DOCSLIB.ORG

Process of Formic Acid Production by Hydrolysis

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Process of Formic Acid Production by Hydrolysis (19) TZZ ¥_T (11) EP 2 747 883 B1 (12) EUROPEAN PATENT SPECIFICATION (45) Date of publication and mention (51) Int Cl.: of the grant of the patent: B01J 14/00 (2006.01) C07C 51/09 (2006.01) 15.02.2017 Bulletin 2017/07 C07C 53/02 (2006.01) B01J 10/00 (2006.01) B01D 3/10 (2006.01) C07C 51/44 (2006.01) (21) Application number: 12751504.7 (86) International application number: (22) Date of filing: 27.08.2012 PCT/EP2012/066622 (87) International publication number: WO 2013/030162 (07.03.2013 Gazette 2013/10) (54) PROCESS OF FORMIC ACID PRODUCTION BY HYDROLYSIS OF METHYL FORMATE VERFAHREN ZUR HERSTELLUNG VON AMEISENSÄURE DURCH HYDROLYSE VON METHYLFORMIAT PROCÉDÉ DE PRODUCTION D’ACIDE FORMIQUE PAR HYDROLYSE DE FORMIATE DE MÉTHYLE (84) Designated Contracting States: • TREJBAL, Jiri AL AT BE BG CH CY CZ DE DK EE ES FI FR GB 278 01 Kralupy nad Vltavou (CZ) GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO • ROOSE, Peter PL PT RO RS SE SI SK SM TR 9831 Sint-Martens-Latem (BE) (30) Priority: 27.08.2011 US 201161528204 P (74) Representative: Gevers Patents Intellectual Property House (43) Date of publication of application: Holidaystraat 5 02.07.2014 Bulletin 2014/27 1831 Diegem (BE) (73) Proprietor: Taminco (56) References cited: 9000 Gent (BE) WO-A1-00/39067 US-A- 4 262 140 US-B1- 6 713 649 US-B2- 6 696 603 (72) Inventors: • PASEK, Josef 160 00 Praha 6 (CZ) Note: Within nine months of the publication of the mention of the grant of the European patent in the European Patent Bulletin, any person may give notice to the European Patent Office of opposition to that patent, in accordance with the Implementing Regulations. Notice of opposition shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention). EP 2 747 883 B1 Printed by Jouve, 75001 PARIS (FR) 1 EP 2 747 883 B1 2 Description - The temperature in the bottom of the column is 150 °C at a pressure of 3,5 bar, and the extent of decom- FIELD OF THE INVENTION position of formic acid to CO and water is very re- markable at this temperature. Depending on the [0001] The present invention relates to methods and 5 magnitude of the liquid hold-up in the bottom of the apparatus for the production of formic acid by hydrolysis column, 4 to 10 % of formic acid decompose. The of methyl formate. formed water then further dilutes formic acid. [0002] The present invention further relates to meth- - The specific heat consumption is considerable, and ods for the removal of methanol which is formed as a the heat duty of the reboiler is around 2400 kWh/t of side product during this production. 10 formic acid 85 %. This value is valid for inlet concen- tration of formic acid to the rectification column of 45 BACKGROUND OF THE INVENTION %. - For the conditions of the rectification, the column, [0003] Hydrolysisof methyl formate is a dominantproc- packing, distributors, reboiler and even the condens- ess of formic acid production. Formic acid of a concen- 15 er have to be manufactured from non-metallic ma- tration of 85 % wt. is sold predominantly on the market, terials. Formic acid corrodes even the most high- only a minor part requires a concentration of 90 % and quality stainless steels under the conditions of the higher. rectification. [0004] Methyl formate usually containing 3 to 8 % of methanol is typically hydrolyzed at 100 to 140 °C using 20 [0006] Formic acid production is described e. g. by pat- water and methyl formate as starting components at a ents Leonard Jackson Day US 4299981, Bethlehem molar ratio of water/ester of between 0,8 and 7. Hydrol- Steel Corp. US 3907884. However, it is assumed by mis- ysis of methyl formate has an unfavorable chemical equi- take in the second of the mentioned patents that formic librium [equilibrium constant K = 0,18 to 0,24]. In the acid forms with water an azeotrope with minimum of b.p., present industrial processes, non-reacted ester and25 but it forms an azeotrope with maximum of b.p. in a matter formed methanol are separated after the completion of of fact. the reaction from the reaction mixture by distillation. For- [0007] It has been found in the context of the present mic acid of a concentration of between 20 to 50 % is invention that the extent of formic acid decomposition obtained depending on the starting molar ratio of H 2O/es- can be limited by decreasing the temperature in the rec- ter. During rectification of the reaction mixture to dilute 30 tification column at the expense of decreasing the con- formic acid, very volatile methyl formate gets separated centration of formic acid in the