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J. C. WEBER - General Offices - B2SK May 3. 1976 RGBs - KGK JEL EPA R. A. Fobl Flint A, Leisy C. Buckley D. B* Boomer Attached are the pertinent pages from the Versar Report of 2/3/76 concerning the abatement of PCBs concentrations in industrial effluents* The Table of Contents is also included* Please keep me posted on what develops. J. C. WEBER bh i .' .. ( .\ DS\N 330450 STLCOPCB4077094 ABSTRACT This document presents the findings of a study of available wastewater management and treatment technology for the purpose of determining toxic pol lutant effluents concentrations and daily load achievable in three industrial categories: polychlorinated biphenyls (PCBs) manufacturing; capacitor manu facturing; and transformer manufacturing. . All plants in the above categories have PCB discharges to either water ways or sewage treatment plants, under normal operating conditions. All plants have discharges to storm sewers or directly to waterways under heavy rainfall conditions. Extensive survey of wastewater treatment technologies and cooperative laboratory work with several suppliers of treatment equipment and research facilities has confirmed that carbon adsorption technology is the best current candidate for successful removal of PCBs from the wastewaters. As an alterna tive uv-ozonation was considered. This technology is still in the research stage; however, it offers potential of complete destruction of PCBs all the way to C>2' water and HCl. Another adsorbent technology now in the development stage, AMBEELITE polymeric adsorbents, has demonstrated a PCBs removal efficiency roughly equivalent to carbon during laboratory tests. Further testing is needed with this adsorbent to accurately assess its potentiality. For scrap oils and burnable solid wastes generated at these plants, high temperature, controlled incineration offers a straightforward method of de struction, whereas scientific landfilling appears to be the best suited mode of disposal for nonbumable contaminated solids. Zero discharge objectives can be best achieved by eliminating discharge streams and developing recycle systems. All non-contact cooling water would be segregated, cooled, and recycled. All other wastewater streams would be pretreated. The portion of the pretreated water which would be used in the plant would be treated with carbon, while the excess water would be i. DSW 330451 STLCOPCB4077095 incinerated in a specially designed system which would allcw for energy recovery. Supporting data, rationale for the selection of above recommended treat ment technologies and associated costs are contained in this report. DSW 330452 n. STLCOPCB4077096 TABLE OF CONTENTS SECTION I - INTRODUCTION............................................................................ Pa9e 1 1.0 OBJECTIVE OF THIS STUDY..........................................................................................1 2.0 SCOPE OF THIS STUDY ............................................................................................... 2.1 Industry Characterization................................. ............................. 2.2 Control and Treatment Technologies for PCBs Wastes . . 2.3 Capital and Operating Costs for Selected Treatment Technologies ...................................... ............................................... 1 2 2 3 3.0 REPORT CONTENT. . .................................................................................... 3 SECTION II - SUMMARY AND CONCLUSIONS . .................................................................. 4 SECTION III - RECOMMENDATIONS.......................................................................................... 15 SECTION IV - WATER USE AND WASTE CHARACTERIZATION ........................................... 18 1.0 INTRODUCTION ............................................................................ ....... 18 2.0 SPECIFIC WATER USES.............................................................................................. 18 3.0 INDUSTRY AND PROCESS WASTE CHARACTERIZATION...................................... 19 3.1 Manufacturing Process - Polychlorinated Biphenyls (PCBs) 20 3.1.1 Process Description................................................................... 20 ' 3.1.1.1 PCB Production and Usage ....... 22 3.1.2 Raw Wastes............................................................................'. . 3.1.3 Plant Water Usage.................................................................. 3.1.4 Wastewater Treatment and Housekeeping................... 24 24 27 3.1.4.1 Treatment Facility for the Effluent frcm Sauget Complex..................................... 31 3.1.5 Plant Effluents. ....................................................................... 31 3.2 Askarel Capacitor Manufacturing Industry............................. 32 3.2.1 Askarel Capacitor Manufacturing Plants.................. 34 3.2.1.1 Askarel Handling. ............................................... 36 3.2.1.2 Process Description ... ............................. 37 3.2.1.3 Raw VJastes....................... 42 . 3.2.1.4 Water Use....................................................... 42 Ui- SW 330453 STLCOPCB4077097 TABLE OF CONTENTS (Con't) Page SECTION IV (Con't) 3.2.1.5 Wastewater Treatment........................................ 46 3.2.1.6 Effluent Composition ...................................... 52 3.3 Askarel Transformer Manufacturing Industry..................................52 3.3.1 Transformer Manufacturing Plants.......................................59 3.3.1.1 Askarel Handling . . ...................................... 61 3.3.1.2 Process Description.......... 62 3.3.1.2.1 Assembly and Askarel Filling Procedure for the Distribution and PowerTransformers. ... 62 3.3.1.3 3.3.1.4 3.3.1.5 3.3.1.6 Raw Wastes .................................................................. 68 Water Use.............................................................................69 Wastewater Treatment................................................71 Effluent Corrposition .........................................75 SECTION V - SELECTION OF POLLUTANT PARAMETERS.............................................................79 1.0 INTRODUCTION.......................................................................................................................79 2.0 SIGNIFICANCE AND RATIONALE FOR SELECTION OF POLLUTANT PARAMETERS ....................................................................................................... 80 2.1 . 2.2 2.3 2.4 2.5 2.6 Polychlorinated Biphenyls .................................................................. 80 Chemical Oxygen Demand (CCD)...................................................................81 Fats, Oils and Greases.................................................................................82 Suspended Solids ......................................................................................... 