DOCSLIB.ORG

Acrylic Acid Obtaining by Acetic Acid Catalytic Condensation With

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Acrylic Acid Obtaining by Acetic Acid Catalytic Condensation With Восточно-Европейский журнал передовых технологий ISSN 1729-3774 6/6 ( 66 ) 2013 UDC 541.128.13 Досліджено процес одержання акрилової кис- лоти методом альдольної конденсації оцтової кис- лоти з формальдегідом на B2O3–P2O5–WO 3/SiO2 ACRYLIC ACID каталізаторі в газовій фазі. Показано перспективність даного методу як такого, що OBTAINING BY ACETIC не потребує використання сировини нафтового походження. Встановлено вплив температури та ACID CATALYTIC часу контакту на процес конденсації; визначено оптимальні умови його здійснення CONDENSATION WITH Ключові слова: акрилова кислота, гетероген- ний каталіз, газова фаза, альдольна конденсація, FORMALDEHYDE акрилатні мономери R. Nebesnyi Исследован процесс получения акриловой кис- PhD* лоты методом альдольной конденсации уксусной Е-mail: nebesnyi@ukr.net кислоты с формальдегидом на B O -P O -WO / 2 3 2 5 3 V. Ivasiv SiO катализаторе в газовой фазе. Показана пер- 2 PhD* спективность данного метода как такого, кото- Е-mail: el.spectre.x@gmail.com рый не требует использования сырья нефтяного происхождения. Установлено влияние темпера- Y. Dmytruk туры и времени контакта на процесс конденсации, Postgraduate student* определены оптимальные условия его осуществле- Е-mail: yulia.nu.lp@gmail.com ния N. Lapychak* Ключевые слова: акриловая кислота, гетеро- Е-mail: mycarpathians@gmail.com генный катализ, газовая фаза, альдольная конден- *Technology of Organic Products Department сация, акрилатные мономеры Lviv Polytechnic National University S. Bandery st., 12, Lviv, Ukraine, 79013 1. Introduction production by AcA aldol condensation with FA has fair im- plementation prospects. Acrylic acid (АA) is a valuable organic synthesis product The great interest of chemical products manufacturers in having wide application in production of high-quality polymer the implementation of condensation processes by carbonyl materials, super sorbents, paint-and-varnish materials etc. group is related to the possibility of acrylic monomers proh- Wide application of AA and its derivatives causes annual duction in low number of stages [6]. In addition, advantages expansion of AA production capacity. The latter reaches over of AA obtaining by condensation method include: 4.5 million ton per year to date. Main industrial method of AA - expanding of raw materials base for the synthesis of production is propylene oxidation. However, the expedience of AA and the possibility to avoid using of oil-derived raw propylene use as raw material is directly related to petroleum materials. It is known that in industry FA and AcA are and oil products availability in certain region and to the costs synthesized from methanol produced from synthesis gas, for them persistently trending to grow. Besides, when AA and a feedstock for synthesis gas obtaining is methane or is produces by propylene oxidation, great number of various coal. Considering the much larger global reserves of methane oxidation by-products, in particular CO and CO2, is formed and coal compared to oil, the use of these raw materials for [1]. That is why development and improvement of alternative organic synthesis is more promising; AA production methods is very topical. - more complete utilization of raw materials. This is achieved by the higher selectivity of the desired product formation. 