Hydrothermal and Supercritical Water Processes, Volume 5

683 Pages·2014·27.926 MB·English

by  Gerd Brunner

Supercritical Fluid Science and Technology
Volume 5
Hydrothermal and Supercritical
Water Processes
SupercriticalFluidScienceandTechnology
SeriesEditor– ErdoganKiran
Vol.1 SupercriticalFluidsandOrganometallicCompounds:FromRecovery
ofTraceMetalstoSynthesisofNanostructuredMaterials.
ByCanErkey
Vol.2 High-PressureFluidPhaseEquilibria:PhenomenologyandComputation.
ByUlrichK.DeitersandThomasKraska
Vol.3 SupercriticalFluidScienceandTechnology:PhaseEquilibrium
Engineering.
ByEstebanBrignoleandSelvaPereda
Vol.4 IntroductiontoSupercriticalFluids:ASpreadsheet-basedApproach.
ByRichardSmith,HiroshiInomata,andCorPeters
Supercritical Fluid Science and Technology
Volume 5
Hydrothermal and
Supercritical Water
Processes
Gerd Brunner
Hamburg University of Technology
Hamburg, Germany
Amsterdam (cid:129) Boston (cid:129) Heidelberg (cid:129) London (cid:129) New York (cid:129) Oxford
Paris (cid:129) San Diego (cid:129) San Francisco (cid:129) Singapore (cid:129) Sydney (cid:129) Tokyo
Elsevier
Radarweg29,POBox211,1000AEAmsterdam,TheNetherlands
TheBoulevard,LangfordLane,Kidlington,OxfordOX51GB,UK
Copyright©2014ElsevierB.V.Allrightsreserved
Nopartofthispublicationmaybereproduced,storedinaretrievalsystem
ortransmittedinanyformorbyanymeanselectronic,mechanical,photocopying,
recordingorotherwisewithoutthepriorwrittenpermissionofthepublisher
PermissionsmaybesoughtdirectlyfromElsevier’sScience&TechnologyRights
DepartmentinOxford,UK:phone[phone];fax[phone];
email:[e-mail]tyourrequestonlineby
visitingtheElsevierwebsiteathttp://elsevier.com/locate/permissions,andselecting
ObtainingpermissiontouseElseviermaterial
Notice
Noresponsibilityisassumedbythepublisherforanyinjuryand/ordamagetopersons
orpropertyasamatterofproductsliability,negligenceorotherwise,orfromanyuse
oroperationofanymethods,products,instructionsorideascontainedinthematerial
herein.Becauseofrapidadvancesinthemedicalsciences,inparticular,independent
verificationofdiagnosesanddrugdosagesshouldbemade
BritishLibraryCataloguing-in-PublicationData
AcataloguerecordforthisbookisavailablefromtheBritishLibrary
LibraryofCongressCataloging-in-PublicationData
AcatalogrecordforthisbookisavailablefromtheLibraryofCongress
ISBN:978-0-444-59413-6
ISSN:2212-0505
ForinformationonallElsevierpublications
visitourwebsiteatwww.store.elsevier.com
PrintedandboundinGreatBritain
14 15 16 17 18 10 9 8 7 6 5 4 3 2 1
Contents
Foreword xi
Preface xv
1. Introduction 1
2. Properties of Pure Water 9
2.1 Introduction 9
2.2 StructureofH2O 12
2.3 PhaseDiagram 16
2.3.1 SupercriticalRegion 17
2.3.2 Meta-StableStates 18
2.4 ThermodynamicProperties 18
2.4.1 ThermodynamicFunctions 18
2.4.2 P,V,T-Behavior 20
2.4.3 CalculationofP,V,T-Behavior 23
2.4.4 Joule–ThomsonEffect ofWater 34
2.4.5 ThermodynamicPropertiesofWaterat Saturation 34
2.4.6 HeatCapacity (SpecificHeat) ofWater 36
2.4.7 Enthalpy 40
2.4.8 Entropy 41
2.4.9 SteamTables 43
2.5 TransportProperties 43
2.5.1 Viscosity 43
2.5.2 ThermalConductivity 61
2.5.3 Diffusion 65
2.6 ElectricalProperties 71
2.6.1 ElectricalConductivity ofWater 71
2.6.2 DielectricConstant 74
2.7 MiscellaneousPropertiesofWater 80
