DOCSLIB.ORG

Study of Paraffin Oxidation in a Batch Reactor

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Study of Paraffin Oxidation in a Batch Reactor International Journal of Innovation in Science and Mathematics Volume 2, Issue 1, ISSN (Online): 2347–9051 Study of Paraffin Oxidation in a Batch Reactor S. J. Purohit1, Dr. Milind Pradhan 1Research Scholar at Bhagwant University and working in Chemical Engineering Department, Thadomal Shahani Engineering College, Mumbai University, India Email: [email protected] Abstract – The oxidation of paraffin has been keen interest and the unreacted charge stock is recycled. Perchenko3 by several workers from all over the world as the oxidation employed a mixture of potassium permanganate and leads to various functional groups in Hydrocarbon chain manganese dioxide and recommended optimum both saturated and unsaturated one. concentration of oil. Further increase in the concentration Liquid phase Oxidation of paraffin wax to fatty acids was of catalyst resulted in retardation of the oxidation process. first exploited in Germany to replace partly the import of 2 fats, during Second World War, since than the process has Triandafilidi reported improvement in air uptake and been successfully commercialized in several countries like reduction by 50 % of air requirement. The maximum USA, USSR and East Germany. permissible temperature for air oxidation in the foam The oxidation leads predominantly to the formation of phase, with manganese naphthenate as a catalyst was secondary alcohols consisting of a mixture of all possible reported to be 180 0C18 , higher temperature were found to isomers with the same number of carbon atoms in the cause formation of Tar. An optimum temperature of 140- molecules as the initial hydrocarbons. The secondary 160 OC was recommended. .Zilberg et al7 and Ignonin and alcohols which are oxidation products of paraffin exhibit co –workers 12,13 have investigated the oxidation of excellent hydrolytic, oxidative and color stability, because of branched chain paraffin hydrocarbons to branched chain the nature of their branching. These alcohols have lower acids. melting points than straight chain alcohols of corresponding 1,3,6 length, while retaining their high temperature stability. The N.M Emanuel has carried out paraffin oxidation by oxidation of paraffin wax to fatty acids is carried out in ozonized air at different induction periods and proved that temperature range 110 0C- 140 0C. rate of reaction increases manifold with varying induction Paraffin oxidation which is carried out by ALFOL, Oxo- periods processes, are high temperature, high pressure processes Paraffin oxidation mechanism which utilize expensive catalysts, making them energy intensive as well as expensive. Keywords – Paraffin Oxidation, Catalyst, Batch Reactor, Fatty Acids, and Fatty Alcohols. I. INTRODUCTION Company like Petrolite Corporation and Alox Corporation manufacture a wide range of oxygenated hydrocarbons. These products are produced by the Available Technologies controlled liquid phase partial oxidation of various The oxidation of paraffin wax to fatty acids is normally petroleum fractions. Normally these oxides are mixtures of carried out in temperature range 110 0C- 140 0C14. In the organic acids, oxy acids etc.They vary from one another in reaction, the effect of mass transfer can be eliminated by molecular weight (determined by raw material selected). keeping sufficiently high value of air flow rate initially. And esters of oxidation. These oxidates are used in rust BASHKIROV PROCESS1 is largely used on an preventives, oil soluble lubricating agents, emulsifiers, or industrial scale, is based on paraffin oxidation at 165- demulsifies, corrosion inhibitors etc. 170oC using 5 Weight % boric acid, and using a mixture The Oxidation of paraffin played a special role in the of nitrogen and oxygen with oxygen content of 3.5 to 4.2 case of saturated hydrocarbons containing 20 -25 carbon vol %.drastic oxidation could lead to glycols and id- atoms. Oxidation leads to various fatty acids of higher carboxilic acids. To increase the selectivity of oxidation molecular weight, from formic acid