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KlausWeissermel

Hans-JurgenArpe

Industrial

OrganicChemistry

Translatedby CharletR. Lindley

Third Completely RevisedEdition

A Wiley company

ThisThisThisThisThisThisThisThisThisThisThisThisThisThisThisThisThisThisThisThisThisThisThisThisThisThisThisThis PagePagePagePagePagePagePagePagePagePagePagePagePagePagePagePagePagePagePagePagePagePagePagePagePagePagePagePage IntentionallyIntentionallyIntentionallyIntentionallyIntentionallyIntentionallyIntentionallyIntentionallyIntentionallyIntentionallyIntentionallyIntentionallyIntentionallyIntentionallyIntentionallyIntentionallyIntentionallyIntentionallyIntentionallyIntentionallyIntentionallyIntentionallyIntentionallyIntentionallyIntentionallyIntentionallyIntentionallyIntentionally LeftLeftLeftLeftLeftLeftLeftLeftLeftLeftLeftLeftLeftLeftLeftLeftLeftLeftLeftLeftLeftLeftLeftLeftLeftLeftLeftLeft BlankBlankBlankBlankBlankBlankBlankBlankBlankBlankBlankBlankBlankBlankBlankBlankBlankBlankBlankBlankBlankBlankBlankBlankBlankBlankBlankBlank

Weissermel,Arpe IndustrialOrganicChemistry A Wiley company
Weissermel,Arpe
IndustrialOrganicChemistry
A Wiley company

ThisThisThisThisThisThisThisThisThisThisThisThisThisThisThisThisThisThisThisThisThisThisThisThisThisThisThisThis PagePagePagePagePagePagePagePagePagePagePagePagePagePagePagePagePagePagePagePagePagePagePagePagePagePagePagePage IntentionallyIntentionallyIntentionallyIntentionallyIntentionallyIntentionallyIntentionallyIntentionallyIntentionallyIntentionallyIntentionallyIntentionallyIntentionallyIntentionallyIntentionallyIntentionallyIntentionallyIntentionallyIntentionallyIntentionallyIntentionallyIntentionallyIntentionallyIntentionallyIntentionallyIntentionallyIntentionallyIntentionally LeftLeftLeftLeftLeftLeftLeftLeftLeftLeftLeftLeftLeftLeftLeftLeftLeftLeftLeftLeftLeftLeftLeftLeftLeftLeftLeftLeft BlankBlankBlankBlankBlankBlankBlankBlankBlankBlankBlankBlankBlankBlankBlankBlankBlankBlankBlankBlankBlankBlankBlankBlankBlankBlankBlankBlank

KlausWeissermel

Hans-JurgenArpe

Industrial

OrganicChemistry

Translatedby CharletR. Lindley

Third Completely RevisedEdition

A Wiley company

Prof. Dr. KlausWeissermel

Prof. Dr. Hans-JiirgenArpe

HoechstAG

Dachsgraben1

Postfach800320

D-67824Feilbingert

D-65926Frankfurt

FederalRepublicof Germany

FederalRepublicof Germany.

This book wascarefullyproduced,Nevertheless,authorsandpublisherdo not warrantthe informationcontainedtherein to be free of errors.Readersare advisedto keepin mind that statements,data,illustrations,proceduraldetailsor other itemsmay inadvertentlybe inaccurate.

1stedition 1978 2nd edition 1993 3rd edition 1997

Publishedjointly by VCH VerlagsgesellschaftmbH,Weinheim(FederalRepublicof Germany) VCH Pubiishers,Inc., New York, NY (USA)

Editorial Director:Karin Sara

ProductionManager:Dip1.-Ing.(FH)HansJorgMaier

British Library Cataloguing-in-PublicationData: A cataloguerecordfor thisbook is availablefrom theBritish Library.

DeutscheBibliothek Cataloguing-in-PublicationData:

Weissermel,Klaus:

Industrial organicchemistry/ Klaus Weissermel; Hans-JiirgenArpe. Transl.by CharletR. Lindley. ~ Weinheim: VCH, 1997 Dt. Ausg.u.d.T.: Weissermel,Klaus:IndustrielleorganischeChemie ISBN 3-527-28838-4Gb.

3., completelyrev.ed. ~

0 VCH VerlagsgesellschaftmbH, D-69451Weinheim(FederalRepublicof Germany),1997

Printedon acid-freeandchlorine-fieepaper,

All rights reserved(including thoseof translationin otherlanguages).No part of this book may be reproducedin any form

- by photoprinting,microfilm, or any other means- nor transmittedor translatedinto a machinelanguagewithout written permissionfrom the publishers.Registerednames,trademarks,etc. usedin this book, evenwhennot specifically markedas such,arenot to be consideredunprotectedby law. Composition:FilmsatzUnger& SommerGmbH,D-69469Weinheim Printing: betz-druckgmbh,D-64291Darmstadt Bookbindung:Wilhelm Osswald& Co.,D-67433Neustadt Printedin theFederalRepublicof Germany.

Prefaceto the Third Edition In the few yearsthat havepassedsince the publication of the 2nd English
Prefaceto the Third Edition
In the few yearsthat havepassedsince the publication of the
2nd English edition, it hasbecomeclear that interestin Indus-
trial InorganicChemistryhascontinuedto grow,making a new
Englisheditionnecessary.
In the meantime,hrther translationshave been published or
arein preparation,andneweditionshaveappeared.
The availability of
large amountsof new information and up-
to-date numerical data has prompted us to modernize and
expandthebook,at the sametime increasingits scientificvalue.
Apart from the scientific literature, a major help in our
endeavorswas the supportof colleaguesfrom HoechstAG and
numerous other chemical companies.Once again we thank
VCH Publishersfor the excellentcooperation.
February1997
K. Weissermel
H.-J.Arpe
Prefaceto the SecondEdition The translationof Industrial OrganicChemistry into seven languageshasproved the worldwide
Prefaceto the SecondEdition
The translationof Industrial OrganicChemistry into seven
languageshasproved the worldwide interestin this book. The
positive feedbackfrom readerswith regardto theinformational
contentand the didacticoutline, togetherwith the outstanding
successof the similar work Industrial Inorganic
Chemistry
haveencouragedus to producethis new revisededition.
Thetext hasbeengreatlyextended.Developmentalpossibilities
appearingin the 1st Edition havenow beenrevisedanduptated
to the currentsituation.The increasinglyinternationaloutlook
of the 1st Edition hasbeen further extendedto cover areasof
worldwideinterest.Appropriatealterationsin nomenclatureand
style havealsobeenimplemented.
A special thank you is extended to the Market Research
Departmentof Hoechst AG for their help in the collection of
numericaldata.It is alsoa pleasureto expressour gratitudeto
VCH Verlagsgesellschaftfor their kind cooperationandfor the
successfulorganizationand presentationof the books.
February1993
K. Weissermel
H.-J. Arpe
Prefaceto the First Edition Industrial organicchemistryis exhaustivelytreatedin a whole seriesof encyclopediasand
Prefaceto the First Edition
Industrial organicchemistryis exhaustivelytreatedin a whole
seriesof encyclopediasand standardworks as well as, to an
increasingextent, in monographs.However, it is not always
simple to rapidly graspthe presentstatusof knowledge from
thesesources.
There was thus a growing demandfor a text describingin a
concisemannerthemostimportantprecursorsandintermediates
of industrialorganicchemistry.Theauthorshaveendeavoredto
reviewthematerialandto presentit in a form, indicativeof their
daily confrontation with problemsarising from researchand
development,which canbe readily understoodby the reader.In
pursuingthis aim they could rely, apart from their industrial
knowledge, on teaching experiencederived from university
lectures,and on stimulatingdiscussionswith manycolleagues.
This book addressesitself to a wide range of readers: the
chemistry student should be able to appreciatefrom it the
chemistyof importantprecursorsandintermediatesaswell asto
follow the developmentof manufacturingprocesseswhich he
might onedayhelpto improve.Theuniversityor collegelecturer
cangleaninformation aboutappliedorganicsynthesesandthe
constantchangeof manufacturingprocessesand feedstocks
alongwith the resulting researchobjectives.Chemistsandtheir
colleaguesfrom other disciplines in the chemicalindustry -
suchas engineers,marketingspecialists,lawyersand industrial
economists- will be presentedwith a treatisedealingwith the
complex technological,scentific and economicinterrelation-
shipsand their potentialdevelopments.
This book is arrangedinto 14chaptersin which precursorsand
intermediatesarecombinedaccordingto their tightestpossible
correlationto a particulargroup.A certainamountof arbitrari-
ness was, of course, unavoidable. The introductory chapter
reviewsthe presentand future energyand feedstocksupply.
As a rule, the manufacturingprocessesaretreatedafter general
descriptionof the historicaldevelopmentand significanceof a
product, emphasisbeing placed on the conventionalprocesses
and the applicationsof the product and its simportantderiva-