bottom stream of the col- rapidly in the column, and this enables reverse esterifi- umn. Decomposition of formic acid has high activation cation of formic acid by the methanol which still remains energy, and it is strongly inhibited by the presence of after removal of the methyl formate. water. Decreasing temperature by 10 °C and increasing This rectification is performed at as low temperature as 35 water concentration from 15 % to 20 up to 25 % decreas- possible, and thus optionally at a pressure lower than es the rate of the decomposition of the acid to one third. atmospheric pressure (US 4299981). However, the nor- The acid which obtained by this method and has a con- mal b.p. of methylformate is 32 °C, and it is not possible centration of 75 to 80 % is then rectified to the acid of 85 to use common cooling water in the condenser at a re- % and higher at a reduced pressure. duced pressure. The extent of the reverse esterification 40 [0008] Formic acid can be extracted from diluted solu- in the rectification column can eliminate up to 20 % of tions to various solvents, such that water does not have formic acid that has been originally formed in the reactor. to be separated from formic acid by distillation. Extraction Methyl formate that formed in the rectification column by and extraction agents based on amides of acids are de- this reverse reaction can be returned to the hydrolysis, scribed in e.g. patent publications DE2914671, thoughwater formed by theesterification dilutes obtained 45 US6867329, US6696603 and DE4444979. More in par- formic acid, and it increases heat consumption. ticular, US6696603 discloses a process for obtaining an- [0005] Separation of 85 % of formic acid from diluted hydrous or substantially anhydrous formic acid, in which acid is complicated by nearly the same b.p. of water and the aqueous formic acid is supplied to a separate extrac- formic acid (the normal b.p. of the acid is 101 °C) and tion column in which it is partly dehydrated by means of further by formation of an azeotropic mixture with maxi- 50 carboxylic acid amide. mum of b.p. To obtain formic acid with a concentration [0009] Extractive rectification of a mixture of water and of 85 % in the bottom of a dewatering column, it would formic acid is also patented, which uses similar solvents be necessary to rectify the diluted acid at a pressure as used in the above mentioned extraction methods. This around 3,5 bar. Water with a low content of formic acid process described in e.g. DE2545730, US4935100, up to 1 % distillates via the top of the column, it is sent 55 US5006205, US5173156 and CN101481304. back to the hydrolysis. This procedure of isolation of for- [0010] There is a need to obtain improved methods for mic acid of 85 % is complicated by several circumstanc- formic acid production wherein a greater conversion of es: methyl formate into formic acid is obtained such that heat 2 3 EP 2 747 883 B1 4 for both distillation of non-reacted ester and for separa- formate vapor is introduced per kg of formic acid formed. tion of water from formic acid can be saved. Unfortunate- With an increasing volume of methyl formate vapours ly, methyl formate has the lowest b.p. (32 °C) among the concentration of formic acid in the reaction mixture leav- all concerned components, and the higher equilibrium ing the last unit of the cascade increases as well. conversion of hydrolysis can not be achieved by sepa- 5 [0015] In embodiments of these methods, the passing ration of the product from reactor by distillation. Further- of the methyl formate vapor stream is performed in a more, formic acid can not be extracted selectively, be- countercurrent flow. cause all solvents extract methyl formate preferably. [0016] In embodiments of these methods, the hydrol- [0011] Prior art methods for formic acid production ex- ysis of methyl formate to formic acid is performed con- ist wherein weak bases are added to the reaction mixture, 10 tinually in a reactor-mixer cascade and wherein methyl which bond formic acid and thus increase the conversion formate vapor is fed to the last unit of the reactor-mixer of methylformate. Methyl formate and methanol are then cascade and wherein water is fed to the first (through the distilled from the obtained salt of formic acid with the middle) reactor-mixer. base, and then the base is separated from formic acid at Embodiments of methods of the present invention envis- a higher temperature by distillation. Various bases are 15 age a batch design of methyl formate hydrolysis wherein described in DE2744313. Also dialkylamides can be methyl formate vapours are passed through the reaction used to shift the equilibrium of hydrolysis DE3411384.
