Document NeMdVZoGdbN9p3gERemNY4LpE

PED TRAINING PROGRAM CONOCO "ALFOL" ALCOHOL PROCESS GENERAL INTRODUCTION Conoco*s "ALFOL" alcohol process manufactures normal primary alcohols with an even number of carbon atoms in each chain. The process uses aluminum alkyl chemistry developed by Karl Ziegler in Germany in the 1930's. Conoco pays Ziegler's research institute a license royalty based on alcohol sales for the use of this technology in Conoco*s process. Conoco research began development of the "ALFOL" alcohol process in 1955. The process in its entirety was developed by Conoco through an extensive and ongoing research and engineering effort. Conoco holds more than 50 patents in the u.s. and other countries covering production of aluminum alkyls and their derivatives--alcohols, olefins, etc. The nature of the materials handled throughout the process creates many problems.. Dense slurries of aluminum in ATE and solvent must be handled in pipelines and pumped to high pressures. ATE burns on contact with air and decomposes explosively in the presence of water and can be very dangerous if not handled properly. Dilution of ATE with solvent makes handling somewhat easier, but much care must be taken to prevent spills or leaks of any stream that contains aluminum alkyls. All vessels and tanks containing aluminum alkyls must be blanketed with nitrogen from a highly reliable source. The polymerization reaction (growth reaction) in the process is highly exothermic and takes place at high pressures. The reaction conditions must be watched very carefully in order to prevent a runaway reaction. The growth reactors are provided with automatic blowdown systems which quickly depressure and empty the growth reactors if the reaction temperature gets above a safe operating level. The properties and high purity of the "ALFOL" alcohols make them very useful in a wide variety of applications. See Table I for a summary of alcohol products, their properties and uses. A by-product of the hydrolysis section of the process is alum (acid hydrolysis) or alumina (water hydrolysis). -Ui cs ^ Oo 3 U r-4 *s <i> u N --O * C** 4-> -- 01 er, O V 1--1 O! Q* C+ flj O 05 <N O 4J C0) I cn o OJ o ao SAL 0G0C1C355 SAL QC0C1C356 er>n 0, t ,Q CO I <-i CO | OQt -tI ( TABLE I "ALFOL" ALCOHOL PROPERTIES AND USES CONOCO "ALFOL" ALCOHOL PROCESS Product Range Plasticizer Range (C4 to C10) Intermediates "ALFOL" Phthalates "ALFOL" Esters Detergent Range *C10 " C2 0+^ co > r~ O o o o o w `.n O' PGB-bp 11-13-73 "ALFOL" Sulfates "ALFOL" Ether-Sulfates "ALFOL" Nonionics Important Properties Low Volatility Good Heat Stability Low Temperature Char acteristics Surface Active Properties, Foaming and Wetting Proper ties, Detersive Pro perties, High Solu bility Typical Usee Imitation Coatings Cable Industry, Leatherclothe, PVC Sheetings, PVC Plate; , Films, Bag Makers, Foar:ing Materials, Extreme Thermostable Sheetings Detergents, Emulsifier^, Demulsifiers, Defoamers, Ore Flotation Agents, Textile Processing Agents, Cosmetics, Shampoos, Ointments GENERAL INTRODUCTION (CONTINUED) Alum ia used as a flotation agent in waste water treatment and in making alumina; and alumina is used primarily as a hydrotreating catalyst. LAKE CHARLES "ALFOL" ALCOHOL PLANT Conoco's Lake Charles "ALFOL" alcohol plant is located in Westlake, Louisiana. This plant was the first in the world to start commercial production of normal primary alcohols. Construction of the plant began in 1959, and plant startup was in 1961. The plant was originally designed for 100 MM pounds/year C6_^g alcohols at 4.0 "M" value. In 1971 the plant was expanded to 150 MM pounds/year. The plant is currently operating at an official capacity of about 200 MM pounds/year of Cg_^Q alcohols