowable emlualon rale In  po(ir.ds  |:,--r                                                                             eitv  line.
                limn ,  and

            I' •-  Troeess  uol^lit  rale  In Ions j>cr  hour

-------
                              I,,1,1,1  ,-i  .'.. nl,|,,  Si ilf  Ki-Kiilal Inn  A|i|il Ii-Ml. 11- It" Ill  M.iimf11 tin 11.1
oo


I'l.i.il :i
II,,. lln ,,!,., w
l,i. II II y III
Cl.vil.li,,! l-t
Hill. ,fi:l In
M. -HI- Hit"
wel 1 ;IH lii -
• .1 1 rt-'-lll .1 -
1 Inns ..I III.'
Ill 1 II -III. Ill-
till If I Klllls-.lnll
1 Illlltli
KiKiil.il li»i l/.Vi-
1 /-1 1 I.I lilt Illtltl
.Ml ! .il Inl li.n t nil-
1 ml iii-Kiil, n |, in...
limits till ImliiH-
t In- iii.iri- si r 1 n^f nl
nf lu.i l.v.-l-i: (I)
.1 pi III1. SU Wf 1 I'.llt

t'l.nU'H.-i UVIj;lu
i:.|n u inn is,',- i- lu, ii LIP :
K. Y Ini l.npl.in.it Inn) VlHlLli Kiul :IH I.IIIH Kn^lllv. 1 ml us l.i.i.l Ai.iMrnI
U Si. Hv Ki|!ul Jt I.. ii 1745- Suit.- Ri'ijiil. il I..II Not .ippl If.ililu
17-07 vi.t, •!>! Hlim a lien- J745-17 OS n--
or.nl t'l'~ ,.| i, liy limit tpilies an.l i-iiiimu-
(t;,.. 1 II h,ti, 1, m.inn) Inr rales lla- "tr.ititmn-
ti 1 1 sttiirei's. A i~mlnutR-b)r pri-i. .iiit IOIIH"
Inwinri- ul up ti> AtlZ Vt-nt p.ii l icu l;ii »-
(Nti. 1 Rlnxli'mliill) Id M.lttrr flora lif-
lirnvl.lftl I'ur . fitmlnp, ,il rli.n in- .
. ._

ilunil.ii.lu Olhf i Appl
1 n.lii., l.-n-i H, i-iil.il 1
Nnl nppl 1, ,i|.|f HIM 1 Km
117 nl U
l;,-,.,,il.n l
K.-I.I i-.il
Will ill pi
pnt 1 nt If
WntllJ III
ll.lllll pvil
III v/f 1 1 i
               ,irc  prt'si'iii i
               III Illltt  I  till
l.lly  of  Cl.-v-   limit  (uff n. /.t
I (n.I.    Iliu       ...I	u) in  (2)
                    u  |n-i c( IIL  i'f f i t IIMI
                    cy  i«>|M->tiiiitfii in hi?,.
                    H-l.    | Iguru  H-l (i l.iu-s
                    lint uutrol U (I  H.ISM K.itti
                    u(  r.nlMsl.m  (.itisrlssa)
                    In  m.ixIfHiidi a tlnw-il'] <•
                    tnasM r.itf  «>I  t-inlriajoii
                    (..i ,1 [.Hi.-) .    'I he piii-
                    fi-;is Urli'J.t   1 In.ll  r.'

                    iif  lit It i.'I 1.1 Is  i lt( 1 n

                    f Ir  prm CHS  fli it  m.iy
                    r.ni'K'  any  ciui ss i«>r.  tit
                    (in ( U n I.it <• in it tc-r
                    I (i  m ts j mi nit  a I low tb 1 «•
                    in »:. i r.it f  i»t   -x-i,,l ss 1-iti.
                    l!tt  | i". •••(., w*-!/l.t  t  iml |
                    >.h.i t i   ji|'|< I y  f ti  ii"ti
                    at  t ,i lint'iil  ill o.i f;  Inr   I'll1
                    wln-ir  (I,,   M.H.on* t.>| |  •.!
                    tl.i .-, K.ilr i>(   IjalKslon
                    .•.iinu.l  hr  ;i..i r,  lal.,..l

                    I (H I oi  rh.ll ,t» I rr t /,,il  I on
                    lor  the (ft IK i;:;s  is  ini-
                    t> n»un.   Citi vi-  I'  I    nl
                                                                                                                                                                                                      .il Inns  I H .1
                                                                                                                                                                                                      .il  |>rUH  .t
                                                                                                                                                                                                      t Ion  uliJch
                                                                                                                                                                                                       nut f.i.'ion ilil
                                                                                                                                                                                                      iv.il.l 1.-  In-all
                                                                                                                                                                                                      II ,ii,' or  i on
                                                                                                                                                                                                 tile  a  I'tilil Ir
                                                                                                                                                                                               nil I n.imc .
                                                                                                                                                         SS WK.IOIIT  h:<)UATIi>NS
                                                                                                                                                          (A)   i:  = 4.10  (l')°'6/    (Ki-Barillpsii  .if  P  V.iltiu)

                                                                                                                                                          (II)   L  - It. 10  (I1)"'6'    (T <  tuiki/hr)

                                                                                                                                                                K  - IS3.0 (l')0'"l  -  4)1.0  (I- -1   10  i DIM /hi)
                                                                                                                                                                I* ~'  A) Itiw.lli I L- i-niluslnn l;ir.-  Ill  |.mititl-i  |ii-i
                                                                                                                                                                     lnxii ,  .mil

                                                                                                                                                                I1 -  I'i.iiTSK wrl'',lil  lillo  In  t.tlis  pL'l lintii

-------
<  ' '  "x tn -- |


                            -79-

-------
o


on


UJ
     10-'
on
on
   <

   5 10*
   u.
S o


I   100
                                   CURVE P-l


                                   CURVE P-2


                                   CURVE P-3
                  (I)-COLLECTOR EFFICIENCY REQUIRED (S)*
                                                                 100
                               103
                                                       10s
                  U-UNCONTROLED MASS RATE OF EMISSION Ib/hr
  NOTE:  AFTER JULY 1,  1975, CURVE P-l APPLIES IN ALL CASES

        WHERE THIS REQUIREMENT IS DEEMED APPLICABLE.
              Figure 8-1:  Ohio  Collector Efficiency Curve1*
10s
                                     -80-

-------
                                         -3

                                       - e
                                    ^
                                   *± —
           «!* I Ut'.'i -    ^3 *: j 22 4 251^
           Sllll^lil   ipHl =-| - = ±i

           -^11iilr = ?=  I^^ M * S?^ fill
               *  ,  s:r     -
       '4 ;
=  "t
                             -81-

-------
TAKI.K. H-fi.   I'L-iul-.yl v.iul.l  I CMIIIIIIMIV-', :ll I li  KrKii I n t liHIN  Appl J r.ilili.  lo  UK Mainlfai'1 111 Inf.

I'l.illl M
Me 1 ( (in I ho
A:. hi Hid 1,1, :l
Illy .11 (.1, li
dun li,tr t hr
Allliil i> 1 l li.ihli-
| to :;UL|I opi>-
OO iai Inns are
^ In. In.l.'d lor
till Hi IH.IL lOIKli
purposHH.




l';irt lrnl.it t.' 1'rort'as Weight
M.iLlL'i I'JulHaloti Kijnatli'ii (.'lu,'
l.lmltii K,-y loi r,«| 1. in. ll lull)
!)frlloii 123, 11 of Not At>ii 1 1 r.tli 1 1>
Lit.' IV'msy I v.'inld
Al r hi'Hunr* cni
Id'i;, il.it Icnu rt^u-
in'illur eml si. loiu.
1 roii. p» oct'as opc-
r.il Inn a. Tor pru-
rir>:.'i upor.it IOIIM not
hpi1* II 1. al ly 1 IsLcd
(UK H.innl art urine
1 s .111 unl l:il rd
pr.i.tviri) allow-
able; tml.'i:ilons
arc grHfililcally
(Hunt rated In
FIHini' H-2.






Vlall>U< EmlaNluna
S.'rt Ion J **A 41 i>ro~
hlhllii vtsilile
i-'ulsalmin. 1 In- o|i.i-
r lly nl which:
I) cr|uj|lt; or ex-
Lei^!] 20! fur an
aggregate or Mure
than 1 minute* In
any one lu>nr, or

2) equal « ur ex-
ci'i-.lu 6l)t at any
lime.

Thin ll»lt.lt lull
ilocR not iipi'ly
to fugitive mls-
Klonn which arc1
(MTHlttoJ tllldur
hLTtlOII 12J.I
(MUU twxt column).

Kii|;ll Ivu Min|.,itloiiH
Si'i'Llon 1 / J I ( ti ) ( 9 )
prolilhllii f,i(;lllv..
.•UI|K.S|IMIH unlt'HH the
I'cniisylv.inla DI.K di'-
alonu ar.r ul minor
«I«nll 'Ir.incc and
nro not provfnt Ing
the- at 1,-tliMK'nl or
m.ilnl oii.in, r of .my
ami, lent stnnJnrd.
Sor. 121. !(.:) s|irrl-
flou err 1.1 In t i'/i:iiiii-
• ililc |>ri'Caut Ions In
pi evrnt f ny 1 1 ivft
tm I -is ions -lii-i:. 1 2 I, 2
jirohlblts riij>
part Iculat o emlHtiloiiH
al the |,io|..'i ty I In.!
ulilrh nro IIN

tin. I'l'iniKyl- I2/.72, o|iri.i not :i lorlh ,i
v.inla KL-T.ula- ilni; I'.'i'mll )},'iier>il |i..r-
I luns rsl.ili- appl lint lona iillilllon .i)ialii!;l
IUHII riuot l.li! i|ii.-st flhow
hl.lndard of th.il 1 llf
*> |ii;/M3 (lo- uoiirrt1 will
lal si.lnhlr n, i| vlul.iti'
uti UK) . Any iimMi'iit
air fpi.il Ity
R| and. ml.












