United States
             Environmental Protection
             Agency
            Office of Air Quality
            Planning and Standards
            Research Triangle Park NC 27711
EPA-450/3-91-023
September 1992
             Air
                                PBR3-1.
&EPA
Carbon  Disulfide Emission

        Control Options
             control
           technology center

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                                                     EPA-450/3-91-023
Carbon Disulfide Emission Control Options
          CONTROL TECHNOLOGY CENTER
                      Sponsored by

                Emission Standards Division
         Office of Air Quality Planning and Standards
            U.S. Environmental Protection Agency
             Research Triangle Park, NC 27711
       Air and Energy Engineering Research Laboratory
            Office of Research and Development
            U.S. Environmental Protection Agency
             Research Triangle Park, NC 27711

                                     U.S. Environmental Protection Agency
                                     Region 5, Library (PL-12J)
                                     77 West Jackson Boulevard, 12th Floor
                     September 1992   ChiCa8°' IL  60604-3590

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                                                   EPA-450/3-91-023
                                                     September 1992
Carbon  Disulfide Emission Control Options
                           by

                R. Gupta, L. Harris, and D. Tulis
                TRC Environmental Corporation
                      100 Europa Drive
                         Suite 150
                   Chapel Hill, NC 27514
           EPA Prime Contract 68D00121
           Work Assignment Number 1-62
                      Project Manager

                      Deborah Elmore
                  Emission Standards Division
        Office of Air Quality Planning and Standards (OAQPS)
              U.S. Environmental Protection Agency
               Research Triangle Park, NC  27711
                       Prepared for:

                  Control Technology Center
              U.S. Environmental Protection Agency
           Research Triangle Park, North Carolina 27711

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                                   DISCLAIMER
      This report has been reviewed by the Control Technology Center (CTC) established by
the  Office of Research and Development (ORD) and Office  of  Air Quality Planning  and
Standards (OAQPS) of the U.S. Environmental Protection Agency (EPA), and has been approved
for publication.  Approval does not signify that the comments necessarily reflect the views and
policies  of the  EPA, nor does mention of trade names or commercial  products constitute
endorsement or  recommendation for use.  This document was not prepared in support of any
rulemaking effort.

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                             ACKNOWLEDGEMENTS
      This report on  emissions control options for carbon disulfide was  prepared for  Ms.
D. Elmore of EPA's Control Technology Center (CTC) by R. Gupta, L. Harris, B. ScheU, and
D. Tulis of TRC Environmental Corporation (TRC),  Chapel Hill, NC.  Assisting in the project
were J. Durham of the EPA, B. Blaszczak of the CTC, and S. Samuels of TRC.  The authors
would like to thank the many individuals who supplied the information necessary to make this
report possible. These include the individuals at the EPA library who ran the Chemical Abstracts
(CA) literature search; F. Vollero of Procedaire Industries; J. Jacox of Nucon  International Inc.;
M. Macintosh of Argonne National Laboratory; R. Hagen of Akzo Chemicals; C.D. Cannon and
associates  at BASF;  T.  Moore of Texaco  Chemical  Company; and R.  Rafson  of Quad
Environmental Technologies Corporation.
                                        ui

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                                      PREFACE

       This project was funded by EPA's Control Technology Center (CTC) and prepared by
 TRC Environmental Corporation (TRC).

       The CTC was established by EPA's Office of Research and Development (ORD) and
 Office of Air Quality Planning and Standards (OAQPS) to provide technical assistance to State
 and local air pollution control agencies.  Several levels of assistance can be accessed through the
 CTC.  First, a CTC Hotline has  been  established to provide  telephone assistance on matters
 relating to  air pollution control technologies.  Second, more in-depth engineering assistance can
 be provided when appropriate. Third, the CTC can provide technical guidance through designing
 technical guidance documents, developing personal computer software, and presenting workshops
 on  control  technology matters. The CTC is also the focal point of the Federal Small Business
 Assistance  Program, and maintains the Reasonably Available Control Technology/Best Available
 Control Technology/Lowest Achievable Emission Rate (RACT/B ACT/LAER) Clearinghouse and
 the Global  Greenhouse Gases Technology Transfer Center.  Information concerning  all CTC
 products  and services can be accessed through the CTC Bulletin Board System (BBS), which is
 part of the  OAQPS Technology Transfer Network (TTN) bulletin board system.

       The technical guidance projects, such as this one, focus on topics of national or regional
 interest and are identified through contact with State and local agencies or private organizations.
 In this case, the  CTC Hotline was accessed by  numerous  agencies seeking information on
 controlling  carbon disulfide emissions.  The interest in this topic warranted development of a
technical document on carbon disulfide emissions control options.   This document briefly
discusses various options available to public and private industry for controlling carbon disulfide
emissions, and serves as a reference source for those seeking  further information.

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                            TABLE OF CONTENTS

Section                                                                   Page

DISCLAIMER  [[[  ii

ACKNOWLEDGEMENTS ............................................  ft

PREFACE  [[[  iv

LIST OF FIGURES
                                                                           v
1.0    INTRODUCTION
      1.1    Purpose of Report
      1.2    Project Methodology
2.0    CARBON DISULFIDE: BACKGROUND INFORMATION ................   3
      2.1    Physical Properties  .......................................   3
      2.2    Chemical Properties .......................................   4
      2.3    Production and End-Uses ...................................   4
      2.4    Health Effects Summary  ................................. [\   5
  f                                          f
3.0    EMISSION SOURCES FOR CARBON DISULFIDE  ....................   7
      3. 1    Viscose Process .........................................   7
      3.2    Carbon Tetrachloride Production ..............................   9
      3.3    Other Processes .........................................    10

4.0    CONTROL TECHNIQUES  ......................................  12
      4.1    Absorption  ....................................             p
            4.1.1   Method 1: Oil Absorption .............................  12
            4.1.2   Method 2: International Patent No.  WO 86/02283  ...........  13
            4.1.3   Method 3: Diglycolamine Agent  ........................  16
            4.1.4   Conclusions  ...................................       16
      4.2    Adsorption  ..................................               17
            4.2.1   Method 1: Activated Carbon  .......................       17
            4.2.2   Method 2: Synthesized Sorbent: European Patent EP 189606  ....  20
            4.2.3   Conclusions  ................................         21
      4.3    Ventilation and Condensation Recovery System  ..............        i\
      4.4    Absorption/Oxidation: U.S. Patent 4,049,775 ................... ' .  24

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                      TABLE OF CONTENTS (continued)



Section                                                               „
                                                                     Page




      4.7   Control with a Bioreactor	                          -71

      4.8   Wet Scrubbing  	'.'.'.'.'.'.'.'.'.'.'.'.'.'.'.'.'.'.'.	  31

      4.9   Current Research	[[	  33



REFERENCES  	                                               „,

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                                LIST OF FIGURES
Number                                                                      Page
1.  Viscose Process 	   g
2.  Oil Absorption System  	   \\
3.  Carbon Tetrachloride Production	   14
4.  Adsorption Recovery System	   19
5.  Ventilation and Recovery System	   22
6.  BASF Carbon Disulfide  Recovery System	   23
7.  Wet Method of Carbon Disulfide Control  	   25
8.  Thermal Oxidation System	   28
9.  Catalytic Conversion	   30
10. Control With a Bioreactor	   32
11. Wet Scrubbing	•	   34
                                       vu

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                     CARBON BISULFIDE CONTROL OPTIONS

 1.0    INTRODUCTION

 1.1    Purpose of Report

       The EPA Control Technology Center (CTC) has received a number of inquiries regarding
 control options for carbon  disulfide emissions. This report presents a description of methods or
 techniques to control carbon disulfide emissions from a variety of source categories (Section 4.0).
 The control techniques presented represent potential control  options, as many of them have not
 yet been proven in an  industrial environment.  The report also contains background information
 on carbon disulfide (Section 2.0) and a discussion of carbon disulfide emission source categories
 (Section  3.0).