to soap fatty acid. mixed catalysts are frequently used ie. Manganese, Available Literature: 6, 7 potassium and sodium. Catalyst helps in increasing Nesmelov and coworkers have reported significant conversion of paraffin oil. improvement in yield and quality of fatty acids by Paraffin oxidation which is carried out by ALFOL, Oxo- continuous foam phase oxidation. And recommended use processes, are high temperature, high pressure processes of 5 %alcohol from sperm whale oil along with soda ash to which utilize expensive catalysts, making them energy obtain homogeneity in foam phase. Higher conversion intensive as well as expensive. The maximum conversion levels beyond 50 % leads to the formation of more achieved yet by existing processes is 15% for a batch time oxygenated and water soluble acids and hence the of 4 hours. oxidation is stopped when the degree of conversion is The rate of oxidation may be increased by increasing the between 30 to 50 %. Higher conversion levels decolorized inter -facial area by Foam in a reactor,12 where we can get the products therefore, conversion is generally restricted Copyright © 2014 IJISM, All right reserved 167 International Journal of Innovation in Science and Mathematics Volume 2, Issue 1, ISSN (Online): 2347–9051 significant improvement in the yield and quality of fatty Samples were collected from bottom (50 ml app.) and acids by continuous foam. were analyzed for acid contents by titration. The fatty Extensive information is available regarding paraffin alcohol analysis has been performed using GC -mass oxidation mechanism. However; most of the information’s Spectrophotometer. Visible range 400-700 nm are relevant for paraffin oxidation processes and its studies spectrophotometer is used extensively. And readings are in batch and continuous operations, Very little information taken every 20nanometersalong the visible range. And is available for the paraffin oxidation studies in foam produce a spectral reflectance curve. Fatty acids contained reactor and its kinetic studies. in the alcohols were separated by Saponification and In this paper paraffin Oxidation has been carried out in a subsequent distillation. Alcohols have been set free by foam reactor at moderate temperature and pressure with Hydrolysis. Primary alcohols were prepared by vacuum suitable catalyst. The Effect of concentration vs distillation.5,6 conversion of products have been studied. The bottom Products contained only secondary alcohols. Which were analysed by GC –mass Spectrophotometer. II. METHODOLOGY The product stream was separated into organic layer and aqueous layer using a separating funnel. The major products of paraffin oxidation are The properties of paraffin oil 1. Fatty Acids 1. Appearance: Clear colourless, viscous liquid. 2. Fatty Alcohols 2. Odour: Odourless 3. Esters 3. Solubility: Negligible (<0.1 %) 4. Aldehydes and Ketones. 4. Specific gravity: 0.86-0.91 The raw materials used are paraffin oil, combination of 5. Volatiles by volume at 21°C: Nil catalyst such as potassium permemegenate (KMNO4), 6. Melting Point: -18 to -25 °C magnesium oxide (MgO) and mixture of potassium 7. Vapour Pressure: <0.5 mm Hg at 20 °C permegagent and magnesium oxide. Paraffin oil is pre 8. Flash Point: 220 °C heated to 120oc and charged to a reactor along with catalyst in slurry form foam is generated with the reagent Experimental Set –Up sodium lauryl sulphate. The reaction is carried out for 2, 3 hours. The samples are analyzed using UV spectroscopy. Experimental Details The foam reactor used in the present experimental work was a laboratory scale reactor similar to that described by Bashkirov and Solviet process,1,11,12 having 6.38 cm diameter; and100cm length. Reactor has been made from glass; advantage is non-corrosive in nature, transparent, and resistant to many chemicals. Glass reactors were packed with packing material, rasching rings, up to 15 cm height; size of rasching rings 12*12 mm.For measuring flow rates, rota meters were installed at the inlet for both air and water having Range (1-250 lpm).Paraffin oil was heated in SS vessel having capacity 5lits.SS vessel was provided with internal cladding of alumina with