DOCSLIB.ORG

United States Patent (19) 11) Patent Number: 4,575,562 Hsu Et Al

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
United States Patent (19) 11) Patent Number: 4,575,562 Hsu Et Al United States Patent (19) 11) Patent Number: 4,575,562 Hsu et al. 45) Date of Patent: Mar. 11, 1986 (54) DIMETHYL ADIPATE FROM BUTADIENE (56) References Cited U.S. PATENT DOCUMENTS 75 Inventors: Charles K. Hsu, Pensacola; Frank 4,169,956 10/1979 Kummer et al. .................... 560/204 Dobinson, Gulf Breeze, both of Fla. 4,171,450 10/1979 Kesling et al. ... ... 560/204 73 Assignee: Monsanto Company, St. Louis, Mo. 4,171,451 10/1979 Kummer et al. .................... 560/204 Primary Examiner-Natalie Trousof Assistant Examiner-Vera C. Clarke (21) Appl. No.: 652,049 Attorney, Agent, or Firm-Thomas N. Wallin (22 Filed: Sep. 19, 1984 57 ABSTRACT Dimethyl adipate is produced from dimethylhex-3-ene 51) Int. Cl. .............................................. CO7C 67/38 dioate which is prepared by carbonylation of butadiene 52 U.S. C. .................................... 560/204; 560/183; under reactive conditions in the presence of an alcohol, 560/207; 562/590; 568/673 a platinum-group-metal catalyst and quinone oxidant. 58) Field of Search ................ 560/204; 502/152, 155, 502/162, 166, 171; 562/590 19 Claims, No Drawings 4,575,562 1. 2 diene in methanol containing palladium chloride and DIMETHYL ADPATE FROM BUTADIENE cupric chloride under carbon monoxide and oxygen pressure gave 10 molar 26 yield of methyl 2,4-pen FIELD OF THE INVENTION tadieneoate, 25 molar 76 yield of a mixture of methyl A. Background 2-pentenoate and methyl 3-pentenoate, and only about Adipic acid is conventionally made by the catalyzed 2.5 molar % yield of dimethyl hex-3-enedioate. Only nitric-acid oxidation of cyclohexanol or cyclohexanone the last named product is a dicarbonylated product. or mixtures, the alcohol or ketone or mixtures being Kesling and Zehner (U.S. Pat. No. 4,166,913) de made by air oxidation of cyclohexane or by hydrogena scribe the catalytic oxidative carbonylation of conju tion of phenol. 10 gated dienes in the presence of a salt of a platinum As the relative cost of phenol or benzene-derived group metal, an iron or copper "oxidant salt' com cyclohexane increases with respect to linear hydrocar pound such as cupric chloride, plus equimolar amounts bons, it becomes important to seek ways to make indus of an alcohol and an enol ether such as methyl vinyl trially important adipic acid from other feedstocks. This ether or a cyclic ketal such as 1-methoxycyclohexene. invention is concerned with a process for making di 15 methyl adipate by carbonylation of butadiene. In U.S. Pat. No. 4,171,450, essentially the same art is B. The Prior Art taught, but instead of the equimolar mixture of alcohol Catalyzed carbonylation of hydrocarbons to give and enol ether or alkoxycycloalkene, the use is taught of monocarboxylated and/or dicarboxylated products is two molar equivalents (based on butadiene) of a dehy well known. 20 drating agent such as 1,1-dimethoxycyclohexane and no Tsuji reported the carbonylation of complexes of more than catalytic quantities of an alcohol. The 1,1- palladium chloride and olefins to give f3-chloroacyl dimethoxycyclohexane clearly serves to provide the chlorides (J. Amer. Chem. Soc., 86,4851-3, 1964) which hydrocarbyl (in this case, methyl) radical of the ester could be esterified to give the corresponding 3-chloro products, being itself the diketal formed from methanol esters. Fenton disclosed the oxidative carbonylation of 25 and cyclohexanone by removal of water. In both cases, hydrocarbon olefins in the presence of an alcohol and a butadiene reacts with carbon monoxide, and oxygen soluble salt of a multivalent metal