Document reY6m1E0p57OMKboGzpkbKgLq

S.M -riPc *>.</, DEER PA :K MfC COM? -EX SHELL IL ocr o 976 -n I GcNi. UA?< CEB ?UFTCHe CAL MANUFACTURING - ENVIRONMENTAL CONSERVATION DEPARTMENT MANAGER COMPANY/ r' OATE OCTOBER 7, 1976 FROM SENIOR STAFF ENffht flANUFACTURING - ENVIRONMENTAL CONSERVATION DEPARTMENT t'JTT OPt* Ots subject WASTE WATER RESEARCH ANO DEVELOPMENT - 1977 PROGRAM This memorandum has been prepared to update the objectives of Manufacturing's ste Water Research and Development Program in light of recent court actions d to outline R&D activities for 1977. Briefly, the purpose of the R&D program n-GsupjMEiJ|s to provide a data base to achieve cost effective compliance with the next //)3'jm*jicGijound of NPDES permits which will be issued in 1978 and 1979 for five year E J'yV.XJL "peerriiooddss,. Iinformation obtained in thne RK&Du program will be used, in the near flT'Tferm, to support Shell's position relative to effluent regulations being developed suni^H E^y the EPA. For the longer term, the information will be used to select and ^ 'r* "COperate treatment facilities required by the new regulations. VI UGP. E$ Effluent guidelines for organic chemicals, refineries and plastics and IT C ynthetics were remanded to the EPA this year. The entire 1983 refinery guide- USA l'A(NT ines (Best Available Technology Economically Achievable) have been remanded tpysiiuRinbecause the EPA relied on multimedia filtration and carbon sorption technology, ^iuweryi<rwhich had not been demonstrated to be effective in commercial scale applic< ation ^ ciEfiec. Ej|oth 1977 (Best Practical Control Technology Currently Available) and 11998!3 supt<4ji. Standards were recinded for organic chemicals and plastics and synthetics. IT [fevelopment data were used improperly by the EPA which led to unsupportable f-jJ/I/h foer-generalizations. As a result of other court action, the EPA are developing Affluent limitations and guidelines, new source standards and pretreatment surropaj|w standards for toxic pollutants. Controls are to be established for 65 toxic pollutants. Catagories of point sources for 12 other toxic pollutants are to be ijdentified although specific control is not required. The toxic pollutants are !j listed in Attachment I. A court directed schedule (Attachment II) calls for 7un^inniipjromu 1 gation of final toxic pollutant regulations in 1979. Shell is participating in the development of the new effluent regulations W hjn direct contact with the EPA and with trade organizations. In the very near KGB EA|__ ruture we expect detailed inquiries from the EPA concerning waste loads at ^Manufacturing locations and the effectiveness of treatment technology. Surveys' __K__G_B__U_&LBucufey EPA contractors are expected which will include collection and analysis of . affluents at selected locations. In addition, the EPA will evaluate the effecliveness of carbon sorption at some locations using a mobile laboratory. UGUWPRH To meet informational needs for the development of regulations and to lievelop cost/effective treatment strategies, a comprehensive waste water R&D program has been initiated. This program is keyed to the development of -tp!* Analytical methods, the development of optimum biotreater performance and an j -.irJUCH.'GS 6Evaluation of the cost/effectiveness of non-biological waste treatment technology. ~Effluents from both refineries and chemical plants will be evaluated in this csautojh program. Qdtd Ad to/j -JU> 'ZsiA' od dtA /> A A,. o .u..,r `OvTX. DPMC-08871 Gesrtfal J jLL fi u\f LAM 002739 2 The 1977 waste water treatment program contemplates staffing for 24 total man-years compared to a 1976 commitment of 22 total man-years. The program provides for 1.6 man years of R&D assistance to locations and Head Office functions. The remainder of the program is described in more detail in the following summaries. Analytical Support (2.0 man-years) High priority will be given to the development of a Shell (Westhollow Research Center) capability to analyze for toxic pollutants. The list of toxic pollutants includes 17 inorganic