2. Problem statement However, industrial production of unsaturated acids, in particular AA, by carbonyl compounds aldol condensation The most promising AA production methods include: method has not been set up, because of low efficiency of the 1) AA synthesis from renewable raw materials using process catalyst known. enzymes [2]; 2) AA synthesis by direct propane oxidation [3]; 3) AA synthesis by acetic acid (AcA) aldol condensation 3. Latest research review with formaldehyde (FA) [4]. The main disadvantage of the enzymatic AA production In scientific and technical literature there are much in- method is considerable process duration [5] negatively af- formation about AA gas-phase production when using both fecting the reaction equipment productivity. Direct propane basic [7] and acidic catalysts [8]. However, most of them oxidation to AA has very low target product formation provide high conversion of AcA and FA only in case of con- selectivity [3]. Among listed methods the method of AA siderable excess of one of the reactants. 40 R. Nebesnyi, V. Ivasiv, Y. Dmytruk, N. Lapychak, 2013 Технологии органических и неорганических веществ In our earlier researches it has been determined that the 683 К and contact time 8 sec. the least AA formation selec- B2O3–P2O5/SiO2 catalyst promoting by transition metals tivity is 74.7 %, while MAA formation selectivity under the oxides allows achieving high conversion of propionic acid same conditions is only 32.4 % [11]. (PA) and FA to the methacrylic acid (MAA) production process even at equimolar ratio of the reactants [9, 10]. The S, % catalytic system B2O3–P2O5–WO3/SiO2 is most efficient 100 563 among developed ones in methacrylic acid production by 593 623 aldol condensation [10]. 90 653 80 683 4. Optimal conditions of the process determination 70 The present study is aimed on determination of main regularities of AcA aldol condensation with FA to AA on the 60 B2O3–P2O5–WO3/SiO2 catalyst. The catalytic systems based on mixtures of boron, 50 phosphorus and tungsten oxides with different components 40 ratios have been prepared for the research. All catalysts 0 5 10 15 20 were prepared by impregnation method. Silica was used as t, sec a support. The catalytic properties of the developed catalysts were studied in flow setup with fixed-bed catalyst. Fig. 2. Contact time t effect on acrylic acid formation Formalin obtained from paraformaldehyde immediately selectivity S; temperature is 563 – 683 K before usage was used as a FA source. The process was carried out at temperature ranged from The contact time effect on AA yield is similar to its effect 563 to 683 К and contact time ranged from 2 to 16 sec at on AcA conversion. As is clear from Fig. 3, the rapid increase equimolar initial reagents ratio. The reaction products were of the product yield is observed until contact time reaches analyzed by chromatography. 4 sec. hereafter until 8 sec. the yield increases more gradually. As is shown on Fig. 1, when increasing contact time AcA, The further contact time increase over 8 sec. virtually does conversion substantially increases until the contact time val- not lead to AA yield increase due to the insignificant ue is 8 sec. Further contact time increase has almost no effect AcA conversion increase under these conditions. So, 8 sec. on AcA conversion. When raising the process temperature, may be considered to be the optimal contact time of AcA AcA conversion rapidly increases reaching maximal value – condensation with formaldehyde on the studied catalyst. It 65.8 % at contact time of 16 sec. is also clear from Fig. 3 that 653 К is the optimal temperature in terms of AA yield. 70 X, % 16 Y, % 12 8 60 60 4 653 50 50 683 2 623 40 40 593 30 30 563 20 20 10 10 0 533 563 593 623 653 683 713 0 0 4 8 12 16 20 T, K t, sec Fig. 1. Temperature T and contact time effect on acetic acid conversion X; contact time is 2-16 sec Fig. 3. Contact time t effect on acrylic acid yield Y; temperature is 563 – 683 К The contact time dependence of AA formation selectivity is shown on Fig. 2. There is almost no effect of contact time When comparing the experimental results of the FA on AA formation selectivity in the whole studied temperature condensation with PA and AcA, it becomes clear that AA range. The process temperature decrease results in the target yield is higher than MAA yield [11]. It is because of the product formation selectivity