with an oxidation that is also present re-oxidizes the iron or copper "oxi potential greater than the platinum-group-metal catalyst dant salt'. also present (U.S. Pat. Nos. 3,397,225 and 3,397,226), In U.S. Pat. No. 3,509,209, Fenton teaches the carbo forming esters of unsaturated acids. Thus the reaction of 30 nylation of butadiene in the presence of a palladium carbon monoxide with ethylene in the presence of palla containing catalyst and an aqueous hydrohalic acid dium chloride yielded methyl methacrylate in good (hydrochloric or hydrobromic). In one example, about selectivities. When the Cui +/Cut couple was used, 2M% of adipic acid was isolated, based on butadiene high conversions were obtained, since the cupric ion charged to the reactor. In another example, a 9.2 molar maintains palladium in its Pd form; air or oxygen 35 % yield of pentenoic acid was obtained. Another exam bubbled through the reactants converted cuprous ion to ple showed the carbonylation of 2-pentenoic acid, cupricion, thus maintaining the redox cycle. Cupricion under the same general conditions to yield 55 molar 2% used to oxidize Pd to Pd2+ may also be kept in the of adipic acid. Cu2+ state by anodic oxidation (Fenton, U.S. Pat. No. The two-step carbonylation of butadiene to methyl 3,481,845). pentenoate followed by further carbonylation to di In U.S. Pat. No. 3,755,421 (Fenton et al), quinones or methyl adipate is known (e.g., U.S. Pat. Nos. 4,169,956 hydroquinones of benzene or naphthalene are used as and 4,171,451 to BASF). The patents show the use of a redox agents in the carbonylation or discarbonylation of cobalt carbonyl catalyst. The first step appears to be hydrocarbon olefins containing only one double bond, slow and to require high pressures (e.g. about 9000 such as ethylene. A Group VIII nobel metal compound 45 is used, where the metal ion is in an elevated oxidation psig). These constraints would tend to make such a state. Oxygen or air is used to regenerate the quinone process much less economical than one based on a faster from the hydroquinone in this redox reaction. The pa process carried out at significantly lower pressures. tent also states that a suitable dehydrating agent may be SUMMARY OF THE INVENTION beneficial in the carbonylation process. Among those 50 dehydrating agents mentioned are acetals and ketal This invention describes the preparation of dimethyl s-including 1,1-dimethoxycyclohexane, derived from adipate from 1,3-butadiene via dimethyl hex-3-enedio methanol and cyclohexanone-and orthoesters such as ate. methyl orthoformate. The dimethyl hex-3-enedioate is produced by react Palladium-catalyzed carbonylation of 1,3-butadiene 55 ing 1,3-butadiene with carbon monoxide at elevated in an alcohol solvent was described by Tsuji in 1971 (S. temperatures and pressures, in the presence of metha Hosaka and J. Tsuji, Tetrahedron, 27, 3821-29, 1971). nol, and a catalytic amount of both a platinum-group Using ethanol as solvent and palladium acetate as cata metal compound in its high oxidation state and an or lyst, a 97.8% selectivity to ethyl 3-pentenoate was ob ganic oxidant such as a quinone. The term "platinum tained at 16% conversion of the butadiene. No di-ester group metal' is used to refer to the elements ruthenium, was produced. At higher conversions (36.5%) using the rhodium, palladium, osmium, iridium and platinum. The same catalyst, 8.6% of di-esters were formed, together alcohol is employed in a quantity that is at least stoichio with only 47.4% of ethyl 3-pentenoate and about 43% metric, based on the dicarboxylic ester to be formed. of branched or saturated monocarboxylic esters. Optionally, dehydrating materials such as ketals, ace Japanese Kokai No. 75,130,714 (Teijin, Ltd.) de 65 tals, orthoesters or