DOCSLIB.ORG

United States Patent (19) (11 Patent Number: 4,795,824 Kippax Et Al

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
United States Patent (19) (11 Patent Number: 4,795,824 Kippax Et Al United States Patent (19) (11 Patent Number: 4,795,824 Kippax et al. (45) Date of Patent: Jan. 3, 1989 54 PROCESS FOR THE PRODUCTION OF Primary Examiner-Werren B. Lone DALKYL MALEATES Assistant Examiner-Vera C. Clarke 75 Inventors: John W. Kippax, Bedale; Colin Attorney, Agent, or Firm-Bernard, Rothwell & Brown Rathmell, Yarm, both of England 57 ABSTRACT 73) Assignee: Davy McKee (London) Limited, A process is described for the production of a dialkyl London, England maleate by reaction of maleic anhydride with an alkyl alcohol in a monoesterification zone to form the corre (21) Appl. No.: 80,060 sponding monoalkyl maleate, followed by reaction of (22 Filed: Jul. 31, 1987 resulting monoalkyl maleate with further alkyl alcohol 30 Foreign Application Priority Data to form the corresponding dialkyl maleate, which in cludes the steps of supplying a first liquid feed compris Aug. 1, 1986 GB United Kingdom ................. 86.18888 ing said monoalkyl maleate to a secondary esterification 51 Int. Cl'.............................................. CO7C 67/03 zone containing a charge of a solid esterification cata 52 U.S. C. ...................................... 560/204; 203/14; lyst, supplying a second feed stream comprising said 203/DIG. 2; 203/DIG. 11; 502/11; 560/191; alkyl alcohol to said secondary esterification zone, 562/595 maintaining said secondary esterification zone at an 58 Field of Search ................ 560/204, 191; 562/595; elevated temperature sufficient to form or to maintain 502/11; 203/14, 2, 11 therein a vaporous stream containing said alkyl alcohol, 56 References Cited intimately contacting said first liquid feed in said sec ondary esterification Zone in the presence of said cata U.S. PATENT DOCUMENTS lyst with said vaporous feed stream, recovering from 3,862,147 1/1975 Cooley et al. .................. 560/204 X said secondary esterification zone a vaporous effluent 3,886,199 5/1975 Suter et al. ..................... 560/204X stream containing, in addition to alkyl alcohol vapor, 4,032,458 6/1977 Cooley et al. .................... 60/190 X 4,314,947 2/1982 Hohenschultz et al. ... 260/410 also water in vapor form, said water being produced in 4,361,710 1 1/1982 Weitz et al. ............. ... 568/864 said secondary esterification zone by esterification of 4,481,146 11/1984 Leupold et al...... ..., 260/40 said monoalkyl maleate with said alkyl alcohol, and 4,562,283 12/1985 Schnabel et al. ................... S60/204 recovering from said secondary esterification zone a liquid product stream containing said dialkyl maleate. FOREIGN PATENT DOCUMENTS 0143634 5/1985 European Pat. Off. 34 Claims, 6 Drawing Sheets U.S. Patent Jan. 3, 1989 Sheet 1 of 6 4,795,824 SS n n n S ON S NoN ON NonSc SS s Q-4 r n NC V *-N s NQ s No MC) n N. ss R. ( s ) U.S. Patent Jan. 3, 1989 Sheet 2 of 6 4,795,824 U.S. Patent Jan. 3, 1989 Sheet 3 of 6 4,795,824 S SS s Nu s S Rs.ss: SS SS U.S. Patent 4,795,824 U.S. Patent Jan. 3, 1989 Sheet 5 of 6 4,795,824 yž U.S. Patent Jan. 3, 1989 Sheet 6 of 6 4,795,824 4,795,824 1. 2 liquor. Although it would be theoretically possible to PROCESS FOR THE PRODUCTION OF DALKYL recover the monoalkyl maleate from the resulting aque MALEATES ous liquors and to recycle this to the process for the production of further dialkyl maleate, this is not eco This invention relates to a process for the production 5 nomically feasible. Hence the monoalkyl maleate is lost of dialkyl maleates. to the process in these aqueous liquors which are a The production of dialkyl maleates by esterification potential pollution hazard. Moreover the loss of mono of maleic anhydride, of maleic acid or of a mixture alkyl maleate and disposal of these waste liquors repre containing both maleic anhydride and maleic acid has sent a significant operating cost. been described on many occasions in the literature. As O Similar procedures can be used for batch production maleic acid is dibasic, esterification proceeds stepwise of other dialkyl maleates using other alkyl alcohols in via the monoalkyl maleate. In the case of maleic anhy place of ethanol. dride this stepwise esterification can be described by the Although it would be possible to adapt this known equations: process for continuous operation with relatively simple 15 modifications thereof, the resulting process would still CH.CO.OR (1) suffer from the drawback of significant loss of potential product, in the form of monoalkyl maleate and of the other organic acid materials present in the reaction 20 product mixture. Moreover, as the acid catalyst is de and stroyed in the product recovery steps, the consumption of sulphuric acid or derivative thereof would add to the