 1.2    Project Methodology

       The project was initiated by a comprehensive literature search involving several computer
 databases (i.e., Chemical Abstracts, PTS-Prompt, Chemical Economics Handbook, Kirk-Othmer).
 The computer search provided information primarily on foreign applications by locating patents
 related to control of carbon disulfide emissions.  The reader  should be aware that these patents
 may represent carbon disulfide emissions control options that are still in research or experimental
 stages.   The  computer  search  was  also  able  to  provide  some  information  on domestic
 applications;  however, the bulk of the information for domestic  applications  came  from
 discussions with vendors and plant operators.

       Vendors were able to supply substantial information on equipment and solvents that they
 felt may be used as control  options.'  Industry, however, was very conservative with information
about their process conditions and particular control configurations.  It should be noted that any
information ootamed from  plant  operators  may not be complete to the  extent ot supplying

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technical process  descriptions/diagrams.  The Chemical Manufacturer's Association (CMA)
provided significant information for this document

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2.0    CARBON BISULFIDE: BACKGROUND INFORMATION

       The following  four  subsections  outline the physical/chemical properties  of  carbon
disulfide, current production information and trends, major end-uses of carbon disulfide, and
health effects of carbon disulfide exposure.

2.1    Physical Properties

       Carbon disulfide is a clear and colorless liquid with a mild ethereal odor; however, minor
impurities impart a disagreeable sulfurous odor.  It is slightly soluble in water and an excellent
solvent for many organic  compounds. The physical properties are listed below (1,2,3).
PROPERTY

latent heat of fusion kJ/kg
boiling pt at 101kPa,°C
flash point at 101kPa,*C
ignition temp in air, *C
10-s kg tune
0.5 -s lag time
critical temp, "C
critical density, kg/m3
critical pressure, k/Pa
Liquid at temp, "C
density, kg/in3
specific heat, Jfkgxk)
latent heat of vap kj/kg
surface tension, mN/m3
thermal conductivity, W/mxK
viscosity, mPaxs
refractive index
soly in HjO, g/kg sol'n
vapor pressure kPa
Gas at temp, °C
density, kg/m3
specific heat. JfkgxK)
viscosity, mPaxs
thermal conductivity, WYrnxK

0(32"F)
1293 (98.1 Ib/ft3)
984
377 (33634 caWb)
35.3 (35.3 dynes/cm)
0.429
1.6436
2.42
16.97 (0.17 atm)
4(5.25 (114.8°F)
2.97(0. 19 Ib/ft3)
611
0.0111
0.0073
1 hermocnemical data at 298 K (77°F)
heat capacity, Cp, J(mokK)
sntropy, S, J(mokK)
neat 01 formation. Hf. kJ/mol
~ ""•"' " "' -• i-"^— •— • __B^ _.. ~^-____
VALUE ~]
161.11 (-169.7'F)
57.7 (5148 cal/lb)
46.25 (114.8*F)
-30 (-22-F)

80-120 (176-248'F)
156 (31Z8'F)
273 (523.4'F)
378 (28.7 Ib/fO
7700 (76 atm)
20(68T)
1263 (95.8 Ib/ft3)
1005
368 (32832 caWb)
32.3 (32.3 dynes/cm)
0.161
0.367
1 6276
2.10
39.66 (0.39 atm)
200 (392°F)
1.96 (0.12 Ib/ft3}
(V7Q
0.0164

46JS (114.8°F)
1224 (9Z9 Ib/ft3)
i fyin
355(31671 cal/lb)
28.5 (28.5 dynes/cm)
0305

048
101.33 (1.00 atm)
400 (752°F)
1.37 (0.09 Ib/ft3)
730
0.0234

45.48
237 8
117.1 (27,988 cal/mol)
free energy of formation, W/moi ™ '15'989 «"""»

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 Carbon disulfide is soluble in most organic solvents and completely miscible with many liquid
 hydrocarbons, chlorinated hydrocarbons, and alcohols.

 2.2    Chemical Properties

       Carbon disulfide is highly  flammable and is  easily ignited by sparks or hot surfaces.
 Greater availability of oxygen or lower pressure may cause a considerable lowering of the flash
 point temperature. The flammability or explosive range of carbon disulfide with air is very wide
 and  depends upon  the conditions.  Concentrations of 4  to 8 percent carbon disulfide in  air
 explode with maximum violence.  The upper explosive limit (UEL) and lower explosive limit
 (LEL) for carbon disulfide in air are 50 percent and 1 percent, respectively (4). In practice, for
 safety reasons control equipment must be designed to operate above the UEL or below the LEL.
 The  thermal energy released in carbon disulfide explosions is low compared to that from other
 flammable substances.  The maximum absolute pressure developed is reported as 739 kPa (7.30
 atm).

 2.3    Production and End-Uses

       In  1989, carbon disulfide was primarily used as a chemical intermediate, and production
 was  estimated to be 340 million  pounds.  At one time, carbon disulfide was used mainly as a
 solvent.  However, most carbon  disuifide 1S currently used in the synthesis of other chemical
 products. Approximately 40 percent of U.S. production of carbon disulfide  Ls used in the viscose
 process of regenerating cotton and wood cellulose to make rayon and cellophane.   Carbon
 tetrachloride production also accounts for over  40  percent of U.S.  consumption of carbon
disulfide. This usage level of carbon disuifide is expected to decline through  the 1990s, because
the demand for carbon tetrachloride is expected to decline (its predominant end  use  is in the
production  of fluorocarbon gases).  Other products made from carbon  disulfide include  rubber
                                          4

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 accelerators for vulcanization, mercaptans added to fuel gases to impart detectable odors, certain
 synthetic polymers, oils, fats and waxes.  It is also used as a solvent for paraffins and waxes in
 oil wells because it is relatively non-corrosive.

        The end use pattern for  carbon disulfide in 1989 is listed below (2).

        Derivative                 Percentage
        Carbon tetrachloride               43
        Rayon                           35
        Cellophane                        4
        Rubber chemicals                  9
        Misc.                             9

 2.4     Health Effects Summary

        No data exist that classify carbon disulfide as an animal or human carcinogen. However,
 at very high levels (10,000 ppm carbon disulfide in air), carbon disulfide is highly toxic to the
 central nervous  system,  and  death  can occur  due  to respiratory failure.  Carbon disulfide can
 cause  neurotoxic effects  through inhalation and dermal contact (1,5). Carbon disulfide can also
 be highly toxic when ingested in large doses (2).

        Various local effects  and symptoms may occur from exposure to carbon disulfide.  In
 sufficient quantities, carbon  disulfide  vapor  is  severely irritating to  eyes,  skin, and mucous
 membranes.  Permanent visual impairment and  retinal cell degeneration occurred in monkeys that
 breathed 256 ppm for 6  hours a day, 5 days a week for  5-13 months  (1). Contact  with liquid
 carbon disulfide may cause blistering with second and third degree burns. Skin sensitization may
 occur.   Skin absorption  may result in  localized  deterioration of peripheral nerves,  most often
 noted in the hands. Respiratory  irritation may result in bronchitis and emphysema (6).

       Subjective psychological and behavioral disorders have been observed following repeated
carbon disuifide exposure.  Acute exposures  may  result in extreme irritability, uncontrollable

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 anger, suicidal tendencies, and a toxic manic depression psychosis.  Chronic exposures have
 resulted in insomnia, nightmares, impaired memory, and impotency. Less severe changes include
 headache, dizziness, and diminished neutral and motor ability, with staggering gait and loss of
 coordination (6).

