Document zd8G7bnqrGBDDbXjyKbbGNqJg

DOW CHEMICAL U.S.A. October 9, 1986 David Liou 2509 Jim Akers - 2513 Gary Camp - 2501 Ed Pittman -- 2502 John Gross -- 2511 John Henley -- 2514 Seb Corbino - 2503 Mike Holbrook - 2511 Cal Esneault -- 2501 Bill Davis - 2506 Ted Westlake - 2503 John Green -- 2503 LOUISIANA DIVISION P. O. BOX ISO PLAQUEMINE. LOUISIANA 70766-0160 B04 38S-S000 cc: Project Rep: Jimmy Mack _ 2505 Safety Supt: Carl Strange - 2509 AS&TL Mgr: Dave Courter - 2501 David Runt - 2502 Sam Washington - 2505 Mike Nutt - 2505 Joan Pennington - 2510 REACTIVE CHEMICALS COMMITTEE REVIEW - METHYL, 3-METBQXY PROPIONATE Attached is a review packet prepared by Jimmy Mack, Sam Washington, and David Hunt for the upcoming Reactive Chemicals review on Production/Pistillation of Methyl, 3-Methoxy propionate. Please review this before the meeting which will be held in the library conference room on October 16, 1986 at 12:15. Gerald Wagener, Chairman LA. AS&TL REACTIVE CHEMICALS COMMITTEE attachment rcb CONFIDENTIAL an operating unit of the d w chemical company 003368 DO REACTIVE CHEMICALS REVIEW FOR METHYL, 3-METHOXY PROPIONATE PRODUCTION IN LAS&TL MINIPLANT JIMMY MACK SAM WASHINGTON DAVID HUNT CONFID^NTIAI DO 00339 PROCESS DESCRIPTION JHM 10/6/86 PURPOSE The purpose of this project is to produce 25 gallons of methyl 3-methoxy propionate to sample potential customers in the paint and coating markets. An additional goal is to verify the technical and economic feasibility of a larger scale effort in vhich market development or commercial quantities may be made. CHEMICAL REACTIONS The reaction conditions will be at ambient temperature (25 C) up to 35 C and the pressures from atmospheric to 50 psig. The reaction uses 2 mole percent sodium methoxide as a catalyst and goes as follows: CH30H + CH2=CHCOOCH3 --------- > CH30-CH2CHC00CB3 I H METHANOL METHYL ACRYLATE MMP There are no side reactions at the temperatures of operation and the only other known reaction in this system is the polymerization of the methyl acrylate. The heat of reaction to MMP has been estimated by Dave Firrup of the Michigan labs to be -2.6 kcal/mole of methyl acrylate. The heat of reaction as reported from the literature is -18.81 kcal/mole methyl acrylate. PROCESS EQUIPMENT The process will follow the basic flow sheet included on page 3. The reactor is a 26 gallon, medium pressure, 316 stainless steel unit previously used for the distillation of recycle toulene from the Triblocks Market Development Plant. It is rated at 220 psig at 375 F (191 C) and is equipped with a single speed turbine type agitator. A steam and water jacket provides temperature control. Auxiliary equipment on the reactor includes a 4 inch stainless steel packed column, reflux condenser, total condenser, and 20 gallon receiver pot. The methyl acrylate will be handled in two 7.5 gallon LPG tanks equipped with dip and vent pipes. These will be placed on a digital scale and the contents pumped using a diaphragm metering pump through a control valve to the reaction vessel. All of these units are protected by pressure relief devices and are on the pressure vessel program. The reactor and distillation column is handled by a PDP-11 computer. PROCEDURES The reactor, column, receiver, and interconnecting piping will be cleaned and dried. The methyl acrylate cylinders will be filled in a lab hood from 5 gallon cans. The filled cylinders will be padded to 100 psig with a dry gas mixture of 6% oxygen and the balance being nitrogen. The sodium methoxide will be weighed out and loaded by vacuum into the reactor which has been nitrogen purged. The methanol vill CONFIDENTIAL DO 003390 then be batch loaded from the drum scale using residual vacuum and the loading pump. The agitator vlll be started and the catalyst allowed to mix for 1/2 hour. With full cooling water flowing on the jacket of the reactor, the methyl acrylate will be metered into the reaction mixture at a rate controlled to maintain the temperature below 35 C and to limit the amount of unreacted acrylate to 0.5-1.OX of the total by GC analysis. This amount should allow us to keep the reactor isothermal even if all of the unreacted acrylate polymerizes. The addition will continue until all of the methyl acrylate in the two cylinders is exhausted. The