internal heater (0-200 oc) and temperature indicator. Samples after oxidations were collected in a flask having capacity 250 ml. Experimental procedure The initial temperature has been maintained between 120-130°C. The air flow-rate has been maintained between 1-5 liters per minute and water flow rate, one lit/min.. The catalysts used were: Potassium permanganate; Magnesium Oxide. The surfactant used was Sodium laurel sulphate in a slurry form; Concentration was kept max 5 % by weight. Chemicals used Paraffin oil, a combination of catalyst such as Fig.2. Experimental Set-up magnesium Oxide (MgO), Potassium paramagnet (KMnO4). Sample calculation: for Table no -8 Absorbance = K1*concentration +K0 K1= 0.0960 K0= The reaction has been carried out for about 2, -3 hrs. 0.0007 The samples were collected at the interval of one hr. 1.510=0.0960*concentration+0.0007 Copyright © 2014 IJISM, All right reserved 168 International Journal of Innovation in Science and Mathematics Volume 2, Issue 1, ISSN (Online): 2347–9051 Therefore concentration = 3.55 gmol/lit [7] Zil’berg, G.A. and Smirnova, S.M. Dok. Akad. Nauk, USSR, C = C (1-X ) 166(3), 643 (1966); C.A. 64, 11046 (1966). A A0 A [8] Neftepereab Neftekhim, C.A., 98, 91367m(1982). CAo= 14.33(pure paraffin oil), CA = 3.55, Therefore XA= [9] Paraffins Chemistry and Technology by Asinger, Pergaman
Load more

Recommended publications
  • United States Patent (19) 11) 4,282,163 Suzuki Et Al
    United States Patent (19) 11) 4,282,163 Suzuki et al. 45) Aug. 4, 1981 (54) METHOD OF PRODUCING (56) References Cited HYDROGENATED FATTY ACIDS U.S. PATENT DOCUMENTS 1,247,516 11/1917 Ellis ...................................... 260/409 75 Inventors: Masao Suzuki, Nishinomiya; Takeshi 1927,850 9/1933 Schellmann et al. ................ 260/409 Matsuo; Naomichi Yamada, both of 2,862,943 12/1958 Wheeler ............................... 260/419 Amagasaki, all of Japan 3,197,418 7/1965 Maebashi ... 260/409 3,896,053 7/1975 Broecker et al. 260/409 4,163,750 8/1979 Bird et al. ............................ 260/409 73) Assignee: Nippon Oil and Fats Co., Ltd., Japan 4,179,454 12/1979 Mehta et al. ......................... 260/409 Primary Examiner-John F. Niebling (21) Appl. No.: 102,533 Attorney, Agent, or Firm-Stevens, Davis, Miller & Mosher 22 Filed: Dec. 11, 1979 57 ABSTRACT Hydrogenated fatty acid having excellent color and 30 Foreign Application Priority Data stability can be obtained by hydrogenating fatty acid, oil or fat, and distilling the crude hydrogenated fatty Dec. 19, 1978 JP Japan ................................ 53-157101 acid; or splitting the hydrogenated oil or fat into crude hydrogenated fatty acid and distilling the crude 51) Int. Cl.............................. .................. C11C3/12 hydrogenated fatty acid. 52) U.S. Cl. ..................................... 260/409; 260/419 58 Field of Search ................................ 260/409, 419 10 Claims, No Drawings 4,282,163 2 and acid oils formed as a by-product in the purification
    [Show full text]
  • Summaries of FY 1991 Research in the Chemical Sciences
    )Is - I~ )~i~TiI ~i*ii i~T -~~~~~~~~~~~~~~~~~~-l 9~~~~~~~~~~rsrr A S.~~~~~~~:Ir I... - - 0~Iii Available to DOE and DOE contractors from the Office of Scientific and Technical Information, P.O. Box 62, Oak Ridge, TN 37831; prices available from (615) 576-8401, FTS 626-8401. Available to the public from the National Technical Information Service, U.S. Department of Commerce, 5285 Port Royal Rd., Springfield, VA 22161. DOE/ER-01 44/9 (DE91011221) August 1991 Distribution Categories UC-400 and UC-401 Summaries of FY 1991 Research in the Chemical Sciences U.S. Department of Energy Office of Energy Research b^~~~~~~~~~~~~ ~~~~~Division of Chemical Sciences I This report was compiled for the Office of Energy Research from project summaries contained in the Research-In-Progress (RIP)database of the Office of Scientific and Technical Information, Oak Ridge, ; ^<-<~~~~~~~~~~~~~~ ~~Tennessee. The RIP database describes new and jr';(;-i~~~~~~~~ l ~~~~~~ongoingenergy and energy-related research projects carried out or sponsored by the Department of Energy. s .» \ Contents PREFACE vii University of Arizona 34 CHEMICAL SCIENCES DIVISION viii Boston University 34 PROGRAM SUMMARIES ix Brandeis University 34 LABORATORY ADMINISTRATION xi California Institute of Technology 35 University of California, Berkeley 35 NATIONAL LABORATORIES University of California, Irvine 35 Photochemical and Radiation Sciences University of California, Los Angeles 36 Ames Laboratory 1 University of California, Santa Barbara 36 Argonne National Laboratory 2 Clemson University