at 4.2 "M" value. Raw material feedstocks to the plant are: (1) Aluminum powder (2) Ethylene frcm Conoco's ethylene unit (3) Hydrogen from Conoco's Lake Charles Refinery and ethylene unit (4) Air (5) Sulfuric acid PROCESS DESCRIPTION (Refer to attached flow diagrams) The plant is divided into seven processing units. All are operated continuously except the batch 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 aluminum powder is activated by ball milling to remove oxide coating on powder particles. The feeds are aluminum powder and kerosene solvent contaminated with ATE from Section 200. The product of Section 100 is an activated aluminum powdersolvent slurry to Section 200. CCfU0 35^ PROCESS DESCRIPTION (CONTINUED! Section 200 - ATE Preparation The function of Section 200 is to manufacture ATE in solution with kerosene solvent. The aluminum-solvent 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 offgas ethylene from Section 300 to form ATE. The process reactions are: 2A1(C2H5)3 + A1 + -------- 3A1(C2H5)2H (Hydrogenation) 3A1(C2H5)2H + 3C2H4 --------*-3Al(C2H5)3 (Ethylation) For every three mols of ATE product from the ethylation reaction, two are recycled to hydrogenation and one is withdrawn as pro duct. The product ATE-solvent-Al slurry stream (containing 4-8 weight percent Al fines) is centrifuged to remove as much of the Al 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-solvent-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 - Alkvl Grcwth 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 and 250F and is described as follows: psig The alkyl chains formed vary in length approximately PROCESS DESCRIPTION (CONTINUED) Section 300 - Alkvl Growth (Continued) according to a poisson distribution. The effluents are growth product (A1 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. 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*502 -------* AMOR) 3 The reaction takes place in batch reactors from which the nitrogen rich offgas is vented to the atmosphere. The oxidized growth product is then fed to Section 425. Impurities formed in the oxidation reaction constitute a 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 hydro carbon impurities from aluminum alkoxide by three-stage flashing and stripping under vacuum conditions. Natural gas is used as stripping gas 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 fresh solvent. Section 500 - Acid Hydrolysis In Section 500, the alkoxide from Section 425 is hydrolyzed with sulfuric acid from battery limits to form alum and alcohols. The hydrolysis reaction equation is: ai(or)3 + 1*sH2S04 *-3R0H + *5A12 (SO4) 3 SAL 0C0C10359 > PROCESS DESCRIPTION (CONTINUED) Section 500 - Acid Hydrolysis (Continued) Excess acid from hydrolysis is neutralized by ammonium hydroxide from battery limits. Also in Section 500 is the distillation capability to separate water and butanol product from crude alcohol. Effluents from Section 500 are crude C0-C20+ alcohol, butanol product, alum product, and spent wash water for disposal. Alum solution is traded to the sulfuric acid supplier in return for sulfuric acid. Ethanol that is produced is discarded in the wash water. Section 600 - Alcohol Fractionation In Section 600 the crude alcohols from Section 500 are fractionated into useful cuts. The alcohol products are hydrogenated 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-OC-C-C-OH + Hj Ni catalyst^ c_c_c_c_c--C-OH Another function performed in Section 600 is reduction of the diol content of the 12+ alcohols via reaction using alumina catalyst. Alumina OH catalyst C-C-C-C-C-C-OH --------------------C-C--OC--C-C-C-OH + f^O The effluents from Section 600 are C^, C0_1q, C]_2-14' C16-18 C-^0_2Q or <^20+ alcbols