Load more

Recommended publications
  • Methyl Formate
    SIGMA-ALDRICH sigma-aldrich.com Material Safety Data Sheet Version 5.0 Revision Date 09/17/2012 Print Date 03/13/2014 1. PRODUCT AND COMPANY IDENTIFICATION Product name : Methyl formate Product Number : 291056 Brand : Sigma-Aldrich Supplier : Sigma-Aldrich 3050 Spruce Street SAINT LOUIS MO 63103 USA Telephone : +1 800-325-5832 Fax : +1 800-325-5052 Emergency Phone # (For : (314) 776-6555 both supplier and manufacturer) Preparation Information : Sigma-Aldrich Corporation Product Safety - Americas Region 1-800-521-8956 2. HAZARDS IDENTIFICATION Emergency Overview OSHA Hazards Flammable liquid, Target Organ Effect, Harmful by ingestion., Irritant Target Organs Eyes, Kidney GHS Classification Flammable liquids (Category 1) Acute toxicity, Oral (Category 4) Acute toxicity, Inhalation (Category 4) Eye irritation (Category 2A) Specific target organ toxicity - single exposure (Category 3) GHS Label elements, including precautionary statements Pictogram Signal word Danger Hazard statement(s) H224 Extremely flammable liquid and vapour. H302 + H332 Harmful if swallowed or if inhaled H319 Causes serious eye irritation. H335 May cause respiratory irritation. Precautionary statement(s) P210 Keep away from heat/sparks/open flames/hot surfaces. - No smoking. P261 Avoid breathing dust/ fume/ gas/ mist/ vapours/ spray. P305 + P351 + P338 IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing. HMIS Classification Health hazard: 2 Sigma-Aldrich - 291056 Page 1 of 7 Chronic Health Hazard: * Flammability: 4 Physical hazards: 0 NFPA Rating Health hazard: 2 Fire: 4 Reactivity Hazard: 0 Potential Health Effects Inhalation May be harmful if inhaled. Causes respiratory tract irritation. Skin Harmful if absorbed through skin.
    [Show full text]
  • UC Irvine UC Irvine Electronic Theses and Dissertations
    UC Irvine UC Irvine Electronic Theses and Dissertations Title Steps Toward CO2 Reduction to Methanol via Electrochemical Cascade Catalysis Permalink https://escholarship.org/uc/item/4wx6g1vm Author Mercer, Ian Patrick Publication Date 2020 License https://creativecommons.org/licenses/by/4.0/ 4.0 Peer reviewed|Thesis/dissertation eScholarship.org Powered by the California Digital Library University of California UNIVERSITY OF CALIFORNIA, IRVINE Steps Toward CO2 Reduction to Methanol via Electrochemical Cascade Catalysis THESIS submitted in partial satisfaction of the requirements for the degree of MASTER OF SCIENCE in Chemistry by Ian Patrick Mercer Dissertation Committee: Professor Jenny Y. Yang, Chair Professor William J. Evans Professor Andy S. Borovik 2020 © 2020 Ian Patrick Mercer ii Table of Contents Acknowledgements iv Abstract v Chapter 1: Methyl Formate and Formaldehyde Reduction by Metal Hydrides 1 Chapter 2: Synthesis of Group 8 Metal Complexes of LDMA for the Study of Outer Sphere Interactions 25 Conclusion 33 Experimental 34 References 37 iii Acknowledgements I would like to express my sincere appreciation to my committee, especially my chair, Professor Jenny Y. Yang. Her commitment to science, mentoring, and ‘doing the right thing’ will forever inspire me. Financial support was provided by the University of California, Irvine and US Department of Energy, Office of Science, Office of Basic Energy Sciences Awards DE-SC0012150 and DE- 0000243266. iv Abstract of the Thesis Steps Toward CO2 Reduction to Methanol via Electrochemical Cascade Catalysis by Ian Patrick Mercer Master of Science in Chemistry University of California, Irvine, 2020 Professor Jenny Y. Yang, Chair Research on two independent projects is presented: (1) Homogeneous cascade catalysis has been used for the hydrogenation of CO2 to methanol as it allows for rational tuning of catalyst reactivity and lower reaction temperatures compared to heterogeneous catalysis.