reaction vill be allowed to post react until the residual acrylate is less than IX. An equal molar charge of acetic acid will be added from a sample cylinder to neutralize the sodium methoxide. This will be allowed to react for 2 hours. The resultant mix of methanol, methyl acrylate, and MMP will then be distilled to separate essentially pure MMP. The methanol and residual methyl acrylate will be taken over in a lights cut at atmospheric pressure, and then the MMP vill be distilled over under vacuum. The bottoms of the still which vill contain acetic acid, sodium acetate, and MMP will be dumped and burned as waste. CONFTDFNTTAL DO 003391 E-27 REFLUX CONDENSER REACTIVE CHEHICALS DATA JMM 10/7/86 LIBRARY LISTS: 17 DTA, FP, AND ARC DONE TO DATE OF PARTICULAR INTEREST: RCM 82-874: ARC FOR FLAMMABILITY LIMITS IN 02-N2 ATMOSPHERE RCT 83-195: DTA OF METHYL ACRYLATE RCM 86-967: HEAT OF REACTION ESTIMATION RCL 86-204A: DTA OF METHYL ACRYLATE, METHANOL, AND SODIUM METHOXIDE RCL 86-204B: DTA OF METHYL ACRYLATE RCL 86-204C: DTA OF METHYL ACRYLATE AND METHANOL KNOVN REACTIVE CHEMICAL HAZARDS: EXOTHERMIC POLYMERIZATION OF METHYL ACRYLATE AS LOW AS 37 TO 40 C HEAT OF REACTION: -18.81 KCAL/MOLE METHYL ACRYLATE INHIBITED FOR THIS WITH A COMPOUND SENSITIVE TO LACK OF OXYGEN AND MOISTURE SLIGHT EXOTHERMIC REACTION OF METHANOL AND METHYL ACRYLATE IN THE PRESENCE OF SODIUM METHOXIDE HEAT OF REACTION: -2.6 KCAL/MOLE (ESTIMATE TO +/- 3 KCAL/MOLE) CONFIDENTIAL DO 003393 POTENTIAL CHEMICAL HAZARDS JMM 10/6/86 CHEMICAL METHANOL HAZARDS FLAMMABLE--FP: 60,8 F FLs 6.0-36.5Jt TOX--SKIN, EYE, INHALATION INGESTION METHYL ACRYLATE FLAMMABLE--FP: -8.3-2.8 C FL: 2.8-25% TOX--EYE, SKIN, INHALATION INGESTION (SEVERE) SODIUM METHOXIDE FLAMMABLE--FPs 60.8 F FL: 6.0-36.5* TOX--EYE, SKIN, INHALATION INGESTION (STRONG BASE) ACETIC ACID FLAMMABLE--FP: 104 F FL: 4-16% TOX--EYE, SKIN, INHALATION INGESTION (STRONG ACID) MMP FLAMMABLE--FP: 108 F FL: NOT DETERMINED TOX--PRELIMINARY ACUTE ON INHALATION AND INGESTION INDICATES MODERATE TOXICITY CONp T DFNT T Al. DO 003394 PROTECTIVE EQUIPMENT REQUIRED CHEMICAL METHANOL METHYL ACRYLATE SODIUM METHOXIDE ACETIC ACID CRUDE MMP REACTOR SAMPLES LIGHTS CUT SAMPLES FINISHED MMP BOTTOMS OF STILL RUBBER GLOVES, MONOGOGGLES RUBBER GLOVES, MONOGOGGLES, SAMPLING RESPIRATOR (HANDLE IN LAB HOOD) RUBBER GLOVES, MONOGOGGLES RUBBER GLOVES, MONOGOGGLES RUBBER GLOVES, MONOGOGGLES, SAMPLING RESPIRATOR RUBBER GLOVES, MONOGOGGLES, SAMPLING RESPIRATOR RUBBER GLOVES, MONOGOGGLES, SAMPLING RESPIRATOR RUBBER GLOVES, MONOGOGGLES, SAMPLING RESPIRATOR CONFIDENTIAL DO 0C3395 PROCESS ALARHS REACTOR HIGH PRESSURE HIGH TEMPERATURE AGITATOR SHUTDOWN HIGH REACTOR LEVEL LOW REACTOR LEVEL LOW CYLINDER WEIGHT HIGH PUMP DISCHARGE TEMPERATURE JMM 10/6/86 CURRENT LIMIT 100 PSIG * 37 C * 0 RPM * 80 X * 20 X 37 LB 35 C * DISTILLATION COLUMN HIGH CONDENSER TEMPERATURE HIGH RECEIVER TANK LEVEL LOW RECEIVER TANK LEVEL 30 C 80 X * 80 X * THESE ARE TIED INTO A SHUT DOWN SEQUENCE THAT STOPS THE FEED AND PUTS THE REACTOR AND DISTILLATION SYSTEM ON FULL COOLING DO 003396 GENERALIZED PROCEDURES JHM 10/6/86 REACTION CLEAN AND DRY THE REACTOR AND DISTILLATION SYSTEMS LOAD SODIUM METHOXIDE LOAD THE METHANOL AGITATE THE SOLUTION FOR 1/2 HOUR AT AMBIENT TEMPERATURE PUMP THE METHYL ACRYLATE INTO THE REACTOR AT A RATE TO KEEP THE TEMPERATURE BELOW 35 C AND THE UNREACTED METHYL ACRYLATE BELOV 0.5-1.0 X POST REACT THE METHYL ACRYLATE UNTIL THE RESIDUAL IS LESS THAN U LOAD THE ACETIC ACID TO NEUTRALIZE THE SODIUM METHOXIDE REACT THE MIXTURE FOR 2 HOURS DISTILLATION HEAT UP THE COLUMN UNDER TOTAL REFLUX SLOWLY STRIP OFF THE METHANOL AND METHYL ACRYLATE DRAIN THE RECEIVER TANK COOL THE SYSTEM DOWN AND ADD MORE METHANOL STRIP OFF THE EXTRA METHANOL TO WASH THE LINES DRAIN THE RECEIVER TANK PUT THE COLUMN UNDER VACUUM AND,STRIP OFF THE MMP DRAIN THE RECEIVER TANK AND STILL POT FILLING THE ACRYLATE CYLINDERS CLEAN AND DRY THE CYLINDERS FILL THEM IN THE LAB HOOD CONNECT THEM TO THE CYLINDER STATION AND PAD WITH PAD GAS DISCONNECT AND DEPAD IN THE LAB HOOD FILLING THE ACID SAMPLE CYLINDER CLEAN AND DRY THE CYLINDER FILL IT WITH A WEIGHED AMOUNT IN THE LAr CO' DO 003^7 CONNECT TO THE PROCESS TIE POINT PAD INTO THE REACTOR USING NITROGEN DISCONNECT AND DRAIN IN LAB CONFIDENTIAL DO 003398