CCS Co Su Dung FT, Hinh Anh Dep

8/12/2019 CCS Co Su Dung FT, Hinh Anh Dep

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Agri-Based Biofuels, L.L.C.

Converting Biomass or Coal to Middle Distillate FuelsUsing Fischer Tropsch Synthesis

Designed by

Carbon Cycle Solutions, LLC


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Distillate Fuel Objectives

To produce clean alternative fuels priced significantlyless than petroleum fuels.

Benefits

Energy Security Negligible Emissions Price Stability No Drilling


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Overview

Motivational FactorsHistory of Fischer TropschSASOL Project

Process DescriptionProcess Flow DiagramEquipmentCatalyst Data

Conclusions


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Motivational Factors

Need for Renewable Energy Alternate Energy Demand

Reduction of GHG Emissions Environmentally Friendly

Reduce Imported Fuel

Energy Independence National Security Trade Balance


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Background (Development)

Fischer-Tropsch (F-T) developed in1920s Germany to producetransportation fuels from coal.

Germany used F-T gasoline in WorldWar II to effectively displace scarcepetroleum fuels.

F-T fuels abandoned after WWII due to

high production cost and the availabilityof cheap petroleum.


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Background (SASOL)

1970s - United Nations

imposed oil embargo againstSouth Africa because ofapartheid.

1980s South Africa achieved

transportation fuel self-sufficiency using the F-Tprocess on coal and natural gas.

1955 - SASOL produced its first commercial gasolinefrom coal in the Republic of South Africa. The plant laterswitched from coal to natural gas.


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Background (SASOL)

Two coal-to liquid (CTL) F-Tplants were built in South Africato produce gasoline, dieselfuel, kerosene and otherhydrocarbon fuels.

The F-T facilities built in 1976are fully amortized andoperating profitably.

Major capacity expansionunderway due to current highoil prices.

SASOL has produced F-T fuelsfor over 50 years. It is a wellestablished and well known

process.


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Gasification(Step 1)

F-TReaction/

Condensing(Step 2)

Distillation(Step 3)

Feedstock Syngas

Products

DieselJet Fuel

Gasoline

General F-T Process Description

Liquid Product(Mixed Hydrocarbons)


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Step #1: Gasification (Steam reforming)

The Fischer-Tropsch process is really three processes:

Process 1- Coal, natural gas or biomass feedstock areconverted to synthesis gas ( syngas ) by a process called

steam reforming. The chemical reactions are as follows:

For coal:C + H2O CO + H2 (notice a 1 to 1 hydrogen tocarbon monoxide ratio)

For natural gas (methane):CH4 + H2O CO + 3H2 (notice a 3 to 1 hydrogen tocarbon monoxide ratio)


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Step #1: Gasification (Steam reforming)

For biomass: The reaction is more complicated. The hydrogen tocarbon monoxide ratio is approximately 2 to 1.

If the hydrogen to carbon monoxide ratio is insufficientfor the next step (Fischer-Tropsch synthesis), syngasconditioning through PressureSwing Absorption (PSA) orother method is required.


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Step #2: Fischer-Tropsch Synthesis

The second step

After dedusting, scrubbing, purification and conditioning, thesyngas is compressed to high pressure and passed through acatalyst-filled reactor to produce a mixture of hydrocarbons.

The catalyst selection is critical to process success.

Two reactor types can be used : fluidized bed or.granular bed.


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Step #2: Fischer-Tropsch Synthesis

The F-T synthesis reaction process is highly exothermic.Removing excessive heat is an important technicalchallenge in designing the system.

CCSs design uses excess heat from the synthesisreaction to provide thermal energy required by theendothermic gasification process.

CCSs design uses un -reacted gases purged from thesynthesis reaction to fuel the gasifier making the use ofsyngas energy nearly 100% efficient.


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Step #3: Fractional Distillation

The final step is separating hydrocarbon products producedin the synthesis reactor according to their molecule chainlength. Hydrocarbons from this mixture have molecularlengths ranging from C1 to C20:

C1 to C2 hydrocarbons are non-condensable and theirvalue is mainly as fuel for the steam reformer.

C3 to C4 hydrocarbons can be condensed and sold as

liquefied petroleum gas (LPG) or combusted as fuels for thereformer.

C5 to C9 hydrocarbons are naphtha which can beconverted into gasoline.


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Step #3: Fractional Distillation

C10 to C14 hydrocarbons are essentially kerosene andcan be converted to various grades of jet fuel (JP-A, JP-5,JP-8, etc.)

C15 to C19 hydrocarbons are converted to diesel fuel.

Hydrocarbon products are separated by traditionalatmospheric pressure fractional distillation (e.g. mini -

refinery).

Sulfur content for the fuel products is nearly zero. Theircommercial value is higher than standard fuels notremoving the sulfur.


