DOCSLIB.ORG

Dehydration of Proplyene Glycol

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Dehydration of Proplyene Glycol PRODUCTION OF PROPYLENE OXIDE FROM PROPYLENE GLYCOL A Thesis presented to the Faculty of Graduate School University of Missouri-Columbia In Partial Fulfillment of the Requirements for the Degree of Master of Science by SURUPA DIMPLE ABRAHAM Dr. Eric J. Doskocil, Thesis Supervisor DECEMBER 2007 ACKNOWLEDGEMENTS I wish to express my sincere and deep appreciation to Professor Eric J. Doskocil, for his encouragement, insightful guidance, all the patience, support, and enthusiasm. His guidance throughout this work has not only been of invaluable help to me during my Master's study, and in my life beyond school. I would like to thank Professors Stephen J. Lombardo and Tushar Ghosh for serving on my committee, and for their time and efforts to help me in innumerable ways. I would also like to thank my undergraduate colleagues, Mr. Samuel Yoder, and Mr. Morgan Dean, for their support and help in the laboratory. The financial support provided by the Missouri Soybean Merchandizing Council (MSMC) is gratefully acknowledged. Finally, I extend the warmest thanks and appreciation to my parents, Dr. T.K. Abraham, and Sallykutty Abraham, and to my husband, Anupam Radhakrishnan, whose unwavering support, patience, and encouragement that made the completion of this thesis possible. ii TABLE OF CONTENTS ACKNOWLEDGEMENTS............................................................ii LIST OF FIGURES ....................................................................... vi LIST OF TABLES.......................................................................viii ABSTRACT .................................................................................. ix CHAPTER 1: INTRODUCTION TO MANUFACTURE OF PROPYLENE OXIDE.................................................................... 1 1.1. Introduction .......................................................................................... 1 1.2. Properties of propylene oxide .............................................................. 2 1.3. Reactions of propylene oxide............................................................... 3 1.3.1. Reaction with water .......................................................................................... 3 1.3.2. Isomerization and Hydrogenolysis ................................................................... 3 1.3.3. Carbonyl Compounds ....................................................................................... 4 1.4. Commercial production of propylene oxide ........................................ 4 1.4.1. Chlorohydrin Process........................................................................................ 5 1.4.2. Hydroperoxide Process ..................................................................................... 7 1.5. Other Processes .................................................................................. 10 1.6. Motivation of this project................................................................... 12 CHAPTER 2: DEHYDRATION OF PROPYLENE GLYCOL... 15 2.1 Introduction ......................................................................................... 15 iii 2.2 Catalyst preparation............................................................................. 16 2.2.1. Preparation of Na/Al2O3 catalyst..................................................................... 16 2.2.2. Preparation of Cs-ETS-10 catalyst.................................................................. 17 2.2.3. Preparation of Na acac/MgO catalyst ............................................................. 17 2.3. Experimental Section ......................................................................... 17 2.3.1. Reactor set up.................................................................................................. 17 2.3.2. Catalyst pre-treatment..................................................................................... 20 2.3.3 Dehydration reaction........................................................................................ 20 2.3.4. Analysis and calculation ................................................................................. 23 2.4 Results and Discussions ...................................................................... 23 2.4.1. Dehydration reaction with Na/Al2O3 as catalyst............................................. 23 2.4.2. Dehydration reaction with Cs-ETS-10 catalyst .............................................. 30 2.4.3. Dehydration reaction with Na acac/MgO catalyst.......................................... 36 2.5. Reactive distillation............................................................................ 40 2.6. Conclusions ........................................................................................ 