Document YjgKp9zzB47GaZ4dMVYoVbBMy

ORIENTATION PROGRAM PROCESS ENGINEERING DEPARTMENT VOLUME I I 1982 Process Engineering Department Ponca City, Oklahoma 3m % o mLO OCO 73 cr> \o CN>O ) 5 0 (7 /0 0 0 0 Table of Contents PROCESS ENGINEERING DEPARTMENT ORIENTATION PROGRAM 1982 VOLUME II TABLE OF CONTENTS CONOCO CHEMICALS LAKE CHARLES CHEMICAL PLANT "ALFOL" Alcohol Unit Alumina Unit CDRTM Unit Ethoxylation Unit n-Paraffins Unit Methyl Chloride Unit Ethylene Unit LAKE CHARLES LAB PLANT LAKE CHARLES VCM PLANT ABERDEEN PVC PLANT OKLAHOMA CITY PVC PLANT BALTIMORE CHEMICAL PLANT ''NALKYLENE" Alkylate Unit STXS Unit HAMMOND CHEMICAL PLANT NEWARK CHEMICAL PLANT MATAGORDA HOPE PLANT CHOCOLATE BAYOU CHEMICAL PLANT JOINT VENTURES AND INTERNATIONAL ENGINEERING SERVICES DIVISION OIL, GAS, AND COAL DIVISION SPECIAL PROJECTS DIVISION REFINING DIVISION DOOC Conoco Chemicals $ f\L ccoo 0 oo ORIENTATION PROGRAM PROCESS ENGINEERING DEPARTMENT CHEMICALS DIVISION VOLUME I I SEPTEMBER 1982 NOTICE This Orientation Manual Is the property of Conoco Inc. The information contained herein includes information which is proprietary and confidential to Conoco and information which may have been received under obligation of confidence from licensors. Under no circumstances shall any information contained in this Manual be disclosed to others outside Conoco. Each recipient of this Manual Is reminded of his/her confidentiality obligations contained in the Invention Agreement which he/she signed upon employment by Conoco. THE MANUAL IS TO BE RETURNED TO THE PROCESS ENGINEERING DEPARTMENT, PONCA CITY, OKLAHOMA, WHEN IT IS NO LONGER NEEDED BY THE RECIPIENT IN PERFORMANCE OF HIS/HER DUTIES. oo,00?7 PED ORIENTATION PROGRAM CONOCO CHEMICALS COMPANY Conoco Chemicals Company's business efforts originated in the manufacture of detergent feedstocks. This continues to be a major part of the business with plants producing biodegradable "NALKYLENE" alkylate at Baltimore, Maryland; surfactant-range "ALFOL" alcohols and ethoxylates at Lake Charles, Louisiana; and sulfonates and sulfates at Hammond, Indiana. Major additions to business included PVC resins and compounds, ethylene, and vinyl chloride monomer. In October 1980, the Chocolate Bayou Joint Venture with Monsanto was successfully started up. This added approximately four billion pounds per year of olefins and aromatics petrochemicals capacity to the Conoco Chemicals system. In August 1981, as a result of the merger between Conoco- anti >u Pont,--Conoco and Monsanto were reqttf-red, by the Justice Department, to dissolve the joint venture. Conoco purchased Monsanto's half interest of the venture and now controls the entire production capacity (approximately eight billion pounds per year total petrochemicals at Chocolate Bayou). A further major business area is the production of carbon black for tire manufacturers. This is operated as a separate company whose president reports to the Chief Operating Officer of Conoco Chemicals. This subsidiary operates four plants in the United States and eight other plants internationally. Headquarters operations for Conoco Chemicals are located in Houston, Texas. These include specialized support groups for supply and transportation, marketing, product management, project development, business research, and environmental activities. Corporate service divisions also provide specialists in purchasing, financial accounting, recruiting, etc, to cope with problems unique to the chemicals Industry. Conoco Chemicals have branch sales offices across the United States, Europe, South America, and Asia. Europe and Communist block countries are serviced primarily by the office in Brussels, Belgium. Japan, China, and Southeast Asia are serviced by the sales office in Tokyo, Japan. South American sales are handled by an office In Sao Paulo, Brazil. Conoco Chemicals have shipping terminals in Brazil and Belgium. In addition, they have a portable terminal in the form of an ocean-going tanker which can be anchored at customer receiving areas. This tanker has served as a temporary or supplementary terminal In England, Norway, and Belgium. In addition to these facilities, Conoco Chemicals also use those of affiliate companies in Japan, Spain, and Germany to solve temporary logistics problems created by periodic supp1y/demand imbalances throughout the world. A summary of Conoco Chemicals facilities and products is shown in Table 1 attached. 5^(_ocooioos<? PD ORlENInT ICN PROGRAM IAHI.L I CONOCO CHCMIIAIS FACILITIES l o. ,i l i 11M j ( I >< I [ .j I - . lot- l I'., I, , i ,,i i . i.|M.I Nat .1'!' >1 .1,1 , I .a , ft J l t i 1 jr ' , M Jf V I iind Ni w.)i k. til w Ji ' a.-v Hum- lord , | i.| i ,iri ,| al - i I < *ri , Ml . I , *. i 11;: F OKI | I -l !,, 1. I I , , I Ik I , I hi MM. | Su'H.iy, ) C' i')! ,i 1 i y , lift I ,imirm ) Bake. ,( i.- Ill , Cal lorn i a) I'll M-II lx 1 I | Y , a 1 ltiai'1.1 ) L ui11(11 C . ki a BrunsPjttel, West Germany P-.-ti-esa A Igc i ras, Spain Ci >a 1 i iii'ii I a I ( a....... . I I....... K a i r a ,ini, Mill 1. 111.1 1 i i a , '!....... Bo r pea us, Tr ani T I'l-ca U' . I tJ 1 y 'i i s . jf Com., c i u nI Iv.l , Japan Nippon a 1 nninui i alkyl-. S-lkai , _ a par Tort i n-Ti tal Car hi m 'i-'k,i >. h i oa . Japan Sydney . An- I r ,t I i a t n, lion , Ni 11 . a S ju Ch rime- r i ca Petroquimica Argentina. S.A. Rosari o , Argen tina I'ni'lm I . I t hy I. if VI. M i AB Linear A Icoho|s Alcohol Ethoxylates n-Para ffin s Mo thy 1 Chloride A1 mu j n.i A I mu I I' A St* 1 v 111 II i c|li D.-ii-. I l y Pu I y.a hv I in L i nr ar Alkylbenrone Hyd rot ropes Mai I,<i ip A- I il A I uni i n uni Chloride I .'a . i Cr.-.-.yUu-. Acids SuI Funic Acid ) Su1fonate s ) Ether Sulfates) I'Vr. R.-sin-, t' VC Compounds I' I a . I 11 i /r r -, I'VI. Ki-.in. Cai lion fl l,n k ! ( hy I .-lie l.it.il I'.- t i a. h.-.iii. .i K Linear A1 coho Is AIunina Na tura 1 A K oho Is n-ParafFins L i nea r Alkyl Ben Amt.ai In m II I a. k Llni ar Alky Itn.n/.-ri. A 1 uni nun Alkyls a Hn i| nnm Alkyl Ch I m i J, C. a i lx in B I ,n. k Carbon fi I ,u h C a r bi in K I a i k Synthetic Rubber Aromatics and Naphtha Capa! i ty . 1 l.-./Yi <1 ,11 f.-/t) iso 235 70 330 100 A0 370 60 A? 5 ,"20 13 1 15 1? so ;o A so : r, A SO 1 , 600 H.nno 165 ?5 66 265 330 / 110 AO 1 35 90 ft5 5 I (111 An (0 82 AOO Owner sh 1 (> b 1.1 lus Who 1 1 y Owni'ii Wliot ly- Owned Who 11y-Ownrd Who 11y-Owned Wholly-Owned Who 11y-Owned Wholly-Owned Whol1y-Owned Who 1 1 y-0wneil Wh.*l 1 y - Owned Who 1 1y-Owned (1902 SU) Who 11y-Owned U9R.3 MO Wholly-Owned Who 11y-Owned Who 11y-Owned Wholly-Owned Wtul !y-0wm*d Whol1y-Owned Whol1y-Owned Wholly-Owned Who 11y-Owned Who 11y-Owned Wholly-Owned Who 1 1y Owned Who 1 1y-Owned Cl ini >{ (i, 6 07,; hoa s an 111, 607. win 111 y Own ni .,(1,a 50% Each Conoco and Texaco 50% Each Conoco and Cepsa C. 1111 no. III tc I ll.lt I 1 ill.1 I Syn t In-1 I 1. Muhin i Conoid. Cities Servile Conoi.t', A-.h loud, Cep-.il Conoco, Phillips Conoco, Cities Service 50 V: Ear h Conoco ori.i Ni-.s,jn Chi-in'i i n 1 Company 75% Conoco, 75`- Mitsui fo.i 1 su Limoi o, Mitsui Who I Iy-Owned CrinoLU-Banilo Trad i no Company 25% Each Conoco. Witco, Uniroyal. Cities Service CT. 56C LCCP or Lake Charles Chemical Plant 5 A l c c o O i 5o 9 I ? LAKE CHARLES CHEMICAL PLANT OCOO J 6C9oL 3-1-000-69-43311 V ORGANIZATION CHART -- LAKE CHARLES COMICAL PLANT fr&QQiQQQO 7t ' V.. ~*x c * I 00OOlOO'fS PED ORIENTATION PROGRAM "ALFOL" ALCOHOL UNIT LAKE CHARLES CHEMICAL PLANT Conoco's "ALFOL" Alcohol Process produces linear straight-chain alcohols with an even number of carbon atoms. The basis of the process is aluminum alkyl chemistry developed by Professor Karl Ziegler in Germany in the 1930`s. The "chemistry" was licensed by Conoco in 1955. The process development was carried out by Conoco1 s research personneil. Conoco's "ALFOL" Alcohol Unit is located in Westlake, Louisiana. This plant was the first in the world to start commercial production of normal primary alcohols. Construction of the unit began in 1959, and startup was in 1951. The unit was originally designed for 100 MM pounds per year C]8 alcohols at 4.0 "M" value. in 1971, the plant was expanded to 150 MM pounds per year. The plant Is currently operating at an official capacity of about 250 MM pounds per year of C&18 alcohols at 4.2 'W vaiue. The short-chained aluminum alkyls are pyrophoric. Above 35 or 40 percent concentration in solvent, they will ignite almost Immediately in the presence of oxygen. They react violently when contacted with water or oxygen-containing compounds. Weaker solutions and growth product (aluminum tri-alkyls with longer side chains) may not flame immediately In air. However, a rapid oxidation reaction with substantial heat evolution may raise the fluid temperature rapidly to the flash point. These characteristics require use of special design and operating conditions. RAW MATERIALS 1. Aluminum powder 2. Ethylene from Conoco's ethylene unit 3. Hydrogen from Conoco's ethylene unit with hydrogen from Conoco's Lake Charles Refinery as backup. 4. Air 5. Sulfuric Acid or water. GENERAL DESCRIPTION (Refer to attached flow diagrams) The plant is divided into seven processing units. All are operated continuously except the oxidation process In Section 400- Section 100 - Aluminum Preparation The primary purpose of Section 100 is to introduce powdered aluminum into the process for reaction in Section 200. The feeds are Aluminum powder and kerosene solvent contaminated with ATE from Section 200. The product of Section 100 is an aluminum powder-solvent slurry to Section 200. GENERAL DESCRIPTION (CONTINUED) Section 200 - ATE Preparation The function of Section 200 is to manufacture aluminum triethyl (ATE) in solution with kerosene solvent. The aluminum-soIvent slurry from Section 100 is combined with recycle ATE-solvent and reacted with hydrogen gas to form aluminum diethyl hydride (ADEH). The ADEH is then reacted with off gas ethylene from Section 300 to form ATE. The process Reactions are: 2A1CC2H5)3 + A1 + 1 1/2 H2 -*-3Al(C2H5)2H (Hydrogenation) 3A1 (C2H5)2H + 3C2H1* ----- 3A1(C2H5)3 (Ethylation) For every three mols of ATE product from the ethylation reaction, two are recycled to hydrogenation and one is withdrawn as product. The product ATE-solvent-Al slurry stream (containing 4-8 weight percent A1 fines) is centrifuged to remove as much of the A1 fines as possible. The products of Section 200 are crude ATE (containing solvent and aluminum) to Section 225 and offgas hydrogen and ethylene to fuel. Section 225 ~ ATE Distillation The function of this section is to distill crude ATE from Section 200 to produce a clear, solids-free ATE solvent feed to Section 300. The feeds consist of ATE-soIvent-Al slurry from Section 200 and fresh solvent. The effluents from Section 225, in addition to purified ATE-solvent feed to Section 300, are bottoms ATE and solids to waste drowning (quench reactor) and decomposition offgas to fuel or flare. Section 300 - Alkyl Growth The purpose of Section 300 is to form long chain aluminum alkyls from ATE by addition of ethylene molecules. The feeds are ATE-solvent from Section 225 and ethylene from battery limits. The process reaction takes place at 1,600 psig and 250F and is described as follows: A1 (C2H5) 3 + 3nC2Hj4 > A1 [ (C2Hit) nC2H5) 3] The alkyl chains formed vary in length approximately according to a Poisson distribution. The effluents are growth product (aluminum, alkyls and solvent) to Section 400 and offgas ethylene to Section 200. Thermal olefins are also formed in the growth reaction by thermal cracking of the aluminum alkyls. The lighter thermal olefins are flashed off with the offgas ethylene, while the heavier ones remain in the growth product. 5fiC 0000)009-7 GENERAL DESCRIPTION (CONTINUED) Section 400 - Oxidation The purpose of this section is to oxidize aluminum alkyls to form aluminum trialkoxide. The feeds are growth product from Section 300 and air. The process reaction is: A1R3 + 1 1/2 02 A1 (0R)3 The first part of the reaction step proceeds in a continuous flow-through stirred reactor to yield mono-alkoxy dialkyl aluminum. The remaining two alkyl groups are oxygenated batchwise in stirred reactors. Nitrogen-rich offgas is vented to the atmosphere. The oxidized growth product is charged to Section 425. Impurities formed in the oxidation reaction constitute the major yield loss in the plant. Some are vented to the atmosphere, but most remain in the oxidized growth product leaving Section 400. Section 425 ~ Solvent Stripping The function of Section 425 is to remove solvent and hydrocarbon impurities from aluminum alkoxide by three-stage flashing and stripping under vacuum conditions. Natural gas is used as a stripping medium in the third stage. The effluents from Section 425 are stripped alkoxide to Section 500, offgas to fuel, and recovered solvent returned to the refinery for reprocessing. Section 550 ~ Hydrolysis Conoco used to hydrolyze stripped alkoxide with sulfuric acid in Section 500 to yield crude linear alcohols and alum (aluminum sulfate hydrate). This operation yielded alum via the following chemistry: A1(OR)3 + 11/2 H2S04 + 18 H20 --3R0H + 1/2 A12(504)3 18 H20 The crude reaction products were then phase split and alum was sent to product storage. The crude alcohols were distilled successively to remove water, ethanol, and butanol. The remaining alcohols were then sent to the main alcohol fractionation train in Section 600. Section 600 - Alcohol Fractionation In Section 600 the crude alcohols are fractionated into Individual one or two alcohol range products. The alcohols are hydrogentated to remove unsaturates. Hydrogen gas from battery limits is reacted under pressure with unsaturated alcohols in the presence of a nickel catalyst as follows: C-C-C=C-C-C-0H + H2 .Nl..iat^iy^ C-C-C-C-C-C-OH Conoco now operates exclusively a water hydrolysis process to yield crude SfXCCiOOOLOo^i GENERAL DESCRIPTION (CONTINUED) Section 600 - Alcohol Fractionation (Continued) linear alcohols and alumina. Due to the complexity of this unit and the importance of the alumina product, this process is covered in a subsequent section. Another function performed in Section 600 is reduction of the diol content of the 12+ alcohols via reaction using alumina catalyst. OH A1umina C-C-C-C-C-C-OH Catalys^. C-c-c=C-C-C-C-0H + H2O The effluents from Section 600 are C, Cq|q, C|?l4 ^1618* ^1620 or ^20+ alcohols from normal fractionation. A utility fractionation section is used to produce heart-cuts of the alcohols such as Cfc, C3, Cjq, etc. PLANT UTILITY SUPPLIES Solvent is supplied by the LPA solvent portion of the n-Faraffins Unit. Steam is obtained from the ethylene unit boilers. The plant has its own furnaces for hot oil supply and its own cooling towers for cooling water. Nitrogen gas, fuel gas, and electricity are purchased. PED ORIENTATION PROGRAM TABLE I "ALFOL" ALCOHOL PROPERTIES AND USES CONOCO "ALFOL" ALCOHOL PROCESS Alcohol Product Range Plasticizer Range (C4 to Cio) Detergent Range (C1Q-C20+) Intermediates "ALFOL" Alcohol Phthalates "ALFOL" Alcohol Esters "ALFOL" Alcohol Sulfates "ALFOL" Alcohol Ether- Sulfates "ALFOL" Alcohol Nonionics Typical Uses Imitation Coatings, Cable Industry, Leathercloths, PVC Sheetings, PVC Plates, Films, Bag Makers, Foaming Materials, Extreme Thermo stable Sheetings Detergents, Emulsifiers, Demulsifiers, Defoamers, Ore Flotation Agents, Textile Processing Agents, Cosmetics, Shampoos, Ointments DOOO )Ot This sheet is CONFIDENTIAL and should not be distributed outside Continental Oil Company Spec. No. 06-4000 ALFOL 4 Alcohol Special Identification: 1-butanol Teat Total Alcohol, Wt. % Dlstribution (100X alcohol basis): C2 OH, Wt. % C^ OH, Wt. % OH, and higher, Wt. X Alcohol Color, APHA Water, Wt. Z Acid, as Acetic , Wt. Z Iodine Number Boiling Point Range, C Specifications 99.0 min. Typical Proper t 9 9.5 1.0 max. 98.0 min. 1.0 max. 10 max. 0.1 max. 0.01 max. 0.2 max. 4 max. TR 99.8 0.2 0 0.05 0.001 0.05 2.5 Test Me thod 1.055 1.055 1.025 1.016 1.024 1.031 AS TM-D-10 7 8 8.-15-73 (Replaces. .10-1-72) This sheet Is CONFIDENTIAL and should not be distributed outside Continental Oil Company Spec. No. 06 -4010 ALFOL 6 Alcohol Special Identification: 1-hexanol Test Total Alcohol, Wt. % Distribution (100% alcohol basis); C6 OH, Wt. % Alcohol Color, APHA Water, Wt. % Acid, as Acetic, Wt. X Iodine Number Specifications 98.5 min. Typical Property 99.A Test Method 1.055 98.0 min. 10 max. 0.15 max. O.OOSmax. 0.2 max. 98.6 0 0.06 0.001 0.06 1.055 1.025 1.016 1.024 1,031 8-15-23 (Replaces 10-1-72) O^Oo/Olo^y This sheet Is CONFIDENTIAL and should not be distributed outside Continental Oil Company Spec . No. 06-4020 ALFOL 8 Alcohol Special Identification: 1 -octanol Test Specifications Total Alcohol, Wt. X 99.0 min. Dis tributlon (100% alcohol basis); C OH and lower, Wt. % 0.5 max. Cg OH (normal primary) Wt. % 98.8 min. C^o OH and higher, Wt. % 0.5 max. Alcohol Color, APHA 10 max. Water , Wt. X 0.10 max. Acid, as Acetic, Wt. % 0.005 max . Iodine Number 0.2 max. Carbonyl, as C*0, ppm 80 max. Typical Property 99.5 TR 99.7 0.3 0 0.05 0.001 0.05 50 Test Method 1.055 1.055 1.025 1.016 1.024 1.031 1.026 I 0-15-73 (Replaces 10-1-72) 5^-1 OOOr>) Aln-3 This sheet le CONFIDENTIAL and should not be distributed outside Continental Oil Company Spec. No. 06-4030 ALFOL 10 Alcohol Special Identification: 1-decanol Test Total Alcohol, Wt. X Distribution (100X alcohol basis): Cg OH and lower, Wt. % C1Q OH, Wt, X C12 OH and higher, Wt. X Alcohol Color, APHA Water, Wt. X Acid, as Acetic, Wt. X Iodine Number Carbonyl, as C-0, ppm Specifications 98.5 min. Typical Property 99.2 Test Method 1.055 - 98.0 min. - 10 max. 0.15 max. 0.005 max. 0.2 max. 100 max. 0.1 99.3 0.6 0 0.04 0.001 0.06 25 1.055 1.025 1.016 1.024 1.031 1.026 1-26-76 (Replaces 8-15-73) Sf\ L This sheet Is CONFIDENTIAL and should not be distributed outside Continental Oil Company Spec. No. 06-4040 ALFOL 12 Alcohol Special Identification: 1-dodecanol Test Specifications Total Alcohol, Wt. X 98.5 min. Distribution (100% alcohol basis): C12 OH Normal Primary, Wt. % Alcohol Color, APHA 98.5 min. 15 max. Hydroxyl Number 295-302 Water, Wt. % Iodine Number 0.1 max. 0.2 max. Carbonyl* as C*0, ppm 100 max. Typical Property 99.4 99.2 0 300 0.04 0.03 64 Test Method 1.055 1.055 1.025 1.029 1.016 1.031 1.026 8-15-73 (Replaces 10-l*-72) IfjPtL 0600 10^05 This sheet is CONFIDENTIAL and should not be distributed outside Continental Oil Company Spec. No, 06-4050 ALFOL 14 Alcohol Special Identification: 1-Tetradecanol Test Total Alcohol, Wt. % Distribution (100% Alcohol Basis): Ci2H and Lower, Wt. % , C140H, Wt. X C160H and Higher, Wt. % Alcohol Color, APHA Hydroxyl Number Water, Wt. % Iodine Number Carbonyl, as C*0, ppm Specification 98.5 min. 2.0 max. 96.0 min. 2.0 max. 20 max. 255-264 0.1 max. 0.4 max. 200 max. Typical Property 99.0 0.9 98.4 0.7 0 258 0.04 0.05 100 Test Method 1.055 1.055 1.025 1.029 1.016 1.031 1.026 5-23-79 (Replaces 8-15-73) SR^ooooidjo^ This sheet Is CONFIDENTIAL and should not be distributed outside Continental Oil Company Spec. No. 06-4060 ALFOL 16 Alcohol Special Identification; 1-hexadecanol Test Total Alcohol, *Wt. % Distribution (As-is sample basis): OH and lower, Wt. Z C16 OH, Wt. % C18 OH and higher, Wt. % Alcohol Color, APHA Saponification Number Hydroxyl Number Water, Wt. % Iodine Number Carbonyl, as CQ, ppm Specifications 97.5 min. Typical Property 98.9 Test Method 1.055 3,0 max. 95.0 min. 3.0 max . 40 max. 1.0 max. 218-238 0.1 max. 0.6 max. 350 max. 0.7 97.4 0.8 25 0.8 227 0.03 0.15 140 1.055 1.025 1.030 1.029 1.016 1.031 1.026 8-15-73 (Replaces 10-1-72) C0C1CIC7 This sheet is CONFIDENTIAL and should not be distributed outside Continental Oil Company Spec. No, 06-4070 ALFOL 18 Alcohol Special Identification: 1-Octadecanol Test Total Alcohol, Wt. % Distribution (As-Is Sample Basis): C14OH and Lower, Wt. % CigOH and Lower, Wt. % C10QH, Wt. % C2oQH and Higher, Wt. % Alcohol Color, APHA Saponification Number Hydroxyl Number Water, Wt. % Iodine Number Carbonyl, C=0, ppm Specification 98.0 0.5 max. 3.0 max. 95.0 min. 3.0 max. 40 max. 1.5 max. 200-220 0.1 max. 1.0 max. 700 max. Typical Property 98.2 0.2 0.7 96.6 0.9 20 0.4 200 0.05 0.58 600 Test Method 1.055 1.055 1.025 1.030 1.029 1.016 1.031 1.026 5-23-79 (Replaces 8-15-73) 5[_ crccincs / / -L L a-> =o 51 IK --R SAl_ 0C001C1C9 r `tilt j PuQg ATg TUWSH PA-ac.a BTMi. ^uuran- OA Z6 I ATE - iOLVEUT TQWEB orr. SA6 to &*'2fcQ tn (i^-ae.9 1 I *72 T<74JMIU& f*nO&Ti/VNf EO 'AC ol_j ISU DATE DESCRIPTION T CKO APD o CONTINENTAL OIL COMPAN1f o INOINEIIINO CCN1EK PONCA CTTY, OKLAHOMA o SllwlPt, Ficra r^fjoceai Flow DiA&nAM "TIPo (S>* 74 2T7 IT70O w It l Tu fl n17sr I1S0 nsrora * Ti. G*^. TTT I C >? J-i *S t 1, !-l. S . J SCALES FOI MICCRtOOFFILUMMEDD D0 RAWINGS I0 0li u il 111I1 n LL l|! n 11 n 11 n n 11 n 11 u } I n 111 n 11111 il UJ1111111 Id affd: /* oati: L-24ZS 'il A/>l* r=> ALIT USC SORDER SCALE'. l*o. CT A " c. M2S SAL OOCClClll I FB- ' &QOWTH OC--QOI A OAT AM OXIOATIOM (2EACTO ra 1 OX I OAT 1 OM oc-*ioie. OATC.M ORXEIOAACTTIOOMt EXT rLACTOra FB-gQte j rg??><-^EEDDli/ATg E>TQFAjSE > r~ o o o o C3 *-* - TTTTTTW2W0 'Tl W 1* U "1f3tl T1I0SfT (S> L-L--L uct 'L'0i'U`uy]<S)(3^ --2r SCALES FO f't MICftOPILMED D' ftAWWGS U } l ?!<g)(g> ? , I 'ItU 73 TQAIKIIWb ISU date DESCRIPTION EC mpnrro CONTINENTAL OIL COMPANY ENOINEI1INQ CENTEI PONCA CITl, OKLAHOMA TTT SuvPi-ine-j P.OW Ol.io'iAM VO w --nkE CwAni-fc^, 'ii.FVL' PucoMot, Plani use lOKCEft scale: tl 111111 u 111 n 11 n J11 ni-il 1111 h 11111 I-LlI AftPD: H -3 Fbvu-. date: r-j- No. ' T- II gA-<iao 14? STAgg OVUD. C.OKJO. 2Hg m&e OVHO. C.OMO 1 E/..USI 34? WAftt QvMQ. c OKjra eg-r.^sz i~tT.ra eo(^LE.a CT3-*I2C. OXIPIZEO MOWTH PPQDOC.T 6TQBA66 I V 6TA6C VAC. F=-|_ASH PA-33 2t &TA6E. VAC. FA-H27 3~ST46 VAC. 4LA>M FA-426 AtCUMULATOH PA-43Q FA-4Z9 oaf.uOM. 4 SK6DCoMT400 CjAS TO FUEL ---------------------------------------^ 5TDiWPer> Al_kCJX'.OS TO SECT 300 ^ SOUVewT t IMPQglTIgS TO.