    [Show full text]
  • ACTIVATION of N-HEXANE USING VANADIUM-EXCHANGED ZEOLITES by THIRUSHA NAICKER
    ACTIVATION OF n-HEXANE USING VANADIUM-EXCHANGED ZEOLITES BY THIRUSHA NAICKER Submitted in fulfilment of the academic requirements for the degree of Doctor of Philosophy in the School of Chemistry, University of KwaZulu-Natal, Durban July 2010 As the candidate’s supervisor I have/have not approved this thesis/dissertation for submission Signed: _______________ Name: _______________ Date: __________ DEDICATION To my dad and mum, I love you lots. ii ABSTRACT The influence of the form of the ZSM-5 zeolite, vanadium content and the elimination of the exterior surface acidity on the activity and selectivity of n-hexane oxidation was studied using a fixed bed reactor. Blank reactor studies (carborundum packed reactor) showed no conversion below 450°C with the highest conversion (8%) at 500°C. The dominant products were found to be carbon oxides (Sel./% = 90) with minor selectivities to the hexene isomers (7%) and the remainder being cracked products, THF and benzene. H-ZSM-5 with different SiO2/Al2O3 ratios (100 and 320) and Na-ZSM-5 (SiO2/Al2O3 ratio of 100) were tested under non-oxidative and oxidative conditions. Under oxidative conditions as the ratio of the SiO2/Al2O3 increased, the aluminium content decreased and so too did the cracking ability of the zeolite (i.e. yield of cracked products dropped from 36% to 8%). However, the use of the Na- form of ZSM-5 completely eliminated acid cracking. Under oxidative conditions H-ZSM-5 (100) was found to be more active and resulted in higher formation of cyclic and aromatic compounds. With increasing time on-stream and higher temperatures the catalyst was found to deactivate.
    [Show full text]
  • Paraffin Oxidation Studies
    International Journal of Engineering Innovation & Research Volume 2, Issue 1, ISSN: 2277 – 5668 Paraffin Oxidation Studies Mrs. S. J. Purohit, Dr. Milind Pradhan Prof. Purohit S. J. is a Research Scholar at Bhagwant University & Working at Thadomal Shahani Engg. College, Bandra Mumbai-50. Email:[email protected] Abstract – The oxidation of paraffin has been studied with Many processes were developed to manufacture fatty keen interest by several workers from all over the world; as acids of various molecular weights. The manufacture of oxidation leads to the introduction of various functional higher fatty alcohols; which have potential uses as starting groups in hydrocarbon chains. Processes involving the material for the manufacturing of lubricating oil, additives, Oxidation of Paraffin’s in the liquid phase, using air or synthetic lubricating oil, plasticizers and others. A more oxygen are of great importance to industrialized economies because of their role in converting petroleum hydrocarbon selective process for the oxidation of paraffin to alcohols feed stocks such as alkanes, olefins and aromatics into has been conducted by Bashkirov , khim and co workers; industrial organic chemicals important in the polymer, who conducted the reaction in the presence of Boric acid. petrochemicals ,cosmetics and detergent industries. The alcohols are stabilized in the form of their esters; The oxidation leads predominantly to the formation of which are resistant to further oxidation and hence very secondary alcohols consisting of a mixture of all possible high selectivity is achieved.[2,3] isomers with the same number of carbon atoms in the Paraffin oxidation mechanism molecules as the initial hydrocarbons. The secondary 1st stage alcohols which are oxidation products of paraffin exhibit excellent hydrolytic, oxidative and color stability, because of Hydrocarbon → Hydro peroxide the nature of their branching.