VIII

Preface to the First Edition

tives. Thesectionsrelating to heavyindustrialorganicproducts are frequently followed by a prognosis concerning potential developments.Deficienciesof existingtechnologicalor chemical processes,aswell aspossiblefutureimprovementsor changesto other more economicor more readily availablefeedstocksare briefly discussed.

Theauthorsendeavoredto providea high degreeof quality and quantity of information. Threetypes of informationareat the reader sdisposal:

1. The main text.

2. The synopsisof the main text in the margin.

3. Flow diagrams illustrating the interrealationshipof the productsin eachchapter.

Thesethreetypesof presentationwerederived from the wide- spreadhabit of many readersof underliningor making brief

noteswhen studyinga text. Thereaderhasbeenrelievedof this work by the marginal noteswhich briefly presentall essential pointsof themaintext in alogical sequencetherebyenablinghim

to be rapidly informed without havingto studythe main text.

Theformulaor processscheme(flow diagram)pertainingto each

chaptercan be folded out whilst readinga sectionin orderthat

its overall relevancecan be readily appreciated.There are no

diagramsof individual processesin the main text asthis would resultin frequentrepetitionarisingfrom recurringprocesssteps. Instead,the readeris informedaboutthe significant featuresof

a process.

Theindex,containingnumerouskey words,enablesthereaderto rapidly find the requiredinformation.

A first version of this book was originally published in the

Germanlanguagein 1976.Many colleaguesinsideandoutside

HoechstAG gaveus their supportby carefully readingparts of the manuscript and providing valuable suggestionsthereby ensuringthe validity of the numeroustechnologicalandchemi-

cal facts.In particular,we would like to expressour thanksto Dr.

H. Friz, Dr. W. Reif (BASF); Dr. R. Streck, Dr. H. Weber(Hiils

AG); Dr. W. Jordan(Phenolchemie);Dr. B. Cornils, Dr. J. Falbe,

Dr. W. Payer(RuhrchemieAG); Dr. K. H. Berg, Dr. I. F. Hudson

(Shell); Dr. G. Konig, Dr. R. Kiihn, Dr. H. Tetteroo(UK-Wesse-

ling).

We arealsoindebtedto many colleaguesandfellow employeesof Hoechst AG who assisted by reading individual chapters, expandingthe numericaldata,preparingthe formula diagrams

Preface to the First Edition IX andtyping the manuscript.In particularwe would like to thank Dr.
Preface to the First Edition
IX
andtyping the manuscript.In particularwe would like to thank
Dr. U. Dettmeier,M. Keller, Dr. E. I. Leupold,Dr. H. Meidert,
and Prof. R. Steiner who all carefully read and corrected or
expandedlargesectionsof themanuscript.However,decisivefor
the choiceof materialwasthe accessto the experienceand the
world-wide information sourcesof HoechstAG.
Furthermore,the patienceandconsiderationof our immediate
families and close friends made an important contribution
during the long monthswhen the manuscriptwas written and
revised.
In less than a year after the first appearanceof Industrielle
OrganischeChemie thesecondeditionhasnow beenpublished.
The positive responseenjoyed by the book places both an
obligation on us as well as being an incentive to producethe
secondeditionin not only a revised,but alsoan expandedform.
This secondedition of the Germanlanguageversion has also
been the basis of the present English edition in which the
numericaldatawere updatedand, wherepossible,enrichedby
datafrom severalleadingindustrialnationsin orderto stressthe
internationalscope.
Additional productswere included along with their manufac-
turing processes.New facts were often supplementedwith
mechanisticdetails to facilitate the reader scomprehensionof
basicindustrial processes.
Thebook wastranslatedby Dr. A. Mullen (RuhrchemieAG) to
whom we areparticularlygratefulfor assumingthis arduoustask
which he accomplishedby keepingas closely as possibleto
the
original text whilst also managingto evolve his
own style. We
would like to thanktheBoard of RuhrchemieAG for supporting
this venture by placing the company s facilities at Dr. Mullen s
disposal.
We are also indebtedto Dr. T. F. Leahy, a colleaguefrom the
AmericanHoechstCorporation,who playedan essentialpart by
meticulously readingthe manuscript.
Verlag Chemiemust also be thanked - in particular Dr. H. F.
Ebel - for its supportandfor ensuringthat the Englishedition
shouldhavethe best possiblepresentation.
Hoechst,in January1978
K. Weissermel
H.-J. Arpe

ThisThisThisThisThisThisThisThisThisThisThisThisThisThisThisThisThisThisThisThisThisThisThisThisThisThisThisThis PagePagePagePagePagePagePagePagePagePagePagePagePagePagePagePagePagePagePagePagePagePagePagePagePagePagePagePage IntentionallyIntentionallyIntentionallyIntentionallyIntentionallyIntentionallyIntentionallyIntentionallyIntentionallyIntentionallyIntentionallyIntentionallyIntentionallyIntentionallyIntentionallyIntentionallyIntentionallyIntentionallyIntentionallyIntentionallyIntentionallyIntentionallyIntentionallyIntentionallyIntentionallyIntentionallyIntentionallyIntentionally LeftLeftLeftLeftLeftLeftLeftLeftLeftLeftLeftLeftLeftLeftLeftLeftLeftLeftLeftLeftLeftLeftLeftLeftLeftLeftLeftLeft BlankBlankBlankBlankBlankBlankBlankBlankBlankBlankBlankBlankBlankBlankBlankBlankBlankBlankBlankBlankBlankBlankBlankBlankBlankBlankBlankBlank

Contents

1.