    [Show full text]
  • Process for Producing Methyl Methacrylate Verfahren Zur Herstellung Von Methylmethacrylat Procede Pour La Fabrication De Methacrylate De Methyle
    ~™ II 1 1 III II II 1 1 II II I Ml II I II I II (19) J European Patent Office Office europeen des brevets (11) EP 0 406 676 B1 (12) EUROPEAN PATENT SPECIFICATION (45) Date of publicationation and mention (51 ) |nt. CI.6: C07C 69/54, C07C 67/20 of the grant of the patent: 27.03.1996 Bulletin 1996/13 (21) Application number: 90112194.7 (22) Date of filing: 27.06.1990 (54) Process for producing methyl methacrylate Verfahren zur Herstellung von Methylmethacrylat Procede pour la fabrication de methacrylate de methyle (84) Designated Contracting States: • Ebata, Shuji, DE ES FR GB IT NL C/o Mitsubishi Gas Chem. Com. Tayuhama, Niigata-shi, Niigata-ken (JP) (30) Priority: 04.07.1989 JP 171190/89 (74) Representative: Turk, Gille, Hrabal, Leifert (43) Date of publication of application: Brucknerstrasse 20 09.01.1991 Bulletin 1991/02 D-40593 Dusseldorf (DE) (73) Proprietor: MITSUBISHI GAS CHEMICAL (56) References cited: COMPANY, INC. DE-A- 3 436 608 Chiyoda-ku, Tokyo (JP) • PATENT ABSTRACTS OF JAPAN vol. 14, no. 68 (72) Inventors: (C- 686)(401 1 ), 8 February 1 990; & JP-A-1 290653 • Higuchi, Hirofumi, (MITSUBISHI GAS CHEM) 22.11. 1989 C/o Mitsubishi Gas Chem. Com. Tayuhama, Niigata-shi, Niigata-ken (JP) Remarks: • Kida, Koichi, The file contains technical information submitted C/o Mitsubishi Gas Chem. Com. after the application was filed and not included in this Tayuhama, Niigata-shi, Niigata-ken (JP) specification CO CO CO o 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.
