United States Environmental Protection Agency Industrial Environmental Research Laboratory Cincinnati OH 45268 Research and Development EPA-600/S2-84-115 Aug. 1984 Project Summary Logan Wash Field Treatability Studies of Wastewaters from Oil Shale Retorting Processes B.O. Desai, D.R. Day. and I.E. Ctvrtnicek Treatability studies were conducted on retort water and gas condensate wastewater from modified in-situ oil shale retorts to evaluate the effective- ness of selected treatment technologies for removing organic and inorganic contaminants. At retorts operated by Occidental Oil Shale, Inc., at Logan Wash, Colorado, treatability studies were conducted on retort water using filter coalescing, steam stripping, acti- vated sludge treatment (both with and without powdered activated carbon addition), sand filtration, and granular activated carbon adsorption. Retort water had high concentrations of ammonia-nitrogen, total Kjeldahl nitro- gen, alkalinity, dissolved organics, phenols, sulfide, total dissolved solids, boron, potassium and sodium. Steam stripping removed ammonia-nitrogen, alkalinity, and sulfide from retort water and organics removal was low. Gas condensate wastewater had high con- centrations of ammonia-nitrogen, total Kjeldahl nitrogen, dissolved organics, alkalinity, phenols, sulfide, and pyridine compounds. The overall scheme for the gas condensate treatment removed ammonia-nitrogen, total Kjeldahl nitro- gen, alkalinity, sulfide, biochemical oxygen demand, dissolved organic carbon, chemical oxygen demand, and phenols. This Project Summary was developed by EPA 's Industrial Environmental Research Laboratory. Cincinnati, OH, to announce key findings of the research project that is fully documented in a separate report of the same title (see Project Report ordering information at back). Introduction To assess the characteristics and treatability of wastewaters generated from the processing of oil shale, the U.S. Environmental Protection Agency (EPA) contracted with Monsanto Research Corporation (MRC) in 1979 to conduct a five-phase program entitled "Assessment of Oil Shale Retort Wastewater Treatment and Control Technology." The program had the following objectives (phases): I Summarize available information concerning oil shale retort waste- water sources and characteristics; II Identify control technologies that are potentially applicable for treat- ment of the identified wastewater streams; III Design pilot-scale units capable of evaluating the applicable technol- ogies at oil shale processing sites; IV Construct the pilot-scale units; and V Operate the units and evaluate treatment technology perform- ance. Based on the results of Phases I and II, it became apparent that not much informa- tion existed on which to evaluate and select potentially applicable technologies for testing and that laboratory bench- scale testing and wastewater characteri- zation were warranted. Wastewater cha- racterization and bench-scale treatability studies were conducted using samples of oil shale wastewaters available at the time. Steam stripping, hyperfiltration, carbon adsorption (batch isotherm and column), and activated sludge treatment tests were conducted on a bench-scale level. The results of these studies and the ------- information previously collected during Phases I and II were used to select the treatment schemes and units for con- struction and field testing under the follow-up Phases III through V. The schemes and units approved by EPA with some modifications were field tested at the modified in situ retorts operated by Occidental Oil Shale, Inc., in Logan Wash, Colorado. Oil shale retorts generate gases and an oil/water mixture from shale pyrolysis, combustion of carbonaceous residues, and decomposition of inorganic carbonates. As shown in Figure 1, off-gases generated from an in-situ retort exit the retort bottom and are brought to the surface for treatment. The retort oil/water mixture accumulates in the product