DOCSLIB.ORG

Process Development for Upgrading Low Value Α C8-Olefin from Fischer-Tropsch to 2-Hexyl-Nonanal

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text

Load more

Process development for upgrading low value α C8-olefin from Fischer-Tropsch to 2-hexyl-nonanal by Simbarashe Fidelis Denhere (BEng. Chemical) Thesis presented in partial fulfilment of the requirements for the Degree of MASTER OF ENGINEERING (CHEMICAL ENGINEERING) in the Faculty of Engineering at Stellenbosch University Supervisor Dr. Percy Van der Gryp Co-Supervisor/s Professor Manie Vosloo December, 2016 Stellenbosch University https://scholar.sun.ac.za i DECLARATION By submitting this thesis electronically, I declare that the entirety of the work contained therein is my own, original work, that I am the sole author thereof (save to the extent of explicitly stated), that reproduction and publication thereof by Stellenbosch University will not infringe any third party rights and that I have not previously in its entirety or in part submitted for any publication. Signature:………………………………….. S. F Denhere, Date:……………………………………. Copyright © 2016 Stellenbosch University All rights reserved. Stellenbosch University https://scholar.sun.ac.za ii ABSTRACT A wide variety of speciaIty chemicals are now available from technology based on the olefin metathesis reaction. This versatile reaction aIIows the conversion of simpIe, relatively inexpensive olefins into specialty, high-purity olefins which are useful intermediates in the fragrance, agricuIturaI, and many other specialty chemical industries. Literature has shown that low value (C5-C9) olefins produced from a Fischer-Tropsch reaction can be used as important feedstocks for the manufacture of high value, detergent range linear internal alkenes (C10-C18). These detergent range internal alkenes could then be subsequently functionalised during hydroformylation to asymmetric aldehydes, which can be used as intermediates for manufacturing Guebert-type surfactants. The DST-NRF Centre of Excellence in Catalysis (change) have investigated the efficacy of homogeneous catalysts towards upgrading low value, unique olefinic feedstocks from a Fischer-Tropsch product stream through the RSA Olefins programme. The homogeneous catalysts are reported to be highly selective and reactive but are not employed industrially because they are expensive and decompose as the high boiling products are distilled from the reaction medium. Hence, the RSA Olefins programme of the DST-NRF Centre of Excellence in Catalysis has been active in developing organic solvent nanofiltration (OSN) membrane technology to allow for efficient separation and subsequent recycling of the homogeneous catalysts. Using literature sources and industrial catalogues, an initial screening of catalyst systems was done to select candidate catalytic systems for the metathesis of low value 1-octene (C8) and the subsequent hydroformylation of 7-tetradecene (C14) to detergent range products. The criteria such as catalyst cost, selectivity (product distribution), turnover number (TON) together with economic potential (EP) values determined at five levels of design were used to develop candidate processes using the Douglas hierachichal method. The Hoveyda-Grubbs 2 (HGr-2) precatalyst and water-soluble Rh-TPPTS were selected for the metathesis of 1-octene and Stellenbosch University https://scholar.sun.ac.za iii hydroformylation of 7-tetradecene respectively. Two process scenarios A (liquid multiphase system) and B (OSN membrane) were developed and evaluated using a techno-economic analysis (TEA) model. The viewpoints of design and performance were developed by integrating the technical and economic information through Aspen PlusTM process simulation and sensitivity analysis of the key operating parameters. The goal was to detect promising process concepts as early as possible and to single out the crucial parameters such that experimental and modelling work can be focused on those alternatives that most likely will lead to an economic process. The discounting cash flow (DCF) method was used to evaluate the two process scenarios A (liquid multiphase system) and B (OSN membrane process) producing 10 000 tonnes per annum of 2-hexyl-nonanal at a purity of 99 wt. %. The feedstock to be used is low value 1- octene a Fischer-Tropsch Synthol product stream. The performance criterion is to maximise the net present value (NPV) of the process. The NPV included revenues, total capital investment and depreciation costs was determined based on interest rate of 15 % and the lifetime of 15 years. Economic parameters such as internal rate of return (IRR %) and payback period (PBP) were calculated for each scenario. The results were then used to determine the configuration with the most favourable economic indicators. The two process scenarios studied proved to be profitable with IRR % ranging between 58 % and 83 % with scenario B having the highest NPV and IRR %. The NPV for scenario A and scenario B were $ 439 M and $ 563 M respectively at the end of project life of 15 years. The IRR % for process scenario A was 59 % compared to scenario B of 83 % for the same pay back period of 3 years. Sensitivity analysis were performed on the two process scenarios. The parameters investigated were: 2-hexyl-nonanal selling price; Rh-TPPTS catalyst cost; 1-octene feed cost; HGr-2 catalyst cost and tax rate %. Their impact on NPV and IRR % was evaluated. Curve diagrams were constructed to illustrate the effect of variation of different cost parameters on NPV and IRR %. The most effective input variables for the two process scenarios were 2-hexyl-nonanal selling price, Rh-TPPTS and HGr-2 catalyst cost on both NPV and IRR. The Stellenbosch University https://scholar.sun.ac.za iv process scenario B which considers OSN membrane technique for catalyst recovery was the most profitable configuration and the NPV was 22 % better than the liquid multi phase system. Keywords: Low value olefins, metathesis, hydroformylation, functionalized hydrocarbons, OSN membrane, techno-economic evaluation, DCF, NPV, IRR %. Stellenbosch University https://scholar.sun.ac.za v OPSOMMING Proses ontwikkeling vir die opgradering van lae waarde alpha-C8 olefiene vanaf die Fischer-Tropsch proses na 2-heksiel nonaal. ʼn Groot verskeidenheid gespesialiseerde chemikalieë is hedendaags beskikbaar te danke aan tegnologie wat gebaseer is op die olefiene-metathesis reaksie. Hierdie veelsydige reaksie laat die omskakeling van eenvoudige en relatief goedkoop olefiene toe na meer gespesialiseerde, suiwer olefiene. Hierdie meer gespesialiseerde olefiene, is bruikbare oorbrugging chemikalieë vir die parfuum, landbou en verskeie ander chemiese industrieë. Literatuur wys daarop dat lae-waarde (C5-C9) olefiene, wat geproduseer word vanaf die Fisher-Trospch reaksie, gebruik kan word as belangrike roumateriale vir die vervaardiging van waardevolle, lineêre interne skoonmaakmiddel-reeks alkene (C10-C18). Hierdie reeks internerne skoonmaakmiddel alkene, kan gevolglik gefunctionaliseer word tydens hidroformilasie tot asimmetriese aldehiede, wat gebruik kan word as intermediêre middels vir die vervaardiging van Geubert-tipe benatters. Die doeltreffendheid van homogene katalisators om lae waarde, unieke olefiene voerstowwe van die Fischer-Tropsch synthol produkstroom op te gradeer, is ondersoek deur die olefiene program DST-NRF Centre of Excellence in Catalysis. Dit word gerapporteer dat die homogene katalisators hoogs selektief asook reaktief is, maar dat dit nie industrieel in werking gestel word nie, omdat dit baie duur is en ontbind tydens die distillasie proses, wanneer die produkte gedistilleer word vanaf die reaksie medium. Daarom is die olefiene program van die DST-NRF Centre of Excellence in Catalysis aktief besig om organiese oplosmiddel-nanofiltrasie (OSN) membraan tegnologie te ontwikkel, wat effektiewe skeiding en daaropvolgende herwinning van die homogene katalisator, toe te laat. ʼn Aanvanklike keuring van katalisators is gedoen, om kandidaat katalisator sisteme te identifiseer deur die gebruik van literatuur bronne en industriële katalogusse, vir die metatesis van lae waarde 1-okteen (C8) en daaropvolgende hidroformilasie van skoonmaakmiddels Stellenbosch University https://scholar.sun.ac.za vi 7-tetradekeen (C14) produk alkene. Katalisator koste, selektiwiteit (produk distribusie), TON tesame met EP waardes (teen 5 ontwerpsvlakke) is gekies vir die kriteria om katalisator sisteme te skep. Hierdie sisteme is geskep deur die hiërargiese metode soos gestipuleer in Douglas (1988). HGr-2 voor-katalisator en water oplosbare Rh-TPPTS was gekies vir die metatesis van 1-okteen en daaropvolgende hidroformilasie van 7-tetradekeen, onderskeidelik. Twee proses scenario’s, scenario A (vloeistof multi-fase sisteem) en scenario B (OSN membraan) was ontwikkel en deur ʼn tegno-ekonomiese analise (TEA model) te ondersoek. Die ontwerp en prestasie oogpunte was ontwikkel deur die tegniese en ekonomiese inligting in die simulasie program (Aspen PlusTM) te integreer, asook deur die sensitiwiteitsanalises van die kern bedryf parameters. Die doel was om belowende proses konsepte so vroeg as moontlik te identifiseer, en dus ook die kern parameters, sodat eksperimentele en modelleringswerk só opgestel kon word om te lei na die mees belowende ekonomiese prosesse. Die verdiskontering kontantvloei (DCF) metode was gebruik om die twee proses scenario’s, A (vloeistof multifase sisteem) en B (OSN membraan proses), te evalueer teen 10 000 ton per jaar 2-heksiel-nonanal, met ʼn massa suiwerheid van 99% vanaf die lae waarde 1-okteen Fischer-Tropsch Synthol produkstroom. Die Ekonomiese parameters, soos die internerne opbrengskoers (IRR %), terugbetalingstydperk
Recommended publications
  • Synthetic Turf Scientific Advisory Panel Meeting Materials