-. ]__C. QEF'IVJ&OS' l/' r O o o o TO-* (S> <s>? vises &A-42A * -Mg'? VACUUM coMr-oe&stw TnT >i IV 3TA&E PBgH&ATER E/.43A 2g> STAAE PHE4EATEB EA-427 3f STA66 r>f2cit~i g Atea EA429 5THIPP6Q AUKOXlOE COOLER ; | 1 >W-73j TPAIUIWA PBO&OAM tsu DATCJ PESctirriOM --n 0 *=J ihehes ^) [~~| PBSSS., hM My ASS TEMR, F- CONTINENTAL Oil COMPANY INOrIoNNCEAllaIrNr.OokuhCoCmHa1 C I it MPUFif.r; T-tiow i,1,; 't.u1 ai1 ra1 u i.y *-iii1 ur! uj 1 w1 i<sxg>j nJ i I l I |-T lo Sectiqm -125 ALE CmAQLEL. AlfOL AcC&UCh. p-ljamT use ftOKDEE scale: i i tt ii i I 7 i v T '( 1 '. 3iJ * i<jxs>.I.m..,ili.uLuliiuii 111111! m i! li nlm 111li 11 n 1111 n 1111111 AFPO: Cr-~- date: Hsj.:-* No. CT- 1C- c. Alumina Unit - SAL CC001C114 PED ORIENTATION PROGRAM SECTION 550 - ALUMINA UNIT ("ALFOL" Alcohol Unit) LAKE CHARLES, LOUISIANA The chemistry of the "ALFOL" Alcohol Process requires that some type of aluminum-containing compound issue as a by-product of the aluminum trialkoxide hydrolysis reaction. The Lake Charles plant started up with acid hydrolysis yielding alum by-product. (The acid hydrolysis unit was described within the framework of the "ALFOL" Alcohol Unit). The Condea plant startup three years later produced alumina. Ultimately, the alumina became an important sales factor. Conoco then updated the prior technology and installed a 40 MM pound per year Alumina Unit at Lake Charles. Lake Charles currently operates only the Alumina Unit. The Alumina Unit is presented as a separate entity reflecting the complexity of the process and the importance of the product. Raw materials for the process are water and aluminum trialkoxide from Section 1*25 of the "ALFOL" Alcohol Unit. GENERAL DESCRIPTION Section 550 of the Lake Charles "ALFOL" Alcohol Unit provides for water hydrolysis of solvent-free aluminum alkoxide (produced in Section 425) with the formation of alumina and straight-chain alcohols containing even carbon numbers. High purity alumina, denatured ethanol, and sol vent-grade butanol are recovered in this section while Cg+ alcohols are sent to Section 600 for further processing. Three processing systems are contained in Section 550: A. Hydrolysis-Extraction System B. Fractionation System C. Alumina Recovery System In the hydrolysis-extraction system, stripped aluminum alkoxide reacts with water according to the following equations: 2A1(OR)3 + 3H20 --- AI2O3 + 6R0H (Monoaluminum Alkoxide) (Alumina) (1) ai2(or)ao (Dialuminum Alkoxide) + 2H20 --A12O3 + 4R0H (2) Ti(OR)4 (Titanium Alkoxide) + 2H20 --*.Ti02 + 4RQH (3) The above reactions are exothermic and carried out at 200F in the presence of excess water. The two products from the reaction a,re an alumina-water slurry and crude alcohols. These are mutually insoluble and separate in the hydrolysis reactor. Any C^+ alcohols contained in the alumina-water slurry from the hydrolysis reactor are removed in a two-stage countercurrent extraction with butanol. SAL JCJCU0115 GENERAL DESCRIPTION (CONTINUED) In the fractionation system, the wet crude alcohol from,the hydrolysis reactor is sent to a dehydrator tower where the water is removed. The condensed overheads from the dehydrator tower and the butanol stripper (in the alumina recovery system) are combined and sent to the dehydrator tower overhead accumulator. This combined stream, which consists of water, ethanol, and butanol, separates into two phases in this accumulator. The water phase is combined with makeup condensate and barometric condenser blowdown water ana recycled to the hydrolysis reactor. The alcohol phase is fed to an ethanol tower where a 93 percent ethanol product is recovered. The bottoms from the ethanol tower consists of water and butanol which is used for extraction in the hydrolysis-extraction system. The water-free crude alcohol from the dehydrator tower is sent to a butanol tower where a high purity butanol product is taken overhead. Most of the butanol product is recycled to the process while the net make butanol is sent to the hydrogenation section. The bottoms from the butanol tower is transferred to Section 600 for further fractionation. In the alumina recovery system, the alumina-water slurry from the hydrolysis-extraction system Is sent to a butanol stripper where butanol is stripped from the slurry with steam. The alcohol-frlee slurry Is then sent to a spray dryer for recovery of a high purity, high surface area powdered alumina. The spray dryer utilizes direct heating with air and flue gases which enter at 1,400F and exit at 300-350F. The alumina product (75 percent alumina/25 percent water) from the spray dryer is transferred to product storage where it is loaded into railcars and trucks for bulk shipment. DETAILED PR0CES5 DESCRIPTION A. Hydrolysis-Extraction System Stripped aluminum alkoxide is received from Section 425 at 160F. The alkoxide is pumped from intermediate storage tanks FB*506A or FB-508, heated to 200F with steam in EA-551, and injected into the hydrolysis reactor, DV-551, through a small diameter nozzle which promotes turbulence. The alkoxide enters the reactor in the slurry phase between the two impellers of the reactor mixer. It reacts rapidly to form crude "ALFOL" alcohols and hydrated alumina. The hydrolysis water to the reactor consists of makeup condensate, barometric condenser blowdown water, recycle water from the distillation system, and ammonium hydroxide solution from the ammonia absorber. Condensate is used as process water to prevent contamination of product alumina with foreign minerals. The hydrolysis water is pumped from the hydrolysis water tank, FB-551, to the hydrolysis reactor, DV-441 , via the steam ring heater, PA-551- In this heater, the water temperature is raised to about 170F by direct steiam injection. SAL JCCC1C116 DETAILED PROCESS DESCRIPT/ON (CONTINUED) A. Hydro Iys fs-Extraction System (Continued) An ammonia concentration of about 0.15 weight percent Is maintained In the hydrolysis water. The ammonia prevents formation of emulsions In downstream equipment. This concentration Is maintained by injection of ammonium hydroxide into this stream intermittently. A wet butanol stream from the extraction system also enters the slurry phase of the reactor to enhance removal of heavier alcohols. A crude alcohol phase and an alumina-water slurry phase are produced in the hydrolysis reaction. A nitrogen pressure of 80 psig is maintained In the hydrolysis reactor to permit transfer of slurry by pressurization rather than pumping. In normal operation, most of the crude alcohol is pressured directly from the reactor to the dehydrator tower to conserve energy. The remaining alcohol is cooled in EA-553 to 175F and sent to the alcohol surge tank, FB-553- Five recycle alcohol streams also flow into this tank: 1. Remelted barometric condenser cooling tower sump scrapings. 2. Remelted railcar scrapings. 3. Tower "G" overheads from Section 600. A. Off-spec alcohols from Section 600. 5. Skimmed alcohols from hydrolysis water tank, FB-551- These alcohols are pumped from FB-553 to the dehydrator tower continuously during normal operation. The alumina-water slurry phase from the hydrolysis reactor contains dissolved and entrained alcohols. The alcohols must be removed and recovered to avoid an unacceptable carbon content tn the alumina product and avert an alcohol product loss. A two-stage countercurrent extraction with butanol is used to remove the C^+ alcohols from the slurry. The alumina slurry is pressured from the hydrolysis reactor, DC-551, to the first stage mixing drum, FA-553- Here contact is made with the butanol phase from the second stage phase separator drum, FA-55A. The effluent from the first stage mixer is phase split in the first stage phase separator drum, FA-552. The alcohol phase from FA-552 is pumped to the hydrplysis reactor. The alumina slurry from the first stage phase separator is pressured to the second stage mixing drum, FA-551- Here it contacts fresh recycle butanol from the recycle butanol tank, FB-5152. In order to maintain the alumina slurry at 185F, the recycle butanol is preheated to 169F in EA-552. The alcohol/siurry mixture from the second stage mixer Is transferred to the second stage phase separator, FA-55^. The alcohol phase from this separator is pumped to the.ffrst stage mixing drum. The slurry is pressured to the butanol stripper, DA-55A. SAL C0QC1C117 DETAILED PROCESS DESCRIPTION (CONTINUED) A. HydroTysis-Extraction System (Continued) Parameters affecting the operation of the reaction-extraction system are reaction and extraction temperature, hydrolysis water and recycle butanol flow rates, and ammonia and ethanol concentration. The most economical operation is at the following conditions; 1. Minimum Hydrolysis Water Flow (or Maximum Slurry Concentration)-- Since" the water in the siurryIs evaporated during spray dryYng, less water results in less condensate makeup and fuel requirements. 2. Minimum Butanol Recycle Flow--Since less butanol decreases the load on the fractionation system. Hydrolysis water flow rate should be set to give a jautanol stripper slurry feed concentration of 9-12 weight percent solids; higher solids concentrations can cause slurry transfer problems. Recycle butanol flow rate should be set at the minimum value which consistently gives acceptable extraction. The design hydrolysis reaction temperature is 200F. Higher temperatures will decrease alumina product surface area and increase butanol solubility in the slurry. The reaction temperature is regulated by adjusting hydrolysis water and alkoxide feed temperatures. Temperature of the second stage extraction is set biased on butanol solubility in the slurry and slurry flow characteri 1st 1 cs. Emulsions can occur in the reaction-extraction system due to ammonia deficiencies or excess ethanol concentrations. The ethanol tower removes the net make ethanol and is designed to give minimum ethanol recycle. B. Fractionation System Crude alcohol containing approximately 11 weight percent water Is fed to the dehydrator tower, DA-551, directly from the reactor, DC-551, and from the alcohol surge tank, FB--553 Before entering the tower, the feed Is filtered in FD-551 to remove any entrained alumina particles and then heated to its bubble point of 208F in EA-555- The dehydrator removes the water as a butanol/water azeotrope alonp with the ethanol and ammonia. High purity butanol from the butanol tower Is "refluxed" to the top tray of the tower to minimize C^+ alcohol carryover. The water-free crude alcohol bottoms from the dehydrator tower is fed to the butanol tower, DA-553- A 99+ percent butanol product is distilled overhead in the butanol tower. The butanol tower overhead product provides reflux to the dehydrator tower and supplements the recycle butanol requirements (to the hydrolysis-extraction system). The net make butanol is sent to the hydrogenation section. The butanol-free tower bottoms is transferred to intermediate storage located in Section 600. The dehydrator tower overhead is condensed, subcooled to 160F, and combined with the butanol stripper overhead (also at 160F). The combined stream enters the dehydrator tower overhead accumulator, FA-555, and separates into an alcohol phase and an aqueous phase. The aqueous phase is pumped to the steam ring heater, PA-551, for recycle to the hydrolysis reactor. SAL CC0C1C113 DETAILED PROCESS DESCRIPTION (CONTINUED) B. Fractionation System (Continued) The alcohol phase from the dehydrator tower overhead accumulator is fed to the ethanol tower, DA-552. The ethanol tower removes the net make ethanol and minimizes ethanol recycle to the hydrolysis-extraction system. Low ethanol recycle rates reduce emulsion formation in the hydrolysis reactor. The ethanol product is removed as an ethanol/ water azeotrope (about 93 weight percent ethanol) from a sidedraw on Tray 11 of the ethanol column. The ethanol sidedraw product gravity flows to product storage FB-506C. The top ten trays of the ethanol tower remove ammonia from the ethanol product. The overhead vapor consisting of most of the ethanol and water and essentially all of the ammonia is partially condensed In EA-56O and enters the overhead accumulator, FA-558. The liquid in FA-558 is returned as reflux to the ethanol tower. The uncondensed vapor from FA-538 is partially condensed in the ethanol tower vent condenser, EA-562, and returned by gravity flow to FA.-558. The purpose of EA-562 is to minimize ethanol recycled to the hydrolysis-extraction system. The uncondensed vapor from EA-562 which is mostly ammonia with some ethanol and water, is absorbed with service water in the ammonia absorber, DA-55. The ammonium hydroxide solution gravity flows from DA-535 to the hydrolysis water tan, FB-551 This enables almost all the ammonium hydroxide introduced into the process to be recycled, minimizing fresh ammonium hydroxide makeup and pollution problems. The ethanol tower bottoms is cooled to 50F in EA-558 and transferred to the recycle butanol tank, FB-552. C. Alumina Recovery System The alumina slurry from the second stage separator drum, FA-55**, is pressured directly to the butanol stripper, DA-55**. The slurry is fed to the top tray. Live steam, desuperheated in PA-552 to process conditions, is used to strip all butanol (as a butamol/water azeotrope) and lighter components from the slurry. A cyclone,,FA-560, is provided in the butanol stripper overhead vapor stream to remove any entrained alumina particles. The overhead is condensed and subcooled to 160F in EA-565 and combined with the dehydrator tower ovterhead stream (see above). The alcohol-free slurry is pumped from the butanol stripper using a positive displacement pump with a variable-speed drive. This slurry first enters EA-566 where it is cooled to 195F and then it flows to the alumina slurry surge tank, FB-55**. The alumina slurry is pumped from FB-55** through the spray dryer feed filter, FD-552, to the spray dryer, EC-55, using another positive displacement pump with a variable-speed drive. The slurry enters the spray dryer through a centrifugal wheel atomizer. The resulting slurry droplets contact the hot air and flue gases from the spray dryer air heater, BA-551. Combined stripper overhead from Section **25 (liquid fuel) is pumped in from FB-555 to fire the heater. The inlet hot air SAL COOOlCil? DETAILED PROCESS DESCRIPTION (CONTINUED) C. Alumina Recovery System (Continued) temperature Is maintained at 1,400F by using excess air supplied by GB-551, the combustion air blower. The exhaust gases and alumina leave the spray dryer at 300-500F and enter a baghouse, FD-444, which recovers the alumina product. The alumina-free exhaust gas Is vented to the atmosphere from the spray dryer exhaust fan discharge, GB-552. The al umifia. product-from the baghouse is transferred, to one of the alumina check bins, FB-556A, B,~and C (one for each shift). After product testing, the alumina is.transferred to one of the product silos, FB-557A, B, C, and D. The product is loaded into trucks and railcars. Inventories are measured by load cells on the silos. An off-specification product silo, FB-558, is also available when needed. PRODUCT "CATAPAL-SB" is the tradename for the high purity, high surface area, powdered alumina product. In contrast to alumina produced from mineral deposits, "CATAPAL-SB" and the alumina products can be tailored to have a variety of physical properties. The major use of alumina Is catalyst support material for petroleum refining processes. See the following page for typical product specifications. SAL CC0010120 This sheet is CONFIDENTIAL an 1 should not be distributed outside Continental Oil Company. Spec. No. 06-5400 CONOCO CATAPAL SB ALUMINA Test AI2O3, Wt. % Carbon, Wt. X Si02, Wt. % Fe203, Wt. % Na20, Wt/% Physical Properties Particle Si2e Distribution Smaller than 45 microns Greater than 90 microns Bulk Density, Loose, gms/liter Pore Volume (0-800A)*, ml/grm 2 Spec. Surface Area (BET)*, m /gm > Crystallite Structure Specifications 70 min.-78 max. 0.5 max. 0.01 max. 0.01 max. 0.01 max. 55X max. 15% max. 660-740 0.4 min. 230 min. Boehmite Type * After calcination for 3 hours at 900F. Test Method 1.400 1.401 1.402 1.403 1.404 1.405 1.406 1.407 1.408 1.409 7-15-77 (Replaces 11-15-74) SAL 30CC1C121 $&L ccaciri2> PED ORIENTATION PROGRAM CDRTM DRAG REDUCER PLANT LAKE CHARLES CHEMICAL PLANT CDR^ drag reducer is a very high molecular weight poly alpha-olefin. It was developed by Chemicals Research In cooperation with Production Research for use in crude oiil pipelines and as a friction reducer in hydraulic fracture treatments of oil wells. Conoco was awarded a patent in 1972 for CDRTM drag reducer use in pipelines. The material and its applications were developed during the late 1960`s. It was tested in a number of pipelines with its performance being a technical success. However, in each case, economic considerations indicated expansion of pipeline capacity through equipment changes and additions rather than using CDRTM drag reducer. This situation prevailed until 1977 when interest In CDR^M drag reducer was dramatically revived as a result of the fire at pump station No. 8 shortly after startup of the Trans Alaska Pipeline System (TAPS). The problem reduced crude oil flow from 1.2 MM BPD to 730*000 BPD. At that time, Alyeska Pipeline Service Company approached Conoco with an emergency interest In CDRTM drag reducer. However, the pump station outage was to last "only" six months, not enough time to allow for commercialization of CDRTM drag reducer. Although the immediate need could not be met, enough information was developed to point to a potentially attractive future use of CDRTM drag reducer In TAPS to give additional incremental throughput. A pilot plant, including a 3,500-gallon reactor, was operated in Ponca City during 1978 to produce an optimum product. Very successful test runs were made in a Conoco eight-inch pipeline and In an Arco fourteeninch pipeline transporting North Slop crude oil. Finally, a full scale test run was made in TAPS on April 1, 1979. The test was successful and led to a contract with the Alyeska Pipeline Service Company, with supply to begin in July 1979- The CDRTM drag reducer plant was designed by PED in Ponca City. The plant was then built in Lake Charles and started up on July 13, 1979* The original plant included an olefin storage tank, a chiller, a reactor, catalyst addition, and two loading spots with a capacity of 3 MM gallons per year of CDRTM drag reducer. Since that time, a feed storage tank, a second reactor, an improved catalyst addition system, three more loading spots, and railcar loading facilities have been added with the capacity now being about 9 MM gallons per year.. The Improved catalyst addition system enabled production of a more effective drag reducer which, in turn, led to a new long range contract with Alyeska beginning in 1982. 3AL 0CQC1C-123 General Process Description CDRTM drag reducer is made by charging chilled olefin and plant solvent to a stirred reactor. Catalysts are then charged and a polymerization reaction takes place. When the polymerization reaction is complete, the CDRTM drag reducer is pumped to loading with additives being injected to deactivate the catalysts. The CDRTM drag reducer is loaded into either railcars or sea containers for shipping. SAL CC0C10124 SOLVENT C. ;--------------- - - olef:\ I STORAgg 1/1 T llsrsssr o ro w. peep storage T I II He CAT/M-YSTS c~o RE/ACTORS i c>o o^c ;oouec i ADPIT;VS r TO LOADING; i ------------------------[-/ 1 ORlEMT/VTIOM 0373 ISU DATE desckphon BY CKD APD CONOCO INC. ENGINEERING CENTER PONCA CITY, OKLAHOMA PROCESS FICW DIAGRAM CPR^ POAG REDUCER PLANT LvAKE CHARLES CHEMICAL PLANT APPO: DATE: r/zo/j-z. SWT NO | NO. CT-Gi -e> IMT AREA ""EHF This sheet is CONFIDENTIAL and should not be distributed outside Conoco Inc. Spec. No. 11-5590 CONOCO CDR Test Polymer Content, Wt % Viscosity, Inherent (300 sec-^) Chlorides, Total, Wt % Metals Analysis, WT % Sodium T1tanium Aluminum Lead Nickel Copper Ash, Total, Wt % Sped f ication 10 min 8.5 min 0.12 max 0.09 max 0.03 max 0.05 max 0.002 max 0.005 max 0.002 max 0.30 max Typ1 cal Property 10.3 9 0.07 0.05 0.02 0.03 <0.001 <0.001 <0.001 0.19 Test Method 1.085-79 1.08*1-79 1.083-79 1.086-79 1.087-79 8-1-80 (Replaces 7-16-79) SAL unC01Cl?6 SAL 0C0C1C127 PED ORIENTATION. PROGRAM ETHOXYLATI ON UNIT LAKE CHARLES CHEMICAL PLANT The ethoxylation technology was developed by Conoco and practiced commer cially beginning in 1962. The plant is located adjacent to the "ALFOL" Alcohol Unit In Westlake, Louisiana. The unit has production capability for up to 77 MM pounds per year of "ALFONIC" ethoxylates. These products are excellent feedstocks for detergent manufacturers and are completely biodegradable. Raw materials required include ethylene oxide and linear "ALFOL" alcohols. GENERAL DESCRIPTION The process chemistry is represented typically as follows: ClUH290H + 6 CjH^O "ALFOL" 14 Ethylene Alcohol Oxide Cata1ystfc cI4h29(c2hZ*)6 "ALFONIC" 14 Ethoxylate (6 Mol Adduct) The plant is operated in batch style. The following description is that of a typical batch cycle (see attached process flow diagram). A batch of "ALFOL" alcohol is pumped from storage to the stirred pot ethoxylation reactor vessel. The reactor Is mounted on a weight indicator (load cells) so that the exact amounts of reactants can be determined. The alcohol is circulated through a heater-cooler back to the reactor and heated with steam to 300F. Caustic catalyst (about 0.14 weight percent based on alcohols charge) is then injected into the reactor. The reactor is then pressured with nitrogen, and the alcohol,is further heated to 360F. Ethylene oxide is then fed to the reactor from storage. Heat of reaction is removed by circulating the reaction mass through the watercooled heater-cooler. Addition of ethylene oxide Is continued until the desired amount has reacted. At the end of the batch, a sample from the reactor is titrated to check basicity; and the required amount of glacial acetic acid for neutralIzation of caustic is added to the reactor from a small acid hopper. The neutralization salts are soluble in the ethoxylate product, and the product Is water clear. The product is then cooled and transferred to a. rundown tank and to storage. Total batch time is about 2 hours 45 minutes to four hours, depending on product. Ethylene oxide is volatile, flammable, extremely reactive, and toxic. vapor Is subject to explosive decomposition at high temperature and pressure. During addition of ethylene oxide to the reactor, the unit operator must watch reactor operation very closely. The 5ftL cccciciza PRODUCT Major products volumewise are: "ALFONIC" 10-12-60 "ALFONIC" 16-18-65 "ALFONIC" 10-14-40 "ALFONIC" 14-12-40 "ALFONIC" 14-12-60 Ethoxylated "ALFOL" 10-12 Alcohol Containing 60 Weight Percent E0 Ethoxylated "ALFOL" 16-18 Alcohol Containing 65 Weight Percent E0 Ethoxylated "ALFOL" IQ-14 Alcohol Containing 40 Weight Percent E0 Ethoxylated "ALFOL" li-12 Alcohol Containing 40 Weight Percent E0 Ethoxylated "ALFOL" 14-12 Alcohol Containing 60 Weight Percent E0 "ALFONICS" are sold to detergent manufacturers for use in liquid and powder detergent formulations. Some "ALFONICS" are also sold as defoamlng agents. "ALFONIC" 10-12-60 Is used "as is" as nonionic detergent in light duty liquid detergent formulations. "ALFONIC" I6-I8-65 is used "as is" as nonionic detergent in heavy duty powder detergent formulations. "ALFONIC 10-14-60 and 14-12-40 are sulfonated with SO3 and neutralized with NaOH or NH3 to form cationic or anionic detergents for use in light duty liquid detergent formulations. SAL 000010129 This sheet is CONFIDENTIAL end should not be distributed outside Continental Oil Company Spec. No. 06-4300 ALFONIC 610-50 Alcohol Ethoxylate Special Identification: Typical 50% Ethoxylate of ALFOL 610 Alcohol (Spec. No. 06-4110) Test Hydroxyl Number pH, IX in Water Water, Wt* X Suspended Matter Typical Specifications Property Test Method 196 10 196 1.029 6-7 6.8 1.047 0.1 max. 0.03 1.016 Substantially Free Visual r \i \ 11-30-78 (Replaces 10-1-72) sal OCGC10130 This sheet is CONFIDENTIAL and should not be distributed outside Continental Oil Company Spec* No. 06-4321 ALFONIC 1012-40 Alcohol Ethoxylate Special Identification; Typical 40 1 Wt. % Ethoxylate of ALFOL 1012-GB Alcohol (Spec. No. 06-4152) Test Hydroxyl Number Color, AFHA pH, 1% in Water Water, Wt. % Cloud Point, ml of Water Specification 190-205 50 max. 6.0-8.0 0.1 max. 33 4 TypicaJ. Property 201 5 6.8 0.03 33 Test Method 1.029 1.025 1.047 1.016 1.056 7-15-77 (Replaces 5-01-7^ SAL J0CC1C131 This sheet is CONFIDENTIAL {and should not be distributed outside Continental Oil Company Spec . No. 06-4320 ALFONIC 1012-60 Alcohol Ethoxylate Special Identification: Typical 57+2 weight percent ethoxylate of ALFOL 1012-HA (Spec. No. 06-4150) Test Hydroxyl Number Color, APHA pH, IX in Water Water, Wt, Z Cloud Point, 12 in Water, C Glycol, Wt, X Specific Gravity (25/25C) Specifications Typical Proper tv 140-155 143 50 max* 10 6,0-8.0 7.0 0.1 max. 0.03 32-38 1.0 max. 34.0 0.8 0,972 + 0.003 Passes Test Method 1.029 1.025 1.047 1.016 1.049 1.034 - 7-15-77 (Replaces 5-01-77) 0C0C1C132 SAL 1 XX*feise-sA_ a. fcEtu-ViHoYKQitwVf. soVxw-,ofC.ft. st^SwEt 6fty*-Bi*.