Document RpJdbjQj1v7X1q1MaXZy9JJbB

''L - TECHNOLOGY RISK EVALUATION REVIEW CF.A 3306 PARACKLOROPHENO' REHABILITATION W. G. KRUMMRICH- PLANT SAUGET, ILLINOIS MARCH 14, 1978 COMPANY CONFIDENTIAL BY R. A. YEO Techno le gy Ris k Evaluation Review CEA 3306 March 14, 1973 Poe 1 of 6 I IKTRODUCTIC On May 5, 1977 a Safety .Audit was completed of the chlcrophenol processes at the W. G. Krummrich plant. It had been ten years since the last major process improvements had been made to this area. Further, the Italici', dioxin incident triggered a concern at many levels of Monsanto management since dioxins could bo produced in this area. The Audit identified twelve areas where 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 Mice's Detergents & Phosphate Division to go out of this business. The remaining six findings in the Audit are related to operations in the parachiorophenol (PCP) production area. The largest use for PCP is as the raw material in Santophen-1 manufacture, 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 6. Work practices and the working environment permit excessive contact with chlorophenols. Following the Audit, a number of changes to work practices and revisions to plant procedures were made by supervision in the PC? productic-n aroa. The plant initiated a number of capital projects aim;ed at correcting those problems requiring im.mc6ia tc- i11cut ion. A t the sarte ime, a $4M cap 1te 1 p rcj oc t v;ns in itiar.ee in CEO under C A 3306 to rehabilitate the entire PCI1 a r e a . The CED o ojcct is targeted for July, 1978 approval. Techno 1ony his); Ev a 1nation Review CEA 3306 March 14, 1978 Page 2 of 6 The objectives of the rchabi iitatior. projec t are to produce PCP at minimum cost, in a safe work er environr:er.t, arid with adequate cent rol over spills . Because of uncertainties related to mar keting and our intent to provide new technology, the rehabilitation is to extend the useful life of the PC? area six y e a r s , .hrouch 1S83 With this as background, the project objecti\ four major thrust areas. deludes ' 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 nesting TWA limits and improving the working environment are included. 4. Reduce environmental impact cue 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 PC?. One, the para-rich cut, chlorinates directly to 2,4 dichlorophenol (2,4 DC?). A second cut, orthochloropher.ol (OC?) may be refined for sale or used to produce 2,4 DC?. Those cuts not required for the production of PCP or 2,4 DC? are used to make OC? Crude, which is sold to manufacturers to make Penta or incinerated. Chemistry Phenol and chlorine react .is follows to form m.onochlorophenols: on Cl2 9 0C on iit I Cl PCP 60 -- 65'; + on + HCl OC? 30-- 35i Evaluation itevicw CEA 3305 March 14, 1978 Pago 3 of 6 Additional chlorine w til produce <]i-chlorop] shown below1: OH - ! 1. R " - 0:i ,r- " - , c i it ; .<' + OH Cl^ * S `-i V^ Cl Cl g * bn'v\.>.i 2, G Z 92% 8% + 2C1 Since PCP chlorinates directly to 2,4 DC?, , 2,4 DCP can be producai from the mono-chlorinated crude after the bul': of the .CP has been removed. Production of 2,4 DCP fr:r. CCP, r.:vever, gives a prcauct wnicn contains only about Z-.\ 2,4 D C ? . Refining is necessary, to seDarate o u t the unie sir able 2,6 DCP. Hanufacturinm Procesr as The manufacturing pre:ussus for parachlcrophcr.ol and 2,4 dichlorophenc1 are ill-istrated on Figures 1 and 2. PCP can be produced v:ith :r without phenol recycle. The former reduces CCP Crtie production; the later increases PCP production rates. Referring to Figure 1, 2,4 DC? is normally made from th pa a -r ich cut which a1re ady con tains some of o:iis pr:iuct. Additional 2,4 DC? can be made from either the :m h o crude or from the phenol/pararich/para cut illustrired in Figure 2. Other products are OCT Crude and refined CCP. In order to meet specif ication^ for Penta production, CC? Crude must contain a minimus o f .70% equivalent phenol. It may be necessary u o dilut= OCR Crude with Phenol to meet this specifica cion. "rfined CC? will be made from CCP Crude as necce c to raer. sales. Waste Treatment Since phenols and chl:rophenols increase COD in waste streams, and adversely affect the taste of fish and drinking water, the department /astos are treated before being rei<?a^ to the WGK plant sewe: system. The waste treatment p r o c e s s " is illustrated in Fic_re 3. Chlorophonols are r'emr'ed from the by-prcduct KC1 gas stroam by cor.t acting : a gas v;ith r.uIfuric acid. Caustic scrubbing is jsed to ::mcvo chicroyhc-nols from the vent fumes. Ciilor tpncnoli _n^v:aste water and in spent caustic arc removed ir. the 'a - . fe-r. here, spent sulfuric acid is used to acidify the waste streams, and the chlcrcchcnols Te ch:-Oio-qy Ri sk Evluiiricn Revig w CEA 3306 March 14, 1978 Page 4 of 6 arc extracted by absorption into Santophen residue. The oil layer from the acidifier mast be neutralized before it is incinerated, and the water layer is severed. Overall / about 65 of the chlorophcnols- in the waste streams are removed and incinerated. Chances to the Manufacturing Area fcv CEA 3306 Upgrading the PCP facilities will be accomplished by replacing structural 'steel, equipmen- , piping, and electrical Corrosion will be min an steam to 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 PCP can be mace 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 anc 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. All 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. HCi will continue to be drowned. Vias te water in t_he sump s w i11 be collected and monitored in a central sump, a first step towards treatment of those streams. There will be improved handling systems for the organic waste streams. Eva 1v.at:o:: Re viow CE 330G isrch 1-1, 19 73 Pago 5 or 6 tecenical incerta irti cr. and ribes Tho followinq is intcnded as on outlino cf th risks. The re v;ill he a cerai lcc assessment of thon curine th review. A. Related to Oberati or; throumh 19 83 The rehabilitation project will replace most of 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 chloropher.ol discharges to the river may not satisfy state and federal requirements. The State of Illinois specifies that chlorcphenols should not exceed 0.3 mg/Iiter in the discharge to the river. Presently, the Village of Sauget, which processes -Voncanto*123s waste water, is operating under a variance permitting 19 mc/liter based ona 30 day average. It is expected that this variance wTill be extended until the new secondary treatment plant goes on stream ( '-32). Risks in this area are as follows: 1. That an extension may not be granted. 2. That chlorophonols may prove difficult to treat. 3. That federal action on the Priority Pollutants list may require chiorophenol reduction before the treatment plant is ready. B. Related to Adjustments from the Per.ta Shutdown With the shutdown of the Penta a r e a , there is no longer an easy, assu red method to dispose of the OCP Crude. Present] y, two Penta manufacturers have expressed an in terest in purchasing OCP Crude, Tg guard against cut backs in sales, the project has provided floxibi lity to minimize production of OCP Crude. Should o ther measures not prove adequate, 13'ia curp 1un OC ? C ru ;a would be ski r.pod to Rolli ns Environ;a nta 1 Scrvic es, Inc. at-New Orleans and incinerated. 0 * Evaluation Review Cil. .`O 0c March 14, 19 7G Page 6 cf 6 The risk is that the PCP production area nay not be able to dispose of the OCP Crude predust - One cause night be that the new project facilities do not achieve, the desired reduction in OCP Crude production. A second cause night be the inability of the incinerator contractor to dispose of the OC? Crude. C . Re dated to Improvement of Worke: Cb e--. JTO -it.-, 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 chioropher.ols was estimated at 5.2 r.ig/cu ra (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 vjill 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 unforseen incident. The situation would be complicated should hazardous dioxins be present. Fortunately, conditions necessary tc form these hazardous dioxins are very unlikely to occur during PC? or 2,4 DC? production. In order to produce these dioxins, 2,4,5 trichlorophenol must first be made. Considerable production experience has demonstrated that the meta chlorinated phenol is rarely found in the product, making it highly unlikely that hazardous dioxins could be mace. Related to Reduction of Soi],Is The project will provide dikes, curbs, and cs tc contain spills and prevent them from reaching .the pi nt sewer system, All organic storage and handling operations ill be protected except for tank car load ing and unloading. The risk is that a tank car ma y be overfilled, creating a large s;pill'which would not be contlined. Instrumentation and plant operating procedures will be used to control this problem. ... I------lKci 1 1 I \ i eVTN(-KET hl m > b u c T i o M WITH r*H !;>!'- Sirr.V^Ltl \ >*C ,\CA'TI * r 21 K vDUc t >;o y-pEi' L'2. --. i... r Arret 7*conc.T rate': `/no K . Airks: H / 03 EC T ' [R(V T ; St-fJ-VC H-, |r-.o ' K.'` 'rv-ivrir\*j rtfr tuk. /*i i*t- M.*vf ?r T ,'Ma rty" f-, Tr* <TA' I t \ R I G - U R E - !' .3,4 S>CP- ri?0l>t'CTIM F S D M f^ C ? J = I r S S A T M c ^ r PROCESS