Document ZJjzG86YpLaap6QJ6aqO4BBMd

SURVEY REPORT UN I ROYAL CHEMICAL 1. DISCHARGER IDENTIFICATION PI ant: Uni royal Chemical Division of Uniroyal, Inc. P. 0. Box 460 Painesville, OH 44077 AC 216-357-7574 Corporate: Uni royal, Inc. Oxford Management and Research Center Middlebury, CT 06749 AC 203-573-2387 Receiving Waters; Grand River NPDES Application Number: OH 070 0X2 2 000 118 NPDES Permit Number; OH 0000353 (not issued) Responsible Officials: Plant: Benton R. Leach, plant Manager c Corporate: . Robert C. Niles, Director, Environmental Control 2; DATES OF SURVEY- May 6-7, 1974 3. :PAKT-TCTPANTS . . ' i Uniroyal Walter M. Iliff, Plant Engineer . . Raymond W. Kenney, Utilities Engineer Ohio EPA Notified but did not participate US EPA Martin G. Trembly Philip E, Gehring Charles J. Beier Joseph S. Good Charles E. Ilenricks Harold J. Henris Roland J. Hartranft 4 6ENC 01268? 4. DESCRIPTION OF FACILITIES A. Description of Discharger Uniroyal's Painesville facilities produce PVC by sus pension and emulsion polymerization, and nitrile rubber (tutadiene-acrylonitrile copolymer). Nitrile rubber and PVC are also compounded to produce an ozone-resistant rubber. Volume of production is about 342,000 pounds of PVC and 82,000 pounds-of nitrile rubber daily. Raw materials include butadiene, acrylonitrile, and vinyl chloride monomer, which is received by rail. Various suspend ing agents (soaps) and coagulants such as acetic acid-brine solution, alum, magnesium sulfate, and others, are also classi fied as raw materials. Process water is purchased as raw lake water from Diamond Shamrock, and filtered, demineralized and softened at Uniroyal. Other potable water is purchased from the City of Painesville. Present employment at Uni royal is about 450 persons, 350 of which are hourly workers. Operations are on an around- the-clock basis. . " t Sanitary wastes are treated in two trickling filter systems, which are operated only when the accumulated volume of sanitary wastewater warrants their use. B. Process Description The Uniroyal facility is divided into two separate pro duction areas - Area 1 and Area 4, Area 1 contains 27 kettle reactors for both emulsion and suspension polymerization of PV o 5 GENC 012690 In emulsion polymerization vinyl chloride monomer, water, and .various plasticizers and suspending agents are reacted for 8 to 10 hours and the contents are sent to concentrator tanks wherein the volatile vinyl chloride is removed. The PVC is then spray-dried, ground to a finer particle size, and packaged, most frequently in bags. Water discharges from the emulsion polymerization areas result'from three processes; jacket cooling of the reactors, cleaning of reactors, and zeolite regeneration. Uni royal is presently closing the reactor cooling system such that there is to be no cooling water discharge within a few months (June 197*0- Physical reactor cleanout is done, most often by hand, normally after every fifth batch. The company' is also experi menting with tetrahydrofuran (THF) dissolution of reactor deposits. With this system, the tank is washed with THF and the THF is flashed off from the solids and reused. Additional waste may be expected from blowdown from concentrator tanks and releases of faulty batches from the kettles. . t Formerly, all wastes from Area 1 were discharged to a ditch on the west end of Uniroyal property, directly to Grand River along with sanitary effluent. Presently, these wastes are sent to a combined treatment system. According to Uni royal personnel, the only discharge directly to Grand c River from Area 1 at present is storm runoff. 6 GENC 012691 Area 4 includes the suspension PVC polymerization and nitrile rubber processes. In suspension polymerization of PVC, vinyl chloride and water are mixed and heated until a reaction is sustained. After about ten hours, the contents of the reactor vessels are pumped to slurry tanks in which vinyl chloride monomer is pulled off. The slurry is then centrifuged, the solid PVC being air dried, while the centrifuged water is discharged to a sewer system leading to the treatment area. Reactor cleanout wastes and defective reaction mixes also go to this sewer. A closed cycle system is employed for process cooling with blowdown being discharged to a sewer leading to the treatment system. Nitrile rubber is formed by mixing butadiene and acrylo nitrile in 10,000 gallon reactors, along with various emulsifiers, for about 20 Hours. The