    [Show full text]
  • Methyl Formate Mfm
    METHYL FORMATE MFM CAUTIONARY RESPONSE INFORMATION 4. FIRE HAZARDS 7. SHIPPING INFORMATION 4.1 Flash Point: -26°F C.C. 7.1 Grades of Purity: Technical, practical, and Common Synonyms Liquid Colorless Pleasant odor 4.2 Flammable Limits in Air: 5%-22.7% spectro grades: all 97.5+% Formic acid, methyl ester 4.3 Fire Extinguishing Agents: Dry 7.2 Storage Temperature: <85°F Mixes with water. Flammable, irritating vapor is produced. Boiling point chemical, alcohol foam, carbon dioxide 7.3 Inert Atmosphere: No requirement is 88°F. 4.4 Fire Extinguishing Agents Not to Be 7.4 Venting: Pressure-vacuum Used: Water may be ineffective. 7.5 IMO Pollution Category: D Evacuate. 4.5 Special Hazards of Combustion Keep people away. Products: Not pertinent 7.6 Ship Type: 2 Shut off ignition sources. Call fire department. 4.6 Behavior in Fire: Vapor is heavier than 7.7 Barge Hull Type: Currently not available Notify local health and pollution control agencies. air and may travel considerable distance to a source of ignition and flash back. FLAMMABLE. 8. HAZARD CLASSIFICATIONS Fire 4.7 Auto Ignition Temperature: 853°F Containers may explode in fire. 8.1 49 CFR Category: Flammable liquid Flashback along vapor trail may occur. 4.8 Electrical Hazards: Currently not 8.2 49 CFR Class: 3 Vapor may explode if ignited in an enclosed area. available Extinguish with dry chemicals, alcohol foam, or carbon dioxide. 4.9 Burning Rate: 2.5 mm/min. 8.3 49 CFR Package Group: I Water may be ineffective on fire. 4.10 Adiabatic Flame Temperature: Currently 8.4 Marine Pollutant: No Cool exposed containers with water.
    [Show full text]
  • Working Fluid Selection for Space-Based Two-Phase Heat Transport Systems
    NBSIR 88-3812 Working Fluid Selection for Space-Based Two-Phase Heat Transport Systems Mark O. McLinden U.S. DEPARTMENT OF COMMERCE National Bureau of Standards Gaithersburg, MD 20899 May 1988 Issued August 1988 75 Years Stimulating America's Progress 1913-1988 Prepared for: National Aeronautics and Space Administration Goddard Space Flight Center NBSIR 88-3812 WORKING FLUID SELECTION FOR SPACE-BASED TWO-PHASE HEAT TRANSPORT SYSTEMS Mark O. McLinden U.S. DEPARTMENT OF COMMERCE National Bureau of Standards Gaithersburg, MD 20899 May 1988 Issued August 1988 Prepared for: National Aeronautics and Space Administration Goddard Space Flight Center U.S. DEPARTMENT OF COMMERCE, C. William Verity, Secretary NATIONAL BUREAU OF STANDARDS, Ernest Ambler, Director , ABSTRACT The working fluid for externally-mounted, space-based two-phase heat transport systems is considered. A sequence of screening criteria involving freezing and critical point temperatures and latent heat of vaporization and vapor density are applied to a data base of 860 fluids. The thermal performance of the 52 fluids which pass this preliminary screening are then ranked according to their impact on the weight of a reference system. Upon considering other non-thermal criteria ( f lagimability toxicity and chemical stability) a final set of 10 preferred fluids is obtained. The effects of variations in system parameters is investigated for these 10 fluids by means of a factorial design. i * . I . INTRODUCTION In order to remove the heat generated by electronics and other payloads on spacecraft some type of heat transport system is required. The heat generating equipment is typically attached to a 'cold plate'.
    [Show full text]
  • VAPOR-LIQUID EQUILIBRIUM DATA COLLECTION Chemistry Data Series
    J. Gmehling U. Onken VAPOR-LIQUID EQUILIBRIUM DATA COLLECTION Esters Supplement 2 Chemistry Data Series Vol. I, Part 5b Published by DECHEMA Gesellschaft fur Chemische Technik und Biotechnologie e. V. Executive Editor: Gerhard Kreysa Bibliographic information published by Die Deutsche Bibliothek Die Deutsche Bibliothek lists this publication in the Deutsche Nationalbibliographie; de­ tailed bibliographic data is available on the Internet at http://dnb.ddb.de ISBN: 3-89746-041-6 © DECH EMA Gesellschaft fOr Chemische Te chnik und Biotechnologie e. V. Postfach 15 01 04, D-60061 Frankfurt am Main, Germany, 2002 Dieses Werk ist urheberrechtlich geschutzt. Alle Rechte, auch die der Obersetzung, des Nachdrucks und der Vervielfi:Htigung des Buches oder Teilen daraus sind vorbehalten. Kein Teil des Werkes darf ohne schriftliche Genehmigung der DECHEMA in irgendeiner Form (Fotokopie, Mikrofilm oder einem anderen Verfahren), auch nicht fOr Zwecke der Un­ terrichtsgestaltung, reproduziert oder unter Verwendung elektronischer Systeme verarbei­ tet, vervielfaltigt oder verbreitet werden. Die Herausgeber Obernehmen fOr die Richtigkeit und Vollstandigkeit der publizierten Daten keinerlei Gewahrleistung. This work is subject to copyright. All rights are reserved, whether the whole or part of the material is concerned, including those of translation, reprinting, reproduction by photo­ copying machine or similar means. No partof this work may be reproduced, processed or distributed in any form, not even for teaching purposes - by photocopying, microfilm or other processes, or implemented in electronic information storage and retrieval systems - without the written permission of the publishers. The publishers accept no liability for the accuracy and completeness of the published data. This volume of the Chemistry Data Series was printed using acid-free paper.