metaboric acid or esters may be scribes the formation of esters by carbonylating a conju included. The platinum-group metal compound may gated diene in the presence of monohydric alcohols, optionally contain ligands. Oxygen used to regenerate molecular oxygen and a suitable redox salt. Thus buta the quinone oxidant may be added along with the car 4,575,562 3 4. bon monoxide, in an alternating manner with the carbon Small amounts of acids like acetic, trifluoroacetic, monoxide, or in a separate vessel. sulfuric, hydrochloric, hydrobromic or hydroiodic acid The reaction may be carried out in a single reactor or, may be added to the reaction mixture if desired. where it is desired to keep the oxygen and carbon mon The quinone additive used to maintain the platinum oxide separated for safety reasons, for example, in multi 5 group metal in its oxidized state may be 1,4-benzoqui ple vessels. The reaction may be run in a batch, continu none, 2,5-dichloro-1,4-benzoquinone, 2,6-dichloro-1,4- ous, or semi-continuous mode. By semi-continuous is benzoquinone, tetrachloro-1,4-benzoquinone(p- meant a system where reactants are continuously fed to chloranil), 2,3-dicyano-1,4-benzoquinone, 2,3-dichloro a reactor but no reaction products are drawn from the 1,4-naphthoquinone, tetramethyl-1,4-benzoquinone, reactors until the cycle is completed. 10 2,3-dichloro-5,6-dicyano-1,4-benzoquinone, 2,5-diphe The methanol is employed in this invention at a level nyl-1,4-benzoquinone, 2,3-dimethyl-1,4-naphthoqui of at least 2 moles per mole of diester to be produced. none, 1,4-napthoquinone, etc. The preferred internal Dehydrating agents which may optionally be added oxidant is p-chloranil(tetrachloro-p-benzoquinone). in small amounts to the reaction mixture, and which Optionally, the corresponding hydroquinone or serve only to maintain desirable anhydrous conditions, 15 quinone/hydroquinone mixtures may be used. include compounds such as methyl orthoformate, The quinone or hydroquinone may be adsorbed on an metaboric acid, 2,2-dimethoxypropane, 1,1-dimethox inert material such as natural or synthetic zeolites, zir ycyclohexane, methyl vinyl ether, 1-ethoxy-cyclohex conium phosphate, etc., or it may be combined as part ene, etc.
Load more

Recommended publications
  • Inventory Size (Ml Or G) 103220 Dimethyl Sulfate 77-78-1 500 Ml
    Inventory Bottle Size Number Name CAS# (mL or g) Room # Location 103220 Dimethyl sulfate 77-78-1 500 ml 3222 A-1 Benzonitrile 100-47-0 100ml 3222 A-1 Tin(IV)chloride 1.0 M in DCM 7676-78-8 100ml 3222 A-1 103713 Acetic Anhydride 108-24-7 500ml 3222 A2 103714 Sulfuric acid, fuming 9014-95-7 500g 3222 A2 103723 Phosphorus tribromide 7789-60-8 100g 3222 A2 103724 Trifluoroacetic acid 76-05-1 100g 3222 A2 101342 Succinyl chloride 543-20-4 3222 A2 100069 Chloroacetyl chloride 79-04-9 100ml 3222 A2 10002 Chloroacetyl chloride 79-04-9 100ml 3222 A2 101134 Acetyl chloride 75-36-5 500g 3222 A2 103721 Ethyl chlorooxoacetate 4755-77-5 100g 3222 A2 100423 Titanium(IV) chloride solution 7550-45-0 100ml 3222 A2 103877 Acetic Anhydride 108-24-7 1L 3222 A3 103874 Polyphosphoric acid 8017-16-1 1kg 3222 A3 103695 Chlorosulfonic acid 7790-94-5 100g 3222 A3 103694 Chlorosulfonic acid 7790-94-5 100g 3222 A3 103880 Methanesulfonic acid 75-75-2 500ml 3222 A3 103883 Oxalyl chloride 79-37-8 100ml 3222 A3 103889 Thiodiglycolic acid 123-93-3 500g 3222 A3 103888 Tetrafluoroboric acid 50% 16872-11-0 1L 3222 A3 103886 Tetrafluoroboric acid 50% 16872-11-0 1L 3222 A3 102969 sulfuric acid 7664-93-9 500 mL 2428 A7 102970 hydrochloric acid (37%) 7647-01-0 500 mL 2428 A7 102971 hydrochloric acid (37%) 7647-01-0 500 mL 2428 A7 102973 formic acid (88%) 64-18-6 500 mL 2428 A7 102974 hydrofloric acid (49%) 7664-39-3 500 mL 2428 A7 103320 Ammonium Hydroxide conc.