2.7.1 RefractiveIndex 80
2.7.2 SurfaceTension 83
2.7.3 IonicDissociationConstantofWater 84
References 89
3. Properties of Mixtures with Water 95
3.1 Introduction 95
3.2 PropertiesofMixtures 96
3.2.1 ThermodynamicsofMixtures 96
3.2.2 PropertiesofMixtures withWater 98
v
vi Contents
3.3 PhaseBehaviorofMixtureswithWater 111
3.3.1 ThermodynamicsofPhase Equilibrium 111
3.3.2 PhaseEquilibriumin BinaryAqueous Systems 114
3.3.3 PhaseEquilibriaof TernarySystems 122
3.3.4 CalculationofP,V,T-Behavior andPhase Behavior of
Mixtureswith Water 123
3.4 WaterandNonelectrolytes 132
3.4.1 SolubilityofNonelectrolyteGases inWater 132
3.4.2 PhaseBehavior andCritical Curves 142
3.4.3 WaterandOrganicNonelectrolyte Compounds
(Waterand Hydrocarbons) 146
3.5 WaterandElectrolytes 170
3.5.1 Equilibriawith DissociatingCompounds 173
3.5.2 WaterandVolatile Electrolytes 180
3.5.3 OtherInorganicand OrganicCompounds 198
3.6 WaterandMetalOxides 201
3.7 WaterandNonvolatileElectrolytes (Salts) 205
3.7.1 BinarySystems 206
3.7.2 TernarySystemsandthe InfluenceofSalts onPhase
Equilibrium 210
References 215
4. Heat Transfer 227
4.1 Introduction 227
4.2 HeatTransfer toPureWater 227
4.2.1 Overviewon HeatTransfer Regions 227
4.2.2 HeatTransfertoGas andLiquid (RegionsIand II) 228
4.2.3 BoilingofPureWater 231
4.2.4 BoilingofMixtures 236
4.3 HeatTransferintheCriticalandSupercriticalRegion
(RegionIV) 237
4.3.1 Near-Critical HeatTransfer 237
4.3.2 PseudocriticalProperties 239
4.3.3 HeatTransfertoSupercriticalWater 239
4.4 Condensation 247
4.4.1 CondensationofPureFluids 247
4.4.2 CondensationofMixtures 250
4.5 HeatTransfer forFlowThrough BedsofParticles 258
4.6 HeatTransferCoefficients inHeatExchangers 259
References 261
5. Reactions in Hydrothermal and Supercritical Water 265
5.1 Introduction 265
5.2 ChemicalEquilibrium andChemicalKinetics 267
5.2.1 ChemicalEquilibrium 267
5.2.2 ChemicalKinetics 268
Contents vii
5.3 SpecificReactionsinSupercriticalWaterasa ReactionMedium 278
5.3.1 Introduction 278
5.3.2 ExperimentalMethodsforReaction Mechanisms
andReaction Kinetics 280
5.3.3 HydrothermalReactions ofHydrocarbons 282
5.3.4 Hydrolysis/Cleavage 285
5.3.5 Acidsand Bases 310
5.3.6 MiscellaneousOrganicReactions 310
5.3.7 CatalyzedReactions 312
References 315
6. Extraction Processes 323
6.1 Introduction 323
6.2 FundamentalsoftheExtractionProcess 323
6.2.1 GeneralDescription 323
6.2.2 InfluenceofProcessParameters 325
6.2.3 Influenceofthe Conditionofthe SolidSubstrate 327
6.2.4 Modelingof theExtraction Process 327
6.3 SoilCleaning 334
6.3.1 Materials 335
6.3.2 ExtractionResults 335
6.3.3 Extractionof HeavyMetals andOrganic Compounds 339
6.4 Various ExtractionsfromMineral Substrates 341
6.4.1 Extractionof PAHfromFlyAshes 341
6.4.2 BitumenExtraction fromAsphalt 341
6.4.3 Regenerationof ActivatedCarbon 341
6.5 SeparationofOrganicCompounds fromBoneMaterial 342
6.5.1 Extractionof ProteinsfromDefattedBone Material
withHigh-Temperature Water 343
6.5.2 Extractionof FatandProteins withHigh-Temperature
Water 344
6.5.3 Extractionof LargerBone Structures 346
6.5.4 Investigationofthe Influenceof CO onHydrolysis
2
andExtraction 349
6.5.5 Characterizationand Separationof theProtein Extract 350
6.6 ExtractionofNatural Substances 352
References 358
