WILLIAM “SANDY” DUNCANSPEAKER
CHEMICAL ENGINEERING GRADUATE STUDENTUNIVERSITY OF WYOMING (UW)
RICHARD HORNER DIRECTOR SPECIAL PROJECTS AND TECHNOLOGY
SCHOOL OF ENERGY RESOURCES
JOHN MYERSCONSULTANT, SCHOOL OF ENERGY RESOURCES
CARL BAUERCONSULTANT, C. O. BAUER CONSULTING INC.
Attractiveness of Wyoming Powder River Basin (PRB) coal as a valuable resource from which to manufacture non-energy
and fuel products.
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Coal to Non Energy & BTU Products The possibilities are vast!
2Reference: US Geological Survey
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Some of these chemicals and materials can only economically come from coal!
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The Coal RefineryAdding Premium Value Beyond Energy Value
Current Product
Slate
Derivative Coal Products
Coal chemicalsØ PitchØ Activated CarbonØ Carbon Based
resinsØ Soil Amendment
PRB Coal Coal Refinery(Carbon Rejection)
Petroleum Refinery(Hydrogen Addition)
PetrochemicalsØ Olefins Ø AcetylsØ AlcoholsØ AromaticsØ Asphalt
• Gasoline• Diesel• Naptha• Aromatics• Base Oil & Lubes
CommonProductFamilies
• PetrochemicalsØ AcetylsØ AlcoholsØ AromaticsØ AsphaltØ Carbon FiberØ CarboxylatesØ AerogelsØ GrapheneØ Building materialsØ Needle Coke
New Carbon Product
Solutions
New Carbon
Conversion Solutions
Investment in Carbon Engineering
Coal IntermediateProducts
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Summary of Coal Conversion…TODAY
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• Some specialty chemical productstoday are derived only from coal
• Unlike crude oil, coal is not readily fractionatable.
• Coal constituent polycyclic hydrocarbons readily react and polymerize.
• Understanding conversion behavior – thermal impacts on molecular chemistry is crucial to exploit coal’s ‘hidden’ value
Coal is converted using high temperature decomposition.
Advantage: (1) Can aggressively and deliberately breakdown coal into intermediate liquids and solids that are convertible into valuable products
Disadvantage: (1) Reduced O2 atmosphere – needs H2 or CH4 gasses
Gasification Coal is blown with oxygen and steam (water vapor), while heated (pressurized).
Advantage: (1) Turn coal into multi-use feedstock i.e. syngas
Disadvantage: (1) Managing – separating the CO2 is costly(2) Converting to chemicals is energy intensive & costly(3) Requires air separation unit for pure oxygen
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Coal LiquefactionCoal converted to liquids by hydrogen addition
Advantage: (1) Multiple Product Yields (2) Possible – Hedge Against crude oil!)
Disadvantage: (1) Qualities generally poor for chemicals(2) CO2 production challenge (3) Consumes large volumes of water and/or hydrogen
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Existing ApproachesPyrolysis
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Coal DifferencesUltimate Analysis HV Bituminous Sub-Bituminous LigniteWt% Dry Illinois #6, IL PRB, WY Beulah-Zap, NDCarbon Hydrogen NitrogenSulfurChlorine OxygenAsh
71.725.061.412.820.337.75
10.91
69.214.700.890.300.03
18.676.20
61.884.290.980.980.00
16.4415.43
Moisture, wt% 11.72 27.42 36.08NETL, Detailed Coal Specifications, January, 2012
• High Oxygen in PRB• Liquid and solid products have significant oxygen
• Can make oxygenated products such as phenols, xylenols, etc.
• Investigating how to keep oxygen in liquids and solids rather than expel it as CO2
• New Opportunities !!!
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Coal Fed Refinery Goals & ConstraintsGoals• Product slate worth is > coal BTU value• Full conversion of primary (PRB) coal feed – maximize liquids production
• Include other feeds - /gas/LNG/shale oil/biomass feeds in support of this prerequisite
Constraints• Extraction & complete process use only water extracted from coal
• Zero effluent discharge & water consumption neutrality• PRB coal contains 20% or more water
• Zero or minimal pure stream CO2 emissions• Not producing it in the first place?
• Optimal energy consumption• Exothermic rather than endothermic processing
• Reject and manage carbon rather than adding hydrogen• Differentiate
• Maximize atom utilization and minimize waste
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Evaluating Coal Conversion Approaches
Two ways to convert coal• Thermally
• Pyrolysis, gasification and liquefaction• Chemically
• Solvent extraction (Single phase, Low temperature)
Deciding on coal conversion approaches to pursue• Considerations
• oxygen in liquids/solids• managing CO2
• Result• The best research opportunities are solvent extraction and pyrolysis
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Systems & Process Engineering Approaches
Direct and validate technology development strategy• Atomic balances
• Know where CHNOS goes; critical for value-added products• Process flowsheet development
• Identify processing sequences and unit operations required• Identify recycles• Identify likely separation and physical properties issues (i.e., azeotropes,
LL)• Identify simulation and process design requirements
• Parametric studies• Extra lab data required• Industrial design studies (i.e., realistic recycled gas compositions)• Catalyst deactivation studies• Greater industrial focus
• Simulation çè Experimentation • See effects of new data on recycles• Identifies key variables for parametric studies
Solvent Extraction IntegratedExample
2 stage extraction, dry methane reforming, phenol
recovery, calcining, Carbidization
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Hydrocarbon Solvent
Extraction
Gas Clean-Up
Coal
Gas
Phenol
HC Liquids
This is an example of how multiple technologies can be integrated into a multi-high volume product, low energy consumption & CO2 emissions complex
Hydrothermal (super-critical H2O / CO2
extraction)
Mixed -Liquid
Phenol Extraction
NH3, S
CO2 Dry MethaneReforming
NatGas
Syngas
Carbidization
Hi-Ash Char
LimeSyngasCaC2 (to acetylene)
Calcine Low Ash Coke
Biomass?