    [Show full text]
  • Ethylene Glycol
    Ethylene glycol Ethylene glycol (IUPAC name: ethane-1,2-diol) is an organic Ethylene glycol compound with the formula (CH2OH)2. It is mainly used for two purposes, as a raw material in the manufacture of polyester fibers and for antifreeze formulations. It is an odorless, colorless, sweet-tasting, viscous liquid. Contents Production Industrial routes Biological routes Historical routes Uses Coolant and heat-transfer agent Antifreeze Precursor to polymers Other uses Dehydrating agent Hydrate inhibition Applications Chemical reactions Toxicity Environmental effects Names Notes Preferred IUPAC name References Ethane-1,2-diol External links Other names Ethylene glycol 1,2-Ethanediol Production Ethylene alcohol Hypodicarbonous acid Monoethylene glycol Industrial routes 1,2-Dihydroxyethane Ethylene glycol is produced from ethylene (ethene), via the Identifiers intermediate ethylene oxide. Ethylene oxide reacts with water to CAS Number 107-21-1 (http produce ethylene glycol according to the chemical equation: s://commonche mistry.cas.org/d C2H4O + H2O → HO−CH2CH2−OH etail?cas_rn=10 7-21-1) 3D model (JSmol) Interactive This reaction can be catalyzed by either acids or bases, or can occur image (https://ch at neutral pH under elevated temperatures. The highest yields of emapps.stolaf.e ethylene glycol occur at acidic or neutral pH with a large excess of du/jmol/jmol.ph water. Under these conditions, ethylene glycol yields of 90% can be p?model=OCC achieved. The major byproducts are the oligomers diethylene glycol, O) triethylene glycol, and tetraethylene glycol. The separation of these oligomers and water is energy-intensive. About 6.7 million tonnes 3DMet B00278 (http://w are produced annually.[4] ww.3dmet.dna.af frc.go.jp/cgi/sho A higher selectivity is achieved by use of Shell's OMEGA process.
    [Show full text]
  • Preferential Synthesis of Ethanol from Syngas Via Dimethyl Oxalate Hydrogenation Over an Integrated Catalyst Chemcomm Chemical Communications Rsc.Li/Chemcomm
    Showcasing research from Professor Yujun Zhao’s laboratory As featured in: at Tianjin University, Tianjin, China. Volume 55 Number 39 14 May 2019 Pages 5527–5672 Preferential synthesis of ethanol from syngas via dimethyl oxalate hydrogenation over an integrated catalyst ChemComm Chemical Communications rsc.li/chemcomm The cooperation of Fe5 C2 and CuZnO–SiO2 remarkably inhibited the formation of byproducts, resulting in a significantly high ethanol yield of about 98%. It opens a new route for the preferential synthesis of ethanol from syngas via hydrogenation of dimethyl oxalate. ISSN 1359-7345 COMMUNICATION Ying He et al . Enantioselective iridium catalyzed α-alkylation of azlactones by a tandem asymmetric allylic alkylation/aza-Cope rearrangement See Yujun Zhao et al ., Chem . Commun ., 2019, 55 , 5555. rsc.li/chemcomm Registered charity number: 207890 ChemComm COMMUNICATION Preferential synthesis of ethanol from syngas via dimethyl oxalate hydrogenation over an Cite this: Chem. Commun., 2019, 55, 5555 integrated catalyst† Received 27th March 2019, Accepted 11th April 2019 Xin Shang, Huijiang Huang, Qiao Han, Yan Xu, Yujun Zhao, * Shengping Wang and Xinbin Ma DOI: 10.1039/c9cc02372k rsc.li/chemcomm An integrated catalyst that contains Fe5C2 and CuZnO–SiO2 with a (B553 K) is necessary for the synthesis of ethanol via DMO hydro- dual-bed configuration was designed for the preferential synthesis of genation, the formation of C3–4OH via the Guerbet reaction would ethanol via dimethyl oxalate hydrogenation. The cooperation of the two be highly facilitated by the surface basic sites on the Cu-based catalyst components remarkably inhibited the formation of various catalysts.17 Li’s group18 achieved a high ethanol yield of 95% by byproducts, resulting in a significantly high ethanol yield of about 98%.