-------
   C.C4
   0.03
c
o",
m
:?  0.02
    100,000
    1	I	1
 200,000       300,000   400,000

E = EFFLUENT GAS VOLUME, dry scfm
                    THIS  GRAPH TRANSLATES  AS  FOLLOWS:

                    (i) 0.04  GRAINS  PER DRY STANDARD CUBIC FOOT,
                    WHEN  THE  EFFLUENT GAS  VOLUME IS LESS THAN
                    150,000 DRY  STANDARD CUBIC FEET PER MINUTE.
                    (ii)  THE  RATE  DETERMINED  3Y THE FORMULA:
                    A = 6COOE-1, WHERE:

                    A = ALLOWABLE  EMISSIONS IN GRAINS  PER DRY
                    STANDARD  CUBIC- FOOT, AND
                    E = EFFLUENT GAS VOLUME IN DRY STANDARD PER
                    CUBIC FEET PER MINUTE,
                    WHEN  E IS EQUAL  TO OR  GREATER THAN 150,000
                    BUT LESS  THAN  300,000.
                    (iii)  0.02 GRAINS PER  DRY STANDARD CUBIC
                    FOOT,  WHEN THE EFFLUENT GAS VOLUME IS
                    GREATER THAN 300,000 DRY  STANDARD  CUSIC
                    FEET  PER  MINUTE.
                  Figure 8-2:   Pennsylvania Allowable  Emissions Curve
                               for Sources Not Listed  in Section 123.136

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                       IA I'I !•.  rt  /.  •|i>r..iti  Slillt- k.-KM!.II I.ins A|.|.l I, ilil,-  l.i IIF  ll.ulnf .ir t nt in|>
                                 I'.ill li -iilad*             I'luri-iu  Mi>l|;hl
                              ll.illi-i  Mn, fusion             l-i*. ,.M Ion  (Si-i1                                                             _  Flnorlih> 4jlan;l I !«''  t'wl uu Ions       Amlilfitl         I'ml MM lon.q         KIT," Inl IOIIM


            Tin' Me 113,      K»l«  105  nf  Texas   Hut. ,\|'|i> I ral>U           Kuli-  101 of  Toxin Ki't'i-  Hiiltf  lO/i of  I.'/ rj  !>uu Kli;n[it      Sn:  I l|>uii<      Hole  S  I :i .1  ,;cn
            li'i|"'nl  ..n. I      Hi |;i"l.it Ion  |  I'Ml.lli-                             l.ll loll")  1 nrnlillilltl ex-  Kl'glllal Inn  I  UN-    K  ">.             fl - 1 .              rl.ll  nil I I:;IIIIT
            :'i|.inf I i r        I I.', IK'S  |i,-irt liiil.llr                              ir:i:il"«  vliilMe cinln-     I ul. I I i.luiin  from .IHV cncloseil  mrr.Ht^  "vra::cn:i|il<'                                    hit- in  .ill |>oll
            I'-lnl  I,.H.,|.r.'< .ml IUIIK"  wl. I rli                                     lion.
            l.i  I'd i I r .nut    .louiLt'H oil, .-i                                     Ullli rofi|io, I  tu stack     mist  lie  ailo|»t c.l to
            (jrouiiM  Hiiyoti    (li.ui tlio^c  piiir-                                 i:i»l MHloiis, i IIP rule       pin-vent  pan Irn-
            r»;»l>ci:l 1 vi-l y    UHiilug  iir li^inil-                                  t;p^cifiiii u  10£ p|>d^      Intcn  from lid'omlnfr
            ait-  all  null-    1 1 iiy a;',r ten 1 1 in -                                 rliy jlrolt»  -ivci jiged      alrliomu In aroau
            In i  u.  CI.H.V   n| ciununilli II-H.                                  over a 5-mlnuio pel I oil,   wlilrli  «ic nonal-
            Sl.ii,. All  I'ol                                                       Stac-ks i  un.'il riu li d  af-    talimiMil tor  i lie
            1'itlon  Con-     SonrriM snl,|i-ii                                  I IT  .l.inuiiiy  31, 1972,     jmhlcnt  (inrt 1 1 iil.il .'
            liol  lii';;ol.i-    to Uol.   100 mil: l                                  nru  limited  lo ?f)2         m.iild.iril.
            lions.           I'orloim lo  I In-                                   o|i.irtty  on .1  "i-mlnntc
                              u I lowiili !<• cmlx-                                  avfki:igo.
 '                             i. Ion i al rH a:i
_|^                            hllOWII  III  KI|',IIIH
 i                             H-!  ai!.!/oi  tl{-
                              uri-  8-'i.   K.-ir.li
                              ri'j;n l.u rM i-ini*;-
                              HlniiM  ari-orillng
                              to the c-l I liienl
                              flow I. He ol  UK-
                              for Hl.i, t  hflglit.
                              In .nl, II t Jon, Hull-
                              ID'S L'Sl.lllllsllCN
                              an amli I'.-ii I  all
                              >|ii.-il llv r«'la| ul
                              fm I sf: I on ;ii. aii«|;irJ
                              vlid h  prill, !l>l ts
                              part lfiil.it i*  <-i,il M-
                              alon whl<'li won!,!
                              rausi*  anv  of I hi'
                              t Imt'-nveia^i'd  net
                              y,i omul Irvr i |>ar -
                              I i filial >• ronn-n-
                              I i. it l"ir. lo  l>r

-------
- -A  = = =
                  -85-

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Effluent Flow Rate
acfm
1,000
2,000
4,000
6,000
8,000
10,000
20,000
40,000
60,000
80,000
100,000
200,000
400,000
600,000
800,000
1,000,000
Sate of Emission
Ib/hr
3.5
5-3
8.2
10.6
12.6
14.5
22.3
34.2
44.0
52.6
60.4
92.9
143.0
184.0
219.4
252.0
Interpolation and extrapolation of  the  data in this table shall be
accomplished by the use of  the equation E  * 0.048 q^*°2 where E is
the allowable emission rate in Ib/hr  and q is the stack effluent
flow rate in acfm.
        Figure 8-3:  Texas Allowable Particulate Emission
                     Rates for Specific Flow Rates7
                                -86-

-------
c

I/I
ca
*^»
o
   10°
                                                               105
                                STACK EFFLUENT FLOW RATE  (acfm)
                     "igure  S-4:   Texas  Allowable  Participate Emission
                                  Rates  for  Specific  Flow Rates
                                              -87-

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co
CO
     The Board declarea that concentration* of gaseou* Inorganic fluoride
     cuoi|>oiinda In tha atmoaphara,  calculated  aa UF,  In excess of I

           .5 ppb for eny 12-hour  parlod
           .5 ppb for any 24-hour  period
           .0 p|>b for any 7-day parlod
           •0 ppb for any }0-day period

     by vo urn* at 760 m llg and 2) degree* C  average conetltute undealr-
     sbla  evela, whether th* aourcea ara froai natural causes or froai tha
     actlvltlea of man. and that a atate of air pollution exlste when con-
     centrations of any gaseous Inorganic fluoride compound, calculated aa
     IIF, exceed any of than* levela.

b.   The Board further declaroa that concentrations of Inorganic fluoride
     compounds In forage located In a Type D  land uae area. Including In-
     organic  fluoride compound* both absorbed In snd deposited on forage,
     calculated aa fluoride Ion, In axcaa* of any of the following levela
     Indicate the presence of undesirable levels In the area In uhlch th*
     forage I* grown, whether th*  aourcea ara froai natural cause* or frost
     the activities of man; and that • state of air pollution exist* when
     concentrat lone of Inorganic fluorid* confound*, calculated •* fluorid*
     Ion, exceed any of th* specified levels!

     (I)  An  everage of 40 parts per Billion by weight baaed on staple*
          taken once a month over  • period of 12 consecutive cslendsr
          nonthsj or

     (2)  An  sversg* of 60 part* per Billion by weight based on aimplea
          taken once a month over  • period of three conaacutlve calendar
          monthii or

     (J)  Ar.  average sf 30 parts par at it Ion by weight baaed on **mp»ea
          taken one* a month over  • period of two consecutive calendar
          month*.

     To assist In meeting th* ambient air quality standard*, th* loard
hereby establishes • Halt on th*  million of gaseous inorganic fluoride
coapotinda,  calculated a* IIF.  which may b* made from any property not to
exceed 6 pert* per billion by volume average during a parlod of ) consecu-
tive hours.  The contribution of Inorganic fluorid* coeipound* by •
•ingle property aha11 be measured  by th* difference betwaan th* upwind
level and the downwind level  of Inorganic fluoride compounda for the
property, or  by atack aampllng calculated to a downwind concentration.
     The Milmum allowable  fluoride emission rate which may be mad* turn
• stack on a property  to  comply with the cmlaaion Halt sat forth In this
Regulation My be calculated by Button's Equation which ha* bean modified
to consider th* critical  wind apeed and 'to correspond to a J-liour air
lampl*.  Th* aquations used for fluorid* for cold and hot atack* are!

     1.   For exit  stack  gaa for temparaturea of lea* than 121 degree*  F.

          (•)  All  land us* types

                                                  1
                                                                                                                q» • 5.8 x 10"*V d *
                                                                                                                                                       1.29
                                                                                                              Wharst

                                                                                                                Qa - emission rat* lb*/hr.
                                                                                                                V  - atack exit velocity,  ft/sec.
                                                                                                                d  - exit *t*ck dlanater,  ft.
                                                                                                                h( - phyalcal atack height,  ft.