CHCO.OR (2) cost of operation of a large scale continuously operating plant. A further disadvantage of the known process is the CHCOOH 25 risk of contamination of the dialkyl maleate product with sulphur-containing impurities, which may rule out where R is an alkyl group. These reactions can be car ried out in two substantially separate steps in separate its use for some purposes, for example as a feedstock for reactors or simultaneously in a single reactor. The hydrogenation to yield butane-1,4-diol, tetrahydrofuran monoesterification step of equation (1) can be effected 30 and/or gamma-butyrolactone. Further teaching regard non-catalytically, conveniently by use of elevated tem ing use of dialkyl maleates (such as, for example, diethyl peratures. The diesterification step of equation (2) can maleate) for this purpose can be obtained, for example, likewise be carried out non-catalytically; however, it is from EP-A-No. 0143634, from WO-A-B No. 6/O3189 usually preferred to use an esterification catalyst in the or from WO-A-B No. 86/07358. As the catalysts used diesterification step of equation (2), such as an acid 35 for such duty are poisoned by the presence of sulphur catalyst (e.g. sulphuric acid). containing compounds in the feedstock. ester (or in the Diethyl maleate is produced as a fine chemical on a hydrogen-containing gas), stringent purification mea commercial scale, usually by a batch reaction process. sures may be required in order to reduce the sulphur In this known process maleic anhydride or a mixture of content of the ester to an acceptably low level. Such maleic anhydride and maleic acid, in either case possi 40 additional purification steps add significantly to produc bly containing a minor amount of fumaric acid, is re tion costs. acted with excess ethanol in the presence of a homoge Various proposals which avoid the use of catalysts neous liquid phase esterification catalyst, such as sul have been described. Thus U.S. Pat. No. 4,361,710 pro phuric acid or a derivative thereof. The reaction condi poses washing a gaseous mixture containing maleic tions are generally selected so as to cause substantially 45 anhydride with a monohydric or polyhydric alcohol all of the maleic anhydride to react. However, as the boiling above 180 C. (e.g. 2-ethylhexanol or dodecan diesterification reaction of equation (2) above is revers 1-ol) to form a solution of the corresponding maleic acid ible, the reaction product does not yield solely the de half-ester in the alcohol followed by heating the solu sired diethyl maleate; usually the reaction yields at most tion to remove water and to form a solution of maleic about 95 mole % diethyl maleate, the balance compris 50 acid diester in the alcohol. As water boils at a tempera ing mainly monoethyl maleate, besides smaller amounts ture well below that of the alcohol it is readily removed of monoethyl fumarate, diethyl fumarate, maleic acid from the reaction mixture, thus enabling the diesterifica and fumaric acid. The reaction mixture also contains tion reaction to be driven to completion. excess ethanol and water produced by the esterification U.S. Pat. No. 4,032,458 describes a process for the of the mono-esters formed as intermediates, i.e. mono 55 production of 1,4-butanediol in which maleic acid is ethyl maleate and monoethyl fumarate. esterified at elevated temperature and pressure and then In order to recover the dialkyl maleate product the subjected to a two step hydrogenation procedure. Ac catalyst must first be removed, prior to attempting puri cording to the description of the drawing it is preferred fication by distillation techniques, by neutralisation with to use for esterification a monohydric alcohol which alkali and then washing with water. These neutralisa 60 forms a heterogeneous azeotrope with water, such as tion steps produce significant quantities of aqueous li n-butanol. The esterification step is carried out in a quors and remove not only the catalyst but also any distillation zone from which an n-butanol-water azeo monoalkyl maleate and any other acid materials present, trope is removed overhead. According to column 11, such as traces of unreacted maleic anhydride or maleic lines 23 to 27, this azeotrope is condensed and allowed acid. 65 to separate into two layers. The n-butanol layer is de In addition, as diethyl maleate is somewhat soluble in canted, redistilled, and recycled to the distillation zone. water, some of the desired diethyl maleate product is The n-butanol-water azeotrope has a boiling point lost, together with the acidic materials, in the wash (92.7 C. at atmospheric pressure) which is appreciably 4,795,824 3 4. lower than the boiling point of the alcohol itself (117.4 maleate is avoided thereby obviating the risk of contam C. at atmospheric pressure), thus permitting the water ination of the product dialkyl maleate.
