Hydrothermal Catalytic Deoxygenation of Fatty Acids and Upgrading Algae Biocrude

211 Pages·2015·8.78 MB·English

Hydrothermal Catalytic Deoxygenation of Fatty Acids
and Upgrading Algae Biocrude
by
ThomasM.Yeh
Adissertationsubmittedinpartialfulfillment
oftherequirementsforthedegreeof
DoctorofPhilosophy
(ChemicalEngineering)
intheUniversityofMichigan
2015
DoctoralCommittee:
ProfessorSuljoLinic,Co-chair
ProfessorPhillipE.Savage,Co-chair
ProfessorAdamJ.Matzger
ProfessorLeviT.Thompson

©ThomasM.Yeh
Allrightsreserved.
2015
Tomyfamilyandfriends.
ii
A C K N O W L E D G M E N T S
I thank my committee members, Phil, Suljo, and Adam for their guidance and
support during my time at Michigan. Each member has asked many thought pro-
vokingquestionsthathaveresultedinhigherqualityresearch. Theircontributions
havebeeninstrumentaltomysuccess.
My wife, Karen, has provided unending support throughout this time. She
has been with me every step of the way, and she has never asked me the most
dreadedquestionofthePhDstudent–“How’syourresearchgoing?”.
Myparentshelpedinthebestwayparentscan–withfreefood. Theskillsmy
parents taught me through maintaining apartments has been used repeatedly in
thelabthroughreactorconstructionandgeneralequipmentmaintenance.
Professional statistical analysis, career advice, and general support was al-
ways a phone call away. My in-laws support has consistently far exceeded expec-
tationsovertheyears.
The Savage and Linic group members have provided valuable feedback
throughdiscussionsandthoughtprovokingquestionsduringgrouppresentations.
My friends provided much needed escapes from research. Leonid Pavlovsky
introduced me to the art of beer brewing. As a result, I have slowly transformed
into a beer snob, and Michelle Przybylek held a birthday party for me every year.
Matt Morabito, Julia Faeth, Lilian Hsiao, Chad Huelsman, Ryan Franck, and Luke
Griffith played Dungeons & Dragons with me and fulfilled my innate desire to
nerd-out. Peter Valdez and I went on many outings to the shooting range, and
he offered me training in the art of tact. Youngri Kim provided many rides to
the airport and helped fulfill my love of being cheap and not paying for airport
parking. Jenn Jocz was a good tennis partner, and she was able to put up with
being in my office and not be offended. Yang Guo and Donghai Xu taught me
Chinese and corrected my accent. Because of Yang, I also ate more bacon in one
yearthanIhaveinmyentirelifethusfar.
Lastly, I am grateful for the staff. Kelly Raickovich, Susan Hamlin, Shelley
Fellers, Pam Bogdanski, and Laura Bracken have provided a lot of administrative
support. Kelly provided copious amounts of free food and literally provided the
energyforalotofthiswork.
iii
Preface
AllworkpresentedwasperformedattheUniversityofMichi-
gan. This work contains both published and unpublished
workthatistheoriginalworkoftheauthor,ThomasYeh.
Portions of Chapter 2 are published as a review paper. Some
of Chapter 4 and most of Chapter 5 has been published, but
Chapter5hasbeenmodifiedtoincludeunpublishedmaterial.
Finally, Chapter 6, has been submitted for publication and is
underreviewatthetimeofthiswriting.
iv
TABLE OF CONTENTS
Dedication . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ii
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . iii
Preface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . iv
ListofFigures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . viii
ListofTables . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xi
ListofAppendices . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xiii
ListofAbbreviations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xiv
Abstract . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xv
Chapter
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.1 BackgroundandMotivation . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.2 Biomass . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.2.1 FirstandSecondGenerationBiofuels . . . . . . . . . . . . . . 4
1.2.2 ThirdGeneration–Algae . . . . . . . . . . . . . . . . . . . . . . 5
1.3 Hightemperaturewater . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
1.3.1 SupercriticalWater . . . . . . . . . . . . . . . . . . . . . . . . . . 7
2 LiteratureReview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
2.1 HydrothermalLiquefactionOil . . . . . . . . . . . . . . . . . . . . . . . 9
2.2 DeoxygenationofFattyAcids . . . . . . . . . . . . . . . . . . . . . . . . 12
2.2.1 DecarboxylationofSaturatedFattyAcids . . . . . . . . . . . 13
2.2.2 DecarboxylationofUnsaturatedFattyAcids . . . . . . . . . . 17
2.3 UpgradingofBiocrudefromHydrothermalLiquefactionandModel
Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
2.3.1 CatalyticHydrothermalDeoxygenation . . . . . . . . . . . . 21
2.3.2 CatalyticHydrothermalDenitrogenation . . . . . . . . . . . . 24
2.3.3 CatalyticHydrothermalDesulfurization . . . . . . . . . . . . 26
2.3.4 HydrothermalCatalyticUpgradingofRealBiocrudeOils . 27
2.4 HydrothermalCatalystStability . . . . . . . . . . . . . . . . . . . . . . 31
v
3 ResearchObjectives. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
3.1 Objectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
4 ExperimentalMethods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
4.1 Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