*WMo*p% fcmA&t-'f^wWK ~*>**<I*V^rtS'Mht -281 S V: T> r o a 1 o' o "-5* V.J L*J C.SM COO'wXWd. .. CRON- caouNb tONijia aa-s 2 TK# rrKc THAIKJ* FfCSRAM 1 0 NVM HC CONTINENTAL OIL COMPANY ENGINEERING CENTER PONCA CITY. OKLAHOMA PROCUI f\.OW OiattRkW- -.KWt Cm VS Afro: i^s mm "kLPOw" A.UC&OUO\. PVfcWT scale: No. CT- ZZ-B * e % SAL 000010134 PED ORIENTATION PROGRAM n-PARAFFIN UNIT LAKE CHARLES CHEMICAL PLANT The n-Paraffin Unit was started up late In 1964 to produce straight-chained paraffin feedstock for thfc Baltimore plant's "NALKYLENE" iAlkyiate Unit and the Lake Charles LAB Plant (on stream, 1982). The niParaffln Unit utilizes Universal Oil Products' (UOP) proprietary "Unifapn" and "Molex" technologies to recover normal paraffins from refinery kerosene at the rate of 330 MM pounds per year (beginning the first quarter of 1982). A portion of the raffinate remaining from the extraction step is hydrogenated in an auxiliary unit (originally a cyclohexane plant) to yield a low polynuclear aromatic solvent. The latter is used as the solvent in the "ALFOL" Alcohol Process and is also marketed. The remaining raffinate, significantly enhanced in armoatics content, is returnedito Conoco's Lake Charles Refinery for use in making gasoline. The feedstocks include a 310F-490*F virgin kerosene from the refinery and hydrogen from the ethylene unit. PROCESS DESCRIPTION (See attached Overall Process Flow Diagram) Light virgin kerosene from Conoco's Lake Charles Refinery is supplemented with outside purchases of highly paraffinic kerosene. Tlpe mixture, containing 18-21 percent n-paraffins. Is preheated and stripped of light hydrocarbons. After gravity removal of any contained water, the kerosene is elevated to 600*F in a fired heater. The hot kerosene Is mixed with hydrogen and enters the Unibon reactor at 585"600oF and 775 psig. Olefinic materials are hydrogenated and sulfur-bearing cpmpounds are reduced to hydrogen sulfide (among other things). The hot reactor effluent exchanges heat with the heater feed and is flashed to remove light gaseous hydrocarbons to fuel. The degassed stream! is processed through a stabilizer tower to remove hydrocarbons boiling lower than decane. The stabilized kerosene is feedstock for the "Molex" process. The "Molex" process uses 5A molecular sieves to selectively adsorb straight chain paraffins from a mixture of hydrocarbons. The sieves are loaded in a fixed bed adsorbent chamber which has a number of beds. Above each bed is an access line which is connected to a rotary distributing valve. The net streams to the adsorbent chamber (feed ahd desorbent) pass through the rotary valve and are directed to the appropriate access line. Simultaneously, the two product streams (extract and raffinate) are flowing from the chamber via their appropriate access lines through the rotary A/alve. After a predetermined Interval, the valve automatically switches the four net flows to the next adjacent access line. This periodic change of net Inlet and outlet points approximates the motion of the adsorbent past fixed inlet and outlet lines. All flows are continuous through the distributor, and the only motion is the periodic partial rotation of this valve. The adsorbent chamber is divided into four zones; oro a PROCESS DESCRIPTION (CONTINUED) Zone 1 - Normal paraffins are selectively adsorbed onto the sieves. The adsorbed paraffins displace desorbent and non-nqrmal hydrocarbons from the sieves Into the circulating liquid stream. Zone 2 - This is the primary rectification zone in which the desorbtlon of "non-normals" Into the circulating liquid stream is completed. Zone 3 - The adsorbed normal paraffins are displaced from the sieves by desorbent into the circulating liquid stream, the desorbent enters the chamber at the base of Zone 3, while!the extract stream containing only normal paraffins and desorbent Is removed from the chamber at the top of Zone 3. Zone 4 - This is the secondary rectIffeat ion zone In which the desorbent is displaced from the sieves with "non-normals" In the circulating liquid from the top of Zone 1. The circulating liquid leaving Zone 4 and entering Zone 3 contains only desorbent. The raffinate stream removed from the bottom of Zone 4 contains only "non-normal" hydrocarbons and desorbent. The liquid In the adsorbent chamber is circulated from the top bed back to the bottom bed to complete the countercurrent contactingj sequence. Since the required liquid flow is different for each of the four zones, the circulating pump is programmed to change the flow rate ejach time a new zone Is switched from the top bed to the bottom bed. The raffinate and extract streams leaving the sieve chamber each contain desorbent. These two streams are routed through the rot|ary valve to their respective fractionation columns. Normal paraffin product and raffinate are produced as bottoms from their respective columns. The overhead desorbent streams are recovered and returned to the adsqrbtlon chamber. The n-paraffin recovery is approximately 95 percent, wltjh a purity of 99.1 percent. It is fractionated in a tower at Conoco'sj Lake Charles Refinery into a C^q-Cjo cut and a Ci2~^i6 cut* Both ar4 shipped via tanker to Baltimore. The Ciq-C.o cut is used to make N4500 "NALKYLENE" alkylate. The }%+ cut is fractionated into anc) cuts. The former is used to make N-600 "NALKYLENE" alkylate while the latter is sold. A portion of the raffinate Is charged to the "Solvent Urtlt.," which is actually the reaction portion of a cyclohexane unit built In 1963-1964. The raffinate is subjected to a severe hydrotreating over catalyst to saturate polynuclear aromatlce (PNA). This qualifies the solvent for use In the "ALFOL" Alcohol Process and other external solvent uses subject to the FDA's 50 ppb limit on PNA. PRODUCTS AND BY-PRODUCTS CiQ~C]2 n-Paraffins C] 3-C^ n-Paraffins - To Baltimore Chemical Plant ahd LAB Plant - To Baltimore Chemical Plant, f.AB Plant, and Sales LPA 5olvent - To "ALFOL" Alcohol Unit and Sqles Fuel Gas - Used in Lake Charles Chemical Plant Aromatic-Rich Raffinate - Returned to Lake Charles Refinery SAL w0C01Cl?6 This sheet is CONFIDENTIAL and should not be distributed outside Continental Oil Company. Spec. No. 06-3000 CONOCO C1Q-C12 Normal Paraffins Special Identification: Cjj Average n-Paraffins Test Total n-?araffins, Wt. Z Homolog Distribution, Wt. % C9 and Lower c10 C11 Cl 0 + Cl 1 C12 C10 + Cn + C12 C13 Cm and Higher Aromaties, X Bromine Number Color, Saybolt Molecular Weight Pounda/Gailon, 60F Specification 97.5 min. - 2.0 max. 25.0 max. 50.0 min. 25.0 min* 85.0 min. 15.0 max. 2.0 max. 1.0 max. 0.2 max. 25+ min. - Typical Property 97.7 - 0.4 18.3 38.9 - 33.9 - 8.0 0.5 0.75 0.01 30+ 160 6.22 Test Method 1.072 1.053 _ - 1.036 AStM D-1491-60 1.011 1.053 3-1-79 (Replaces 4-30-76) \ SAL QCOOICI`37 This sheet Is CONFIDENTIAL and should not be distributed outside Continental Oil Company Spec* No* 06-3005 CONOCO C11-C13 Normal Paraffins Test Total N-rParaffins Wt. % Homolog Distribution, Wt. X CIO and Lover Cll C12 C13 C14 and heavier Aromatics, Wt. X ASTM Distillation (Typical) 1 BP *F 5% 50Z 951 EP API at 60*F (Typical) Sulfur, Wt. ppm Nitrogen, Wt. ppm Carbonyl No., as co, ppm Bromine Number Specification 97.0 Min 1.0 Max Balance 1.0 Max 0.6 Max 390 400 410 445 450 56 1 Max 1 Max 100.0 Max 0.02 Max Teat Method 1.072 1.053 1.036 ASTM D-86 ASTM D-287 ASTM D-1266 ASTM D-148 1.026 1.012 10-25-76 (Replaces 10-17-75) SAL 0 COC1C 13 ^ This sheet is CONFIDENTIAL and should not be distributed outside Continental Oil Company. Spec. No. 06-3012 CONOCO Ci2"Cie Paraffins Special Identification} C13 Average n-Paraffins Test V, * Specification Total n-Parafflns, Ut. X 97.0 min. Homolog Distribution, Wt. X C11 and C12 C1 3 C14 C15 C 1 6+. Lower Aromatics, Wt. X 1.0 max. 8-25 - 1.5 max. Bromine Number 0,2 max. Color, Saybolt - Typical Property 97.3 0.5 11.0 53.0 27.0 7.0 1.5 0.9 0.02 15+ Test Method 1.072 1.055 1.036 1.012 1.011 1-21-77 (Replaces 4-30-76) K This sheet is CONFIDENTIAL and shou Id no t be distributed outside Continental Oil C omp any Spec . No . 06-4600 CONOCO LPA SOLVENT Special Identification: An aliphatic hydrocarbon with a low polynuclear aromatic hydrocarbon content Test Gravity API Distillation, P IBP 10% evaporated 20% evaporated 50% evaporated 90% evaporated 95% evaporated End Point Sulfur, ppm by Wt. Aniline Point, F Aromatics, Vt. % Plash Point, P.M., F Particulate Matter, mg/gal. Color, Saybolt Nitrogen, ppm Bromine Index Cerbonyl, as C-0, ppm Kauri Butanol Value Water, ppm by Wt. , UV Absorbance Specifications 350 min. 530 max. 1.0 max, 140 min. +25 min. 100 max. Passes Test Typical Property 44 370 395 405 430 ; 475 480 518 . <1 ' 160 0.10 144 2 + 30 <1 <200 10 31.5 20 Passes Test Test Method ASTM-D-287 ASTM-D-86 ASTM-D-12 6 6 ASTM-D-611 1.036 ASTM-D-93 ASTM-D-2276 ASTM-D-15 6 ASTM-E-148 A STM-D-2 710 1.026 ASTM-D-1133 1.016 (1) (1) Test method to satisfy FDA requirements--CFR 121.1182 and CRF 121.2594 12-15-73 CReplaces 10-1-72) SAL CC0G1014J o'o p uu/acA/' ~~ocsss OrO kaffmo/vte. TO PSRUSKV FEED TO =CLVS>JT UKJIT 1 i 5-^ v. v .3 *A/ i.-- -i-' isg DATE OESCfl IPTION e>- CKD APC. CONTINENTAL OIL COMPANY ENGINEERING CENTER PONCA CITY, OKLAHOMA *tExtract APPO J ' r - DATE NO.CT- SAL CCCG1C1**! e p tio m o '3AL 0rcCiC142 PED ORIENTATION PROGRAM METHYL CHLORIDE UNIT LAKE CHARLES CHEMICAL PLANT The methyl chloride plant was bu ilt at Westlake in 1961 ds a joint 50/50 venture of Conoco and Ancon Chemi cal. Conoco operated th^ plant and Ansul marketed the product. Design ca pacity of the Reactor wa^ 20 MM pounds per year. Design capacity of downst ream equipment was 40 MM pounds per year, Conoco and Ancon did the process design based on pilot p ant data from Ancon. Blow-Knox built the plan t. Shortly after startup, the plant operated at 28 MM pounds per yea r. Several changes and additions were completed prior to 1966 based on a design by PED which increased the capacity to 55 MM pounds per yea r. Near the end of 1966, a design was issued by PED to expand the plan t capacity to 78 MM pounds per year. The plant was expanded to 98 MM poun ds per year capacity in 1970. In 1972, Conoco acquired full ownership of the methyl chloride plant in return ''tor some concessions to Ancon. Another expansionj was completed late in 1973 to raise production capability to 112 MM pounds per year. GENERAL DESCRIPTION Methanol and HC1 are reacted at approximately 320F and 12 psig in the presence of 60-70 percent ZnCl solution catalyst to yield methyl chloride and water as shown in the following reaction: ' CH3OH + HCl 320^7*^ CH3C1 + h2 Theoretical conversion for CH3OH and HCl is approximately 97 to 98 percent at these conditions. Actual reaction conversions typicailly run above 94 percent for HCl and approximately 89 percent for methanol. Overall plant yields for both HCl and methanol are 94 percent. Jhe methanol recovery unit recycle raises the overall methanol yield jabove reaction conversion. An undesirable side reaction also occurs which produces dimethyl ether. This tends to reduce methanol conversion to methyl chloHide. 2CH3OH -- CH3OCH3 + H20 Operating experience has shown that this reaction can be minimized by limiting the reaction temperature to under 350F and feeding a slight excess of HCl. Typical mol feed ratios are 1.05~1 -10 HCl to methanol PROCESS DESCRIPTION Methanol Is partially vaporized in the preheaters and mi^ed with anhydrous HC1 vapor as the reactor feed. The HC1-methanol mixture!Is sparged through zinc chloride catalyst solution and reacts to form methyl chloride and water at approximately 320F and 22 pslg. Some dimethyl ether is also produced in a side reaction. The reactor effluent vapor is condensed at 85F, The va|f>or-l Iquid mixture is separated in the vapor-liquid separator. The liquid HC1-methanol solution is fed to the methanol recovery column, and the impure methyl chloride vapor enters the brine scrubbers. Methanol in the feed to the methanol recovery column (approximately 9 percent) is separated by steam distillation from the HCl solution and taken overhead at a concentration of approximately 80 percent. The recovered methanol is recycled to the reactors. The HCl solution pottoms is used to preheat the column feed and is then neutralized In an!oyster shell pit or with waste caustic before discharging to settling ponjis. The vapor mixture to the brine-caustic scrubbers is mostfly methyl chloride with about 2 percent dimethyl ether and smal1 amounts of ivater and HCl vapor. Inerts such as nitrogen and CO2 are also presentj. The brinecaustic scrubbers neutralize all of the HCl. Small amoupts of methyl chloride product liquid are flashed into the scrubbers as a direct contact refrigerant to counteract the heat of reaction between HCl and NaOH. Brine-caustic is circulated from the brine-caustic receivers to the scrubbers which are packed with polypropylene intalox saddles. Fresh brine-caustic is metered into the second brine-caustic receiver, and spent brine-caustic is discarded from the first brine-caustic ireceiver. i The vapor flows through a knockout pot before entering tpe sulfuric acid scrubbers. This prevents entraining caustic solution into the acid scrubbers during upset operation. The sulfuric acid scrubbers remove dimethyl ether and water from the methyl chloride stream. Methyl chloride refrigerant Is flashed into each scrubber to compensate for heats of solution and lower the temperature to 50F out the last scrubber. Acid is circulated from the acid receivers to the scrubbers which are also packed with polypropylene intalbx saddles. Fresh 93 percent H2SO4 is metered into the last acid receiver land spent acid removed from the first acid receiver goes to storage. The methyl chloride flows throu gh a knockout pot to prevent any sulfuric acid from entering the carbon bed or compressor suction. The carbon bed removes impurities which would foul the compressor cylinders. The methyl chloride is compressed from 10 to I65 psig in the two-stlage reciprocating lubricated compressors and is cooled to 120F in the aftercoolers. Oil from the compressor cylinders, along with a small amount! of condensed methyl chloride, is separated from the main process vapor stream in the oil knockout pot. This materi al goes to slop storage ard Is recycled to tha process. SAL 00 001C 14 4 PROCESS DESCRIPTION (CONTINUED) THe methyl chloride vapor is condensed at 100F and 160 psiig. Most of the CO2 also condenses in the methyl chloride stream. The condenser vent gas containing methyl chloride, nitrogen, and some CO2 goes tel a vent gas chiller which uses methyl chloride as a refrigerant to condense most of the remaining methyl chloride before venting the gas to the atmosphere at 20F. The refrigerant methyl chloride is recycled to the compressors. The methyl chloride product containing CO2 goes to intermediate storage where it is pumped to the C02 stripper. Heat for stripping is furnished by a steam reboiler. The C02-rich vapor is taken overhead and goes to an overhead condenser similar to the vent gas chiller. Most of the methyl chloride in the gas stream is condensed and recovered before venting the CO2 stream at 40F. As in the vent chiller, methyl chloride is used as a refrigerant and is recycled to the compressors. The purified methyl chloride product (stripper bottoms) cooled to 100F in the product cooler and flows to product storage vjrhere it is loaded Into tank cars. PRODUCT Approximately 500 MM pounds of methyl chloride are produced per year in the U.S. However, 300 MM pounds are for captive requirements, and the other 200 MM pounds are marketed. Conoco market all of their methyl chloride making it the supplier of 50 percent of all methyl chloride available for sale in the U.S. Conoco are the only true [jiarketer since the other 100 MM pounds sold are excess production from companies with captive uses. The main uses of methyl chloride are as follows: 1. Si 1icones 2. Tetramethyl lead 3. Additive in synthetic rubber 4. Propellant gas in aerosol spray bombs 5. Weed Ri1lers Silicones and tetramethyl lead combined account for approximately 75 percent of the methyl chloride end use. At present, usage for each product is about the same, but usage for silicones will increase while tetramethyl lead will decrease due to environmental regulations concerning lead content, in gasoline. The third important use for methyl chloride Is in synthetic rubber produc tion. All other uses of methyl chloride, such as weed kil lers and pro pellant in aerosol spary bombs, are minor. 0^ 0^ METHYL CHLORIDE Test Methyl Chloride, Wt % Dimethyl Ether, ppm Wt Lower Boiling Compounds, ppm Wt Higher Boiling Compounds, ppm Wt Water, ppm Wt Acidity, as HC1, ppm Residue, ppm Wt T> pi cal Test Specificat ion Prc >perty Method 99.95 Min 99.97 1.500 20.0 Max <5 1 .500 250.0 Max 50 1 .500 100.0 Max <2$ 1 .500 80.0 Max 3$ 1 .500 10.0 Max <4 1 .501 100.0 Max <5^ 1 .502 i3&L 000oioi44 n u n w w fAma stL ocacici4d PED ORIENTATION PROGRAM ETHYLENE UNIT LAKE CHARLES CHEMICAL PLANT The Lummus-designed ethylene unit was brought on stream In February 1968 after a record-low startup period of nine days. The nameplate capacity was 500 MM pounds per year ethylene using ethane feedstock. Subsequent debottlenecking* including addition of a new cracking heater, has elevated capacity to 650 MM pounds per year using both ethane and propane feedstock. The technology employs Lummus1 "SRT" high severity cracking heaters to maximize ethylene yield. The primary feedstock is ethan^, although supplemental quantities of propane are charged during periods when ethane is in short supply. j PROCESS DESCRIPTION ' The following is a brief description of the processing sequence as shown on the overall process flow diagram, Reaction chemistry is represented typically as follows: C2H6 Heat C2H4 + H2 c3h8 A. Cracking and Quench Heat C2Hi| + CH 4 Ethane and propylene-propane recycle are cracked in tubular heaters the presence of dilution steam to an outlet temperat ure of 1 ,560F. The heater effluents are cooled to 600F in transfer 1ine exchangers which generate high pressure steam at 650 psig. n The effluents from the transfer line exchangers are combined and directed to the quench tower. By direct contact water cooling, the greater part of the dilution steam and some heavier hydrocarbons are condensed. Net overhead vapor at 110F flows to the compressor system. Quench water plus condensed steam is separated from the condensed hydrocarbons in a quench water surge drum which is operated at 180F. The circulating hot water is used to preheat the ethane furnace feed and further cooled in the air-cooled q ench water coolers and against cooling water. Condensed dilution stea is sent to the process water stripper, where it is stripped of dis olved gases and light hydrocarbons, vaporized against 200 psig stea . and reused as heater dilution steam. B. Charge Compression and Acid Gas Removal The quench tower overhead vapors are compressed in four centrifugal compressor stages to a. pressure of 535 psig, with interstage cooling to 110F. Between the third and fourth stages, the gas is treated for acid gas removal In the caustic and water wash tower. The fourth SAL COO01C1A? PROCESS DESCRIPTION (CONTINUED) B. Charge Compression and Acid Gas Removal (Continued) stage discharge is cooled with water and with propylene refrigerant to 60F. Liquid condensate is separated and the vapor is sent to the desiccant dryers. Interstage hydrocarbon and water condensates from the first three stages are sent back to the quench water surge drum. Fourth stage condensate is recycled to the third stage discharge drum. 1. Drying and Feed Chilling The final compressor discharge gas at 60F and 525 psig is dried in packed bed dryers using activated alumina before passing to the low temperature recovery section. Three dryers are provided. Two are on stream in series, while the third is regenerated. Both regeneration and cooling of the dryers are accomplished using hydrogen-rich offgas on a once-through basis. A regeneration heater and a cooler are provided for the regeneration operation. The dried gas at 60F is progressively chilled and partially condensed, with condensate removal at -30F, -95*F, -145'F, and -185F. The remaining vapor is the hydrogen-rich offgas. The condensates are fed to the demethanizer. The chilling is achieved with propylene and ethylene refrigeration, vaporizing feed and recycle ethane and reheating hydrogen and methane offgas streams. An expander is used on the hydrogen-rich offgas to provide the lowest level refrigeration. The hydrogen-rich offgas and the methane-rich offgas are sent to fuel after reheating in the chilling train and against liquid propylene refrigerant. 