Single-Step Catalytic Conversion of Ethanol to N-Butene-Rich Olefins and 1,3-Butadiene Chemical Coproduct
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Butenes Separation, Supp. A
PROCESS ECONOMICS PROGRAM SRI INTERNATIONAL Menlo Park, California 94025 Abstract Process Economics Program Report No. 71A BUTTLENES (October 1982) Demand is fast increasing for lsobutylene, especially that used in manufacturing methyl tertiary-butyl ether, and for high purity butene-1 to use as a copolymer in linear low density polyethylene. Because of their wide availability, mixed butane-butylene streams from oleflns plants and petroleum refineries are being increasingly fed to plants to separate butylenes for use in chemicals. This first supplement to Report No. 71 updates demand projections, production capacities, and separation techniques for high purity butene-1 and lsobutylene. The processes that are now available for separating and purifying both butene-1 and lsobutylene from mixed butyl- ene streams are evaluated and compared. Other procedures for obtaining butylenes, such as dehydrogenatlon, lsomerleatlon, and disproportion&ion, are not updated in this report. PEP’81 JLC Report No. 71A - BUTYLENES SUPPLEMENT A by JOHN L. CHADWICK I I October 1982 f-F0 0 A private report by the m PROCESS ECONOMICS PROGRAM 0 Menlo Park, California 94025 0 For detailed marketing data and information, the reader is referred to one of the SRI programs specializing in marketing research. The CHEMICALECONOMICS HANDBOOK Program covers most major chemicals and chemical products produced in the United States and the WORLDPETROCHEMICALS Program covers major hkdrocarbons and their derivatives on a worldwide basis. In addition, the SRI DIRECTORYOF CHEMICALPRODUCERS services provide detailed lists of chemical producers by company, prod- uct, and plant for the United States and Western Europe. ii CONTENTS 1 INTRODUCTION . 1 2 SUMMARY . -
Isobutylene Polymer Having Unsaturated Group and Preparation
Europaisches Patentamt European Patent Office Office europeen des brevets (11) EP 0 452 875 B2 (12) NEW EUROPEAN PATENT SPECIFICATION (45) Date of publication and mention (51) |nt CI.6: C08F 10/10, C08F 2/42 of the opposition decision: 18.08.1999 Bulletin 1999/33 (45) Mention of the grant of the patent: 09.08.1995 Bulletin 1995/32 (21) Application number: 91106042.4 (22) Date of filing: 16.04.1991 (54) Isobutylene polymer having unsaturated group and preparation thereof Isobutylenpolymer mit ungesattigter Gruppe und seine Herstellung Polymere de I'isobutylene ayant un groupe insature et sa preparation (84) Designated Contracting States: (74) Representative: BE CH DE ES FR GB IT LI NL SE Hansen, Bernd, Dr. Dipl.-Chem. et al Hoffmann Eitle, (30) Priority: 16.04.1990 JP 10102990 Patent- und Rechtsanwalte, 29.11.1990 JP 33636490 Postfach 81 04 20 81904 Miinchen (DE) (43) Date of publication of application: 23.10.1991 Bulletin 1991/43 (56) References cited: EP-A- 0 265 053 EP-B- 0 322 241 (73) Proprietor: Kanegafuchi Chemical Industry Co., CA-A- 467 049 GB-A- 1 059 580 Ltd. US-A- 4 31 6 973 US-A- 4 327 201 Kita-ku Osaka-shi Osaka-fu (JP) US- A- 4 524 1 88 US-A- 4 758 63 1 US-A- 4 929 683 (72) Inventors: • Noda, Koji Remarks: Kobe-shi, Hyogo-ken (JP) The file contains technical information submitted • Fujisawa, Hiroshi after the application was filed and not included in this Kobe-shi, Hyogo-ken (JP) specification • Yonezawa, Kazuya Kobe-shi, Hyogo-ken (JP) CM DO 10 Is- 00 CM IO ^- o a. -
Model Vulcanization Systems for Butyl Rubber and Halobutyl Rubber Manual
Exxon™ butyl and halobutyl rubber Model vulcanization systems for butyl rubber and halobutyl rubber manual Country name(s) 2 - Model vulcanization systems for butyl rubber and halobutyl rubber manual Model vulcanization systems for butyl rubber and halobutyl rubber manual - 3 Abstract The vulcanization of isobutylene-co-isoprene rubber (IIR), brominated isobutylene-co-isoprene rubber (BIIR), chlorinated isobutylene-co-isoprene rubber (CIIR), and brominated isobutylene-co-para-methylstyrene elastomer (BIMSM) differs from that of general-purpose rubbers (GPR). Butyl rubber has approximately 2% unsaturation in the backbone. Halobutyl rubber (BIIR and CIIR) incorporates the butyl backbone