                                                                                                              (See Graph 1.)

                                                                                                    2,   tor exit stsck gee for temperatures greater  than  125 degree* F.

                                                                                                         <•)  All lend type*
                                                                                                                                                   ti   i
                                                                                                                                        1.5 t 0.82 (=M
                                                                                                                                                  \  •/   •     "t
                                                                                                              wherei

                                                                                                                Qa - eataalon rat*,  Ibt/hr.
                                                                                                                V  • atack exit velocity, ft/aee.
                                                                                                                d" - exit atack dlaaater, ft.
                                                                                                                •>, • physical atack  halt lit. ft.

                                                                                                         AT • teuparatura difference between atack gas and tlia wit-
                                                                                                              door temperature* of 90*P.  (550*a) la aasimod in pra-
                                                                                                              parlng dlaperalon graph*.

                                                                                                         T  • atack axlt  temperature In 'Rankina.

                                                                                                              (Sea Graph  2.)
                                                           Figure a-5:
                                                                     Texas Fluoride  Standards
                                                                     (Key  Excerpts  from Regulation  III)7

-------
 C
 o
     10C
  .. 10-1
  o
    10-2
                                                EXIT STACK GAS VELOCITY IN ft/sec


                                                5        10        20  30  40   60 80  100
       IO"1                        10°                         1C1



                                 STACK EMISSION RATE  IN  Ib/hr

                                       HYDROGEN FLUORIDE


                      FOR USE WHEN' THE EXIT TEMPERATURE IS LESS THAN 125°F
  TO PLOT GRAPH 1, ASSUME A BASIC STACK  HEIGHT  OF  100  FEET

AND PLOTS 4f_ 1.23 FGR VARIOUS STACK  DIAMETERS  VERSUS  STACK

VELOCITY. '°°
                             Figure 8-5:   (continued) Graph 1

-------
   c

   c£
    _

    t—
    C/l
      1C3
       10-
    STACK EXIT INSIDE DIAMETER  IN  FEET

     2       3    4       5      6    7
                                                                             3   9 10  11 12
        10-1
10°
10*
                                    STACK EMISSION RATE IN Ib/hr
                                         HYDROGEN 'FLUORIDE
                     FOR USE WHEN THE EXIT TEMPERATURE IS GREATER THAN 1253?
   TO PLOT GRAPH 2, ASSUME A  BASIC STACK HEIGHT OF ICO
FIET AND AN EXIT VELOCITY OF  20  ft/sac.  LET STACK GAS
                             Figure 8-5:  (continued)  Graph 2
                                            -90-

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                                        I'iiri I.nl.Hi-               l'io,i'3H Wi-lj;l\l                                                                                                   ....   t  i
                                     M.mi.,  riiMHKlon             K,t,,.ill,.,, (So,,                                                            ...  .  M,M,rUsl..n«       Awl.l.-.H          Kmlssln.m          R,.e.,l.,t I	


                   II,,. A,,,,..,       K,T.,,l.,tlon III            N.,1  ,Vpll,  ,l.lr        S«,:«l..»  2  of  «,-,;„-     Si- I U-n 4  of RoRi.M-    II,, t  A,,p 11 mhlo  N,,t  An,l 1. a|, I,.  S.,. I I „,,  1. 11  ..I
                   , ..-llliv.il      ,.r  the  W,.s,  VI,                                    Lillon VII  i-ruhlLHn   tloi, VII r.-.|,,1ro»                                              Ko,;»  .,11..,, VII
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                   ,1,  .,(,||M||,,n   I.Hu i-mlsulonn                                     An nl Inu-iiff  Inr        ti-u.-j lopfll.rr  will,
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                                     ii,ti<>n:i.   iir at  Id                                 rlod.n  .iKKri-K-itl'ig       prai I leu Dl.iiid.inl.M
                                     i.:iu,il.-i.-LiirliiK  Is                                  '"> •«'••«.•  H"»«  5          K>  ...nlrul
                                     ,1  type  "vi" ciMire,.                                 mlnntiM  in  any I-       iliinl.
                                     ,ii>.lf'i  It.-KHl'ill'.n                                  I" •  period.
                                     VII ittttl w.xi Itl
                                     lln-.virc li .-illy Im
                                     61,1, | ell  to I III'
                                     ptl.rv'NS wt'l^lil
 |                                    I linll.1l I"lis  il|'|>l I-
^O                                   f.'thl*'  I,i fi,,,-l,
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                                     MllliM-ll  lit: III Cllllf!~
                                     Hlini urc it,,! f»v-
                                     cn.l by tlic  SI.II.-'H
                                     pr.i«'i:'>'. wrl^l.)
                                     rr|;ul;il Itni.   hi.rlliri-
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                                     Mll,.M'i>l  ;l.:l  if,
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-------
iii  :
           3 r

           c" 5


               | 1 x j-s] f
               — c ; •_• s w i
               ?c.?-i1'".
         — X j ,. —
       ~ "    • j  5   •••
                                -92-

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                                        TABLE 8-10

                SUMMARY OF STATE REGULATION ON ALLOWABLE FLUORIDE EMISSIONS
STATE
California
(Bay Area)
Kentucky
Louisiana
New Jersey

Ohio
Pennsylvania
Texas
Ves t
1 Virginia
COMPANY
Allied
Penwalt
Allied/
Kaiser
Lssex

Harshaw
Allied
Alcoa/
Dupont/
• Stauffer
Allied
1
LOCATION
Pittsburg
Calvert City
Baton Rouge/
Geismar /Cramer cy
Paulsboro

Cleveland
i
Marcus Hook
Point Comfort/
La Porte/
Green Bayou
I
! Nitro
ALLOWABLE EMISSION RATE
4.10 (P)°-67
4.1CKE)?:67 P < 30 tons/hr
155 (P) -40 P 1 30 tons/hr
Same as Above
.At: w«oi*
*n» *»ion A.' w*ol«
• t« t-e man
p4*«fit:al '.b« o«r -v . ; »aurc* <(*• a;«
>of« saurca »V titi- score* 3j ft »n
-pwauan .11 tic;- if (Scacdvd •:». 0 0 CJin*
,1tn.F*thr.i ;»l •cnom :: . ptram.) ?- ;CD
50 or !«*• 0 5 J-'XJO cr !•>• J i
100 1.0 i.OCO I J
I'joo o.o is.:oo i J
:ooo 0.3 ro.ooo : o
2000 ;r 4r«*t«r 0.0 1*0 OCO 4 J
.7! ."00 ir 
-------
8.3  Definition of Plant Modification

     The Clean Air Act defines a "modification" as


               " ...... any physical change in, or change in the method
               of operation of, a stationary source which increases
               the amount of any air pollutant emitted by such source
               or which results in the emission of any air pollutant
               not previously emitted.  (§100 (a) (4)).


     EPA NSPS regulations (40 CFR 60) implement the modification concept by

narrowing its applicability to specific facilities within an entire source.  As

such, the regulations define a modification as any physical or operational

change to an existing "-facility which results in an increase in the emission rate

of any pollutant covered by a new source performance standard.

     Typical examples of a modification within an HF plant would be:



     1.   Use of different packing in  the  scrubber.

     2.   Change in liquid to  gas ratio in the scrubber.

     3.   Higher J^SQ^  to spar ratio.
     The determination of whether  a  physical or operational change will

increase the emission rate  is based, wherever possible, on AP-42 emission

factors.  However, where AP-42  factors  do  not yield  a  clear-cut answer,

material balances, continuous monitoring data or manual emission tests must

be  employed.  In cases where emission rate changes are difficult to determine

or  where industry-specific  guidance  is  necessary the Administrator has

the authority to promulgate industry-specific definitions of  what constitutes

a modification for any particular  facility in that industry.   Regardless of

the definition or method employed, however,  compliance with all applicable

performance standards must  be achieved  within 180 days after  completion of

the modification.
                                      -94-

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     Under EPA regulations, a modification was not deemed to occur if the

source owner was able to offset an emissfon rate increase by reducing emissions

elsewhere within the plant.  This bubble concept allows a plant operator who

altered an existing facility in a way that Increased its emissions to avoid

application of the standards by decreasing emissions from other facilities

within the plant.  This concept was rejected in the recent case of ASARCO, INC.

v. EPA 11 ERC 1129 (D.C C.R., 1978) and EPA is currently in the process of

removing this provision from the regulations.

     It should be pointed  out that the modification section of the NSPS regulations

specifically exempt several types of activities including:

     1.   Routine maintenance, repair or replacement;

     2,.   An increase in production rate accomplished without a capital
          expenditure;

     3.,   An increase in the hours of operation;

     4.   Use of an alternative fuel or raw material if, prior to the date
          any standard under the part becomes applicable to that source type,
          as provided by §60.1, the existing facility was designed to accom-
          modate that alternative use;

     5.   The addition or  use of any system or device whose primary  function
          is the reduction of air pollutants, except when an emission control
          system is removed or is replaced by a system which the Administrator
          determines  to be less environmentally beneficial;

     6.   The relocation or change in ownership of  an existing facility.
                                      -95-

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1.4   References  *

     1.    Copy of  applicable regulations  sent from the Bay Area Air Pollution
          Control  District in San Francisco,  California.

     2.,    Environment  Reporter - State Air Laws,  pp.  386:0501 et.  seq.

     3.,    Environment  Reporter - State Air Laws,  pp.  391:0501 et.  seq.