    [Show full text]
  • Octadecenoic Acid
    SAFETY DATA SHEET In accordance with 453/2010 and 1272/2008 (All references to EU regulations and directives are abbreviated into only the numeric term) Issued 2015-06-04 SECTION 1: IDENTIFICATION OF THE SUBSTANCE/MIXTURE AND OF THE COMPANY/UNDERTAKING 1.1. Product identifier Dimethyl Oxalate Trade name 1.2. Relevant identified uses of the substance or mixture and uses advised against Identified uses Laboratory chemicals 1.3. Details of the supplier of the safety data sheet Company Larodan AB Karolinska Institutet Science Park Retzius väg 8 SE-171 65 SOLNA Sweden Telephone +46 20 15 22 00 E-mail [email protected] Website www.larodan.com 1.4. Emergency telephone number In case of emergency contact toxicological information, emergency tel 112 (within Europe) or 1-800-222-1222 (for USA). For other countries, use the built-in emergency number in your cell phone For non-emergency poison information, see http://www.who.int/gho/phe/chemical_safety/poisons_centres/en/ SECTION 2: HAZARDS IDENTIFICATION 2.1. Classification of the substance or mixture Classification in accordance with 1272/2008 Upon assessment, this substance is not classified as hazardous according to 1272/2008. 2.2. Label elements Label information in accordance with 1272/2008 Hazard pictograms Not applicable Signal words Not applicable Hazard statements Not applicable 2.3. Other hazards Not relevant. SECTION 3: COMPOSITION/INFORMATION ON INGREDIENTS This product is composed of a pure or almost pure substance. 3.1. Substances Synonyms Ethanedioic acid, 1,​2-​dimethyl ester Chemical formula C4H6O4 Molecular weight 118.09 Constituent Purity DIMETHYL OXALATE >98% CAS No 553-90-2 Occurrence of any impurity, stabilising additive, or individual ingredients other than the main ingredient is indicated by the chemical name and the purity level.
    [Show full text]
  • Palladium Supported Catalysts in CO + RONO Reactions by X.-Z
    Palladium Supported Catalysts in CO + RONO Reactions By X.-Z. Jiang Department of Chemistry, University of Zhejiang, Hangzhou, P. R. China In the past decade much effort has been This article is a summary of our recent studies directed towards the synthesis of dialkyl oxalates on palladium supported catalysts in CO + and dialkyl carbonates directly from carbon MeONO (or EtONO) reactions at atmospheric monoxide and alcohols over palladium supported pressure in the vapour phase (6 - 8). It was found catalysts, under mild reaction conditions (I -4). that the carbonylation reactions of RONO, Although the mechanism of the reactions has not where R represents a methyl or ethyl group, been fully elucidated, the key reactions can be were very sensitive to the support, and that the illustrated by the following equations: main product was particularly dependent on the ,0-R nature of the support, as illustrated in Figure I. CO + 2RONO O=C + 2NO (i) -. Monocarbonylation ‘0- R 0 = C-OR The monocarbonylation of methanol or ethanol 2CO + 2RONO- I + 2NO (ii) can be achieved by introducing the correspon- 0 = C-0-R ding nitrites (methyl nitrite, MeONO, with b.p. (where R represents an alcohol residue). -12OC, or ethyl nitrite, EtONO, with b.p. The conditions required for these chemical 17OC) which were prepared according to reactions to take place are quite mild; for exam- established procedures (9). The nitrite was then ple, dimethyl or diethyl carbonate and oxalate able to react directly with carbon monoxide to can be efficiently prepared in the vapour phase form dimethyl carbonate or diethyl carbonate by bringing carbon monoxide into contact with over fured catalyst beds of palladium supported methyl nitrite or ethyl nitrite, respectively, on on active carbon catalysts, in the gas phase and a palladium fixed bed catalyst, at atmospheric at atmospheric pressure.
    [Show full text]
  • Recent Developments in Homobimetallic Reagents and Catalysts for Organic Synthesis
    Review Organic Chemistry June 2011 Vol.56 No.17: 1753–1769 doi: 10.1007/s11434-011-4470-7 SPECIAL TOPICS: Recent developments in homobimetallic reagents and catalysts for organic synthesis WU Wei, GU DeLiang, WANG ShiMeng, NING YingNan & MAO GuoLiang* Provincial Key Laboratory of Oil and Gas Chemical Technology, College of Chemistry and Chemical Engineering, Northeast Petroleum University, Daqing 163318, China Received September 13, 2010; accepted November 4, 2010; published online May 10, 2011 Organometallics are a family of useful organic chemicals because they play important roles in organic synthesis as reagents and as catalysts. They can be classified according to the number of metals they contain. Bimetallic compounds are important or- ganometallics and they are either homobimetallic or heterobimetallic depending on whether the two metals are the same or dif- ferent. In this paper, we focus on homobimetallic compounds. Homobimetallic compounds are generally used as dianions to react with electrophiles in organic synthesis. Recently, homobimetallics have also been used as catalysts in organic reactions such as in asymmetric reactions. homobimetallics, reagent, catalyst, synthesis, application Citation: Wu W, Gu D L, Wang S M, et al. Recent developments in homobimetallic reagents and catalysts for organic synthesis. Chinese Sci Bull, 2011, 56: 1753−1769, doi: 10.1007/s11434-011-4470-7 1 Homobimetallic reagents for organic um exchange, transmetalation reactions, carbon-heteroatom synthesis bond cleavage and the lithiation of multiple carbon-carbon bonds, etc. [3]. Homobimetallic reagents can be classified according to the relative positions of the two carbon atoms that bear the 1.1 1,1-Bimetallic compounds metal atoms.