46 CHAPTER 3: REACTION PATHWAY FOR DEHYDRATION OF PROPYLENE GLYCOL........................................................ 48 3.1. Introduction ........................................................................................ 48 3.2 Catalyst preparation............................................................................. 49 3.3 Experimental section ........................................................................... 49 3.3.1. Reactor set up.................................................................................................. 49 3.3.2. Catalyst pre-treatment..................................................................................... 50 3.3.3. Dehydration reaction....................................................................................... 51 iv 3.4. Results and discussion........................................................................ 54 3.4.1. Dehydration reaction with Na/Al2O3 catalyst ................................................. 54 3.4.2. Dehydration reaction with Cs-ETS-10 catalyst .............................................. 55 3.4.2. Dehydration reaction with Na acac/MgO catalyst.......................................... 57 3.5. Conclusions ........................................................................................ 59 CHAPTER 4: SUMMARY AND FUTURE WORK ................... 61 4.1. Summary............................................................................................. 61 4.2. Future work ........................................................................................ 63 REFERENCES ............................................................................. 65 v LIST OF FIGURES Figure Page 2.1: Experimental set up of a plug flow reactor............................................................... 18 2.2: GC trace of a sample performing the dehydration of propylene glycol over Cs-ETS- 10 catalyst ......................................................................................................................... 22 2.3: Selectivity to major products formed over 0.1 g of adsorption, basic and acidic alumina at 400 °C and N2 flow rate of 20 SCCM............................................................. 24 2.4: Selectivity to major products formed with 2-wt% Na acetate adsorption alumina at o 400 C , N2 flow rate of 20 SCCM.................................................................................... 26 2.5: Selectivity to major products formed with 2-wt% Na acetate basic alumina at o 400 C, N2 flow rate of 20 SCCM..................................................................................... 27 2.6: Selectivity to products formed over 0.1 g of varied sodium loadings on adsorption o alumina at 400 C and N2 flow rate of 20 SCCM............................................................ 28 o 2.7: Selectivity to PO and DPG over Cs-ETS-10 catalyst at 400 C and at N2 flow rate of 20 SCCM .......................................................................................................................... 30 2.8: Selectivity to various products (except for DPG) over Cs-ETS-10 catalyst at 400 oC and at N2 flow rate of 20 SCCM....................................................................................... 31 2.9: Selectivity to PO and DPG over 0.1 g of Cs-ETS-10 catalyst at various temperatures and N2 flow rate of 20 SCCM........................................................................................... 33 2.10: Selectivity to various products (except for DPG) over 0.1 g of Cs-ETS-10 catalyst at 400 °C and at N2 flow rate of 20 SCCM....................................................................... 33 o 2.11: Selectivity of various products over Na acac/MgO catalyst at 400 C and at N2 flow rate of 20 SCCM ............................................................................................................... 36 2.12: Selectivity to various products at different temperatures over 0.1g of Na acac/MgO catalyst at N2 flow rate of 20 SCCM ................................................................................ 38 2.13: Reactive distillation apparatus................................................................................ 41 3.1: GC trace of a sample performing the dehydration of dipropylene glycol over Cs- ETS-10 catalyst................................................................................................................. 53 vi o 3.2: Selectivity to various products over 0.1 g of 2-wt% Na/Al2O3 at 400 C and at a N2 flow rate of 20 SCCM....................................................................................................... 54 3.3: Selectivity to various products over 0.1 g of Cs-ETS-10 at 400 °C and N2 flow rate of 20 SCCM .....................................................................................................................