Load more

Recommended publications
  • Evaluation of Maleate, Fumarate, and Succinate Diesters As Potential Green Plasticizers
    Evaluation of maleate, fumarate, and succinate diesters as potential green plasticizers by Hanno Christian Erythropel A thesis submitted to McGill University in partial fulfillment of the requirements of the degree of Doctor of Philosophy Department of Chemical Engineering McGill University Montréal, Canada December 2015 ©Hanno C. Erythropel, 2015 Être homme, c’est précisément être responsable. C’est connaître la honte en face d’une misère qui ne semblait pas dépendre de soi. C’est être fier d’une victoire que les camarades ont remportée. C’est sentir, en posant sa pierre, que l’on contribue à bâtir le monde. -Antoine de Saint-Exupéry Gewidmet meinen lieben Eltern Eda & Karl-Heinz, sowie Thilo mit Marla. Abstract The industrial success of poly(vinyl chloride) (PVC) would not have been possible without compounds known as plasticizers, the most important class of additives to brittle polymers such as PVC. Plasticizers facilitate the processing of PVC and render the final product soft and flexible, and plasticizer content can reach up to 50 weight-percent. Due to the ever-increasing use of flexible PVC, plasticizers are produced in the range of several million metric tonnes per year. The most important class of plasticizers are phthalate diesters and di (2-ethylhexyl) phthalate (DEHP) is the most frequently used compound. The vast majority of plasticizers is simply blended with a polymer at elevated temperatures and thus is not bound to the polymer matrix, which results in their tendency to leach from the material over time, ultimately ending up in the environment. Once in the environment, the microbial biodegradation rates of phthalates are low, leading to their omnipresence in environmental samples.
    [Show full text]
  • Guide to Chemical Hazard Information
    GUIDE TO CHEMICAL HAZARD INFORMATION 3 1 0 EHS Ratings 2001 [v1] This Guide is intended to provide chemical hazard ratings for use with the EHS HMIS Labeling System. If a chemical is not listed, then please refer to the procedures for rating chemical hazards detailed in the EHS Chemical Hazard Reference Information Sheet and EHS HMIS Instruction Sheet. For more information contact Environmental Health and Safety at 882-7018 or visit our web site at http://web.missouri.edu/~muehs/. The information contained in this document was based on information from the Office of Radiation, Chemical & Biological Safety, Michigan State University. EHS Ratings 2001 [v1] Index Click within the blue outline to jump to the first page of chemical names that begin with the letter indicated. A M B N-O C P-R D S-T E-G U-Z H-L EHS Ratings 2001 [v1] CHEMICAL HAZARD RATINGS -- (A) Compound H F R SP HAZ Acetal 2 3 0 Acetaldehyde 3 4 2 Acetanilide 3 1 0 Acetic Acid (glacial) 3 2 0 Acetic Anhydride 3 2 1 W Acetoacetanilide 2 1 0 Acetoacet-ortho-toluidide 2 1 1 Acetoacet-para-phenetide 2 1 1 Acetone 1 3 0 Acetone cyanohydrin 4 2 2 Acetonitrile 2 3 0 Acetonyl acetone 1 1 0 Acetophenone 1 2 0 Acetyl Chloride 3 3 2 W Acetylene 0 4 3 Acetyl Peroxide. 1 2 4 Acrolein 4 3 3 Acrolein Dimer 1 2 1 Acrylamide 2 2 2 Acrylic Acid (glacial) 3 2 2 Acrylonitrile 4 3 2 Adipic Acid - 1 0 Adiponitrile 2 2 1 Adipoyl chloride 2 2 0 Adipyldinitrile 4 2 - Aldol 3 2 2 Allyl Acetate 1 3 0 Allyl Alcohol 4 3 1 Allylamine 4 3 1 Allyl Bromide 3 3 1 Allyl caproate 1 2 0 Allyl Chloride 3 3 1 Allyl
    [Show full text]
  • Identification of Carboxylesterase Metabolites of Residual Malathion