2. Demethanization and Deethanization The demethanizer, which operates at 445 psig, has a bottoms temperature of 3lF and an overhead temperature of -113F. The column is reboiled with propylene refrigerant, and reflux is condensed with ethylene refrigerant. The demethanizer overhead is the methane offgas, which is sent to fuel after reheating in the chilling train and against liquid propylene refrigerant. The demethanizer bottoms flow to the deethanizer where C2's are separated from the C3 and heavier fraction. The deethanizer operates at 395 psig with 16F and 182F overhead and bottoms temperature, respectively. The reboiler utilizes low pressure steam and reflux is condensed with propylene refrigeration. The bottoms product is sent to the depropanizer and the overhead flows to the acetylene removal system. SAL JCGG1C150 PROCESS DESCRIPTION (CONTINUED) B. Charge Compression and Acid Gas Removal (Continued) 3- Acetylene Removal and Ethylene Fractionatton The deethanizer overhead vapor, after feed-effluent exchange and preheat, Is sent to the acetylene converter. Acetylene is hydrogenated over a palladium catalyst in the packed bed reactor. Hydrogen offgas after enrichment, methanation, and drying over molecular sieves is Injected into the converter feed to provide the hydrogen requirements. Two vessels are provided, one is on stream while the other is on standby. A fired heater is provided for regeneration. The converter effluent is used to preheat the feed and sent to the ethylene fractionator. The feed to the ethylene fractionator consists of ethylene, ethane, and unreacted hydrogen and methane from the acetylene removal system. The tower operates at 285 psig with overhead and bottoms temperatures of -20F and 21F, respectively. Condensing and reboiling are done by propylene refrigeration. The ethylene product is withdrawn as a side stream from the tower, and unreacted hydrogen and methane from the acetylene removal system are recycled from the reflux drum to the charge compressor. The liquid ethylene product is vaporized and delivered to the battery limits at 600 psig and 225 psig. The fresh ethane feed is dried over molecular sieves, combined with the bottoms ethane product from the ethylene fractionator, and vaporized against demethanizer feed. The total ethane vapor stream is superheated against propyiene refrigerant and circulating quench water and then charged to the cracking heaters. A. Fractionation of Propane and Heavier Components The depropanizer, operating at 160 psig with 77F and 228F overhead and bottoms temperatures, respectively, receives feed from the deethanizer bottoms. Steam and propylene are the reboiling and condensing mediums, respectively. The overhead vapor product is recycled to the cracking furnace.* The bottoms product con taining Cl* and heavier is sent to the debutanizer. The debutanizer operates at 65 psig with 119F top and 2A9F bottom temperatures. Cooling water Is the reflux condensing medium, while steam is used for reboiling. The overhead liquid is the mixed product which is sent to battery limits, and the bottoms is the light aromatic distillate product which is cooled to 120F and sent to battery limits. *The overhead is now being sold as product and is not recycled to the furnaces. SAL JCCC1C1S1 PROCESS DESCRIPTION (CONTINUED) B. Charge Compression and Acid Gas Removal (Continued) 5. Propylene Refrigeration The propylene refrigeration system is a closed, multistage system using a centrifugal compressor. It provides refrigeration at four levels: -35F, "5F, 37F, and 60"F. The compressor effluent is cooled and condensed against cooling water and subcooled against various produce and process streams. Interstage condensing at the various levels is obtained from reboiling the demethanizer and the ethylene fractionator and also from the vaporization of the liquid ethane feed and ethylene product. 6. Ethylene Refrigeration The ethylene refrigeration system is a closed, multistage system using a centrifugal compressor. The ethylene system has three levels of refrigeration: -150F, -100F, and -65F. The compressor effluent is desuperheated against propylene refrigerant and then condensed against the lowest level propylene refrigerant. SAL COCCI0!*? This sheet Is CONFIDENTIAL and should not be distributed outside Continental Oil Company. Spec. No. 07-5100 ETHYLENE Test Ethylene, Wt. % Other Hydrocarbons, Wt. % Propylene, ppm Acetylene, ppm Carbon Dioxide, ppm Carbon Monoxide, ppm Hydrogen, ppm Oxygen, ppm Sulfur, ppm Water, ppm Specification 99.8 min. 0.2 max. 65 max. 20 max. 350 max. 10 max. 10 max. 5 max . 2 max. 5 max . Test Method By difference 1.251 1.251 1 .252 1.253 1.25*4 1.255 1.254 1.256 - 12-15-73 SAL 00 GC 1C If? 3 This sheet is CONFIDENTIAL and should not be distributed outside Continental Oil Company. Spec. No. 07-5122 Propane-Propylene Test Distribution Cit's and lower, wt.% Propylene, wt.% Propane, wt.% C4 * s and higher, wt.% Sulfur, ppm wt. Specification 2.5 max. 65 rain. 35 max. 3 max. 10 max. Typical Property 1.2 79.5 18.5 0.8 <1 Test Method GC 1.256 5-01-77 S4L 00001C154 V Test Distribution C3*s and lower, vt.% Butanes, wt.% Butenes, wt.% 1,3 Butadiene, wt.% 1,2 Butadiene, vt.% Ct, Acetylenes, wt.% C5 and higher, wt.% Peroxides, ppm as H2O2 Sulfur, ppm Antioxidant (TBC) ppm This sheet is CONFIDENTIAL and should not be distributed outside Continental Oil Company. Spec. No. 07-5142 BUTADIENE Specification 2.0 max. 65.0 min. 2.0 max. 1.0 max. 10 max. 10 max. a Typical Prop ty 1.2 12.0 14.0 71.3 0.2 1.2 0.1 <1 <1 100 Test Method GC ASTM D-1G22 MOD 1.256 LC-EU-8 5-01-77 ,>rooi This sheet is CONFIDENTIAL and should not be distributed outside Conoco Inc. Spec. No. 07-5180 Light Aromatic Distillate Test Benzene, Wt. Z C4's and Lower, Wt. % 90% Evaporation Point, F Specification 40.0 rain. 3.0 max. 400 max. Typical Property 48.6 1.5 340 Test Method GC GC ASTM D-86 10-15-79 j 0CC101 O C'J o o M o U1 --4 jjNVid saiavw 3>ivn j_v xiNn 3N31ahih co > ^ aaM dS xv o A x A n oi ej .-9V An Av ^ a a x vaMa d d S ia '& is a^ o .. a d aaA A O x H ^rsa n o g a a -L v a M rs iP io v a :? S*L `^vOClClS.o D W G . NO-E5877-2A ua* o n a iie s u m d P lant sal 000010159 PED ORIENTATION PROGRAM LAB PLANT LAKE CHARLES, LOUISIANA Preface The LAB plant is presently under construction and plant startup is scheduled for late 1982. SAL SO001016C PED ORIENTATION PROGRAM LAB PLANT LAKE CHARLES, LOUISIANA INTRODUCTION The HF Detergent Alkylation Process is a catalytic processi to alkylate benzene with linear olefins to form linear alkyl benzene. The linear alkylbenzenes produced from the linear olefins are useful detergent intermediates and can be readily sulfonated (treatment wTtjh oleum or sulfur trioxide and neutralization with NaOH) to yield linear a 1 kjy 1 benzene sulfonates. These compounds constitute the '`active11 ingredients of many household detergents. They are surface active compounds (surfactants) which are combined with various builders (often inorganic salts) to make up a detergent formula. (See Table I). During the 40`s and 50's, the detergent market was primarily captured by dodecylbenzene (DDB), product formed by alkylation of benzene with propylene tetramer in a hard detergent alkylation unit. It was fourjd, however, that the branched structure of the alkyl group was responsiblejfor the poor biodegradabi1ity of the detergent and the linear alkylbenienes (LAB) introduced in the early 60's have substantially replaced their branched counterparts. Some of the new alkylation units are designed for the dual purpose of taking care of present markets (hard detergent) and future markets (soft detergents); they can be charged with propyl|ene tetramer or Pacol linear olefin and yield the respective alkylbenzene^. Sodium linear alkylbenzene sulfonate (LAS) is a high quality, safe and biodegradable detergent which is produced at competitive costs. It is one of the most important sources of detergent and the world-wide annual production of LAB was 820,000 MT in 1973 while the production of DDB was 230,000 MT during the same period. The first unit in a detergent complex is an n-paraffin extraction unit (like the UOP Molex Unit) which extracts n-paraffins fromla kerosene feed. Pure n-paraffins are then dehydrogenated in the UOl5 Pacol Unit and the mixture of about 12 percent n-olefins and 88 percent n-paraffins is charged to the detergent alkylation unit. The unreacted normal paraffins are continuously recycled to the Pacol feed after going through the alkylation section while the n-olefins are completely alkylated in the alkylation reactors. It was found that adjusting the Pacol reactors to about 12 weight percent olefin conversion is the most Economical way to operate the units in terms of product quality and operating costs. ' C c i c if 1 PROCESS DESCRIPTION OF THE PACOL UNIT The UQP Pacol* Process is a process to dehydrogenate high purity linear paraffins to their corresponding mono-olefins. An olefin-free stream from the process downstream of the Pacol Process is usual 1^ recycled to the Pacol Unit and combined with the fresh feed. This recycle stream may be the raffinate product from an Olex Unit, or the unreacted paraffins from an Alkylation Unit. The Pacol Process Unit consists of a catalytic, fixed-bed feactor wherein a portion of the combined linear paraffin feed is dehydrogenated to the corresponding mono-olefins. The reaction is carried out iifi the presence of hydrogen at low pressure and moderately high temperatures. The feed to the downstream unit is from the product stripper in which light ends and water are taken overhead. PACOL UNIT PROCESS VARIABLES Reactions As is true with other hydrogen-producing processes, the Patol reactor outlet temperature will be lower than the inlet. The reactor conditions are adjusted to maintain a total linear olefin concentration in the reactor separator liquid effluent of about 11.0-12.5 weigh}: percent, depending on the design factors for each particular unit, jThe selecti- vities are such that about 90 percent of the converted linear paraffins are mono-olefins. The remaining ten percent are mainly dij-olefins and aromatics with lesser amounts of light ends, iso-paraffins and iso- oiefins. The gas produced by the dehydrogenation reactor a hydrogen- rich gas ranging from 99 to 76 mol percent H-g over the length of the run. The double bond of the product mono-olefins is randomly distributed along the chain, with about ten percent in the alpha position. There is no difficulty in operating at a lower total normal olefin concen tration than design. Higher concentrations, however, shoujld be avoided because of the excessive amounts of aromatics that would bie formed. At a given temperature, the lower carbon number hydrocarbons in each class are less reactive than the higher carbon number hydrocarbons of the same class. Naphthenes have a lower reactivity than any of the paraffins. The aromatics are essentially non-reactive, except for the small amount that may be hydrocracked. Thus, on startup and following each change in conversion rate in the reactor, the equilibrium concentrat ions will shift, When the conversion rate is increased, the recycle paraffl n stream will slowly become enriched with the lower carbon number paraff ins. As the conversion rate is decreased, the recycle stream will beco me enriched with the higher carbon number paraffins, with the resulting rec uction in the lower carbon number paraffins. ^Registered Trademark SAL CC,C` PACOL UNIT PROCESS VARIABLES (CONTINUED) Hydrogen Recycle Ratio (Continued) The reason that low a hydrogen:hydrocarbon ratio is bad is that the rate of coke formation increases as the ratio decreases below 8.0. Above 8.0, however, the rate of coke formation is not a function of (lydrogen:hydrocarbon ratio. The big disadvantage in operating at a ratio too ijnuch above 8.0 is that a higher reactor temperature Is required, apparently because of the higher velocities in the catalyst bed. This higher temperature results in shorter runs as well as poorer selectivity. The recommended operating rage is 6.0 to 6.5- Water Injection Water injection facilities are provided to maintain 2,000 weight ppm water in the combined hydrocarbon feed to the catalyst. More water than this has little or no effect. Less water, however, tends to decrease catalyst stability. The most consequential result of insufficient water is that the lost catalyst stability cannot be regained by additional wat< injection. Therefore, it is very important to assure that the proper water injection rate is always maintained. PROCESS DESCRIPTION OF THE SOFT DETERGENT ALKYLATION UNIT! The n-olefins produced In the Pacol Unit are alkylated with benzene in the alkylation reactor in the presence of an HF acid catalyst to yield linear alkylbenzene. The Friedel-Crafts reaction proceeds through an inter mediary carbonium ion created on the original olefin by migration of the two electrons of the double bond induced by the electrophjyl ic catalyst. The catalyst is liquid hydrofluoric acid and is continuously circulated in the system. The reaction is carried through a two-sta|ge reactor settler system. The reactor effluent proceeds to a ser 1 es of f racjt ionat ion columns where the various compounds are separated, the reagents bbing recycled and the products sent to storage. The first column is tht HF stripper, where HF is removed overhead and HF-free components flow bff the bottom to the "non-acid" part of the unit. The benzene is then recycled to the alkylation reactor from the overhead of the benzene column and the n-paraffins are recycled to the Pacol Unit from the paraffin column. The final rerun column splits out the alkylate product into two streams, the LAB overhead and the heavy alkylate bottoms. The n-paraffins are alumina treated for removal of combined fluorides before being recycled to the Pacol Unit. The purity of the HF acid is maintained higfj by continuously sending a slipstream to an acid regenerator column and returning the r regenerated acid into the system. The product composition and quality is a function of various operating parameters which will be discussed in more detail in the jfollowing pages. Refer to Figure 1 for a simplified flow diagram of the process. SAL JC001C163 PROCESS DESCRIPTION OF THE SOFT DETERGENT ALKYLATfON UNIT j(CONTINUED) Effluent Control Hydrofluoric acid handling and disposal is a delicate operation and the plant is designed with safety of both equipment and personnel as a major objective. All effluents containing acid or trace acid are treated before leaving the unit. Some Chemistry The main reaction is the alkylation of benzene with the straight chain olefins to yield a linear a 1kylbenzene: 1. R-C-C-C=C-C-R+ HF R-C-C-C-C-C-R 6 At the existing conditions, some formation of dialkylbenzene. Q2. 2R-C-C-OC-R+ HF side reactions take R-C-C-C-C-C-R fl R-C-C-C-t-C-R placq like the or the formation of diphenylalkanes 3. R-C-C-C=C-C-R+2 0 HF R-C-C-C-C-C-C-R 66 or the formation of heavier components by combination of the above reactions. Quality Control of the Products !* 1 The most desired product is the linear alkylbenzene described in reaction 1 and the unit is operated such that more than 90 percent of the crude alkylate produced will be LAB. The linear alkylbenzene is fractionated from the heavy alkylates in the rerun column, where one c^n adjust the split to get the desired product purity. Typically, the rerun column overhead will contain about 97 percent alkylbenzene with )j percent indans and tetralins and Sk percent of linear alkyl benzene (see!Table II). The rerun column bottoms will contain five to twenty percent |-AB, 30 to 40 percent dialkylbenzenes, $0 to AO percent diphenylalkane and other heavier components. The linear olefins produced in the Pacol Unit are a mixture of the various isomers in similar proportion except for the olefins which are less than ten percent of the total isomers. (In the case of a! chain of even carbon number, the olefin with the double bond in the cenjtral position will be in lower concentration because there is only one possibility to generate it.) SAL 0 r 0 C1016 A PROCESS DESCRIPTION OF THE SOFT DETERGENT ALKYLATION UNIT (CONTINUED) Quality Control of the Products (Continued) The alkylation reaction will respect the above distribution, except that the 1 phenyl-n alkane will not exist. Because of the low^r content of alpha olefins, the 2 phenyl n-alkane will exist in lower proportion but all the other isomers will be about equally distributed. 1 Because of the higher foaming properties of the 2 phenyl 4^ane some customers wil! require upper limits in its concentration dnd the UOP detergent process will meet them because of the preceding considerations. It should also be noted that because the Pacol process produces pure normal olefins with little branched chain olefins, the detergent alkylatd_.^_ produced has excellent biodegradability and compares favorably with the . competition's detergent quality. Another important quality control element is the Bromine Index of the LAB product which is an indication of the degree of unsaturation and condensed aromatic rings. Since these components will discolor the:suIfonated LAB, a maximum bromine index of ten to twenty is usually specified for the LAB product. The olefins and polyaromatic compounds dissolvejto some extent in HF and will be removed as HF regenerator bottoms as lotfig as HF acid is not saturated with aromatics. The Bromine Index of the LAB is usually a function of the efficiency of the regeneration in the HF regenerator. The Bromine Index of the overhead product is also a function of the split performed in the rerun column. The d1-alkylbenzene component of the heavy alkylates produced from the bottom of the rerun column have been used to produce lube!oil detergents. Their color is an important specification and usually is directly related to the performance of the HF regenerator. The viscosity must also be kept high to be used as lube oil additives. ALKYLATION UNIT PROCESS VARIABLES HF/Hydrocarbon Most units are designed with an HF to hydrocarbon volume (ratio of two. This normally provides sufficient acid to obtain the expected yield structure and product quality. Increasing the ratio should theoretically improve the yield structure but this effect has not been conclusively observed in commercial units. Most commercial units operate at HF/HCBN ratios of 1.5 to 2.0, and the lower ratios have been obtained at higher than design throughputs which probably improved the mixinjg. Reducing the HF circulation does not significantly affect the utilities consumption; it does, however, tend to increase the bromine index of the final product. SAL 'JCGClCi^ ALKYLATION UNIT PROCESS VARIABLES (CONTINUED) Benzene/01efin Most units are designed with a benzene to olefin mol ratio of ten. This normally provides enough olefin dilution to obtain the expected yield structure. Above a ratio of ten, how&ver, the improvement is usually , insignificant. Decreasing the ratio increases the formation of di-alkylbpnzene and heavy alkylate. Most commercial units operate with a benzene/ol(efin ratio between five and twelve. The lower ratios generally produce a yield structure that would not meet a typical UOP guarantee. Reducing the benzene circulation saves a large amount of l^eat because all the circulated benzene is a fractionator overhead productj Some trade-off in lower yield for lower utilities may be economically justified In most plants. Temperature The reactors are usually operated around 100F. Since the soft detergent is more thermally stable than the hard detergent, the temperature of the second reactor can sometimes be increased to 140F to eliminate the last traces of olefins. However, the reaction is very rapid apd Is usually complete in the first reactor; so the observed effect of temperature is minimal. Pressure I The pressure has essentially no effect on the reaction. !lt should be kept high enough to keep all components in the liquid phase. HF Regenerator Feed/LAB Product HF has the property to selectively extract some heavy aromatic byproducts of the alkylation reaction which would otherwise wind up |in the finished products. The HF regenerator is the recovery column of this extraction process, where pure solvent Is recovered in the column overhead