Load more

Recommended publications
  • 36Th ITC Report
    Thursday August 17, 1995 Part V Environmental Protection Agency Thirty-Sixth Report of the TSCA Interagency Testing Committee to the Administrator; Receipt of Report, Request for Comments, Solicitation of Use and Exposure Data; Notice federal register 42981 42982 Federal Register / Vol. 60, No. 159 / Thursday, August 17, 1995 / Notices ENVIRONMENTAL PROTECTION comments and data in electronic form ``OPPTS±41043'' (including comments AGENCY must be identified by the docket number and data submitted electronically as OPPT±41043. No CBI should be described below). A public version of [OPPTS±41043; FRL±4965±6] submitted through e-mail. Electronic this record, including printed, paper Thirty-Sixth Report of the TSCA comments on this notice may be filed versions of electronic comments, which Interagency Testing Committee to the online at many Federal Depository does not include any information Administrator; Receipt of Report, Libraries. Additional information on claimed as confidential business Request for Comments, Solicitation of electronic submissions can be found in information (CBI), is available for Use and Exposure Data Unit III of this document. inspection from 12 noon to 4 p.m., FOR FURTHER INFORMATION CONTACT: Monday through Friday, excluding legal AGENCY: Environmental Protection Susan B. Hazen, Director, holidays. The public record is located in Agency (EPA). Environmental Assistance Division the TSCA Nonconfidential Information ACTION: Notice. (7408), Office of Pollution Prevention Center, Rm. NE-B607, 401 M St., SW., and Toxics, Environmental Protection Washington, DC 20460. SUMMARY: The TSCA Interagency Agency, 401 M Street, SW., Rm. E± Electronic comments can be sent Testing Committee (ITC), established 543B, Washington, DC 20460, (202) directly to EPA at: under section 4(e) of the Toxic 554±1404, TDD (202) 554±0551, [email protected] Substances Control Act (TSCA), Internet: TSCA- transmitted its Thirty-Sixth Report to [email protected].
    [Show full text]
  • Dipropylene Glycol Ethyl Ether (DPGEE) [Ethyl DIPROXITOL] Product Stewardship Summary December 2017
    DiPropylene Glycol Ethyl Ether (DPGEE) [Ethyl DIPROXITOL] Product Stewardship Summary December 2017 DiPropylene Glycol Ethyl Ether (DPGEE) [Ethyl DIPROXITOL] Product Stewardship Summary (CAS number 30025-38-8) Chemical Formula for DPGEE C8H18 O3 What is DPGEE? DPGEE is a glycol ether based on Propylene oxide and ethanol. It is a speciality solvent having a bi- functional nature (ether-alcohol). It is a clear liquid with an ethereal odour. The Shell Chemicals range of Propylene oxide-based glycol ethers are sold under the trade name PROXITOL. How is DPGEE Used? It is used as an intermediate and in formulations in industrial, professional or consumer applications, mainly in surface coatings and printing inks and paints, cleaners, agrochemical or de-icing/anti-icing formulations. Health, Safety and Environmental Considerations DPGEE is flammable liquids with a flashpoint of 180 0F/82 0C. DPGEE is an isomer mix, of which the main component is 1-Ethoxypropanol-2 (typically 98% or more). Shell PROXITOLs are not classified as carcinogens or mutagens, are not expected to cause cancer in humans, nor do they impair fertility or damage the developing foetus. DPGEE is of low toxicity towards aquatic organisms. They are completely miscible with water, biodegradable and not expected to bio-accumulate. Storing and Transporting DPGEE DPGEE is transported by tank truck, rail car and vessel, primarily in bulk quantities, but also as packed product. Due to its flammability, they are classified as hazardous for transport under transport regulations. Glycol Ethers should be stored at ambient temperatures away from sources of ignition and substances with oxidising or corrosive properties.