    92 Journal of Health Science, 53(1) pp 92–98 (2007) Identification of Carboxylesterase Metabolites of Residual Malathion in Wheat Kernels Using Semi-Micro Radio Liquid Chromatography Kimihiko Yoshii,∗,a Yasuhide Tonogai,b Jun’ichi Katakawa,c Hitoshi Ueno,c and Katsuhiko Nakamuroc aOsaka Prefectural Government, Pharmaceutical Affairs Division, Department of Public Health and Welfare, Otemae 2, Chuo-ku, Osaka 540–8570, Japan, bOsaka Pharmaceutical Association, 1–3–8 Izumi-cho, Chuo-ku, Osaka 540–0019, Japan, and cFaculty of Pharmaceutical Sciences, Setsunan University, 45–1 Nagaotoge-cho, Hirakata, Osaka 573–0101, Japan (Received September 16, 2006; Accepted September 30, 2006; Published oneline November 10, 2006) Since residual malathion in wheat kernels is shown to be enzymatically decomposed during sample preparation using the Japanese official method for pesticide analysis, the decomposition products were identified by semi-micro radio liquid chromatography (LC). The reaction mixture of the supernatant of wheat kernel homogenate incubated with [14C] malathion for 0–8 hr was fractionated, and the radioactive decomposition products in the fractions were identified by comparison with the retention time of fifteen reference standards. Twelve of these products occurring in the environment, diethyl fumarate, diethyl maleate, diethyl malate and diethyl succinate, and their hydrolysate and desmethyl malathion dicarboxylic acid were not detected in the reaction mixture, indicating no contribution of organophosphorus hydrolase or methyl transferase. A trace amount of desmethyl malathion was observed, however, this seemed to be non-enzymatically produced. Malathion monocarboxylic acid and malathion dicarboxylic acid were identified as the major products by the LC condition with and without an ion pair reagent, respectively.
    [Show full text]
  • Designing Green Plasticizers
    DESIGNING GREEN PLASTICIZERS Hanno Erythropel Department of Chemical Engineering McGill University Montréal, Québec, Canada February 2011 This thesis is submitted to McGill University in partial fulfillment of the requirements of the degree of Master of Engineering © Hanno C. Erythropel, 2011 i Abstract Plasticizers are additives in poly (vinyl chloride) (PVC) formulations that render the material flexible. This is important for many applications. Because these plasticizers are not bound to the polymer chemically, they will eventually leach out upon disposal. Considering also the widespread use of flexible PVC, it is not surprising that some plasticizers, such as di(2-ethylhexyl) phthalate (DEHP), are considered ubiquitous contaminants in the environment. Previous studies have shown that DEHP, upon degradation, forms stable, toxic metabolites. Because of this and other concerns, DEHP and other phthalates have already been banned in certain products in Canada and other countries. Hence, there is a strong incentive to develop new, green plasticizers. A series of diesters based on maleic acid, which resembles a part of the phthalate chemical structure, was tested, along with other series based on the structural isomer of maleic acid, fumaric acid, and the saturated analogue, succinic acid. The alcohols used to form the ester bonds varied in length from ethanol to octanol and, also, included the branched 2-ethyl hexanol. Each of these diesters was incorporated into unplasticized PVC at about 30 weight-percent and then evaluated for plasticizer properties such as glass transition temperature Tg and tensile strength. These data were compared to each other and to results with DEHP. Pure samples of the diesters were tested for their biodegradability by the common soil bacterium Rhodococcus rhodocrous (ATCC 13808) while it was growing on hexadecane as a primary carbon source.