with either bromine or chlorine, which significantly increases the chemical reactivity of the isoprenyl units located in the butyl backbone. Similarly, in BIMSM the bromine atom is bonded to the para-methylstyrene (PMS) group, thus affording the completely saturated polymer backbone a site of chemical reactivity. Utilization of the unique attributes of butyl rubber and halobutyl rubbers with their minimal backbone unsaturation and of BIMSM elastomers with no backbone unsaturation is found in many areas of industry. These properties are excellent vapor impermeation, resistance to heat degradation, and improved chemical resistance as compared to general-purpose rubbers. However, this low amount of reactivity requires special consideration to vulcanize these isobutylene-based polymers. The type of vulcanization system selected is a function of the composite structure in which it is used, and the cured product performance requirements. Therefore, vulcanization systems vary and may include an accelerator package along with resins, zinc oxide, zinc oxide and sulfur, and quinoid systems. This review will discuss the types and selection of appropriate vulcanization systems for isobutylene-based elastomers. -
FID Vs PID: the Great Debate
5/5/2017 FID vs PID: The Great Debate 2017 Geotechnical, GeoEnvironmental, and Geophysical Technology Transfer April 11, 2017 Raleigh, NC Why is it Important? As consultants, we are expected to produce data that is Reliable Repeatable Representative Defensible We can only meet these criteria if we understand the instruments we use and their limitations 1 5/5/2017 PID=Photo Ionization Detector Non-destructive to the sample Responds to functional groups Can operate in non-oxygen atmosphere Does not respond to methane Affected by high humidity FID=Flame Ionization Detector Destructive to the sample Responds to carbon chain length Must have oxygen to operate Responds to methane Not affected by high humidity 2 5/5/2017 Combination FID/PID TVA 1000B Main Concepts Ionization Energy Minimum amount of energy required to remove an electron from an atom or molecule in a gaseous state Response Factors The response factor is a calculated number provided by the instrument manufacturer for each compound, which is used to calculate the actual concentration of said compound in relation to the calibration gas. 3 5/5/2017 Ionization Energy Basis for FID/PID operations and measurement Measurements are in electron volts (eV) Ionization in a PID Energy source for ionization with PID is an ultraviolet light Three UV lamp energies are used: 9.5 eV, 10.6 eV, and 11.7 eV The higher the lamp energy, the greater the number of chemicals that can be detected. Detection range of 0.1 to 10,000 ppm 4 5/5/2017 Ionization in a FID Energy source for ionization -
Supplement of Compilation and Evaluation of Gas Phase Diffusion Coefficients of Reactive Trace Gases in the Atmosphere
Supplement of Atmos. Chem. Phys., 15, 5585–5598, 2015 http://www.atmos-chem-phys.net/15/5585/2015/ doi:10.5194/acp-15-5585-2015-supplement © Author(s) 2015. CC Attribution 3.0 License. Supplement of Compilation and evaluation of gas phase diffusion coefficients of reactive trace gases in the atmosphere: Volume 2. Diffusivities of organic compounds, pressure-normalised mean free paths, and average Knudsen numbers for gas uptake calculations M. J. Tang et al. Correspondence to: M. J. Tang ([email protected]) and M. Kalberer ([email protected]) The copyright of individual parts of the supplement might differ from the CC-BY 3.0 licence. Table of Contents 1 Alkanes and cycloalkanes ............................................................................................ 1 1.1 CH 4 (methane), C 2H6 (ethane), and C 3H8 (propane) ............................................. 1 1.2 C 4H10 (butane, methyl propane) ............................................................................ 3 1.3 C 5H12 (n-pentane, methyl butane, dimethyl butane) ............................................. 5 1.4 C 6H14 (n-hexane, 2,3-dimethyl butane) ................................................................ 7 1.5 C 7H16 (n-heptane, 2,4-dimethyl pentane).............................................................. 9 1.6 C 8H18 (n-octane, 2,2,4-trimethyl pentane) .......................................................... 11 1.7 C 9H20 (n-nonane), C 10 H22 (n-decane, 2,3,3-trimethyl heptane) and C 12 H26 (n- dodecane) ................................................................................................................. -