increase. higher selectivity of the target product formation in case The higher selectivity values, namely 92.5 – 96.1 %, are of AcA, that allows carrying out the process at higher tem- observed in the temperature range 563 – 623 К. it should be perature, at which the reactants conversion is considerably noted that at high temperatures of AcA condensation with higher. FA the unsaturated acid formation selectivity is considerably Thus, the research showed that the catalytic system higher than in case of PA condensation with FA 11[ ]. Thus, at B2O3 – P 2O5 – WO 3/SiO2 is efficient in FA condensation 41 Восточно-Европейский журнал передовых технологий ISSN 1729-3774 6/6 ( 66 ) 2013 with AcA. Using of the developed catalyst under the op- 6. Acknowledgement timal conditions (temperature 653 К, contact time 8 sec.) allows to achieve AA yield equal to 50.6 %, while AA for- The work was supported by the Grant of President of mation selectivity is 88.8 % and AcA conversion is 57.0 %. Ukraine for young scientists (GP/F49/149). When recycling the unreacted AcA and FA, the AA yield would be 88.8 %. 7. Conclusions 5. Results approbation The B2O3–P2O5–WO3/SiO2 catalyst use in AcA aldol condensation with FA allows AA obtaining with selectivity – The method of AA acid obtaining by AcA aldol 88,0 %, single-pass yield – 50,6 % and AcA conversion – 57,0 % condensation with FA when using the catalyst developed at equimolar reactants ratio. Acrylic acid production by the by us has not been industrially implemented to date. But aldol condensation method would enable diversifying the in prospect it may be used for acrylic and methacrylic acid raw materials base of acrylic monomers production. High production from ethylene at operating ethylene producing efficiency of the developed catalyst confirms the expedience plants, in particular at „Karpatnaftokhim” Ltd., Kalush, of the method as an alternative. Ivano-Frankivsk region. References 1. Method for production of acrolein and acrylic acid from propylene [Text]: patent 6545178 US / Michio Tanimoto, Daisuke Nakamura, Tatsuya Kawajiri; assignee: Nippon Shokubai Co., Ltd. (Osaka, JP). – № 314719/09 filing date: 18.05.1999; publication date: 08.04.2003.
Load more

Recommended publications
  • Acid-Base Properties, Deactivation, and in Situ Regeneration of Condensation Catalysts for Synthesis of Methyl Methacrylate
    ACID-BASE PROPERTIES, DEACTIVATION, AND IN SITU REGENERATION OF CONDENSATION CATALYSTS FOR SYNTHESIS OF METHYL METHACRYLATE MAKARAND R. GOGATE', JAMES J. SPIVEY', AND JOSEPH R. ZOELLER2 'Research Triangle Institute, 3040 Cornwallis Road, RTP, NC 27709-2 194 2Eastman Chemical Company, Kingsport, TN, 37662-5 150 ABSTRACT Condensation reaction of a propionate with formaldehyde is a novel route for synthesis of methyl methacrylate (MMA). The reaction mechanism involves a proton abstraction from the propionate on the basic sites and activation of the aliphatic aldehyde on the acidic sites of the catalyst. The acid-base properties of ternary V-Si-P oxide catalysts and their relation to the MMA yield in the vapor phase condensation of formaldehyde with propionic anhydride has been studied for the first time. Five different V-Si-P catalysts with different atomic ratios of vanadium, silicon, and phosphorous were synthesized, characterized, and tested in a fixed-bed microreactor system. A V-Si-P 1:10:2.8 catalyst gave the maximum condensation yield of 56% based on HCHO fed at 300 "C and 2 atm and at a space velocity of 290 cc/g cateh. A parameter called the "q-ratio" has been defined to correlate the condensation yields to the acid-base properties. The correlation of q-ratio with the condensation yield shows that higher q-ratios are more desirable. The long-term deactivation studies on the V-Si-P 1: 10:2.8 catalyst at 300 "C and 2 atm and at a space velocity of 290 cc/g cat-h show that the catalyst activity drops by a factor of nearly 20 over a 180 h period.