    [Show full text]
  • WHITE LABEL PRODUCT INGREDIENTS All the Information You Need When Creating Your Own Label Artwork
    WHITE LABEL PRODUCT INGREDIENTS All the information you need when creating your own label artwork. SPRAY TAN SOLUTION - LIGHT - 8% DHA INGREDIENTS: Aqua (Water), Dihydroxyacetone, Alcohol, Hamamelis Virginiana (Witch Hazel) Leaf Extract, Propylene Glycol, Caramel, Phenoxyethanol, Caprylyl Glycol, Potassium Sorbate, Hexylene Glycol, Polysorbate 20, Xanthan Gum, Glycerin, T-Butyl Alcohol, Helianthus Annuus (Sunflower) Seed Oil, Beta Vulgaris (Beet) Root Extract, Panthenol, Solanum Lycopersicum (Tomato) Fruit Extract, Vaccinium Macrocarpon (Cranberry) Fruit Extract, Ascorbic Acid (Vitamin C), Tocopheryl Acetate (Vitamin E), Theobroma Cacao (Cocoa) Seed Butter, Rosa Canina (Rose Hip) Fruit Oil, Glycine Soja (Soybean) Oil, Cucumis Sativus (Cucumber) Fruit Extract, Brucine Sulfate, Yellow 5 (CI 19140), Green 5 (CI 61570), Red 40 (CI 16035), Red 33 (CI 17200), Blue 1 (CI 42090), Yellow 6 (CI 15985) SPRAY TAN SOLUTION - MEDIUM - 10% DHA INGREDIENTS: Aqua (Water), Dihydroxyacetone, Alcohol, Hamamelis Virginiana (Witch Hazel) Extract, Propylene Glycol, Caramel, Phenoxyethanol, Caprylyl Glycol, Potassium Sorbate, Hexylene Glycol, Polysorbate 20, Xanthan Gum, Glycerin, T-Butyl Alcohol, Helianthus Annuus (Sunflower) Seed Oil, Beta Vulgaris (Beet) Root Extract, Panthenol, Solanum Lycopersicum (Tomato) Fruit Extract, Vaccinium Macrocarpon (Cranberry) Fruit Extract, Ascorbic Acid (Vitamin C), Tocopheryl Acetate (Vitamin E), Theobroma Cacao (Cocoa) Seed Butter, Rosa Canina (Rose Hip) Fruit Oil, Glycine Soja (Soybean) Oil, Cucumis Sativus (Cucumber) Fruit
    [Show full text]
  • Comparison of Ethylene Glycol and Propylene Glycol Based Aircraft
    Comparison of Ethylene Glycol- and Propylene Glycol-Based Aircraft Deicing Fluids Agenda • Executive Summary • Chemistry • Operational Properties (for the aircraft) o Freezing Point (efficiency) o Lowest Operational Use Temperature o Holdover Time and Allowance Times • Mammalian Toxicity o Operator Precautions • Environmental Toxicity o Aquatic Toxicity o Air Emissions / Vapor Pressure o Biodegradation Executive Summary • Both ethylene glycol- (EG) and propylene glycol- (PG) based aircraft deicing fluids (ADFs) consist of the base glycol plus water and additives • Operationally, EG-based fluids perform better: • Less EG is required to produce the same freezing point than PG. • Lower viscosity means EG-based fluids provide better aerodynamic performance at colder temperatures. • As a result, EG-based fluids have superior Holdover Times (HOTs) compared to PG-based fluids, as presented by the SAE G-12 HOT Committee in May 2017. • Mammalian Toxicity • EG and PG both have low to moderate acute toxicity. • If ingested in a large, single oral dose, EG is more toxic to mammals than PG. • Oral dosing is an unlikely route of exposure during deicing. • History in Canada, where EG fluids have been used safely for many years, confirms operator procedures can appropriately manage this risk. Executive Summary • Environmental Properties • EG-based fluids in concentrated form generally demonstrate better aquatic toxicity than PG-based fluids; however, both are non-toxic. • Mixtures of EG-based ADFs exhibit less air emissions than PG based fluids.1 • Both EG and PG are biodegradable in the environment and neither bio accumulates. • PG has higher Theoretical Oxygen Demand and requires a higher usage concentration than PG fluids.