    [Show full text]
  • Related Properties from Molecular Structures
    Electronic Supplementary Material (ESI) for Green Chemistry. This journal is © The Royal Society of Chemistry 2021 1 SUPPORTING INFORMATION 2 A multi-task deep learning neural network for predicting flammability- 3 related properties from molecular structures 4 Ao Yang‡a,b, Yang Su‡c,a, Zihao Wanga, Saimeng Jina, Jingzheng Renb, Xiangping Zhangd, 5 Weifeng Shen*a and James H. Clarke 6 aSchool of Chemistry and Chemical Engineering, Chongqing University, Chongqing 400044, China 7 bDepartment of Industrial and Systems Engineering, The Hong Kong Polytechnic University, Hong 8 Kong SAR, China 9 cSchool of Intelligent Technology and Engineering, Chongqing University of Science and Technology, 10 Chongqing 401331, China 11 dBeijing Key Laboratory of Ionic Liquids Clean Process, CAS Key Laboratory of Green Process and 12 Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing, 100190, China 13 eGreen Chemistry Centre of Excellence, University of York, York YO105D, UK 14 *Correspondence should be addressed to: Weifeng Shen ([email protected]) 15 ‡These authors contributed equally to this work. 16 S1. Signature descriptors 17 The signature descriptor1 is an effective tool for encoding molecular structures with all 18 atomic neighborhood into strings. This descriptor involving two forms: the first one is the 19 atomic signatures generated at a specified root atom in a molecule, the other one is the molecular 20 signatures combined from all atom signatures linearly. The size of each atomic signature is 21 determined by a parameter named “height”, h. An atomic Signature is a tree subgraph including 22 all atoms/bonds extending out to the predefined distance h without backtracking.
    [Show full text]
  • In-Situ Preparation of Polyaspartic Ester Mixture In-Situ Herstellung Von Polyasparaginestermischungen Preparation in Situ D’Un Melange D’Esters Polyaspartiques
    Europäisches Patentamt *EP001208135B1* (19) European Patent Office Office européen des brevets (11) EP 1 208 135 B1 (12) EUROPEAN PATENT SPECIFICATION (45) Date of publication and mention (51) Int Cl.7: C08G 73/10 of the grant of the patent: 01.10.2003 Bulletin 2003/40 (86) International application number: PCT/US00/19808 (21) Application number: 00948828.9 (87) International publication number: (22) Date of filing: 21.07.2000 WO 01/007504 (01.02.2001 Gazette 2001/05) (54) IN-SITU PREPARATION OF POLYASPARTIC ESTER MIXTURE IN-SITU HERSTELLUNG VON POLYASPARAGINESTERMISCHUNGEN PREPARATION IN SITU D’UN MELANGE D’ESTERS POLYASPARTIQUES (84) Designated Contracting States: (72) Inventor: ROESLER, Richard, R. AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU Wexford, PA 15090 (US) MC NL PT SE (74) Representative: Bramer-Weger, Elmar et al (30) Priority: 23.07.1999 US 145451 P Bayer AG Konzernbereich RP, (43) Date of publication of application: Patente und Lizenzen 29.05.2002 Bulletin 2002/22 51368 Leverkusen (DE) (73) Proprietor: Bayer Corporation (56) References cited: Pittsburgh, PA 15205 (US) US-A- 5 502 117 US-A- 5 807 968 Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention). EP 1 208 135 B1 Printed by Jouve, 75001 PARIS (FR) EP 1 208 135 B1 Description FIELD OF THE INVENTION 5 [0001] The invention relates to a method for making polyaspartic esters.