    [Show full text]
  • Submitted To
    I 1 RTI PROJECT NO. 9611-6048 DOE Contract No. DE-AC22-94PC94065 January 1,1995 through March 31,1995 SYNTHESIS OF ACRYLATES AND METHACRLYATES FROM COAL-DERIVED SYNGAS Quarterly Technical Progress Report Submitted to US. Department of Energy Pittsburgh Energy Technology Center P. 0. Box 10940 Pittsburgh, Pennsylvania 15236-0940 Submitted by Research Triangle Institute P. 0. Box 12194 Research Triangle Park, NC 27709 DOE COR: Richard E. Tischer RTI Project Manager: James J. Spivey DISCLAIMER This report was prepared as an account of work sponsored by an agency of the United States Government. Neither the United States Government nor any agency thereof, nor any of their employees, makes any warranty, express or implied, or assumes any legal liability or responsi- bility for the accuracy, completeness, or usefulness of any information, apparatus, product, or process disclosed, or represents that its use would not infringe privately owned rights. Refer- ence herein to any specific commercial product, process, or service by trade name, trademark, manufacturer, or otherwise does not necessarily constitute or imply its endorsement, recom- mendation, or favoring by the United States Government or any agency thereof. The views and opinions of authors expressed herein do not necessarily state or reflect those of the DiCJTRlBfllQN THIS DOWMENT mm United States Government or any agency thereof. OF %”/ - DISCLAIMER Portions of this document may be illegible in electronic image products. Images are produced from the best available original document. Executive Summary Task 1-Synthesis of Propionates The objective of this Task is to develop the technology for the synthesis of low-cost propionates.
    [Show full text]
  • The Effect of Cation Type and H+ on the Catalytic Activity of the Keggin Anion [Pmo12o40]3- in the Oxidative Dehydrogenation Of
    Journal of Catalysis 195, 360–375 (2000) doi:10.1006/jcat.2000.2987, available online at http://www.idealibrary.com on The Effect of Cation Type and H+ on the Catalytic Activity 3 of the Keggin Anion [PMo12O40] in the Oxidative Dehydrogenation of Isobutyraldehyde Ji Hu and Robert C. Burns1 School of Biological and Chemical Sciences, The University of Newcastle, Callaghan 2308, Australia Received March 23, 2000; revised July 4, 2000; accepted July 5, 2000 such as the oxidative dehydrogenation of isobutyric acid The oxidative dehydrogenation of isobutyraldehyde to metha- and the oxidation of methacrolein, both of which yield 3 crolein over [PMo12O40] -containing catalysts has been shown to methacrylic acid (1–5). Methacrylic acid is, in turn, reacted proceed through bulk catalysis-type II, which depends on the rates with methanol to yield methyl methacrylate, an extremely + of diffusion of the redox carriers (H and e ) into the catalyst bulk. important acrylic monomer, which is then polymerized to Variations in catalyst behaviour have been shown to change with give poly(methyl methacrylate). Heteropolyoxometalates the countercation and appear to be related to the polarizing abil- are also active acid catalysts, and processes based both on ity of the cation, which can be represented by the ionic potential their redox and acid–base properties have found commer- (charge/ionic radius). This, in turn, may indicate that the active 3 cial applications (3–5). site at the [PMo12O40] ion is close to an attendant countercation. For the alkali metal ions Li+,Na+,K+,Rb+, and Cs+ as well as the The study of heteropolyoxometalates as oxidation– (isoelectronic) ions of the series Cs+,Ba2+,La3+, and Ce4+, the stud- reduction catalysts has involved primarily Keggin-based 3 ies have shown that conversion generally decreases with increasing structures, principally [PMo12O40] , as well as substi- ionic potential, while selectivity to methacrolein is less affected by tuted species involving replacement of one or more changes in this property.
    [Show full text]
  • Design and Optimization of a Process for the Production of Methyl Methacrylate Via Direct Methylation
    processes Article Design and Optimization of a Process for the Production of Methyl Methacrylate via Direct Methylation Taotao Liang 1,2, Xiaogang Guo 2,3,*, Abdulmoseen Segun Giwa 1,4, Jianwei Shi 3, Yujin Li 3, Yan Wei 3, Xiaojuan Wang 5, Xuansong Cao 3, Xiaofeng Tang 3 and Jialun Du 3 1 Green Intelligence Environmental School, Yangtze Normal University, Chongqing 408003, China; liangtaotao2018@foxmail.com (T.L.); giwasegun25@yahoo.com (A.S.G.) 2 Faculty of Materials and Energy, Southwest University, Chongqing 400715, China 3 College of Chemistry and Chemical Engineering, Yangtze Normal University, Chongqing 408003, China; sjwyznu@foxmail.com (J.S.); weihezong@foxmail.com (Y.L.); wwwei9840@foxmail.com (Y.W.); caoxuansong@foxmail.com (X.C.); ql_06@foxmail.com (X.T.); dujialun0209@foxmail.com (J.D.) 4 State Key Joint Laboratory of Environment Simulation and Pollution Control, School of Environment, Tsinghua University, Beijing 100084, China 5 College of chemistry and bioengineering, Guilin University of Technology, Guilin 541004, China; wangxiaojuan0117@163.com * Correspondence: guoxiaogang@yznu.edu.cn; Tel.: +86-023-72782170 Received: 25 April 2019; Accepted: 6 June 2019; Published: 18 June 2019 Abstract: Methyl methacrylate (MMA) plays a vital role in national productions with broad application. Herein, the production of MMA is realized by the improved eco-friendly direct methylation method using Aspen Plus software. Three novel kinds of energy-saving measures were proposed in this study, including the recycle streams of an aqueous solution, methacrolein (MAL), and methanol, the deployment of double-effect distillation instead of a normal one, and the design of a promising heat-exchange network.