1.1.

1.2.

1.2.1.

1.2.2.

1.2.3.

1.2.4.

1.3

1.4.

1.4.1.

1.4.2.

2.

2.1.

2.1.1.

2.1.1.1.

2.1.1.2.

2.1.2.

2.2.

2.2.1.

2.2.2.

2.3.

2.3.1.

2.3.1.1.

2.3.1.2.

2.3.2.

2.3.2.1.

2.3.2.2.

2.3.3.

2.3.4.

2.3.5.

2.3.6.

2.3.6.1.

2.3.6.2.

Various Aspects of the Energy and Raw Material Supply

1

Present and Predictable Energy Requirements

 

2

Availability of Individual Sources

3

Oil

3

NaturalGas

 

4

Coal

.

.

5

Nuclear

5

Prospects for the Future Energy Supply

 

7

Present and Anticipated Raw Material Si

8

Petrochemical Primary Products

8

Coal Conversion Products

11

Basic Products of Industrial Syntheses

13

Synthesis Gas

13

 

13

14

17

19

Production of the Pure Synthesis Gas Components

21

Carbon Monoxide

 

21

Hydrogen

 

24

C -Units

21

 

27

Manufacture of Methanol

 

28

 

30

35

Formaldehyde from Methanol

 

36

Uses and Potential Uses of For

e

38

Formic Acid

40

 

44

49

Halogen Derivatives of Methane

 

50

 

50

55

XI1

Contents

3.

Olefins

59

3.1.

Historical Developmentof Olefin Chemistry

59

3.2.

Olefins via Crackingof Hydrocarbons

59

3.3.

SpecialManufacturingProcessesfor Olefins

63

3.3.1.

Ethylene,Propene

63

3.3.2.

Butenes

66

3.3.3.

Higherolefins

74

3.3.3.1.

UnbranchedHigher Olefins

75

3.3.3.2.

BranchedHigher Olefins .

83

3.4.

Olefin Metathesis

85

4.

Acetylene

91

4.1.

PresentSignificanceof Acetylene

91

4.2.

ManufacturingProcessesfor Acetylene

93

4.2.1.

ManufactureBasedon Calcium Carbide

93

4.2.2.

ThermalProcesses

94

4.3.

Utilization of Acetylene

98

5.

1.3.Diolefins

105

5.1.

1.3.Butadiene

105

5.1.1.

TraditionalSynthese

106

5.1.2.

1,3-Butadienefrom

107

5.1.3.

1,3.Butadienefrom

109

5.1.4.

Utilization of 1, 3-8

112

5.2.

Isoprene

115

5.2.1.

Isoprenefrom C5C

115

5.2.2.

Isoprenefrom SyntheticReactions

117

5.3.

Chloroprene

120

5.4.

Cyclopentadiene.

123

6.

SynthesesInvolving Carbon Monoxide

125

6.1.

125

6.1.1.

126

6.1.2.

Industrial Operationof Hydroformylation

129

6.1.3.

132

6.1.4.

I34

6.1.4.1.

0x0 Alcohols

134

6.1.4.2.

136

6.1.4.3.

137

6.2.

Carbonylationof Olefins

139

Contents XI11 7. Oxidation Products of Ethylene . 143 7.1. EthyleneOxide . 143 144 7.1.1.
Contents
XI11
7. Oxidation Products of Ethylene .
143
7.1.
EthyleneOxide .
143
144
7.1.1.
144
7.1.2.
EthyleneOxideby Direct Oxidation
7.1.2.1.
ChemicalPrinciples
144
7.1.2.2.
ProcessOperation
146
7.1.2.3.
PotentialDevelopmentsin EthyleneOxide Manufacture
148
7.2.
SecondaryProductsof EthyleneOxide
149
7.2.1.
150
7.2.1.1.
151
7.2.1.2.
Usesof EthyleneGlycol
153
7.2.1.3.
SecondaryProducts~ Glyoxal, Dioxolane, 1,4-Dioxane
154
7.2.2.
156
7.2.3.
Ethanolaminesand SecondaryProducts
157
7.2.4.
EthyleneGlycol Ethers
160
7.2.5.
Additional Productsfrom EthyleneOxide
162
7.3.
Acetaldehyde
163
7.3.1.
Acetaldehydevia Oxidationof Ethylene
164
7.3.1.1.
ChemicalBasis
164
7.3.1.2.
ProcessOperation
166
7.3.2.
Acetaldehydefrom Ethanol
167
7.3.3.
168
7.4.
SecondaryProductsof Acetaldehyde
169
7.4.1.
Acetic Acid
169
7.4.1.1.
Acetic Acid
by
Oxidation of
Acetaldehyde.
170
7.4.1.2.
Acetic
Acid
by
Oxidation of
Alkanes and A1
172
7.4.1.3.
Carbonylationof Methanolto Acetic Acid
175
7.4.1.4.
PotentialDevelopmentsin Acetic Acid Manufacture
177
7.4.1.5.
Usesof Acetic Acid
178
7.4.2.
Acetic AnhydrideandKetene
180
7.4.3.
Aldol Condensationof Acetaldehydeand SecondaryProducts
184
7.4.4.
186
7.4.5.
188
8.
191
8.1.
Lower Alcohols
191
8.1.1.
191
8.1.2.
Isopropanol
196
8.1.3.
Butanols
8.1.4.
Amy1 Alcohols
8.2.
203
8.2.1.
Oxidation of Para Alcohols
8.2.2.
Alfol Synthesis
208

XIV

Contents

8.3.

PolyhydricAlcohols

 

210

8.3.1.

Pentaerythritol

210

8.3.2.

Trimethylolpropane

211

8.3.3.

NeopentylGlycol

212

9.

Vinyl-Halogen and Vinyl-Oxygen Compounds

. 215

9.1.

Vinyl-Halogen Compounds

 

215

9.1.1.

Vinyl

Chloride

215

9.1.1.1.

Vinyl

Chloride from

Acetylene

. 216

9.1.1.2.

Vinyl Chloridefrom Ethylene

 

217

9.1.1.3.

PotentialDevelopmentsin Vinyl ChlorideManufacture

220

9.1.1.4.

Usesof Vinyl Chloride and 1,2-Dichloroethane

221

9.1.2.

VinylideneChloride

 

223

9.1.3.

Vinyl FluorideandVinylidene

ride

223

9.1.4.

Trichloro- andTetrachloroethylene

. 225

9.1.5.

Tetrafluoroethylene

 

227

9.2.

Vinyl EstersandEthers

 

228

9.2.1.

Vinyl Acetate

 

9.2.1.1.

Vinyl

AcetateBasedon Acetyleneor Acetaldehyde

 

9.2.1.2.

Vinyl AcetateBasedon Ethylene

 

229

9.2.1.3.

Possibilitiesfor Developmentof Vinyl AcetateManufacture

233

9.2.2.

Vinyl

Estersof Higher Carboxylic Acids

234

9.2.3.