    [Show full text]
  • Oxidation Stability of Fuels in Liquid Phase Karl Chatelain
    Oxidation stability of fuels in liquid phase Karl Chatelain To cite this version: Karl Chatelain. Oxidation stability of fuels in liquid phase. Chemical engineering. Université Paris- Saclay, 2016. English. NNT : 2016SACLY020. tel-01958391 HAL Id: tel-01958391 https://pastel.archives-ouvertes.fr/tel-01958391 Submitted on 18 Dec 2018 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. NNT : 2016SACLY020 THÈSE DE DOCTORAT DE L’UNIVERSITE PARIS-SACLAY préparée à L’ENSTA ParisTech ÉCOLE DOCTORALE N±579 Sciences Mécaniques et Énergétiques, Matériaux et Géosciences (SMEMAG) Spécialité de doctorat : Génie des procédés par Karl CHATELAIN Etude de la stabilité à l’oxydation des carburants en phase liquide Thèse présentée et soutenue à Rueil-Malmaison, le 15 décembre 2016 Composition du jury : Dr. André NICOLLE Président IFP Energies nouvelles, R102 Pr. Richard WEST Rapporteur Northeastern University, Boston, CoMoChEng Pr. Pierre-Alexandre GLAUDE Rapporteur CNRS Nancy, LRGP Dr. Mickael SICARD Examinateur ONERA, DEFA Dr. Thomas DUBOIS Examinateur TOTAL ACS Dr. Laurie STARCK Examinateur IFP Energies nouvelles, R104 Mme. Arij BEN AMARA Examinateur IFP Energies nouvelles, R104 Pr. Laurent CATOIRE Directeur de Thèse ENSTA ParisTech, Université Paris-Saclay, UCP ii Acknowledgements This work was made possible thanks to the support of the IFP Energies nouvelles (IFPEN) and the chemical engineering laboratory (UCP) of the ENSTA ParisTech, Université Paris-Saclay.