82 Dissolved Solids ...............................................................................................83 Other Constituents....................... . ....................................................83 SECTION VI - WASTEWATER TREATMENT TECHNOLOGIES.........................................................84 1.0 .... . INTRODUCTION....................................................................... 84 1.1 Similarities and Contrasts Between PCBs Wastes and Con trol Practices in their Production, and in their Use as Dielectrics ......................................................................................... 84 1.2 Suimary of Waste Management Problem Areas....................... . 85 . 1.2.1 Waste Liquid PCBs and Contaminated Scrap Oil . . 85 1.2.2 PCBs in Wastewaters........................................................................86 1.2.3 PCBs Contaminated Solid Wastes . . .............................86 1.2.4 Air Emissions of PCBs...................................................................87 iv. DSW 330454 STLCOPCB4077098 v . SECTION VI (Con't) TABLE OF CONTENTS (Con't) i.. Page 1.3 Summary of Current PCBs Waste Control Practices . .. . . 87 1.3.1 1.3.2 1.3.3 1.3.4 Control of Waste Liquid PCBs and Contaminated Scrap Oils................................................................................. Control of PCBs in Wastewaters....................................... Control of Solid Wastes Contaminated with PCBs . Control of Air Emissions ,of PCBs .................................. 87 88 89 91 2.0 CANDIDATE PCBs WASTE TREATMENT TECHNOLOGIES CONSIDERED ... 92 2.1 Treatment of Waste Liquid PCBs and Contaminated Scrap Oils. .......... . ............. 93 2.1.1 Incineration . . . . r......................................................... 2.1.2 Sanitary or Scientific landfill................................. 93 95 2.2 Treatment of Wastewaters Containing PCBs............................ 95 2.2.1 Carbon Adsorption . .............................................................. 95 2.2.1.1 PCBs Adsorption Testing by Carborundum ' Company ............................................... 97 2.2.1.2 PCBs Adsorption Testing by ICI-US ... 98 2.2.1.3' PCBs Adsorption Testing by Calgon Corp. 102 - 2.2.1.3.1 Adsorption Treatment of the Wastewater............................ 105 2.2.1.3.2 Reactivation of the Granular Carbon. . . ............................ . 106 2.2.1.3.3 Carbon Treatment ........................ 107 2.2.1.3.4 Materials of Construction . . 107 2.2.1.4 2.2.1.5 Carbon Regeneration Alternatives - Wet Catalytic Oxidation ...................................... 108 Further Applications Data ..............................109 2.2.2 Ultraviolet-Assisted Ozonation ............................................109 2.2.2.1 Molecular Responses to Ultraviolet Region Energy..................................... Ill -. 2.2.2.2 Photodegradation of PCBs., ...... 112 . ,... . 2.2.2.3 Experimental Factors in UV-Assisted - , Ozone Oxidation of PCBs..................................113 ` 2.2.2.4 Destruction of PCBs and Refractory Organics at Houston Research, Inc.. . 114 ''' 2.2.2.4.1 PCBs Destruction Data .... 114 - ' - .. . 2.2.2.4.2 Operating Data Obtained frctn . : - ,. Refractory Organics Tests . 114 v. DSW 330455 STLCOPCB4077099 SECTION VI (Con't) TABLE OF CONTENTS (Con't) Page 2.2.2.5 Destruction of PCBs and Refractory Organics at Westgate Research Corp. . . 116 2.2.2.5.1 PCBs Destruction Data ................... 116 2.2.2.5.2 Pilot Scale Tests of Refractory Organics Decomposition . . . 122 2.2.2.6 2.2.2.7 Laboratory Test Results from AiResearch Corp. ...............................................................................127 Canroents on UV-Ozone Tests................................127 2.2.3 Non-Carbon Adsorbents for PCBs..................................... . 127 2.2.3.1 The Amberlite XAD Series of Macroreticular Resins. .......................................... 128 2.2.3.1.1 PCBs Adsorption Testing.... 128 2.2.3.1.2 Process Concept for Resin Ad sorption of PCBs. ...... 129 2.3 Treatment of PCBs - Contaminated Solid Wastes........................130 2.3.1 Incineration................................................... 130 2.3.2 Sanitary Landfill..........................................................................132 2.4 Treatment of Air Emissions .....................................................................132 2.4.1 2.4.2 2.4.3 Condensation Methods.....................................................................132 Granular Adsorption Methods..................................................132 Catalytic Oxidation of Organics in Evaporated Effluents...................................................................... 132 2.5 The Potential for Zero Discharge.......................................... 133 3.0 RATIONALE AND SELECTIONS OF CURRENTLY RECOMMENDED WASTE TREAT MENT METHODS............................................................. ................................. 134 3.1 Incineration Recommended for Liquid PCBs and Scrap Oils . 134 3.2 Carbon Adsorption and UV-Assisted Ozonation Recommended for PCBs in Wastewater ..........................................................................135 3.3 Incineration and Landfill Recommended for Contaminated Solids............................ 136 3.4 Dry Carbon Filter Adsorption Recommended for Control of Air Emissions . .............................................................................................136 SECTION VII - COST OF TREATMENT AND CONTROL TECHNOLOGIES ................................138 1.0 SUMMARY . ................................................................................................... 1.1 Plant to Plant Cost Variations..................................... 138 140 vi. DSW 330456 STLCOPCB4077100 SECTION VII - Can't TABLE OF-CONTENTS (Con't) Page 1.2 Activated Carbon Terminal Treatment System............................142 1.3 Costs Based on Volume Flow..................................................................143 2.0 COST REFERENCES AND RATIONALE..................................................................... . 143 2.1 2.2 2.3 2.4 2.5 2.6 2.7 2.8 2.9 2.10 Interest Costs and Equity Financing Charges ...... 143 Time Basis for Costs........................................................................ . 144 Useful Service Life . . . ..................................................................144 Depreciation ........................................................................... . 144 Capital Costs ............................................................................... .144 Annual Capital Costs ...... ................................. .... 144 Land Costs .................................................................. . 144 Operating Expenses .......................................... . 145 Rationale for Incineration Costs ............................................... . 145 Definition of Levels of Treatment..................................... 148 2.10.1 Effect of Varying Effluent PCB Concentrations . . 148 2.10.2 Zero Discharge Definition .................................................... 149 3.0 PCB WASTEWATER TREATMENT PLANT DESIGN PARAMETERS At COSTS . . 