Vinyl Ethers

 

. 235

10.

Componentsfor Polyamides

 

237

10.1.

Dicarboxylic Acids

 

10.1.1.

Adipic

10.1.2.

1,12-DodecanedioicAcid

 

243

10.2.

DiaminesandAminocarboxylicAcids

 

10.2.1.

Hexamethylenediamine

 

244

10.2.1.1.

Manufactureof Adiponitrile

245

10.2.1.2.

Hydrogenationof Adiponitrile

249

10.2.1.3.

PotentialDevelopmentsin Adiponitrile Manufacture

250

10.2.2.

w-AminoundecanoicAcid

 

. 250

10.3.

Lactams

 

251

10.3.1.

c-Caprolactam

251

10.3.1.1.

E-Caprolactamfrom the CyclohexanoneOxime

252

10.3.1.2.

AlternativeManufacturingProcessesfor c-Caprolactam

10.3.1.3.

Possibilitiesfor Developmentin E-CaprolactamManufacture

10.3.1.4.

Usesof 8-Caprolactam

 

260

10.3.2.

Lauryl Lactam

 

262

Contents XV 11. PropeneConversionProducts 265 11.1. Oxidation Productsof Propene 266 11.1.1. PropyleneOxide 266
Contents
XV
11.
PropeneConversionProducts
265
11.1.
Oxidation Productsof Propene
266
11.1.1.
PropyleneOxide
266
11.1.1.1.
PropyleneOxide from the ChlorohydrinProcess
266
11.1.1.2.
Indirect OxidationRoutesto PropyleneOxide
267
11.1.1.3.
Possibilitiesfor Developmentin the Manufactureof PropyleneOxide .
271
11.1.2.
SecondaryProductsof PropyleneOxide
275
11.1.3.
Acetone
276
11.1.3.1.
Direct Oxidationof Propene
277
11.1.3.2.
Acetonefrom Isopropanol
278
11.1.4.
SecondaryProductsof Acetone
279
11.1.4.1.
AcetoneAldolization and Secon
280
11.1.4.2.
Methacrylic Acid andEster
281
11.1.5.
Acrolein
285
11.1.6.
SecondaryProductsof Acrolein
287
11.1.7.
Acrylic Acid andEsters
289
11.1.7.1.
TraditionalAcrylic Acid Ma
289
11.1.7.2.
Acrylic Acid from Propene
291
11.1.7.3.
Possibilitiesfor Developmentin Acrylic Acid Manufacture
293
11.2.
Allyl
Compoundsand SecondaryProducts
294
11.2.1.
Allyl Chloride
294
11.2.2.
Allyl Alcohol andEsters
297
11.2.3.
Glycerol from Allyl Precursors
299
11.3.
Acrylonitrile
302
11.3.1.
TraditionalAcrylonitrile Manufacture
303
11.3.2.
Ammoxidationof Propene
304
11.3.2.1.
SohioAcrylonitrile Process
305
11.3.2.2.
OtherPropene/PropaneAmmoxidationProcesses
306
11.3.3.
Possibilitiesfor Developmentof Acrylonitrile Manufacture
307
11.3.4.
Usesand SecondaryProductsof Acrylonitrile
308
12.
Aromatics .Production and Conversion
311
12.1
Importanceof Aromatics
311
12.2.
Sourcesof Feedstocksfor Aromatics
312
12.2.1.
Aromaticsfrom Coking of Hard Coal
313
12.2.2.
Aromaticsfrom ReformateandPyroly
314
12.2.2.1.
Isolation of Aromatics
317
12.2.2.2.
arationTechniquesfor Non-Aromatic/AromaticandAromatic Mixtures
318
12.2.3.
for Developmentof Aromatic Manufacture
323
12.2.4.
CondensedAromatics
324
12.2.4.1.
Naphthalene
325
12.2.4.2.
Anthracene
326

XVI

Contents

12.3.

ConversionProcessesfor Aromatics

329

12.3.1.

Hydrodealkylation

329

12.3.2.

m-XyleneIsomerization

330

12.3.3.

DisproportionationandTransalkylation

 

332

13.

BenzeneDerivatives

335

13.1.

Alkylation andHydrogenationProductsof Benzene

335

13.1.1.

Ethylbenzene

335

13.1.2.

Styrene

339

13.1.3.

Cumene

342

13.1.4.

Higher Alkylbenzenes

343

13.1.5.

Cyclohexane

345

13.2.

Oxidation and SecondaryProductsof Benzene

 

347

13.2.1.

Phenol

347

13.2.1.1.

ManufacturingProcessesfor Phenol

348

13.2.1.2.

PotentialDevelopmentsin PhenolManufacture

 

355

13.2.1.3.

Usesand SecondaryProductsof Phenol

358

13.2.2.

Dihydroxybenzenes

361

13.2.3.

Maleic Anhydride

365

13.2.3.1.

Maleic Anhydridefrom Oxidation of

Benzene

366

13.2.3.2.

Maleic Anhydridefrom Oxidation of

Butene

368

13.2.3.3.

Maleic Anhydridefrom Oxidationof Butane

 

369

13.2.3.4.

Usesand SecondaryProductsof Maleic Anhydride

370

13.3.

OtherBenzeneDerivatives

373

13.3.1.

Nitrobenzene

373

13.3.2.

Aniline

374

13.3.3.

Diisocyanates

377

14.

Oxidation Products of Xylene and Naphthalene

 

385

14.1.

PhthalicAnhydride

385

14.1.1.

Oxidation of Naphthaleneto PhthalicAnhydride

 

385

14.1.2.

Oxidation of o-Xyleneto PhthalicAnhydride

387

14.1.3.

Estersof PhthalicAcid andDerivatives

389

14.2.

TerephthalicAcid

392

14.2.1.

Manufactureof Dimethyl TerephthalateandTere

lic Acid

393

14.2.2.

Fiber GradeTerephthalicAcid

395

14.2.3.

OtherManufacturingRoutesto TerephthalicAcid andDerivatives

397

14.2.4.

Usesof TerephthalicAcid andDimethyl Terephthalate

400

15.

Appendix

405

15.1.

ProcessandProductSchemes

405

Contents

XVII

15.3.

Abbreviationsfor Firms

427

15.4.

Sourcesof Information

428

15.4.1.

GeneralLiterature

428

15.4.2.