and the extract (in this case, the heavy polyaromatics) found in ithe column bottom, This extraction can be viewed as a two-stage, countercurrient extraction, the two stages corresponding to the two reactors. To set up this countercurrent system, the regenerated acid from the regenerator overhead is directed to the inlet of the second-stage reactor while aj slipstream of acid from the second-stage settler is recycled to the first-stage reactor. To complete the loop, a slipstream of acid from the first^-stage system is fed to the HF regenerator. To maintain a constant acid inventory in both first and second stages, the three flows described above are equal. SAL ; C C101^ ALKYLATION UNIT PROCESS VARIABLES (CONTINUED) HF Regenerator Feed/LAB Product (Continued) The extent of this circulation determines the purity of the HF. As in any solvent system, higher extract loads in the solvent reduce the effectiveness of the solvent. Thus, the purer the acid, t|he better the alkylate quality. These polyaromatics (improperly called (polymers) found in the HF regenerator bottoms are highly unsaturated compounds which would otherwise wind up in the rerun column both in the overhead product and in the bottom product. In the overhead they will increase the bromine index of tfje LAB, and in the bottom they will color the heavy alkylates beyond acceptable specifi cations. One way to characterize these unsaturated compounds is to assign them a "J" number. The "J" number of a product is a measure of the degree of unsaturation of this product. For example, the "Jn nuniber of benzene is 6. These "polymers" have a "J" number as high as If the HF regenerator performs satisfactorily, the amount of feed fed to it will determine the purity of the circulating HF. This number is usually logged in as HF regenerator feed/LAB product, and is usually around 0.5 to 1. It is a very important parameter to control the quality of the final products. If the acid is saturated with polyaromatics, its color will be dark. The color of the acid is a good indication of its purity - the lighter the color, the purer the acid. The color of the acid can ran<jje anywhere between almost white to dark brown and can take all the shades of yellow and brown. Looking at the acid color in the HF regenerator overhead receiver, one can tell immediately if the regenerator is functioning well. The purity of the circulat ion acid is usually maintained a(x>ve 95 percent, with about .5 percent residual water and the rest heavy hydrocarbons. Another feature of the HF regenerator is that it removes all water present in the system. In a distillation column, water and hydrofluoric acid form an azeotrope containing about 40 percent acid and 60s percent water. This azeotrope is normally called CBM (constant boiling mjixture) because of its obvious properties. Any water present in the systfem will come off the regenerator bottoms in the form of CBM. The HF regenerator bottoms will be drained batchwise to a polymer surge drum where CBM will separate from the hydrocarbon phase. CBM is a very corrosive substance and will corrode much more readily'than pure HF. It is to be noted that in normal circumstances the production of CBM should be minima) sin|ce there is very little water entering the system; the n-parafflns are beijng stripped in the Paco! stripper and the benzene is dried in the benzehe drying column. Any excessive CBM made is the result of a faulty operation, most probably a leak somewhere in the startup. Because of the corrosiye properties of CBM, any excessive CBM formation should be checked by clcisely monitoring the water entering the system. The regenerator will eventually move the water, but it is not specifically designed to separate w^ter from HF by distillation; and, in any case, elimination of a given volume of water will cause a loss of HF of almost the same amount. '*"L L000lCl7 ALKYLATION UNIT PROCESS VARIABLES (CONTINUED) Water Injection Water Is not a true variable because It does not affect yifelds or rates. The acid settlers are designed to separate the acid and hydrocarbon phases when the water content of the acid is about 0.3 weight percent. Increasing the water above 0.5 weight percent will increase the corrosion rates in the HF section. Reducing the water below 0.1 weight percent will increase the time required to separate the acid from the hydrocarbop and create an emulsion. At extremely low water contents, the HF-hydrbcarbon mixture will require about one week to separate. : .roOlr'^b S TABLE I STANDARD ANIONIC SURFACTANT FORMULATION FED ORIENTATION PROGRAM LAB PLANT LAKE CHARLES, LOUISIANA 1 Components Sodium Alkylbenzene Sulfonate Sodium Tripolyphosphate Sodium Sulfate Sodium Silicate Carboxymethylcellulose Weight, i 20 j 40 34 5 i1 Un un < n If TABLE II TYPICAL PROPERTIES QF LINEAR DETERGENT ALKYLAT^ i PED ORIENTATION PROGRAM LAB PLANT LAKE CHARLES, LOUISIANA Bromine Number Saybolt Color Unsulfonatable Content, Weight, % Alkylbenzene Content, Weight, % Normal Alkylbenzene, Weight, % Biodegradability, % ASTM D 2667 O.E.C.D. 2-Phenyl Isomer, Weight, % Paraffin, Weight, % Saybolt Color of the Sodium Alkylbenzene Sulfonate Water, Weight, % Doctor Test Average Molecular Weight Specific Gravity at 15.5C Refractive Index, tL.20 Flash Point (ASTM D 93), C Distillation (ASTM D 86), C IBP 10 Vol, % 30 Vol, % 30 Vol, % 70 Vol, % 90 Vol, % 95 Vol, % EP 0 ,01 4-30 1.0 9 7.4 9 4.0 9&.1 9i5.4 20.0 0.1 +26 a .01 Negative 240 0.8)612 837 138 281 286 288 . 290 1 293 298 302 309 SAL 0CJC1Q17 {Conoco) NALKYLENE 550L LINEAR DETERGENT ALKYLATE TENTATIVE SPECIFICATIONS Properties Alkylate Homolog Dist. wt.% C,o c,, Cio + Cit C12 c13 Cu Ci3 + C,4 C15 + higher 2*Phenyl isomer, wt.% Total Material < C10 LAB, wt.% Average Molecular Weight 1 Bromine Number Saybolt Color Completeness of Sulfonation, % Doctor Test Specific Gravity {60F/60F) Water, wt.% Color of Na Sulfonate, Klett (5% AI)(oleum) Biodegradability Specification 5-15 -- 30-50 -- -- 10 max 30 max 2 max 12-22 0.5 max 240-248 0.01 max 29 min 98 min Negative 0.860-0.870 0.1 max 60 max Must pass Typical 8.1 27.9 36.0 377 25.8 0.5 26.3 0.5 17,0 0.2 242 '.0.01 30 + 98.5 Negative 0.8620 0.004 50 Pass Test Method 1.090 1.090 1.090 1.090 ASTM D 2710-72 1.011 1.059 ASTM D-484 1.023 1.016 1.042 SDA Test SAL soGmr. 171 (conoc NALKYLENE 600L LINEAR DETERGENT ALKYLATE TENTATIVE SPECIFICATIONS Properties Homolog Distribution, Wt.% Cio Cti Cio + Cii Ciz Ci3 C,4 Cl3 + Cl4 C15 + higher 2-Phenyl Isomer, Wt.% Total Material < C10 LAB, Wt.% Average Molecular Weight Bromine Number Saybolt Color Completeness of Sullonation, % Doctor Test Specific Gravity (60F/60F) Water, Wt.% Color of Na Sulfonate, Klett (5% AI)foleum) Biodegradability Specification 2 max -- 5 max -- -- 45 max 70-90 5 max 10-20 0 5 max 258-266 0.01 max 29 min 97.5 min Negative 0.858-0.868 0.1 max 90 max Must pass Typical nil 0.2 0.2 : 14.2 51.1 31.3 82.4 ; 3.2 15.0 0.1 ; 263 : <0.01 30+ i 98 ! Negative ' 0.8600 0.004 ; 75! Pass; Test Method 1.090 1.090 1.090 1.090 1.091 1.011 1.059 ASTM D-484 1.023 1.016 1.042 SDA Test Revision 06-01-82 SAL 0CQC1C1T2 SAL CCCCICI73 'X J ) L.C.VCM Plant SAL -5CCC1C176 PED ORIENTATION PROGRAM VCM PLANT LAKE CHARLES, LOUISIANA In 1966 Conoco entered into an agreement with the Stauffer Chemical Company concerning use of the Stauffer-developed VCM technology. Conoco and Stauffer proceeded with a 50/50 joint venture to construct a 600 MM pound per year plant in Lake Charles, Louisiana. The plant was engineered by Stauffer. Plant construction began in late 1966. A court ruled in 1966 that the Stauffer-Conoco arrangement was in violation of Federal anti-trust laws*. It ordered Stauffer to divest itself of its interest in the Lake Charles plant to Conoco. In turn, Conoco was required to self their PVC interests in Massachusetts. We were allowed to continue operating the Aberdeen, Mississippi, PVC facility. Control of the Lake Charles plant officially became Conoco1s on January 1, 1968, approximately one month prior to startup. At startup, the Lake Charles plant was the largest VCM plant in the world. A series of minor plant debottlenecking projects and operational improvements have resulted in a current plant capacity of 670 MM pounds per year. GENERAL DESCRIPTION A block flow drawing of a typical VCM production facility is shown on drawing CT-48-A. Such a facility would typically include the following sections: A. Direct Chlorination EDC Production B. Oxychlorination EDC Product ion C. EDC Purification D. EDC Cracking E. HC1 and VCM Purification A brief description of each of the processing units follows (refer to drawing CT-20-L, "Overall Process Flow Diagram--VCM Plant"): A. Direct Chlorination EDC Production Direct chlorination is accomplished via a liquid phase reaction utilizing ferric chloride as a catalyst. The reaction is: Cl2 + C2H4 --^^-3.------ C2HitCl2 Chlorine Ethylene 1,2-Dichloroethane (EDC) The reaction is highly exothermic and proceeds to completion, producing a high quality product. Reactor product contains about 99-7 mol percent EDC with 1,1,2-trichloroethane and ethyl chloride as the main by-products. The necessary catalyst, ferric chloride, is carried into the reactor SAL 0CG017177 GENERAL DESCRIPTION (CONTINUED) A. Direct Chlorination EDC Production (Continued) with the chlorine or results from selective corrosion within the reactor itself. FeCl^ concentrations in the reactor are 25 to 50 ppm. The reaction conditions are A5C and 22 psig. The heat of reaction is removed via an internal cooling water exchanger. All materials of construction are carbon steel. B. Oxychlorination EDC Production The Stauffer ethylene oxychlorination process is based on vapor phase reaction of ethylene, anhydrous hydrogen chloride, and oxygen in the presence of copper chloride catalyst to form ethylene dichloride and water. The reaction which occurs is: C2H4 + 2HC1 + 1/2 02 Ethylene Hydrogen Oxygen Chloride CuCl 2 ----------- C2H4C12 + H20 1,2"EDC Water Oxygen for the reaction is obtained by use of air as a feed to the system. Three oxychlorination reactors are used in series. The total hydrogen chloride and ethylene, together with about 1/3 of the total air, are mixed and fed to the first reactor. The products and unreacted feed from the first reactor plus an additional 1/3 of the total air are mixed and fed to the second reactor. The final 1/3 of the total air and the effluent from the second reactor are fed to the third reactor. Reaction temperature in each of the reactors is controlled between 280C and 320C. The lowest temperatures consistent with acceptable yields are used, as low temperatures tend to prolong catalyst life. The reactor hot spot temperature and the rate of reaction can be adjusted through varying the stoichiometric feed ratios, the reactor coolant temperature (by adjusting the steam pressure), or the air split ratio to the three reactors. The system is operated with an 8-10 percent excess ethylene and a 20 percent excess air relative to the HC1 feed. Excess ethylene is recovered by converting it to EDC via a vapor phase direct chlorination reaction over copper chloride catalyst. Remaining chlorine and ethylene pollutants are removed from the oxychlorination vent gas stream in a fifth reactor by cata1ytical1y converting these components to chlorinated organic compounds. The principal organic product is 1,2-dichioroethane (EDC). This is recovered in the existing plant EDC recovery system. SAL Grj0iC17 GENERAL DESCRIPTION (CONTINUED) C. EDC Purification EDC produced in the direct chlorinator and EDC produced in the oxy section flow to an acid wash vessel. Here they are washed with a 4 percent solution of HC1 , which is produced in the oxy section. The purpose of this step is to remove the FeClj from the EDC. The ferric chloride promotes by-product reactions which form tars. It must be removed prior to distillation, or the additional tars production will lower yields and foul the equipment. The acid-washed crude EDC is phase-separated and then neutralized by washing with a weak NaOH solution. This neutralized EDC is then fed to a light ends distillation column. The light ends column removes water and light boiling components from the crude EDC. The overhead stream from this column Is phase-separated. A small light ends product stream is removed and sent to storage. The water phase is combined with water from the acid and caustic wash systems and flows to a steam stripper which removes EDC. Recovered EDC flows to the caustic wash system while the water stream flows to the waste treating section. The bottoms stream from the light ends column flows to a heavy ends column which fractionates out the heavy boiling impurities. The purified EDC is sent to the cracking section. The bottoms stream from this .tower flows to a tars column where residual EDC is recovered and returned to the caustic wash section. A tars product is recovered and sent to storage. D. EDC Cracking Purified EDC flows to an EDC vaporizer and then to one of two cracking furnaces. The furnaces crack EDC at about 180 psig and 500C to VCM and HCl. C2H4CI2------ CzHjCl + HCl EDC VCM About 50-55 percent of the EDC is cracked per pass. The furnace outlet stream flows to a quench column. Here the hot EDC, HCl, and VCM gases are cooled with use of a circulating cooling system. The quenched product streams are recovered from the top of the quench tower and flow to the purification towers. A small amount of by-products is recovered from the bottom of the quench column. The stream flows to a VCM tar still system. The recovered overhead from this system is sent to the heavy ends tower in EDC purification or returned to the quench column while the tars are sent to tars storage. GENERAL DESCRIPTION (CONTINUED) E. HC1, VCM Purification Products from the quench column flow to the HC1 column where HC1 Is purified and fed to the oxy unit. The bottom stream from this column contains EDC and VCM and is sent to the VCM column. The VCM column performs the final purification on the product. The overhead stream is product VCM. It flows through flake caustic dryers to remove any residual HC1 and then is sent to product storage. The bottoms stream from .the VCM column is EDC. This stream is recycled to the EDC Purification Section for removal of unwanted impurities. JO I* VCM PLANT ORGANIZATIONAL CHART 4/1/82 W % l . 8P -10 ? B I0 1 JC 1VS ip r 0 c0 0 7C 5 n r 20 0 0g > o D ! i a 'a n ^ id This sheet is CONFIDENTIAL and should not be distributed outside Continental Oil Company Spec. No. 08-5000 VINYL CHLORIDE MONOMER Special Identification: General sales specification Test Acetylene* Methyl Chloride* 1,3 Butadiene* Acetaldehyde* Nonvolatiles* Water* Iron* Sulfur* Acidity* (as HC1) Color Appearance Specifications 2.0 100.0 15.0 0.7 100.0 200.0 0.5 1.0 2.0 Colorless Clear and free from suspended matter Test Method 1.100 1.100 1.100 1.114 1.113 1.110 1.112 1.115 1.111 *p_arts er million by weight, maximum Remark (for plant use only): Oxygen: 1000 ppm max. before loading 500 ppm max. after loading 10-1-72 SAL 0CCC1C133 This sheet is CONFIDENTIAL and should not be distributed outside Continental Oil Company. Spec. No. 08-5010 VCM Light Ends By-Product Special Identification: General Sales All specifications and tests must be approved by VCM plant personnel prior to customer contact because stream composition will continue to change as process improvements are made. Typical compositional component ranges are shown below: Wt. % Vinyl Chloride 1-5 Ethyl Chloride 25-50 1,1-Dichloroethene 1-8 1,1-Dichloroethane 2-6 T-l,2-Dichloroethene 3-7 C-l,2-Dichloroethene 1-5 Trichloromethane (Chloroform) 15-30 Tetrachloromethane (Carbon Tetrachloride) 5-12 1,1,2-Trichloroethylene Nil - 0.3 1,2-Dichloroethane 3-12 Water 1000-3000 ppm 5-16-78 (Replaces 12-15-73) SAL ccooioie* This sheet is CONFIDENTIAL and should not be distributed outside Continental Oil Company, Spec. No. 08-5015 VCM Tars By-Product Special Identification: General Sales All specifications and tests must be approved by VCM Plant personnel prior to customer contact because compositions will continue to change as process improvements are made. Typical compositional component ranges are shown for those components analyzed. EDC 1 ,1,2-Trichloroethane Acid (as H.C 1) Water Non-volatiles 8 - 25% 35 -- 65% 500 - 2000 ppm Nil - 400 ppm 2.0 - 6.0% 12-15-73 SAL JCGClCieo This sheet is CONFIDENTIAL and should not be distributed outside Continental Oil Company. Spec. No. 08-5050 ETHYLENE DICHLORIDE Special Identification: For Public Sale Test Purity, Wt. % Specific Gravity (20C/20C) Distillation Range Acidity (as HC1), ppm Residue on Evaporation, ppm Water Content, ppm Appearance Specifications 99.0 min 1.252-1.259 100% within 2C including 83.5QC 10 max 20 max 100 max clear and free of suspended matter Test Method 1.120 ASTM-D-1298 ASTM-D-86 1.117 1.113 1.110 Visual Note - These specifications apply only to material FOB Lake Charles, LA 9-30-76 (Replaces 2-7-73) SAL JCCC1C1?6 rcu O a cj o -J CO Aberdeen PVC Plant CO CO i-H o o o fjo PED ORIENTATION PROGRAM ABERDEEN PVC PLANT ABERDEEN, MISSISSIPPI The Aberdeen plant, and other facilities on the East Coast, were acquired from Thompson-Apex Company in early 1965- This entry into the PVC business was temporarily set back in late 1967 when the U.S, Government, by consent decree, forced Conoco to divest of all Thompson-Apex plants except that at Aberdeen. This edict occurred partially as a result of the ConocoStauffer joint venture VCM facility then under construction at Lake Charles, Louisiana. The original Aberdeen plant was built In 1962-1963* It Included a reactordryer building, a PVC compound line, a plasticizer plant, garden hose manufacturing unit, and a large warehouse. Expansion in 1965 essentially doubled plant facilities. Subsequent expansions raise output to 200 MM pounds per year PVC resins from sixty 2,200-gallon polymerizer vessels. An 18,000-gallon prototype reactor installed in 1970 proved highly successful. As a result, the plant constructed seven more large reactors while shutting down all small polymerizers. This latter shutdown was prompted by OSHA's promulgation of the "VCM Ambient Air Standard" in 1974 and EPA's promul gation of the "VCM Emission Standard" in 1976. The plant was further expanded with the addition of two 32,000-gallon reactors which started up In early 19&2. Plant capacity is now 455 MM pounds per year of PVC res in. Plant feedstock is vinyl chloride monomer from Conocols VCM plant at Lake Charles, Louisiana. GENERAL DESCRIPTION f-------------------------------- -- PVC Is produced by batch polymerization of VCM fn a water suspension. VCM Is charged to the reactor along with water, a methyl cellulose suspending agent to stabilize the VCM in water suspension, and a peroxide initiator. Major features of the polymerization reaction are: 1. Polymerization temperature determines the PVC molecular weight which in turn influences resin characteristics. Molecular weight is not dependent on conversion. Since a narrow molecular weight distribution is desired, isothermal polymerization conditions are used. Typical number average and weight average molecular weights are 30,000 and 60,000, respectively. 2. Particle size and distribution are influenced by the suspension agent concentration. Typical mean particle size is 165 microns. 