       Atherosclerosis and  coronary heart  disease have  been significantly linked to carbon
 disulfide exposure.  A significant increase in coronary heart disease mortality has been observed
 in carbon disulfide  workers.   The  Federal  Occupational Safety  and Health Administration
 (OSHA) has determined that a 4 ppm 8-hour time-weighted average (TWA) limit and a 12-ppm
 STEL (Short-Term Exposure Limit)  are necessary to reduce the risk of cardiovascular disease
 among carbon disulfide-exposed workers. Studies also reveal higher frequency of angina pectoris
 and hypertension (6,7).

       Other specific effects of chronic carbon disulfide exposure include chronic gastritis with
the possible development of gastric and duodenal  ulcers; impairment of  endocrine  activity,
specifically adrenal and testicular; abnormal erythrocytic development with hypochromic anemia;
and possible liver dysfunction with abnormal serum cholesterol.  Chronic menstrual disorder may
occur in women.  These effects usually occur as a result of chronic  exposure of carbon disulfide
and are subordinate to the other symptoms (6).

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 3.0    EMISSION SOURCES FOR CARBON BISULFIDE

       This section presents information on the main source categories that emit carbon disulfide
 (i.e., rayon production and carbon tetrachloride production)(2,3,8,9).  Included in the discussion
 of each source category is a technical description of the emitting process and, where available,
 a mention of the specific emission points.

 3.1    Viscose Process

       Viscose processes emitted approximately 500 Ibs carbon disulfide per ton of rayon fiber
 produced in 1989  (9).  Estimates from 1989 indicate that  the viscose process of regenerating
 cotton and wood cellulose to make rayon and cellophane accounts for about 40 percent of the
 carbon disulfide consumed in the United States (2). Most of the world's rayon is made by the
 viscose process (10). In addition to being used to manufacture rayon, cellulose food casings are
 also manufactured  by the viscose process.

       Emissions from the viscose process are  often high volume/low concentration streams
 (approximately 400,000 cubic  feet  per minute   (cfm)  of  water-saturated  air  containing
 approximately 100  parts per million (ppm) of carbon disulfide (11)). This can result in difficult
 and costly  emission  control problems. Section 4.0 of this report discusses various potential
 carbon disulfide control options and their limitations.

 Process Description

       The viscose process used to make rayon is shown in Figure 1  (10).  A brief description
of the steps involved and those steps wherein emissions can be expected to occur are given
below (10,  12).

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r
                                        Figure 1.   Viscose Process*
                  Cellulose
                   sheets
                                Sleeping pressing
                                 18\vt %NaOlI
                                                                                Aging
                                                                                             Xanlhation
                                        Shredding
                      Ripening
               	  Dei
Deaenilion   ••<-
                                                 Filtration
                                                  Fiber production


                                                Stretching
                                                                                        	>
                                                                              o—DO   o
                                                       Dissolving
                                                         Dilute
                                                         NaOH
                                                                                  Finishing
                         Acid Hath
                                                                                                                   *See Reference 10

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 Steeping:



 Shredding:



 Aging:


 Xanthation:



 Dissolving:


 Ripening:
This step converts cellulose-pulp sheets to alkali cellulose by placing the sheets
in a steeping press and filling the press with sodium hydroxide. After steeping, the
cellulose is pressed under high pressure.

This step is used to convert the alkali-cellulose to a "crumb-like" material.  This
step also helps distribute the caustic more uniformly in the cellulose while heating
the "crumbs" to a temperature favorable for aging.

Aging is used  to decrease  and control the degree of polymerization of the
cellulose.

This is a critical step in which the alkali-cellulose  crumb is reacted with carbon
disulfide to form cellulose xanthate.  To control the carbon disulfide vapor that
escapes, an enclosure system is  generally used for xanthation.

This step uses cold dilution in caustic solution to form the cellulose xanthate into
a clear, honey-like viscous dope known as viscose.

This step allows the clear viscose to coagulate and "ripen" to the proper xanthate
level.
Spinning/
Regeneration: In this step, viscose is extruded into a bath containing both salt and acid.  The
              primary  goal  of the spinning stage is the  control  of the coagulation versus
              regeneration rate and the maximal use of the differences in these rates to obtain
              maximum response to stretching. Carbon disulfide is  released during spinning in
              an open bath.

Stretching:    This step allows for better molecular alignment of the viscose  fibers through a
              fixed amount of stretching.   Since  enclosure is difficult, carbon  disulfide is
              released from  the fibers as they are stretched and cut.

Finishing:     After the fibers are spun, cut and washed, finishes are applied to give the proper
              frictional performance in subsequent textile processing.
3.2    Carbon Tetrachloride Production
       The carbon tetrachlonde production process is also an emitter of carbon disulfide.  Carbon

tetrachloride is produced by the chlorination of carbon disulfide or the chlorination of methane

or higher hydrocarbons.  Since caroon disuifide is emitted only tiom me chionnauon or carbon

disulfide, only  that process is discussed.  In the carbon disulfide process, a mixture  of carbon

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disulfide  and  sulfur monochloride in  carbon tetrachloride is chlorinated under  controlled
conditions.  This yields a mixture of carbon tetrachloride and sulfur monochloride, which are then
separated by distillation. The sulfur monochloride is recycled.  Carbon disulfide is emitted from
the chlorinator, the storage facilities, handling (i.e., loading of trucks, tank: cars, barges), and as
process fugitives.  Figure 2 presents a diagram of this process  (8).

3.3    Other Processes

       Other processes  that emit carbon disulfide include  the manufacture of thiocyanates and
high-purity metal sulfides.  Miscellaneous applications include direct uses of carbon disulfide for
the cold vulcanization  of rubber, as  a  flame lubricant in  cutting glass, and for  generating
petroleum catalysts.  In addition, carbon disulfide is used for dissolving free sulfur, phosphorus,
and iodine (2).
                                           10

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         Figure 2.   Carbon Tetrachloride  Production*
            CIII.ORINATOH
  CAklUJN
TETRACIII OklDE
  CAIIllON
  1)1 S 1)1 HI) D
     CAUSTIC -
                 CAUSTIC
                PURIFICATION
  CARUON
TETRACHLORIDE
  STORAGE
           LOADING
                                                                     'Sec Reference 8

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 4.0    CONTROL TECHNIQUES

        This section describes control techniques for carbon disulflde. These techniques include
 existing applications as well as potential applications that are currently being researched.  Certain
 carbon disulflde emission streams are high-volume air streams with low concentrations of carbon
 disulflde. Some of the control techniques described herein may only be applicable to low-volume
 air streams with high concentrations of carbon disulflde.   Therefore, the nature of the stream
 needs to be considered when deciding which techniques to apply. These techniques are described
 for the general case.  For a process specific application, consult the particular reference cited.
 A  list of  additional  references can  be  found  in  the October 1988  edition  of Pollution
 Engineering (13).

 4.1     Absorption

        This subsection outlines the following absorption methods: oil absorption (Methods 1 and
 2) and diglycolamine agent absorption  (Method 3).

 4.1.1   Method 1: Oil Absorption

        Vendors of liquid absorption recovery systems claim that carbon disulfide emissions can
 be controlled by oil absorption systems. The basic process  set-up  is similar for each vendor in
 that a combination of carbon  disulfide and an absorption liquid are mixed in an absorber tower
 and then sent to a stripper tower where  they are heated and the carbon disulfide flashes out. The
 nature of the absorption liquid is proprietary information.

       The carbon disulfide recovery system operates in two continuous stages.  The first stage
involves the removal of carbon  disulfide from the exhaust stream in  an absorber  using  the
absorption liquid.  The vapors are absorbed in  a counter-flow packed tower absorption vessel.
 in me second stage the absorption liquid that is now rich  with carbon disulfide is passed from
the  absorber to a  series of heat exchangers. This increase in temperature enhances the release

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 rate  of carbon disulfide from  the  absorption liquid in the stripping  column.  The stripped
 absorption liquid is recycled back into the absorber for continuous operation.  The separated
 carbon disulfide vapors are then condensed to the liquid phase.  Figure 3 presents a process
 diagram of this control technique (14).  Potential applications for this control technique include
 textiles, furniture  finishing and manufacturing,  electronics  manufacturing,  pulp  and  paper
 industries, and petrochemical industries.