    [Show full text]
  • I Finai Summary
    NASA CONTRACTOR NASA CR-1104 REPORT I Finai Summary , NATIONAL AERONAUTICS ,4ND SPACE ADMINISTRATION WASHINGTON, D. C. JULY 1968 NASA CR-1104 STUDY OF METHODS FOR CHEMICAL SYNTHESIS OF EDIBLE FATTY ACIDS AND LIPIDS Final Summary Edited by John W. Frankenfeld Distribution of this report is provided in the interest of information exchange. Responsibility for the contents resides in the author or organization that prepared it. Prepared under Contract No. NAS 2-3708 by ESSO RESEARCH AND ENGINEERING COMPANY Linden, N.J. for Ames Research Center NATIONAL AERONAUTICS AND SPACE ADMINISTRATION For sale by the Clearinghouse for Federal Scientific and Technical Information Springfield, Virginia 22151 - CFSTI price $3.00 PRECEDING PAGE BLANK NOT FILMED. I* The authors wish to express their appreciation for the assistance V PRECEDING PAGE BLANK NOT FILMED. CONTENTS Page LIST OF FIGURES ix LIST OF TABLES X SUMMARY 1 INTRODUCTION 2 Human Energy Requirements - Advantages of Fats 2 Statement of the Problem 3 Approach - Assumptions 4 TECHNICAL Di SCiiSSION 6 Historical - The German Process 6 REDUCTIVE POLYMERIZATION OF CARBON MONOXIDE 10 The Fischer-Tropsch Synthesis 10 Wax Cracking and Oxidative Dehydrogenation 19 The Ziegler Reaction 20 Telomerization of Ethylene and Acetylene 25 SYNTHESIS OF ETHnENE AND CONVERSION OF Cog TO CO 26 Ethylene y& Methane and Acetylene 26 Reduction of Carbon Dioxide to Carbon Monoxide 29 Conversion of Carbon Monoxide to Ethylene 31 CONVERSION OF HYDROCARBONS TO ACIDS 34 Oxidation of Paraffins 34 Oxidation of Olefins 34 Ozonolysis
    [Show full text]
  • United States Patent Office Patented Aug
    ..., 2,846,330 United States Patent Office Patented Aug. 5, 1958 1. 2 2,846,330 mixing may be carried out in the presence of Solvents, for example benzine or turpentine oil, and it is not neces WAX CoMPOSITIONS sary to separate the wax components before they are Erich Berthold, Hans Hoyer, and Guido von Rosenberg, finally worked up to yield, for example shoe creams or Gersthofen, Germany, assignors to Farbwerke Hoechst floor waxes. - . Aktiengesellschaft vormals Meister Lucius & Bruning, The preferred ratio of wax acids to fatty acids is be Frankfurt am Main, Germany, a corporation of Ger tween 75 and 97 parts of wax acids and 25 and 3 parts many of fatty acids, a ratio between 85 and 96 parts of wax No Drawing. Application December 31, 195 acids and 15 and 4 parts of, fatty acids being especially Serial No. 479,213 10 advantageous. The metal content generally ranges from 0.5 percent to 10 percent, preferably from 1 percent to Claims priority, application Germany December 31, 1953 5 percent, calculated upon the total amount of the par 8 Claims. (Cl. 106-268) tially saponified mixture of esters. The ratio of calcium and the second metal may be chosen at will, the preferred The present invention relates to compositions of wax, ratio lying within the range from 1:5 to 5:1. w fatty acid esters and fatty acid salts. Among the salts mentioned above zinc salts are of It is known to prepare and use waxes containing, in special advantage. - addition to the esters of the acids obtained by chromic Particularly suitable acid components are, beside the acid oxidation of montana wax, calcium salts of the said oxidation products of montana wax having an acid num acids.
    [Show full text]
  • BACTERIAL HYDROCARBON OXIDATION Davis
    BACTERIAL HYDROCARBON OXIDATION I. OXIDATION OF n-HEXADECANE BY A GRAM-NEGATIVE COCCuS' JAMES E. STEWART,2 3R. E. KALLIO, D. P. STEVENSON, A. C. JONES, AND D. 0. SCHISSLER Department of Bacteriology, State University of Iowa, Iowa City, Iowa, and Shell Development Company, Emeryville, California Received for publication March 17, 1959 The pioneering work of Sohngen (1913) es- (Brown and Strawinski, 1958; Dworkin and tablished that a variety of aerobic microorganisms Foster, 1956). Many reports in the literature are capable of growing at the sole expense of indicate that fatty acids, aldehydes, or alcohols diverse paraffins. These findings have been have been recovered from cultures oxidizing extended and corroborated so often since then aliphatic paraffins (see Beerstecher, 1954, for that detailed documentation does not seem neces- complete citations). In no case, however, has a sary here, especially since the subject of microbial fatty acid (or other intermediate) been identi- hydrocarbon oxidation has been comprehensively fied which has a carbon skeleton identical to the and frequently reviewed (Beerstecher, 1954; alkane being oxidized, thus leaving in question Davis and Updegraff, 1954; ZoBell, 1950). the locus of the primary enzymatic attack on the Despite the extensive literature on the subject alkane molecule. of the mechanisms by which bacteria and other This paper summarizes preliminary findings of microorganisms attack hydrocarbons, the re- a study undertaken to investigate the mecha- actions have not been subjected to intensive
