Direct Methane to Methanol: Foundations and Prospects of the Process

320 Pages·2014·20.018 MB·English

by  Vladimir Arutyunov

DIRECT METHANE TO METHANOL
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DIRECT METHANE
TO METHANOL
Foundations and Prospects
of the Process
V A
LADIMIR RUTYUNOV
AMSTERDAM(cid:129)BOSTON(cid:129)HEIDELBERG(cid:129)LONDON(cid:129)NEWYORK(cid:129)OXFORD
PARIS(cid:129)SANDIEGO(cid:129)SANFRANCISCO(cid:129)SINGAPORE(cid:129)SYDNEY(cid:129)TOKYO
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Contents
Introduction vii 6.TheRoleofHeterogeneousProcessesinthe
PartialOxidationofMethanetoOxygenates 85
OntheInterplaybetweentheHomogeneous
1.HistoricalReviewontheDMTM 1
andHeterogeneous-CatalyticProcesses
ofMethaneOxidation 85
2.OxidationProducts 5
InfluenceoftheReactorSurfaceMaterial 91
MainProductsoftheDMTMProcess 5
DecompositionoftheProductsontheReactor
TheRatioCH OH/CH O 8
3 2 Surface 96
TheRatioCO/CO 13
2 EffectofCatalystsontheGas-PhaseDMTM
Byproducts 14
Process 99
ResidualOxygen 16
Short-timeCatalysisandthePossibilityof
TheDCH /DO Ratio 18
4 2 ControllingtheDMTMProcess 104
YieldofMethanolandOxygenates 19
OxidationProductsofMethane
7.RoleofPressureintheDMTMProcess 109
Homologues 27
StationaryModeofBranched-ChainReaction 110
3.TheMainParametersoftheProcess 29 EffectofPressureontheRateofBranched-Chain
EffectofPressureontheTemperatureandRate QuasistationaryReactionandtheMethanol
oftheProcess 29 Yield 110
EffectofPressureontheYieldofthePartial RoleofDiffusionoftheReactantstotheReactor
MethaneOxidationProducts 31 Surface 112
EffectofTemperatureontheYieldofthe
Products 38 8.ThermokineticPhenomenainPartial
EffectoftheOxygenConcentration OxidationofMethane 115
(CH /O Ratio)ontheSelectivityandYield ExperimentallyObservedThermokinetic
4 2
PhenomenainthePartialOxidationof
oftheProducts 45
Methane 115
InfluenceoftheOxygenConcentrationonthe
ReactionTemperatureandReactionRate 52 MechanismofNonlinearPhenomenainthe
OxidationofAlkanes 126
ReactionTime 55
SpecificsoftheOrganization
oftheProcess 59 9.PromotionoftheProcess 129
HomogeneousChemicalPromotionofthe
4.EffectoftheGasComposition 65 Process 129
Hydrocarbons 65 PhysicalMethodsforInitiatingtheProcess 145
Hydrogen 68 PartialOxidationofAlkanesinSCConditions 157
CarbonMonoxide 69
Inerts 70 10.PartialOxidationofMethane
Homologues.GeneralPrinciplesofthe
5.KeyFeaturesoftheMechanism 75 PartialOxidationofLightAlkanesto
MechanismoftheGas-PhaseOxidationof Oxygenates 167
MethaneintheMedium-TemperatureRange 75 PartialOxidationofEthaneandMethaneeEthane
MainKineticFeaturesoftheDMTMProcess 81 Mixtures 167
v
vi
CONTENTS
Propane 179 12.PlaceoftheDMTMamongthe
Butane 184 otherProcessesofPartialOxidation
GeneralFeaturesoftheOxidationofAlkanesat ofLightAlkanes 245
HighPressures 191 PartialOxidationofLightAlkanesasaBasisofthe
RelativeConversionofAlkanesinTheirJoint MostImportantGas-ChemicalProcesses 245
Oxidation 197 OxidativeConversionofMethanetoSyngas 248
OxidativeCouplingofMethane 259
11.PromisingTechnologiesBasedonthe SelectiveOxycrackingofHeavierComponents
DMTMProcess 201 ofNaturalGas 261
IndustrialExperienceofthePartial GeneralConceptoftheModernLow-ScaleGas
OxidationofHydrocarbonGasesto Chemistry 264
Oxygenates 201 13.Conclusions 269
ConceptualSchemesofthePartialOxidationof
References 273
NaturalGastoOxygenates 216
InnovativeTechnologiesBasedontheGas-Phase Appendix 1 287
OxidationofHydrocarbonGasesto
Appendix 2 299
Oxygenates 224
Index 303
Direct Methane To Methanol:
Foundations and Prospects
of the Process
Vladimir Arutyunov
Semenov Institute of Chemical Physics, Russian Academy of Sciences, Moscow, Russia
The direct conversion of methane and other reactions,theseprocessesevennowseemso-
light hydrocarbons to methanol (DMTM) and phisticatedandinexhaustible,likethenature
otheroxygenateshasbeenalong-soughtgoalof
itself. On the other hand, the chemical con-
the gas industry for decades. In spite of some
version of light alkanes, the main compo-
experience of industrial applications in the
1930(cid:1)1940s, nowadays this process remains in nents of natural and associated gas, has
thesphereofacademicratherthanpracticalin- becomeone of the most important trendsin
terest. However, some new tendencies in the modern petro-chemistry and in a full-
world’s gas industry rekindled interest in this
fledgednewindustrialsector:gaschemistry.
process. The monograph reviews the modern
Thewidevarietyofproductsoftheoxida-
state of knowledge in this area and discusses
somepromisingpracticalapplications. tive conversion of natural gas includes
hydrogen,syngas,ethylene,otherolefins,ox-
ygenates, and aromatic compounds. The
INTRODUCTION scopeofthepresentmonographismuchnar-
rower,limitedtothedirectconversionofnat-
Intensescientificresearchandtechnologi- ural gas to oxygen-containing compounds
caldevelopmentinthefieldofdirectconver- (oxygenates), mainly methanol and formal-
sion of natural gas to chemicals has been dehyde,underpredominantlyhomogeneous
goingonforacentury.Thereasonfortheun- gas-phase conditions. Nowadays, this direc-
flagging interest in this problem is twofold. tion revealed potentiality for new practical