        There are some limitations to the oil absorption method. Although oil scrubbing may be
 feasible for emissions  with high concentrations of carbon disulfide, a potential concern with this
 method is that it may not be feasible for emissions with low  parts-per-million concentrations.
 A study of carbon disulfide control options at a cellulose food casing manufacturing facility has
 shown that  gas absorption  could be  used to remove carbon disulfide from its  emissions.
 However,  the recovery  of  carbon disulfide from the large absorption liquid  flow would be
 economically infeasible.  Furthermore, because the absorption  liquid could not be regenerated,
 using gas absorption as the only removal method would  be impractical (11). In addition,  CMA
 is concerned that the oil absorption system will require large volumes of oil and that the fugitive
 emissions of volatile organic compounds from the scrubbing oil will be  significant (15).

 4.1.2  Method 2: International  Patent No. WO 86/02283
                  Title:  Air Scrubbing Process

       This technique  (16) relates to  the purification of air by scrubbing with an effective liquid
 that can be recycled. This invention presents an air scrubbing process (similar to Method 1) that
 utilizes a scrubbing liquid which is a complete or  partial fatty  oil, particularly a drying, semi-
 drying or saponifiable vegetable, marine, or land animal oil or liquid fat.  If the scrubbing liquid
 is  not entirely fatty oil, a substantial portion of the remainder of the scrubbing liquid is water
 with which the oil  or  fat forms  an emulsion.   The scrubbing  liquid can also  include a small
proportion  of a detergent or wetting agent.
                                           13

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from
plaul
                                     Figure 3.   Oil Absorption System*
                                                      recovered solvent
        ABSORPTION TOWI:R
                                                                         VACUUM
                                                                          PUMP
I
A
    non—condcnsablcs return
                 recovered
                 solvent to
                  plant
                                                                               DHCANTTANK
                                                                                                 *See Reference 14

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        According to the patent, carbon disulfide is one of the  many pollutants that may be
purified from an air stream using this process.  After treatment of the air, the scrubbing liquid
can be precipitated readily from the air stream so that no appreciable  amount of the scrubbing
liquid will be lost in the air discharged from the  treatment process.  The patent also states  that
the scrubbing liquid is readily available and inexpensive  (16). The reader should be aware  that
this air scrubbing process  is an experimental process and has not vet been demonstrated to he
effective in an industrial setting.

Selection of Scrubbing Liquid

       The following fatty oils are  suggested for use for the scrubbing liquid because of their
ready availability and effectiveness.

       soybean oil
       cottonseed oil
       groundnut or peanut oil
       corn oil
       safflower oil
       sunflower seed oil
       rapeseed oil

Reference 16 contains an extensive listing of other oils that may be used.

       In order to facilitate spraying and dispersion of the scrubbing liquid containing fatty  oil,
it is preferred that the oil be emulsified with water to provide a scrubbing liquid with a viscosity
lower than the viscosity  of the oil.  In order to condition the oil for reuse,  the oil and water  are
separated and pollutants removed from the air are stripped  from the oil or fat.  Such stripping
can be effected by the use  of steam  in accordance with known procedures. Steam stripping of
fatty oils is  disclosed in  Wecker U.S. Patent 1,622,126  (1927) (17).  Stripping of fatty oils can
also  be accomplished continuously by use of the deodorization procedure disclosed in Dean U.S.
Patent 2,280,896 (1942)(18).  The reader  is encouraged  to locate these patents if this control
technique is considered.

                                            15

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 4.1.3  Method 3:  Diglycolamine Agent

       Diglycolamine (DGA) agent is manufactured by Texaco Chemical Company and is the
 brand name for 2-(2-aminoethoxy)-ethanol.  It was first introduced in the United States in 1965
 and is primarily used for removal of hydrogen sulfide and/or carbon dioxide from gas streams.
 DGA agent is a clear, viscous liquid at room temperature and a white crystalline solid below its
 freezing point of 9.5° F (19).  Although DGA agent is used primarily for hydrogen sulfide and
 carbon dioxide absorption, it may be possible to  use DGA agent to control carbon  disulfide
 emissions through  a gas absorption system as discussed in Method 1 (19).  Although  there are
 no existing applications of this technology for the purpose of carbon disulfide control, it may still
 be considered as a potential control.   DGA agent reacts with carbon disulfide to produce the
 major degradation  product N,N'-bis(hydroxyethoxyethyl) urea.  The chemical equation for this
 reversible reaction  is
                                           H   S   H
                                    A      I    ||    I
                    2R— NHj + CS.  **  R— N— C— N— R +
where
                    R = HO— CH^— CH2— O— CHj— CH2
This degradation product has  a  much lower toxicity  than  the  parent  compound,  carbon
disulfide (19).

4.1.4   Conclusions

       Absorption may be a feasible control technique for high-concentration, low-volume carbon
disulfide air emissions.  However, it may not be feasible for low-concentration streams.  It is
recommended that the reader further research the absorption methods presented herein prior to
considering using these  methods.  The selection  of the absorption medium  is critical to the
                                          16

-------
 success of the control technique.  The preceding sections have identified absorption liquids that
 are thought to be effective in removing and/or eliminating carbon disulfide.  According to some
 industrial contacts, there are certain problems with using oil absorption in that it  is not as
 effective as vendors claim.  Also,  gas absorption is equipment intensive and for that reason may
 be more costly than other alternatives. For example, a study conducted by Argonne National
 Laboratory showed that application of conventional gas absorption processes for carbon disulfide
 removal is relatively expensive mainly due to low equilibrium carbon disulfide loadings in all
 possible absorbents.  There are requirements for high liquid flow and relatively low superficial
 gas velocities to avoid flooding in absorption towers. From this study  it was determined that
 13 conventional  absorption towers (12 ft in diameter) would be  required for carbon disulfide
 removal for a stream with a 100 ppm  carbon disulfide concentration (11).  Pilot plants studies
 or trial plant runs  may  be  required to determine effectiveness and suitability of this control
 technique to a particular carbon disulfide stream.

 4.2    Adsorption

       This subsection presents adsorption methods  using  activated carbon  and a synthesized
 sorbent technique.

 4.2.1  Method 1: Activated Carbon

       Carbon adsorption is a traditional control technique used  for solvent recovery, energy
 recovery, odor removal, and regulatory compliance.  This control technique employs the use of
 activated  carbon  as an adsorption  medium.  Air contaminated with carbon disulfide is passed
 through a bed of the activated carbon. Carbon disulfide is adsorbed onto  the internal surface of
 the adsorbent  and the purified air  is exhausted  to the atmosphere.  For most applications, the
 adsorbent bed is then regenerated, generally with steam. In terms of carbon disulfide adsorption,
 the primary problem  associated with steam regeneration is the possibility of fires since the
autoignition temperature  of  carbon disulfide is  below the  temperature of steam.  The carbon
disulfide is then extracted from the steam through condensation.
                                          17

-------
       One method of eliminating the fire problem associated with steam regeneration is to use
 dry nitrogen for regeneration. In this application, hot, inert gas (nitrogen) is passed through the
 adsorbent bed and desorbs the adsorbed carbon disulflde.  The carbon disulfide-rich inert gas is
 cooled and passed through  the compressor side of a  turbo unit.   It is further cooled in  an
 interchanger and enters  the  expansion  side where cooling  as low as -80 °F is accomplished.
 Condensed  liquid is separated and the  inert gas is passed through a mechanical pump and is
 returned to the adsorber.   Figure 4 presents a complete  process  diagram of  this recovery
 system (20).