materials and 60 organic compounds or classes of compounds. The class designations are broad categories containing many individual compounds. The analytical procedures considered appropriate by the EPA are still in the development stages. Briefly, metals are to be analyzed by atomic absorption, and organics are to be analyzed by gas chromatographic and mass spectrographic analyses of solvent and gas extracts. The EPA are using a criterion of 1 part per billion (ppb) as a limit of analytical sensitivity. Pollutants, will be considered to be absent at lower concentrations. One of the objectives of the analytical program is to'narrow the list of pollutants for control by establishing their absence at concentrations of 1 ppb. To simplify regulation, the EPA will be searching for surrogate control parameters which will provide practical means for monitoring and control. For example, surrogate controls could employ analyses such as total organic chloride and total organic carbon. Because of interferences in the analytical methods and the potential for*compositional variation in waste streams, positive exclusion of toxic pollutants will be difficult at the 1 ppb level. However, the analytical program will indentify the major pollutants which pass through secondary waste treatment facilities and therefore are candidates for removal by other means. It follows that analytical programs to characterize waste streams must be closely coupled with programs designed to determine cost/effective treatment technology. To be most useful the analytical methods should be understood and in hand as soon as possible. This is necessary to be able to independently check samples secured in EPA sampling programs anticipated in 1976 and to provide guidance for the evaluation of treatment technology. Eventually it will be necessary to characterize effluents from all manufacturing locations with NPDES permits. The scope of the analyses (77 toxic pollutants) is so large that relatively few samples can be fully characterized. In the absence of a sufficient number of analyses to establish variability, each analyzed sample must be defined within the context of current plant production, waste water treating conditions, and general effluent parameters. Deer Park - Chemical effluent has been selected for initial characterization with the analytical procedures now under development. Sampling will take place DPMC-08372 LAM 002740 3 in October 1976. This selection was made because of the potential for a broad range of pollutants in the effluent and because a high performance waste treat ment facility is operational. A refinery effluent will be characterized next. Sample scheduling and prioritization will depend on a number of factors. Locations sampled by the EPA will receive priority in the Shell analytical program to insure an independent check on EPA data. Locations discharging into public water supplies, such as the Mississippi and Ohio Rivers, would be given priority also. By way of illustrating the analytical approach, the sampling schedule for Deer Park - Chemical is given in Attachment III-. In addition to the treated effluent, samples will be secured to characterize the biotreater influent and the biological status of the biotreaters. The analyses thus obtained will be placed into operational context with the data on plant operations listed in Attachment IV. Organic Chloride Removal (2.0 man-years) Twenty-seven of the toxic pollutants are organic chlorides. This large bloc of toxic pollutants can be monitored as a class (as total organic chloride) and may be so controlled in new regulations. Deer Park - Chemical effluent has NPDES limitations on total organic chlorides. Although Norco Chemical effluent does not have these limitations now, future NPDES permits will limit organic chloride discharges (as a class or as individual toxic pollutants). Organic chlorides enter the waste water system from a limited number of sources which are candidates for treatment to remove or detoxify the organic chlorides. The`purpose of this program is to evaluate treatments