    [Show full text]
  • PATENT OFFICE 2,101,820 PROCESS for the PREPARATION of POLYMERIZABLE UNSATURATED COM POUNDS John C
    Patented Dec. 7, 1937 2,101,820 UNITED STATES PATENT OFFICE 2,101,820 PROCESS FOR THE PREPARATION OF POLYMERIZABLE UNSATURATED COM POUNDS John C. Woodhouse, Wilmington, Del, assignor to E. I. du Pont de Nemours & Company, Will mington, Del, a corporation of Delaware No Drawing. Application December 5, 1933, Serial No. 701,053 10 Claims. (Cl. 260-106) This invention relates to a process for the prep included under the term aryl include benzyl, aration of unsaturated polymerizable organic naphthyl, and analogous aryl compounds. It will compounds and more particularly to the prepara be appreciated by those skilled in this art that tion of Such compounds from Saturated organic altho the Substitutions in the X and Y positions 5 compounds containing an isopropyl radical at Will alter the reaction rates and in many in 5 tached to a carbonyl group which likewise carries stances the by-products resulting from the de a hydrogen, hydroxy, aryl, or aralkyl group. hydrogenation, these substitutions are to be given An object of the present invention is to provide but secondary consideration for, generally speak an improved process for the preparation of poly ing, if the compound to be dehydrogenated has the O merizable unsaturated aliphatic and/or aromatic basic formula 10 organic compounds. Another object of the in vention is to provide an improved process for the chi-qi- - O preparation of esters of the unsaturated mono it may be dehydrogenated to an unsaturated poly carboxylic aliphatic organic acids. Another ob merizable compound. ject of the invention is to provide an improved The compounds containing an isobutyryl group, 15 process for the preparation of methacrylic acid.
    [Show full text]
  • Methacrylic Acid, CAS No. 79-41-4; March 1996ECETOC (1995A): Joint Assessment of Commodity Chemicals, Methacrylic Acid, CAS No
    N port O N N COMMISSIO 837 E INT RESEARCH CENTRE lic acid OH 3 EINECS No: 201-204-4 EUR 19 EUROPEA JO y CH methacr C 2 H CAS No: 79-41-4 European Union Risk Assessment Re Protection 25 : Substances Priority List st European Institute for Health and Consumer 1 Bureau Chemicals Existing Volume European Chemicals Bureau European Union Risk Assessment Report CAS: 79-41-4 EC: 201-204-4 methacrylic acid 25 PL-1 European Union Risk Assessment Report METHACRYLIC ACID CAS No: 79-41-4 EINECS No: 201-204-4 RISK ASSESSMENT LEGAL NOTICE Neither the European Commission nor any person acting on behalf of the Commission is responsible for the use which might be made of the following information A great deal of additional information on the European Union is available on the Internet. It can be accessed through the Europa Server (http://europa.eu.int). Cataloguing data can be found at the end of this publication Luxembourg: Office for Official Publications of the European Communities, 2002 ISBN 92-894-1273-9 © European Communities, 2002 Reproduction is authorised provided the source is acknowledged. Printed in Italy METHACRYLIC ACID CAS No: 79-41-4 EINECS No: 201-204-4 RISK ASSESSMENT Final Report, 2002 Germany The risk assessment of methacrylic acid (MAA) has been prepared by Germany on behalf of the European Union. Contact point: Bundesanstalt für Arbeitsschutz und Arbeitsmedizin Anmeldestelle Chemikaliengesetz (BAuA) (Federal Institute for Occupational Safety and Health Notification Unit) Friedrich-Henkel-Weg 1-25 44149 Dortmund Germany Fax: +49 (231) 9071-679 e-mail: chemg@baua.bund.de Date of Last Literature Search: 1995 Review of report by MS Technical Experts finalised: 1999 Final report: 2002 (The last full literature survey was carried out in 1995 - targeted searches (for example on grouting) were carried out subsequently, and information found through scanning certain sources has also been included).