     4.    Environment  Reporter - State Air Laws,  pp.  476:0501 - 476:0541

     5.    Copy of  applicable regulations  sent from the City of Cleveland

     6.    Environment  Reporter - State Air Laws,  pp.  491:0541 - 491:0741

     7.    Environment  Reporter - State Air Laws,  pp.  521:0521 - 521:0581

     8.    Environment  Reporter - State Air Laws,  pp.  546:0501 et.  seq.

     9.    Environment  Reporter - State Air Laws,  pp.  451:0501 et.  seq.
 NOTE - All literature references were verified through the applicable state
and local air pollution control agencies.
                                      -96-

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9.0   HF MANUFACTURE EMISSION SOURCE SAMPLING AND ANALYSIS




     There are three major groups of pollutants that can be encountered in




Hr manufacture.




     1.  Particulates, primarily CaF2-



     2.  Fluorides, primarily HF and Sir,.



     3.  Combustion related pollutants:  SO  , NO  , and CO.
                                           X    X


     Table 9-1 presents a list of identified pollutants in HF manufacture




and summarizes sampling and analysis techniques.



     Determination of the emission rates is basically the same for all of the



potentially emitted pollutants.  It is necessary  to measure the concentration



of the pollutant by analyzing a sample which is representative of that in the




duct or  stack  and which is characteristic  of normal process operating condi-



tions.   It is  also necessary to measure  the  volumetric flow rate of  the gases



in the duct or stack  at the time of sampling.  The substance mass emission rate



is then  calculated  from the measured concentration and volumetric flow rate.



     The following  sections contain concise  descriptions  of the recommended




sampling and  analysis methods  for  the  emissions  from  the  HF manufacturing



process. Not  all  methods have  documented  precision and  accuracy and this



information is provided only as available  in the  literature or  determined




bv the. contractor.
                                        -97-

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TABLE 9-1   SAMPLING AND ANALYSIS TECHNIQUES FOR THE EMISSIONS FOR HF
     POLLUTANT
SAMPLING TECHNIQUE
ANALYSIS TECHNIQUE
     Particulate,
     CaF;>,
     fugitive
     Si02>
     impurities
Isokinetic with
collection on glass
fiber filters.  Methods
5 or 17.
Gravimetric Method
5 or 17.
     Total Fluorides,
     HF, SiF.
Isokinetic with membrane
filter and impingers with
distilled water
Method 13.
                             Simplified Train
                             Remote  sensing
SPADNS - Zirconium
Lake or specific
ion electrode.
                               SPADNS - Zirconium
                               Lake or specific
                               ion electrode.
                               Infrared absorption
                               and Emission Spectroscopy.
      Sulfur  dioxide
      S00
Sampled at constant rate
through midget bubbler
containing isopropanol  and
midget impingers  containing
hydrogen  peroxide.
Method o.
Barium-thorin
filtration
      Carbon  Monoxide
      CO
 Integrated  bag  or
 continuous
 NDIR (Non-dispersive
 infra-red)
      Nitrogen oxides
      NO
        x
 Grab  sample  collected  into
 evacuated  flask containing
 a dilute sulfuric acid-
 hydrogen peroxide absorbing
 solution
 Method 7.
 Colorimeteric  using
 phenoldisulfonic  acid
(PDS)  procedure.
                                       -98-

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  9.1   Particulates


        Particulate emission rates can be measured using the sampling and analy-


  sis techniques specified by Method 5 - Determination of Particulate Emissions -


  from Stationary Sources  or Method 17 - Determination of Particulate Emissions

                                                      2
  from Stationary Sources  (Instack Filtration Method).   Sampling and analysis


  procedures in both methods are essentially the same, the only difference


  being the location of the filter.  Method 5 has a filter located outside the


  stack and thus the sample stream temperature must be maintained above  the con-


  densation point.  Diagrams of the sampling trains for Methods 5 and 17 are


  presented in Figures 9-1 and 9-2, respectively.





  9,2  Total Fluorides


       The fluorides emission from HF manufacture expected to be in gaseous


  fora consist of HF and SiF/ .




         'The emission rates of total fluorides can be measured using the samp-


  ling and analysis techniques specified in either Method 13 - Determination of


  Total Fluoride Emissions from Stationary Sources -  SPADNS Zirconium Lake


  Method  or Method 13 B - Determination of Total Fluoride Emissions from Sta-


  tionary Sources - Specific Ion  Electrode Method?    The sample collection sys-


  tem and technique are similar to those of Method 5 for particulate.


       Upon completion of sampling, the filter, impinger catch, probe wash and


impinger wash are placed in a sample container.  The weight of total fluorides


collected is determined either by the SPADNS Zirconium Lake colorimetric method


or by a specific ion electrode.  To obtain the emission rate, the weight of the


total fluorides is divided by the sample volume corrected to standard condi-


tions and multiplied by the volumetric flow rate in the duct corrected to stan-


dard conditions.
                                         -99-

-------
        L
TEMPERATURE SENSOR


       ^- I'ROUE
   O~
PI TO i  Hint
    I'HOUE-
T
                                                           IMPINGEU TRAIN OPTIONAL, HAY BE REPLACED
                                                                   liY  AN EQUIVAUNT CUNDENSOK
                                         THERMOMETER v
                           STACK WAIL
                                                     \    rl:ILTER IIOLUER
                                HEATED AREA
                                                   ,1?
                                        n	1
 REVERSE TYPE-
  PI TOT  THHE
                                         3
                        I'llOI  MANOMETER
                                                 THERMOMETERS
                    OKU ICE
                                                           r^_,£    u

                                                                       MAIN VALVE   \
                                                                                     Y-.I
                                                                                                              VACUUM 1.1 III
                                                                                                IVACUUM GAUUE
                                               DRY  TEST  METER     Alfl-TKUlf PUMP
                               Figure  9-1:   Mctlunl  5 particul ale-snmp] ] nj1, train

-------
=3
•o
     -101-

-------
     Analysis by the SPADNS Zirconium Lake colorimetrie method of twenty repli-




cate stack emission samples with a concentration range of 39 to 360 mg/1 resulted




in a relative standard deviation of 3 per cent.  A phosphate rock standard with




a certified value of 3.84 per cent fluoride was measured to have an average value




of 3.88 percent fluoride based on 5 determinations.  The accuracy of fluoride




electrode measured has been reported to be in the range of 1 to 5 per cent in




the concentration range of 0.04 to 80 mg/1.  The collection efficiency of




Method 13 sampling train is presented in reference 4.

-------
     9.2.1  TRC's Experience with Fluoride Sampling and Analysis




     At the end of August. 1977, TRC and EPA carried out the field program




at CF Industries plant near Bartow, Florida.  The purpose of the program was to




validate the ROSE (Remote Optical Sensing of Emission) for the measurement of




fluoride emission from the gypsum pond and to estimate the fluoride emission




rate.




     During the field program wet sampling/analysis was employed to determine




fluoride emission at various points around the gypsum pound.  The schematic of




the sampling station is shown in Figure 9-3.




     The results obtained during the field program were somewhat inconclusive




and some questions were raised about the applicability of the simplified sampling train.




Consequently,  the calibration of the sampling train and fluoride analysis was




carried out in controlled lab conditions to determine methods, precision and




accuracy.




     The ROSE method  is based  on absorpotion  of  hydrogen  fluoride  (HF)  in  0.1N




aqueous solution  of  sodium  hydroxide and subsequent spectrophotometric




determination  of  dissolved  fluoride (using  the SPADNS method).   The experimental




arrangement  is  shown in  Figure 9-4.




     The experimental arrangement  incorporated a dynamic  dilution  system in




which  a stream of known  concentration  of HF was  mixed with  a  stream of  air




taken  from outside  the building.   Mixing occurred in  a  7.5  ft.  long section




of a polyvinyl chloride  duct  6  inches  in dia.meter.  Air velocity in the duct




was  2,000  ft/Qi.n.   The gases  were  absorbed  with  five  impinger trains  operated




simultaneously.   Each impinger train consisted of two  impingers  in series




followed by  a  flow  meter  and  a gas volume meter.




     The  influence  of the following parameters on accuracy and precision




were studied:
                                      -103-

-------
                                                    VALVE
EiPIKCERS
                     DRY GAS METER
_J
PUMP
                                      ROTAMETER
                                                                      CENERATG?.
      •7ESTICAL TRAVERSE SAMPLING' STATION
                                                                     GENERATOR
    Figure 9-3:  Schematic of a Ground Upwind-Downwind and Vertical
                 Traverse Sar.pling Station
                                    -104-

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I
I-1
o

I
              400 ACfH
              All) FINK I
             ours MIL  OF
                     ri  I
                 7.5  ft.
                                                                    I Pilot  tube I
                                                                    K201)0 ft/mln)l
                           I   It IIP In II2  I
                           comprcsscJ gisl
Iconipresseii »ir|
                                                                               10 GUIS IDE
                                                                              THE nUILOIIIG
                                           Fif.tirt; 9-4:   Experimental Arrangement  Cor Kvnl un L Ion of

                                                          llydroj;iMi  nuurlik: Sampling  and  Analysis

-------
          -sampling  time (1  hr.  to 2.5 hrs.)

          -concentration of  HF (50 ppb, 20 ppb)

          -effect of inpinger type (Greenberg Smith,  standard tip)

          -effect of tubing  used in train assembly (Tygon,  polypropylene)

          -length of tubing  used in train assembly (Tygon,  polypropylene)

          -presence  of ice around the impingers

          -liquid volume in the impingers (100, 80, 60, 40  ml in the
           first impinger, 100 ml in the second impinger)

          -gas sampling rate through the train (21, 26, 36, 47 1/min)

     The maximum number of identical tests was four,  corresponding to four

sampling trains operating simultaneously under the same conditions.  The basic

precision and accuracy of the method were determined in this way.  Standard

deviation was calculated for each group of four tests.  The error for each

group was expressed as a difference between the HF concentration as analyzed

and the HF concentration as prepared.  HF concentration as prepared was

considered the true concentration.

