Document 1g72aJOnv3LzB4R9jn8eJqKpd

'U TECHNOLOGY RISK EVALUATION REVIEW CEA 3306 PARACHLOROPHENOL REHABILITATION W. G. KRUMM RICH' PLANT SAUGET, ILLINOIS MARCH 14, 1978 COMPANY CONFIDENTIAL BY R. A. YEO C J2'i 4 Technology Risk Evaluation Review CEA 3306 March 14, 1973 Page 1 of 6 I. IETRODUCT On May 5, 1977 a tSafety Audit was completed of the chlorophenol processes at the W . G . Krumrurich plant. It had been ten years since the last major process improvements had been made to this area. Further, the Italian dioxin incident triggered a concern at many levels of Monsanto management since dioxins could bo produced in this area. The Audit identified twelve areas v;here corrective action was needed. Six were directly related to the production of Pentachlorophenol (Penta), the process where dioxin formation is a potential hazard. These were resolved by. . the decision of MICC's Detergents & Phosphate Division to go out of this business. The remaining six findings in the Audit are related to operations in the parachlorophenol (PCP) production area. The largest use for PCP is as the raw material in Santophen-1 nsnufacture, also at the Krummrich plant. These findings are summarized below: 1. TWA limits for exposure to chlorophenol vapors have been exceeded on occasion. 2. Leakage of water into the process greatly accelerates corrosion. 3. Badly corroded equipment jeopardizes personnel safety. 4. Leaks and spills of chlorophenols cause excessive sewer loadings. 5. The emergency notification procedure after a spill was too cumbersome. 6 . Work practices and the working environment permit excessive contact with chlorophenols. Followinq the Audit, a number of changes to work practices and revisions to plant procedures were made by supervision in the PCP production area. The plant initiated a number of capital projects aimed at correcting those problems requiring immediate aLteutior.. At the same time, a $4M capital project w:is initiated in CED under CPA 3306 to rehabilitate the entire PC? area. The CED project is targeted for July, 197 8 approval . Technology Ris: Eva 1uaticn Rc v iew CEA 3306 March 14, 19 7G Page 2 of 6 The objectives of the rehabilitation project are to produce PCP at minimum cost, in a safe worker environ ment, arid with adequate control over spills. Because of uncertainties related to marketing and our intent to provide new technology, the rehabilitation is to extend the useful life of the PCP area six years, through 1S83. With this as background, the project objective includes four major thrust areas. 1. Extend the useful life of the PCP area six years, through 1983. Included is replacement of corroded facilities and prevention of corrosion caused by water leakage. 2. Make the adjustments necessitated by the shutdown of the Penta area. 3. Minimize worker exposure. Concerns for meeting TWA limits and improving the working environment are included. 4. Reduce environmental impact due to spills. II. DISCUSSION Synopsis of the Process Parachlorophenol (PC?) is produced by chlorinating phenol and then refining the crude product. Both steps are * batch processes. The batch refining process produces a number of cuts besides PCP* One, the para-rich cut, chlorinates directly to 2,4 dichlorophenol (2,4 D C P ) . A second cut, orthochloropher.ol (OC?) may be refined for sale or used to produce 2,4 DCP. Those cuts not required for the production of PCP or 2,4 DCP are used to make OCP Crude, which is sola to manufacturers to make Penta or incinerated. Chemistry Phenol and chlorine react ns follows to form monochlorophenols: on Cl 2 + : i>0c'C OH .t j' 'i Cl PCF 60-65 + OH Cl + IIC1 OCP 30- 35 Tccimoioqy .*<isx Evaluation Review CEA 3305 March 14, 1970 Page 3 or 6 Additional chlorine ve shown below: 9 !i * v*'J 2ci9 + ' : ------ ^ produce c}i-chlorophenols as OIH ' ..Cl OH cv V 1 ! 1 + 2IC1 " Cl 2,4 DC? 92% 2, G DC? 8% Since PCP chlorinates irectly to 2,4 DCP, a high purity 2,4 DCP can be proauc' from the mono-chlorinated crude after the bul'.: of the CP has been removed. Production of 2,4 DCP fret OCP, ! rover, gives a product v:hich contains only about 2,4 DCP. Refining is necessary to separate ou r the u: esirable 2 , G D C ? . Manufacturine P r o ce.-rei The manufacturing pro dichlorophenc1 are il can be producei with former reduces CCP Cr PCP production ra t e s . normally made tains some of this pr made from e iah a r tns rich/para cut illustr ssos for parachlorophcnol and 2,4 aerated on Figures 1 and 2. PCP without p h e n o l 'recycle. The e production; the later increases Referring to Figure 1, 2,4 DC? is para-rich cut 'which already conuct. Additional 2,4 DCP can be oho crude or from the phenol/parfl ed in Figure 2. Other products are CCI Crude and refined OCF. In order to meet specification; for Fenta production, OCP Crude must contain a minimus of ,7C% equivalent phenol. It may be necessary uo diluts OCP Crude with Phenol to meet this specification. fined OCP will be made from OCP Crude as needed to mer. sales. Wa ste Tr catma r t Since phenols and chl:rophenols increase COD in waste streams, and eversei; affect the taste of fish and drinking water, the de arumene /astes are treated before being released to the WGK pi nt sewer system. The waste treatment process is illustrate in Fic-ure 3. r Chlorophcnols are rer.m'ed from, the by-product HCl~gas stream by cor. acting tvs gas with sulfuric acid. Caustic scrubbing is sea to iim.ovo cn 1croyb.or.olo from. the vont fumes. Chlor ph ono 1 -n v;es te water and in spent caus tic are removed i uhe ar.rarer. liere, spent sulfuric acid is used to acidi y tne v:nitc streams , and the ch 1crcphcno 1s Technology Risk Evaluation Review CEA 3306 March 14, 1978 Page 4 of 6 arc extracted by absorption into Santophen residue. The oil layer from the acidifier must be neutralized before it is incinerated, and