More SpecificLiter e (publications,monographs)

429

Index

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1. Various Aspectsof the Energy and Raw Material Supply The availability andprice structureof energyandraw materials
1. Various Aspectsof the Energy and Raw Material Supply
The availability andprice structureof energyandraw materials
have always determinedthe technologicalbase and thus the
expansionand developmentof industrial chemistry.However,
theoil crisiswasnecessarybeforethegeneralpublic onceagain
becameawareof this relationshipand its importancefor the
world economy.
fossil fuels
natural gas,petroleum,coal
havetwo functions:
1. energysource
2. raw material for chemicalproducts
Coal,naturalgas,andoil, formedwith the help of solarenergy
during the courseof millions of years,presentlycovernot only
the energy, but also to a large extent chemical feedstock
requirements.
Thereis no comparablebranchof industryin which thereis such
a completeinterplaybetweenenergyandraw materialsasin the
chemicalindustry.Everyvariationin supplyhasa doubleimpact
on thechemicalindustryasit is oneof thegreatestconsumersof
energy.In additionto this, the non-recoverablefossil products,
which are employedas raw materials, are convertedinto a
spectrumof syntheticsubstanceswhich we meetin everydaylife.
The constantlyincreasingdemandfor raw materials and the
limited reservespoint out theimportanceof safeguardingfuture
energyand raw materialsupplies.
All short-andmedium-termefforts will haveto concentrateon
the basicproblem as to how the flexibility of the raw material
supplyfor thechemicalindustryontheonehand,andtheenergy
sectoron the other hand, can be increasedwith the available
resources.In the long term, this double function of the fossil
long rangeaims for securingindustrial raw
material and energysupply:
1. extending the period of use of the fossil
raw materials
2. replacing the fossil raw materialsin the
energysector
fuelswill beterminatedin orderto maintainthis attractivesource
of
supplyfor the chemicalindustry for aslong aspossible.
In orderto betterevaluatethepresentsituationandunderstand
the future
consumptionof primary energy sourcesand raw
materials, both aspectswill be reviewed together with the
individual energysources.
2 I. VariousAspects of the Energy and Raw Material Supply 1.1.Presentand Predictable Energy Requirements primary
2 I. VariousAspects of the Energy and Raw Material Supply
1.1.Presentand Predictable Energy Requirements
primary energyconsumption(in 10 kwhr)
1964 1974 1984 1989 1994
During the last twenty-fiveyears,the world energydemandhas
more than
doubled and in 1995 it reached94.4x 10 kwhr,
World
41.3 67.5
82.6 95.2
93.6
USA
12.5 15.4
19.5 23.6
24.0
W.Europe
7.9 10.7
11.6 13.0
13.2
correspondingto the energy from 8.12x lo9 tonnes of oil
(1 tonne oil =11620 kwhr = 10x lo6 kcal = 41.8 x lo6 kJ).
The averageannualincreasebefore 1974was about5%, which
decreasedthroughthe end of the 198Os, asthe numbersin the
adjacenttableillustrate.In the 1990s,primary energyconsump-
tion has hardly changeddue to the drop in energydemand
causedby the economicrecessionfollowing the radical changes
in the former East Bloc.
However,accordingto the latestprediction of the International
Energy Agency (IEA), global population will grow from the
current 5.6 to 7 x lo9 people by the year 2010, causing the
world energydemandto increaseto 130x 10l2kwhr.
In 1989, the consumptionof primary energyin the OECD
(Organization for Economic Cooperationand Development)
countrieswas distributed as follows:
31To for transport
34% for industrial use
35%
for
domesticand agriculturaluse,and othersectors
energy
consumption of
the
chemical
industry:
6%
of
total consumption, i.e., second
The chemical industry accountsfor 6% of the total energy
consumptionand therebyassumessecondplacein the energy
consumptionscaleafter the iron processingindustry.
greatestindustrialconsumer
changes in
primary energy distribution
worldwide (in 070) :
1964
1974
1984
1995
oil
41
48
42
38
coal
37
28
27
23
naturalgas
15
18
19
19
nuclearenergy
6
6
7
6
waterpower/
others
13
514
(othersinclude, e. g., biomass)
Between 1950 and 1995, the worldwide pattern of primary
energyconsumptionchangeddrastically.Coal ssharedecreased
from ca. 60% in 1950to the valuesshownin the accompanying
table. In China and someof the former EasternBloc countries,
40% of the energy used still comes from coal. Oil s share
amountedto just 25% of world energyconsumptionin 1950,
and reacheda maximum of nearly 50% in the early 1970s.
Todayit has stabilizedat ca. 38%, and is expectedto decrease
slightly to 3770by 2000.
reasonsfor preferreduseof oil and natural
gasasenergysource:
1. economicrecovery
The reasonsfor this energysourcestructurelie with the ready
economicrecoveryof oil and natural gas and their versatile
applicability as well as lower transportationand distribution
2. versatileapplicability
costs.
3. low transportationand distributioncosts
restructuring of energy consumptionnot
possiblein the shortterm
oil remainsmain energysourcefor the near
future
In the following decades,the forecastcalls for a slight decrease
in
the relative amountsof energyfrom oil and naturalgas,but
1.2. Availability of Individual Sources 3 a small increasefor coal andnuclearenergy.An eventualtran- sition to
1.2. Availability of Individual Sources
3
a small increasefor coal andnuclearenergy.An eventualtran-
sition to carbon-free and inexhaustible energy sources is
desirable,but this developmentwill be influencedby manyfac-
tors.
In any event,oil and natural gaswill remain the main energy
sourcesin predictionsfor decades,as technologicalreorienta-
tion will takea long time dueto the complexityof the problem.
1.2. Availability of Individual Sources
1.2.1.Oil
New datashowthat the provenand probable,i.e., supplemen-
tary, recoverableworld oil reservesare higher than the roughly
520x lo9 tonnes, or 6040x 10l2 kwhr, estimated in recent
years. Of the proven reserves(1996), 66% are found in the
Middle East, 13% in SouthAmerica, 3% in North America,
2% in WesternEuropeandtheremainderin otherregions.With
about 26% of the proven oil reserves,Saudi Arabia has the
greatestshare,leading Iraq, Kuwait and other countriesprin-
cipally in the Near East.In 1996,the OPECcountriesaccoun-
ted for ca. 77 wt% of worldwideoil production.Countrieswith
thelargestproductionin 1994wereSaudiArabia andthe USA.
oil reserves(in 10l2kwhr):
1986
1989
1995
proven
1110
1480
1580
total
4900
1620
2470
A furthercrudeoil supplywhichamountsto tentimestheabove-
reservesof synthetic oil from oil shaleand
oil sands(in 10 kwhr):
mentionedpetroleumreservesis foundin oil shale,tar sand,and
oil sand. This source, presumed to be the same order of
magnitudeasmineral oil only a few yearsago, far surpassesit.
1989
1992
proven
1550
1550
total
13840
12360
Thereis a greatincentivefor the exploitationof oil shaleand oil
sand.To this end,extractionand pyrolysisprocesseshavebeen
developedwhich, under favorablelocal conditions,arealready
economicallyfeasible.Largecommercialplantsarebeingrun in
Canada,with a significant annualincrease(for example,pro-
duction in 1994was 17% greaterthan in 1993),and the CIS.
Although numerouspilot plants have been shut down, for
instancein the USA, new onesare plannedin placessuch as
Australia. In China, oil is extracted from kerogen-contain-
ing rock strata. An additional plant with a capacity of
kerogen is a waxy, polymeric substance
foundin mineralrock, which is convertedto
synthetic oil on heating to >5OO”C or
hydrogenation
oil consumption(in lo9 t of oil):
1988
1990
1994
World
3.02
3.10
3.18
USA
0.78
0.78
0.81
W. Europe
0.59
0.60
0.57
CIS
0.45
0.41
n.a.
Japan
0.22
0.25
n.a.
n.a. = not available
0.12x lo6 tonnesper year was in the last phaseof
in 1994.
construction
aidsto oil recovery:
recovery
recovery
oil
phase
agent
recovered
At currentratesof consumption,provencrudeoil reserveswill
last an estimated43 years(1996).If the additional supply from
oil shale/oilsandsis included,thesupplywill last for morethan
(in Vo)
100years.
primary well headpressure 10- 20
secondary water/gasflooding -30
tertiary chemicalflooding
(polymers,tensides) -50