    [Show full text]
  • The PO Production Chain and Possibilities for Energy Saving
    The PO production chain and possibilities for energy saving Public Summary Report Delft, January 2012 Author(s): Ewout Dönszelmann Ab de Buck Harry Croezen Lonneke Wielders Publication Data Bibliographical data: Ewout Dönszelmann, Ab de Buck, Harry Croezen, Lonneke Wielders The PO production chain and possibilities for energy saving Public Summary Delft, CE Delft, January 2012 Energy saving / Chain Management / Products / Chemical industry / Propylene Oxide / Styrene / Iso-butylene FT: Tert-butyl alcohol (TBA) Publication code: 12.2232.12 CE publications are available from www.cedelft.eu. Commissioned by: Agentschap NL Further information on this study can be obtained from the contact person, Ewout Dönszelmann. © copyright, CE Delft, Delft CE Delft Committed to the Environment CE Delft is an independent research and consultancy organisation specialised in developing structural and innovative solutions to environmental problems. CE Delft’s solutions are characterised in being politically feasible, technologically sound, economically prudent and socially equitable. 2 January 2012 2.232.3 – The PO production chain and possibilities for energy saving Contents 1 Introduction 5 1.1 General background 5 1.2 The project 5 1.3 Approach 6 1.4 Reading guide 6 2 The production chains 7 2.1 The two processes 7 2.2 Expanded polystyrene 9 2.3 Polyols 11 2.4 TBA/iso-butylene applications 13 3 Conclusions, recommendations 17 3.1 Conclusions 17 3.2 Recommendations 17 4 Background of the Long-term Agreement Energy Efficiency ETS enterprises (LEE) 19 References 21 3 January 2012 2.232.3 – The PO production chain and possibilities for energy saving 4 January 2012 2.232.3 – The PO production chain and possibilities for energy saving 1 Introduction 1.1 General background The Dutch Industry and the Dutch government have made long term agreements on energy efficiency (LEE) for companies that are under the European Trading Scheme (ETS).
    [Show full text]
  • EPA Method 8315A (SW-846): Determination of Carbonyl Compounds by High Performance Liquid Chromatography (HPLC)
    METHOD 8315A DETERMINATION OF CARBONYL COMPOUNDS BY HIGH PERFORMANCE LIQUID CHROMATOGRAPHY (HPLC) 1.0 SCOPE AND APPLICATION 1.1 This method provides procedures for the determination of free carbonyl compounds in various matrices by derivatization with 2,4-dinitrophenylhydrazine (DNPH). The method utilizes high performance liquid chromatography (HPLC) with ultraviolet/visible (UV/vis) detection to identify and quantitate the target analytes. This method includes two procedures encompassing all aspects of the analysis (extraction to determination of concentration). Procedure 1 is appropriate for the analysis of aqueous, soil and waste samples and stack samples collected by Method 0011. Procedure 2 is appropriate for the analysis of indoor air samples collected by Method 0100. The list of target analytes differs by procedure. The appropriate procedure for each target analyte is listed in the table below. Compound CAS No. a Proc. 1b Proc. 2 b Acetaldehyde 75-07-0 X X Acetone 67-64-1 X Acrolein 107-02-8 X Benzaldehyde 100-52-7 X Butanal (Butyraldehyde) 123-72-8 X X Crotonaldehyde 123-73-9 X X Cyclohexanone 108-94-1 X Decanal 112-31-2 X 2,5-Dimethylbenzaldehyde 5779-94-2 X Formaldehyde 50-00-0 X X Heptanal 111-71-7 X Hexanal (Hexaldehyde) 66-25-1 X X Isovaleraldehyde 590-86-3 X Nonanal 124-19-6 X Octanal 124-13-0 X Pentanal (Valeraldehyde) 110-62-3 X X Propanal (Propionaldehyde) 123-38-6 X X m-Tolualdehyde 620-23-5 X X o-Tolualdehyde 529-20-4 X p-Tolualdehyde 104-87-0 X a Chemical Abstract Service Registry Number.