the water layer is sewered. Overall, about 65% of the chlorophenols- in the waste streams are removed and incinerated. Chaness to the Manufacturing Area by CEA 3305 Upgrading the PCP facilities will be accomplished by replacing structural 'steel, equipment, piping, and electrical systems which have deteriorated. Corrosion will be minimized by using electrical tapes rather than steam to heat tanks and by segregating the different process materials. Adjustments due to the Penta shutdown include relocation of the 2,4 DCP chlorinator to the PCP area and the installation of mixing equipment for OCP Crude storage tanks. Improvements will be made to the still to increase capacity. As a result, more PC? can be made with phenol recycle, decreasing OCP Crude production and our dependence on Penta manufacturers to consume this product. Several improvements are being made to the operator's environment. Overflows and ruptures will be contained, in new tanks. Organic residues will be handled in new pipelines. Instruments will be provided to monitor tank levels. A new drumming area, control room and eating room are being provided. Spill controls will be provided through a system of curbs or dikes for all organic tanks. A pad and a sump will be built under the tank truck loading area. Till materials collected in these areas will pass through a monitoring station before they are released into the sewers, and waste water high in chlorophenols will be diverted for treatment. Changes to the Waste Treatment Area by CEA 3306 Relatively few changes are being made to the waste treatment facilities. There will be fewer open vents. HC1 will continue to be drowned. Waste water in the sumps will be collected and monitored in a central s u m p , a first step towards treatment of these streams. There will be improved handling systems for the organic waste streams. Tociii'.cJ ogy Risk Evolvati on Review CEA 330G March 1*1-, 1973 Page 5 of 6 III. technical uncertainties and rises The following is intended as an outline of the risks. There will be a detailed assessment of them during the review. A . Related to Operation through 19S3 The rehabilitation project will, replace most ox the PCP facilities with the exception of the majority of the tanks and pumps. Recently, some tanks not included in the project have leaked, and been repaired. The risk that some of these tanks may require replacement before 1933 is a known risk assumed by the Business Group. A greater concern is that the KGK plant program for reducing chlorophenol discharges to the river may not sati sfy state and federal requirements. The State of Illinois specifies that chlcrcphenois should not exceed 0.3 mg/liter in the discharge to the river Presently, the Village of S a u g e t , which proces ses Monsanto's waste water, is operating under a vari ance permitting 19 mg/liter based ona 30 day ave rage . It is expected that this variance wil 1 be extended until the new secondary treatment pi ant goes on stream ( 1932). Risks in this area ar e as follows: 1. That an extension may not be granted. 2. That chlorophenols may prove difficult to treat. 3. That federal action on the Priority Pollutants list may require chlorophenol reduction before the treatment plant is ready. B . Related to Adjustments from, the Per.ta Shutdown With the shutdown of the Ponte area, there is no longer an easy, assured method to dispose of the OCP Crude. Presently, two Penta manufacturers have expressed an interest in purchasing OCP Crude. T9 guard^against cutbacks in sales, the project has provided flexibility to minimize production of OCP Crude. Should other measures not prove adequate, the surplus OCP Crude would be shipped to Rollins Environmental Services, inc. at-New*Orleans and incinerated. Technology Risk Evaluation Review CEA 3305 March 14, 1978 Page 6 of 6 The risk is that the PCP production area may not be able to dispose of the OCP Crude produet One cause might be that the new project facilities do not achieve the desired reduction in OCP Crude production, A second cause might be the inability of the incinerator contractor to dispose of the OCP Crude. Related to Improvement of Viorker Safe A survey was taken to determine the eight hour average exposure level .by operators to phenols and chlorcphenols in the PCP production area. Phenol exposure was not shown to be a problem. The average exposure to chiorophenols was estimated at 3.2 mg/cu m (TWA), slightly above the limit of 3.0 mg/cu m (TWA). The survey also pinpointed certain operator activities as major contributors to this level. This project will take positive action to reduce operator exposure in each of the problem areas. The risk is that the new facilities may not give adequate operator protection in the event of an uhforseen incident. The situation would lie complicated should haz'srdous dioxins be present. Fortunately, conditions necessary to form these hazardous dioxins are very unlikely to occur during PCP or 2,4 DC? production. In order to produce these dioxins, 2,4,5 trichlorc-phenol must first be made. Considerable production experience has .demonstrated that the mata chlorinated phenol is rarely found in the product, making it highly unlikely that hazardous dioxins could be made. Related to Reduction of Sni11s The project will provide dikes, curbs, and pads to contain spills and prevent them from reaching .the plant sewer system. All organic storage and handling operations will be protected except for tank car loading and unloading. The risk is that a tank car ms y be overfilled, creatin g a large spill which 'would not bo contained. Instrumen tation and plant operating procedures will be used to control this problem. ! i t-- o F Ct UIR =. _L r t ^ 'r;Oii:J C V ! O N - - i tNlkhT JEl ?K,ObUCTIGNl W ITH PME*!*1:- Sc-'VitLu. 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