    [Show full text]
  • Methycryolic Acid and Esters, Supp. A
    Report No. 11 A METHACRYLIC ACID METHACRYLIC ESTERS Supplement A by DONALD C. THOMAS Contributions by Brij M. Sood and Leslie A. Carmichael May 1974 A private report by the PROCESS ECONOMICS PROGRAM I STANFORD RESEARCH INSTITUTE MENLO PARK, CALIFORNIA I - - CONTENTS 1 INTRODUCTION . 1 2 SUMMARY................,.......... 3 Methyl Methacrylate via Acetone Cyanohydrin . 5 Methyl Methacrylate from Isobutylene via Methacrylonitrile . 6 Methyl Methacrylate from Isobutylene via Methacrylic Acid . 7 3 COMPARISON OF PROCESSES . 9 4 INDUSTRY STATUS . 15 5 METHYL METHACRYLATE VIA ACETONE CYANOHYDRIN ......... 19 Review of Processes ..................... 19 Hydrogen Cyanide Production ................ 19 Acetone Cyanohydrin Production .............. 21 Hydrolysis and Esterification ............... 24 Recovery of Methyl Methacrylate .............. 25 Handling and Disposition of Ammonium Bisulfate ...... 26 Process Description ..................... 29 Hydrogen Cyanide Production ................ 29 Acetone Cyanohydrin Production .............. 32 Hydrolysis and Esterification ............... 33 Purification ....................... 34 Sulfuric Acid Regeneration ................ 34 Process Discussion ..................... 49 Waste Treatment ....................... 50 Cost Estimates ....................... 52 6 METHYL METHACRYLATE FROM ISOBUTYLENE VIA METHACRYLONITRILE ...................... 61 Review of Processes ..................... 61 Methacrylonitrile Production ............... 61 Treatment of Ammoxidation By-Products ........... 65 Hydrolysis and
    [Show full text]
  • Toxicological Review of Methyl Methacrylate
    TOXICOLOGICAL REVIEW of METHYL METHACRYLATE (CAS No. 80-62-6) In Support of Summary Information on the Integrated Risk Information System (IRIS) January 1998 U.S. Environmental Protection Agency Washington, DC TABLE OF CONTENTS DISCLAIMER ............................................................ i FOREWORD ............................................................ ii CONTRIBUTORS AND REVIEWERS ........................................ iii 1. INTRODUCTION ....................................................... 1 2. CHEMICAL AND PHYSICAL INFORMATION RELEVANT TO ASSESSMENTS . 2 3. TOXICOKINETICS/TOXICODYNAMICS RELEVANT TO ASSESSMENTS ........ 4 3.1. ABSORPTION ...................................................... 4 3.2. DISTRIBUTION .................................................... 4 3.3. METABOLISM ..................................................... 6 3.4. EXCRETION ...................................................... 8 4. HAZARD IDENTIFICATION ............................................. 10 4.1. STUDIES IN HUMANS ............................................. 10 4.1.1. Human Noncancer Studies ....................................... 10 4.1.2. Human Cancer Studies .......................................... 15 4.2. PRECHRONIC, CHRONIC, AND CANCER BIOASSAYS IN ANIMALS ...... 16 4.2.1. Acute Inhalation Studies ......................................... 16 4.2.2. Subchronic and Chronic Inhalation Studies ........................... 19 4.2.3. Acute Oral Studies ............................................. 26 4.2.4. Subchronic and
    [Show full text]
  • Properties and Interactions of Oral Structures and Restorative Materials