150 3.1 Introduction......................................................................................... 150 3.2 Pretreatment . . ...............................................................................................154 3.2.1 Equalization and Separation Basin............................ . 154 3.2.1.1 3.2.1.2 Equalization Basin Capital and Operating Cost . . ........................................................ 156 Equalization Basin Costs.......................................156 3.2.2 Multimedia Filtration .............................................. 156 3.2.2.1 Filtration Costs ............................................... . 160 3.3 Activated Carbon Treatment System for Removal of PCBs From Wastewater...............................................................................................160 3.3.1 Activated Carbon System Design ............................................167 3.3.1.1 3.3.1.2 Regeneration of Spent Carbon . ................... 175 Economic Analysis of Carbon Treatment of PCB Contaminated Wastewater.........................178 3.3.2 UV-Ozonation - Potential Alternative..................................180 3.3.2.1 3.3.2.2 3.3.2.3 3.3.2.4 Description of System Components and Rationale for Cost Evaluation. .... 180 Capital Costs. ............. 188 Operating Costs.........................................................188 Total Treatment System Cost for Zero Discharge System ............................................... 200 vii. DSW 330457 STLCOPCB4077101 SECTION VII (Con't) TABLE OF CONTENTS {Can't) Page 3.3.3 3.3.4 3.3.2.5 . Total Wastewater Treatment Plant Costs Using Activated Carbon or Ultraviolet Light Catalyzed Ozonation ......................... Cost of Implementing Carbon Adsorption Treatment for Selected Plants ..................................... Zero Discharge ..... .... ........ 200 205 212 3.3.4.1 Description of Dry Cooling Tower . . . 212 . 3.3.4.2 Design Criteria ............ 213 3.3.4.3 Capital Cbsts . . . ................................. 213 3.3.4.4 Operating Costs............................... 213 3.3.4.5 Cost of "Zero Discharge" for Selected Plants . .............................................................. 218 3.3.5 Comparison of "Zero Discharge" with Discharge to Surface Waters..................................................................... 218 3.4 Scrap Oil Incineration............................................................. 222 3.5 Solid Waste Incineration. . . . . . . . . . . . 223 3.6 Total Industry Treatment Costs . ... . .... . .... . 224 APPENDIX A - Plant 106's Position Statement on Dow's XFS-4169 Capacitor Dielectric Liquid APPENDIX B - PCB Adsorption Testing by XAD-4 Resin APPENDIX C - Description of Macroreticular Resins from Rohn and Haas Co. .APPENDIX D - Non-Carbon Adsorption and Other Research Stage PCB Treatment Technologies ' ' . ... APPENDIX E - Energy Requirement for Various Treatment Options viii. DSW 330458 STLCOPCB4077102 SECTION II SUMMARY AND CONCLUSIONS The table on the succeeding page gives a quantitative summary of daily PCB waste loads achievable by PCB manufacturer and the two major PCBs users (capacitor and transformer industries). This information was derived fron data supplied by these industries and presents estimates of anounts of PCB wastes currently discharged by these industries to the environment via water, land and scrap oil generated and destroyed by these facilities via inciner ation. The results of this study are grouped into three broad categories. First, those dealing with industrial characterization, production, use and emissions. The second group contains those giving an overview of available technologies for treatment of various PCB wastes and the third summarizes the costs associ ated with currently recommended waste treatment methods. Industrial Characterization* 1. The domestic annual production of PCBs in 1974 was 40,466,000 lbs of which approximately 22,000,000 lbs was used by capacitor manufacture ers and 12,000,000 lbs was used by transformer industries. The balance reflects inventory changes and about 5,395,000 lbs of export sales. 2. There are a total of 37 PCB user (capacitor and transformer) plants in the U.S. and one PCBs manufacturer. Of the 38 plants, 10 dis charge their effluents into the water ways while the remainder dis charge PCBs into the sewage treatment plants. All plants in these categories have discharges under heavy rain fall conditions. 3. In addition to air emissions, there are three types of waste materi als generated at these plants that require treatment and proper handling in order to minimize the PCB entry into the environment. These are: DS^M0*69 STLCOPCB4077103 PCB Manufacturer Capacitor Industries Transformer Industries TABLE 1 SUMMARY OF WASTE LOADS PCB Discharge in Waterways or Sewers 3.06 lbs 5.86 lbs 0.17 lbs Daily Average Land-Destined PCB Wastes 301 lbs 4440 lbs Unknown Scrap Oils to Incineration 1425 lbs 3968 lbs 1750 lbs 5 DSW 330460 STLCOPCB4077104 (a) waste waters containing trace quantities of PCBs (10 to 500 ppb PCBs) (b) waste PCBs, scrap oils and small quantities of process water highly contaminated with PCBs (c) burnable and non-bumable solid materials contaminated with PCBs. Quantitative estimates of these wastes are given in Table 1. 4. The quantities of land-destined wastes originating at the PCBs and capacitor manufacturing plants were estimated from sparse data sup plied by a few plants. Similar information is not available fran the transformer industry. These plants normally drum their solid wastes and have incomplete information on the number of drums ac cumulated annually. Some plants compact their wastes prior to drum ming; others drum their wastes without the benefit of compacting. There are no adequate records to quantify these wastes. At sane plants, the majority of this waste category, however, exists in an enormous total waste volume and probably at relatively lev; concen trations of PCBs. Further efforts are needed to adequately define these wastes . 5. As yet, very little is being done to control air emissions. The general assumption is that the vapor pressure of PCBs is so low that there will be essentially no air contamination. A few facilities, however, were reported to be filtering and chilling exhaust air from PCBs impregnation areas. 6. VJhile the emissions of PCBs to water are expected to decrease due to improved pollution abatement of waterborne wastes, the release of PCBs to air and land is expected to increase. The primary source of increasing air emissions is the increase in the load of incineration materials due to proper handling of wastes which were previously discharged into the waterways or sewers. The quantities of landdestined, wastes will also increase due to improved housekeeping measures. 6 DSW 330461 STLCOPCB4077105 7. Since most water used at these facilities is for non-contact cooling purposes, at most plants it is possible to significantly reduce the effluent volume by segregation of wastewaters, recycling and proper housekeeping measures. 8. Most plants have already undertaken PCBs containment programs in order to minimize the entry of PCBs into the environment. 