3. The polymerization is autocatalytic; that is, the rate increases with conversion. Reaction rate also depends on the type of initiator and the polymerization temperature. Typical temperatures are 120F to 150F. SAl 'lC\o9 GENERAL DESCRIPTION (CONTINUED) PVC is never used In its "pure*' form but rather is mixed with filler, plasticizer, stabilizer, etc, enroute to the final product. The quality of the final material rests not only on its molecular weight and particle size but also on the PVC particle morphology. Quality is generally defined by how well it processes, ie, rate of plasticizer adsorption or heat stability during extrusion. PROCESS DESCRIPTION (See Attached Simplified Process Flow Drawings) The PVC polymerization process is straightforward. A typical reactor batch cycle is described below. The empty polymerization reactor is evacuated to remove air and then charged with VCM, water, and suspension agent. Following charge, the peroxide Initiator (which is stored at -20F because of its instability) is poured into a small charge pot and pressured into the reactor with water. The polymerization then proceeds under temperature control with cooling water removing the heat of polymerization. The reaction is terminated at 75 to 85 percent conversion of VCM to PVC (determined by reactor pressure). The excess monomer is recovered by depressuring the reactor. During this stage, the polymer slurry is heated by injecting steam to facilitate VCM removal from the polymer. The PVC water slurry Is then drained from the reactor and pumped to inter mediate storage. The slurry is displaced with air. The reactor is rinsed with a hot caustic solution which retards polymer buildup in the vessel, rinsed with water, and evacuated for the next batch. Typical batch cycle time is around eight hours, with a polymerization time of six hours. Th slurry is pumped from intermediate storage to continuous solid bowl centrifuges for gross dewatering. The "wet cake" gravity flows into a gas-fired rotary drum dryer or a fluid bed dryer. The dried resin is screened and is then pneumatically conveyed to product storage. "Aberdeen has additional facilities to produce dry blend (for rigid PVC applications such as pipe) and compounds (for flexible PVC applications). The dry blend unit prepares a uniform mixture of PVC resin, filler, color, stabilizer, and lubricant. The most common filler is atomite. Capacity is 77 MM pounds per `year. All the raw materials are fed to use bins of the dry blend area which in turn gravity feed to the weigh tanks. When all the raw materials are fn the use bins, the dry blending process is started. All raw materials are automatically weighed, based on the amount of each that have been preset on the weighing control panel in the dry blend control room. When all the ingredients are weighed, they are automatically discharged in a Welex intensive mixer. The Welex mixer vigorously mixed the ingredients so that a homogeneous mixture Is achieved quickly. During mixing, mechanical energy is transferred to the dry blend material causing the temperature to rise. SAL 90 PROCESS DESCRIPTION (CONTINUED) The dry blend is automatically dropped at a preset temperature, usually about 220F, to a ribbon blender where the dry blend is cooled to about 120F before being transferred to product storage. The plant has three compound units. A compound unit produces a fused and homogeneous mixture of PVC resin, plasticizer, stabilizer, color, filler, and other miscellaneous small additives. Total capacity is 80 MM pounds per year. The process flow for compound line III Is as follows: The raw materials are weighed and added to a ribbon blender where the mixture is allowed to blend until uniform throughout. The mixture is then fed to a Farrell continuous mixer. This mixer fuses the material into a "rubberlike" mass. The fused material Is then sent to a two-roller mill where a ribbon (8-1** Inches wide, 1/8 inch thick) of compound is made which is then cooled in cooling troughs and cooling tanks before being diced into pellets. After dicing, the pellets are screened to remove oversize and fines and conveyed by air pressure to product storage. Aberdeen also produces plasticizer mostly for internal consumption. Capacity is 25 MM pounds per year. There are a variety of plasticizers produced, depending on compound formulation. The most popular one is made by reacting phthalic anhydride with either 2-ethy1hexanol or "ALFOL" 610 alcohol to form the ester. An acid catalyst Is used. When the batch reaction is complete, the reactant mass is neutralized and steam stripped to remove excess alcohols. The ester is then filtered and stored. PRODUCTS Aberdeen produces five separate grades of PVC resin which are ultimately used for electrical Insulation, shoe soles, automobile parts, toys, up holstery, floor mats, and plastic pipe. The largest market is for resin used to make plastic pipe. sal 0CCC1C191 Monoger J friend Plant Superintendent C.R, Millor Chief Plant Chemist R.D. Jackson Operations Supt. R J, Kober Oporationf Supt. Rl. Martov Mechanical Supt. ___ C.R. Snowdon Cmpd. Dev. ChemJ.V Hartman Mlg. Chniit OS.Co* Operations Engr. Operation* Engr. Maintenance tngT lUwality Cntrl Supv. 1 J.R. Williams SB. Vick M.P. Blackwoll J.P. Windham 1 Supervisors C. L. Flynn O. J. Knight H. A. Pruitt B.P Siiemore 1 lab Trainees 4 4 12 2 Prod.Scheduler frod. Scheduler D. L. Milsteod Opr*. Supv.Cmpd. R.G. Gilroath rl Opr*. Supv, Vinyl ________Opon Cmpd.Shift Supv. A.L, Barr R.L. Bristol O. O Knight C-L Smith C.L.Worlow ... !______ Compounders 12 Cmpd. Operators IV Cmpd. Utilities IS Plasticizer Opr*. 4 General Helpers 0 Vinyl Shill Sup* R.A. Cellini D. F. Johnson B.F. HowUn* R E. McGeo A.L. Roovo* Chief Opr*. 4 Load Opr*. 12 "tC Operator* 18 Lltilitiot 8 Gonorol Helper* 5 Director Of AdmMstiatrvel Servi is 1 W. F. Higgi bolhom | ford Supervisor 4 2 .H" oneycutt Yard Oprs."A" Maintenance Supt. Mechanical J.L. Horstman Maintenance Supv. IE CE. Davis ;; t ..... [Electricians5 [instrument Tech. 5 Maint. Supervisors FW. Frantz R W Rye M.H. Willioms Open Planner M.E. Skinner Machinist Painter/lnsulatoriCorp. General Mechanics Utility Technician Helpers Building Attendants ,__ Sr. Mech.Engmeer J.A. Oixon Mech Engineers J.L. White M.S. Richords OA.Mill*, K.S. Allan Elect. Engineer R.B. Horned Contract Supv. G. A. Morgan Sr. Drafter C.A.Clark Droller* J O Walker --I R E. Rickert Director Of Employee Relations R.A. Miller Employee Relation* Clerk C.J. Wood. Safety Inspector J. G. Roberts Safety Director A. H. Sother | Solely Supervisor 1 J V. Uptain Security Guards G. D. Bird Jr. S.H. Hill R. P. Beouregard S O Carter V. A. BeIk Plant Accountant Open Accountants M.J. Donald ^ W. ftfihinipn ng cleric 1 Ichei* yPayroll Clerk J.A. Frostard Order Clerk J R. Frederick __ Buyer B.JP&pe Accounting Clerics T.A. Pounder* C. Wren _1 Clerk Typists B.l. Smith l. P. Ingram R.O. Holloway Chief Process Engineer R.A. Frohreich 5r. Process Engr f V.E. Messick Process Engineers J.8. Prows S.C. Hillman M.L. Nothan Fnviromr*~**ii Engr. I O.L. tier Sr. Process Engr. V.L. Thornhill Process Engineers J. Perez Velasco AL. Barlield J.C.Greene CO O Cl fo~V .1 O ORGANIZATION CHART ABERDEEN. MISS. AUG. 1,1982 This sheet is CONFIDENTIAL and should not be distributed outside Conoco Inc. Spec. No. 15-1822 CONOCO PVC RESIN NO. 5305-1 Special Identification: Generally for Flexible Applications Test Specification Typical Property Test Method Total Volatility, % Moisture, % Bulk Density, gms/cc Contamination Count Inherent Viscosity Particle Sl2e Distribution. % On 40 Mesh Through 140 Mesh Through 200 Mesh Color, Gardner b Heat Stability Static Flow Residual VCM, ppm 0.50 max 0.30 max 0.528-0.624 50 max 0.72-0.77 0.25 0.20 0.58 20 0.74 0.1 max 25.0 max 5.0 max 3.5 max Equal to Standard Free Flow 10.0 max Trace 15.0 2.5 2.8 Passes Passes 3.0 8.004 8.020 8.007 8.017 8.009 8.018 8.012 8.011 8.016 8.014 4 2-3*81 (Replaces 8-1-80) SAL OCOCICI^ This sheet is CONFIDENTIAL and should not be distributed outside Conoco Inc. Spec. No. 15-1849 CONOCO PVC RESIN NO. 5385-1 Test Total Volatility, % Moisture, % Bulk Density, gms/cc Contamination Count Inherent Viscosity Gel Rating Brabender Dry Time, Minutes Particle Size Distribution, % On 40 Mesh Through 140 Mesh Through 200 Mesh Color, Gardner b Heat Stability Static Flow Residual VCM, ppm Specification 0.50 max 0.30 max 0.512-0-576 25 max 0.90-0.95 3 max 6.0 max 0.1 max 20.0 max 5.0 max 3.0 max Equal to Standard Free Flow 10.0 max Typical Property 0.25 0.20 0.53 15 0.92 2 5.5 Trace 15.0 2.5 2.5 Passes Passes 1.5 Test Method 8.004 8.020 8.007 8.017 8.009 8.015A 8.008 8.018 8.012 8.011 8.016 0,014 2-3-81 (Replaces 8-1-80) ' SAL 0 G 0 01Cl 4 '?*t': 1 This sheet is CONFIDENTIAL and should not be distributed outside Conoco Inc. Spec. No. 15-1302 if CONOCO 34431 VINYL COMPOUND Special Identification: SPT1 and 2 Cords, T & TW Building Wire, 80C Appliance Wire, UF & WMC Insulation and Jacket Test Specification Typical Property Test Method f Specific Gravity 1.37 0.03 1.37 ASTM D792 Hardness, Aged Instantaneous 15-Sec Delay D-443 -- D-46 D-35 8.005-76 Tensile Strength, psi 2540 ASTM D638 100% Modulus, psi 1630 ASTM D638 Elongation, % 315 ASTM D638 Brittlepoint, eC -23 ASTM D746 VR, ohm-cm 8.Q06B-77 - -r J:; r i -: r i ti s* : Lr ? si*? I*: * 7-1-81 (Replaces 8-1*80) i;... ' ........ . ' ........ SAL GCC01C.193 " This sheet is CONFIDENTIAL and should not be distributed outside Conoco Inc. CONOCO 610-P Spec. No. 15-1900 Special Identification: Phthalate Diester of ALFOL ADE 610 Alcohol (Spec, No. 03-411401} Test Specification Typical Property Test Method Specific Gravity at 25V25C Color, APHA Moisture Content, wt % Acidity (as Acetic Acid), wt % Refractive Index at 25C Alcohol Content, wt % Odor Appearance 0.974 0.004 25 max 0.10 max 0.01 max 0,30 max Characteristic Free From Haze 0.974 10 0.05 0.005 1.483 <0.1 1.023 1.025 1.016 1.024 ASTM D1218 7-1-81 (Replaces 8-1-80) SAL 0C001C196 This sheet is CONFIDENTIAL and should not be distributed outside Continental Oil Company. Spec. No. 09-1410 CONOCO 90281 PVC Dry Blend Special Identification: White Vinyl Siding Dry Blend Test Fusion Time (Tj) Minutes Stability Time (T?-Ti), Minutes Equilibrium Torque Meter Grains Specific Gravity Specification 0.35 minutes from control blend Minimum two minutes less than control blend 150 M-gm from control blend 1.47 .02 Typical Property 0.7 17.5 1750 Test Method 8.013 8.013 8.013 3-1-78 (Replaces 10-26-77) OCOOlOl'JT This sheet is CONFIDENTIAL and should not be distributed outside Conoco Inc. Spec. No. 15-1910 CONOCO DOP Special Identification: Phthalate Diester of 2-Ethyl Hexanol Test Specification Typical Property Test Method Specific Gravity at 250/25C Color, APHA Moisture Content, wt % Acidity (as Acetic Acid), wt % Refractive Index at 25C Ester Content, wt % Alcohol Content, wt % Odor Appearance 0.983 0.003 0.983 25 max 10 0-10 max 0.05 0.01 max 0.005 1.4850 99 min 99.6 0-10 max 0.05 Characteristic Free From Haze 1.023 1.025 1.016 1.024 ASTM D1218 7-1-81 (Replaces 8-1-80) ] I i i1 li1 ) COkJDEuSER COOLILK3 WATER RETURkj hot water & COLLOID CHARGE VCM CHARGE U) * o o o o AMI 5 o Mi ;wem.cceamujs soll/tiou SUPPLY COOLIMG WATER eoRRLv HEATED AlR CHEM, CUBAM4MG SOLUTION RE"URU PVC SLURRY BLSVJO TANK CEWTRtPUGe EXHALTST AMR DLP5T g^"ira. OVER-SIZE TO -STORACSe OWED PVC.TO PRODUCT s--STORAGE lOADi KXS i |n - -7 -r$ pec tbaj*jwj6 program !-f C- |/V/f j OATer tXVKJ CLD jAPO CONT INENTAL OIL CO MPANY EN G1N 1 ER1NG : e n TER PONCA ClTT. OKLAI-LOMA 'ol ('-'L -1=. L- ^LE5S FlOw f.'.AcSAM LARGE REACTOR PvC PLANT ABEROEEsJ, KMlSS- scale: amd: 351* date: H(i<f7!9 | No. CT-49-A 96225 izot SNINfltlS 1 PV 2 .'.E'.cSv-. fAN-K S-CALE "AMK PUA" :-zer wE'Sr- -A^K wJt-1 =^kaPS FARREL SCR6W V1>R g g g~Tg~y "ALI o o <n o UM S o o I PROOL-CT -Si-O rAAKcK 2 w-tf-kj e v s r o < ii.TT5 PST "RA. k!ikj(S PRO&RAM C.ATC >cr r C5WVJ j &C AFC CONTINENTAL OIL ClDMPANY iNGINEEKINO CENTER PONCA CITY, OKLAHOMA 5i^PL'"SC PSOCE'3`5' FUDW DlA<?RAs CC AREA At-g^yfeEkl. \Ar3S. appo: ^ -*-e date: a.v ____________ SCALE: No. C.T- 27-> Oklahoma City PVC Plant CJ rg o o Oo o <t co PED ORIENTATION PROGRAM OKLAHOMA CITY PVC PLANT OKLAHOMA CITY, OKLAHOMA The Oklahoma City plant became operational in April of 1971. It was con structed primarily to provide pipe-grade PVC resin to an adjacent Carlon Plastics Company plant. The plant scope included a four-reactor (large volume) module with associated resin drying facilities, utilities, and offsites. While the initial design nameplate capacity was 70 MM pounds per year, the plant's output far exceeded that from the start. Subsequent expansions have added two new large reactors and other facilities which have elevated output to 275 MM pounds per year. Details of the process for PVC resin production are similar to those described for the Aberdeen PVC Plant. ORGANIZATIONAL CHART OKLAHOMA CITY PLANT PLANT SUPT. A.W. Sirmons PLANT MANAGER R. A. Conrad PROCESS SUPT. C.W.Turner SHIFT SUPERVISOR O.L. English SHIFT SUPERVISOR J.D. Gibson SHIFT SUPERVISOR J. B. Bello SHIFT SUPERVISOR G.H. Freeman OFFICE MANAGER D.L.Womble MATERIALS COORDINATOR .N't A, Lee... YIELD ANALYST J.J. Hall SECRETARY M. M. Robison MAINTINANCE CLERK T. L. Hoover Rev 8/82 This sheet is CONFIDENTIAL and should not be distributed outside Conoco Inc. Spec. No. 15-1050 CONOCO PVC RESIN NO. 5385-3 Test Specification Typical Property Test Method Total Volatility, % Moisture, % Bulk Density, gms/cc Contamination Count Inherent Viscosity Brabender Dry Time, Minutes Particle Size Distribution, % 0.50 max 0.30 max 0.512-0.576 100 max 0.90-0.95 7.0 max 0.25 0.20 0.53 60 0.92 6.0 8.004 8.020 8.007 8.017 8.009 8.008 8.018 On 40 Mesh Through 140 Mesh Through 200 Mesh Color, Gardner b Heat Stability Static Flow 0.1 max 20.0 max 5.0 max 3.5 max Equal to Standard Free Flow Trace 15.0 2.5 2.5 Passes Passes 8.012 8.011 8.016 Residual VCM, ppm 10.0 max 2.0 8.014 Note: This product also manufactured at Oklahoma City, OK, plant -- see Specification 16-1850. 2-3-81 (Replaces 8-1-80) VCM OWLO/AD"^ \m5" ifcRAtoE A lW-" ou> VCM TAWK CAA Ir f\ VCM l I <aTORAe ulcletts PPESH \CM `STOHAGe TAk-lK - s M ATM mf COMP SCREAMER EXHAUST BLOWER OVERSIZED PROOUCT 6LURPV OUMT SCREEU6R -a 1 ReC=NEBGO vcm -srcR/see TA*JIC5 <5u*eucuj& . ASeur. PWOCS*y5 WATER.- . CON 'MOM ATM &XLWCW EiECTR "3TEAM -- (2) RECOVERED VCM :_ica DRUMS -SL shocks WATER ` a ,payMSftz*Tcw SACTDRS AUXIUIARCS PCOVeKV VACUUM PUMPS RECOVERY COMPRESSORS 1--0 ^COVERED VCM COUDEUSERS SEAL WATER 6SRBRATOA9 \ SEAL WATER XRAUKia) SLURRV ftCEMD TAUCS REACTORCLEANING C SLimSE .. WATERS 2) ucxjo ) DRAOJ C2) "SWTRAIPTPEERRS r------------ ~Si CEMTRlFUCES CEUTRAT6 CjWATeB CO BACTYPC PRODUCT & DUST COLLECTORS COTASTY DRYERS PROOUCT SIFTERS OVERSIZED PRODUCT s PNAEIRUMCAOTIMCPRCOESVJSVOERYSlkJS _ATM~ VCM i INCINECATOB Ca^TBOL 2 Josv/ce J_k. SPT RFAIjCR.ACriO*J -^V' refrigcraht RECOVERED VCM RECEIVER <2> 1___ JCCSfrffCU. DEV*Z WASH WATER EFR.UEWT r REACTOR CUEAkjlMS ^V6TEM PROCESS SSWCR reWTVCk. DWC MZt.lav? >. =CY&Y (2) REACTOR CLEAAiKJCi 4ySTEM EYHAUST SLOWER -- WESTS WATER TREATMENT _________ .PONOS OVERSIZED . product DKVEP iMDUCED CRAFT PANS CE " IN SETTuiNS OASIN -OfPER RAJL CARS G> TTTToI I. 44 (S? I 4^33 S , I I ! . II , I I I'l , I ! 1st 1121 Il41 1201 l24l 12 B! '32' '36' !40l 42 40 38 36 34 32 30 28 26 11 10 i 10 I 141 US' 24 22 Is41 Its); i ' i | i | ; i : ! i IS21 l36> .601 20 *8 16 14 12 S I 22 4 I I7l2IllI7l61l ;`s1ol 10 8 6 32 24 I 26 i IIsl4ii 1 IIals|i I |I917 4 2 O' SCALES FOR MICROFILMED 0RAWINGS i cyr's/'T'vo 28 I 30 1 AZOTES'' fn ccunuuoo,s plow til IWfEBMITTCUT FLOW 18 1 ---- 20 1^ 22 32 10 ii CPORWCCVEEV5-K=D:LTGOPAL OaJlAtCEMT 3 S 1 ISU .4*?OAT6 $`NBAL WPO/VTC e*vs kep^cjy DESCRIPTION Lk. * 'Ai A~ v Cit'j ..pr> CONTINENTAL OH. COMPANY ENGINEERING CENT'R PONCA CITY. OKLAHOMA 24 J<0 ..---------- ----------USE BORDER SCALE: 12 appo: date: No. - - . . -- i ! j Baltim ore Plant PROCESS ENGINEERING DEPARTMENT ORIENTATION PROGRAM - 1982 OIL AND GAS PROCESSING DIVISION SEPTEMBER 9, 1982 TABLE OF CONTENTS 1982 ORIENTATION PROGRAM OIL AND GAS PROCESSING DIVISION Page No. I. ORGANIZATION CHART 1 II. PREVIOUS YEARS WORK HISTORY 2 A. Man-hours B. Major Projects 2 3 III. HISTORY 4 IV. GENERAL INFORMATION 6 A. Gas Processing B. Offshore Oil Production C. Coal D. Shale E. Tar 6 8 *0 12 13 V. PRESENT PROJECTS 14 A. Gillis B. Maljamar C. Cashion D. East Clinton E. Hamlin F. Mustang G. Dubai H. Udang I. Netherlands K/18 J. Murchison K. Coal Gasification L. Flue Gas Desulfurization M. Shale Oil N. South Texas Tar (SOTTS) 14 14 15 15 16 16 16 17 19 20 21 21 22 22 VI. DRAWINGS 24 A. Typical Expander Plant (GasProcessing) B. Typical Straight RefrigerationPlant (Gas Processing) C. Typical Offshore Oil ProductionFacility D. Coal Gasification Block Flow Diagram E. Shale Oil Plant Block FlowDiagram PED ORIENTATION PROGRAM BALTIMORE CHEMICAL PLANT BALTIMORE, MARYLAND The Baltimore Petrochemical Plant was originally the Prudential Oil Refinery. It was converted to the production of dodecylbenzene, better known by the tradename "NEOLENE", in the early 1950's. "NEOLENE" alkylate was produced from dodecene and benzene by aluminum chloride alkylation. "NEOLENE" alkylate and similar alkylates produced by otljier companies were sulfonated with sulfuric acid or oleum to produce most of the detergents sold in the 1950's and 1960's. Detergents made from "NEOLENE" alkylate were cl assified;as "hard" because they are not biodegradable. The increased use of synthetic detergents led to foaming in rivers and lakes near major population centers. Conoco Research recognized the problem and developed a new detergent alkylate. "NALKYLENE" alkylate, which produced "soft" or biodegradable detergents. "NALKYLENE" alkylate is also an a 1kylbenzene, but the ajkyl group is linear, whereas "NEOLENE" alkylate had a branched paraffin sidedhain. A "NALKYLENE" alkylate pilot plant was operated at Ponca City in 1962. The Baltimore plant was converted to "NALKYLENE" alkylate production in 1965. Production increased from 150 MM pounds per year in 1967 to 220 MM pounds per year in 1976. The increase was made possible by debottlenecking projects in the fractionation section and more recently, the chlorination and HC1 absorption sections. Muriatic acid and aqueous aluminum chloride are produced as byproducts of the process. The bottoms frorii fractionation are sold as feedstock for oil soluble sulfonate production. The Specialty Alkylate Unit (SAU) in the Baltimore planf produced high molecular weight alkylbenzenes that were used for the production of oil soluble sulfonates. Baltimore Base Oil (BBO) and DN-500 (a low pour lubricating oil) were produced in the SAU. This unit was shut down in 1979 and the technology for producing specialty alkylatfe was transferred to Witco Chemical Company. BBO and DN-600 are toll processed by Pilot Chemicals. The Baltimore plant also includes the STXS Unit, a small batch reaction process that is used to produce sodium toluene and xylene solfonates and ammonium xylene sulfonate (STS, SXS.STXS, and AXS). These materials are known as hydrotropes and are used as anticaking agents for powdered detergents and clarification agents for liquid detergents. Total production is about 3 MM pounds per year. WASTE TREATMENT* 1 Baltimore's waste treatment system consists basically of: 1. API Separator 2. Dissolved Air Floating Unit 3. Gravity Dewatering System A. Storm Water Diversion System 5. Acid Neutralization Pit 3AL 0C0C1C2C6 WASTE TREATHENT (CONTINUED) Effluent from the acid neutralization pit is transferred , to the API separator. Once this system is operated as designed, the Baltimore plant will tie into a new minicipal water treatment plant. Doing this will eliminate the need for further additions to Baltimore`s waste treatment system. When the entire system is operating, waste water is neutralized before it enters the API separator, in the API separator, oil and some solids are removed. The effluent from the separator is saturated with air at about kO psig. The air-saturated effluent enters the flotation cell. Air bubbles encapsulate solids and bring them to the top of the cell where they are skimmed off. A polymer is added to the flotation cell to enhance solids coagulation. Water from the flotation cell enters a holding pond. From the holding pond, the water is discharged to the Patapsco Rover or the municipal treatment plant. Solids from the flotation cell enter a holding tank. From here they are pumped through a rotating drum filter where some of the water fs removed. The solids are then trucked to a disposal site. The acid neutralization pit is banked with limestone. Muriatic acid is neutralized when it is off-specification or when the storage capacity is exhausted. Effluent from the acid pit is pumped to the API separator where it joins the waste water from the rest of the plant. The storm water diversion system consists of four 3,000 gpm pumps and a storm water holding tank. When heavy rain increases waste water flow above the capacity of the treatment system, water is automatical1y pumped on level control to the holding tank. Water in the holding tank Is later purged on control through the treatment system. SA>- CCICIC2C7 CONOCO CHEMICALS BALTIMORE PLANT PLANT MANAGER T. H. Huffman SAL GCQ0102C9 PED ORIENTATION PROGRAM "NALKYLENE" ALKYLATE UNIT BALTIMORE CHEMICAL PLANT BALTIMORE, MARYLAND The "NALKYLENE" Alkylate (NAB) Unit became operational in 1965. It was constructed In the midst, and using some equipment, of its predecessor, the "NEOLENE" Alkylate Unit. The latter had been in operation since 1947 and had been Conoco's first petrochemical plant. The nucleus of the "NEOLENE" Alkylate Unit was then converted to a Specialty Alkylate Unit (SAU) described in a later section. The "NALKYLENE" Alkylate Process was developed by Conoco to meet the need for a fully biodegradable detergent feedstock. The original unit had a production capability of approximately 50 MM pounds per year. It has subsequently been expanded several times to its present capacity of 220 MM pounds per year. Feedstocks for the unit are normal paraffins from the Lake Charles Chemical Plant, benzene, and chlorine. The plant operates on blocked-out operation to produce alternately a 10-12 carbon chain alkylbenzene (N-500) or a 12-14 carbon chain alkylbenzene (N-600). Plant throughput capability is essentially the same with either product and is divided approximately 70 percent N-500 and 30 percent N-600. In addition to these flexibilities, the plant also can vary alkylation reaction conditions (basically benzene/chloroparaffin mol ratio) to yield various dialkylbenzene bottoms products. These are sold to Witco and other companies to produce oil soluble sulfonates. GENERAL DESCRIPTION Crude normal paraffins are fractionated into desired cuts each having a three carbon range. Each paraffin cut is alternately (blocked-out operation) reacted in excess with chlorine at elevated temperatures. The resulting chloroparaffins are reacted with benzene in the presence of an aluminum chloride catalyst to yield the desired alkylbenzenes. By-product HC1 is recovered and marketed as food-grade muriatic acid. The chemistry of the "NALKYLENE" Alkylate Process is represented as follows: 5 R-H + C12 (g) R-Cl + 4 R-H + HC1 +4 R-H + HC1 PROCESS DESCRIPTION The attached Overall Process Flow Diagram illustrates the "NALKYLENE" Alkylate Process. sal 00001021Q PROCESS DESCRIPTION (CONTINUED) Section 150 - Paraffin Fractionation Normal paraffins are received from the Lake Charles plant by tanker either as a C|q to Cj^ crude or as Cjq to Ci2 anc* ^12 to ^14 cuts The C|q to C|2 cu^ 's used for the production of N-500 and the C]2 to C]4 cut for the production of N-600. The crude is fractionated into these cuts in two towers which comprise Section 150. Section 200 - Chlorination The paraffins are chlorinated in Section 200. The feed is heated by exchange with the chlorinated product and then by steam up to 250F. From the steam heater, the paraffin enters a packed glass-lined steel column where it absorbs residual chlorine from the HCl gas leaving the chlorination reactor. The paraffin is then pumped to the first stage (top) of the chlorination reactor. Chlorine is received in tank cars, vaporized by steam, and fed to the reactor. The chlorination reactor is a five-section, glass-lined steel tower. Chlorine is fed to each of the sections, and the reaction temperature is maintained between 250F and 330F. Temperatures above 330F cause coking in the reactor. The partially chlorinated paraffin overflows from the first stage through a downcomer into the second stage and out of the chlorlnator into the first of two HCl separator drums. The ,chloroparaffin is cooled from 330F