    1 NBSIR 80-2168 Properties and Interactions of Oral Structures and Restorative Materials James M. Cassel, J. A. Tesk, G. M. Brauer, J. M. Antonucci, W. Wu, J. E. McKinney, R. P. Whitlock, and R. Hinman Dental and Medical Materials Polymer Science and Standards Division Center for Materials Science National Measurement Laboratory National Bureau of Standards Washington, DC 20234 Annual Report for Period October 1, 1979 thru September 30, 1980 November 1980 Interagency Agreement YOI-DE-4001 5-1 — r ed for QO nal Institute of Dental Research 100 isda, MD 20014 . U56 80-2163 1980 Ci 2 I 1 . national bureau of standards NBSIR 80-2168 LIBRARY AUG 7 1981 PROPERTIES AND INTERACTIONS OF not dec - c; rc ORAL STRUCTURES AND RESTORATIVE CXcfdo MATERIALS no- %0'c5/6# James M. Cassel, J. A. Tesk, G. M. Brauer, J. M. Antonucci, W. Wu, J. E. McKinney, R. P. Whitlock, and R. Hinman mo Dental and Medical Materials Polymer Science and Standards Division Center for Materials Science National Measurement Laboratory National Bureau of Standards Washington, DC 20234 Annual Report for Period October 1, 1979 thru September 30, 1980 November 1980 Interagency Agreement YOI-DE-4001 5-1 Certain commercial materials and equipment are identified in this report to specify the experimental procedure. In no instance does such identification imply recommendation or endorsement by the National Bureau of Standards or that the materials and equipment identified are necessarily the best available for the purpose. Prepared for National Institute of Dental Research Bethesda, MD 20014 U S. DEPARTMENT OF COMMERCE, Philip M. Klutznick, Secretary Luther H.
    [Show full text]
  • Selective Oxidation of Isobutane to Methacrylic Acid and Methacrolein: a Critical Review
    catalysts Review Selective Oxidation of Isobutane to Methacrylic Acid and Methacrolein: A Critical Review Li Zhang ,Sébastien Paul , Franck Dumeignil * and Benjamin Katryniok * University Lille, CNRS, Centrale Lille, University Artois, UMR 8181–UCCS–Unité de Catalyse et Chimie du Solide, F-59000 Lille, France; li.zhang@centralelille.fr (L.Z.); sebastien.paul@centralelille.fr (S.P.) * Correspondence: franck.dumeignil@univ-lille.fr (F.D.); benjamin.katryniok@centralelille.fr (B.K.) Abstract: Selective oxidation of isobutane to methacrolein (MAC) and methacrylic acid (MAA) has received great interest both in the chemical industry and in academic research. The advantages of this reaction originate not only from the low cost of the starting material and reduced process complexity, but also from limiting the use of toxic reactants and the production of wastes. Successive studies and reports have shown that heteropolycompounds (HPCs) with Keggin structure (under the form of partially neutralized acids with increased stability) can selectively convert isobutane to MAA and MAC due to their strong and tunable acidity and redox properties. This review hence aims to discuss the Keggin-type HPCs that have been used in recent years to catalyze the oxidation of isobutane to MAA and MAC, and to review alternative metal oxides with proper redox properties for the same reaction. In addition, the influence of the main reaction conditions will be discussed. Keywords: Keggin-type HPCs; isobutane; oxidation; methacrolein; methacrylic acid Citation: Zhang, L.; Paul, S.; 1. Introduction Dumeignil, F.; Katryniok, B. Selective Hydrocarbons are generally issued from coal, oil, and natural gas. They are still the Oxidation of Isobutane to Methacrylic main feedstock of the chemical industry.