9. There is no commercial scale wastewater treatment for PCBs removal being practiced tteyond those of gravity settling of the heavy PCBs layers as a sludge from the bottom of sumps or tanks, and skirrming of a contaminated oil-layer from the water surfaces. 10. Wastes in PCBs production and PCB wastes in capacitor and transformer manufacturing differ primarily in that the producer generates some higher boiling, highly chlorinated and polycyclic materials referred as "Montar" that are separated from the Aroclor products and in cinerated. Thus the users of PCBs do not receive the higher boiling materials. Aroclor 1016 is the principal PCB used by capacitor industry; at seme plants Aroclor 1242 and 1221 are also being used in limited quantities. Mineral oil is the principal coolant oil used by the transformer industry. PCB transformer oils (blends of 60 to 70 percent Aroclor 1254 or 1242 and 40 to 30 percent trichloro benzene) are used in only 5-10 percent of these plants1 manufacturing volume. Hcwever, it has been concluded that the characteristics of the waste materials and effluents generated in all these facilities are, in general, similar enough so that the same kinds of treatment technologies can be utilized for purposes of controlling PCB entry into the environment. 11. Most industrial analysis for PCBs in wastewaters are based on grab samples and probably have not been more accurate than about - 50% at the one and ten ppb level. os^ 7 STLCOPCB4077106 12. Rivers receiving PCBs discharges for a number of years vary greatly in PCBs content with time, apparently depending upon PCB content in storm water runoff 'and the degree to which bottom sediment is agi tated and suspended. 13. Wherever there have been PCB operations in the past, there are proba bly high concentrations in local waterways bottan sediments. 14. All water streams have greatly lcwered PCBs contents: (a) when solids are removed (b) when dispersed or dissolved oils are removed (c) When the stream ccmes in contact with a wide variety of solid surfaces (d) when no surface active agents are present. 15. Over the past 45 years, waste PCBs from transformer and capacitor operations have been used as local road oiling compounds. Sometimes they were discarded in duirps adjacent to manufacturing facilities. These are sources of long term leaching of PCBs into waterways, par ticularly with storm water runoff. Overview: of Available Technologies for the Treatment of Various PCB Wastes 1. The most advanced treatment technology in use is incineration. The PCBs manufacturer and one user have plant scale incineration capable of destroying PCBs with very high efficiency. There are at least two commercial services (Rollins Environmental Services and Chemtrol Pollution Services) available, with four incinerator locations in the Eastern and Southern U.S., that destroy PCBs. 2. Incineration is primarily applicable to waste PCBs and scrap oils contaminated with PCBs. All installations have the capacity of "burning" some contaminated wastewater but, of course, the pro portion of that water to the exothermic oil burning must be kept lew. 8\ STLCOPCB4077107 3. Only one commercial incineration service (Rollins) can routinely handle all kinds of PCBs contaminated transformer and capacitor ccmponents, sludges, fuller's earth and other solids, as long as they can be contained in a 47 gallon fiber drum. One PCB user caipany incinerates transformer internals for purposes of metal recovery. 4. Adequate methodology is available for those plants wishing to con trol the release of PCBs to the environment. Currently available technologies can be applied to the efficient removal of PCBs frcm wastes, or their destruction with the other wastes. 5. The PCBs content of wastewaters, can be lowered to the 1 ppb level or below by carbon adsorption, macroreticular polymer resins and proba bly other adsorbents. . 6. Carbon adsorption is currently the best available technology for plant scale treatment of PCBs wastewaters. This conclusion is based on laboratory tests with PCBs in water, and on the long background of plant scale use of carbon adsorption for removal of organics from water. 7. UV-ozonation technology is the best demonstrated method, on the labo ratory scale, for destruction of PCBs in wastewaters when the streams occur in large volume, on a relatively continuous flow basis and with PCBs at the ppb concentration levels. This technology has the po tential for conversion of PCBs to CC^, H^O and HCl. 8. Waste liquid PCBs and scrap oils contaminated PCBs are best handled, as a guideline, by high temperature (2000-2400F) and long residence time (2-3 seconds) incineration. However, because of incinerator design variables, the conditions should be chosen in each case to lead to 99.999% destruction. 9. Incinerators should be equipped with low tenperature alarms, and low temperature shut down of PCBs feed. They should have high efficiency water scrubbers to prevent HCl dissemination. 9 DSW 330464 STLCOPCB4077108 10. The bast incinerator combination for handling wastes fran these in dustries is a rotary burner fired by a liquid burner, and followed by an afterburner and scrubber system. The rotary burner can be designed to handle a variety of solid materials, and the liquid burner can handle both the oily and water type wastes. 11. Polymeric resins (AI4BEKLITES) were found in laboratory tests to be approximately as effective as carbon in removing PCBs fran water. Further pilot scale testing is needed with this newer (than carbon) technology to accurately assess its potential. 12. Although still in the laboratory stage, catalytic reduction of PCBs offers the possibility of reduction to biphenyl and HC1? and cata lytic oxidation offers a potential for destruction of PCBs to C00 H20 and HC1. 13. Reverse osmosis and ultrafiltration appear to offer a long term po tential for a more maintenance-free, and lower operational cost method of separation of PCBs from water. Success is dependent upon specialized membrane development now being carried out at several facilities. 14. It is believed that treatment systems eirplcying activated carbon and possibly UV-ozonation could produce effluents which would be at or below the limits of detectability for PCBs with currently available analytical techniques. However, since no full scale systems for the treatment of PCBs are in operation at this tine, this possibility cannot be confirmed. 15. Unfortunately, no methodology is presently available which can guarantee "zero discharge" to the environment. "Zero discharge" ob jectives can be best met now by eliminating discharge streams and developing recycle systems. All streams that are high in pollutants and can't be treated for reuse and the rainwater runoffs should be collected and incinerated. DSW 330465 10 STLCOPCB4077109 Posts Associated with Currently Beccrnmsnded Waste Treatment Methods 1. The Table on the succeeding page summarizes the estimated maximum capital and annual costs for the treatment of wastes generated in each industry category. As shewn treatment of all contaminated and potentially contaminated wastewaters, the incineration of scrap oils and the incineration of contaminated solid waste generated in the domestic production and utilization of PGBs is $35.50 million and $9.61 million, respectively. The total annual cost given above represents $0.28 per pound of PCS utilized within the U.S., based on 1974 data. 2. Rainwater contribution to the capital and annual wastewater treatment costs was estimated at 15 and 25 percent, respectively. If significant isolation of the contaminated areas can be achieved these costs will be somewhat reduced. 