to 260F by forced circulation through an air-cooled exchanger and put back into the third stage of the chlorinator. Overflowing' through downcomers, the chloroparaffin passes through third, fourth, and fifth stages of the chlorinator. HCl gas from the first four stages and the first separator drum enters a second knockout drum. Chloroparaffins from the fifth stage enter the second knockout drum at 330F. ChloroparaffIn product goes to the alkylation section after going through a feed-to-product Interchanger. HCl gas from the chlorine absorber goes to the benzene absorber in Section 450. Section 300 ~ Alkylation The reaction of chioroparaffins and benzene occurs in Section 300. This is a conventional aluminum chloride-catalyzed Friedel-Krafts reaction. The chloroparaffins are fed to one of two agitated batch reactors on flow control along with aluminum chloride sludge from the slurry drum. Benzene is dried with molecular sieves and fed to the batch reactors on flow control. About 90 percent of the chloroparaffins are reacted at an alkylation temperature of about 165F. This reaction does not appear to be either exothermic or endothermic. * The reaction mixture is pumped from the batch reactors to the multistage reactor. Upon leaving the multistage reactor, greater than 99+ percent of the chloroparaffins have been reacted. A second multistage reactor is available and can be used to increase the reaction time. However, the second multistage reactor is generally used only as a spare for the sal orcciezn PROCESS DESCRIPTION (CONTINUED) Section 300 - Alkylation (Continued) first, since the reaction is essentially complete in the first multistage reactor. Product from the multistage reactor is pumped to a large horizontal drum where most of the catalyst sludge settles out. The crude "NALKYLENE" alkylate product overflows the supersettler and goes to Section 400. HCl gas from the batch and multistage reactors is compressed, absorbed, and purified in Section 450. Some of the catalyst sludge from the supersettler is purged to the aluminum chloride liquor unit. The remainder of the sludge flows to the slurry drum. Just enough fresh dry aluminum chloride is added to the slurry drum to maintain the unreacted chlorides out of the multistage reactor around 0.2 percent by weight. The catalyst slurry is then pumped back to the batch reactors. The aluminum chloride liquor unit dilutes the sludge that is purged from the reaction system with water. The aluminum chloride is then recovered as a 26 percent water solution, and the hydrocarbons that were complexed with the aluminum chloride are separated out in a decanter. The considerabl amount of heat generated In the process is removed by circulating the mixture through a water-cooled exchanger. This process generally works very well when processing sludge from the "NALKYLENE" Alkylate Unit. However, sludge from the SAU Unit is also processed and sometimes causes problems because of emulsions. The sprung oil is used for fuel after benzene is stripped out. Host of the aluminum chloride liquor produced Is sold to sewage treatment plants as a coagulating agent. Section 400 - Crude Cleanup Crude "NALKYLENE" alkylate from the supersettler is fed to the HCl stripper which vents to the suction of one of the HCl compressors. Most of the dissolved HCl is removed in the stripper. The crude alkylate then flows to the secondary settler where a small additional amount of catalyst sludge settles out. This sludge is pumped back to the primary settler along with a small amount of the crude alkylate. Thus no sludge layer accumulates in the secondary settler. Crude alkylate is subjected to a water washing operation to neutralize any remaining aluminum chloride. A settling stage is used to separate the aqueous phase and an emulsion which forms at the interface. Crude alkylate flows from the phase separator to the first caustic settler through an orifice mixer. A dilute recycle caustic stream from the bottom of the second stage caustic wash is added to the crude just before it enters the mixer. The crude alkylate overflows from the top of the first caustic settler, is mixed with a 5 percent NaOH solution, and then goes to a second stage settler. Neutralized crude from the top of the second stage settler is ready for fractionation and goes to crude storage. Spent caustic is purged from the first stage caustic settler. PROCESS DESCRIPTION (CONTINUED) Section 500 - Fractionation Neutralized crude alkylate is pumped from storage to Section 500 Fractionation. The crude alkylate is heated by interchange with the paraffin tower vapor before going to the benzene vaporizer. The benzene vaporizer is a kettle reboiler in which some of the excess benzene is flashed. The remaining stream is then fed to the benzene tower where benzene is removed. The bottoms from the benzene tower are pumped to the paraffin tower where the excess paraffin is removed. The alkylate then flows from the bottom of the paraffin tower to the product tower. Product is removed as a sidedraw and pumped to intermediate storage. The bottoms from the product tower are fed to the bottoms stripping tower. The overhead diphenyl alkylate stream from the bottoms tower goes to fuel. The dialky1 benzene bottoms from the stripping tower are high boiling by-products from alkylation. Some of this material is sold to producers of oil soluble sulfonates. The paraffin tower, product tower, and bottoms stripping tower all operate under vacuum. The product tower operates at about 10 rm Hg. Section 600 - Product Cleanup The distilled "NALKYLENE" alkylate product is pumped from intermediate storage to Section 600 for final cleanup. The product is contacted twice with sulfuric acid which is then separated out with electrostatic separators. After acid separation, the alkylate is contacted with dilute caustic which is also separated in an electrostatic separator. The final cleanup step Is to pass the alkylate through a bed of caustic pellets, a bed-of activated clay, and a cotton filter before going to finished product storage. The caustic removes traces of water, the clay some of the color, and the filter any remaining foreign particles. The spent acid is returned to the supplier. Most of the dilute caustic that is purged from the system is sold, if necessary, the waste caustic can be neutralized with muriatic acid. Section 450 ~ HC1 Recovery Section HC1 gas from Section 200 goes directly to the benzene absorber. HC1 gas from Sections 300 and 400 is compressed and then sent to the benzene absorber where HC1 gas is contacted with some of the chioroparaffin before it goes to Section 300. This removes most of the benzene from the HC1 gas. HC1 is absorbed in water in a two-stage water-cooled absorber system. The muriatic acid produced still contains a small amount of benzene, most of which is removed in deoilers. Each deoiler contains three stages of plastic mesh pads. The last traces of benzene are removed from muriatic acid in a large carbon bed familiarly known as a jolly green giant. When the carbon bed is exhausted, as is shown by a significant amount of benzene passing through the bed, the carbon in the bed is dumped. The first muriatic acid through a new bed is high In benzene and Ts normally run to the neutralization pit. Themuriaticacid produced is of very high quality. When sales of muriatic acid do not keep up with production, the excess is neutralIzed. This sheet is CONFIDENTIAL and should not be distributed outside Continental Oil Company. Spec. No. 01-3000 CONOCO C]Q-Ci2 Normal Paraffins Special Identification; Cn average n-paraffins Test Total n-Paraffins, Wt. X Homolog Distribution, Wt. X Cg and Lower Cio cn Cio + Cn cc12 Cio + Cn + 12 Cl 3 C114 and Higher Aromatics, X Bromine Number Color, Saybolt Molecular Weight Pounds/Gallon (60F) Specification 97.5 min. 2.0 max. 25.0 max. 50.0 min25.0 min. 85.0 min. 15.0 max. 2.0 max. 1.0 max. 0.2 max. 25+ min. Typical Property 97.7 0.4 18.3 38.9 33.9 8.0 0.5 0.75 0.01 30+ 160 6.22 Test Method 1.072 1.053 -- 1.036 ASTM D-1491-60 1.011 1.053 - ;WV'' 'i'1 -13' *: 3-1-79 (Replaces 4-30-76) SAL 00001C21A This sheet is CONFIDENTIAL and should not be distributed outside Continental Oil Company. Spec. No. 01-3011 CONOCO Ci2~Cm Normal Paraffins Special Identification: Average n-Paraffins Test Total n-Paraffins, Wt. X Homolog Distribution, Wt. % Cin and Lover Cu c10 + Cu c 12 c13 Cl4 Cl3 + Ci4 C15 and Higher Aromatics, X Bromine Number Color, Saybolt Molecular Weight Pounds/Gallon (60F) Specification 97.0 min. 2.0 max. - S.O max. - 45.0 max. 70.0-90.0 5.0 max. 1.2 max. 0.2 max. 25+ min. Typical Property 97.5 0.8 1.7 - 10.6 55.3 30.4 1.2 0.82 0.02 30+ 186 6.34 Test Method 1.072 1.053 _ - - - - - 1.036 ASTM D-1491-60 1.011 1.053 3-1-79 (Replaces 4-30-76) V This sheet Is CONFIDENTIAL and should not be distributed outside Conoco Inc. Spec. No. 01-3012 CONOCO Cj2-c16 Paraffins Special Identification: C13 Average n-Paraffins Test Total n-Paraffitis* Wt. % Homolog Distribution* Wt. % C11 and Lower Ci2 C13 c14 C15 C16+ Aromatics, Wt. % Bromine Number Color* Saybolt Specification 97.0 min. 1.0 max. 8-25 -- 1.5 max. 0.2 max* - Typical Property 97.3 0.5 11.0 53.0 27.0 7.0 1.5 0.9 0.02 154- Test Method 1.072 1.053 1.036 1.012 1,011 7-16-79 (Replaces 3-1-79) SAL QCC01C216 This sheet is CONFIDENTIAL and should not 1> distributed outside Continental Oil Company Spec. No. 01-3020 CONOCO C14-C16 Normal Paraffins Special Identification.? Normal Paraffins (W-9 Tower Bottoms) Made at Baltimore Plant Test Specification Total n-Paraffins Wt. X Homolog Distribution, Wt. X (100% n-paraffins basis): 96.0 min. Cj3 and Lower C14 c15 C16 Ci7 and Higher 20 max. 25.0 max. - 6.0 max. Aromatics, Wt. % 3.0 max. Isoparaffins, Wt. % 5.0 max. Bromine Number 0.15 max. Color, Gardner 7 max. Appearance, @ 100 F Clear and free of suspended matter Specific Gravity, @ 60F Flash Point, Pensky-Martens, F Melting Point, F Molecular Weight (on n-paraffins) Distillation Range, F IBP 90% FBP Typical Property 96.5 1.0 20.0 61.9 13.1 4.0 2.2 2.4 0.07 5 same 0.7762 250 47.0 215 503.0 518.0 546.0 Test Method 1.053 1.053 1.036 1.053 1.012 1.022 visual 1.023 ASTM D-93 1.050 1.053 ASTM D-86 3-1-79 (Replaces 4-30-76) SAL 0CCC1C217 This sheet is CONFIDENTIAL and should not be distributed outside Conoco Inc. Spec. No. 01--3100 NALKYLENE 500 Linear Alkylbenzene Special Identification: Linear Dodecylbenzene Tes t Alkylate Homolog Distribution, Wt. % <C10 Ci0 Cio + Cn Ci2 c10 + Cl 1 + Ci2 C13 014 and Higher 2-Phenyl Isomer, Wt. % Total Material Lighter Than Ciq LAB, Wt. X Bromine Number Molecular Weight Saybolt Color Completeness of Sulfonation, % Specific Gravity @ 60F Water, Wt. % Organic Chloride, Wt. % Color of Sodium Sulfonate, Klett (5% AI) (S03 Derived) Biodegradability Pounds/Gallon, 60F Specification 0.5 max. 25.0 max. 50.0 min. 25.0 min. 85.0 min. 15.0 max. 2.0 max. 25.0-35.0 0.5 max. - 0.01 max. 231-241 29 min. 98.0 min. 0.850-0.870 0.1 max. 0.1 max. 35 max. must pass Typical Property 0.1 19.2 57.3 33.2 90.7 7.8 0.9 28.3 0,4 0.003 237 30+ 98.4 0.8660 0.004 0.05 33 pass 7.214 Test Method 1.087 1.087 ASTM D-2710-72 1.087 1.011 1.059 1.023 1.016 5.004 1.042 SDA test *Soap and Detergent Association procedure for the determination of ABS and LAS biodegradability (JAOCS, Nov. 1965 Issue, Vol. 42, No. 11, pages 986993). 10-15-79 (Replaces 9-4-79) sal CC001C213 This sheet is CONFIDENTIAL and should not be distributed outside Conoco Inc. Spec. No. 01-3101 NALKYLENE 550 Linear Alkylbenzene Special Identification: 244 Molecular Weight Linear Alkylbenzene Test Alkylate Homolog Distribution, Wt. % Specification Typical Property Test Method 1.087 <c10 Cio C11 Cio + C11 c12 c13 C14 C1 3 + c14 >c14 2-Phenyl Isomer, Wt. % Total Material Lighter Than C10 LAB, Wt. % 0.5 max. 5-15.0 - 30-50.0 - - 10.0 max. 30.0 max. 2.0 max. 25-35.0 0.5 max. nil 12.7 29.5 42.2 30.5 18.3 7.4 25.7 0.9 26.5 0.3 1.087 Average Molecular Weight Range Preferred Bromine Number Saybolt Color Completeness of Sulfonation, X Doctor Test Specific Gravity (60F/60F) Water, Wt. % Organic Chloride, Wt. % Color of Sodium Sulfonate, Klett (5% AI) (Oleum Derived) 240-248 244 0.01 max. 29 min. 98.0 min. negative 0.860-0.870 0.1 max. 0.1 max. 60 max. 244 1.087 0.003 ASTM D-2710-72 30+ 1.011 98.3 1.059 negative ASTM D-484 0.8658 1.023 0.004 1.016 0.05 5.004 50 1.042 Biodegradability Pounds/Gallon, 60F must pass -- pass 7.205 SDA test *Soap & Detergent Association procedure for the determination of ABS and LAS biodegradability (JAOCS, Nov. 1965 issue, Vol. 42, No. 11, pages 986-993). 10-15-79 (Replaces 9-4-79) SAL 000010219 This sheet is CONFIDENTIAL and should not be distributed outside Conoco Inc. Spec. No. 01-3104 NALKYLENE 600 Linear Alkylbenzene Special Identification: Linear Tridecylbenzene* Test Homolog Distribution, Wt. % Specification Typical Property Test Method 1.087 c10 Cio + Cn c14 Ci 3 + Cm >Cm 2.0 max. 5.0 max. 45.0 max. 70-90 5.0 max. 0.7 4.2 26.5 75.7 3.2 2-Phenyl Isomer, Wt. % Total Lighter Than Ciq LAB, Wt. % Average Molecular Weight Preferred Bromine Number Saybolt Color Completeness of Sulfonation, % Doctor Test Specific Gravity @ 60F Water, Wt. % Organic Chloride, Wt. % Color of Sodium Sulfonate, Klett (5% AI)^ (Oleum Derived) Biodegradability 20-30 0.5 max. 23.5 0.3 1.087 258-266 262 0.01 max. 29 min. 97.5 min. negative 0.860-0.870 0.1 max. 0.1 max. 90 max. 261 1.037 0.003 ASTM D-2710-72 30+ 1.011 98.0 1.059 negative ASTM D-484 0.8651 1.023 0.004 1.016 0.05 5.004 76 1.042 must pass pass SDA test Pounds/Gallon, 60F - 7.206 *Not for release outside Conoco Inc. 2Soap & Detergent Association procedure for the determination of ABS and LAS biodegradability (JAOCS, Nov. 1965 issue, Vol. 42, No. 11, pages 986-993). 10-15-79 (Replaces 9-4-79) *AL 000C1C220 This sheet is CONFIDENTIAL and should not be distributed outside Continental Oil Company. Spec. No. 01-3400 Hydrochloric Acid Special Identification: Technical Grade 20 Baume, 31.45% HC1 Test Specification Assay, Baume 20.0-20.4 Sulfite, ppm* 10 max. Sulfate, ppm 15 max. Iron, ppm (as Fe) 1.0 max. Free Chlorine, ppm 1.0 max. Arsenic, ppm 0.05 max. Sodium, ppm* 6 max. Aluminum, ppm^ 1 max. Heavy Metals, ppm (as Pb) 1.0 max. Color, APHA 15 max. Nonvolatile Matter, ppm 200 max. Residue on Ignition, ppm 100 max. Organic Matter, ppm^ 2.0 max. Odor Characteristic Typical Property 20.2 4 10 0.2 * * 5 0.5 0.5 10 90 70 0.5 Test Method 1.035 1.035 1.035 1.035 1.035 1.035 1.035 1.035 1.035 1.035 1.035 1.035 1.035 *Nondetectable. * Specification for Foote Mineral only, specification for Diamond Shamrock only. J0ne ppm maximum for J. T. Baker only. 3-1-79 (Replaces 5-16-78) This sheet is CONFIDENTIAL and should not h distributed outside Continental Oil Company Spec. No. 01-3450 Aqueous AICI3 Regular Grade Special Identification: Aluminum Chloride Test Aluminum Chloride, Wt. % Hydrogen Chloride, Wt. % Organic Matter, ppm Iron-, ppm Specification 23.0 min. 3.0 max. 30 max. 800 max. Typical Property 24.0 1.5 5 300 Test Method 1.077 1.077 1.077 1.077 3-1-79 (Replaces 8-15-73) g - iM tg /v F B A tm -M iT ra */ S iFO TV C W O O P - Q -/LO J91M st.T tO H 6C T /C W ^ S O M CS C O N TM D fTAL OH. SAL 000010224 SAL 000010224 PED ORIENTATION PROGRAM STXS UNIT BALTIMORE CHEMICAL PLANT BALTIMORE, MARYLAND The STXS Unit manufactures hydrotropes for use in the production of liquid detergent formulations. The unit is run batchwise in se veral steps on blocked-out operation to produce one of three products, Production capability is 13"15 MM pounds per year of sodium toluene sulfonate (STS), sodium toluene xylene sulfonate (STXS), and ammonium xyl ene sulfonate (AXS) GENERAL DESCRIPTION The purpose of this unit is to produce a 40 percent aqueous solution of sodium toluene sulfonate by sulfonation of toluene with 99 percent sulfuric acid and neutralization of the sulfonic acid wi th 50 percent caustic. One hundred percent excess toluene is used in the reaction to assure that most of the sulfuric acid is consumed, thereby minimizing the Na2S0i formed on neutralization. Sulfonation R-H + H2SO4 R-SO3H + H2O Sulfonic Acid where R-H is toluene or xylene. Neutralization R-SO3H + NaOH R-S03Na + H20 SXS or STS R-SO3H + NH4OH --^ R-SO3NH/1 + h2o AXS PROCESS DESCRIPTION (The following description is typical for STS production) SLi 1 fonat ion Sect ion There are two parallel systems with the same function a did capacities in the sulfonation section. Each consists of a standard g ass-lined reactor, an overhead condenser, and a water separator. The reactants are measured by means of positive displacsment meters with automatic shutoff valves. The reaction mixture is heatjd to the boiling point (230F) with steam and held there during the cours Water of reaction and toluene are removed overhead as vkpors which are condensed. The condensate flows into the separator from which toluene overflows continuously and passes back to the reactor b/ gravity. The sal 000010225 PROCESS DESCRIPTION (CONTINUED) Sulfonation Section (Continued) water flows continuously out the bottom and is collected in measuring drums. Heat is applied to the reaction mixture until 8C percent of the water of reaction and all of the water in the sulfuric a cid are removed, The reaction mixture is then cooled to 100F and transfe rred to the nuetralizer. Neutralization Section Water is added to the sulfonic acid and toluene in the neutralizer in order to make a 40 percent aqueous solution of the final product. Heat is evolved, and the temperature increases to 160F. Fi f ty percent NaOH is injected into the sulfonic acid for neutralization, nd the material is circulated through a heater-cooler to hold it at 200 F, thereby avoiding vaporization of the excess toluene. The sulfor ate formed separates from the toluene on settling as the bottom la^ er, which is pumped out to the slurry rundown tank. The intermediate layer, or cuff, is withdrawn to an accumulator for the recovery of any c(Jood product and toluene. The top toluene layer is cooled and pumped to storage. The toluene is separated mechanically instead of by distill cktion to avoid a concentration of ditolyl sulfone in the product which ci uses insolubi1ity in water. The sulfonate product is returned to the neu ralizer and heated to remove any dissolved toluene. The toluene vapor pas; es overhead and Is condensed by direct contact with a cold water spray. Th e product is then cooled and pumped to the slurry rundown tank. It is tr;i nsferred to heated storage after control tests are run. The same operational procedures are used for the production of sodium xylene sulfonate and ammonium xylene sulfonate. For th^ latter case, ammonium hydroxide is used as the neutralizing agent. PRODUCTS The hydrotrope products are sold as 40 percent solution^ in water to liquid detergent manufacturers. They use the hydrotrop^s at levels of 1-3 percent to maintain other components of the formula ions in solution, Hydrotropes also contribute wetting and cleansing chara cteristics. They are clear solutions with a slight yellow tint. SAL CC0C1022 5 This sheet is CONFIDENTIAL and should no. bu distributed outside Continental Oil Company. Spec. Nb 01-3200 CONOCO AXS Ammonium Xylene Sulfonate Special Identification: Hydrotrope Test Specification Typica l Proper ty Active, Wt. % 40 min. 42.1 Active/Total Solids 0.93 min. 0.93 Iron, ppm (as Fe) (Solids Basis) 5.0 max. 0.2 Copper, ppm 1.0 max. 0.1 Sulfate (as SO4), Wt. % - 2.9 Water, Wt. % - 55.0 Chloride (as Cl"), Wt. % 0.1 max. 0.03 Free Oil, Wt. % 0.10 0.03 pH, "as is" 7.0-8.5 7.7 Color, Klett 40 max. 21 Flash Point (Pensky-Martens, F) Shall not flash 0 200 Above 21C Odor Pass Pass Davis Vaportester Reading 0.5 max. Pounds/Gallon 0 60F 9.5 Tes t Method 1.018 Calculated 1 .019 - 1.052 1.018 1.010 1.002 2.008 1.042 ASTM D-93 Baltimore Baltimore 1.023 3-1-79 (Replaces 10-1-72) O-non 0 *c. This sheec is CONFIDED TIAL and should not distributed outside Cc ntinental Oil Compa: Spec. No. 01-3210 CONOCO SXS Sodium Xylene Sulfonate Special Identification; Hydrotrope Test Specification Active, Wt. % 40.0 min. 42.0 max. Active/Total Solids2 0.93 min. Water, Wt. % Chloride (as Cl"), Wt. % 0.1 max. Sodium Sulfate, Wt. % Free Oil, Wt. % 0.1 max. Iron (as Fe) (solids basis), ppm 5 max. Color, Klett 40 max. pH, "as is" 7.5-10.5 Flash (Pensky-Martens, F) Shall not flash 0 200 Odor Passes Pounds/GalIon, 60"F Davis Vaportester Reading 0.5 max. Typical Property 41.4 0.97 57.7 0.03 1.16 0.01 0.20 21 9.7 210 Pass 9.84 Nil Tes t Method 1.018 Calculated 1.018 1.010 1.052 1.002 1.019 1.042 2.008 ASTM D-93 Baltimore (Lever) 1.023 Baltimore (Lever) *For Texize only. ?Total solids - active + inorganic salts. 3-1-79 (Replaces 3-1-74) This sheet is CONFID KNTIAL and should not b distributed outside Continental Oil Company Spec. No. 01-3250 CONOCO STXS Sodium Toluene Xylene Sulfonate Special Identification: Hydrotrope1 Test Specification Active, Wt. % 40.0 2.0 Water, Wt. % Sodium Sulfate, Wt. % Chloride (As Cl"), Wt. % 0.1 max. Free Oil, Wt. % 0.1 max. Iron, ppm 5.0 max. Copper, ppm 1.0 max. Crystallization Temperature, *C 5-15 Color, Klett, "as is" 40 max. Ph, "as is" 7.5-10.5 Flash (Pensky-Martens, F) Shall not flash 0 200 Active/Total Solids * 0.88 min. Pounds/Gallon, 60F - Sodium Toluene Sulfonate, % of Active 25 max. Odor Pass Davis Vaportester Reading 0.5 max. Typical Pro aerty Test Method 4 1.5 1.018 5 6.4 1.018 2.0 L.052 0 .03 1.010 C .03 1.002 C .20 1.019 C .20 1.045 14 1.020 26 1.042 9.7 2.008 At ove 210 ASTM D-93 ( .92 Calculated ! . 94 1.023 20 1.074 1 'ass Baltimore Nil Baltimore 1 Total solids active + inorganic salts. 3-1-79 (Replaces 10-1-72) SAL G00r>lo229 CT-SO- c-1' tJ, 5o; ><; jCt f-H 0- z D1 1 X < TO X 3o|j ' <o 7.' 'A wi XH <Oi J <i Ul V) H in <r _l to w . to X < --V)' X to ai <11 4-1 'll r; C cnO 4-> 0 c '-4 0 '4_ o 1--^ 3 Vg 3 "U 3 r--H to 0 'A 3 u a O to oc C 0 <U c ---i D >> rH i--4 X 0 >- 6- X 3 E L *^ 3aC H W TJ TJ 0fc 00 to < *7 "1 C -4 O 0 C S' gJ * H H 0 -1 c 4J U 44 r-M 4) <r. tn c 3 3 3 3< U< ITS -J o u ro 33 (U Z< .Q o 4 u o C 4i o ITS 0 C ,7 O ft aa O TJ H u 4> 0 '^1 TJ 41 H X X >< U* \ oCOcio^ SAL I 1I _____ I____ s<ui~r o/>/^ rots NtornAu f <*. iCCU' rwqp u cjr wuwoQtyfy IT~1 C.W*/ I (7;cooi.