    [Show full text]
  • Hydrogenation of Dimethyl Oxalate to Ethylene Glycol Over Silica Supported Copper Catalysts
    University of South Carolina Scholar Commons Theses and Dissertations Fall 2020 Hydrogenation of Dimethyl Oxalate to Ethylene Glycol Over Silica Supported Copper Catalysts Xinbin Yu Follow this and additional works at: https://scholarcommons.sc.edu/etd Part of the Chemical Engineering Commons Recommended Citation Yu, X.(2020). Hydrogenation of Dimethyl Oxalate to Ethylene Glycol Over Silica Supported Copper Catalysts. (Doctoral dissertation). Retrieved from https://scholarcommons.sc.edu/etd/6129 This Open Access Dissertation is brought to you by Scholar Commons. It has been accepted for inclusion in Theses and Dissertations by an authorized administrator of Scholar Commons. For more information, please contact [email protected]. HYDROGENATION OF DIMETHYL OXALATE TO ETHYLENE GLYCOL OVER SILICA SUPPORTED COPPER CATALYSTS by Xinbin Yu Bachelor of Science Ningxia University, 2012 Master of Science Tianjin University, 2015 Submitted in Partial Fulfillment of the Requirements For the Degree of Doctor of Philosophy in Chemical Engineering College of Engineering and Computing University of South Carolina 2020 Accepted by: Christopher T. Williams, Major Professor John R. Monnier, Committee Member Andreas Heyden, Committee Member Aaron K. Vannucci, Committee Member Cheryl L. Addy, Vice Provost and Dean of the Graduate School © Copyright by Xinbin Yu, 2020 All Rights Reserved. ii DEDICATION I would like to dedicate this work to my family. iii ACKNOWLEDGEMENTS I would like to thank my family for encouraging and supporting me to pursue PhD degree abroad. I also would like to thank my advisor for giving me valuable suggestions in the research and thank national science foundation and industrial companies for sponsoring the research. I would like to thank my committee members for giving me a lot of valuable help and inspiring feedbacks and attending my defense.
    [Show full text]
  • ||||||||||||III USOO5292.917A United States Patent (19) (1) Patent Number: 5,292,917 Nishihira Et Al
    ||||||||||||III USOO5292.917A United States Patent (19) (1) Patent Number: 5,292,917 Nishihira et al. 45 Date of Patent: Mar. 8, 1994 54 PROCESS FOR PURIFYING DIMETHYL 58) Field of Search ......................................... 558/277 CARBONATE 56 References Cited 75 Inventors: Keigo Nishihira; Shinichi Yoshida; Shuji Tanaka, all of Ube, Japan U.S. PATENT DOCUMENTS 4,467,109 8/1984 Tahara et al. ....................... 560/193 73) Assignee: Ube Industries, Ltd., Yamaguchi, Japan 4,663,477 5/1987 Crandall et al. .................... 560/204 Primary Examiner-Mary C. Lee 21 Appl. No.: 56,891 Assistant Examiner-Michael Ambrose 22 Filed: May 5, 1993 Attorney, Agent, or Firn-Finnegan, Henderson, Farabow, Garrett & Dunner Related U.S. Application Data 57 ABSTRACT 63 Continuation of Ser. No. 837,881, Feb. 9, 1992. Disclosed a process for purifying dimethyl carbonate (30) Foreign Application Priority Data which comprises distillating a mixture of dimethyl car bonate and methanol in the presence of dimethyl oxa Feb. 26, 1991 (JP Japan .................................. 2-053148 late to separate and remove methanol. 51) int. Cli.............................................. CO7C 69/96 52 U.S.C. .................................................... 558/277 4 Claims, 1 Drawing Sheet U.S. Patent Mar. 8, 1994 5,292,917 F. G. ... O O.9 | | | | | | U-2 O. 8 | | | | I-4-31 O.7 | || 424 y O.6 41 || 4 || O.5 4 || 4 || | O. 4 /YA/P | 14 | ||| | ||| | | O.3 // 1 | | | | | | O.2 //1 || | | | | | O. 4 || | | | | || O O O. O.2 O.3 O.4 O5 O.6 O.7 O.8 O.9 1.O X o Without addition of dimethyl oxalate O Addition of dimethyl oxalate F.