    Synthetic Turf Scientific Advisory Panel Meeting Materials

    California Environmental Protection Agency Office of Environmental Health Hazard Assessment Synthetic Turf Study Synthetic Turf Scientific Advisory Panel Meeting May 31, 2019 MEETING MATERIALS THIS PAGE LEFT BLANK INTENTIONALLY Office of Environmental Health Hazard Assessment California Environmental Protection Agency Agenda Synthetic Turf Scientific Advisory Panel Meeting May 31, 2019, 9:30 a.m. – 4:00 p.m. 1001 I Street, CalEPA Headquarters Building, Sacramento Byron Sher Auditorium The agenda for this meeting is given below. The order of items on the agenda is provided for general reference only. The order in which items are taken up by the Panel is subject to change. 1. Welcome and Opening Remarks 2. Synthetic Turf and Playground Studies Overview 4. Synthetic Turf Field Exposure Model Exposure Equations Exposure Parameters 3. Non-Targeted Chemical Analysis Volatile Organics on Synthetic Turf Fields Non-Polar Organics Constituents in Crumb Rubber Polar Organic Constituents in Crumb Rubber 5. Public Comments: For members of the public attending in-person: Comments will be limited to three minutes per commenter. For members of the public attending via the internet: Comments may be sent via email to [email protected]. Email comments will be read aloud, up to three minutes each, by staff of OEHHA during the public comment period, as time allows. 6. Further Panel Discussion and Closing Remarks 7. Wrap Up and Adjournment Agenda Synthetic Turf Advisory Panel Meeting May 31, 2019 THIS PAGE LEFT BLANK INTENTIONALLY Office of Environmental Health Hazard Assessment California Environmental Protection Agency DRAFT for Discussion at May 2019 SAP Meeting. Table of Contents Synthetic Turf and Playground Studies Overview May 2019 Update .....
  • Identification of Volatile Compounds (Vcs) in the Leaves Collected from ‘Gemlik’, ‘Halhalı’ and ‘Sarı Hasebi’ Olive Tree Varieties

    Identification of Volatile Compounds (Vcs) in the Leaves Collected from ‘Gemlik’, ‘Halhalı’ and ‘Sarı Hasebi’ Olive Tree Varieties