    [Show full text]
  • R Graphics Output
    Dexamethasone sodium phosphate ( 0.339 ) Melengestrol acetate ( 0.282 ) 17beta−Trenbolone ( 0.252 ) 17alpha−Estradiol ( 0.24 ) 17alpha−Hydroxyprogesterone ( 0.238 ) Triamcinolone ( 0.233 ) Zearalenone ( 0.216 ) CP−634384 ( 0.21 ) 17alpha−Ethinylestradiol ( 0.203 ) Raloxifene hydrochloride ( 0.203 ) Volinanserin ( 0.2 ) Tiratricol ( 0.197 ) trans−Retinoic acid ( 0.192 ) Chlorpromazine hydrochloride ( 0.191 ) PharmaGSID_47315 ( 0.185 ) Apigenin ( 0.183 ) Diethylstilbestrol ( 0.178 ) 4−Dodecylphenol ( 0.161 ) 2,2',6,6'−Tetrachlorobisphenol A ( 0.156 ) o,p'−DDD ( 0.155 ) Progesterone ( 0.152 ) 4−Hydroxytamoxifen ( 0.151 ) SSR150106 ( 0.149 ) Equilin ( 0.3 ) 3,5,3'−Triiodothyronine ( 0.256 ) 17−Methyltestosterone ( 0.242 ) 17beta−Estradiol ( 0.24 ) 5alpha−Dihydrotestosterone ( 0.235 ) Mifepristone ( 0.218 ) Norethindrone ( 0.214 ) Spironolactone ( 0.204 ) Farglitazar ( 0.203 ) Testosterone propionate ( 0.202 ) meso−Hexestrol ( 0.199 ) Mestranol ( 0.196 ) Estriol ( 0.191 ) 2,2',4,4'−Tetrahydroxybenzophenone ( 0.185 ) 3,3,5,5−Tetraiodothyroacetic acid ( 0.183 ) Norgestrel ( 0.181 ) Cyproterone acetate ( 0.164 ) GSK232420A ( 0.161 ) N−Dodecanoyl−N−methylglycine ( 0.155 ) Pentachloroanisole ( 0.154 ) HPTE ( 0.151 ) Biochanin A ( 0.15 ) Dehydroepiandrosterone ( 0.149 ) PharmaCode_333941 ( 0.148 ) Prednisone ( 0.146 ) Nordihydroguaiaretic acid ( 0.145 ) p,p'−DDD ( 0.144 ) Diphenhydramine hydrochloride ( 0.142 ) Forskolin ( 0.141 ) Perfluorooctanoic acid ( 0.14 ) Oleyl sarcosine ( 0.139 ) Cyclohexylphenylketone ( 0.138 ) Pirinixic acid ( 0.137 )
    [Show full text]
  • Toxicological Profile for Formaldehyde
    TOXICOLOGICAL PROFILE FOR FORMALDEHYDE U.S. DEPARTMENT OF HEALTH AND HUMAN SERVICES Public Health Service Agency for Toxic Substances and Disease Registry July 1999 FORMALDEHYDE ii DISCLAIMER The use of company or product name(s) is for identification only and does not imply endorsement by the Agency for Toxic Substances and Disease Registry. FORMALDEHYDE iii UPDATE STATEMENT Toxicological profiles are revised and republished as necessary, but no less than once every three years. For information regarding the update status of previously released profiles, contact ATSDR at: Agency for Toxic Substances and Disease Registry Division of Toxicology/Toxicology Information Branch 1600 Clifton Road NE, E-29 Atlanta, Georgia 30333 FORMALDEHYDE vii QUICK REFERENCE FOR HEALTH CARE PROVIDERS Toxicological Profiles are a unique compilation of toxicological information on a given hazardous substance. Each profile reflects a comprehensive and extensive evaluation, summary, and interpretation of available toxicologic and epidemiologic information on a substance. Health care providers treating patients potentially exposed to hazardous substances will find the following information helpful for fast answers to often-asked questions. Primary Chapters/Sections of Interest Chapter 1: Public Health Statement: The Public Health Statement can be a useful tool for educating patients about possible exposure to a hazardous substance. It explains a substance’s relevant toxicologic properties in a nontechnical, question-and-answer format, and it includes a review of the general health effects observed following exposure. Chapter 2: Health Effects: Specific health effects of a given hazardous compound are reported by route of exposure, by type of health effect (death, systemic, immunologic, reproductive), and by length of exposure (acute, intermediate, and chronic).