    [Show full text]
  • Oxygenated Fuel from Bio-Oil Via Methylation of Acids and Phenolics
    Oxygenated Fuel from Bio-oil via Methylation of Acids and Phenolics Suh-Jane Lee, Evgueni Polikarpov, Huamin Wang and Karl Albrecht Chemical and Biological Process Development Group Pacific Northwest National Laboratory 902 Battelle Blvd., Richland, WA 99352, USA 1 Background The Co-Optimization of Fuels and Engines (Co-Optima) project is a collaborative project between national labs, universities and industry to develop new fuels and engine architectures in tandem to maximize performance and carbon efficiency with low GHGs emission. Objectives for Future Fuels: 1. Reduce petroleum consumption 2. Improve fuel economy 3. Decrease pollutants and GHG emission 4. Accelerate the speed of advanced biofuel deployment 2 Future Fuels-Oxygenated Fuel 1. Advantages a. No need for addition of hydrogen to remove oxygen during upgrading process b. Atom efficiency without loss of oxygen c. Enhance Octane Number 2. Market interests: “Industry is experiencing an Octane lovefest; Petroleum marketers have talked about higher octane demand for future fuels.” -Ron Lamberty in the April, 2016 issue of EPM 3. Aryl ethers are particularly effective anti-knock additives for gasolines. Dolhyj et al. USA Patent 4,412,847, 1983“ Motor Fuel Additive” Compound RON MON AKI (R+M)/2 n-Octane -20 n-Heptane 0 0 0 n-hexane 25 26.0 26 n-pentane 62 61.9 62 ethanol 107 n-butanol 92 71 83 Methyl acetate >120 Anisole 103 Methyl acetate as a component octane commercial gasoline by Amirkhanow K. Sh. and Kislitsyn, A. A. Oil and Gas Business, 2014, 1, 178-192 3 Esters and Aryl Ethers from Bio-oil? 1.
    [Show full text]
  • Thyl Triflates Using Aryl Formates As CO Surrogates
    The Pd-Catalyzed Carbonylation Reaction of Naphthyl and Binaph- thyl Triflates Using Aryl Formates as CO Surrogates by Christina Grace Na A dissertation submitted in partial fulfillment of the requirements for the degree of Bachelor of Science (Honors Chemistry) in the University of Michigan 2015 Acknowledgements I want to start off by thanking my advisor Dr. Masato Koreeda, who has been an amazing mentor for me. My interest in chemistry, which was first fostered by Dr. John Montgomery in CHEM 210, was cemented after taking CHEM 215 taught by Dr. Koreeda. Dr. Koreeda has guided me with patience for close to three years now, and I can say confidently that I have been able to improve my techniques and critical thinking through my undergraduate research experience. Gratitude to my labmates, most notably Ryan Soheim and Caitlin Utt, for their company in the lab, and Emiko Nogami, a graduate student at Ochanomizu University, Tokyo, Japan, who was involved with the initial stage of the research on the carbonylation reaction as a visiting scholar during the month of August, 2014, in the laboratories of Professor Koreeda. In addition, I would like to thank all of my professors: Drs. Kathleen Nolta, Roseanne Sension, Zhan Chen, Kristina Hakansson, Brandon Ruotolo, Ted Goodson III, Raoul Kopelman, Bart Bartlett, Paul Zimmerman, Mark Banaszak Holl, Nathaniel Szymczak, John Wolfe, Corinna Schindler, and Pavel Nagorny, for their instruction and guidance. I’d like to extend a special thank you to Drs. Bart Bartlett and Brandon Ruotolo for their overall encouragement and for graciously writing my letters of recommendation despite their busy schedules.