3. The estimation of total maximum costs anticipated for the manufacturer and users of PCBs was facilitated by preparing cost estimates for each plant site visited during the course of this study and then aggregating to the total industry category on the basis of the percentage of the total industry represented by the visited plants. 4. The treatment system includes settling for solids removal, oil skimming, equalization, fine media filtration, terminal PCB treatment, flow measure ment and sampling, and discharge to surface receiving waters. All sludges and free floating oils are disposed of through incineration. All backwash waters used in the system are recycled back to the gravity settling basin for treatment. All spent adsorbent is destroyed by incineration (for wastewater flows up to 300 gpm) or regenerated on-site for reuse (for waste flows above 300 gpsn). 5. An activated carbon system was selected as the terminal PCB treatment method for purposes of estimating the maximum total costs. A potentially viable alternative to carbon adsorption, UV-ozonation, has less well de fined capabilities. .Additionally, it is believed that unless the UVozonation system can do an equal or better jcb of destroying PCBs at a lower cost, it.will not be selected by these industries. CSV* S30486 STLCOPCB4077110 TABLE 2 Industry MAXIMUM PCB INDUSTRY TREATMENT COSTS Capital Cost Total Annual Cost PCB Producer Capacitor Manufacturing Transformer Manufacturing Total $ 1,600,000 16,600,000 17,300,000 $35,500,000 $ 595,000 4.200.000 4.815.000 $9,610,000 Total Cost Per Pound of PCB utilized Total Cost Per Pound of PCB discharged to waterways $ 0.28 $ 2896 Cost Per Pound Produced or Used $0,015 0.190 0.401 12 DSW 330467 STLCOPCB4077111 6. A carbon adsorption system will remove PCBs from industrial effluents to a level of one ppb or less. It is impractical to design an activated carbon system to obtain a choice of effluent oonoentrations. The operat ing cost savings for operations at various effluent PCB concentrations are expected to be too small to justify designing carbon adsorbers for PCBs removal at higher than one ppb level. 7. The work performed by Houston Research and Westgate Research on UVozonatian indicates that the final concentration is a function of resi dence time, and that UV-ozanation systems can be designed to achieve any desired effluent PCB concentration. 8. Preliminary comparisons of the capital costs of the two systems show at least a 100 percent greater cost for the ozone system over the carbon. When pretreatment costs are combined with treatment, the UV-ozonation process is about 10 percent higher than the carbon process. 9. The design and fabrication of incineration equipment is a highly proprie tary industry, it is believed that any attempt to estimate the cost of such systems on a rational basis would be fruitless. In addition, it seems quite improbable that the smaller PCB user plants would find it economically justifiable to install and operate such a system for de struction of scrap oils and solid wastes contaminated with PCBs. The al ternative to on-site incineration is contract incineration. For purposes of cost estimation and based on the range of prices quoted by service companies, a flat rate of $0.10 per pound has been assumed for all scrap oil and solid wastes even if they are generated by facilities which have an on-site incinerator. 10. Contract incineration of large volume, dilute aqueous streams dees not seem to be a feasible alternative due to the logistics and transportation cost. For purposes of achieving "zero discharge", capital costs for on site incineration systems were developed. In this case, the accuracy of ____capital cost estimates are not deemed as critical in view of the high. operating cost, primarily fuel cost, associated with this system. 13 STLCOPCB4077112 11. The least cost "zero discharge" system comprises segregation of waters .. used in the plant and cooling and recycling all non-contact cooling water. All other wastewaters will be routed to a central system for equalization, settling and fine media filtration. The portion of the water to be utilized in the plant will be subjected to terminal treat ment with carbons, the excess water will be subject to incineration in a specially designed system viiich would have the potential of energy recovery. 12. Capital and total annual costs to achieve "zero discharge", based on the system described above, was developed for selected plants. It was con cluded that the total annual costs for "zero discharge" was about 2.0 to 12.0 times the cost of the carbon system (close loop cooling water case) when rainwater was included. 13. Rainwater runoff is a direct function of the locations1 rainfall and run off area. The rain runoff area may or may not be dictated by the size of the production facility. This single flaw could provide the largest flew variation for all production facilities. 14. For the "zero discharge" system the rainwater contribution to the annual wastewater incineration cost is very high, comparison of the two "zero discharge" cases [ (1) inclusion of rainwater runoff as incinerating material and (2) exclusion or rainwater runoff] indicates the annual cost of the case 1 to he 2 to 42 times the cost of the case 2 for the various plants under study. 15. As a rough approximation, energy requirement for waste incineration i.s directly proportional to the hydraulic load of the unit. Water inciner ation is far more energy intensive than scrap oil incineration. 16. Energy requirement of each plant is proportional to the total hydraulic load of the pretreatmant and terminal treatment systems. 14 DSW 330469 STLCOPCB4077113 SECTION III im)MMENDATICNS There are indications within the PCBs manufacturer and PCBs user indus tries that progress is being made in air and water pollution abatement; how ever, little is being dene to assure that the land-destined wastes are dis posed of in an environmentally sound manner. This shortcoming can be attributed to higher costs associated with handling large volumes of wastes further information is needed regarding methods and costs of handling landdestined wastes. Based on the summary and conclusions cited in Section II, the following reccsrrrendations are made: 1. Verification sampling should be conducted under controlled conditions in order to define the levels of PCBs discharged into the environ ment with higher degree of accuracy. 2. Promulgation and enforcement of regulations for water pollution abatement frem stationary sources should be continued. Regulations for non-point sources should be initiated to minimize the entry of PCBs into the environment. 