4

1. VariousAspects of the Energy and Raw Material Supply

However,the following factorswill probablyhelp ensurean oil supply well beyond that point: better utilization of known depositswhich at presentareexploitedonly to about 30% with conventional technology, intensified exploration activity, re- coveryof difficult-to-obtainreserves,theopeningup of oil fields under the seabedas well as a restructuringof energy and raw material consumption.

natural gas reserves(in 10 kwhr):

 

1985

1989

1992

1995

proven

944

1190

1250

1380

total

2260

3660

3440

3390

(1m natural gas = 9.23 kwhr)

at the presentrate of consumptionthe pro- ven naturalgasreserveswill be exhaustedin ca. 55 years

rapid developmentin naturalgasconsump- tion possibleby transportoverlong distances by meansof

1. pipelines

2. speciallydesignedships

3. transformationinto methanol

substitutionof the natural gas by

naturalgas(SNG)not before2000 (CJ: Sec-

synthetic

tion 2.1.2)

1.2.2. Natural Gas

The proben and probable world natural gas reserves are

somewhat larger than the

estimatedat 368 x 1012m3, or 3390x 1012kwhr. Provenreser-

vesamountto 1380x 1012kwhr.

In 1995,39% of thesereserveswerelocatedin the CIS, 14% in Iran, 5% in Qatar,4% in eachof Abu Dhabi andSaudiArabia, and 3% in the USA. The remaining 31% is distributedamong all other natural gas-producingcountries.

oil reserves, and are currently

Based on the natural

the provenworldwide reservesshouldlast for almost 55 years.

gas output for 1995 (25.2 x 10 kwhr),

In 1995,North America and EasternEuropewere the largest producers,supplying32 and 29%, respectively,of the natural gas worldwide.

Natural gasconsumptionhassteadilyincreasedduring the last two decades.Up until now, naturalgascouldonly beusedwhere the correspondingindustrial infrastructure was available or

wherethe distanceto the consumercould be bridged by means

of pipelines. In the meantime,gas transportationover great distancesfrom the sourceof supply to the most important consumptionareascan be overcomeby liquefactionof natural gas (LNG = liquefied natural gas) and transportationin speciallybuilt shipsasis donefor examplein Japan,which sup- plies itself almost entirely by importing LNG. In the future, natural gascould possibly be transportedby first convertingit into methanol - via synthesisgas - necessitating,of course, additional expenditure.

The dependenceon imports,aswith oil, in countrieswith little or no naturalgasreservesis thereforeresolvable.However,this situation will only fundamentallychangewhen synthesisgas

technology -

establishedand developed.This

will probably take placeon a

larger scaleonly in the distantfuture.

basedon brown (lignite) and hard coal -

is

1.2. Availability of Individual Sources

5

1.2.3.Coal

As far asthe reservesare concerned,coal is not only the most

widely spread but also the most important source of fossil 1985 1989 1992 1995

energy.However,it must be kept in mind that the estimatesof

coaldepositsarebasedon geologicalstudiesanddo not takethe mining problemsinto account.The provenand probableworld ~~~~~ac~~l tar and hard coal reservesare estimatedto be 61920x lo1*kwhr. The proven reservesamountto 4610x 10 kwhr. Of this amount, ca. 35 % is found in the USA, 6 % in the CIS, 13% in the

Peoples Republicof China, in Africa. In 1995,3.4 x lo6

worldwide,with 56Ya comingout of the USA andChina.

hard coal reserves(in

proven 5600

total

54500

4090

58600

kwhr):

5860

67800

4610

61920

13YOin WesternEurope,and 11 % tonnesof hard coal wereproduced

In 1989,the world reservesof brown coal were estimatedat

are proven

6800~10

kwhr, of

which 860 x 10

kwhr

reserves.By 1992,these proven reserveshad increasedby ca.

30To.

With the huge coal deposits available, the world s energy requirementscould be met for a long time to come.According to studiesat severalinstitutes,this could befor severalthousand yearsat the current rate of growth.

brown coal reserves(in 10 kwhr):

1985

1989

proven

total

n.a. = not available

1360

5700

860

6800

1992

n.a.

1994

n.a.

1.2.4.Nuclear Fuels

Nuclearenergyis - asa resultof its stageof development- the only realisticsolutionto the energysupp!y problemof the next decades.Its economicviability hasbeenproven.

The nuclear fuels offer an alternativeto fossil fuels in impor- tant areas,particularly in the generationof electricity.In 1995, 17% of the electricity worldwide wasproducedin 437 nuclear reactors,and an additional 59 reactorsare under construction.

Most nuclear power plants are in the USA,

andJapan.The uraniumandthorium depositsareimmenseand arewidely distributedthroughoutthe world. In 1995,the world productionof uranium was 33000 tonnes.Canadasuppliedthe largestportion with 9900tonnes,followed by Australia,Niger, the USA andthe CIS.

followed by France

energysourcesfor electricity(in %):

USA

Western

World

Europe 1975 1987 1974 1995 1975 1995

natural gadoil

coal

nuclear energy

hydroelectric/

others

176

9

15

13

53

17

17

36

34

6

24

21

29

35

I5

35

37

5

23

25

38

I7

20

reservesof nuclear fuels (in lo6 tonnes):

 

uranium

thorium

proven

2.2

n.a.

total

4.0

2.2

n.a. = not available

In the low andmediumpricerangethereareca.4.0 x lo6tonnes of uranium reserves,of which 2.2 x lo6 tonnes are proven; the correspondingthorium reservesamountto around2.2 x lo6 tonnes.