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Fractional Distillation Column

Gasoline

Diesel


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Fischer Tropsch Synthesis


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CCS Technology Application

Sawdust Wood chips

Rice straw

Uses any coalor coal fines

Bituminous Anthracite

Lignite

Lignite preferred dueto low cost, availabilityand ease to gasify


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Natural Gas (Methane)

Excellent F-T feedstock F-T Conversion to liquid

hydrocarbon increasesvalue on Btu basis

Liquid fuel production atwell-head allows easytransport from off-shorewells or from stranded

gas wells In US, 40-60% of gasreserves are stranded


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Environmental waste streamssewer sludge and trash


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CSC Technology Application

Use of biomass feedstock worldwide for producingtransportation fuels, fuel gas, chemicals and power.

Sugarcanebagasse

Sawdust Wood chips

Corn stoverRice straw
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ABBF Technology Application

Premium low-sulfur auto,.diesel and aviation fuels


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ABBF Technology Application

Sawdust Wood chips

Rice straw

Fuel Gas & Power


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Chemical Production

Ethanol, methanol, polymersand other chemical productspossible with F-T


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Distillate Production Block Flow Diagram


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Reformer Syngas Composition

* Primarily from instrument purging with nitrogen.

Whatever biomass is used, the syngas produced by theCCS Reformer will have comparable compositionsdepending upon the operating conditions.

Wood Wood Wood Sugarcane CornCondition 1 Condition 2 Condition 3 Bagasse Stover

Hydrogen 33.59 46.76 51.12 49.47 52.72Oxygen 0.12 0.02 0.01 0.02Nitrogen* 4.91 1.56 0.65 1.63Carbon Monoxide 32.82 26.73 23.73 24.00 24.07Carbon Dioxide 15.22 16.93 17.07 17.57 18.06Methane 9.53 6.95 6.32 7.01 5.15Ethylene 3.58 1.08 0.30Btu/cubic foot 371 324 310 323 251

Syngas Produced UnderDifferent Operating Conditions


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Process Distillate Fuel Production

Distillate fuel production consists of three primaryoperation areas:

1. Feedstock preparation: drying and grinding ofbiomass for feeding to the reformer.

2. Gasification / reforming and gas cleanup: feedstock is gasified by steam reforming in anoxygen starved environment. Depending on thedesired end product, adjusting the reformeroperating conditions may be necessary to producesyngas with a H 2:CO ratio suitable for thatparticular end product.


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Process Distillate Fuel Production

Dryer

BiomassFeedstock

Grinder

PearsonReformer (gasifier)

HeatRecovery

GasCleanup

CO2Removal

CatalyticConversion(liquid fuelsynthesis)

ProductSeparation

Syngas

Ash CO2

Steam

LiquidFuel

By-products

3. Gas-to-Liquids Conversion and separation: inaddition to suitable syngas, production of other liquidfuel utilizes a distillate catalyst designed for the desired

end product.


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Eggshell Co/SiO 2 Fischer Tropsch Catalyst

Innovation

Significance

Performance

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Factors For Catalyst Innovation

Increase surface contact area for improved yields Improve durability to decrease plant down-time and

reduce operations costs Find materials to lower catalyst cost Increase catalyst selectivity to eliminate less

desirable products Reduce distillation energy costs Create cleaner burning fuels


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Eggshell Catalyst

Polar Zone

Non-Polar Bulk

MagnifiedImages ofEggshell

Silica gel core

Active metaldeposition

Polar/ Non-Polar

boundary

(Patent Pending Technique)


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Hydrated Silica Surface

Increased Dispersion

Water covers the entiresurface. This stagnant auqalayer avoids direct Metal-Support interaction.

Ethanol attaches vertically andits surface coverage ensuresdirect Metal-Supportinteraction.

Ethanol (After Ion Exchange)

(via solvent choice)


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Catalyst Performance


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Liquid ProductObtained from BiomassDerived Synthesis Gas

Selectivity Using Biomass Synthesis Gas


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Catalyst Conclusions

Over 70% conversion rate per pass 95% selectivity to middle and light distillates (10%

naphtha) Produces less than 5% wax) Fuel product distribution with current catalyst 44%

diesel fuel, 41% jet fuel and 10% gasoline The catalyst is tunable to optimize production of

desired product Excellent for use with biomass produced syngas


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Gasification system produces quality syngas for makingF-T products from coal, natural gas or biomassfeedstock.

Gasifier system produces low-cost syngas with near-zero carbon emissions and no sulfur.

CCSs Superior catalyst produces distillate fuel that canbe refined to super clean diesel fuel, jet fuel (all grades),and gasoline using standard distillation methods.

CCSs catalysts can be tuned to produce only middle tolight distillates (no asphalt, heavy oils or other low valueproducts associated with standard crude).

F-T Process Conclusions


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F-T Process Conclusions (continued)

The CSSs Fisher -Tropsch system represents asignificant improvement of the well-known andunderstood Fischer-Tropsch process:

Produces F-T fuels for less than petroleum fuels Replaces petroleum fuels in virtually all

transportation fuel uses Can feasibly use fossil fuel, gas and biomass

feedstock Produces near-zero emissions Eliminates production of low-value products Greatly reduces energy costs

CCS Co Su Dung FT, Hinh Anh Dep

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