    [Show full text]
  • Coal to Desired Fuels and Chemicals
    Coal to Desired Fuels and Chemicals Maohong Fan SER Professor in the Department of Chem. & Petroleum Eng. UNIVERSITY OF WYOMING 2-4-2013 [email protected] Phone: (307) 766 5633 1 I’m dirty I’m sticky I’m smelly Oil Coal Without me, life isn’t easy! I’m picky I’m rusty I’m sneaky Trona Iron ore Rare earth Maohong Fan’s Research Group UW’s Clean Coal Technology Development Map CO + small amout of CH CO 2 4 H2 IGCC Electric Dried coal impregnated Separation Power with catalysts Light tar separation Catalytic pyrolysis (note: One of the (into naphthalene, 1‐ objectives is to minimize Synthetic mode in the same naphthaleneacetic Urea Feed gases: CO2 + ammonia reactor CH4 production in acid, anthracene, limited O2 DME pyrolyis and gasification phenol, diesel modes) Olefins High‐value Synthesis of Char/coke carbon based methanol H2O Chemicals 1st choice of feed gases: materials Synthesis conversion Gasoline CO2 + H :CO≈2 + near zero CH F‐Tsynthesis Catalytic gasification (converting the CO & H 2 4 limited O2 2 nd nd mode in the same obtained with 2 choice Jet/Diesel 2 choice of feed gases: CO2 reactor CO2 of feed gases) higher + CH4 (natural gas) alcohols limited O2 + H2O CO+CO2 CO + zero H + zero CH Cleaning & Catalytic CO coupling 2 4 Oxalic acid separating CO +CO2 (converting the CO obtained with 1st obtained with 1st choice choice of feed gases of feed gases) Ethylene Polyester glycol CO2 Ethanol Three Sample Projects to Be Presented Catalytic Coal Pyrolysis and Gasification ◦ Na-Fe based Syngas to liquids ◦ Ethylene glycol Environmental management
    [Show full text]
  • Safety Data Sheet
    SAFETY DATA SHEET Creation Date 17-May-2010 Revision Date 15-Jan-2021 Revision Number 4 SECTION 1: IDENTIFICATION OF THE SUBSTANCE/MIXTURE AND OF THE COMPANY/UNDERTAKING 1.1. Product identifier Product Description: Dimethyl oxalate Cat No. : A15359 Synonyms Methyl oxalate CAS-No 553-90-2 EC-No. 209-053-6 Molecular Formula C4 H6 O4 Reach Registration Number - 1.2. Relevant identified uses of the substance or mixture and uses advised against Recommended Use Laboratory chemicals. Uses advised against No Information available 1.3. Details of the supplier of the safety data sheet Company Thermo Fisher (Kandel) GmbH . Erlenbachweg 2 76870 Kandel Germany Tel: +49 (0) 721 84007 280 Fax: +49 (0) 721 84007 300 E-mail address [email protected] www.alfa.com Product safety Tel + +049 (0) 7275 988687-0 1.4. Emergency telephone number Carechem 24: +44 (0) 1235 239 670 (Multi-language emergency number) Poison Information Center Mainz www.giftinfo.uni-mainz.de Telephone: +49(0)6131/19240 Exclusively for customers in Austria: Poison Information Center (VIZ) Emergency call 0-24 clock: +43 1 406 43 43 Office hours: Monday to Friday, 8am to 4pm, tel: +43 1 406 68 98 SECTION 2: HAZARDS IDENTIFICATION 2.1. Classification of the substance or mixture CLP Classification - Regulation (EC) No 1272/2008 Physical hazards ______________________________________________________________________________________________ ALFAAA15359 Page 1 / 10 SAFETY DATA SHEET Dimethyl oxalate Revision Date 15-Jan-2021 ______________________________________________________________________________________________ Based on available data, the classification criteria are not met Health hazards Skin Corrosion/Irritation Category 2 (H315) Serious Eye Damage/Eye Irritation Category 2 (H319) Environmental hazards Based on available data, the classification criteria are not met Full text of Hazard Statements: see section 16 2.2.