    [Show full text]
  • Mechanism of the Hydroxyl Radical Oxidation of Methacryloyl Peroxynitrate (Mpan) and Its Pathway Toward Secondary Organic Aerosol Formation in the Atmosphere
    335 Appendix C MECHANISM OF THE HYDROXYL RADICAL OXIDATION OF METHACRYLOYL PEROXYNITRATE (MPAN) AND ITS PATHWAY TOWARD SECONDARY ORGANIC AEROSOL FORMATION IN THE ATMOSPHERE Nguyen, T. B., K. H. Bates, J. D. Crounse, R. H. Schwantes, X. Zhang, H. G. Kjaergaard, J. D. Surratt, P. Lin, A. Laskin, J. H. Seinfeld, and P. O. Wennberg (2015). “Mechanism of the hydroxyl radical oxidation of methacryloyl perox- ynitrate (MPAN) and its pathway toward secondary organic aerosol formation in the atmosphere”. In: Phys. Chem. Chem. Phys. 17.27, pp. 17914–17926. : 10.1039/C5CP02001H. Abstract Methacryloyl peroxynitrate (MPAN), the acyl peroxynitrate of methacrolein, has been suggested to be an important secondary organic aerosol (SOA) precursor from isoprene oxidation, but the mechanism by which MPAN produces SOA through re- action with the hydroxyl radical (OH) remains unclear. We systematically evaluate three proposed mechanisms in controlled chamber experiments and provide the first experimental support for the theoretically-predicted lactone formation pathway from the MPAN + OH reaction, producing hydroxymethyl-methyl-↵-lactone (HMML). The decomposition of the MPAN-OH adduct yields HMML + NO ( 75%) and 3 ⇠ hydroxyacetone + CO + NO ( 25%), out-competing its reaction with atmospheric 3 ⇠ oxygen. The production of other proposed SOA precursors, e.g. methacrylic acid epoxide (MAE), from MPAN and methacrolein are negligible (<2%). Furthermore, we show that the β-alkenyl moiety of MPAN is critical for lactone formation. Alkyl radicals formed cold via H-abstraction by OH do not decompose to HMML, even if they are structurally identical to the MPAN-OH adduct. The SOA formation from HMML, from polyaddition of the lactone to organic compounds at the particle in- terface or in the condensed phase, is close to unity under dry conditions.
    [Show full text]
  • Methacrylic Acid and Methacrylic Esters
    PROCESS ECONOMICS PROGRAM ..-. SRI INTERNATIONAL Mm10 Park, California Abstract 9402E Process Economics Program Report No. 11C METHACRYLIC ACID AND METHACRYLIC ESTERS (September 1984) For the last fifteen years, processes have been developed to supplant the established process for making methyl methacrylate from acetone, hydrogen cyanide, and methanol. The acetone cyanohydrin route suffers from production of acidic wastes; the newer processes avoid these wastes and offer lower costs. Since our most recent previous report on the subject (Report LlB, issued in July 1980), a methyl methacrylate process based on a C4 feed- stock has been commercialized in Japan. This process oxidizes a t-butanol feed to methacrolein and methacrylic acid in two stages, then esterifies the acid to methyl methacrylate. We have evaluated this process and several variations, including the alternative use of isobutane feed and the supplementary use of isobutyraldehyde (by-product from 0x0 alcohol plants). We have also evaluated an attractive process based on propylene hydrocarboxylation to isobutyric acid, followed by dehydrogenation to methacrylic acid. We have updated some of the processes evaluated in Report llB, including the acetone cyanohydrin process. For a newly constructed plant, and at market prices for HCN and acetone, the acetone cyanohydrin process is more expensive than several of the newer processes. PEP'83 RHS - ReportNo. 11C a METHACRYLIC ACID AND ESTERS SUPPLEMENT C by ROBERT H. SCHWAAR ETSUO MATSUNAGA SHOICHI KIKUCHI a- and WATARU NISHIMOTO September 1984 - Cl a A private report by the PROCESS ECONOMICS PROGRAM a m Menlo Park, California 94025 For detailed marketing data and information, the reader is referred to one of the SRI programs specializing in marketing research.
    [Show full text]