    [Show full text]
  • Fischer-Tropsch Refining
    Fischer-Tropsch Refining by Arno de Klerk A thesis submitted in partial fulfillment of the requirements for the degree Philosophiae Doctor (Chemical Engineering) in the Department of Chemical Engineering Faculty of Engineering, the Built Environment and Information Technology University of Pretoria Pretoria South Africa February 2008 Fischer-Tropsch Refining Author: Arno de Klerk Promoter: Prof. Philip L. de Vaal Department: Department of Chemical Engineering, University of Pretoria Degree: Philosophiae Doctor (Chemical Engineering) Synopsis Energy carriers, such as coal, natural gas and biomass, can be converted by Fischer-Tropsch technology into synthetic crude (syncrude). Fischer-Tropsch derived syncrude can then be refined to transportation fuels, such as motor-gasoline, jet fuel and diesel fuel. These fuels meet the same specifications as crude oil derived transportation fuels. Conventional refining technologies have to be adapted to deal with Fischer-Tropsch syncrudes, because they differ significantly from crude oil with respect to composition. Some of the key differences are the high concentration of oxygenates and olefins and absence of sulphur in Fischer-Tropsch syncrude. Imposing a crude oil refining methodology on syncrude can lead to unwieldy and expensive refineries. Yet, despite an abundance of literature of Fischer-Tropsch synthesis, there is little literature that deals with the refining of Fischer-Tropsch syncrude. The present study investigated current refining practice for both crude oil and Fischer- Tropsch syncrude in order to identify fundamental differences in their refining focus and conversion behaviour. This was followed by a critical evaluation of the compatibility of syncrudes from high temperature Fischer-Tropsch (HTFT) and low temperature Fischer- Tropsch (LTFT) synthesis with the chemistry and catalysis of various conversion processes.
    [Show full text]
  • LD5655.V856 1987.C666.Pdf
    DESIGN AND C.HARACTERrZA'.rION OF ZEOLITE SUPPORTED COBALT CARBONYL CATALYSTS by Melissa Clare Connaway Dissertation sul::xnitted to the Faculty of the Virginia Polytechnic Institute and State University in partial fulf illroent of the requirements for the degree of OOCTOR OP PHILOSOPKY in Chemistry APPROVED: a. E. Hanson, Chairman J. G. Dillard J. M. Tan'i?o M.. E. Davis July, 1987 Blacksburg, Virginia DES!G~ AND CHARACTERIZATION OF ZEOLITE SUPPORTED COBALT CARBONYL CATALYSTS by Melissa Clare Connaway Comlni ttee Chairman: Brian E. Hanson Chemistry (ABSTRACT) Transition metal compounds such as co2 (C0) 8 have often been used to catalyze variuus organic reactions. Severe difficulties may be ancountered when atte1npts are made to recover and separate the soluble ~atalysts. A heterogeneous system consisting of co2 (C0) 8 impregnated on zeolites with faujasitic structure has been designed and investigated using a variety of techniques. In situ FTIR spectroscopy and carbon monoxide evolution were used to identify the major products generated, namely co4 (C0) 12 and Co(C0) 4 • Disproportionation may be induced thus forming Co(C0) 4 and an associated cation from the supported subcarbonyls by additi.on o.t various ligands such as methanol. The location of the supported cobalt carbonyls is determined by their reactivity toward various pnosphi.1es wi.tn various kineti.c diameters. rhe materials prepared in chis manner were found to be active in cat.ilyzing tae metha11ol carbonylation reaction and following thermolysis w~re also found to be active Fischer-Tropsch catalysts. Major products observed in the carbunylaciJn of methanol were methyl acetate and an acetaldehydd dimetnyl aceta1.