     Standard deviation of  the  results for groups of four  simultaneous

experiments ranged  from 14% to  27%, with  18% as the average value.  The

error ranged from 1%  to 35%, with an  average value of  18%,  and  was

positive  for all  the  groups of  experiments.

     Different sampling conditions were often used for each of  the  four

simultaneously operating  sampling trains.  This provided a faster way for

evaluation of  the effect  of individual sampling variables  on  method accuracy

and precision.   A variable  was  considered to have  no effect when the

difference between  the  concentration  of  HF as  analyzed and as prepared were

within  the experimental error.

     Within  experimental  error, none  of  the  variables  investigated  in  this

study was found  to  have  an  effect on  the  accuracy and  precision of  the

method.

                                       -106-

-------
     Over 90% (mcst frequently close to 100%) of the total HF absorbed in




trains was absorbed in the first impinger whenever the initial liquid volume




in the first impinger was above 40 mis.  The only exception was noted when




the sampling rate through the inipingers was reduced to 21 1/min.  Then




81% HF was absorbed in the first impinger.  These preliminary results thus




indicate that a reduction in sampling  rate may reduce absorption  efficiency




probably due to less intense turbulence.




     The conclusion of this study is that a simplified sampling train can be




used lor relatively simple and reasonably reliable determination  of  fluorides,




It is recommended for field work when  high accuracy is not required  and  the




emission stream contains only gaseous  fluorides.
                                       -107-

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     9.2.2  Remote Sensing of Fluoride Emissions

     During recent years, EPA's Environmentcil Sciences Research Laboratory

at Research Triangle Park (ESRL/RTP) has been developing remote sensing tech-

niques for gaseous pollutants.  In the course of the measurement of fluoride

emissions for a gypsum pond, described in Section 9.2.1, the ROSE System was

used for identification of the fluoride species evolving from the pond.  The

major advantages of the ROSE System over wet sampling/analysis are5:

            a.  It gives a long path  (up to 1 km) average concentra-
                tion.  This makes it a perfect tool for fugitive
                emission measurement.

            b.  It provides practically real time measurement requir-
                ing no sample handling.

            c.  It can distinguish between HF and SiF^.


     ROSE is a high-resolution IR spectrometer system.  It utilizes a Fourier-

transform interferometer to cover the 1.7-15 micron spectral region.  This

system has been installed in a van and can be used in  the long-path absorption

mode with a remote light source, or  in a single-ended  mode to observe emission

signals  from gases at elevated temperatures.  All components necessary  to ob-

tain plotted spectra in  the field are contained  in a van.6

     The main parts of the ROSE System are shown in Figure 9-5.

     For absorption measurements over paths up  to several kilometers, a Dall-

Kirkham  f/5  telescope with a  30 cm  diameter primary mirror is used  to colli-

mate energy  from  a light source.  Originally, a  1500°K blackbody was used as

the source.  Presently,  a 1000 watt  quartz-iodine lamp, which provides  sig-

nificantly more energy in the  near  IR and nearly as much  energy  in  the  middle

IR as compared with  the  blackbody,  is used.  Generally, the  light  source  and

telescope system  is  installed  in a  small  truck  and driven to a desired  loca-

tion; a  small generator  powers  the  light  source.

     The remainder of  the ROSE System has been  installed  in  a 28-foot  van.   A

telescope  identical  to that  described above  collects  energy  from the  remote light

                                     -108-

-------
                                                        VAN WALL
   REMOTE LIGHT
 SOURCE. (/5,30cm
 LIGHT
SOURCE
  -V,'-
                                                                                                 INTERFEROMETER
                                                           I
                                            FPA ROSE Infrared  Specrromocnr System

-------
source through a port in the side of the van.  To measure the signal from warm




gases exiting a smoke stack, an elliptically shaped flat mirror (mounted on




a platform attached to the van) reflects energy through the port into the




telescope.  The telescope focuses energy at the aperture of the interferometer.




The interferometer and peripheral equipment is a standard Nicolet Instrument




Corporation Model 7199 RT-IR System configured to fit into the van.  Major




components consist of a computer with 40K memory, dual-density disc with




4.8 million, 20-bit word capacity, teletype, paper tape reader, oscilloscope




interactive display unit, and a high-speed digital plotter.




     The  interferometer itself is mounted on the telescope support structure.




All other systems  (except the plotter) are arranged in two 19-inch relay racks.




Two beamsplitters, KBr and  CaF2> are currently available for use in the




interferometer.  A dual element, sandwich type detector is mounted in a




liquid nitrogen dewar.  For the 6000 to  1200 cm"1 region InSb  is used and




HgCdTe is used from 1800 to 600 cm"1, with the two regions scanned separately.




     Power  for the ROSE system, including heating or  air conditioning,  is




supplied  by a 10 kw generator.  During  operation of  the system, the generator




is  lowered  from the van to  the ground using  an electrically-operated winch.




This procedure is  necessary to avoid electrical  and  mechanical interference




with  the  operation of the  interferometer.  The entire system,  including




remote  light  source,  can be placed  in operation  at a field  site in about  one




hour  under  normal  conditions.  Auxiliary equipment  carried  in the  van




includes  a  weather station for recording wind  velocity and  temperature  and a




laser  range-finder for measuring  path  lengths.




      The first  field  use  of the  ROSE interferometer  system was at  a phosphate




 fertilizer  plant  gypsum pond.  A series of  these ponds are used at fertilizer-




plants  for  wastewater treatment.   The  ponds, which are generally rectangular
                                      -110-

-------
in shape with boundary dimensions as long as a kilometer, are particularly suitable

for long-path measurements.  The particular environmental problem presented by

these ponds is that they give off gaseous fluorides.  In past studies using wet

chemistry sampling methods, it had been possible to measure only total fluorides.

Analysis of the pond chemistry indicates that expected gaseous fluorides would

be SiF^ and/or HF.  Thus a study was undertaken at the C. F. Industries
fertilizer plant near Bartow, Florida, to determine specifically which gaseous

fluorides are emitted from the ponds.
     A series of measurements were made at various locations around several

ponds with path lengths ranging from 500 to 1000 meters.  Typical spectra
obtained are shown in Figure 9-6.  The upper spectrum was taken over a 900 meter

path at: a location known to be free of HF.  The middle spectrum was taken

over an 860 meter path across a gypsum pond.  Both spectra were taken with a

resolution of 0.125 cm"1 (molecules cm"2)"1 and a half-width of 0.04 cm"1; the

HF concentration was determined using the equivalent-width method.  The

calculations were carried  out with an existing computer  program.  For the

HF line1, shown, the path-averaged  concentration was determined  to be 45 ppb.

(It was not possible to calibrate the HF spectrum with the  sample cell

method  since our  gas handling system  is not resistant to HF.)  Absorption

due  to  the SiF^ fundamental band  centered  at  1031.5  cm"1 could not be
detected.  Calibration  spectra  indicated that 0.5 ppb of SiF,  would have
produced  about 4  percent absorption  over an 860 meter path,  and  this value
is  taken  as  a  reasonable lever  sensitivity  limit.

     Contact  with  regulatory agencies and HF manufacture  plants revealed  no

data on fluoride  emissions from gypsum ponds.   Although  gypsum ponds  used
in HF manufacture probably generate less fluorides  than  phosphate fertilizer
manufacture,  measurement  should _be  carried out  to determine the environmental

impact.   Use of  the  ROSE  System and simplified  sampling  train is recommended
for the measurement  program.
                                     -Ill-

-------
          .EP.Q_.ROSE_SYSJEM.
 o
 Q
UJO
Co..
     RTMOSPHERIC PRTH  900  METERS
     RESOLUTION =0.125 CM  -1
  LTJ
en
4168..- 4170 -  4172   4174   4176
• • '. • • "I-  '=     WflVENUMBERS -
                                 4178
   :_ GYPSUM POND .
   - RESOLUTION =
                   860 METERS
                   0.125 CM -1
  4168 _ 4170   4172   4174   4176  4178
  ._______:	WRVENUMBERS_	
       SUBTRflCTED  SPECTRUM
 «fci73.5 417^.7 4173.9 4171*.! 417*4.3 417li.~5
               WBVENUMBERS
      Figure 9-6:  Gypsum Pond Spectra
                  -112-

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10.0  ENVIRONMENTAL EFFECTS OF FLUORIDE EMISSIONS

     Fluorine is considered a welfare-related rather than a health-related

pollutant because it has no significant effect on human health in the concentrations

found in the atmosphere even under the most adverse conditions.  However, atmospheric

concentrations which can exist around processes emitting fluorine compounds can

adversely affect plants and animals, which may pose an indirect threat to our

economy and general welfare.

     In nature, fluorine is widely distributed in minerals such as fluorspar

and fluoropatite, the prime constituent of phosphate rock.  Atmospheric

fluorine contaminants are  emitted primarily  from heavy chemical industries

which utilize fluorine  compounds as  catalysts or fluxes.  The  major  sources

of these pollutants are phosphate fertilizer, aluminum and steel plants,  and

manufacturers of fluorinated  plastics and  fluorinated hydrocarbons.   The

effects of  fluorides on vegetation have been known  since  the  late  1800's,  but

it was not  until the rapid industrial expansion of  the 1940's  that its  effects

were recognized as  significant.1



10.1  Vegetation Effects

     The severity of injury sustained by vegetation exposed to fluoride con-

taminants is dependent  primarily on  the form taken  by the pollutant.  Fluoride

is taken up by absorption  into  the plant tissues, usually through  the leaves,

where it flows toward the  margins and accumulates.  This gradual accumulation,

combined with the length of exposure and total fluoride concentration in  the

ambient atmosphere, determines  the  degree  of injury.  Gaseous compounds are

probably responsible for most plant  damage since they are easily absorbed.  Most

research to date has dealt mainly with exposure  to  gaseous fluorides such as

hydrogen fluoride,  fluorine,  silicon tetrafTuoride  or fluorosilicic  acid.