    [Show full text]
  • Ethyl Formate Fumigation an Overview Update
    11th International Working Conference on Stored Product Protection Ethyl formate fumigation an overview update Ryan, R.F*#1, De Lima, C.P.F.2 1VAPORFAZE, PO Box 4, Sans Souci NSW 2219, Australia 2Consultant Research Entomologist, Perth WA, Australia *Corresponding author, Email: [email protected] #Presenting author, Email: [email protected] DOI: 10.14455/DOA.res.2014.161 Abstract The historical fumigant ethyl formate [EF] is proving to be a methyl bromide alternative. EF effectiveness against dried fruit insects was published in 1925. Non-flammable mixture of EF (14.4 vol% EF) with carbon dioxide [CO2] was reported by Jones (1933). On-site mixing of EF liquid into a stream of CO2 in export grain structures was trialed by Allen and Desmarchelier (2000). In addition to eliminating the flammability hazard, CO2 has a synergistic effect with an optimal range of 5-20%. Ryan and Bishop (2002) developed a commercial mixture of EF dissolved in liquid CO2which was compressed to 40 bar pressure in an industrial gas cylinder. EF is a highly flammable volatile liquid (b.pt.=54°C) which requires vaporization to minimize adsorption and achieve uniform distribution throughout the fumigation space. Pre- or post (on- site) EF/CO2 mixture is converted to a gaseous mixture using a proprietary high pressure vaporiser. The EF/CO2 gaseous mixture is accurately dispensed into the fumigation chambers by weighing. However, because the application rate of the EF/CO2 mixture is between 75 and 420 g/m3 fumigations need to be done in adequately tested gas-tight structures (De Lima et al., 1994) while vacuum chambers are generally satisfactory.
    [Show full text]
  • Conversion of Green Methanol to Methyl Formate
    catalysts Review Conversion of Green Methanol to Methyl Formate Doreen Kaiser, Luise Beckmann, Jan Walter and Martin Bertau * Institute of Chemical Technology, TU Bergakademie Freiberg, Leipziger Straße 29, 09599 Freiberg, Germany; [email protected] (D.K.); [email protected] (L.B.); [email protected] (J.W.) * Correspondence: [email protected]; Tel.: +49-3731-392384 Abstract: Methyl formate is a key component for both defossilized industry and mobility. The current industrial production via carbonylation of methanol has various disadvantages such as high requirements on reactant purity and low methanol conversion rates. In addition, there is a great interest in replacing the conventional homogeneous catalyst with a heterogeneous one, among other things to improve the downstream processing. This is why new approaches for methyl formate are sought. This review summarizes promising approaches for methyl formate production using methanol as a reactant. Keywords: carbonylation; green chemistry; methanol; methyl formate; synfuel 1. Introduction Methyl formate (MF) is one of the most important building blocks in C1 chemistry and it is of great interest as an emission reducing fuel additive. MF can be synthesized from CO and methanol and can be understood as chemical storage for CO. If methanol is produced Citation: Kaiser, D.; Beckmann, L.; from CO2 and hydrogen, which is generated through water electrolysis by renewable Walter, J.; Bertau, M. Conversion of energy, an access to green MF is created. This way a (partial) substitution for classical i.e., Green Methanol to Methyl Formate. fossil feedstock borne petrochemicals can be realized while reducing CO2 emissions.