Ontheonehand,ithasbeenfoundthat,un- applications,inparticularconcerninglowre-
dercertainconditions,theoxidationofeven sourcesandremotegasfields,shalegas,and
simple hydrocarbons, such as methane, is otherunconventionalgasresources.
accompanied by a rapidly increasing com- Since the predominant and most hardly
plexity of the system, with the formation of convertible component of natural and asso-
a multitude of different products, from wa- ciated gas is methane, with the main prod-
terandcarbonoxidestovariouscarboncom- uct of the direct oxidative conversion of
pounds, including such complex as methane and other light alkanes C (cid:1)C be-
2 4
fullerenes and carbon nanotubes. Therefore, ing methanol, theoverall processofnatural
even though the oxidation of methane and gas oxidative conversion to oxygenates has
its closest homologues gave, in due time, traditionally been referred to as Direct
the main body of data underlying the mod- Methane To Methanol (DMTM), a term
ern concepts of the kinetics of gas-phase that will be used throughout the
vii
viii
DIRECTMETHANETOMETHANOL:FOUNDATIONSANDPROSPECTSOFTHEPROCESS
monograph. It covers the totality of pro- In this connection, a good deal of the
cesses of conversion of natural gas light al- monograph is devoted to the prospects of
kanes to oxygenates. In addition, the practicalapplicationsofDMTManditspos-
partial oxidation of methane to methanol is siblefutureroleinthegasindustry.Thereis
the subject of the overwhelming majority avastroomforfurtherimprovementsofthe
ofpublishedacademicandtechnologicalin- process given that the interest from the in-
vestigationsonthedirectgas-phaseconver- dustry will promote necessary efforts.
sion of alkanes to oxygenates. On the other Thus,theneedinalternativesimpleandflex-
hand, there are only limited number publi- ible low-scale Gas-to-Liquid (GTL) technol-
cations concerning heavier hydrocarbons; ogies may become a real driving force for
therefore, the focus will be on analysis of aDMTM refinement.
methane partial oxidation to oxygenates, Themonographreviewsthemodernstate
with generalization to other alkanes given of knowledge on DMTM with emphasis on
separately. its most evident practical applications. It
As an industrial technology, DMTM has summarizes and supplements our previous
seen a sweeping rise and subsequent reviews [1(cid:1)4] and monographs [5, 6] on
decline, mainly due to the lack of under- thesubject,includingtheproblemofmodel-
standingoftheunderlyingcomplexchemis- ingthehomogeneouseheterogeneousoxida-
try. However, scientific research on the tionoflightalkanes[7],aswellasanumber
process have never stopped, as evidenced of recent interesting but somewhat contra-
byalargenumberofpublications,including dictory experimental results. The mono-
very recent, cited in the monograph. Of the graph covers more than 300 publications on
most attractive features of DMTM, apart the high-pressure low-temperature oxida-
ofitstechnologicalsimplicity,areaveryeffi- tionofmethaneandothergaseoushydrocar-
cient internal energyself-supply by the par- bonsoveraperiodfromthebeginningofthe
tial oxidation of the hydrocarbon itself last century up to now and offers a unique
and the possibility of direct formation of comprehensiveanalysisofpracticallyallrel-
nonequilibrium products that cannot evant experimental and theoretical data on
be produced in significant amounts under the DMTM process. As well it discusses the
thermodynamically equilibrium conditions. realpracticalprospectsof DMTM.
CurrentinterestinDMTMispromptedby Webelievethatitwillprovideresearchers
significant changes in the gas industry, andengineersworkinginthefieldofgaspro-
whichstronglyneedslow-scaletechnologies ductionandprocessingwithnecessarytheo-
capable of operating on low resources, reticalknowledgeandexperimentaldatafor
remote and unconventional gas fields. In development and application of new pro-
the technological niche of relatively simple cessesinvolvingthedirectoxidationofnatu-
small-capacity processes, the direct partial ral gas. We hope that it willbe useful for all
oxidation of natural and associated gas to thosewhoworkinthefieldofgasprocessing
methanol is still one of the most promising andgaschemistrybyfacilitatingtheirefforts
and elaborated directions. Along with fun- in practical development and utilization of
damental advances in studying the mecha- neweffectivegaschemicalprocess.
nism of the oxidation of hydrocarbons at The author feels obliged to express his
moderate temperatures and high pressures, deepgratitudetolateProfessorV.I.Vedeneev
it gives a good chance to revive DMTM as for many years of joint work on the DMTM
anindustrial technology. process and especially its mechanism and
ix
DIRECTMETHANETOMETHANOL:FOUNDATIONSANDPROSPECTSOFTHEPROCESS
tolateProfessorO.V.Krylovforveryfruitful collaboration, which has produced practi-
cooperation and discussions of the whole cally all of our recent results on DMTM.
field of hydrocarbon oxidation. The author Author thanks Dr. V.N. Smirnov for his big
is also grateful to Professor V.I. Savchenko help in preparation of English version of
and Dr. V.M. Rudakov for long-standing thismonograph.