    Int. J. Sec. Metabolite, Vol. 4: 3 (2017) pp. 195-204 Special Issue 1: Research Article ISSN: 2148-6905 online Journal homepage: http://www.ijate.net/index.php/ijsm Identification of Volatile Compounds (VCs) in the Leaves Collected from ‘Gemlik’, ‘Halhalı’ and ‘Sarı Hasebi’ Olive Tree Varieties Ahmet DURSUN1, Zehra GÜLER *1, Dilek ÖZKAN1, Dilşat BOZDOĞAN-KONUŞKAN1 1Mustafa Kemal University, Faculty of Agriculture, Food Engineering Department, Hatay/TURKEY Received: 05 May 2017 – Revised: 19 June 2017 - Accepted: 21 August 2017 Abstract: There is a considerably interest on some fruits and leaves extracts such as olive leaf, due to their beneficial health effects. Olive leaf has been consumed as tea for many years. However, the studies on volatile compounds (VCs) of leaves are scarce. Therefore, this study was aimed to evaluate of VCs in the leaves collected from ‘Gemlik’, ‘Halhalı’ and ‘Sarı Hasebi’ olive trees varieties grown in Hatay province. The VCs were analyzed by gas chromatography-mass spectrometry (GC-MS) using solid phase micro-extraction (SPME). The 97 out of 127 VCs identified were found common in all the olive leaves. Terpenes, aldehydes, alcohols and ketones were identified in the olive leaves as major VCs groups, which accounted for about 36-60%, 20-28%, 6-14% and 4-8% of total VCs identified in leaves, respectively. The relative proportions of these chemical groups showed considerably differences among olive leaves. α-Cubebene was found as major VC followed by trans- caryophyllene, α-farnesene, trans-2-hexenal, benzeneethanol, nonanal, trans,trans-2,4-heptadienal, cycloisosativene, trans-4,8-dimethyl-1,3,7-nonatriene, 2,4-heptadienal, α-humulene, α-muurolene and benzaldehyde.
  • Quantification of Volatile Aldehydes Deriving from in Vitro Lipid

    Quantification of Volatile Aldehydes Deriving from in Vitro Lipid

    molecules Article Quantification of Volatile Aldehydes Deriving from In Vitro Lipid Peroxidation in the Breath of Ventilated Patients Lukas Martin Müller-Wirtz 1,2,* , Daniel Kiefer 1, Sven Ruffing 1, Timo Brausch 1, Tobias Hüppe 1,2 , Daniel I. Sessler 2,3 , Thomas Volk 1,2 , Tobias Fink 1,2, Sascha Kreuer 1,2 and Felix Maurer 1,2 1 CBR—Center of Breath Research, Department of Anaesthesiology, Intensive Care and Pain Therapy, Saarland University Medical Center, Homburg, 66421 Saarland, Germany; [email protected] (D.K.); sven.ruffi[email protected] (S.R.); [email protected] (T.B.); [email protected] (T.H.); [email protected] (T.V.); tobias.fi[email protected] (T.F.); [email protected] (S.K.); [email protected] (F.M.) 2 Outcomes Research Consortium, Cleveland, OH 44195, USA; [email protected] 3 Department of Outcomes Research, Anesthesiology Institute, Cleveland Clinic, Cleveland, OH 44195, USA * Correspondence: [email protected] Abstract: Exhaled aliphatic aldehydes were proposed as non-invasive biomarkers to detect increased lipid peroxidation in various diseases. As a prelude to clinical application of the multicapillary column–ion mobility spectrometry for the evaluation of aldehyde exhalation, we, therefore: (1) iden- tified the most abundant volatile aliphatic aldehydes originating from in vitro oxidation of various polyunsaturated fatty acids; (2) evaluated emittance of aldehydes from plastic parts of the breathing circuit; (3) conducted a pilot study for in vivo quantification of exhaled aldehydes in mechanically Citation: Müller-Wirtz, L.M.; ventilated patients. Pentanal, hexanal, heptanal, and nonanal were quantifiable in the headspace of Kiefer, D.; Ruffing, S.; Brausch, T.; oxidizing polyunsaturated fatty acids, with pentanal and hexanal predominating.

