HYDROGEN HYDROGEN –– FIRING FOR A HIGH FIRING FOR A HIGH

CAPACITY ROTARY KILNCAPACITY ROTARY KILN

Ralph L. Coates, L. Douglas Smoot, Kent Hatfield

Combustion Resources, Inc.

Provo, Utah

29th Oil Shale Symposium

Colorado School of Mines Golden CO

20 October, 20091

PRESENTATION TOPICSPRESENTATION TOPICS

PROCESS Characteristics

KILN Characteristics

KILN FIRING – Hydrogen

PLANS – Full process

demonstration

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Combustion Resources, Inc. / Test Facility

20,000 sq ft

Provo, Utah 3

� First DOE/SBIR grant completed (March 2007)

� Second DOE/SBIR grant completed (June 2009)

� Utah Center of Excellence Grant (June 2009)

� Shale oil process patent application (2007)

� Preliminary designs of 5 tpd pilot, 300 tpd demo, 6000 bpd commercial plants

� Constructed pilot-scale rotary kiln

� Completed kiln firing and heating tests

� Rotary kiln patent application (2009)

� Process water reduction design (2009)

� Spent shale vegetation tests (2009)

� DOE/SBIR Phase II Grant (2009) 4

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�Efficient, flexible continuous plant operation

�Simple, advanced design horizontal kiln

�Minimal process water use

�Upgrading shale oil on-site - gasoline and diesel

�Near-complete elimination of CO2 - Option

�Low cost on-site hydrogen source -Option

�Compliant disposal of spent shale6

�Natural Gas – Kiln Firing with Oil/Gas Separation

�On – Site Shale Oil Upgrading

�Hydrogen Kiln Firing – CO2 Control

�On Site Hydrogen Production

- Kiln Firing with H2

- H2 for Oil Upgrading

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1. INDIRECT-FIRED ROTARY KILN

WITH H2/AIR COMBUSTION

2. CONTROLLED PEAK SHALE ORE KILN

TEMPERATURES – NO CARBONATE

DECOMPOSITION

3. NO RECOVERY OF SPENT SHALE

CARBON

4. RECYCLE OIL SHALE OFF GASES

5. CO2 CAPTURE

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• Simple, horizontal, low fabrication cost

• Advanced design technology

- High throughput rates

- Local control of shale and oil product temperature

- Elimination of shale carbonate – CO2 emissions

• H2 Firing Option

• Handles shale process fines

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Advantages

• No carbon dioxide emissions

• Complete, rapid combustion

• High energy content

• Wide temperature/composition range

Disadvantages

• Flame flash-back

• Cost

• Kiln start-up

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5726324. Spontaneous Ignition

Temperature (air), oC

HydrogenNatural Gas (CH4)Property/Units

2161. Molecular Weight , g/gmol

28.7122. Heat of Combustion, Kcal/g

4.0

75.0

5.0

15.0

7. Flammability Limits (air), vol%

Lean

Rich

29137.36. Max. Laminar Flame Speed,

cm/s

0.366.935. Min. Ignition Energy (10-5 cal)

240022103. Adiabatic (stoich) Flame

Temp. K

(Kanury, Glassman)

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Adiabatic Flame Temperature (K) vs Flammability Limits (vol%)

400.0

600.0

800.0

1000.0

1200.0

1400.0

1600.0

1800.0

2000.0

2200.0

2400.0

4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34

Flammability Limits (vol%)

Adiabatic Flame

Temperature (K)

0

500

1000

1500

2000

2500

3000

3500

4000

Ta, oF

H2 case

CH4 case

2394 K

2228 K

Adiabatic Flame Temperature (K)

CH4 stoich

H2 stoich

H2 case

CH4 case

Volume Percent of Fuel in Air

Adiabatic Flame Temperature, oF

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Maxon-natural gas, hydrogen

Wide Range Burner

Standard Commercial Units

Maximum firing rate –

150,000 BTU/hr

Pre-purge of gas manifold

Ignition with natural gas

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16

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136Tests

HydrogenNatural Gas

91-15191Firing Rate (103 BTU/h)

OrangeTransparentFlame

1500 - 18001409 - 1695Probe Temperature

Range, oF

-86 +910-55 +41% Excess Air Range

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FR 147, H2 -17% xs air FR 90, H2 -52% xs air

FR 147, H2 +32% xs air FR 90, H2 -23% xs air

FR 157, H2 -5% xs air FR 90, H2 -2% xs air

FR 157, H2 +10% xs air FR 90, H2 +50% xs air

NATURAL GAS, +13% xs air

FR 90, H2 +97% xs air

FR = Firing rate,

1000’s BTU/hr

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Excess Air

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Temperature (K)

Temperature (F)

Excess Air

% Stoichiometric Air

Excess FuelLimit 910%

CH4 H2

Calculated (CH4)

Measured (NG)

Adiabatic-

Stoichiometric

� Commercial Burners Available - Hydrogen

� Ignition with NG increases reliability/safety

� Hydrogen – air clearly visible to monitor

� H2 – NG combustion temperatures similar

� Hydrogen-air flames stable over very wide

air/fuel range

- Minimize cost

- Control temperature

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• New DOE contract – 2009

• Demonstrate Full C-SOS Process

- Pilot plant, 5 tpd

- Kiln firing (NG, H2)

- Shale oil separation, recovery

• Demonstrate shale oil upgrading

- Hydrotreating

- Hydrocracking

• C-SOS Commercial Plant Design

- 1000 tpd

- to gasoline, diesel

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AcknowledgmentAcknowledgment

Coauthors Coates and HatfieldCoauthors Coates and Hatfield

U.S. Department of Energy/SBIR GrantU.S. Department of Energy/SBIR Grant

(Chandra Nautiyal, NETL)(Chandra Nautiyal, NETL)

State of Utah Center of Excellence GrantState of Utah Center of Excellence Grant

(Nicole Toomey Davis)(Nicole Toomey Davis)

2929thth Oil Shale SymposiumOil Shale Symposium

20 October 200920 October 2009

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