from normal fractionation. A utility fractionation section is used to produce heart cuts of the alcohols such as Cg, Cg, C]_o, etc. PLAKT UTILITY SUPPLIES Solvent is supplied by Conoco`s Lake Charles Refinery. Steam is obtained from the ethylene unit boilers. The plant has its own furnaces for hot oil supply and its own cooling tower for cooling water. Nitrogen gas, fuel gas, and electricity are purchased. Fuel oil for hot oil heating and steam generation will be used in the future. SAL GC001C360 1 \C ro o o o o o <t CO I rg gj m cj H O o o o <to UIZS S*L 000010363 \ rs^oi 6BowTH SPTBOQfO2UA&CET DC-^OIA 3ATC.H OXIOATIOU Q6AC.TO ra 1 OC.-4C f3ATC.n OXIOATIQM ragAC-Tcaia oe-AJoie. fBiATO-t OXIOATIOM nsACToa FAAOI MIST EXTttACTOtt "TO ATM TO ATK4 fUSTB. AIK <SA- -WZ SA-AQfA GA-Jt)Of IS 4-242 S Ajg CQMPQES&eR 1 'W73 TQAIKjHvj& T=T3CXinAf>-< ED 1*6 ISU PATE DESCRIPTION BVANMrTT]| CONTINENTAL OIL COMPANY ENOINEEKINO CENliK PONCA CfTY, OKLAHOMA SiN*PL.iFieo Pbocess Flow OtAQiaAK* T LAKE C*4Af2X_e^ *Acrt?L.* AlCQUQL f^UAMIT 12 USE tOtOEt scale: APPP: j_____ pate: No. SO l'525-A|i-/5.C. SAL 000010364 SAL CGC01C365 CONOCO MALPQLM ALCOHOL PROCESS (CONTINUED! CONDEA "ALFOL" ALCOHOL PLANT The Condea "ALFOL" alcohol plant is located in Brunsbuttelkoog, West Germany, about sixty miles northwest of Hamburg. The plant is 50 percent owned by Conoco and 50 percent owned by the German Oil Company D.E.A. (D.E.A. was purchased by Texaco in 1967). Plant construction began in 1962, and the plant was started up in 1964. PLANT DESIGN CAPACITY The original plant design capacity was 100 MM pounds/year c6-18 mAUF0L" alcohols at 4.0 "MH value, The plant, is currently operating at 130 MM pounds/year at 4.2 "M" value. RAW MATERIAL FEEDSTOCKS Aluminum powder Ethylene (from O.E.A.'s refinery at Heide, north of Condea) Hydrogen (from D.E.A.'s refinery at Heide) Air Water about 15 miles OVERALL PROCESS REACTION (Theoretical) A1 + 1*iH2 + 15C2H4 + 1*302 + 1*SH20 --------3C2H5 (C2H4) 40H + *gAl203 MAJOR PRODUCTS Same as for the Lake Charles plant. Condea also produces pure alumina monohydrate as a major product. PROCESS DESCRIPTION (Refer to attached simplified process flow diagrams) The plant is divided into eight process units. All units are continuous except the batch oxidation process in Section 400. The entire process is essentially the same as for the Lake Charles plant except for the major differences noted below. SAL 0C0C1C366 PROCESS DESCRIPTION (CONTINUED) Section 300 - Alkvl Growth Condea has two parallel continuous growth reactor systems; each system has three reactor sheila in series. Section 500 - Water Hydrolysis A. Function - Hydrolize stripped alkoxide with water and separate water and butanol from crude alcohol. Dry aluminum hydroxide by-product to form pure alumina monohydrate. Catalyst-support grade alumina is produced by spray drying. B. Feed - Stripped alkoxide from Section 425 and water. C. Process Reactions A1(0R)3 + 3H20 -------------> 3ROH + A1(0H)3 (Hydrolysis) 2A1 (OH) 3"Excess Water------> A^C^'I^O + Water (Alumina Drying) D. Effluent - Crude C^_20+ alcohol to Section 600, pure alumina monohydrate product, butanol product, and waterethanol to disposal. Section 600 - Alcohol Fractionation Instead of removing diols from the 12+ alcohol, as done in Section 500 of the Lake Charles plant, Condea has diol removal facilities for the individual "ALFOL" 12-14 and 16-18 alcohol product streams in Section 600. Section 850 - Solvent Hvdrofiner A. Function - Hydrotreat and fractionate the condensed solvent and hydrocarbon impurities stream from Section 425 (after steaming and water washing) to provide recycle plant solvent. B. Feed - Condensed stripper overhead from Section 425, water, and hydrogen