Reactions of Alkenes and Alkynes
05 Reactions of Alkenes and Alkynes Polyethylene is the most widely used plastic, making up items such as packing foam, plastic bottles, and plastic utensils (top: © Jon Larson/iStockphoto; middle: GNL Media/Digital Vision/Getty Images, Inc.; bottom: © Lakhesis/iStockphoto). Inset: A model of ethylene. KEY QUESTIONS 5.1 What Are the Characteristic Reactions of Alkenes? 5.8 How Can Alkynes Be Reduced to Alkenes and 5.2 What Is a Reaction Mechanism? Alkanes? 5.3 What Are the Mechanisms of Electrophilic Additions HOW TO to Alkenes? 5.1 How to Draw Mechanisms 5.4 What Are Carbocation Rearrangements? 5.5 What Is Hydroboration–Oxidation of an Alkene? CHEMICAL CONNECTIONS 5.6 How Can an Alkene Be Reduced to an Alkane? 5A Catalytic Cracking and the Importance of Alkenes 5.7 How Can an Acetylide Anion Be Used to Create a New Carbon–Carbon Bond? IN THIS CHAPTER, we begin our systematic study of organic reactions and their mecha- nisms. Reaction mechanisms are step-by-step descriptions of how reactions proceed and are one of the most important unifying concepts in organic chemistry. We use the reactions of alkenes as the vehicle to introduce this concept. 129 130 CHAPTER 5 Reactions of Alkenes and Alkynes 5.1 What Are the Characteristic Reactions of Alkenes? The most characteristic reaction of alkenes is addition to the carbon–carbon double bond in such a way that the pi bond is broken and, in its place, sigma bonds are formed to two new atoms or groups of atoms. Several examples of reactions at the carbon–carbon double bond are shown in Table 5.1, along with the descriptive name(s) associated with each. -
4. Production, Import/Export, Use, and Disposal
METHYL tert-BUTYL ETHER 163 4. PRODUCTION, IMPORT/EXPORT, USE, AND DISPOSAL During the 1970s EPA moved to phase out leaded gasolines and to reduce the levels of air pollution from pre- or post-combustion vehicular emissions. This conversion to unleaded fuels tended to reduce the octane ratings. Additives such as benzene or toluene could increase octane levels, but these aromatic volatile organic compounds could lead to serious air pollution problems due to their known toxic properties. Various highly oxygenated blending agents, including several ethers and alcohols, can boost the octane of unleaded gasoline and, since they are less toxic, can mitigate many of the air pollution concerns. MTBE is one such product used in Reformulated Gasoline (RFG). Some states started requiring the seasonal use of RFGs in the 197Os, and this became a requirement for many parts of the country under provisions of the 1990 Clean Air Act. This requirement led to a rapid expansion in the production and use of MTBE starting in the late 1980s. 4.1 PRODUCTION Typical production processes use feedstocks like isobutylene, often in combination with methanol, in adiabatic fixed reactors. The isobutylene and methanol react in the presence of ion-exchange resin catalysts at medium pressures and temperatures. Highly volatile by-products are removed through distillation, and methanol is reclaimed using water washing or molecular sieves. In a variant of this basic technology called reaction distillation, the catalysis and distillation steps take place simultaneously (Shanely 1990). There are numerous variants in these manufacturing processes, the details of which are protected under patents or license agreements (Lorenzetti 1994; Rhodes 1991). -
Minimizing Isobutylene Emissions from Large Scale Tert-Butoxycarbonyl Deprotections