Fluoride in oarticulace form  is hazardous  only when it is  soluble  and therefore

able to be  absorbed into the  plant  tissues.1
                                       -113-

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     Susceptibility

     Although all plants naturally contain varying amounts of fluorine, certain

species are more susceptible to its effects than others.  There are many factors

involved in a plant's reaction to fluorides, often making it difficult to

determine the exact cause of injury.  Certain environmental factors such as

rainfall, temperature and winds may result in Injuries which are almost

impossible to distinguish from pollution damage.3 Table 10-1 is an example

of the pollutant concentrations affecting both sensitive and resistant varieties

of some economically important crops.


                                 TABLE 1Q-12

                     HYDROGEN FLUORIDE CONCENTRATIONS
                      AND EXPOSURES FOR SENSITIVE AND
                          RESISTANT PLANT SPECIES
Plant
Corn
Tomato
Alfalfa
Sorghum
Sensitive Varieties
Concentration
2 ppb
10 ppb
100 ppb
.7 ppb
Exposure
10 days
100 days
120 days
15 days
Resistant Varieties
Concentration
800 ppb
700 ppb
700 ppb
15 ppb
Exposure
A Hrs
6 days
10 days
3 days
Most forage crops are fairly tolerant as are several species of vegetables and

deciduous trees.  Some species sensitive to fluoride are certain conifers,

fruits, berries and grasses.  These sensitive varieties generally exhibit damage

at concentrations between 0.5 ppb and 1.2 ppb for  several consecutive days.1* In

comparison, 5-10 ppm of fluoride are normally accumulated by plants in the

absence of an atmospheric fluoride source.^
                                      -114-

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     Injuries




     Probably the most apparent effect of fluoride on vegetation is necrosis




or tip-burn.  This injury is characterized by discoloration around the edges




of the leaves caused by the accumulation of fluoride in these areas.  This




is the most economically significant impact of fluoride contamination.




Although necrosis does not necessarily har-n the vegetation, the concentra-




tions may be too high to be safely ingested by animals.1*  In addition, if




the marketed portion of a plant is visibly damaged, it could result in great




economic loss, even chough actual injury to the plant may be slight.





     Exposure of vegetation of fluorides may also result in abnormalities or




a decrease  in reproductivity.  Studies have shown abnormalities in growth




including reduced leaf size, longer needles in Douglas Fir, and decreased tree




growth.  Host effects which limit or reduce growth are accompanied by visible




injury; however, if the exposure to the fluoride source occurs late in the




growing season, there may be little or no effect on the vegetation.^









10.2  Effect on Farm Animals^




     Atmospheric fluorides pose an indirect hazard to farm animals  in their con-




tamination  of forage crops by absorption and accumulation in the vegetative tissues,




Generally,  the effects of fluoride contamination are felt only on farms situated




near a fluoride-emitting facility or industries with inferior emission control




systems.  Since the inhalation of industrial emissions contributes very little




to the total intake of atmospheric fluorides, soluble fluorides are more harmful




to farm animals than the dust from phosphate rock or limestone.**




     The fluorine ingested by animals  is deposited almost entirely  in the bones.




While adult animals normally have concentrations of about 500 ppm  in  their  bones,




it takes concentrations of 5000 ppm before' visible signs of  the pollutant's




effects are apparent.3




                                      -115-

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     The studies performed on farm animals to date have revealed a sequence in

which the effects of fluoride contamination appear.  These are:
        Dental lesions, primarily in the incisors
        Hyperostosis, or bone overgrowth
        Lameness
        Loss of appetite
        Decrease in milk production
        Reduced reproduction
The last two effects are believed to occur from the decreased food intake caused

by the loss of appetite.  In one study performed, cattle were fed forage con-

taining 600-1200 ppm of fluoride, resulting in a 50% decrease in food consumption

due to their loss of appetite.  Economically, this is the most serious effect

of fluoride contamination in farm animals.^

     A continuous intake of 40-50 ppm of fluoride eventually results in the

destruction of incisors, meaning inhibited grazing and great economic loss.

However, this damage occurs  slowly; thus the  economic impact would not reach

its maximum until exposure had  continued for  about five years.  Dental injury

would also not be more  likely to occur in young animals, and would not be

expected in adults.14  Table  10-2 lists the fluorine which can be ingested

safely by  livestock.


                                 TABLE 10-2a
                   SAFE LEVEL  OF  FLUORINE IN LIVESTOCK FEED
                                                   Source
Animal
Dairy Cattle
Beef Cattle
Sheep
Swine
Chicken
Turkey
Soluble Fluoride
(ppm)
30-50
40-50
70-100
70-100
150-300
300-400
Rock Phosphate
(ppm)
60-100
65-100
100-200
100-200
300-400
-
                                      -116-

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       Fortunately,  animals  having  high fluoride  concentrations  in  their  bones  do




   not have  contaminated meat or milk.   Their loss of  appetite  will  affect




   their  production,  but the  pollutant  is not passed on.   Nursing calves do not




   suffer from fluorosis  (abnormal calcification of the teeth)  until they  begin




   grazing contaminated forage.2








   10.3   Effects in Man




        Regardless of the  source of the fluoride its effects are  essentially




   the  same; hyperostosis  and fluorosis. Generally these conditions  occur  only in




   growing children.3




        The  current threshold limit value for hydrogen fluoride  is  3 ppm, while




   the  limit for particulate  fluoride is 2.5 mg/m3. Owing to these  occupational




   limits, persons seldom  are exposed to such concentrations, and very few cases




   of adverse effects from atmospheric fluoride occur, even in proximity  to




   industrial sources. The maximum daily concentration inhaled near fertilizer




   facilities is about 150 ug which is insignificant when compared to concentra-




   tions of  1200 yg received  from food and water.2




        In man, the airborne  fluorides are absorbed through the skin and  from the




   respiratory tract and  are  accumulated in bones  and  teeth.  The more soluble




   fluorine  compounds are  absorbed from the gastrointestinal tract into the  blood




'   much more readily than  less soluble compounds.   These are the  forms that  will




   accumulate in the bone  structures.2  Studies have revealed that the body is able




   to absorb 87% of calcium fluoride from cryolite, 62% of sodium fluoride,  and




   37% of calcium fluoride derived from bonemeal.   About half of  the absorbed




   fluoride  is excreted,  with the remainder being accumulated in the bones.3




         Since  research done  to  date  indicates  that airborne fluorides  not not




   present  a direct  threat to man except from  uncontrolled  occupational exposures.
                                        -117-

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Their significant impact to man lies in the potential for economic loss by

contamination of plants and animals.



10.A  Other Effects

     Fluoride is capable of etching glass at concentrations of 590 ppb for a

period of 9 hours and pronounced etching occurs at concentrations of 790 ppl

for 14.5 hours.  However, severe damage seldom or never occurs due to the

emission regulations imposed on industry.1*

     Fluorides also have a damaging effect on the high silica brick lining of

furnace walls used in aluminum processing.1*

     Hydrogen fluoride is especially significant in the reactions between

fluorides and silicon compounds which result in damage to ceramics and glass.

However, it is very difficult to isolate the effects of fluorides from other

background pollutants.



10.5  References

1.  Jacobson, Jay, Hill, A. Clyde,  1970.   Recognition of Air Pollution
    Injury to Vegetation:  A Pictorial Atlas, Informative Report No. 1
    APCA,, Pittsburgh, PA, pp D-l -  D-6.

2.  Office of Air  Quality Planning  and Standards,  1976.  Final Guideline
    Document:   Control  of Fluoride  Emissions from  Existing  Phosphate
    Fertilizer  Plants.   Office of Air and  Waste Management, U.S. Environmental
    Protection  Agency,  pp. 2-1 - 2-10.

3.  Stern, Arthur  C., 1977.  Air Pollution Volume  II, New York, p. 169.

4.  Robinson, J.M. et al.  Engineering and Cost Effectiveness  Study of
    Fluoride Emissions  Control Volume  I.   TRW Systems Group, McLean, VA,
    1972, pp. 5-1  -  5-11.
                                      -118-

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11.0 EMISSION REDUCTION WITH NEW SOURCE PERFORMANCE STANDARDS




11.1 Introduction




     Model IV is a methodology developed by EPA's Emissions Standards and




Engineering Division which quantitatively estimates the anticipated impact of new




or revised standards of performance in reducing atmospheric emissions.  Model IV




mathematically relates emission producing activities, such as industrial growth,




and offsetting emission control activities such as existing regulations, NSPS,




and the Clean Air Act.  The resulting net emissions are projected for target




years.




     Using Model IV, the differential in atmospheric emissions that could be




expected with and without NSPS can be expressed and the potential for additional




controls evaluated.  For example, a maximum emission differential or NSPS impact




would be observed for an industry for which a stringent standard of performance




was technically feasible, but for which there were no existing state emission




limitations.  On the other hand, a minimum or zero emission differential NSPS or




impact would be observed for an industry if a standard of  performance repre-




senting best control technology was generally equal to existing state regula-




tions.  NPS would have  few beneficial effects in  the latter case in reducing




emissions.




