Process development for upgrading low value α C8-olefin from Fischer-Tropsch to 2-hexyl-nonanal

324 Pages·2016·3.88 MB·English

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 (PBP) en netto huidige waarde (NPV), was
bereken vir elke scenario. Die resultate is gebruik om die opset met die mees gunstige
ekonomiese aanwysers te bepaal. Dit is gevind dat die twee proses-scenario’s (A en B),
ekonomies gunstig is, met IRR % waardes wat varieer tussen 58 en 83%. Scenario B het die
hoogste NPV en IRR %. Die NPV vir scenario A en B, teen die einde van die 15 jaar projek
lewe, was $ 439 M en $563 M onderskeidelik. Die IRR % vir proses scenario A was 59 % in
vergelyking met scenario B wat 83 % was vir dieselfde terugbetalingstydperk van 3 jaar. Die
twee proses-scenario’s het ook sensitiwiteitsanalises ondergaan. Die parameters wat
ondersoek is sluit die verkoopsprys van 2-heksiel-nonanal, Rh-TPPTS katalisator koste, 1-
okteen voerstof koste, HGr-2 katalisator koste en rente koerse % in. Die impak van die verkeie
Stellenbosch University https://scholar.sun.ac.za
vii

parameters op die NPV en IRR % is ondersoek. Kurwe diagramme is opgestel om die invloed
van die verskillende parameter kostes op die NPV en IRR % parameters aan te dui. Die mees
doeltreffende inset veranderlikes vir die twee proses scenario’s was die verkoopsprys van 2-
heksiel-nonanal en die prys van die Rh-TPPTS en HGr-2 katalisators op die NPV en IRR %
parameters. Proses scenario B, wat die OSN membraan tegniek insluit vir katalisator
herwinning, is gevind om die mees ekonomiese winsgewende opset te wees. Die NPV was
22 % beter as scenario A, wat die multifase sisteem gebruik het.
Sleutelwoorde: Lae waarde olefiene, Metatesis, Hidroformilasie, gefunksionaliseerde
koolwaterstowwe, OSN membraan, Tegno-ekonomiese evaluasie, DCF, NPV, IRR %
Stellenbosch University https://scholar.sun.ac.za
viii

ACKNOWLEDGEMENTS

To God be the honour, glory and praise!
I would like to appreciate the following individuals and organisations for their assistance and
support.
First, Dr. Percy Van der Gryp and Professor Manie H.C Vosloo for their assistance and
feedback in preparing this work.
The DST-NRF Centre of Excellence in Catalysis (c*change) and Stellenbosch University for
their financial support in this project. I would also like to thank the Catalysis Society of South
Africa (CATSA) for allowing me a myriad of opportunities to present my research at various
academic forums.
Upon completion of this study, I would like to acknowledge several individuals without whom
this work would not have been possible:
 Dr Mandeguiri for his generosity and kindness assistance with Aspen PlusTM.
 Dr Marco Haumann from Technical University of Berlin for his insights into
hydroformylation
 Dr David Muller from Technical University of Berlin for insights into catalyst recovery
systems and product separation
 Dr. Frans Marx from North-West University and Professor Eric Van Steen from
University of Cape Town fruitful discussions.
 My colleagues and friends at Stellenbosch University.
Finally, to Precious my fiancé who changed my life and has been supportive ever since.
Stellenbosch University https://scholar.sun.ac.za
ix

TABLE OF CONTENTS
DECLARATION ..................................................................................................................... I
ABSTRACT ........................................................................................................................... II
OPSOMMING ....................................................................................................................... V
ACKNOWLEDGEMENTS .................................................................................................. VIII
TABLE OF CONTENTS ....................................................................................................... IX
LIST OF ABBREVIATIONS ............................................................................................... XIV
NOMENCLATURE ............................................................................................................ XVI
CHAPTER 1: INTRODUCTION ............................................................................................. 1
Overview ........................................................................................................................................... 1
1.1 Background and motivation ........................................................................................................ 1
1.2 Objectives ................................................................................................................................... 4
1.3 Scope of Investigation and thesis outline ................................................................................... 4
1.4 References .................................................................................................................................. 8
CHAPTER 2: RESEARCH APPROACH ............................................................................. 11
Overview ......................................................................................................................................... 11
2.1 Introduction: Conceptual approach ........................................................................................... 12
2.2 Literature review: Design approach .......................................................................................... 14
2.3 This study: Design approach .................................................................................................... 19
2.3.1 Motivation for the Douglas methodology ............................................................................. 20
2.4 References ................................................................................................................................ 26
CHAPTER 3: LITERATURE REVIEW ................................................................................. 30
Overview ......................................................................................................................................... 30
3.1 Introduction: Centre of excellence in catalysis ......................................................................... 31
3.2 Metathesis ................................................................................................................................. 32
3.2.1 Olefins Conversion Technology (OCTTM) ............................................................................ 33
3.2.2 The Shell Higher Olefins Process (SHOP) .......................................................................... 34
3.2.3 The Meta-4 process ............................................................................................................. 35
3.2.4 The Polynorbornene process ............................................................................................... 35