       There are safety concerns associated with the use of activated carbon to control carbon
 disulfide emissions.  Carbon disulflde differs from organic  compounds typically treated by
 activated carbon systems.  Organic compounds typically controlled by carbon adsorption have
 an  explosion hazard classification of "slight" or "moderate", whereas carbon  disulfide has  a
 "severe"  explosion hazard  classification.  In addition, carbon disulfide exhibits a much lower
 flash point than typical organic solvents treated by activated carbon systems.  Air and/or rust are
 listed as  "incompatible materials" for carbon disulfide but are not considered incompatible for
 conventional solvents handled by activated carbon systems (21).   Carbon disulfide reaction
 products  of  activated carbon  systems are much more corrosive than for typical volatile organic
 compounds. Sulfuric acid is produced by the contact of  reduced sulfur compounds on activated
 carbon systems.  Furthermore, the presence of sulfuric acid requires extensive custom design and
 exotic  metallurgy for pipes, condensers, heat exchangers, valves, etc. to control corrosion (21).

       In addition to the above concerns, carbon disulflde exhibits  a much higher vapor pressure
 than typical organic  solvents.   At stack conditions,  carbon  disulfide  vapor  pressure  is
 approximately 450 mm Hg; at 25°C it is 350 mm Hg. Vapor pressure  of typical organic solvents
range from  2 mm Hg  to 76 mm Hg.   The adverse effect  of a  high vapor pressure is that
condensation of carbon disulfide would require extensive refrigeration rather than conventional
water cooling to condense the vapor after column stripping (21).
                                           18

-------
                                Figure 4.  Adsorption Recovery System*
                             < 1 III «««>»«< KCX:K<>S
                 • • • r
                                    I	-  OO
                                    I
                                                                             TUR HO
                                                                           COMI'KICSSOR
                                                                            EXPANDER
                                                     VACUUM
                                                      PUMP
                                                                ililKtitt
                                                    COOLER
                                                                  LOW TEMP
                                                                  CHILLER
                                                        KILTER
                                                                                   Slllllllll	IIIIIIIIIIIIIMIIIIIlltllllllMllllV-
                                                                                                                     SOLVENT
                                                                                                                     STORAGE
                    SLAIILOWliU
I	
'See Reference 20

-------
        Studies performed by Argonne National Laboratory using various activated carbons for
 carbon disulfide removal indicated that this method is definitely superior to other methods for
 removal and recovery of carbon disulfide from air.  Carbon  has  a  great affinity  for carbon
 disulfide.  It was concluded that activated carbon may make efficient adsorption and recovery
 possible if the other known problems (H2S and H^O poisoning, water loading, and fire hazard)
 can be overcome (11).  Further study of the  carbon adsorption method was recommended by
 Argonne National Laboratory.

 4.2.2  Method 2:  Synthesized Sorbent: European Patent EP 189606

       This patent (22) discusses an invention that involves impregnating a solid material suitable
 for selective and quantitative removal of carbon disulfide.   Some of the solids that can be used
 for the impregnation treatment are silica gel, alumina, clay mineral and zeolites.  The  active
 agents for  the impregnation procedure which  have been found  to be effective are amines and
 amine complexes of their  derivatives.  For the impregnation  procedure, the solid is mixed
 homogeneously with the active agents at temperatures below 200 °C.  The loading of the solid
 material can be controlled by  the initial amount of the active agent in contact with the  solid.
 Afterward, the mixture can be thermally treated (below 300 °C) and dried in air  or in an inert
 atmosphere. This thermal treatment determines the ultimate loading of the active agent on the
 solid.  After a reconditioning of the impregnated material (flow of dry inert gas), the material is
 activated.   This creates high  selectivity for the  impregnated solid for adsorption  of carbon
 disulfide.  The adsorbed carbon disulfide can then be quantitated down to the ppb range with a
 universal S-monitor  (22).

       The patent described above is only  a potential option that should be further researched
before being used.  At this point, the  synthesized sorbent method is experimental  technology

-------
 4.2.3  Conclusions

       Adsorption is a traditional and feasible control technique and is relatively easy to operate.
 However, for carbon disulfide, it is imperative that steam is not used in regeneration due to the
 relatively low autoignition temperature of carbon disulfide. Some other regeneration alternatives
 have been presented (i.e., nitrogen desorption). Although nitrogen desorption solves the problems
 of using  steam, it introduces additional problems (i.e., storage, handling). Carbon adsorption, as
 well as the newer synthesized sorbent process, present beneficial, and potentially useful, control
 technologies for  carbon disulfide emissions.  As previously mentioned,  Argonne  National
 Laboratory determined that activated carbon may make efficient adsorption and recovery possible.

 4.3    Ventilation and Condensation  Recovery System

       A ventilation and recovery  system is used  by the  Shanghai  Number 12 Viscose Rayon
 Factory (12). Since  1972, carbon disulfide vapors  from the spinning process (see Section 3.1)
 have been controlled by a  system of exhaust ventilation and recovery.  The recovery of carbon
 disulfide is achieved after the capture of the vapor in the ventilation  pipe by three successive
 cooling condensers and a collection system.  Figure 5 presents a schematic of this control
 technique (12).   During the  early 1980s, the  average rate of recovery (efficiency) reached 48
 percent of all carbon disulfide added in production.  A similar carbon disulfide control/recovery
 system has been in operation at the BASF Corporation, Fibers Division, Lowland, TN, since
 1956 (23).  This system employs carbon disulfide condensation through a cold caustic solution
 and carbon  disulfide  recovery in a receiving tank.  It  works most  efficiently when carbon
 disulfide  concentrations are at very high levels in a low-volume stream.  The collected carbon
 disulfide  is then transferred  to a storage chamber  as  pure carbon disuifide.  Eleven to twelve
percent total carbon disulfide is recovered for reuse. An additional 20-30 percent of the carbon
disulfide  is converted to hydrogen  sulfide.  Figure  6  shows a diagram of the carbon disulfide
recovery  system used  by  BASF (24).   Recovery  techniques  are  applied by  BASF to high
concentration areas  of me spinning-process instead of to the low  concentration  high  volume
exhaust stream at the final steps of the process (24).
                                          21

-------
               Figure 5.  Ventilation  & Recovery System*
SIJll'URIC ACID BATH
                               I. PRIMARY COOUNG CONDENSER
                               II. SECONDARY COOUNG CONDENSER
                               III. TERMINALCOOLING CONDENSER
                                                                    CS2
                                                                 COMJiCflNO
                                                                  4 TANK 4
                                                                             EXHAUST
                                                                                  CS2
                                                                               TO BE REUSED
                                                                                'See Reference 12

-------
            Figure 6.   BASF Carbon Disulfide Recovery System*
   I.YH
fib Chem
          COOLI.YI2
          KOMUUM OUT)
           VMK1RS
         (PROM SPINNING ROOM)


         N.
                                                                    TO ATM
                                                          NON-CONDENSING
                                                            SEAI.TANK
                                                                        TOCS2
                                                                       STORAGE
                                                                        TANK
                                                                          'See Reference 24

-------
       This particular control technique has already been applied at several existing sites. It can
 be concluded that it is a feasible option for high concentration streams (15). It should be noted,
 however, that this arrangement was designed specifically for the rayon production process and
 may  not  be  suitable for  other sources.   It should be  noted that refrigerated  condensers are
 currently being used in a carbon disulfide production process (25); however, this technique poses
 a disposal problem if the carbon disulfide is not to be recycled back into the process.

       Ventilation and recovery systems could involve prohibitively large energy requirements
 for cooling. For example,  cooling the enormous volumes of water-saturated air typical of viscose
 plant exhaust would be economically  and technically infeasible for low concentration carbon
 disulfide  emission streams (15).  However, condensation technology is  an option that may be
 considered for areas where emission streams with very high carbon disulfide concentrations can
 be captured.