    [Show full text]
  • The Processing of Wax and Wax Additives with Supercritical Fluids
    The processing of wax and wax additives with supercritical fluids By Cara Elsbeth Schwarz Dissertation presented for the Degree of DOCTOR OF PHILISOPHY (Chemical Engineering) In the Department of Process Engineering At the University of Stellenbosch Promoted by Prof. I. Nieuwoudt Prof. J.H. Knoetze Stellenbosch December 2005 Declaration I, the undersigned, hereby declare that the work contained in this thesis is my own original work and that I have not previously in its entirety or in part submitted it at any university for a degree. Cara Elsbeth Schwarz 16 September 2005 i ii Abstract Waxes have many potential uses but large-scale application is hampered by their virtual insolubility. By grafting the wax with a polyethylene glycol segment to form an alcohol ethoxylate, the solubility of the wax in commercial solvents is significantly increased. Alcohol ethoxylates are produced by the polymerisation addition of ethylene oxide onto an oxidised wax. Current methods of alcohol ethoxylate production from alcohols lead to wide ethylene oxide addition distribution and large quantities of residual alcohol. The objective of this study is to provide a method for narrowing the ethylene oxide distribution and to reduce the residual alcohol content. It is proposed to concentrate the alcohol ethoxylate in a post-production separation process using supercritical fluid extraction. The system is modelled to contain three pseudo-components: an alkane, an alcohol and an alcohol ethoxylate. Propane is selected as the supercritical solvent of choice due to the large solubility difference between the alkane and polyethylene glycol. Lower molecular weight alkane phase equilibrium data with propane is abundant but extrapolation to higher molecular weights requires further investigation as it may be complicated by molecular folding.
    [Show full text]
  • METHYL KETONE METABOLISM in HYDROCARBON-UTILIZING MYCOBACTERIA Cane-I-C'4. Aliphatic Alkane-Utilizing Mycobac
    METHYL KETONE METABOLISM IN HYDROCARBON-UTILIZING MYCOBACTERIA H. B. LUKINS' AND J. W. FOSTER Department of Microbiology, The University of Texas, Austin, Texas Received for publication 15 December 1962 ABSTRACT which micro- LUKINS, H. B. (University of Texas, Austin) The most common means by in organisms utilize aliphatic, saturated hydrocar- AND J. W. FOSTER. Methyl ketone metabolism bons is an oxidative attack at a terminal methyl hydrocarbon-utilizing mycobacteria. J. Bacteriol. group (for literature see Fuhs, 1961; Foster, 1962a, 85: 1074-1087. 1963.-Speciesof Mycobacterium especially M. smegmatis 422, produced the homol- b). The usual first, stable product is the homol- ketones the oxidation of ogous primary alcohol which is further converted ogous methyl during to this in turn propane, n-butane, n-pentane, or n-hexane. A the corresponding fatty acid; carrier-trapping experiment demonstrated the undergoes beta-degradation of the carbon chain. formation of 2-undecanone, as well as 1,11-un- As early as 1932, methyl ketones were sus- the oxidation of unde- pected of being involved in paraffin oxidation; decanedioic acid, during Aspergillus versicolor, which grew at the expense cane-i-C'4. Aliphatic alkane-utilizing mycobac- of was teria were able to at the of several long-chain paraffins, also able to grow at grow expense the expense of related methyl ketones (Hopkins aliphatic methyl ketones as sole sources of carbon. and Other ketones which did not support growth Chibnall, 1932). Recently, Pseudomonas were oxidized by resting bacterial suspensions. M. methanica was discovered to produce methyl smegmatis 422 cells grown on propane or acetone ketones, along with alcohols and fatty acids, were simultaneously adapted to oxidize both during the oxidation of gaseous alkanes (Lead- substrates, as well as n-propanol.
    [Show full text]