3. The use of more biodegradable PCB (Aroclor 1016) in transformer ap plications should be encouraged. 4. New regulations should be developed and enforced to ensure that the land-destined wastes fran these facilities are disposed of in an en vironmentally sound manner. 5. Additional data should be developed to adequately characterize solid wastes generated by these three industries and then define methods and costs of handling these wastes. 6. The capability of various incineration facilities should be deter mined for PCBs destruction on a given doctored feedstock using a pre- ...... developed and specific test plan. Analysis of available data indi cated that there are differences of opinions as to optimum tempera ture level and residence time for PCB incineration. 15 STLCOPCB4077114 . 7. Waste PCBs liquids and scrap oils contaminated with PCBs should be incinerated in approved facilities. New incineration facilities can be installed in one year. 8. Every effort should be made at each plant to minimize flews. The source of rain runoff contamination should be traced and efforts should be directed to isolate the contaminated areas. 9. Disposable foot coverings and outer garments should be provided at each plant; work clothing should not be allowed to leave the plant other than via solid waste. 10. All spills should be cleaned via rags or floor dry and disposed of in waste drums for incineration. All solid waste should be disposed of in impervious sealed containers. 11. As a housekeeping measure, all sinks in the PCB impregnation and PCBs handling areas should be contained. The wash water frem these sinks should be properly treated prior to disposal. 12. Wastewaters containing PCBs should be treated by the standard sani tary procedures of settling the sludges and sediments, removal of suspended solids, and skimming to remove floating oils; all prior to specialized terminal treatment for PCBs. 13. Wastewater pretreated as recommended above should then be treated in carbon adsorption columns for removal of PCBs to the ppb levels or less. 14 . Spent carbon should be regenerated in an environmentally sound man ner, or sent to approved incineration along with other PCBs wastes. 15. Waste capacitor and transformer components, absorbent solids, adsor bents, soil, cloth, paper, wood and similar solids contaminated by PCBs should be incinerated in a rotary kiln. The exhaust should be fed to an incineration unit for liquid PCBs, equipped with after burner and scrubber to assure destruction of all PCB vapors. Such facilities can be installed in caie year. 16 . OSNN STLCOPCB4077115 16 . Exhaust air frc*n PCB impregnation areas should be filtered through absorbent carbon, with chilling, if necessary, to meet clean air quality standards. This equipment can be installed in one yaar. 17. Research on the catalytic oxidation of dilute PCB vapors in air streams should be conducted to determine the feasibility of lew temperature destruction of PCBs by an energy saving process. This method will take more than three years to develop. 18. Research on UV-ozonation should be continued to achieve the follow ing goals: a) determination of optimum conditions for a continuous flew reactor system using actual wastewaters - b) conduct on-site demonstration tests using portable equipirent at a PCB using plant, operating on a wastewater slip stream c) design, construct and operate a pilot unit, on actual wastewater, to develop reliable capital and operating cost UV-ozonization treatment technology can be fully developed and in stalled in three years. 19. Pilot scale R&D on reductive dechlorination sliouid be continued to obtain reliable capital and operating costs. This method will proba bly be available for plant scale application in three years time. 20. Laboratory research on catalytic oxidation as a method of PCBs des truction should be initiated. The feasibility of wet catalytic oxidation using suspended commercial catalysts at elevated terrperatures (200-500C) and elevated pressures (500 to 1000 psi) should be determined. This method will take more than five years to develop. ^0 17 O',S^ STLCOPCB4077116 . Treatment and housekeeping measures practiced at the facilities and on-going PCB containment programs . Plant waste effluents found and their composition 3.1 Manufacturing Process - Polychlorinated Biphenyls (PCBs) . 3.1.1 Process Description Monsanto, the sole domestic manufacturer of PCBs, manufactures this chemical in their Sauget, Illinois plant. The basic raw material is biphenyl which is manufactured from pure benzene in another Monsanto plant. The PCB manu facturing operation is conducted in two steps. First, biphenyl is chlorinated with anhydrous chlorine in presence of ferric chloride to produce crude PCBs and then the crude PCBs are distilled to obtain the finished product. A schematic flew diagram of this process is given in Figure 3.1.1-1. The reaction section consists of 6 reactors (3 batch and 3 cascade). Currently Monsanto manufactures four different types of Aroclors (1242, 1016, 1254 and 1221). For the manufacture of any given product, the chlorinator is charged with proper quantities of biphenyl and catalyst and heated beyond the melting point of biphenyl. The flow of vaporized chlorine is then started and the charge is circulated with a pump. Throughout the chlorination, the temperature is kept above the melting point of the mixture, but below 150C to avoid excessive sublimation and plugging of the line discharging the hydrogen chloride produced by the chlorination. The reaction pressure is maintained near atmospheric. The degree of chlorination is principally determined by the tin's of contact with anhy drous chlorine. The contact time varies from 12 to 36 hours for the manufacture of different Aroclor types. The degree of chlorination is measured by the specific gravity of mixture or the ball and ring softening point when the product is viscous. The vapors from the chlorinator (HC1 containing PCBs) are scrubbed with liquid Aroclor and the gaseous HCl is sent to another plant at the Sauget complex for purification. The crude product is held at an elevated tem perature and blown with dry air for several hours, after which it is sent to the raw Aroclor storage tank where a' few tenths of 1 percent of alkali is stirred 20 STLCOPCB4077117 fe 3 a. gx cc x g cc 2 2 O H 3 Z< >z IU CzO 0 2 1 co CO a I b ZaJ o cc cc x 3 UJ o X o 2> X wo oX cc oz Xg o 2 55 0 <r CO 2 Qi UaccJ. CO i 1 < fO CO3' io eDCO X IE DSW 330474 21 STLCOPCB4077118 with the material to react with any remaining hydrogen chloride or ferric chloride. The air from the blower tank is scrubbed with water and vented to the atmosphere through a demister. The raw Aroclor is subsequently batch distilled under reduced pressure to remove the color, and the traces of hydrogen chloride and ferric chloride. The methods of purification are different for the different types of end products. Raw Aroclor 1254, 1242 and 1221, each are distilled in stills under reduced pressure, achieved via steam