    [Show full text]
  • Unclassified ENV/JM/MONO(2016)29
    Unclassified ENV/JM/MONO(2016)29 Organisation de Coopération et de Développement Économiques Organisation for Economic Co-operation and Development 27-Oct-2016 ___________________________________________________________________________________________ _____________ English - Or. English ENVIRONMENT DIRECTORATE JOINT MEETING OF THE CHEMICALS COMMITTEE AND Unclassified ENV/JM/MONO(2016)29 THE WORKING PARTY ON CHEMICALS, PESTICIDES AND BIOTECHNOLOGY GUIDANCE DOCUMENT ON THE REPORTING OF DEFINED APPROACHES AND INDIVIDUAL INFORMATION SOURCES TO BE USED WITHIN INTEGRATED APPROACHES TO TESTING AND ASSESSMENT (IATA) FOR SKIN SENSITISATION Series on Testing & Assessment No. 256 The corresponding annexes are available in the following cotes: ENV/JM/MONO(2016)29/ANN1 and ENV/JM/MONO(2016)29/ANN2 English JT03403923 Complete document available on OLIS in its original format - This document and any map included herein are without prejudice to the status of or sovereignty over any territory, to the delimitation of Or. English international frontiers and boundaries and to the name of any territory, city or area. ENV/JM/MONO(2016)29 2 ENV/JM/MONO(2016)29 OECD Environment, Health and Safety Publications Series on Testing & Assessment No. 256 GUIDANCE DOCUMENT ON THE REPORTING OF DEFINED APPROACHES AND INDIVIDUAL INFORMATION SOURCES TO BE USED WITHIN INTEGRATED APPROACHES TO TESTING AND ASSESSMENT (IATA) FOR SKIN SENSITISATION Environment Directorate ORGANISATION FOR ECONOMIC CO-OPERATION AND DEVELOPMENT Paris, 2016 3 ENV/JM/MONO(2016)29 ABOUT THE OECD The Organisation for Economic Co-operation and Development (OECD) is an intergovernmental organisation in which representatives of 34 industrialised countries in North and South America, Europe and the Asia and Pacific region, as well as the European Commission, meet to co-ordinate and harmonise policies, discuss issues of mutual concern, and work together to respond to international problems.
    [Show full text]
  • Kinetic Investigations on Esterification of Maleic Anhydride with Butanols
    Chemical and Process Engineering 2020, 41 (4), 293–306 DOI: 10.24425/cpe.2020.136014 Kinetic investigations on esterification of maleic anhydride with butanols Maria Bartoszewicz1∗, Maria Kulawska2, Wiesław Organek2 1 Łukasiewicz Research Network – Institute of Heavy Organic Synthesis “Blachownia”, Energetyków 9, 47-225 K˛edzierzyn-Koźle, Poland 2 Polish Academy of Sciences, Institute of Chemical Engineering, Bałtycka 5, 44-100 Gliwice, Poland Kinetic studies of esterification reaction of maleic anhydride with butan-1-ol, 2-methylpropan-1-ol and butan-2-ol were carried out in a semibatch reactor, in the presence of four acidic catalysts: sulfuric acid, phosphotungstic acid, ion exchange resin Dowex 50WX8 and tetrabutyl zirconate. Phosphotungstic acid proved to be the most active catalyst. The temperature range was 383–413 K, the initial molar ratio of alcohol to acid ranged 2.2-5:1. The kinetic parameters were given. The kinetics appeared to be that of the second order with respect both to the acid and to the alcohol. The reaction carried out in the presence of tetrabutyl zirconate was very slow and depended only on acid concentration. The effect of temperature on the reaction rate follows the Arrhenius equation well. Keywords: acidic catalysts, butyl alcohol, dibutyl maleate, esterification reaction, plasticizer 1. INTRODUCTION The esterification reaction of maleic anhydride with butyl alcohol occurs in two stages (Fig. 1). In the first, rapid and practically going to the completion step, monoester monobutyl maleate is formed, which subsequently reacts with one molecule of butyl alcohol forming of diester – dibutyl maleate. This is a slow and reversible stage, therefore a catalyst is used.
    [Show full text]