collection sump at the retort bottom and is subse- quently pumped out and treated to recover the bulk of the shale oil. The separated gas condensate and retort waters are the wastewaters which were studied at the Logan Wash field site. At Logan Wash, treatability studies were conducted for three weeks on retort water using filter coalescing, floccula- tion/clarification, and steam stripping technologies (Figure 2). Also, studies were conducted for 14 weeks on gas conden- sate wastewater using filter coalescing, steam stripping, conventional and pow- dered activated carbon (PAC) activated sludge treatments, sand filtration, and granular activated carbon adsorption technologies (Figure 3). The test equipment and supporting field laboratory for conducting the treatability studies were either provided by EPA or procured by MRC. Equipment layout at the trial location is shown in Figure 4. Analytical methods utilized adhered to Standard Methods when applicable. Test Results Retort Water - Overall Treatment Retort water was treated primarily to remove oil and grease, suspended solids, ammonia, and alkalinity. The filter coalescer, flocculator/clarifier, and steam stripper in series were used to remove these pollutants. The overall treatment scheme was very effective for ammonia and alkalinity removal (Figure 5). Relatively high sulfide, TKN, and phenols removals were also achieved. Due to low levels of oil and grease, and suspended solids, the scheme was not effective in removing these pollutants. Product Oil ^ Off-Gas \~~ (Noncondensible) • Gas Condensate ^ „ , 1 Water "*" Conderuen | Air/Steam—^ m -»• Oil /Water Separation \ Retort Water Rubblized Shale \OH/Water Product Collection Sump Figure 1. Production of gas condensate and retort waters by modified in-situ (MIS) retorting. Raw Retort Water Flocculator Clarifier I Steam Stripper Figure 2. Retort water treatment scheme. Gas Condensate - Overall Treatment Filter coalescing, steam stripping, conventional activated sludge treatment, sand filtration, and GAC adsorption comprised the overall treatment scheme for the gas condensate. The scheme was very effective in removing ammonia, organics, sulfide, alkalinity, and solids from the gas condensate. Assuming conditions listed below, the scheme would produce a final effluent with the expected composition presented in Table 1. ------- Activated Sludge Waste Sludge Overhead Vapor _ Raw Gas ' Condensate Filter Coalescer Light ± Oils " Steam, Steam Stripper Gravity Separator Aeration Basin (With/Without Powdered Activated Carbon) Return Sludge Granulated. Activated Carbon Columns Discharge Light Oils Figure 3. Gas condensate wastewater treatment schemes. Steam stripper: GL/ratio =0.15 kg/liter (1.2lb/gal) Activated sludge system: Hydraulic retention time = 16 hours Sludge age = 32 days GAC column: Contact time = 19 minutes The other treatment scheme comprised filter coalescing, steam stripping, and GAC adsorption. The scheme was effec- tive in removing ammonia, organics, sulfide, alkalinity, and solids from the gas condensate. But, the performance of granular activated carbon adsorption was relatively poor and this scheme was less effective in removing pollutants than the one with an activated sludge system included. Conclusions Pilot-scale field treatability studies on real-time oil shale wastewaters from Occidental in-situ MIS retorts demon- strated that retort water had high concen- trations of ammonia, TKN, alkalinity, dissolved organics, phenols, sulfide, and TDS; and gas condensate had high concentrations of ammonia, TKN, dis- solved organics, alkalinity, phenols, and sulfide. Steam stripping was effective in removing ammonia and alkalinity from the retort water. Steam stripping, acti- vated sludge treatment - both conven- tional and PAC, sand filtration, and GAC adsorption were effective in removing ammonia, alkalinity, TKN, nitrate, soluble COD, soluble BODs. DOC, phenols, sulfide, and TSS from the gas condensate. Pollutant