    [Show full text]
  • Pesticides and Toxic Substances
    UNITED STATES ENVIRONMENTAL PROTECTION AGENCY WASHINGTON, D.C. 20460 OFFICE OF PREVENTION, PESTICIDES AND TOXIC SUBSTANCES CERTIFIED MAIL Dear Registrant: This is to inform you that the Environmental Protection Agency (hereafter referred to as EPA or the Agency) has completed its review of the available data for the antimicrobials propylene glycol and dipropylene glycol. The Reregistration Eligibility Decision (RED) was approved in the form of a decision memorandum which summarized the regulatory decision for propylene glycol and dipropylene glycol on September 30, 2004. Based on its review, EPA is now publishing its Reregistration Eligibility Decision (RED) for propylene glycol and dipropylene glycol and its associated human health and environmental risks. A Notice of Availability will be published in the Federal Register announcing the publication of the RED. The RED and supporting documents for propylene glycol and dipropylene glycol will be available to the public in EPA’s Pesticide Docket EPA-HQ-OPP-2006-0831 at: www.regulations.gov. Please note that the attached RED document pertains only to propylene glycol and dipropylene glycol. This RED presents the Agency’s conclusions on the dietary, drinking water, occupational and ecological risks posed by exposure to propylene glycol or dipropylene glycol alone. This document also contains product-specific data that the Agency intends to require in Data Call-Ins (DCIs). Note that DCIs, with all pertinent instructions, will be sent to registrants at a later date. Currently, there are no generic data requirements. Additionally, for product- specific DCIs, the first set of required responses will be due 90 days from the receipt of the DCI letter.
    [Show full text]
  • PROPYLENE GLYCOL from GLYCERIN (December 2007)
    Abstract Process Economics Program Report 262 PROPYLENE GLYCOL FROM GLYCERIN (December 2007) A variety of economic, environmental and technical factors have encouraged industry attention on producing industrial chemicals from bio-feedstocks, rather than from crude oil derivatives. One such example is producing propylene glycol (PG) from glycerine (GLY), rather than the conventional routes starting with propylene monomer. Propylene glycol has historically been produced in commercial quantities either via the chlorohydrin process or by peroxidation, both using propylene monomer as the starting material. Both routes produce propylene oxide (PO) as an intermediate chemical, which is then hydrated to propylene glycol. The peroxidation routes have evolved from those processes (Arco Chem/Lyondell, Repsol, Shell, BASF) producing a significant amount of by-product (PO/styrene monomer, PO/tertiary butyl alcohol, PO/ methyl tertiary butyl ether), to more recent processes developed by Solvay, Dow and BASF that eliminate the by-product by using hydrogen peroxide as the oxidizing agent. As of 2007, Degussa has announced the design and construction of a commercial scale PG plant using glycerine as its feedstock. Other companies have announced processes to use glycerine to produce polyols and epichlorohydrin. The combination of high crude oil prices and governmental subsidies to produce biofuels (bio-ethanol, bio-diesel) have resulted in an enormous increase in bio-diesel production, resulting in a glut of by-product glycerine (which represents 10% of biodiesel mass). As a result, glycerine market prices have fallen from $US 2/kg down to fuel value ($US 200/mt), or less. The low cost of glycerine combined with the high price of PG offers an opportunity to develop industrial scale processes converting glycerine to propylene glycol.