Organic Process Research & Development 2005, 9, 39−44 Minimizing Isobutylene Emissions from Large Scale tert-Butoxycarbonyl Deprotections Eric L. Dias,* Kevin W. Hettenbach, and David J. am Ende Process Safety and Reaction Engineering Laboratory, Pfizer Global Research and DeVelopment, Eastern Point Road, Groton, Connecticut 06340 Abstract: with scavengers1,7,8 such as thiophenol1,7 to form an unre- Isobutylene off-gas amounts liberated during the methane- active byproduct, 3a; however, in an industrial setting, this sulfonic acid-catalyzed deprotection of N-BOC-pyrrolidine in can be prohibitive in terms of cost, worker exposure, and THF, methanol, ethanol, 2-propanol, toluene, and dichlo- added purification. romethane were measured using on-line gas-phase mass spec- In the absence of a powerful scavenger, 1 can be trapped troscopy. While one full equivalent of isobutylene was released in other manners. When trifluoroacetic acid is used, reaction as an off-gas when THF was used as the reaction solvent, with the conjugate base can form the tert-butyl trifluoroac- emissions were reduced by 65-95% in other solvents. In alcohol etate ester, 3b;6,7,8a,9 however this typically will not occur solvents, the corresponding alkyl tert-butyl ethers are formed with methanesulfonic or other nonnucleophilic strong acids. as byproducts of the reaction as expected. In dichloromethane It has also been noted that water and alcohols will encourage and toluene, oligomers of isobutylene can be formed under the formation of tert-butyl alcohol2a,11b or the corresponding alkyl reaction conditions. These results provided the basis for tert-butyl ethers, 3c,10,11 which may provide a practical developing an effective acid/toluene scrubber for isobutylene approach to reducing isobutylene emissions but will be that was successfully employed on the pilot plant scale. -
Transformation of Phenanthrene by Mycobacterium Sp. ELW1 and the Formation of Toxic Metabolites
AN ABSTRACT OF THE THESIS OF Jill E. Schrlau for the degree of Master of Science in Environmental Engineering presented on September 20, 2016. Title: Transformation of Phenanthrene by Mycobacterium sp. ELW1 and the Formation of Toxic Metabolites. Abstract approved: _____________________________________________________________________ Lewis Semprini Staci Simonich The ability of Mycobacterium sp. ELW1, a novel microbe capable of alkene oxidation, to co-metabolize phenanthrene (PHE) was studied. ELW1 was able to completely co-metabolize PHE, at different concentrations below its water solubility limit, in an aqueous environment. The alkene monooxygenases in ELW1, used to initiate oxidation of PHE, were effectively inhibited by 1-octyne despite some PHE transformation observed. PHE metabolites consisted of only hydroxyphenanthrenes (OHPHEs) with trans-9,10-dihydroxy-9,10-dihydrophenanthrene (trans-9,10-PHE), the primary product, comprising more than 90% of the total metabolites formed in both PHE-exposed cells and 1-octyne controls. Mass balance was estimated by summing the zero-order formation rates of OHPHE metabolites and comparing these to the zero-order transformation rates PHE in PHE-exposed cells. The transformation rates of PHE and were in good agreement with the formation rates of the metabolites. PHE transformation followed first-order rates that, when normalized by biomass, were in the range of those estimated by the ratio of the Michaelis-Menten kinetic variables of maximum transformation rate (kmax) to the half-saturation constant (KS). Estimated values for kmax to KS obtained through both non-linear and linearization methods resulted in kmax/KS estimates that were a factor of ~3 lower compared to experimental values. -
Correction Factors, Ionization Energies, and Calibration Characteristics for BW Rigrat Monitors
Technical Note TN-106D 202005/TM Correction Factors, Ionization Energies, And Calibration Characteristics For BW RigRat Monitors Correction Factors & Ionization Energies* Photoionization Detector sensors (PIDs) can be used for the detection of a wide variety of gases that exhibit different responses. In general, any compound with ionization energy (IE) lower than that of the lamp photons can be measured.* The best way to calibrate a PID to different compounds is to use a standard of the gas of interest. However, correction factors have been determined that enable the user to quantify a large number of chemicals using only a single calibration gas, typically isobutylene. In our PIDs, correction factors can be used in one of three ways: 1. Calibrate the monitor with isobutylene in the usual fashion to read in isobutylene equivalents. Manually multiply the reading by the correction factor (CF) to obtain the concentration of the gas being measured. 