6 I. Various Aspects of the Energy and Raw Material Supply energycontentof uranium reserves (in
6 I. Various Aspects of the Energy and Raw Material Supply
energycontentof uranium reserves
(in 10" kwhr):
Employing uranium in light-water reactors of conventional
690
with conventional reactor
technology
design in which essentiallyonly 235Uis used (up to 0.7% in
natural uranium) and where about 1000 MWd/kg 235Uare
80000
by full utilization via breeders
attainedmeansthat 4 x lo6 tonnesuranium correspondto ca.
690x 10l2 kwhr. If this uranium were to be fully exploited
function of fast breeders
(neutroncapture):
using fast breeder reactors, then this value
could be very
2%~~
239p
232~h~
231~
considerablyincreased,namelyto ca. 80000 x 1Ol2 kwhr. An
additional 44000 x 10j2 kwhr could be obtained if the
aforementionedthoriumreserveswereto beemployedin breeder
reactors.The significanceof the fast breederreactorscan be
readily appreciated from these figures. They operate by
synthesizingthe fissionable 239Pufrom the nonfissionable
nuclide238U(main constituentof naturaluranium,abundance
99.3%) by meansof neutron capture.238Uis not fissionable
using thermal neutrons.In the sameway fissionable233Ucan
be synthesizedfrom 232Th.
The increasingenergydemandcan be met for at least the next
50 yearsusing presentreactor technology.
reactorgenerations:
light-waterreactors
high temperaturereactors
breederreactors
advantageof high temperaturereactors:
high temperaturerange(900- 1000"C)
processheatusefulfor stronglyendothermic
chemicalreactions
The dominantreactortype today, and probably for the next 20
years, is the light-water reactor (boiling or pressurizedwater
reactor)which operatesattemperaturesupto about300"C. High
temperaturereactorswith coolingmedium(helium) temperature
up to nearly 1000"C arealreadyon the thresholdof large scale
development.They have the advantagethat they not only
supply electricity but also processheat at higher temperatures
(cJ Sections2.1.1 and 2.2.2). Breeder reactorswill probably
become commercially available in greater numbers as
generatingplantsneartheendof the 1990sat theearliest,since
severaltechnologicalproblemsstill confronttheir development.
In 1995,JapanandFranceweretheonly countriesthatwerestill
using and developingbreederreactors.
essentialprerequisitesfor the useof nuclear
energy:
It is important to note that the supply situation of countries
highly dependenton energyimportation can be markedly im-
1. reliablesupply of nuclearenergy
2. technicallysafenuclearpower stations
3. safe disposal of
fission products and
recycling of nuclearfuels (reprocessing)
provedby storingnuclearfuels dueto their high energycontent.
Theprerequisitefor thesuccessfulemploymentof nuclearenergy
is not only that safe and reliable nuclear power stationsare
erected,but alsothat the whole fuel cycleis completelyclosed.
This begins with the supply of natural uranium, the siting of
suitableenrichmentunits,andfinisheswith thewastedisposalof
radioactivefission productsand the recycling of unusedand
newly bred nuclearfuels.
Wastemanagementandenvironmentalprotectionwill determine
the rate at which the nuclearenergyprogramcanberealized.
1.3. Prospects for fheFuture Energy Supply 7 1.3.Prospectsfor the Future Energy Supply As seenin the
1.3. Prospects for fheFuture Energy Supply
7
1.3.Prospectsfor the Future Energy Supply
As seenin the foregoingsections,oil, naturalgas,andcoalwill
remainthemostimportantprimary energysourcesfor the long
term.While thereis currentlylittle restrictionon theavailability
of energysources,in light of the importanceof oil and natural
gas as raw materials for the chemical industry, their use for
energyshould be decreasedas soonas possible.
with theprevailingenergystructure,oil and
naturalgaswill be thefirst energysourcesto
be exhausted
competition between their
energy and
chemical utilization
compels structural
changein the energypallette
Theexploitationof oil shalesandoil sandswill not significantly
affect thesituationin thelong term. Thesubstitutionof oil and
natural gas by other energy sources is the most prudent
solution to this dilemma. By thesemeans,the valuable fossil
materialswill beretainedasfar aspossiblefor processingby the
chemicalindustry.
In the medium term, the utilization of nuclear energy can
decisively contributeto a relief of the fossil energyconsump-
tion. Solar energy offers an almost inexhaustible energy
reserveand will only be referred to here with respect to its
industrialpotential.Theenergywhich thesunannuallysupplies
to theearthcorrespondsto thirty timestheworld s coalreserves.
Basedonasimplecalculation,theworld s presentprimaryenergy
consumptioncouldbecoveredby 0.005% of theenergysupplied
by the sun. Consequently,the developmentof solar energy
technology including solar collectors and solar cell systems
remainsan importantobjective.At the sametime, however,the
energystorageandtransportationproblemsmustbe solved.
possiblerelief for fossil fuels by generation
of energyfrom:
1. nuclearenergy(medium term)
2.
solar energy(long term)
3.
geothermalenergy(partial)
4.nuclear fusion energy(long term)
Thelargescaleutilization of theso-calledunlimited energies-
solar energy, geothermalenergy, and nuclear fusion -
will
becomeimportantonly in the distantfuture. Until that time, we
will be dependenton an optimal useof fossil raw materials,in
particular oil. In the near future, nuclearenergyand coal will
play a dominantrolein our energysupply,in orderto stretchour
oil reservesas far aspossible.Nuclearenergywill take over the
generationof electricity while coalwill beincreasinglyusedasa
substitutefor petroleumproducts.
possible substitution of
generationby meansof:
oil
for
energy
1.
coal
2.
nuclearenergy
3.
combinationof coal and nuclearenergy
4.
hydrogen
Beforetheenergysupplybecomesindependentof fossil sources
- undoubtedlynot until thenext century - therewill possibly
be an intermediateperiod in which a combinationof nuclear
energyand coal will be used. This combinationcould utilize
nuclearprocessheatfor coal gasificationleadingto the greater
employmentof synthesisgasproducts(cJ Section2.1.I).
Along
with
the manufacture of
synthesis gas via
coal
gasification,nuclear energycan possibly also be used for the

8

1. Various Aspects of the Energy and Raw Material Supply

manufactureof hydrogenfrom watervia high temperaturesteam

electrolysisor chemical cyclic

water electrolysisusing solar energy,which is being studied widely in severalcountries.This could result in a wide useof hydrogenas an energysource(hydrogentechnology)and in a

processes.The sameis true of

replacementof

hydrogenmanufacturefrom fossil materials(cJ:

Section2.2.2).

long-termaim:

energysupplysolelyfromrenewablesources;

raw material supply from

fossil sources

characteristicchangesin the raw material baseof the chemicalindustry:

feedstocksuntil 1950

gasification

1. coal

products,synthesisgas) 2. acetylenefrom calcium carbide

products

feedstocksafter 1950

(coking

I. productsfrom petroleumprocessing

2. natural gas

3. coalgasificationproductsaswell asacety- lenefrom carbideandlight hydrocarbons

expansionof organicprimary chemicalswas only possibledueto conversionfrom coal to oil

returnto coal for organicprimary chemicals is not feasiblein short and medium term

primary chemicalsare petrochemicalbasis productsfor furtherreactions;e. g., ethylene, propene,butadiene,BTX aromatics

primary chemicalsproduction(lo6 tomes)

 

1989

1991

1993

USA

37.1

39.5

41.7

W.Europe

35.4

38.3

39.4

Japan

15.9

19.2

18.4

feedstocksfor olefins andaromatics:

Japan/WE:naphtha(crudegasoline)

USA

liquid gas(C, - C,) and, increasingly,naphtha

feedstocksfor synthesisgas(CO + HJ:

methaneand higher oil fractions

This phasewill leadto thesituationin which energywill bewon solelyfrom renewablesourcesandoil andcoalwill beemployed only as raw materials.

1.4. Presentand Anticipated Raw Material Situation

The presentraw material situation of the chemicalindustry is characterizedby a successfuland virtually completechangeover from coal to petroleumtechnology.

The restructuring also applies to the conversionfrom the acetyleneto the olefin base(cJ: Sections3.1 and 4.1).