 4.4    Absorption/Oxidation: U.S. Patent 4,049,775

       The method discussed in the patent, developed at the Institute of Synthetic Fibers, Lodz,
 Poland, is experimental and  is being tested on an industrial scale at CHEMITEX-WISTOM
 Synthetic Fibre Industry Plant, Tomaszow Mazowiecki, Poland (26).  This patent discusses a
 process that removes hydrogen sulfide, carbon disulfide, and sulfur dioxide  from the polluted
 air in one operation by absorbing and  oxidizing the gases in a bath.  The specific installation
 discussed in  the  patent is used to remove hydrogen sulfide  and  carbon disulfide from the
 ventilation system air in viscose fiber plants. The installation has a capacity of one million cubic
 meters per hour  and an alkaline bath (pH=  9.6 - 9.8) with a redox system being used for
 absorption purposes. The  carbon disulfide is absorbed by the bath in the presence of hydrogen
sulfide and is subjected to hydrolysis.   The carbon disulfide reaction  and  hydrogen sulfide
absorption products are oxidized with atmospheric air to sodium thiosulfate, elemental sulfur and
a small amount of sulfates.  This technology can reduce carbon disulfide concentrations of 200-
600 mg carbon disuifide per cubic meter by about 70 percent.  Figure 7 presents die process
description for this technique  (26).
                                           24

-------
      Figure 7.  Wet Method of Carbon Bisulfide Control*
1
  0,0
/ /
^\^"
ii
I
r^

/














\




\
•xx
efc
^"-^,
8
          chimney 150
10-S pl'Js  '
                      high, 5-dfecharge  of bath solition' from the tow.   1-bath  solution
                      n reSe™0ir' 8-3parger dr in!st' 9-bat)l ^dution  exponents' inlet
                                                               "See Reference 25
                                    25

-------
       The plant equipment is comprised of 5 towers with 7.8 meter diameter plates.  The
 cylindrical section of a 5 meter high tower ends in a 5 meter high tapered section feeding the
 gases into the chimney.  A liquid condenser is positioned between the cylindrical and tapered
 sections.  The gases are fed into the tower by a fan that delivers from 250,000 to 300,000 cubic
 meters per hour,  which  is equivalent to an average flow rate of gases through  the tower of
 between 1.5 to  1.8  meters per second.  The absorption bath is pumped from the reservoirs
 situated below ground level.  The bath solution flows down the towers into the reservoirs where
 it is regenerated.  Bath regeneration  is achieved by subjecting it to oxidation with air.  The air
 is fed by compressors with an output of 1650 cubic meters per hour. The purified air is emitted
 to the atmosphere by a scattering chimney  150 meters high (26).

       As this is a  foreign installation, it is  difficult to judge its feasibility for a domestic
 application.  As previously stated, this technology is currently experimental.  The patent does
 claim a 70 percent reduction of carbon disulfide emissions and an emission rate of 106 m3 carbon
 disulfide/hour.  Further investigation  into the nature of the bath and its effectiveness for carbon
 disulfide is recommended.

 4.5    Regenerative Thermal Oxidation

       This control technique involves incineration of the gas stream containing carbon disulfide.
 The basic construction for this control option admits process gas into the thermal oxidation unit
 through an inlet manifold. A flow control valve directs this gas into an energy recovery chamber
 in inlet (preheat)  mode.   The process gas and contaminants are progressively heated in  the
 stoneware bed  as they  move toward  the  purification chamber.  High  temperature  thermal
 oxidation  is  accomplished in this central  chamber.   Gas  or oil  burners maintain  a preset
 destruction temperature of up to 1100°C  (2012T) with a residence time of up to  one second.
 Carbon disulfide present in the gas stream will autoignite, releasing energy in the stoneware bed.

      From  the central  chamber,  the  purified process gas stream passes through an  energy
recovery in outlet  (heat recovery) mode. The cleaned  gas can be  handled by a standard  fan

-------
 located in the clean gas side.  Figure 8 presents a schematic of this technique (27).  Several
 applications for this process include chemical processing; metal coating; petrochemical industries;
 pulp and paper industries;  and paint, solvent, and ink manufacturing.

       According to equipment vendors, this technique is feasible and has many applications for
 industry pollutant control.  However, it may be cost prohibitive as the process equipment would
 need to be made of Hastalloy or Stainless Steel due to the corrosive nature of carbon disulfide.
 In  addition,  substantial energy  costs  are  associated  with  using this  option  for  viscose
 processes (15).  Another potential drawback of using thermal oxidation is that sulfur dioxide is
 an oxidation by-product of carbon disulfide.  Control of the resulting sulfur dioxide emissions
 is a  concern.

 4.6    Catalytic Conversion: U.S. Patent 4,374,819

       This patent discussed a system that relates to a multi-stage process for removing noxious
 sulfur containing gases, notably hydrogen sulfide,  sulfur dioxide, carbonyl sulfide and carbon
 disulfide, from waste gas streams (28).  This control technique employs the Claus reaction for
 sulfur recovery:
                                     SO2 -» 2HjO + 3/2 S
The Claus process has  been used to remove hydrogen sulfide from gas streams by reacting
hydrogen sulfide with sulfur dioxide in the presence of a catalyst (i.e., bauxite, alumina, cobalt
molybdates) (28). The first stage involves a Claus reaction, but uses a novel catalyst which also
permits the reduction and/or elimination of the carbon disulfide from the gas stream through the
following reaction:

                                 CS2 + S02-»  Sx + C02

-------
               Figure 8.  Thermal Oxidation System*
Stoneware
Refractory
    lining
   Outlet
 plenum
               Burner
                                                             Stack

                                                             Purification
                                                             chamber
                                                       nergy recovery
                                                      chamber
                                                  /aive
                                                             "See Reference 27
                                  28

-------
       In this first stage, the gas stream is passed through a reactive zone having a temperature
 between 150 °C to 350 °C in the presence of a pre-treated novel catalyst having the following
 formula:
In this formula, Ln is yttrium or a rare earth element, T is cobalt, iron or nickel, and x and y are
independently numbered from 0 to 3. The catalyst is non-crystalline and has a surface area of
about 10 mVg  to about 40 m2/g.  The preferred catalyst is one in which Ln is lanthanum; T is
cobalt; and x and y range from 1 to 3, including non-integers. The first stage yields a product
stream having  a reduced  content of sulfur-containing gases, specifically including substantial
reduction and/or virtual elimination of carbon disulfide.

       An intermediate stage is a Glaus  reaction which may take place in one or more reaction
zones in the presence of known catalysts such as bauxite, alumina or cobalt molybdates.  The
final stage is required to reduce the hydrogen sulfide concentration to about 10 ppm. This stage
involves the air oxidation of hydrogen sulfide at a temperature between 150 °C to 300°C in the
presence of a  catalyst  usable in the first  stage.   Figure 9 presents a diagram of the  three
stages (28). For carbon disulfide removal, only the first stage needs to be executed.

       In  general,  this  technology  applies  to  commercial processes involving  very  high
concentrations of sulfur gases.  It is used primarily to control hydrogen sulfide emissions from
sulfur recovery plants associated with oil refining operations.  The process gases are characterized
as containing 15 percent to 20 percent carbon dioxide and essentially no oxygen  (15).

       This option may also be very costly because the equipment must  be constructed of
HastaUoy or Stainless  Steel.  The other primary  problem with this option is that the carbon
disulfide is not recoverable.   If the particular process requires  a  recycle  stream of carbon
disulfide. this control opaon would not be feasible.  Although tneoreacally it appears  that tnis
                                           29

-------
        Figure 9.   Catalytic  Conversion*
                    CLAUS REACTOR AT 328°C
                    WITH CATALYST OF THIS
                          INVENTION
CLAUS PLANT
  TAIL GAS
(16,600 PPM TOTAL
 SULFUR GASES)
                 COOLED
                 TO 25.9°C
                 ,,, H
                 J%
COS-f-SO^

COS + !%<3
              Sx
FOR FINE TUNING OF
        RATIO
                                                        1st STAGE
  OXIDATION REACTOR AT 1 9 1 °C
WITH CATALYST OF THIS INVENTION
                                                     4170ppm H2S + SO2
                                                      78ppm COS and
                                                     Non-Detectable CS2
                                                      Cooled to23.9°C
                                                       (3% H20(g))
/
SULFUR
PRODUCT
Ipi?