resultant product is an emulsion containing crumb rubber, which Is pumped to 20,000 gallon blowdown tanks, the added capacity being necessary to accommodate large quantities of foam generated in the pumping process. Butadiene is flashed off in the 'blowdown tanks, and acrylonitrile is recovered using steam in a packed column and reused. Recovered ] butadiene is shipped out of the plant by rail for repurification. The emulsion is pumped to blend tanks for equalization and then to a finishing line, in which coagulants are added to increase crumb size. The most common coagulants used are "salt acid" (brine-acetic), alum, magnesium sulfate, calcium chloride, and barium chloride. The choice of coagulant depends on the char acteristics of the rubber being made.' Wastewater originates 7 i GENC 012692  in the finishing line and from boiler blowdown, zeolite re generation, reactor cleanout, and raw material or product spills. Reactor cleanout occurs approximately once per year. Storm water drainage from Area 4 is directed to the 48" i, sewer which.runs along the eastern boundary of Uni royal property. According to the company, there is no other water discharge to the 48" sewer, except the sanitary effluent from * this Area. Procfess water from both Areas 1 and 4 flows through sumps in the respective areas, which act as primary solids traps. Partially polymerized defective batches which'are dumped are effectively caught in these traps and removed manually by laborers and hauled away to landfill. Process wastewaters from Areas 1 and 4 combine and flow to the treatment system. C. Waste Treatment Facilities f The process waste treatment system was started up.in August 1971. V/astes enter an equalization lagoon at a rate of about ' J .5 mgd and a pH of 4 to 5X The capacity of the lagoon is be tween 20 and 25 million gallons, although the water level is held at about 5 million gallons under normal operation. Accord- *r ing to Uni royal, the equalization lagoon will provide about two c weeks of holding capacity should the rest of the treatment system be shut down. Three pipes laid lengthwise in the pond pick up equalized liquid waste at various points in the lagoon and direct this 'a water to a chemical addition facility in which lime is added 8 6ENC 012<593 to bring the pH to the range of 9 to 10, and then alum and polyelectrolyte are added in four mix tanks to facilitate settling. The mixture is pumped to a flocculator-clarificr at a rate of 800 to 1,000 gpm at normal operation. Higher flow- * through rates may be expected if the system has been shut down and must handle additional accumulated wastewater. Clarifier sludge is continuously pumped to one of a pair of sludge lagoons (sand beds), both with-overflow drains for super natant water, which discharge to the same ditch to Grand River which receives clarifier effluent. However,problems in sludge settling and collection in the clarifier are evident. The company is experimenting v/ith different chemicals and/or dosing rates to aid settling in the clarifier, but due to the low density of the sludge, it ?s extremely difficult to achieve adequate settling. Clarifier sludge and some other solid wastes are disposed of in a private disposal area across Route 535 `\ * from Uniroyal. Other PVC-containing solid wastes are hauled to a landfill near Kirtland, Ohio by Geauga Disposal Company. < t Separate trickling filter systems treat sanitary wastes v from Areas 1 and 4. Neither effluent is disinfected. * The sanitary system discharge from Area 1 enters the west drainage ditch, while the effluent from Area 4 is discharged to the 48" sewer. 5. DESCRIPTION OF SAMPLING PROGRAM A. Sampling Locations Composite samples from 1130 EDST on Hay 6 to 0930 EDST on 9 GENC 012-694 Hay 7, 1974, were obtained from Outfalls 001 (Plant 1 drainage ditch), and 002 (main outfall), and the intake pump house. Samples were withdrawn every two hours and composited accord ing to flow at Outfall 002, and equal-volume composited at the intake and Outfall 001. In addition, a grab sample of water overflowing from a clarifier sludge holding lagoon was obtained. * * , Solid waste samples were obtained as follows: t * 1. Clarifier sludge from south sludge holding lagoon. 2. Clarifier sludge and other solid wastes in a company disposal area across Route 535 from the plant. 