gas. SAL ^C0RI0367 PROCESS DESCRIPTION (CONTINUED) Section 850 - Solvent Hvdrofiner (Continued) C. Process Reactions - Hydrogen (over Ni catalyst) reacts with any oxygenated or unsaturated hydrocarbon materials to form saturated hydrocarbons and water. D. Effluent - Plant solvent for recycle, offgas to fuel, naphtha from light hydrocarbon impurities, and heavy bottoms to fuel from heavy hydrocarbon impurities. USE OF PRODUCTS "ALFOL" alcohol product applications are essentially the same as for lake Charles. Condea'a alumina monohydrate product from the rotary dryers is presently sold as raw material for aluminum manufacture. Pure alumina from the spray dryer is marketed as high priced catalyst support material. PLANT UTILITY SUPPLIES The Condea plant has its own boilers to supply steam, its own Linde air separation unit to supply nitrogen gas, and its own furnaces to supply hot oil. The plant has water wells located on plant property to supply cooling water that is used on a once-through basis and dumped to the nearby Kiel Canal. Elec tricity and fuel oil (burned in plant furnaces) are purchased. PGB-bp 11-14-73 SAL 000010368 1973 PED TRAINING PROGRAM BTHOXYIATION UNIT LAKE CHART,Kg "&TJTQL" ALCOHOL PLANT Conoco*s ethoxylatlon unit is located adjacent to the "ALFOL" alcohol plant in Westlake, Louisiana. This unit produces, on a batch basis, Conoco "AlfONICS," which are ethoxylated "ALFOL*1 alcohols. "AliTONICS** are excellent detergents and are completely biodegradable. The unit has been in operation since 1962. r.edstock. to unit "ALFOL" alcohols in the range C^ to c20 Ethylene oxide (Eto.) Flake caustic catalyst Glacial acetic acid (for neutralization of caustic) Process Reaction (Typical) A C14OH + 6C-C --* C140(C-C-0)6H "ALFOL" EtO. 14 -ALFONIC" Major Products "ALFONIC" 10-12-60 "ALFONIC" 16-18-65 "ALFONIC" 10-14-40 "ALFONIC" 14-12-40 Ethoxylated "AjbFOL" 60 Weight % Eto. Ethoxylated "ALFOL" 65 Weight % Eto. Ethoxylated "AUOL" 40 Weight % Eto. Ethoxylated "AUOL" 40 Weight % Eto. 10-12 Containing 16-16 Containing 10-14 Containing 14-12 Containing Production Capacity Capacity is about 75 MM pounds per year "ALFONICS" based on current distribution. This is equivalent to consumption of 40 to 45 MM pounds per year "AUTOL" alcohols. qooo1 ETHOXYLATION UNIT LAKE CHARLES "ALFOL" ALCOHOL PLANT (CONTINUED) Process (Typical Batch Cycle) (Refer to attached proceaa diagram) A batch of "ALFOL" alcohol ia 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. Flake caustic catalyst (about 0.15 weight percent based on alcohols charge) is then added from a hopper mounted on the top of 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 water cooled heatercooler. 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 the catalyst hopper. 'Hie 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 4 hours, depending on product. Ethylene oxide is volatile, flammable, extremely reactive, and toxic. The vapor is subject to explosive decomposition at high temperature and pressure. During addition of ethylene oxide to the reactor, the unit operator roust watch reactor operation very closely. Use of Products "ALFONICS" are sold to detergent manufacturers for use in liquid and powder detergent formulations. Some "ALFONICS" are also sold as defoaming agents. "ALFONIC" 10-12-60 is used "as is" as nonionic detergent in light duty liquid detergent formulations. "ALFONIC" 16-18-65 is used "as is" as nonionic detergent in heavy duty powder detergent formulations. SAL 0C0010370 ETHOXYLATION UNIT LKKB CHARLES "ALFOL" ALCOHOL PIAHT (COHTINUEP) ot Product! (Continued) "ALFONIC" 10-14-40 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. PGB-bp 11-14-73 S*L OQo I037l ' SAL 0C001C372 qOOQ10373 S At 'S ISC *