4.2 CatalystSynthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
4.3 ReactorProcedures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
4.3.1 HighPressureFlowReactorforCatalystDeactivationStudies 40
4.3.2 BatchReactionsforPlatinumTinStudieswithUnsaturated
FattyAcids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
4.3.3 AlgalBiocrudeUpgradingStudies . . . . . . . . . . . . . . . . 43
4.4 AnalyticalChemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
4.4.1 GasChromatography . . . . . . . . . . . . . . . . . . . . . . . . 45
4.4.2 InfraredSpectroscopy . . . . . . . . . . . . . . . . . . . . . . . . 47
4.4.3 CatalystCharacterization . . . . . . . . . . . . . . . . . . . . . . 48
5 Pt/CDeactivationintheDecarboxylationofButyricAcid . . . . . . . . . . 49
5.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
5.2 ReactionProducts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
5.3 DeactivationKinetics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
5.4 CauseofDeactivation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
5.5 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
5.6 Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
6 PtSnCatalystsforDecarboxylationofUnsaturatedFattyAcids . . . . . . . 73
6.1 PtMalloycatalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
6.2 CarbonBalances . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
6.3 ReactionProducts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
6.4 CatalystCharacterization. . . . . . . . . . . . . . . . . . . . . . . . . . . 79
6.5 SourceofHydrogen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
6.5.1 FromH OReactingWithPt/C . . . . . . . . . . . . . . . . . . 82
2
6.5.2 FromReactantAlone . . . . . . . . . . . . . . . . . . . . . . . . 83
6.5.3 FromWaterAlone . . . . . . . . . . . . . . . . . . . . . . . . . . 87
6.5.4 FromBothH OandReactant . . . . . . . . . . . . . . . . . . . 87
2
6.6 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
6.7 Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
7 ActivityScreeningofPotentialHydrothermallyStableCatalysts . . . . . 90
7.1 CatalystSelection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
7.1.1 MetalCatalyst . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
7.1.2 Catalystsupports . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
7.2 ResultsandDiscussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
7.2.1 BiocrudeAnalysis . . . . . . . . . . . . . . . . . . . . . . . . . . 97
7.2.2 UpgradedBio-oil . . . . . . . . . . . . . . . . . . . . . . . . . . . 99
7.2.3 LimitationsoftheExperimentalMethods. . . . . . . . . . . . 112
vi
7.3 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113
7.4 Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115
8 Conclusions,FutureWork,andOutlook . . . . . . . . . . . . . . . . . . . . . 116
Appendices . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 121
Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 179
vii
LIST OF FIGURES
1.1 TotalUSenergydeliveredbysectorfrom1980–2040 . . . . . . . . . . . . 2
1.2 Transportation fuel use by type for North America and Asia Pacific
(Millionsofoil-equivalentbarrelsperday) . . . . . . . . . . . . . . . . . . 3
1.3 Physicalpropertiesofwaterat24MPawithrespecttotemperature . . . 7
2.1 Pt/Cselectivityton-heptadecaneforstearic,oleic,andlinoleicfeedsin
water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
2.2 Total ion chromatograms from crude bio-oil (top) and upgraded prod-
uctoil(bottom)obtainedfromSCWtreatmentwithPt/C,H . . . . . . . 29
2
2.3 BETsurfaceareaofuntreated1%Pt/Al O andafter10htreatmentat
2 3
225Cindifferentsolutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
4.1 Flowreactorschematic . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
5.1 Butyricaciddecarboxylation . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
5.2 Carbonrecoveryingasandliquidphasereactoreffluentfromhydrother-
maltreatmentof0.2MbutyricacidoverPt/Cat350CwithW/ν=300
mgmin/mL. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
5.3 H/C and CO /C H ratios from hydrothermal treatment of 0.2 M bu-
2 3 8
tyricacidoverPt/Cat350CwithW/ν =300mgmin/mL. . . . . . . . . 53
5.4 Molar ratios of lower alkanes to propane for hydrothermal treatment
of0.2MbutyricacidoverPt/Cat350CwithW/ν =300mgmin/mL. . 56
5.5 Flash column modeled as two stirred tanks with exchange between
tanks. V (cid:0)V (cid:0)200mL, ν (cid:0) ν (cid:0)5mL, ν (cid:0) ν (cid:0)3mL, k (cid:0)0.06h(cid:16)1 . . . . . 59
1 2 0 1 min 2 3 min d
5.6 Deactivationdatawithmodelincorporatingmixinginflashcolumn. . . 60
5.7 Variationoffirst-orderrateconstantwithtimeonstreamforhydrother-
mal decarboxylation of 0.2 M butyric acid feed over Pt/C with at W/ν
=300mgmin/mLatroomtemperaturewithareactiontemperatureof
350C . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
5.8 XRD spectra of fresh and used (24 h time on stream at 350 C) Pt/C
catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
5.9 TEMimagesofPt/C . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
5.10 DRIFTS spectra for TiO and Pt/TiO catalysts. From top to bottom:
2 2
P25 titania as received, unused Pt/TiO , Pt/TiO after 24 h time on
2 2
streamat350Cwith0.2MbutyricacidfeedwithW/ν=300mgmin/mL,
Pt/TiO heatedinArat700C . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
2
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