     TRC  in  a 1976  EPA  report1 developed Model  IV data and results for  approxi-




mately 190 industrial categories,  including  hydrofluoric  acid.




     Utilizing  the  best available  1978  data, TRC  has updated  the Model  IV




input variables  to  calculate  the estimated  impact of instituting New  Source




Performance  Standards based on best available control  technology.
                                        -119-

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!1.2 Model IV - Background Information



     The impact of new or revised standard of performance is expressed  in Model  IV




                (T  - T)
Where:    T  * emissions under baseline year control regulations.



          T  = emissions under new or revised standards of performance.
     Factors such as increased production capacity, construction  to replace



obsolete capacity, control technology,  and present  allowable  emissions  are



used to develop the above relationship.  Table  11-1 defines these parameters



used in the Model IV equations.  From the input variables, T   and !„  the



total emissions in the ith year under baseline  year regulations and revised



standards of performance, respectively,  are  calculated, where:



               T  = E K  (A-B) + E K  (B+C)          (11-1)
                S    S           S


                       (A-B) + EL.K  (B+C)           (11-2)
                       = K  (B+C)  (Eg -  F^)         (11-3)
Other related equations  are:




1)  Assumption of compound  growth   B  = A [(1+PA)  """-I]   (11-4)



                                    C  = A [(1+P  )  X-l]   (11-5)
 2)  Assumption  of  simple  growth    B = Ai P            (11-6)



                                    C - Ai P            (11-7)
                                            c
          Where  i  =  elapsed time in years.
                                       -120-

-------
3)  baseline year emissions        T « E KA             (11-8)
                                    A   S
4)   Uncontrolled emissions        T = E K  (A-B) + E K  (B+C)      (11-9)
5)  For pollutants regulated under Sec. lll(d) of  the Clean Air Act.



               TNP" Elll(d)K (A-B)
     Where £..,,,.= allowable emissions as required by  Section  lll(d)


           G_ = total emissions in  ith year under Section  lll(d)
     For these calculations  the baseline  year  is  defined  as- 1977  and  the


ith year, 1987.
                                       -121-

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                               TABLE  11-1.
                         MODEL  IV  INPUT VARIABLES
 T = total emission in i   year under baseline year regulations


      (tons/yr)




                        th
 T = total emission in i " year under new or revised NSPS which

                                    th
     have been promulgated in  the j   year  (tons/yr)





 T = total emissions  in i   year assuming no control  (tons/yr)
 T  =  total  emissions  in  baseline  year  under  baseline  year  regula-


      tions  (tons/yr)
   K=  normal  fractional  utilization rate of  existing capacity,


      assumed constant during time interval





   A=  baseline year production capacity (production units/yr)





   B=  production capacity from construction  and modification to


      replacement obsolete facilities (production units/yr)





   C=  production capacity from construction  and modification to


      increase output above baseline year capacity (production


      units/yr)





  ? =  construction and modification rate to  replace obsolete capacity


      (decimal fraction  of baseline capacity/yr)





  P =  construction and modification rate to  increase industry capacity
   u

      (decimal fraction  of baseline capacity/yr)





E = allowable emissions  under existing regulations  (mass/unit capacity)
                                   -122-

-------
   E« allowable emissions under standards of performance (mass/unit capacity)

   E» emissions with no control (mass/unit capacity)

   For the purpose of this study, the i   year is defined as 1987 and the
jth year, 1977.
                                      -123-

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 11 . 3  Industrial  Factors
K. Factor
     K is the normal fractional utilization rate of existing capacity.  The
fluorocarbon ban and aluminum inventory surplus have affected the product!* n
of hydrofluoric acid and chis significant decrease is reflected in K Factor.
In the baseline year, 1977, production of hydrofluoric acid was 74% of
capacity, based on production and capacity da<_a for the HF industry.  In
the following five year span, plants project a small or zero increase in
production.  In addition, major HF production facilities in Louisiana
and Texas will be ceasing operations, and in 1982 utilization of 70% of
the industry capacity is projected.  The estimated K Factor for the entire
1977-1987 period is  73%.


?  Factor
     ?„  the construction rate to increase  industry  capacity,  is expected
      ^ >
 to be zero during  the  ten year period  1977-1987.   The  1977  baseline capacity
 of 369 thousands tons  of hydrofluoric  acid  is  not  expected  to  be exceeded
?B Faccor
     As with P   ?    the.  construction and  modification rate  to  replace
              L;  a,
obsolete capacity is  projected  to  be  zero  during 1977-1987.


A Factor
     The A Factor is  the  1977 baseline year capacity.   As previously
stated, the 1977 capacity for the  hydrofluoric acid industry is 369
thousands tons of anhydrous  HF.
                                     -124-

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               Assuming 99% particulate removal efficiency,



               E  = 3500 Ib./ton 100% HF
     For allowable emissions, the average process weight rate is calculated



as:
     96__tpn_acid      x       3500 Ib. fluorspar   x           . 34,000/lb./

                                   ton acid           24 hr'     fluorspar hr.
     Allowable particulate emissions are determined for each state based



on the above process weight rate and weighted according to the fractional



capacity occurrence for 1977.  Allowable emissions were calculated to be



19.5 Ib./hr.  It should be noted that West Virginia has no particulate


regulations  for  the HF  industry  based  on an  inconsistency in the state  air



pollution law.
     E  is calculated for 19.5 Ib./hr. and 96  tons of acid per day  to  be



4.9 Ib./ton acid.  However,  35 Ib./ton HF is the best control technologically



feasible.  Therefore, E  = F~^ as  control regulations can  only be  set as
                       S     ^i


low as current technology will permit.
                                      -125-

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     Exit gas streams from the HF process are scrubbed with jets and sprays



to remove SC>2 and fluoride emissions.  The estimated removal efficiency for



sulfur dioxide by the scrubber is 96% - 99%.  Therefore,



               E^ - 0.1 Ib./ton 100% HF







     The allowable sulfur dixoide emissions from process systems vary from



state to state.  West Virgina, Louisiana, Ohio and New Jersey limit sulfur



dioxide process emissions to 2000 ppm.  Other states do not have any appli-



cable regulations.  Assuming an average kiln emission flow rate of 5000 scfo



and an average capacity of 96 tons of acid/day for each of the eleven (11)



existing HF plants, the allowable sulfur dioxide emissions can be calculated



for the regulated states.  For Louisiana, New Jersey, West Virginia, and Ohio,



E  equals 25 Ib./ton 100% KF.
     These limits for E  are greater than E    Therefore, for all states
                       s                   u.


the allowable S02 emissions are equal to uncontrolled S02 process emissions



and E  = E
     s    u.
Particulate Emissions



     Particulates are  released during  the  drying  of  fluorspar.  Literature



values are not available  specifically  on particulate emissions  for  uncontrolled



sources  in hydrofluoric acid manufacture.   However,  use  of  a  baghouse  can



achieve  99% particulate removal.   In addition,  particulate  emissions for a



well-controlled  plant  have  been  estimated  at  20 Ib./ton  fluorspar.2 Using



3500 Ib.  fluorspar/ton 100% HF,  best available  controlled emissions with



a  baghouse are:



               E =  35 Ib./ton 100% HF
                                     -125-

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11.A Emission Factors




Acid Production




     Hydrofluoric acid is produced by the reaction of fluorspar with sulfuric



acid in a rotary kiln.  One ton of anhydrous HF requires 3500 Ib. fluorspar




 '28C' Car-', and 6400 Ib. I^SO^.  While the grade of HF acid produced varies,



952 anhydrous and 5% 70% grade acid is typical of plant production.








Fluoride Emissions



     Uncontrolled fluoride emissions from a rotary kiln have been estimated




at 50 Ib./ton of acid.2




     Therefore, E  = 50 Ib./ton acid.



     The best available control technology for control of fluoride emissions



is use of a wet scrubber j with a removal efficiency over 99%.  E  for  the



controlled emissions of fluorides is estimated at  .2 Ib./ton acid.




     As there are no regulations for fluoride emissions  (other  than  ambient  air




limitations), the allowable emissions of luorides,  E  ,  is  equal to  the  uncon-




trolled emissions.  Therefore,




                E = E  =50 Ib/ton  acid.
                 s    u


Sulfur Oxide Emissions




     While the  sulfuric acid  in the hydrofluoric acid  reaction  produces a



calcium sulfate  slurry, sulfur in acid  grade fluorspar creates  sulfur



dioxide emissions.



     Fluorspar  is approximately 0.03% sulfur content,  assuming  3500  Ib.




fluorspar produces one ton of anhydrons  HF,  1.05  Ib.  S or  2.1  Ib.  S02



are  emitted per  ton of 100% hydrofluoric acid.  Therefore,



                E  = 2.1 Ib./ton 100% HF
                                      -127-

-------
11.5 Results of Model IV Calculations




     Table 11-2 summarizes the Model IV industrial and emission factors




for  the hydrofluoric acid industry.
                                   TABLE 11-2




          MODEL IV INDUSTRIAL AND EMISSION FACTORS - HYDROFLUORIC ACID
Pollutant
Fluorides
Sulfur oxides
Particulates
emission factors
E
u
*N
E
s
Ib/ton 100% HF
50
2.1
3500
0.2
0.1
35
50
2.1
35

K

73%
73%
73%
growth rates
PB
/yr
0
0
0
pc
/yr
0
0
0
industry capacity j
A
B
ton/vr 100% HF
369xl03
36 9x10 3
369xl03
0
0
0
c

0
0
0
     Utilizing the input parameters outlined in Table 11-2, the 1987 impact




of new source performance standards, T  - T  , was calculated to be zero




for the hydrofluoric acid industry.  This is due to the projected lack of




increase in production capacity, a result of the fluorocarbon ban and aluminum




inventory surplus.