jet ejectors; the condensate from the still is the finished product while the bottoms are the Montars which are drummed and sent to incineration. The distillation section for the 1016 product consists of a gas fired retort and a vacuum distillation tcwer. The latter is used to allow the separation of the higher chlorinated, less biodegradable compounds from the relatively lower chlorinated and more biodegradable ones. The raw Aroclor (42% chlorinated material) is fed into the reboiler. The vacuum in the tower is main tained at about 100 mg Hg via steam jet ejectors. The steam is partially con densed and the condensate is discharged into the plant discharge sump. The first cut from this tower is recycled back to the retort. At a preset overhead temp erature the 1016 product is collected and sent to the product storage. The high boiling residue from the tower is sent to a subsequent chlorination cycle and the resulting raw Aroclor is distilled in a still. The overhead frcm this still is the finished product. The bottoms frcm this tower are the Montars, which are sent to incineration. ' For special orders, in order to increase electrical resistivity, the Aroclors are stirred, at an elevated temperature, with a few tenths of 1% of well-dried fuller's earth and then filtered through paper. All Aroclors are stored at 150F. Steam coils are used on the storage tanks for heating these tanks. . 3.1.1.1 PCS Production and Usage The William G. Krurtmrich plant at the Sauget complex has an annual design capacity of 48 million pounds chlorobiphenyls. Table 3.1.1.1-1 22 OSW 330475 STLCOPCB4077119 TABLE 3.1.1.1-1 PCB MANUFACTURE & SALES U.S. production Domestic sales U.S. export sales (Thousands of pounds) 1974 First Quarter 1975 40,466 34,406 5,395 8,532 7,986 1,538 Domestic Sales by PCB Grade Aroclor 1221 Aroclor 1242 Aroclor 1254 Aroclor 1016 . 57 6,207 6,185 21,955 10 2,201 2,115 3,660 Predominant Utilization of Aroclors Aroclor 1221 & 1016 Aroclor 1242 & 1254 : . Capacitor applications Transformer applications 23 OS'N STLCOPCB4077120 present data from Monsanto related to production and sales on PCBs for the year 1974 and the First Quarter of 1975. Table 3.1.1.1-2 presents approximate molec ular composition of these Aroclors as published by Hutzinger et al (0. Hutzinger, S. Safe and V. Zitko, "Chemistry of PCBs", CRC Press, 1974). The majority of the PCBs produced in this plant is marketed domestically. At present, almost all Monsanto's PCB production is being used in "closed electric systems" (transformer and capacitor applications). 3.1.2 Raw Wastes The raw wastes from the manufacturing area consist of the liquor from the scrubber, the condensate from the steam jet ejectors, water used for shcwers and eye baths, miscellaneous floor wash dams, waste oil collected in drip pans and drums, and montars which are the bottom cut from their stills. Hhe composition and the quantities of the individual waste stream are not monitored. All effluent streams generated in the manufacturing area are directed into the sumps in this area. The waste oil collected in the drip-pans and the montars are emptied into 55 gallon drums and sent to incineration. The raw wastes generated in the incinerator consist of the venturi scrubber liquor and the water phase from the separator sump in the incin erator area. The composition of the combined stream is monitored. However, the composition of the individual streams is not known. Non-product PCB discharges are sham in Figure 3.1.2-1. It has been estimated that this plant generates about 25 lbs. of scrap oil and Montar per ton of PCB produced. Additionally the quantities of material sent to landfill approximates to 5.4 lbs. per ton of PCB produced. Additionally, reports that the plant's PCB contribution to air is under 1 lbs/day. 3.1.3 Plant Water Usage On the average, the PCB plant uses a maximum of 388,800 gallons of water and a maximum of 360,000 lbs. of steam, daily. Water is used for non contact cooling purposes in shell and tube condensers, in a water scrubber, for floor washings, for showers and in eye baths. Steam is used in the steam jet 24 & O5' ^ STLCOPCB4077121 TABLE 3.1.1.1-2 APPRQXIMA1E MOLECULAR COMPOSITICN OF ABQCLORS Chlorobiphenyl C12H10 C12H 9 C1 C12H8Cl2 C12H7C13 1221 11 51 32 4 2 Aroclor Type or Grade (percent carposition)* 1242 1254 <0.1 <0.1 -1 <0.1 16 0,5 49 1 25 21 C12H5C15 Ws C12H3C17 C12H2C18 C12Hia9 C12ai0 0.5 ND ND ND ND ND 8 1 <0.1 ND ND ND 48 23 6 ND ND ND 1016 <0.1 1 20 57 21 1 <0.1 ND ND ND ND *ND - Denotes non-detectable DSW 330478 STLCOPCB4077122 < X UJ Z IU e> X UJ CO X o H O U-pJ X CO z < XX o. co ; ro o> m CD CD oK X O o oh UJ "P til CD UJ X H <1x o X H* UJ O '< > UJ s xx < Id oX x to < u- f- UJ cc o 3CO < <o x X 2 X X UJ X o CO UJ UJ I< < UJ t-- CD CO z Sox ooo X oo Xo Id H< CO z Io< Hz o X UJ m UJ o z o O1 z o CD o Xo o z co X Xo o t~ < X s sUJ CO o XX o XX z o CO CD I-- X < H z o 1-- o X ooo mo 26 DSW/ 330479 STLCOPCB4077123 ejectors and for steam tracing purposes. The plant uses municipal water and purchased steam. The process water from this facility consists of the liquor from their scrubber and the steam condensates which are discharged in one of the two sumps in the manufacturing area. Additionally, 273,600 gallons of water are vised in the incin erator daily for quenching the hot gases from the fire box. The resulting weak muriatic acid in the quench pot is used in the venturi scrubber and in the packed tower. The type and quantities of water used and discharged at this plant are sumrarized below. . Water Balance . Manufacturing Plant Quantities, GPP______ Process Water ` in water scrubber misc. floor wash downs condensate from steam jet ejectors Non contact cooling water shavers, eye bath condensate from steam tracers Total Used 14,400 7,200 -- 360,000 7,200 -- 388,800 Discharged 14,400 7,200 14,400 360,000 7,200 28,800 432,000 Incinerator water used for hot gas quenching water phase from the sump Total 273,600 -- 273,600 273,600 14,400 ' 288,000 3.1.4 Wastewater Treatment and Housekeeping Monsanto reports significant environmental controls at their Krummrich, Sauget plant. Since 1969, they have invested more than 22 man-years of work and millions of dollars in this program. The in-house goals have reduced the FCB discharges into water to about three pounds per day. 21 SW 330480 STLCOPCB4077124 A John Zink designed incinerator was erected at Sauget in 197. to safely dispose of PCBs. A schematic flow diagram of this operation is given in Figure 3.1.4-1. Aroclor is steam atomized and fed into the fire box. Natural gas is used for combustion and the feed is incinerated at temperature above 2200F at 5 percent excess oxygen with a retention time of 2-3 seconds. The gases are quenched with water and the exhausts from the quench pot are passed through a high-energy venturi scrubber, then through a packed column which is irrigated by the weak muriatic acid originating from the quench pot. Exhausts are then vented to atmosphere through a demister. These exhausts as well as the effluent from the incinerator section are monitored. In the incineration area, drainage is directed