3. Sample of "off-grade PVC, reactor scale, and other solid PVC wastes from a disposal bin in Area 1 of the plant. These wastes are removed by Geauga Dis posal Co. and hauled away to a landfill near Kirtland, Ohio. The.sample was dry upon collection. 4. Floating residue from a settling pit for reactor clean out and cooling water in Area 1.- This residue goes partly to the treatment system and partly to a landfill via Geauga Disposal Co. * 5- Sample from a waste bln containing nearly dry ."off- grade PVC resin at Area 4, This is also hauled away by Geauga Disposal, 6. Clarifier sludge from the north sludge holding lagoon. Data ore presented in this order in Table 1. 10 GENC 012695 T B. Methods Statement Throughout this survey, standard USEPA Region V sampling, preservation, and custody methods v/ere followed. Analyses were performed by the Region V' Central Regional Laboratory. C. Discharger Participation Una*royal chemical personnel were very cooperative in directing the MODO sampling crews to the proper sampling loca tions. The company did not obtain split samples for purposes of comparison. * 6. GENERAL CONDITIONS Plant operations during this survey were normal. At Cleveland Hopkins Airport, approximately 38 miles southwest of the plant site, weather conditions for the survey dates are summarized below; High Temp. ` Low Temp. Precipitation (inches) 5/6/74 hi 33. ' 0.48 5/7/74 49 . 30 0.01 -1 ' Strong northwest winds predominated during the survey. Rain- fall on these dates may be expected to have diluted plant waste- ,! waters in Outfall 001, as storm drains are connected to this dischargeV fr . point. However, the main treatment system outfall (002) was not appreciably affected by the precipitation. 7. DISCUSSION OF RESULTS A. Wastewater , As expected, the background level of vinyl chloride in 11 ` GENC 012696 i Lake Erie Intake water was undetectable. Based on the waste- water analysis results (Table 1), it appears that significant amounts of vinyl chloride are entrained in water which has been in contact with finished resin. Outfall 001, which contains Indirect cooling water, shows no detectable VC, whil'e Outfall 002, which discharges treated reactor cleanout and centrifuge wastes, contains a significant concentration of vinyl chloride. On Hay 6-7, about 34 pounds of monomer were discharged. It is not possible, however, to determine whether this VC is dissolved in water or contained within suspended solids particles. If further sampling is to be done, this should be evaluated by analyzing both filtered and not filtered samples, * . A'significant concentration of VC is also discharged at the sludge holding lagoons. This is not surprising since fine PVC particles make up the bulk of the clarifier sludge contained in the lagoons. However, the loading is relatively low compared to Outfall 001 based upon flow rates. B.7, Sol Id Wastes ' Fresh residue from the reactor cleanout process and from floor washings yielded the highest concentration of vinyl chloride. Relatively high concentrations were also found in "old" solid waste taken from a company landfill area, and in dry waste which is hauled away by private contractor to an outside landfill. Negli gible amounts appeared in this company's treatment system sludge. It should be noted, however, that Uniroyal Chemical has experienced chronic, problems with adequate sludge settling in their clarifier system. \ 12 GENC 012697 Generally, these data indicate that "old" solid wastes generated by this PVC facility are not necessarily innocuous. Landfilling of these wastes may not be an acceptable final disposal method, as vinyl chloride continues to be given o^f for weeks or months. 13 GENC 012698 mw DISCHARGER: UNI ROYAL CHEMICAL PAIHESVILLE, OHIO TABLE 1 Source Sample Type Sample Date Sample Time(EDST) - Flow (MGD) Vinyl Chloride Concentration Loading V.'a s t cwa t er Intake Outfall 001 Outfall 002 (main) Sludge lagoon overflow 24C 24 C 24C G 5/6-7/74 5/6-7/74 5/6-7/74 5/6/74 1130-0930 1130-0930 1130-0930 1400 - 0.288(est) 1.103 - <200 yg/1 <200 yg/1 3700 yg/1 1100 yg/1 #/day v-n Sol id Wastes South sludge lagoon (2) Company dtsposal area (3) Area 1 waste bin (2) Area 1 settlIng pit (1) Area 4 waste bin (2) North sludge lagoon (2) G G G G G G 5/6/74 5/6/74 5/6/74 5/6/74 5/6/74 5/7/74 14 yg/g 2140 yg/g 620 yg/g 3520 yg/g 1340 yg/g 9 yg/g 00LZW H39 Notes: 1. Composite types - 24C = 24-hcur composite G = Grab .2 Relative solid waste ages 1. Fresh (Two hours or less) .2 Intermediate (Several hours to several, days) 3. Old (Several weeks to several months)