removal efficiencies across individual treatment units for retort water and gas condensate treatment schemes are presented in Tables 2 and 3, respec- tively. ------- Wastewater Supply Tank 28 kiloliters (6.000 gallons) Elevation: 18 meters (60 ft) Above Product Level Retort Water Trailer 2.4 m,x'13.7 m <8'x45') Trickling Filters (Not Used) •5 1 Filter Coalescer Gas Condensate Trailer 2.4mxil3.7m <8'x45l) O O EZU Laboratory Waste Storage 2 kiloliters (500 gal.) Laboratory Trailer 2.4 mx 7.6 m (8'x25') Carbon Adsorbers i Media Filters Stripper Skid 2.4 m x 6.1 m (8'x20') fSteam \Stripper Q Boiler Skid, 2.4 x 4.6 m (8' x 15') Boiler Feed rij- Water Tank 130 liters LJ (35 gal.) Water Softener Fresh Water Storage 15 kiloliters Stripper Overhead _- Storage 870 liters (230 gal.} Air Compressor Trial Location Area __, 18.3 m x 24.4 m (60' x 80') on Product Level Elevation: 2,300 meters (7.700ft) Effluent Sump Tank 1.100 liters (300 gal.) Fresh Water Supply and Distribution System Elevation: Below Product Level Fuel Oil Storage 15 kiloliters (4,000 gal.) Figure 4. Equipment general layout at the trial location. ------- 700 901 70 60 5 50 o i 40 30 20 10 Ammonia ,0 Alkalinity I 0.06 (0.5) 0.12 (1.0) 0.18 (1.5) 0.24 (2.0) 0.30 (2.5) G/L Ratio, kg/steam/liter feed water (Ib steam/gallon feed water) Figure S. Percent ammonia and alkalinity removal from retort water as a function of G/L ratio in the steam stripper. ------- Table 1. Overall Gas Condensate Parameter NH3-N TKN NO3-N Soluble COD Soluble BODs DOC Phenols Sulfide TSS VSS Alkalinity as CaCO3 to pH 4.5 pH* Oil and greasec Treatment Scheme Performance Summary Concentration, Raw wastewater 9.000 6,800 1.1 2.700 8OO 890 120 72 7 5 31.000 8.5 mg/L Final effluent 90 180 0.4 50 20 25 0.02 2 5 5 350 7.5 Percent removal 99 97 64 98 98 97 100 97 29 0 99 NA* 'Standard pH units. "NA - not applicable. "Oil and grease were at low levels (average 18.6 mg/L) in the gas condensate received for testing; however, an oil and grease removal treatment step may be necessary if the raw gas condensate has a relatively high oil and grease level. Table 2. Pollutant Removal Efficiencies Across Individual Units for Retort Water Treatment Scheme*" Parameter Oil and grease Ammonia TKN Soluble BODS DOC Phenols TSS VSS Alkalinity as CaC03 to pH 4.5 Fluorides Chlorides Filter coalescer 6 21 20 Flocculation clarification0 0 7 11 Steam stripper6 97 88 5 4 32 47 "Average removal efficiencies are reported. ''Blanks indicate data not collected. °Lime dosage at 9O mg/L. "G/L = 0.18 kg/L (1.5 Ib/gal). Table 3. Pollutant Removal Efficiencies A cross Individual Units for Gas Condensate Treatment Scheme"'" Treatment unit Filter Parameter coalescer Oil and grease 28 Ammonia TKN Soluble COD Soluble BODs, DOC Phenols Sulfide TSS Alkalinity as CaCO3 to pH4.5 Steam stripped 99 96 56 60 29 97 99 Activated sludge treatment11 6 59 91 52 93 GAC Sand adsorption filter column* 95 70 89 99.5 70 "Average removal efficiencies are reported. ^Blanks indicate data not collected. CG/L = 0.19 kg/L (1.6 Ib/gal) average. "Hydraulic retention time =16 hours, sludge age - 32 days. "Contact time =19 minutes. *USGPO: 1984-759-102-10653 ------- ------- B. O. Desai. D. R. Day, and T. E. Ctvrtnicek are with Monsanto Research Corporation, Dayton, OH 45418. W. W. Liberick. Jr. is the EPA Project Officer (see below). The complete report, entitled "Logan Wash Field Treatability Studies of Waste waters from Oil Shale Retorting Processes," (Order No. PB 84-211 143; Cost: $17.50, subject to change) will be available only from: National Technical Information Service 5285 Port Royal Road Springfield. VA 22161 Telephone: 703-487-4650 The EPA Project Officer can be contacted at: Industrial Environmental Research Laboratory U.S. Environmental Protection Agency Cincinnati, OH 45268 United States Environmental Protection Agency Center for Environmental Research Information Cincinnati OH 45268 Official Business Penalty for Private Use $300 It- ------- |