CLAUS REACTOR
WITH BAUXITR
CATALYST AT 12TC
*
v:
>
\.2J-..^
1
\)
\
SULFUR
PRODUCT
                                                        FINAL STAGE
                              TOTAL < 300ppm
                              SO2   < 250ppm
                              H2S   <  lOppm
                                                             "See Reference 23

-------
 method may  be used to  control carbon disulfide emissions, there have not been any proven
 practical applications yet.

 4.7     Control with a Bioreactor

        This method, entitled the Waagner-Bio/Glanzstoff Austria Process, employs a fixed bed
 bioreactor that is designed as a counter current gas-liquid reactor. The reactor is equipped with
 commercially available packing materials such as polyethylene and polypropylene of different
 specific areas.    The  reactor  is  also  equipped  with  an immobilized mixed  culture  of
 microorganisms, generally  Thiobacillaceae. The packing  material  carries  the immobilized
 microorganisms.  The gas containing the contaminants (Le., carbon  disulfide) flows counter-
 current to the water/activated sludge suspension through the reactor.  As the crude gas passes
 through the reactor, the hydrogen sulfide and carbon disulfide transfer into the liquid surrounding
 the cells and then further through the microorganism cell walls due to the favored rapid oxidation
 of the  hydrogen  sulfide  and  carbon disulfide  by the metabolism of  the  sulfur-oxidizing
 microorganisms.  The oxidation products are released through the cell walls into the liquid and
 are removed continuously by the circulating flow of the water/activated  sludge  suspension and
 are neutralized by the addition  of sodium hydroxide. The formed sulfate is removed from the
 settler by the continuous addition of water. Figure 10 presents a process diagram of this method
 (29).

       This control option has not been proven on an industrial scale, and all data are from pilot
plant studies.  Further investigation into the capability of this option on actual industrial sites is
needed.  Theoretically, this option appears to be feasible.  However, there is concern  that this
technology may not be feasible for low concentration, high volume streams (15).

4.8    Wet Scrubbing

       Based on more than a decade of wet scrubbing  experience, an  odor control system has
been developed that treats air flows from 500 to 70,000 cfm (30). This  method uses a packed
                                           31

-------
                                Figure 10.   Control With a Bioreactor*
                  VI
                                                 PURIFIED GAS
                                                                                                    H20
                                                                                            -o-
                                                                                   P3    B2
                                                                                                P4   B3
              V1 blowei        P3 pump for alkali
              Rl  bioreauor      B2 alkali lank
              M  circulaiion pump  P4 lap water pump
              Ii 1  sedirncnler     B3 lap water lank
              P2  reflux pump
___
                                                                                                 •Sec Reference 29

-------
 tower concept  In operation,  scrubbing  spray  is created by controlled  mixing of  sodium
 hypochlorite (bleach) and/or other chemicals with tap water that has been pretreated to  remove
 hardness. The mixture is then fed to a nozzle located at the inlet of each reaction tower.  While
 odorous air is vented into a reaction tower, the nozzle sprays a fog of very fine droplets which
 travel concurrent with the air.  The nozzle produces droplets with mean diameters of 10-12
 microns, which are ideal for effective odor removal. Enhanced by long gas-liquid contact times
 (typically 10 to 30 seconds), the small fog  droplets achieve optimal contact As a result, odor
 molecules are  completely reacted and clean air is exhausted to the atmosphere.  The  control
 mechanism  for this process involves non-liquid  absorption and subsequent condensation in a
 packed tower.

       A cellulose food casing facility tested this wet scrubbing method at: its facility for carbon
 disulfide removal and determined that it was not feasible on its air stream (31).  However, this
 wet scrubbing method may have the potential to control carbon disulfide emissions upon further
 study. This method is currently employed  at more than 65 wastewater treatment plants in the
 United States (30).  Figure 11  presents a diagram  of the control  system  (30).

 4.9    Current Research

       Researchers at Argonne National Laboratory, in Chicago, Illinois,  in conjunction with the
 Illinois Department of Energy and die Department of Commerce and Community, have examined
 the following four possible options for controlling carbon disulfide emissions.

       1.     gas absorption
       2.     gas adsorption
       3.     membrane separation
       4.     catalytic conversion

Options 1, 2 and 4 have been  presented in  Sections 4.1, 4.2, and 4.6, respectively.  Option 3,
membrane separation, involves the separation of a  gas or liquid through the use  of a permeable
membrane.  The driving force for transport is either pressure or concentration (32).

-------
Figure 11.  Wet Scrubbing*
                    J_l
         INLET ODOROUS AJR DUCT
 LIQUID
METERING
 PANEL
 DRAIN
 LINE
                     NOZZLE
             REACTION CHAMBER
                        EXHAUST
                         FAX
                             V
                     OUTLET
                     DUCT
                                              t
EXHAUST'
 STACK
                                           "See Reference 30

-------
       The following conclusions have been  reached  concerning  the above carbon disulfide
control options based on studies conducted at  a cellulose food casing facility.  Gas absorption
was determined to be relatively expensive and was concluded to be infeasible. Results of studies
showed that although ways  to  alleviate the foe hazard  danger must be  developed,  carbon
adsorption presents the best  current possibility for carbon disulfide recovery.  Pursuing the
membrane separation  option is not recommended at this time because it was determined that
existing ceramic membranes cannot remove carbon disulfide from air effectively, even at high
carbon disulfide emissions.  Finally, it was determined that because the catalytic incineration
process would requke  a catalytic reactor to convert sulfur dioxide to sulfur trioxide and a sulfuric
acid plant, there is little economic incentive to choose this option for carbon disulfide emission
control (11).
                                          35

-------
                                   REFERENCES
 1.     Agency for Toxic Substance and Disease Registry (ATSDR). " Toxicological Profile for
       Carbon Disulfide, Draft for Public Comment", U.S. Public Health Service February 15
       1991.

 2.     Chemical Products Synopsis. Carbon Disulfide. Mannsville Chemical Products, Asbury
       Park, N.J., (908) 776-7888, September 1990.

 3.     Timmerman,  R.;  "Carbon Disulfide"  in Kirk-Othmer  Encyclopedia of  Chemical
       Technology. Vol 4, John Wiley and Sons Inc., NY, 1978, pp 742-754.

 4.     Memorandum from J.M. Stewart, Courtaulds Fibers, Inc., to Susan  R. Howe, Chemstar
       Division, Chemical Manufacturers Association, Washington, DC, April 8, 1992.

 5.     Hazardous Substance  Data Base  (HSDB), Carbon  Disulfide. Bethesda,  MD:  National
       Institutes of Health, National Library of Medicine. 1990.

 6.     Sittig, Marshall, Handbook of Toxic and Hazardous Chemicals and Carcinogens. Second
       Edition, Noyes Publications, Park Ridge, New Jersey, 1985.

7.     Federal Register, Volume 54, No.  12, January 19, 1989, p. 2535.

8.     U.S. Environmental Protection Agency. Locating and Estimating Air Emissions From
       Sources of Carbon  Tetrachloride. EPA-450/4-84-007b, RTP, NC. March 1984.

9.     Pacific  Environmental Services,  Inc.   Emission Factor  Documentation  for  AP-42:
       Section  5.19 Synthetic Fibers.  Prepared for U.S.  Environmental  Protection  Agency,
       Office of Air Quality Planning and Standards, Research Triangle Park, NC.

10.     Lundberg, J.; Turbak, A.; "Rayon" in Kirk-Othmer Encyclopedia of Chemical Technology.
       Vol 19,  John Wiley and Sons Inc, NY,  1978-1984, pp 855-880.