  • Table 1: Chemicals of Concern and Associated Chemical Information

    Table 1: Chemicals of Concern and Associated Chemical Information. PACs Rev. 29a, June 2018 Table 1 is an alphabetical list of the chemical substances, their Chemical Abstracts Service Registry Numbers (CASRNs)1, and pertinent physical constants. Future reviews will result in continuous updates to these data. There are also columns that provide the date of the original derivation of the PAC values, the date of the last technical review of the data used for deriving the PAC values, and the date of the last revision of the data used to derive the PAC values. The information presented in this table is derived from various sources including: . The Handbook of Chemistry and Physics Lide, D. R. (Ed.) (2009). CRC Handbook of Chemistry and Physics, CD Rom (90th Edition-2010 Version). Boca Raton, FL: Taylor and Francis. Hazardous Substances Data Bank (HSDB) The HSDB is “comprehensive, peer-reviewed toxicology data for about 5,000 chemicals” and it is accessible online at http://toxnet.nlm.nih.gov/cgi-bin/sis/htmlgen?HSDB. The Merck Index O’Neil, M. J. (Ed.) (2006). Encyclopedia of Chemicals, Drugs, and Biologicals (14th edition). Merck Research Laboratories. Whitehouse Station, NJ. SAX Lewis, R. J., Sr. (2012). Sax's Dangerous Properties of Industrial Materials (12th Edition). New York: John Wiley & Sons. Sometimes data on physicochemical properties vary among sources. As the physical constants presented in this table are obtained from published sources, users are advised to consult trusted references to verify the accuracy of the information. Information on PAC values and Temporary Emergency Exposure Limits (TEELs) and links to other sources of information are provided on the Subcommittee on Consequence Assessment and Protective Actions (SCAPA) webpage at http://orise.orau.gov/emi/scapa/default.htm provided in Table 1 is described below; it covers two pages.
  • Ozone Artifacts and Carbonyl Measurements Using Tenax GR, Tenax TA, Carbopack B, and Carbopack X Adsorbents

    Ozone Artifacts and Carbonyl Measurements Using Tenax GR, Tenax TA, Carbopack B, and Carbopack X Adsorbents

    TECHNICAL PAPER ISSN 1047-3289 J. Air & Waste Manage. Assoc. 56:1503–1517 Copyright 2006 Air & Waste Management Association Ozone Artifacts and Carbonyl Measurements Using Tenax GR, Tenax TA, Carbopack B, and Carbopack X Adsorbents Jae Hwan Lee Samsung Co. Ltd., Chungcheongnam-do, Korea Stuart A. Batterman, Chunrong Jia, and Sergei Chernyak School of Public Health, University of Michigan, Ann Arbor, MI ABSTRACT 23% for Tenax GR, 101 Ϯ 24% for Carbopack B, and 79 Ϯ Four popular thermally desorbable adsorbents used for air 25% (91 Ϯ 9% for n-aldehydes) for Carbopack X. Ben- sampling (Tenax TA, Tenax GR, Carbopack B, and Car- zeneacetaldehyde recovery was notably poorer (22–63% bopack X) are examined for the potential to form artifacts across the four adsorbents). MDLs for several compounds with ozone (O3) at environmental concentrations. The were relatively high, up to 5 ng. By accounting for both performance of these adsorbents for the ketone and alde- artifact formation and method performance, this work hyde species identified as O3-adsorbent artifacts was also helps to identify which carbonyl compounds can be mea- characterized, including recovery, linearity, and method sured using thermally desorbable adsorbents and which detection limits (MDLs). Using gas chromatography/mass may be prone to bias because of the formation of O3- spectrometry, 13 different artifacts were identified and adsorbent artifacts. confirmed for both Tenax TA and Tenax GR, 9 for Car- bopack B, but none for Carbopack X. Several O3 artifacts not reported previously were identified, including: pen- INTRODUCTION tanal, 3-hexanone, 2-hexanone, hexanal, 3-heptanone, Sampling of airborne volatile organic compounds (VOCs) and heptanal with Tenax TA; pentanal, 3-hexanone, using thermally desorbable solid adsorbents has proven 2-hexanone, hexanal, and 3-heptanone on Tenax GR; and its usefulness in many environmental applications and 1-octene and 1-nonene with Carbopack B.
  • The Trimerization of Aldehydes