Soil Amendments
Construction Materials
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Flash Pyrolysis Integrated Example
hydropyrolysis, dry methane reforming, phenol recovery, HC
fractionation, carbidization
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Flash Pyrolysis&
Fractionation
Gas Clean-Up
Coal
MixedGas
Phenol
Phenol Extraction
NH3, SCO2MethaneEthanePropane
Dry MethaneReforming
CO2
Syngas conversion to methanol and/or, Ethylene Glycol
Carbidization
Hi-Ash Char
Lime
SyngasCaC2 (to acetylene)
Methane / H2
Trans-alkylation
HydroTreatment
BenzeneXylenesParaxylenePolyethylene Terephthalate (PET)
Asphaltenes (asphalts, fibers, cokes)
Resins (Pitch, tars), fibers and surfactants
Heavy Liquids
H2O
Light Liquids
Very heavy Liquids
This is an example of how multiple technologies can be integrated into a maximizing high-value chemical production while minimizing CO2 emissions
C6 to C10 Aromatics
CO2CH4C2C3
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Next Steps Immediate Plan
• Define coal conversion schemes• Validate techno-economic viability of Wyoming located coal
refineries
• Preserve and Protect Intellectual property• 5 Patents filed or in process in FY 2016-17• 15 (est.) by end July 2018
• Attract collaborators & investors who want to demonstrate their technology with PRB coal • Augment with University of Wyoming Coal Conversion
Technologies
• Identify scale & scope of coal refinery• Attract investors
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Thank You
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Example Approach for Determining Products from PRB CoalButadiene, C4 Olefins and Butanes Business: MAN, PAN and derivatives – Phthalic Anhydride (PAN) and derivatives
PAN derivatives• PAN demand growing ~3% pa
• Main use is Plasticisers for PVC
• Carbon fibre growth emerging
• Alkyd resins is an important use:
• Drying resins based on plant and vegetable oils
• Non-drying based on glycerol etc.
• Production of UP resins is a minor use
O-Xylene
PAN derivatives
Esterification
+ polyols
à Alkyd resins
Esterification
+ C6-C10+ alcohols
à Plasticisers
PAN production• Most PAN made from O-X
• Few plants still use naphthalene
• Efficiency, carbon footprint and cost advantage opportunity
Phthalic Anhydride
Catalytic oxidation
Naphthalene
Catalytic oxidation
Polymerisation
+ PG + MAN
à UP Resins
Market Evaluation:
Technical Feasibility: Conventional(catalytic oxidation of ortho-xylene)
Coal Route(catalytic oxidation of naphthalene)
C6H4(CO)2O
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Economic and Product Quality Analysis
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Opportunity Assessment Example: Chemical Products from Coal Using Flash Pyrolysis
CO2
Aromatics
Light Olefins
H2
CH4
CO
C10-14 Liquids Naphthalene
Phenols&Cresols
C9 Aromatics
(Mixed)Xylenes
Toluene
Benzene
C5 liquidsC4H8-10
C3H6-8
C2H4-6
Char
C15+ Liquids- Tars
Slag&Ashes
CO2 Hub
Syngas
Butadiene(&H2)
Propylene
Styrene
Ethylene
Cumene
Para-Xylene(&Benzene)
Phenol
Asphalt
CalciumCarbide
Syngas
Heat&Power
CO2
CaO2 (Lime)
SyngasHub
Sup.Crit.CO2
Methanol
Alcohols
EthyeneGlycol(EG)OtherDiols?(Future)- PG,PDO- Butane-1,2-Diol- BDO
Acetylene
PTA
Ammonia
MTO/FTO
- n-Butanol- PlasticiserAlcohols
- n-Propanol
- Ethylene- Propylene/PolyGd
PAN
Electric Power
PVC Resin
VCM
Brine
CausticSoda
ChlorineCaustic/Chlorine
HCl
Hydrogen
Urea
PETResin
PolyesterFibre
(PVC)Plasticisers
PPResin
PPFibre
FlashPyrolysis
Calcining
CO2Limestone
Butenes
Metathesis/PolyGd Propylene
UPVC compounds & siding
Flexible PVC cpds & sheet
PETSheet&Preforms
Salt
Phenol/Acetone
Acetone
Phenol
BisphenolA
NaturalGas
Slag
PPSheet&Preforms
CO2
Acrylonitrile
Acrylic Fibre
Carbon Fibre
Adiponitrile
Carbon Fibre
Electric CO2 Power Syngas
Main Vectors
MarketSpecification
ChemicalsAmmoniaSC CO2 for EOR MethanolVCMn-Propanoln-ButanolAcrylonitrileAdiponitrilePlasticiser AlcoholsPropyleneButadieneEGPTAPANPhenolNaphthaleneCaustic SodaBTXBenzeneTolueneMixed XylenesC9+ AromaticsStyreneCumenePara-XyleneHCl (Hydrochloric Acid)
Value-Added Products
UreaAcrylic FibreCarbon Fibre (2 types)PP ResinPP FibrePET ResinPolyester FibrePET Sheet & PreformsBisphenol A(PVC) PlasticisersPVC ResinUPVC compounds & sidingFlexible PVC cpds & sheet
CommoditiesAsphaltElectric Power
By-ProductsSlagAshes
ManufacturingIndustrial Park
PRB Coal Primary Products Intermediate Derivative Conversion & Gases Products Products Products
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Abstract
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