2. Calibrate the unit with isobutylene in the usual fashion to read in isobutylene equivalents. Call up the correction factor from the instrument memory or download it from a personal computer and then call it up. The monitor will then read directly in units of the gas of interest. 3. Calibrate the unit with isobutylene, but input an equivalent, “corrected” span gas concentration when prompted for this value. The unit will then read directly in units of the gas of interest. * The term “ionization energy” is more scientifically correct and replaces the old term “ionization potential.” High-boiling (“heavy”) compounds may not vaporize enough to give a response even when their ionization energies are below the lamp photon energy. -
Olefins from Biomass Intermediates: a Review
catalysts Review Review OlefinsOlefins fromfrom BiomassBiomass Intermediates:Intermediates: AA ReviewReview 1 1,2, VasilikiVasiliki Zacharopoulou Zacharopoulou1 andand AngelikiAngeliki A.A. LemonidouLemonidou 1,2,** 1 Department of Chemical Engineering, Aristotle University of Thessaloniki, University Campus, 1 Department of Chemical Engineering, Aristotle University of Thessaloniki, University Campus, Thessaloniki 54124, Greece; [email protected] 54124 Thessaloniki, Greece; [email protected] 2 Chemical Process Engineering Research Institute (CERTH/CPERI), P.O. Box 60361 Thermi, 2 Chemical Process Engineering Research Institute (CERTH/CPERI), P.O. Box 60361 Thermi, Thessaloniki 57001, Greece 57001 Thessaloniki, Greece * Correspondence: [email protected]; Tel.: +30‐2310‐996‐273 * Correspondence: [email protected]; Tel.: +30-2310-996-273 Received: 16 November 2017; Accepted: 19 December 2017; Published: Received: 16 November 2017; Accepted: 19 December 2017; Published: 23 December 2017 Abstract:Abstract: Over the last decade, increasing demand for olefinsolefins and theirtheir valuablevaluable productsproducts hashas promptedprompted researchresearch onon novelnovel processesprocesses andand technologiestechnologies forfor theirtheir selectiveselective production.production. As olefinsolefins are predominatelypredominately dependent on fossil resources, their production is limited by thethe finitefinite reservesreserves and the associated economic and environmental concerns.concerns. The need for alternative routes for -
1-Butanol Dehydration and Dehydrogenation Over Vanadium Aluminium Oxynitride Catalysts
ACADEMIA ROMÂNĂ Rev. Roum. Chim., Revue Roumaine de Chimie 2011, 56(2), 151-159 http://web.icf.ro/rrch/ 1-BUTANOL DEHYDRATION AND DEHYDROGENATION OVER VANADIUM ALUMINIUM OXYNITRIDE CATALYSTS Mihaela FLOREA,a* Stephanie DELSARTE,b Elisabeth van KEULENb and Paul GRANGEb** aDepartment of Chemical Technology and Catalysis, Faculty of Chemistry, University of Bucharest, B-dul Regina Elisabeta 4-12, Bucharest 030018, Roumania bCatalyse et chimie des matériaux divisés, Université catholique de Louvain, Croix du Sud 2, Boite 17, Louvain-la-Neuve, 1348, Belgium Received July 5, 2010 Amorphous high surface area vanadium aluminium oxynitrides (VAlON) are prepared by nitridation of vanadium aluminium oxide precursors. The acid-base and redox properties of VAlON depend on their nitrogen content, as well as on the V/Al ratio of the reactive precursor. The influence of these parameters over the catalytic properties of VAlON for 1-butanol dehydration/dehydrogenation was studied. For the studied samples, the only detected products were 1-butene, butane and butanal. The presence of butane as a major product could be explained by a hydrogen transfer mechanism. INTRODUCTION∗ nitrogen species, may cause important differences in the catalytic behavior .6 Oxynitride systems become extensively studied The reactivity of 1-butanol over catalysts has as a new class of catalysts because of their been extensively used to evaluate the nature, the particular acid-base properties. Nitridation of strength and the concentration of the acid-base amorphous oxide precursors induces a decrease of sites 7-10 since the product selectivities are the number of acid sites and the creation of basic influenced by the acid-base properties of the centers as is shown for aluminophosphate catalysts.