which supplement the sorption studies described in the following program. Non-bioloqical Effluent Treatment (11.2 man-years) As mentioned earlier, the EPA consider multimedia filtreation and carbon soprtion to be leading candidates for BATEA waste water treatment. The general cost/effectiveness of these treatments has been questioned, if required for Shell manufacturing locations, these facilities are estimated to cost $65 million. . Firm data are needed to establish the cost/effectiveness for specific locations while new regulations are still being developed by the EPA. It is important to recognize that cost considerations are very important since the 1983 regulatory objective is to define Best Available Technology Economically Achievable. Therefore the approach of this program is to define realistic cost ranges for these treatment packages and to experimentally determine effectiveness in terms of general and toxic pollutant parameters. Actual waste streams may contain materials which could seriously influence the effectiveness of such treatments at specific locations. This information would be especially useful DPMC-08873 LAM 002741 4 in developing discharge criteria with the EPA to avoid the pitfalls of over generalization. Therefore actual waste streams from chemical plants and refineries will be tested and conceptual treating facilities will be cost estimated. Effluents from Deer Park (Chemical and Refinery) are to be examined first. Alternative waste treatments will be proposed for further study to remove refractory pollutants and to develop more cost/effective methods to control pollutants. The experimental approach will involve on-site testing. This is particularly necessary for filtration studies where prolonged storage would changed the filterability of suspended solids. Biotreating Processes (7.2 man-years) Previous research has indicated that biotreater performance can be influenced by micronutients in the waste water and by salinity. These leads are being applied to Deer Park Chemical effluent. Specifically, bench scale tests show that optimum iron concentrations can increase organics (TOC) removal by as much as 50%. This enhancement is lost when sulfide is present in the waste and iron is precipitated. Proper control of these parameters may provide opportunities to increase pollutant removal as required without heavy investments in capital. Salinity affects the growth and metabolism of biota in biotreaters. The salinity of the waste water changes in current operations at Deer Park depending on which process units are operating. In addition, future plans call for process changes at Deer Park which will reduce the salinity of the waste water. Therefore the effect of salinity on Deer Park Chemical biotreater operations is being defined to insure efficient operation. Finally, the use of powdered carbon in biotreaters has been reported to reduce the toxicity of the effluent and to yield an effluent of more uniform quality. This may provide a cost/effective approach to produce non-toxic effluent at Martinez v/here fish toxicity is becoming an important effluent control parameter. Plans for a plant test at Martinez are being developed. B. N. Bastian Attachments cc - Manufacturing - Plans & Analysis - Oil - General Facilities Support - Manager Engineering - Products - Process Engineering-Support - Manager Deer Park Manufacturing Complex - Environmental Conservation Superintended Shell Development Company - Shell Research Complex ''' Chemical Engineering - R&D - Manager Hydrocarbon Engineering - Mr. W. I. Doty Analytical - Oil - Mr. M. J. O'Neal DPMC-08874 LAM 002742 ATTACHMENT I Toxic Pollutants Substances To Be Controlled Acenapthene Acrolein Acrylonitrile Aldrin/Dieldrin Antimony and compounds Asbestos Benzene Benzidine Beryllium and compounds Cadmium and compounds Carbon tetrachloride Chlordane (Technical mixture and metabolites) Chlorinated benzenes (Other than dichlorobenzenes) Chlorinated ethanes (Including 1,2-dichloroethane, 1,1,1 ,-trichloroethane, and hexachloroethane) Chloroalkyl ethers (chloromethyl, chloroethyl, and mixed ethers) Chlorinated napthaiene Chlorinated phenols (Other than those listed elsewhere; includes trichlorophenols and chlorinated cresols) Chloroform 2-chlorophenol Chromium and compounds Copper and compounds Cyanides DDT and metabolites Dichlorobenzenes (1,2-, 1,3-, and 1,4-dichlorobenzenes) Dichlorobenzidine Dichloroethylenes (1,1- and 1,2-dichloroethylene) 2.4-dichlorophenol Diehloropropane and dichloropropene 2.4-Dimethylphenol Dinitrotoluene Diphenyl ether Diphenylhydrazine Endosulfan and metabolites Endrin and metabolites Ethylbenzene Fluoranthene Haloethers (other than those listed elsewhere: includes chlorophenylphenyl ethers, bromophenylphenyl ether, bis (dichloroisopropyl) bis-(chloroethoxy) methane and polychlorinated diphenyl ethers) Halomethanes (other than those listed elsewhere: includes methyl chloride, methyl bromide, bromoform, dichloro- bromomethane, trichloro- fluoromethane, dichlorodifluoromethane) Heptachlor and metabolites Hexachlorobutadiene Hexachlorocyclohexane (all isomers) Hexachlorocyclopentadiene Isophorone Lead and compounds Mercury and compounds Napthaiene Nickel and compounds Nitrobenzene Nitrophenols (including 2,4-dinitrophenol, dinitrocresol) Nitrosamines Pentachlcrophenol Phenol Phtalate esters Polychlorinated biphenyls (PCBS) Polynuclear aromatic hydro carbons (including benzanthracenes, benzopyrenes, benzofluorathene, chrysenes, dibenzanthracenes, and indenopyrenes) Selenium and compounds Silver and compounds 2,3,7,8,-Tetrachlorodi- benzo-p-dioxin (TCDD) Tetrachloroethylene Thallium and compounds Toluene Toxaphene Trichloroethylene Vinyl Chloride Zinc and Compounds '' DPMC-0887 LAM 002743 Substances To Be Identified But Not Controlled Acetone N-Alkanes (C10-C30) Biphenyl Chlorine Dialkyl ethers Dibenzofuran Diphenyl ether Methyl ethyl ketone Nitrites Secondary amines Styrene Terpenes DPMC-08876 LAM 002744 Toxic P o llu ta n t R egulatory Development Schedule \A 3+ O D o> f-- r^. 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(/) CO LU CL u_ CL *o QJ <r> tr- cd V) 03 r-- o QJ iQJ SI 5 QJ CD r-- UJ 4-> o CD QJ XJ r* U r-* -4-> CD QJ CL X> c 03 CD r-L03 u r- " QJ -C o r-- 03 S3 +-> -- 3 U rScn < .+ DPMC-08877 LAM 002745 ATTACHMENT III Sampling Schedule Prepare 24 hour composite from three 8 hour grab sample periods Biotreater Inlet 3 - 25 ml Vial/8 hours 1 - qt polyethylene/8 hours 1 - gallon glass/8 hours 2 - drums/24 hours Treated Effluent* 3 - 25 ml Vial/8 hours 1 - qt polyethylene/8 hours 1 - gallon glass/8 hours 3 - drums/24 hours Biotreater Basin 1 - 100 ml composited from several thief samples taken once during the day, each basin sampled separately VOA analysis Metals analysis Extraction and NPDES parameters, sulfide, nitrate, Kjeldahl nitrogen, O&G, NH3, COD, TOC, TDS, total organic chlorides Biotreatment and carbon sorption studies VOA analysis Metals analysis Extraction and NPDES parameters + O&G, COD, TOC, TOS, nitrate, NH~, sulfide, Kjeldahl nitrogen, total organic chlorides Carbon sorption studies and fish toxicity ATP, Dehydrogenase MLVSS; Conductivity Pb & Cr in solids *Sampled at location used for NPDES sampling DPMC-08878 LAM 002746 ATTACHMENT IV Operational Information Production Units Production rate, Ib/day, capacity Effluent, gpm Waste Hater Treating Primary treater flow rate, gpm coagulants, type Ib/day pH (after adjustment) Secondary treater inlet, flow, gpm (daily avg. & normal schedule) recycle flow,gpm (daily avg.) wasting rate,gpm (daily avg.) effective retention time, hrs. MLVSS, mg/1; MLSS mg/1 Dissolved oxygen, mg/1 Number of operating aerators GIC analyses of influent Temperature Outfall flow, gpm (avg. & at sample time) pH Pb TOC Cr COD O&G BOD TSS historical Operations Information Variability of NPDES Parameters average, max., min., standard deviation Miscellaneous Information Review of toxic pollutant list to identify possible pollutants in effluent Identification of specific chemicals the the class designations (e.g. diethanol amine might be one of the secondary amines present in the effluent) DPMC-08879 LAM 002747