* -fc^J x e ____y w y o n o c n > o w rmmo 00 CAusr< c ^woouc r sroRAftg aooiuM roLuu suiroKAri in > O o o o o ro T 9- 3 MX CONTINENTAL OIL PROCESS FLOW DIAGRAM STXS PLANT BALTIMORE, MARYLAND COM F A NT I NTCT- 3-aT Hammond Plant AL QCCC1C232 PED ORIENTATION PROGRAM HAMMOND CHEMICAL PLANT HAMMOND, INDIANA The Hammond plant began production In 1969 using the new Chemithon Sulfonation Process. Operation had existed at the site using a batch process since 1958. This operation was discontinued when the new continuous process came on-stream. Throughput capability has been increasec to 70 MM pounds per year from the original 30-^0 MM pounds per year. Th; increase was achieved both through optimization of the process and thr ough evolution of different product slates. The plant uses as feedstoc ks 1 inear alkyl benzenes from Baltimore and "ALFONIC" ethoxylates from L ike Charles. Sulfur trloxide is purchased from an adjacent Stauffer Chemical Company plant, Other feedstocks include sodium hydroxide, ammonium hydr^xide, ethyl alcohol and "ALFOL" alcohols. GENERAL DESCRIPTION Sulfonation/Sul fat ion Feedstock (alkylbenzene, ethoxylate, or alcohol) is char bed to paral1e1 thin film reactors. Sulfur trioxide, in a carrier air s iream, is injected into the reactor also. The exothermic reaction mass is 00led by water in the reactor jackets. Reactor effluent, consisting of liquid sulfonatI on products and air, is phase separated in a cyclone. Effl pent gases are normally passed through knockout drums and transferred ac ross the fence to Stauffer Chemical Company where SO2 and SO3 mists are burned to recover the sulfur. When the Stauffer unit is not running, the Affluent gases are vented to the atmosphere through an SO2 scrubber. Crude sulfonates (alkylbenzene derivatives) from the eye one are subjected to further contacting in "dlgestors" to complete the reac tion of any dissolved sulfur trioxide. Following the digestors, alkylbenzene derivatives are contacted with water in a "hydrator." This converts any anhydrides back to the .sulfonate form. The sulfonate or sulfonic acid i then sent to storage. Sulfates (alcohol or ethoxylate derivatives) a re immediately neutralized to avoid chemical decomposition of the unsta ble sulfate. Sulfonation/Sulfation Chemistry a. Alkyl benzene Sulfonation c 12 Q) (L) + SO3 (g) Ai r Cl2 6- (L) S03H SAL 0C0riC233 b. Ethoxylated Alcohol Sulfation R-(C2H40)X-CH2"0H(L) + $03(9) R-(C2H4O) i:H2-0-CH3H (L) Neutra1izat!on Neutralization is accomplished through injection of NaOH or NH3OH into the sulfonate or sulfate as it enters a centrifugal pump The pump and downstream piping constitute the "reactor11. The heat of reaction i removed in watercooled exchangers. Sodium hypochlorite is then injected to bleach the stream. Sodium xylene sulfonate may also be injected at this stage, depending on the product being made. Sodium carbonate or sodium b carbonate is added to the ether sulfate product as a pH buffer. Neutralization Chemistry a. Alkyl benzene Sodium Sulfonate (Sulfonic Acid) 12 1 + NaOH SO3H C12 6 + H20 S03Na b. Ethoxylated Alcohol Sodium Sulfate (Ether Sulfate-) R-(C2Hit0)x"CH2-0-S03H+Na0H -------- R- (C2Hi|0)x-CH2-0 S03Na + H20 PRODUCTS Sulfonates and sulfates are utilized as surface active acents (surfactants) in biodegradable laundry powders, dishwashing liquids, amd shampoos. Hammond's products Include: Conoco SA-597 Sulfonic Acid Conoco C-550 Slurry Conoco C-56O Slurry "ALFONtC" 1412-A "ALFONfC" 1-412-- S Derived from N-500 Al kv 1 benzene Sodium Sulfonate of SA 597 C-550 Blend with Sodiun Xylene Sulfonate Ammonium Salt of Alcohdl Ether Sulfate Sodium Salt of Alcohol Ether Sulfate 0C0010234 This sheec Is CONFIDENTIAL and should not be distributed outside Continental Oil Company. Spec. No. 02-3300 CONOCO SA-597 Sulfonic Acid Special SO3 suifonated NALKTUatt 500 alkylate Test Active, Wt. Z a. b. Sulfuric Add, Wt. X Free Oil, Wt. X (2) Unsulfonated Oil, Wt. X Water, Wt. X Sulfur Dioxide (S02), Wt. Z (4) Specification 96 min. 97.5 min. 1*6 w 2,5 us 1.0 max 1.0 nex 0.0 6 mak ' yplcal Test I ropertv Method 1.001 97.5 Calculated 1.3 1.052 1.021 0.7 1.063 0.4 0.01 1.016 1.066 Acid Color, Klett (5X active acid) Iron, ppm (3) F0 max 10 -*. 55 2 1.054 1.019 (1) Active, Wt. X 1001 (sulfuric mold, vt. Z + unsulfonated oil, vt. X + veter, wt. Z) (2) Internal speciflcatlon^--fkot.ito be used outside Conoco* (3) For B. F. Goodrich only'*; - ' (4) For P & G only. 7-15-77 w (Replaces 4-10-77) SAL 00001C235 This sheet is CONFX0lENTIAL and should not he distributed outside Continental Oil Company Spec. No. 02-3351 CONOCO C-550 Slurry Special Identification; Sodium sulfonate of SA-597 Test Active, Wt. % Sodium Sulfate, Wt. % Free Oil, Wt. % .Color, Klett (5% solution) pH, 5% aqueous solution 00 i Specifications 50-53 (1) 1.3 max. 1.2 max. 1.1 max. (1) 50 max. 7.0-8.5 (1) Typic al Prope rty 52 1.0 > 1.1 1.0 > 32 7.5 - Test Method 1.001 1,052 1.021 - 1.014 1.047 1.047 (1) For Gateway Only - Add buffer, 0.05%-0.1% Sodium Bicarbonate 4-10-77 (Replaces 10-1-72) This sheet is CONFIDENTIAL and should not b< distributed outride Continental Oil Company. Spec. No 02-3353 CONOCO C-560 Slurry Special Identification: Blend of sodium sulfonate of SA-597 and sodium xylene sulfonate Test Typical Specification. Proper): Total Active, Wt. X (LAS + SXS> 57-60 59 Solids, Wt. X Sodium Xylene Sulfonate, Wt X 63.1 max lmin3*4 C'max 61.2 2 Free Oil, Wt.* 1.6 max^ 1.35 Sodium Sulfate, Wt. X 1.5 max 1.0 pH, 5X aqueous solution 7-8 7.5 Color, Kl'ett, 5X active 50 max _ 40 Iron, ppm 5 max 3 Phosphate (as P2O5) ppm 40 max 2 Test Method Calculated^ 1.064 1.040 1.021 1.052 1.047 1.042 1.019 1.067 (1) Active, Wt. % - Solids, Wt. X - (Sodium Sulfate, Wt X + Free Oil, Wt %> (2) 1.2 Max. for Colgate and Wyandotte (3) For Colgate only -- 1.5-2.5X SXS (4) For Wyandotte only -- 2.0-2.5X SXS \ 7-15-77 (Replaces 2-25-77) SAL 0C0C1C237 This sheet Is CONFIDENTIAL and should not be distributed outside Contlneital Oil Company. Spec. No. 06-4560 ALFONIC 1412-A Alcohol Ether Sulfate Special Identification: Ammonium Salt of ALFONIC 1412-40 (Spec. No. 06-4360) Test Specification Typica] Proper 1;v Test Method Active, Wt. X 58.0- i.O 59.2 1.009 Solids (Active + Free Oil + Salts), Ut. % 62.0 1.5 61.0 Calculated Ethanol, Wt. X 14.0 1.0 13.7 1.057 Unsulfated (Ethoxylate + Alcohol) 3.0 max. 2.2 , 1.038 Total Inorganic Salts, Wt. X 2.5 max. <1.C\ Calculated Alcohol Insoluble, Wt. X 0.75 max. 0.3 1.052 Cl as NH4CI, Wt. % 0.25 max. <0.1 1.010 Irom, ppm 5 max. 2 1.019 Copper, ppm 0.5 max. 0.3 1.045 Peroxide Content, ppm 10.0 max. ni] 1.044 pH < 7.0-7.5 (1) 7.: 1.043 Color, Klett, 5Z Solution 50 max. 30 1.042 Color, Gardner (Purex) 3 max. - Corrosion Test Pass - Odor Equal to Standard - Appearance Clear to slightly viscous liquid Molecular Weight 423-444 436 Ca + Mg as CaC03 5 max. <5 Colgate Method Water, Wt. % 20.0-29.0 25 Calculated (1) 0.2% ^*2003 as buffer 1-26-76 (Replaces 2-7-73) AL Wgci C<? This sheet is CONFIDENTIAL aiid should not be distributed outside Continen tal Oil Company S :e c. No . 06-4565 ALFONIC 1412-S Alcohol Ether Sulfat E Special Identification: Sodium Sulfate of ALFONIC (Spec. No. 06-4360) 412-40 Test Active Wt. % Ethanol, Wt. Z Unsulfa ted (Ethoxylate + Alcohol), Wt. Z Total Inorganic Salts, Wt. % Na2S04, Wt. % NaC1, Wt. % Iron, ppm Copper, ppm pH, 1% Solution Color, Klett, 5% Solution Specifications 58.0-60.0 Typical 'roper tv Test Method 1.009 1.057 o HWi O -i-H 3.0 max. 2.5 max. 1.0 max. 1.5 max. 5 max. 0.5 max. 8-9 (1) 50 max. , 1.038 Computed 1.052 1.010 1.019 1.045 1.047 1.042 .1) Suffer required: 0.2% to 0.3% Na2C0^ recommenced 0-1-72 3AL 00010Z3, ORGANIZATIONAL CHART AMMOND l AI CAL PLANT (I) There may or may not be any people in these positions They are listed to show reporting lines. SAL 00l0540 Newark Plant ] diC00l0E^2 SAL PED ORIENTATION PROGRAM NEWARK CHEMICAL PLANT NEWARK, NEW JERSEY The plant, owned originally by Reilly Tar and Chemical Corti pany, was purchased by Consolidated Coal Company (CONSOL) in August 1955 as part of CONSOL's broad program to create a group of satellite plaiji ts which would refine and market the crude chemical streams derived from the processing of coal. It was contemplated that the Newark plant would fit into this program by first refining and marketing cresylics derived from petroleum industry feedstock (spent caustic from gasoline washing), with this raw material being supplemented at a later date by coal-deriv<id feedstocks. At the time of purchase from Reilly, the plant produced only about 7 MM pounds per year of cresylic acid using an old cumbersome process; however, in 1956, a new facility, the "natural acid" plant, was bu It utilizing a novel extraction process. The new plant was designed for 14 to 15 MM pounds per year of cresylics; but with relatively minor changes, this capacity was increased to over 33 MM pounds per year. This new extraction process also separated a sizable quantity of aromatic sul :ur compounds from the feedstock. Unfortunately, a market was not immediately available for these by-products, so they had to be incinerated. At :empts to market the thio-compounds as rubber peptizers were unsuccessful due to the materials' extremely unpleasant odor. Research and Development efforts showed that this problem could be solved by alkylating tho compounds, A new plant, the "alkylation plant," was built in 1961 when; these compounds were alkylated. Some cresylics were also upgraded by alkylation in this plant. Advances in the technology for desulfurizing gasoline in the petroleum industry reduced the available cresylic feedstock supply, forcing the plant to consider synthetic processes for producing the c*esylic acids. A grass roots "synthetic unit" was built In 1966 to synthesize cresylics from methanol and phenol. In 1969, the plant came under the management of Conoco's Chemicals Division Unlike the "natural plant," the "synthetic unft" primaril produced orthosubstituted compounds with very little of the meta a id para compounds, In order to convert some of the product from the syntheti plant to meta and para type material, an "isomerization unit" was built in 1969. This unit, however, never did go into commercial operation bee ause low-priced meta/para cresols became available from Japan at the time the unit was scheduled to go on stream, rendering operation of the un it unprofitable. Increasing pressure from environmental agencies, decreasi ng avaiIability of spent caustic feedstock from the petroleum industry, a nd low product sales volumes resulted in shutdown of the "natural plant" and reduced operation in the alkylation plant in 1971. Coal-derived feedstock never did become available to the "natural plant" and the plant remains idle. SAL C0001C2A3 A new high pressure methylation unit was started up in mi -1978. It was designed to produce 4.5 MM pounds per year of 2,3,6-trime :hy1phenol by reacting 2,6-xylenol with methanol. It was designed to o Iterate alternatively, producing ortho-cresol from phenol and methanol This reaction step is conducted in the liquid phase rather than the vap<j> r phase as in the "synthetic unit." The alkylation unit was shut down in late 1980 as product sa es prices were unable to keep abreast of rising material and operat ng costs. GENERAL DESCRIPTION Only the Synthetic Unit and Liquid Methylation Unit are c jrrently being operated. However, processes formerly carried out in the equipment now Idle (the "Natural Plant" and the "Isomerization Unit") a -e also described here. A. Natural Plant The Natural Plant employed a process for extracting c resylic acids and aromatic mercaptans from the caustic feedstocks, Therefore, it principally contained only separation equipment and d id not have a reactor. A block flow diagram of the process is s howln in drawing CT-4-A, The feedstock was generally obtained from caustic was Ting of gasol1ne to remove cresylic acids and mercaptans. Those compo unds were removed from gasoline to prevent gum deposits in engines duri ng combustion. The principle reaction in the washing step was: R-OH R-SH + NaOH- R-ONa + R-SNa + HoO Cresylic Acids Aromatic Mercaptans Carbolate The resultant product mixture was referred to as carbolate or spent caustic and usually contained 10 to 20 percent by wei ght cresylic acids and mercaptans. At Newark, the first step in the refining process was to remove the sodium. In a combination springing tower and acid d pcanter, the carbolate was countercurrently contacted with the bo lerhouse flue gas which had been scrubbed free of SO2. The princi pal reaction was R-ONa + R-SNa + C02 Heat R-OH + R-SH + Na2C0 Sprung Acid As the sprung acid left the decanter, it contained about 18 percent by weight sodium carbonate. This was removed by two water washes operated in series. The contaminated acid was mixed with an equal quantity of water and the carbonate-water and acid ph ases allowed to separate in a settling drum. Then the acid was wi thd rawn from the bottom and the procedure repeated in the next drum, Carbonate recovered from the first drum was decanted and sent :o storage to be used for flue gas scrubbing. The very dilute car >onate solution recovered from the second drum was used as wash wate * for the first drum. 000010^ GENERAL DESCRIPTION (CONTINUED) A. Natural Plant (Continued) The washed sprung acid was charged to a distillation t ower for topping and the removal of heavy salts and petroleum fractions . A11 overhead and bottom waste streams were incinerated. The produc t, or heart-cut, was then ready for extraction. A 35_stage Scheibel liquid-liquid extraction tower was used to separate the cresylic acids from the mercaptans. Each stage wa s composed of a twelve-inch calming zone packed with stainless steel n esh and a sixinch high mixing zone agitated by an impeller. The fe ed entered near the top and was contacted with aqueous methanol and h exane which were introduced at the top and bottom, respectively. The c resylic acids were picked up by the methanol and the mercaptans by t he hexane. In the solvent recovery area, methanol and hexane were fractionated from their respective product streams. Water in a fix ed ratio was added to the methanol. The hexane was scrubbed with c austic to remove traces of mercaptans and was then water washed. Both solvents were returned to storage for reuse. The final acid products were obtained by continuous or batch fractionation. Process conditions could be changed enough to allow considerable flexibility in product composition. Some of the products were then upgraded by alkylation while others were rea dy for shipment. The aromatic mercaptans from the hexane recovery tower were sent to the alkylation plant for further processing. B. Alkylation Plant % The Alkylation Plant was composed of a continuous dist illation column, batch still column, batch still reboiler, and batch re actor as shown in drawings CT~5"A and CT-6-A. Fractionation of the aromatic mercaptan stream from th e natural plant (shown in drawing CT-4-A) was accomplished In the syst em shown in drawing CT-5-A. This stream was fed continuously into the fir st column from which the overhead went to storage, and the bottoms w re either further fractionated or stored, depending upon the desired pro duct. All preparation of the mercaptans for the reactor occurred in the columns shown. The plant alkylated many different compounds, mostly a n a smal1 volume basis. Therefore, a batch reactor offered the most fl exibi1ity. (The reactor section will be discussed on a general basis.) There were three possible types of feedstocks: aromatic mercapta ns, cresylic acids, or phenol. The catalysts used depended on the feedstock and product required. As shown in drawing CT-6-A, the fee dstock was alkylated with isobutylene which was bubbled into the reactor be neath the agitator, The operating conditions were mild, usually 300-A00F and a few inches of water vacuum. SAL GOO01O2A5 GENERAL DESCRIPTION (CONTINUED) B. Alkylation Plant (Continued) If fractionation of the reactor products was required the batch still was used. Most recently, the alkylation unit was operated on a for alkylating some phenol and cresylic acids, mainly and 2,4-xylenol. The unit is currently shutdown. mlted basis o-cresol C. Synthetic Unit (See Drawing CT-56-D, "Overall Process Flow Diagram") The Synthetic Unit Is comprised of two process sectlo(is--reactlon and fractionation. 1. Reaction Section The main reaction carried out Is the vapor phase alkylation of phenol by methanol to yield o-cresol. The reactlDn is conducted over alumina catalyst. 2,6-Xylenol is formed to an appreciable extent and the trl- and higher methylated phenols to a lesser extent follows: + CH3OH /S--ch3 U +Hz0 o-Creso OH \ CH3-fr CH 2,6-Xyleno 1 + CH2,6-Xylenol OH CTCH3-- CH3 CH-j 2,3,6-Tri methyl pheno +H The catalyst, "CATAPAL" alumina, is highly "orthc -selective," hence, the preponderance of ortho-substituted coimpounds such as o-cresol and 2,6-xylenol. Meta and para-substiti ted compounds are also formed to a much lesser extent as a rest, It of isomerization of the ortho-substituted compounds. SAL CQ0010 GENERAL DESCRIPTION (CONTINUED) C. Synthetic Unit (Continued) 1. Reaction Section (Continued) The plant currently has two reactors operating in parallei. The reactors are cooled by molten salt circulation anld both reactors share a common salt system (drawing CT~7"A). The methanol-phenol feed to a reactor is vapori zed in a series of feed-product and feed-salt exchangers. Product f rom the reactor is cooled and partially condensed in the feed-prod uct exchangers and finally in a water-cooled condenser. The cir culating molten salt serves as a cooling medium for the reactor a wel1 as a heating medium for the feed. Provision of a cool ant in the reactor is Important in keeping reactor temperatures down to minimize coking that tends to deactivate the catalyst. The product from the final condenser goes to a storage tank from which it is fed to the fractionation section. After about 100-200 hours of operation, conversio n in the reactors decreases and pressure drop across the reactor in creases to a point such that the reactor has to be shut down and the catalyst regenerated. Because they share a common salt system, both reactors are shut down and regenerated simultaneously. Periodically, the catalyst in a reactor has to be discarded and the reactor recharged with fresh catalyst. 2. Fractlonation Section The reactor product is purified by fractionation, The first column in the fractionation train is the "dehydr dtor." Water and light ends removed off the top of this column are condensed and phase separated with the water phase being sent to the sewer and the hydrocarbon phase recycled to the tower. The other three columns in the fractionation sect ion are used on a blocked-out basis for two operations, the^str* ight-run" operation and the "rerun" operation. Bottoms frc m the last fractionator on the "straight-run" operation sen es as feed to the fractionation train on the "rerun" operation Overhead products from the three fractionators obtained during the "straight-run" and "rerun" operations and their disposition are indicated below: Cc 0& lhi GENERAL DESCRIPTION (CONTINUED) C- Synthetic Unit (Continued) 2. Fractionation Section (Continued) STRAIGHT-RUN OPERATION Overhead Product Disposition RERUN OP ERATION Overhead Product Disposition Fractionator Phenol No. 1 Recycled to 2,6-Xylenol Reactor roduct Fractionator o-Cresol No. 2 Product Mixed Xylenols B|atch Still for Further Puri fication or Blending Fractionator 2,6-Xylenol Product No. 3 80^ 2,3,6-TriMethyl Phenol B|atch Still for Further Puri fication The bottoms product from the rerun operation is bu rned In the plant boilers. As noted above, further purificat ion of some of the overhead products from the continuous fractic nation is conducted in batch stills. Two batch stills are used for this purpose. Isomerization Unit In the isomerization reactor, predominantly ortho-sub sti tuteci compounds were isomerized in the vapor phase to meta and para-type compounds over low silica porocel catalyst. Unlike he reactors in the synthetic plant, which have a cooling medium, tho somerization reactor was operated adiabatically. A flow diagram of the reaction system is shown in drawing CT-8-A. High Pressure Methylation Unit (See Drawing CT-56-D) Methanol and 2,6-xylenol feeds are combined and el evited to 500 psig. The material is preheated to 600F in a reactor effl ijent-feed exchanger and elevated to 650F against Dowtherm "A" in a seco nd exchanger. Trim heat is applied to the feed as necessary in an Electric heater prior to reactor entry. Feed enters the vertical shu 11 and tube type reactor in a near critical state. Fluid is directed downward through alumina-packed tubes with cooling/heating provided b hot oil on the shell side. Crude product exits the reactor at 680 . The stoichiometric reaction is: 0H + CH3OH Catalystfc ^3^ 650-680 "3 ch3 Methanol 2,3,6-Tri methy1phen o\ + h2o SAL G0C01C2A8 GENERAL DESCRIPTION (CONTINUED) E. High Pressure Methylation Unit (Continued) Reaction products are cooled to 290F in the effluent /feed exchanger and to 150F in a watei--cooled unit. Pressure is red uced and crude reaction products are transferred to storage. At thi > stage, the materia! contains 2,3.6-TMP, 2,6-xylenoi, methanol, d imethyl ether, water, and higher boiling phenol compounds. Crude reaction products are similar in nature, but di Fferent in composition, than product from the reaction section of the Synthetic Unit. The two crude products are, therefore, stored separately and periodically processed through the continuous fractio nation train of the Synthetic Unit on blocked-out operation. The High Pressure Methylation Unit also has the capab i1ity of producing ortho cresol via the methylation of phenol. This ope ration requires more severe operating conditions than described above for 2,3,6-TMP. oooox^' sM-