    [Show full text]
  • Synthesis, Reactions and Biological Activity of Quinoxaline Derivatives
    American Journal of Organic Chemistry 2015, 5(1): 14-56 DOI: 10.5923/j.ajoc.20150501.03 Synthesis, Reactions and Biological Activity of Quinoxaline Derivatives Ameen Ali Abu-Hashem1,2,* 1Photochemistry Department (Heterocyclic Unit), National Research Centre, Giza, Egypt 2Chemistry Department, Faculty of Science, Jazan University, Saudi Arabia Abstract The review deals with synthesis and reactions of quinoxaline derivatives as well as their diverse pharmacological and biological properties. Quinoxalines and fused ring systems show diverse pharmacological activities. Syntheses of quinoxaline derivatives via many different methods of synthetic strategies have been presented. Keywords Quinoxalines, o-phenylenediamine, Oxidation, Nitration, Diazotization, Alkylation, Addition, Condensation, Cyclization, Substitutions reactions 1. Introduction 2.1. Antimicrobial Activity Quinoxaline-1, 4-di-N-oxide derivatives, Quinoxaline derivatives have different pharamacological pyrazoloquinoxalines and 2-[4-arylidene hydrazinocarbonyl) activities such as bacteriocides and insecticides [1], aniline]-3-methyl quinoxalines (274, 275, 276, 277, 278) antibacterial [2-5], antifungal [2, 6], antitubercular [2, 7-9, respectively have been identified as antibacterial, Antifungal 10], analgesic [4, 11] and anti-inflammatory [11, 12]. The agents and antimicrobial activity [2, 52, 53, 54, 55] as shown importance of quinoxaline derivatives comes from its in (Figure 2). nitrogen contents (heterocyclic compounds). A structure of ring fused with quinoxalines, display 2.2. Anti-Amoebic, Anti-Proliferative Activity diverse pharmacological activities (antibacterial, anticancer 2-(5-substituted-3-phenyl-2-pyrazolinyl)-1, 3-thiazolino and antiviral) [13, 14], antimalarial [15, 16] and anti- [5, 4-b] quinoxaline 279 was tested in vitro as anti-amoebic depressant activities [17]. Quinoxaline-diones derivatives activity against strain of (E. histolytica) [56].
    [Show full text]
  • A Sustainable Process Design to Produce Diethyl Oxalate Considering
    Computers and Chemical Engineering 115 (2018) 198–212 Contents lists available at ScienceDirect Computers and Chemical Engineering journal homepage: www.elsevier.com/locate/compchemeng A sustainable process design to produce diethyl oxalate considering NO x elimination ∗ Jiaxing Zhu 1, Lin Hao 1, Yaozhou Sun, Bo Zhang, Wenshuai Bai, Hongyuan Wei School of Chemical Engineering and Technology, Tianjin University, Tianjin, China a r t i c l e i n f o a b s t r a c t Article history: Diethyl oxalate (DEO) is widely used in fine chemical industry. In comparison with traditional esterifica- Received 15 December 2017 tion process, carbon monoxide coupling process is a novel routine for DEO production. This environmen- Revised 20 March 2018 tally friendly process provides better selectivity and yield. Its unique feature is that a closed regeneration- Accepted 2 April 2018 coupling circulation is formed. Toxic byproduct-nitric oxide (NO) from coupling reaction is recycled to Available online 10 April 2018 re-produce ethyl nitrite through regeneration reaction. This avoids significant amount of NO x emission. Keywords: However, due to a few NO x emission, a contaminant handling system is applied for environmental pro- Design tection. A systematical environmental analysis is also carried out to assess this process. Regeneration- Diethyl oxalate coupling circulation brings interaction behaviors and some trade-offs including reactor size and recycle NOx emission flowrate, regeneration and coupling reaction, loss of reactants and NO emission. Thus, a rigorous steady Contaminant handling system simulation is established to investigate these trade-offs. Then DEO process is optimized to obtain the Systematical environmental analysis optimal design.
    [Show full text]