1.4.1.PetrochemicalPrimary Products

The manufacture of carbon monoxide and hydrogen via gasificationprocessestogetherwith the manufactureof carbide

(for welding andsomespecialorganicintermediates),benzene, and certain polynuclear aromatics are the only remaining processesof thoseemployedin the 1950sfor the preparationof basicorganicchemicalsfrom coal. However,theseaccountfor only a minor part of the primary petrochemicalproducts; currentyca. 95% arebasedon oil or naturalgas.Furthermore, thereis no doubtthat theexpansionin productionof feedstocks for the manufactureof organic secondaryproducts was only possibleasa resultof thechangeoverto oil. This rapid expansion would not havebeenpossiblewith coal dueto inherentmining constraints.It can thus be appreciatedthat only a partial

substitutionof oil by coal, resultingin limited broadeningof the raw materialbase,will bepossiblein thefuture.Thedependence

of

the chemicalindustry on oil will thereforebe maintained.

In

Japanand WesternEurope,naphtha(or crudegasoline)is by

far the most important feedstockavailableto the chemical industry from the oil refineries. A decreasingavailability of

naturalgashas also led to the increasinguseof naphthain the USA. Olefinssuchasethylene,propene,butenes,andbutadiene as well as the aromaticsbenzene,toluene, and xylene can be

1.4. Present and Anticipated Raw Material Situation 9 obtainedby crackingnaphtha.Of lessimportanceareheavyfuel oil
1.4. Present and Anticipated Raw Material Situation
9
obtainedby crackingnaphtha.Of lessimportanceareheavyfuel
oil andrefinerygaswhich areemployedtogetherwith naturalgas
for the manufactureof synthesisgas.The latter forms the basis
for the manufactureof ammonia,methanol, acetic acid, and
‘0x0’ products.The processtechnologylargely determinesthe
contentand yield of the individual cuts.
This technology has been increasingly developedsince the oil
trend in demandfor lighter mineral oil pro-
ducts necessitatesmore complex oil
sing,e.g.,from residualoils
proces-
crisis, so that today a complex refinery structureoffers large
quantitiesof valuable products.Thus heavy fuel oil is
partially
restructuring of
refineries by additional
convertedto lower boiling productsthrough thermal cracking
processessuch as visbreaking and coking processes.Further-
more,theresiduefrom theatmosphericdistillation can,follow-
ing vacuum distillation, be converted by catalytic or hydro-
cracking.This increasesthe yield of lighter productsconsider-
ably, althoughit alsoincreasestheenergyneededfor processing.
conversionplantssuchas:
1.
thermocrackers
2.
catalyticcrackers
3. hydrocrackers
The spectraof refinery productsin the USA, WesternEurope,
and Japanare distinctly different due to the different market
pressures,yet they all show the sametrend toward a higher
demandfor lighter mineraloil fractions:
markets 1973/93 for mineral oil products
showcharacteristicdrop in demand:
1. total of 16-31%
2. heavyfuel oil of 36-54%
Table 1-1. Distribution of refinery products(in wt To).
USA
WesternEurope
Japan
1973
1983
1993
1973
1985
1993
1973
1983
1993
Refinery & liquid gas
Motor gasoline,naphtha
Jet fuel
Light fuel oil, diesel oil
Heavy fuel oil
9
10
8
443
6
11
3
44
49
47
24
26
29
21
24
20
679
457
8
11
15
19
20
20
32
38
37
12
17
32
16
9
8
33
22
21
50
33
23
Bitumen, oil coke 658 353 347
Total refinery products
(in lo6 tonnes)
825
730
690
730
527
577
260
220
179
Theaforementioneddevelopmenttowardlower boiling products
from mineral oil was influencedby the fuel sectoraswell asby
the chemical industry. Even though in principle all refinery
productsare usablefor the manufactureof primary chemicals
such as olefins and the BTX (benzene- toluene-xylene)
aromatics, there is still a considerabledifference in yield.
Loweringtheboiling point of thefeedstockof a crackingprocess
increasesnot only theyield of C, - C, olefins, but alsoaltersthe
olefin mixture; in particular,it enhancesthe formation of the
mainproductethylene,by far themostimportantof thechemical
building blocks (cf. adjacenttable).
olefin yieldsfrom moderateseveritycracking
(in wt%)
ethane naphtha oil
ethylene
82
30
20
propene
2
17
14
C,-olefins
3
11
9
remainder:fuel gas,gasolinefrom cracking,
oil residue
10 1. VariousAspects of the Energy and Raw Material Supply savingoil asan energysourceis possiblein severalways:
10 1. VariousAspects of the Energy and Raw Material Supply
savingoil asan energysourceis possiblein
severalways:
Independentof thehighersupplyof refinery fractionspreferred
by the chemical industry through expandedprocessingtech-
nology,by andlargethevital taskof reducinganduncouplingthe
dual role of oil as a supplier of both energyand raw materials
1. increased efficiency during conversion
into energy
remains.
2. gradual substitutionby coal or nuclear
A first steptowardsavingoil could be to increasethe efficiency
energy
3. gradual substitutionas motor fuel by,
e.g., methanol,ethanol
of its conversioninto electricity,heat,and motive power.
In the industrial sector, currently only 55% of the energyis
actuallyused.Domesticandsmallconsumers,whorepresentnot
only the largestbut alsothe expandingconsumptionareas,use
only 45%, while transportusesonly 17%.The remainderis lost
through conversion,transport,and wasteheat.
The gradualreplacementof oil in energygenerationby coal and
nuclear energycould have an even greatereffect (cf. Section
1.3). This includes the partial or complete replacementof
gasolineby methanol(cf-Section2.3.1.2) or by ethanol,perhaps
from a biological source(cJ: Section8.1.1).
future supplies of primary chemicalsin-
creasingdue to countrieswith inexpensive
raw material base, e.g., oil producing
countries
Overandabovethis, thereareother aspectsof
the future of the
primary raw chemicalsupply for the chemicalindustry. First
among these is the geographic transfer of
petrochemical
typical production,e. g., in Saudi Arabia
(startingin 1984)
ethylene
ethanol
ethyleneglycols
dichloroethane
vinyl chloride
styrene
startingin 1993,e.g, MTBE
(0.86x lo6 tonnesper year)
production to the oil producing countries. Saudi Arabia has
emergedin thelastfew yearsasa large-scaleproducerof primary
chemicalsand the most importantolefins, in order to (among
other things)makeuseof the petroleumgaspreviouslyburned
off. A number of nonindustrializedand newly industrialized
nations have followed this example,so that in the future they
will be ableto supplynot only their domesticrequirements,but
also the establishedproduction centersin the USA, Western
Europe,andJapan.
Thus it can be expectedthat the capacity for production of
primary chemicalsin thesenewly industrializedcountrieswill
increasecontinuously.This is a challengeto the industrialized
countries to increasetheir proportion of higher valued pro-
ducts.
In 1995, the world production capacity for the total area of
petrochemicalproductswas about 200 x lo6 tonnesper year.
Of this, about 29% was in WesternEurope, 23 Yo in the USA,
17 070 in SoutheastAsia, 10Yo in Japan,and 21 Yo in the remain-
ing areas.