11.     Dr. M.J. Mclntosh,  Removal and Recovery of Carbon Disulfide Emitted  bv  the Viscose
       Process, Energy Systems Division,  Argonne National Laboratory, April 1992.

12.     Youxin, L.: Dezhen,  Q.;  1985. "Cost-benefit  Analysis of the Recovery  of Carbon
       Disuifide in the  Manufacturing or Viscose Rayon." Scandinavian Journal of Work
       Environmental Health:  Vol  11, No 4; pp. 60 -63.           ~                     '

13.     Young, R. (editor;;  Pollution Engineering.  Volume XX,  No. 10, pp. 166-348.  October
       1988.

-------
 14.    PROCEDAIR  INDUSTRIES.  VOC  Vapor  Recovery  System  Brochure  liiquid
        Absorption, Contact: Frank Vollero [(201) 455-8821], Cedar Knolls, New Jersey.


 15.    Comments of the Chemical Manufacturers Association Carbon Disulfide Panel on EPA's
        Draft Report on Carbon Disulfide Emission Control Options, December 20,  1991.


 16.    International Patent WO 86/02283  (April  24,  1986), Cox. J.P.; Duffy  R  (identified
        through Chemical Abstracts (CA) library literature search).


 17.    Wecker U.S. Patent 1,622,126 (1927), cited in International Patent WO 86/02283 (April
        24, 1986), Cox, J.P., Duffy, R.                                                F


 18.    Dean U.S. Patent 2,280,896 (April 28, 1942), cited in International Patent WO 86/02283
        (April 24, 1986), Cox, J.P., Duffy, R.


 19.    Texaco  Chemical  Company. Diglycolamine Agent Brochure, Pub  No  102-0108 988
        [(512) 483-0136],  Austin TX.


 20.    NUCON International Inc., Braysorb Brochure Bulletin: IOB7-4/90  1990  Contact- Jaclc
       Jacox [(614)846-5710], Columbus Ohio.                       '      '


 21.    Viskase Corporation. Rationale for Conclusion that Carbon Adsorption Technolooy is
       Not Safe and Therefore  Infeasible for Control of Carbon Disulfide Emission a°t the
       Viskase  Corporation, Bedford Park Facility.


 22.    European Patent 0189606 (January 2, 1985), Vansant, E.; Peeters, G.; De Bievere P • Van
       Gompler. R. (identified through Chemical Abstracts (CA) library literature search).


 23.    Memorandum from D.A. Tulis, Alliance Technologies Corporation, to D.M  Michelitsch
       Control Technology Center, U.S. Environmental Protection Agency  October 10  1991'
       Meeting Report: Carbon Disulfide Emissions  Control  Options:  Meeting with members
       of the BASF organization.


 24.    Memorandum  from C.D.  Cannon,  BASF  Corporation,  Fibers  Division  to  DM
       Michelitsch, Control Technology Center, U.S. Environmental Protection Agency October
       16, 1991. BASF Carbon Disulfide Recovery System.


25.    Hagen, R.; 1991. Telephone conversation between Rudy Hagen of Akzo Chemicals and
       David Tulis of Alliance Technologies Corporation.; Chapel Hill. N C  July  1Q91 TAkzo-
       (205) 675-1310].                                              "   y      L


26.    U.S.  Patent 4,049,775  (October  10.  1975),  Majewska.  I; Grams  W •  Rybicki  ^ •
       Banasiak, I; (to Instytut Wlokien Chermcznvch, (identified through Chemical Abstracts
       (CA) library literature search).

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27.    PROCEDAIR INDUSTRIES. VOC Control System Brochure 2: Regenerative Thermal
       Oxidation, Contact Frank Vollero [(201) 455-8821], Cedar Knolls, New Jersey.

28.    U.S. Patent 4,374,819 (Feb 22, 1983), Palilla, F.; Frank, C; Gaudet, G.; Bagloi, J.; (to
       GTE  Laboratories  Inc) (identified through Chemical Abstracts (CA)  library literature
       search).

29.    Berzaczy, L.; Nierdermayer, E.;  Kloimstein, L.; Windsperger, A.; 1988. "Biological
       Exhaust Gas Purification in the Rayon Fiber Manufacture (The Waagner-Biro/Glanzstoff
       Austria Process.); Chemical Biochemical Engineering Vol 2, No. 4; pp 201-204.

30.    Quad Environmental Technologies Corporation - CHEMTACT Brochure Contact- Rob
       Rafson [(708) 564-5070], Northbrook, Illinois.

31.    Memorandum from J. Webster, Teepak, to S. Howe, Chemical Manufacturers Association
       Washington, DC, March  18, 1992.

32.    Chilton, C;  Perry,  R.; Chemical Engineers Handbook.  McGraw-Hill Book Company
       New York, New York, 6th edition, 1984.

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1. REPORT NO.       ~~~~	
  EPA  -  450/3-91-023
                               TECHNICAL REPORT DATA
                         (Please read Instructions on the reverse before completing
                           2.
4. TITLE AND SUBTITLE

  Carbon  Bisulfide Emission  Control Options
 7. AUTHOR(S)

    Ravila Gupta, Lula  Harris, and David  Tulis

 9-
                                                  6. PERFORMING ORGANIZATION CODE


                                                  8. PERFORMING ORGANIZATION REPORT N
          G ORGANIZATION NAME AND ADDRESS
    T.RC ENVIRONMENTAL  CORPORATION
    100 EUROPA DRIVE
    SUITE 150
    CHAPEL HILL, NC  27514
 12. SPONSORING AGENCY NAME AND ADDRESS
   Emission  Standards  Division
    	— — *•— »*•«.* \»»j ••*•*• »Awj.wu         \.I"1/XJJ
  Office of Air  Quality  Planning  and Standards
  U.S.  Environmental Protection Agency
  Research Triangle   Park,  NC  27711
                                                    3. RECIPIENT'S ACCESSION NO.
                                                    5. REPORT DATE
                                                       September 1992
                                                   1. CONTRACT/GRANT NO.

                                                      EPA - 68-DO-0121
                                                   3. TYPE OF REPORT AND PERIOD COVERED
                                                    4. SPONSORING AGENCY CODE
 15. SUPPLEMENTARY NOTES
   BSD Work  Assignment Manager:   Deborah M.  Elmore
 	MD-13     (919)  541-5437
 16. ABSTRACT         	"~~—"	—	•—.		

      The  EPA  Control Technology  Center, OAQPS,  has received  numerous
      inquires regarding control  options for  carbon disulfide  emissions
      to r««JJ°r P"Sen^S a  Description of   methods or techniques  used
      to control carbon disulfide emissions  from a variety of  source
      categories,  and discusses the feasibility  of application of each
      technique  presented.  This  report briefly  discusses various
      options  available to public and private industry for controlling
      hh^011 di^ulfi^e emissions,  and serves  as  a  reference source  for
      those seeking  further information.
17.

a.
               DESCRIPTORS
                          KEY WORDS AND DOCUMENT ANALYSIS
      Carbon Disulfide  (CS_)

      Emissions Control Technologies

      Emission Source

      Pollutant Control
18. DISTRIBUTION STATEMENT


     -Please  'Jniimi tart
                                     i 19. SECURITY CLASS , Hus Xeoorti

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     Enter information not included elsewhere but useful, such as:  Prepared in cooperation with. I ransbt.,,,. ,,l  I'resenied at u.nieu-nn ,.i
     To be  published in. Supersedes, Supplements,  DESCRIPTORS - Select from the Thesaurus,  of l-.ngmecr-.r.g and Scientilic  Terms Ihe proper jutlmri/ed terms thai  idenuiv the maior
     concept ot  the research and are sufficiently bpecitic and precis to be used as index entries lor cataloiunu.
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     ended  terms written in descriptor form for those subjects for which no descriptor exist*.                     "
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