    [Show full text]
  • Process for Producing Methyl Methacrylate
    luropaisches Patentamt iuropean Patent Office lj) Publication number: J 407 81 1 AZ )ffice europeen des brevets © EUROPEAN PATENT APPLICATION C07C 69/54, C07C 67/327, g) Application number: 90112195.4 © Int. CI.5: C07C 67/20, C07C 231/06, g) Date of filing: 27.06.90 C07C 253/00 CHEMICAL £) Priority 14.07.89 JP 180558/89 © Applicant: MITSUBISHI GAS COMPANY, INC. §) Date of publication of application: 5-2, Marunouchi 2-chome Chiyoda-Ku 16.01.91 Bulletin 91/03 Tokyo, 100(JP) c/o Mitsubishi g) Designated Contracting States: © Inventor: Higuchi, Hirofumi, DE ES FR GB IT NL Gas Chemical Co. Niigata Research Laboratory, 182 Shinwari Tayuhama Niigata-shi, Niigata-ken(JP) Inventor: Kida, Koichi, c/o Mitsubishi Gas Chemical Co. Niigata Research Laboratory, 182 Shinwari Tayuhama Niigata-shi, Niigata-ken(JP) © Representative: Turk, Dietmar, Dr. rer. nat. Turk, Gille + Hrabal Patentanwalte Brucknerstrasse 20 D-4000 Dusseldorf 13(DE) © Process for producing methyl methacrylate. 0 Disclosed is a process for producing methyl methacrylate which comprises: (I) a step of reacting acetone and prussic acid to form acetonecyanhydrin; (II) a step of hydrating the acetonecyanhydrin obtained in the step (I) to form a-hydroxyisobutyric acid amide; (III) a step of reacting the a-hydroxyisobutyric acid amide obtained in the step (II) with methyl formate to form methyl a-hydroxyisobutyrate and formamide; <M (IV) a step of dehydrating the methyl a-hydroxyisobutyrate obtained in the step (III) to form methyl ^ methacrylate; and (V) a step of decomposing the formamide obtained in the step (IV) into ammonia and carbon monoxide. 00 The process can produce methyl methacrylate at high yields without by-production of acidic ammonium js, sulfate.
    [Show full text]
  • Ammonium Formate; Exemption from Exemption from the Requirement of a OPP–2006–0121
    Federal Register / Vol. 75, No. 178 / Wednesday, September 15, 2010 / Rules and Regulations 55991 Administrator of this final rule does not reference, Ozone, Volatile organic Subpart S—Kentucky affect the finality of this action for the compounds. purposes of judicial review nor does it Dated: September 1, 2010. ■ 2. Section 52.920(c) Table 1 is extend the time within which a petition Beverly H. Banister, amended by revising the entries for ‘‘401 for judicial review may be filed, and KAR 51:001,’’ ‘‘401 KAR 51:017,’’ and Acting Regional Administrator, Region 4. shall not postpone the effectiveness of ‘‘401 KAR 51:052’’ to read as follows: such rule or action. This action may not ■ 40 CFR part 52 is amended as follows: be challenged later in proceedings to § 52.920 Identification of plan. enforce its requirements. (See section PART 52—[AMENDED] * * * * * 307(b)(2).) (c) * * * List of Subjects in 40 CFR Part 52 ■ 1. The authority citation for part 52 continues to read as follows: Environmental protection, Air pollution control, Incorporation by Authority: 42 U.S.C. 7401 et seq. TABLE 1—EPA-APPROVED KENTUCKY APPROVED KENTUCKY REGULATIONS State citation Title/subject State effective date EPA approval date Explanation ******* Chapter 51 Attainment and Maintenance of the National Ambient Air Quality Standards 401 KAR 51:001 ......... Definitions for 401 2/5/2010 9/15/2010 [Insert cita- Except the phrase ‘‘except ethanol produc- KAR Chapter 51. tion of publication]. tion facilities producing ethanol by natural fermentation under the North American Industry Classification System (NAICS) codes 325193 or 312140,’’ in 401 KAR 51:001 Section 1 (118)(1)(b)(i) and the phrase ‘‘except ethanol production facili- ties producing ethanol by natural fer- mentation under NAICS codes 325193 or 312140,’’ in 401 KAR 51:001 Section 1(118) (2)(c)(20).
    [Show full text]