to trenches and piping which flow into a 10,000 gallon underground concrete basin. The water layer from this basin is pumped continuously, combined with the scrubber liquor, metered, monitored and discharged into the sanitary sewers of the Sauget complex and from there it is sent to the East St. Louis municipal sewers. Tire organic phase from the sump is periodically pumped into waste storage tanks for inciner ation. The incineration unit has a rated design capacity of 10 million pounds per year. However, since the start of its operation this unit has achieved a service factor of about 0.60. Monsanto reports that this incinerator can achieve a maximum of 6-million pounds of capacity annually; the unit is plagued with various mechanical problems. Monsanto uses their incinerator to process both their own wastes and as a service to other industries. The service charge for incineration is an average of 5 per lb. of material, but the cost appears to be increasing. The incinerator feed is brought into the plant either by truck in 55 gallon sealed drums, by tank trucks or by rail. The drums are opened, picked up by a fork lift and emptied into a concrete pit. The tank truck carrying the waste liquids enters the incinerator area and the liquid waste is then pumped from the truck into the pit. The material in this pit is periodically pumped via a vertical certrifugal pump in one of the four 20,000 gallon, each, incinerator waste feed tanks. 28 DSW 330^81 STLCOPCB4077125 cc 1 ccr UJ z o 2 v: z NH 2 X o 2 < _J Q. UJ X X o H u. 5o=: O'2 z> <x tc 0 < Q to 'o b- ' s 2 < CO U. 2 O K UJ B oc Cl 1 T <fr tf> ouO* in 29 DSW 330482 STLCOPCB4077126 The rail car is brought into a designated area close to the incinerator site. The material from the rail car is normally pumped into a long term, 500,000 gallon storage.tank. The material from this tank is purrped into the incinerator feed tanks located on the incinerator pad, when required. Drainage is provided along the rail tracks. These drains empty into the 10,000 gallon sump located under the incinerator pad. In the manufacturing area, Monsanto has taken a number of significant steps to prevent loss of PCBs to the environment. Drainage is directed to trenches and piping, and then to one of two concrete 3,000-gallon underground settling basins. This insures PCB containment in case of accidental spill or equip ment failure. Relief valve lines and atmospheric vents are routed through catch tanks, or are redirected to settling basins. When small quantities of PCBs are collected in the settling basins of the manufacturing area they are later purrped into 55 gallon drums, and eventually incinerated. The overflow from these sumps is combined with the non contact cooling water used at the plant, monitored and then discharged into the Sauget complex's sanitary sewer and from there to the East St. Louis municipal system. PCBs are pack-.-d and shipped in galvanized-steel 55 gallon drums, or in railroad tank cars. All tank cars are top loaded. In the drum filling area spills are cleaned via rags or floor dry and these materials are drummed and sent to landfill located in the town of Sauget. In the PCB truck or rail car loading area drainage is directed into a snail concrete pit. The material accumulated in this pit is periodically pumped into the basins located in the manufacturing area. Nitrogen blanketing is provided on storage tanks to eliminate any "breathing" of the tanks and resultant PCB escape, . Mist eliminators have been installed in vapor lines to eliminate the possibility of PCBs leaving the manufacturing area through these lines. 30 DSW 330483 STLCOPCB4077127 , Finally, underground servers have been replaced with above ground sewers, and repaired or combined with others, so that the effluent'from the department can be monitored. In addition, this step will prevent any unknown buildup of PCBs in the sewer systems or any contamination of PCBs into other sewers. A high housekeeping level is maintained in the plant itself. Housekeeping responsibilities which the operators have assumed are as follows: . All pumps are checked for leakage on every shift. Drip pans that collect leaks are emptied into scrap PCB drums. All leaks are reported and documented so that corrections can be made and settling basins deserved. . "Floor Dry" is used to absorb any PCBs that have spilled or leaked. If it becomes necessary to flush PCBs to the settling basin, a minimum amount of water is used. ." Sampling drums and scrap PCB drums are quickly palletized, labelled and transferred to the in cineration area. 3.1.4.1 Treatment Facility for the Effluent from Sauget Complex The processing and incineration departments' aqueous effluent enters the plant sewer system, and this system discharges into the Sauget Village waste sewer system. The combined streams then flaw to the village primary treatment plant. The village treatment plant is under expansion to a secondary chemical treatment plant, scheduled for 1976 completion. Additionally, evaluations are being conducted to include the village plant discharge in a projected regional biological treatment plant. ' 3.1.5 Plant Effluents This plant has no point source discharge from their operation. There is a single discharge from the manufacturing operation (the combined stream of process and non-contact cooling water) to the main sewer system of the Sauget 31 0s^0481 STLCOPCB4077128 complex and there is a second discharge from the incinerator area to the same sewer system. The composition of these streams as reported by Monsanto are as follows: flow rate, gpd PCBs, ppm PCBs, Ibs/day Effluent from the Manufacturing Operation 432,000 0.75 2.70 Effluent from the Incineration area 288,000 0.15 0.36 It has been reported that these effluents are clear liquids with essentially no suspended solids. The incinerator effluent nay contain sate amounts of chloride. However, no information is available on the chloride content. 3.2 Askarel Capacitor Manufacturing Industry Presently 90-95 percent of all capacitors manufactured in the U.S. are of the PCB impregnated type. Two important types of capacitors are phase correctors on power lines and ballast capacitors for fluorescent lighting. Aroclor 1016 is the principal PCB used in this application; at some plants Aroclor 1242 and 1221 are also being used in limited quantities. The principal types of Aroclor impregnated capacitors and their applications are given below. A. High Voltage Power Generally AC capacitors are used to improve the power factor of a circuit. Power factor is the ratio of true power in watts to the apparent power as obtained by multiplying the current flowing to the load by the circuit voltage. The power factor correction can be made directly at the load or at utility substations. In the latter case high voltage units will be designed for 4,800 to 13,800 volt service. To the utility engineer the use of capacitors is purely a matter of economics. The main benefits that result from the use of capacitors are: 1. Reduction of losses associated with the delivery of electrical . power to the point of use. 32 DSW 330485 STLCOPCB4077129