     In addition, a  review of emissions control on an industry-wide basis




indicates that most  plants are  currently utilizing best control technology




 (e.g. - baghouse  and scrubbers).  There is not enough data on HF and




fugitive emissions to draw a clear conclusion on plant emissions, but it




appears that little  pollution reduction would be achieved by retrofitting




existing plants.
                                       -128-

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11.6 References
1.   Impact of New Source Performance Standards on 1985 National Emissions
     from Stationary Sources, TRC - The Research Corporation of New England
     Report to EPA - 450/3-017.

2.   Compilation of Air Pollutant Emission Factors (2nd Ed.) EPA Publication
     No. AP-42, April 1973.

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12.0  LIST OF CONTACTS

Plants

ALLIED CHEMICAL
Corporate
Mr. M. C.. Mosher
Supervisor
Environmental Administration
Industrial Chemicals  Division
Allied Chemical
P 0 Box  1139 R
Morristown, N J 07960
Telephone:(201)455-3888
Mr. W. M. Reiter, ?.E.
Director,, Pollution  Control
Corporate Environmental  Services
Allied Chemical
? 0 Box 1057 R
Morristown, N J  07960
Telephone:(201)455-6159
 Baton  Rouge, LA

 Mr. M. Lapari  - Environmental Supervisor
 Mr. D. Templet - Production Manager
 Specialty Chemicals  Division
 Allied Chemical
 P  0 Box  2830
 Baton  Rouge, LA 70821
 Telephone:
Mr. Anthony J. Stewart
Division Patent Council
Industrial Chemicals Division
Allied Chemicals
Law Department
Corporate Headquarters
P 0 Box 1057 R
Morristown, N J 07960
Telephone:(201)455-4033
Geisaar, LA

Mr. W. J. Dessert, Superintendent
    Process & Environmental
    Engineering
    Agricultural Division

Mr. H.L. Arnold, Plant Manager
Allied Chemical
Geismar Complex
P 0 Box 226
Geismer, LA 70734
Telephone:(504)642-8311
 Pittsburg,  CA

 Mr.  F.  G.  Nicar,  Plant Manager
 Industrial Chemicals Division
 Allied  Chemicals
 Nichols Read
 Pittsburg,  CA 94565
 Telephone:(415)453-3292

 Nitro,  T«.  V.
 Contact  through M.  C.  Mosher
 Corporate  Office
                                      -130-

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DUPOHT
Corporate

Mr. R. H. Morgan
Environmental Affairs-N-6537
Petrochemical Department
E. I. DuPont De Nemours & Co.,
1007 Market Street
Wilmington, DE 19898
Telephone:(302)774-7662
Inc.
ALCOA

Corporate

Mr. P. R. Atkins
Manager-Environmental Control
Aluminum Company of America
1501 Alcoa Building
Pittsburgh, PA 15219
Telephone:(412)553-3805
La Porte, TX

Mr. R. H. Johnson
Environmental Coordinator
Biochemicals Department
E. I. DuPont de Nemours & Co.,
Houston Plant
P 0 Box 347
La Porte, TX 77571
Telephone:(713)471-2771
Inc.
Point Comfort, TX

Mr. J. C. Mayfield
Mr. A. A. Rambikur
Operations Environmental Control
    Superintendent
Aluminum Company of America
State Highway 35
Point Comfort, TX 77978
Telephone:(512)987-2631
Mr. A.R. Ceperley
Area  Supervisor-Technical

Mr. C. L. Tice
Engineer-Technical
Biochemical Department
E.  I. DuPont  de Nemours  &  Co.,
Houston  Plant
P 0 Box  347
La  Porte, TX  77571
Telephone:(713)471-2771
Inc.
 EAaSHAW

 Mr.  S.  J.  Gunsel
 Manager, Pollution Control

 Mr.  Joseph Berish
 Director of Environmental  Control
 The  Harshaw Chemical  Company
 1945 E. 97th Street
 Cleveland,  OH 44106
 Telephone:(216)721-8300
                                      -131-

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ESSEX

Corporate

Mr. R. Wagner
Vies President of Operations
Essex Chemical Corporation.
1401 Broad Street
Clifton, N J
Telephone:(201)773-6306
STAUFFER

Corporate

Mr. E. C. Conant

    T. Savers
Stauffer Chemical Company
Westport, CT 06880
Telephone:(203)222-3000
Paulsboro, K J

Mr. James Ferguson
Plant Supervisor
Essex Chemical Corporation
100 Thomas Lane
Paulsboro, N J
Telephone:(609)423-2050
Greens Bayou, TX

Mr. G. W. Fry
Plane Manager
Industrial Chemical Division
Stauffer Chemical Company.
1632 Haden Road
Houston, TX 77015
Telephone:(713)453-7175
KAISER

Mr.  R. W.  Curtis
Chief Environmental  Engineer
Kaiser Aluminum &  Chemical  Corporation
P  0  Box  337
Gramercy,  LA 70052
Telephone:(502)395-7121
 PE3NWALT

 Mr.  C.  ?.  Dalrymple
 Supervisor,  Environmental Affairs
 Pennwalt  Corporation
 Calvert City,  KY 42029
 Telephone:(502)395-7121
                                     -132-

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                  STATE & LOCAL REGULATORY AGENCIES
TEXAS

Mr. T. Palaer
Corpus Christy Office
Texas Air Control Board
1305 Shoreline Blvd. #124
Corpus Christi, TX
Tel:(512-3332961

Mr. W. N. Allen
Texas Air Control Board
8520 Shoal Creek Blvd
Austin, TX 78758
Tel:(512)451-5711
Mr. G. Speller

    N. P. Peer
Texas Air Control Board
Air Quality Control Region 7
5555 West Loop, Suite 300
Bellaire, TX 77401
Tel:(512)451-5711
LOUISIANA

Mr. G. Vonbodungen
Louisiana Air Pollution Control Conmissio:
Baton Rouge, LA
Tel:(504) 563-5120
CALIFORNIA

Mr. W. deBoisblanc
Bay Area Air Pollution Control District
939 Ellis Street
San Francisco, CA 94109
Tel:(415)771-6000
NEW JERSEY

Mr. A.  F. DiGenni
State of New Jersey
Department of Environmental  Protection
100 Larvin Road
Cherry  Hill, N J 08034
Tel:(609)795-7390
                                     -133-

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                STATE & LOCAL REGULATORY AGENCIES (con't)
OHIO

Mr. Lian Ang
Ohio EPA
Division of Air Pollution Control
2735 Broadway Avenue
Cleveland, OH
Tel:(216)664-3508
WEST VIRGINIA

Mr. D. Stone

lie. R. Weiser
West Virginia Air Pollution
Control Commission
1558 Washington Street, East
Charleston, W V 25311
Tel:(304)348-3286
KENTUCKY

Mr. S. M. Murphy

    J. T. Smither
Commonwealth of Kentucky
Department of Natural  Resources  &
    Environmental Protection
Frankfort, KY 40601
Tel:(502)504-3382
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                                   TECHNICAL REPORT DATA
                            (Please read Instructions on the reverse before completing/
  REPORT NO.
  EPA 450/3-73-109
                                                           3. RECIPIENT'S ACCESSION NO.
  TIT.E AND SUBTITLE
  Screening Study on  Feasibility of Standards  .
  Performance for Hydrofluoric Acid Manufacture
 of
             5. REPORT DATE
              October,  1978 Date of Issue
             6. PERFORMING ORGANIZATION CODE
7. AUTHCR(S)

 Vladimir iJoscak
                                                           8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
 The Research Corporation  of New England
 125 Silas Deane Highway
 Wethersfield, CT  06109
                                                            10. PROGRAM ELEMENT NO.
             11. CONTRACT/GRANT NO.
              68-02-2615/Task 6
12. SPONSORING AGENCY NAME AND ADDRESS
   DAA  for Air Quality  Planning  and  Standards
   Office of Air,  Noise,  and  Radiation
   U.S. Environmental Protection Agency
   Research Triangle Park,  NC 27711
             13. TYPE OF REPORT AND PERIOD COVERED
               Final	
             14. SPONSORING AGENCY CODE

                   EPA 200/04
15. SUPPLEMENTARY NOTES
16. ABSTRACT
       This report  contains  background information  on the hydrofluoric  acid  manu-
  facturing industry  such  as the number of  plants,  their size, and location.   This
  information was obtained in the open technical  literature and through  visits  to
  several typical plants.
       The economic profile  of the industry indicates there will be no  growth  in
  the next five years.
       General description of the manufacturing  process, emission sources, emission
  rates, and controls  are  the main part of  the report.   Detailed descriptions  of
  processes, production, emissions, and control  at  eleven plants are  compiled  in EPA's
  confidential files.   State and local emission  regulations and emission  source
  sampling and analysis methods are also discussed.
       The background  information has been  used  in  a simple emission  projection
  model  (Model IV)  to  determine the emission  reductions that could be achieved by
  the application of  New Source Performance Standards.
17.
                                KEY WORDS AND DOCUMENT ANALYSIS
                  DESCRIPTORS
b.lOENTIFIERS/OPEN ENDED TERMS  C.  COSATI Field/Group
 13. DISTRIBUTION STATEMENT

  Release Unlimited
19. SECURITY CLASS /This Report/
  Unclassified
21. NO. Or PAGES
        145
                                               20. SECURITY CLASS (Thispage/
                                                 Unclassified
                                                                          22. PRICE
 EPA rorm 2220-1 (Re». 4-77)   =ie.-lOUS  EDITION IS OBSOLETE

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