    The Trimerization of Aldehydes

    Louisiana State University LSU Digital Commons LSU Historical Dissertations and Theses Graduate School 1958 The rT imerization of Aldehydes. George Neal Grammer Louisiana State University and Agricultural & Mechanical College Follow this and additional works at: https://digitalcommons.lsu.edu/gradschool_disstheses Recommended Citation Grammer, George Neal, "The rT imerization of Aldehydes." (1958). LSU Historical Dissertations and Theses. 462. https://digitalcommons.lsu.edu/gradschool_disstheses/462 This Dissertation is brought to you for free and open access by the Graduate School at LSU Digital Commons. It has been accepted for inclusion in LSU Historical Dissertations and Theses by an authorized administrator of LSU Digital Commons. For more information, please contact [email protected]. THE TRIMERmTION OF AIDEHXDES A Dissertation Submitted to the Graduate Faculty of the Louisiana State University and Agricultural and Mechanical College in partial fulfillment of the requirements for the degree of Doctor of Philosophy in The Department of Chemistry by George Neal Grammar B. S., Northwestern State College of Louisiana, 1952 M. S., Louisiana State University, 1954 May, 1958 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. ACKNOWLEDGMENT Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. The author wishes to express his appreciation for the guidance and encouragement extended to him by Professor J. L. E. Erickson, who planned and directed this investigation, and to acknowledge with much appreciation the award of the University Research Assistantship for the year, 1954--1955* and the Esso Standard Oil Company Research Fellowship for the year, 1956-1957. He is grateful to his wife, Martha Jane, for her encouragement and kind understanding.
  • International Association of Breath Research Breath Summit 2019 8-11Th September 2019 Conference Programme and Abstracts

    International Association of Breath Research Breath Summit 2019 8-11Th September 2019 Conference Programme and Abstracts

    INTERNATIONAL ASSOCIATION OF BREATH RESEARCH BREATH SUMMIT 2019 8-11TH SEPTEMBER 2019 CONFERENCE PROGRAMME AND ABSTRACTS 1 Official Journal of the International Association for Breath Research; Journal of Breath Research is dedicated to all aspects of scientific breath research. The traditional focus is on analysis of volatile compounds and aerosols in exhaled breath for the investigation of exogenous exposures, metabolism, toxicology, health status and the diagnosis of disease and breath odours. The journal also welcomes other breath-related topics. JBR has recently launched two special issues now open for JOURNAL submissions. Most content will be invited by the Guest IMPACT FACTOR Editors, but if you have a paper you would like to be considered for one of these ongoing issues please email the 3.000 journal mailbox at [email protected]. Breath Analysis in Perioperative and Critical Care Medicine Guest Editors Nandor Marczin, Harefield Hospital, UK Simona Cristescu, Radboud University, Nijmegen, The Netherlands Stephen Fowler, The University of Manchester, UK Marcus J Schultz, University of Amsterdam, The Netherlands Optical Spectroscopy for Breath Analysis Guest Editors Simona Cristescu, Radboud University, Nijmegen, The Netherlands Torsten Frosch, Leibniz Institute of Photonic Technology Visit iopscience.org/jbr for more information 2 Table of Contents Sunday 08 September 2019 .................................................................................................. 9 THE TURING EXHIBITION SPACE ........................................................................................
  • Rev. 23 Table 2: Pacs by Chemical Name (Pdf)

    Rev. 23 Table 2: Pacs by Chemical Name (Pdf)

    Table 2: Protective Action Criteria (PAC) Rev 23 based on applicable AEGLs, ERPGs, or TEELs (chemicals listed in alphabetical order) PAC Rev 23 – August 2007 Table 2 presents an alphabetical listing of the chemicals in the PAC data set and provides Chemical Abstracts Service Registry Numbers (CAS RNs)1, PAC data, and technical comments focusing on changes in the PACs since the previous version of the PAC/TEEL data set (Rev 21). PACs are provided for TEEL-0 (i.e., PAC-0), PAC-1, PAC-2, and PAC-3. Values are usually given in parts per million (ppm) for gases and volatile liquids and in milligrams per cubic meter (mg/m3) for particulate materials (aerosols) and nonvolatile liquids. The columns presented in Table 2 provide the following information: Heading Definition No. The ordered numbering of the chemicals as they appear in this alphabetical listing. Chemical The common name of the chemical compound. Compound CAS RN The Chemical Abstracts Service Registry Number for this chemical. TEEL-0 This is the threshold concentration below which most people will experience no appreciable risk of health effects. This PAC is always based on TEEL-0 because AEGL-0 or ERPG-0 values do not exist. PAC-1 Based on the applicable AEGL-1, ERPG-1, or TEEL-1 value. PAC-2 Based on the applicable AEGL-2, ERPG-2, or TEEL-3 value. PAC-3 Based on the applicable AEGL-3, ERPG-3, or TEEL-3 value. Units The units for the PAC values (ppm or mg/m3). Comments Technical comments by the developers of the PAC data set.