    [Show full text]
  • The Toxicology of Glycol Ethers and Its Relevance to Man (Fourth Edition) Volume I
    The Toxicology of Glycol Ethers and its Relevance to Man (Fourth Edition) Volume I Technical Report No. 95 ISSN-0773-8072-95 Brussels, February 2005 The Toxicology of Glycol Ethers and its Relevance to Man ECETOC TECHNICAL REPORT No. 95 © Copyright – ECETOC AISBL European Centre for Ecotoxicology and Toxicology of Chemicals 4 Avenue E. Van Nieuwenhuyse (Bte 6), B-1160 Brussels, Belgium. All rights reserved. No part of this publication may be reproduced, copied, stored in a retrieval system or transmitted in any form or by any means, electronic, mechanical, photocopying, recording or otherwise without the prior written permission of the copyright holder. Applications to reproduce, store, copy or translate should be made to the Secretary General. ECETOC welcomes such applications. Reference to the document, its title and summary may be copied or abstracted in data retrieval systems without subsequent reference. The content of this document has been prepared and reviewed by experts on behalf of ECETOC with all possible care and from the available scientific information. It is provided for information only. ECETOC cannot accept any responsibility or liability and does not provide a warranty for any use or interpretation of the material contained in the publication. ECETOC TR No. 95 The Toxicology of Glycol Ethers and its Relevance to Man The Toxicology of Glycol Ethers and its Relevance to Man CONTENTS - VOLUMES I AND II EXECUTIVE SUMMARY 1 SUMMARY AND CONCLUSIONS 3 Recommendations for further work 13 1. INTRODUCTION 14 1.1 Conversion factors and physico-chemical properties 14 1.2 Production and use 14 1.2.1 Manufacture of ethylene-series glycol ethers 14 1.2.2 Manufacture of propylene-series glycol ethers 15 1.2.3 Uses 15 2.
    [Show full text]
  • Influence of Impurities in a Methanol Solvent on the Epoxidation of Propylene with Hydrogen Peroxide Over Titanium Silicalite‐1
    Supplementary Materials Influence of Impurities in a Methanol Solvent on the Epoxidation of Propylene with Hydrogen Peroxide over Titanium Silicalite‐1 Gang Wang, Yue Li, Quanren Zhu, Gang Li, Chao Zhang, and Hongchen Guo* State Key Laboratory of Fine Chemicals and School of Chemical Engineering, Dalian University of Technology, No. 2 Linggong Road, Dalian 116024, PR China; [email protected] (G.W.); [email protected] (Y.L.); [email protected] (Q.Z.); [email protected] (G.L.); [email protected] (C.Z.) * Correspondence: [email protected]; Tel./Fax: +86‐411‐84986120 Received: 23 November 2019; Accepted: 18 December 2019; Published: date Table S1. Influence of fusel alcohol content on the product distribution and turnover numbers in epoxidation of propylene with H2O2a Conten Selectivity, % Impurity TONb t, wt.% 1M2Pc 2M1Pc PGc DGMEc PGMEc AAc PAc ATc noned 0.00 314.5 0.50 0.52 0.17 0.08 0.00 0.23 0.06 0.00 ethanol 1.00 296.8 0.48 0.46 0.17 0.06 0.01 0.22 0.06 0.00 1.50 286.8 0.45 0.45 0.15 0.05 0.02 0.26 0.06 0.01 2.00 282.9 0.38 0.42 0.14 0.04 0.02 0.28 0.07 0.01 2.50 267.9 0.38 0.41 0.14 0.03 0.03 0.29 0.07 0.01 2‐propanol 0.50 296.8 0.45 0.49 0.17 0.06 0.00 0.21 0.07 0.03 0.75 286.8 0.43 0.47 0.15 0.06 0.00 0.22 0.07 0.05 1.00 282.9 0.41 0.47 0.15 0.04 0.00 0.25 0.08 0.07 1.25 267.9 0.37 0.38 0.14 0.03 0.00 0.26 0.09 0.08 1‐propanol 0.50 297.7 0.51 0.55 0.18 0.06 0.00 0.21 0.11 0.00 0.75 289.0 0.45 0.49 0.18 0.05 0.00 0.22 0.11 0.00 1.00 282.5 0.44 0.49 0.17 0.05 0.00 0.24 0.14 0.01 1.25 266.0 0.43 0.48 0.16 0.05 0.00 0.26 0.14 0.01 Note: a Reaction conditions: pre‐adsorbed TS‐1 powder 0.4 g, fresh methanol or simulated methanol solvents containing ethanol, 2‐propanol and 1‐propanol 35.5 mL, H2O2 (50 wt.%) 4.5 mL, NH3∙H2O (0.32 mol/L) 0.2 mL, propylene pressure 0.6 MPa, 50 ℃, 1 h.
    [Show full text]