7. Processing of Fuel Materials with Hydrothermal
and Supercritical Water 361
7.1 Introduction 361
7.2 ProcessingofCoalwithWater 362
7.2.1 Extractionand LiquefactionofCoalin Hydrothermal
andSupercriticalWater 363
7.2.2 GasificationofCoalin SupercriticalWater 370
7.3 OilShale ConversionwithHydrothermaland
SupercriticalWater 372
viii Contents
7.3.1 KerogenConversion withSupercriticalWater 374
7.3.2 InvestigationofOil Shale Conversionona Green
RiverOilShale 375
7.3.3 FurtherInvestigationson KerogenConversion with
SupercriticalWater 381
7.3.4 Conversionwith SupercriticalBrine 384
7.4 OilSandsProcessing withHydrothermaland
SupercriticalWater 387
7.4.1 Extractionof BitumenfromOil SandswithSub- and
SupercriticalWater 388
7.4.2 Upgradingof Bitumenwith Hydrothermaland
SupercriticalWater 391
References 391
8. Processing of Biomass with Hydrothermal
and Supercritical Water 395
8.1 Introduction 395
8.2 Processing ofPlant-BasedMonomers withHigh-Temperature
andSupercriticalWater 398
8.2.1 Conversionof SugarstoLiquid Products 398
8.3 Processing ofNaturalPolymerswithHigh-Temperature
andSupercriticalWater 411
8.3.1 Starch 412
8.3.2 Pectin 418
8.3.3 Cellulose 420
8.3.4 Hemicellulose 427
8.3.5 Lignin 433
8.3.6 Proteins 449
8.4 Processing ofMixturesofNaturalCompounds of
BiomassinHigh-TemperatureandSupercriticalWater 462
8.4.1 LignocellulosicMaterials 463
8.4.2 MaterialsContaining Proteins 476
8.5 BiomassLiquefaction 483
8.6 BiomassGasification 486
8.6.1 HydrothermalGasification ofModelCompounds
andSeparate NaturalPolymers 487
8.6.2 HydrothermalGasification ofReal Biomass 492
References 499
9. Reactions of Synthetic Polymers with Water 511
9.1 CondensationPolymers 511
9.2 Polyethylene 514
9.3 AdditionPolymerizationPolymers 516
9.3.1 PhenolResins 516
9.3.2 Fiber-Reinforced Plastics 518
Contents ix
9.4 Various Polymers 519
9.4.1 Cross-Linked Polyethylene 519
9.4.2 ChlorinatedPolymers 519
9.4.3 Polystyrene 520
9.4.4 Poly(LacticAcid) 520
References 522
10. Oxidation in High-Temperature and
Supercritical Water 525
10.1 GeneralAspectsofOxidationinWater 525
10.2 WetAirOxidation 526
10.2.1 Introduction 526
10.2.2 Examples 529
10.3 SupercriticalWaterOxidation 538
10.3.1 Principles andFeatures ofSCWO 538
10.3.2 Examples:Specific Compounds 542
10.4 HydrothermalFlames 558
10.4.1 Introduction 558
10.4.2 GeneralFeatures ofHydrothermal Flames 559
10.4.3 Type ofFlames(Diffusion Flames,TurbulentFlames) 560
10.4.4 Characterization ofHydrothermal FlameProcesses 561
10.4.5 Spallation Drilling 563
References 564
11. Hydrothermal and Supercritical Water
Processing of Inorganic Substances 569
11.1 Introduction:What isHydrothermalProcessing? 569
11.2 PrincipleofHydrothermalProcessing 570
11.3 CrystalGrowth 571
11.3.1 Metal Oxides 571
11.3.2 Gems 575
11.4 SynthesisofNewPhasesandCompounds 576
11.4.1 Phosphates andSilicates 576
11.4.2 Metal Sulfides 577
11.4.3 OtherCompounds 578
11.5 HydrothermalPreparationofMaterials,Production
ofFineParticles,Impregnation,Coatings 578
11.5.1 GeneralAspects 578
11.5.2 Hydrolysis 580
11.5.3 Addition ofOxidizing or ReducingAgents 582
11.5.4 Thermal Conversionof Precursors 583
11.5.5 Control ofMorphology DuringHydrothermal
Synthesis 583
11.5.6 Impregnation 584
References 585