# US 9,434,615 B2 · Method and apparatus for producing liquid biofuel from solid biomass

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- Number: US 9,434,615 B2
- Document ID: US9434615B2
- Status: Granted
- Kind: B2
- Application number: 12/669,769
- Filed: 2008-07-18
- Published: 2010-12-02
- Granted: 2016-09-06
- Earliest claimed: 2007-07-20
- Assignees: UPM-Kymmene Oyj
- Applicants: Petri Kukkonen; Pekka Knuuttila; Pekka Jokela
- Inventors: Petri Kukkonen; Pekka Knuuttila; Pekka Jokela
- Web page: https://patentgrep.com/patent/US9434615B2

## CPC

- C01B 3/48: followed by reaction of water vapour with carbon monoxide
- B01D 53/526: {Mixtures of hydrogen sulfide and carbon dioxide}
- B01D 53/8618: {Mixtures of hydrogen sulfide and carbon dioxides}
- C01B 3/38: using catalysts
- C01B 3/52: by contacting with liquids; Regeneration of used liquids
- C10G 2/32: {with the use of catalysts}
- C10J 3/503: {for gasifiers with stationary fluidised bed}
- C10J 3/721: {Multistage gasification, e.g. plural parallel or serial gasification stages}
- C10J 3/84: with means for removing dust or tar from the gas
- C10K 1/002: {Removal of contaminants}
- C10K 1/005: {Carbon dioxide}
- C10K 1/006: {Hydrogen cyanide}
- C10K 1/101: {with water only}
- C10K 1/143: {containing amino groups}
- C10K 3/023: {Reducing the tar content}
- C10K 3/04: reducing the carbon monoxide content {, e.g. water-gas shift [WGS]}
- B01D 2252/2026: Polyethylene glycol, ethers or esters thereof, e.g. Selexol
- B01D 2252/204: Amines
- B01D 2253/1124: Metal oxides
- B01D 2255/20792: Zinc
- B01D 2257/304: Hydrogen sulfide
- B01D 2257/504: Carbon dioxide
- C01B 2203/0233: the reforming step being a steam reforming step
- C01B 2203/0283: containing a CO-shift step, i.e. a water gas shift step
- C01B 2203/0415: Purification by absorption in liquids
- C01B 2203/0475: the impurity being carbon dioxide
- C01B 2203/1235: Hydrocarbons
- C10G 2300/1011: Biomass
- C10G 2300/202: Heteroatoms content, i.e. S, N, O, P
- C10G 2300/4081: Recycling aspects
- C10G 2300/44: Solvents
- C10G 2300/807: Steam
- C10J 2300/0903: Feed preparation
- C10J 2300/0916: Biomass
- C10J 2300/0959: Oxygen
- C10J 2300/0973: Water
- C10J 2300/1618: Modification of synthesis gas composition, e.g. to meet some criteria
- C10J 2300/1659: to liquid hydrocarbons
- C10J 2300/1807: Recycle loops, e.g. gas, solids, heating medium, water
- C10J 2300/1838: Autothermal gasification by injection of oxygen or steam
- C10J 2300/1884: with one stream being synthesis gas
- Y02E 50/30: Fuel from waste, e.g. synthetic alcohol or diesel
- Y02P 20/145: the feedstock being materials of biological origin
- Y02P 20/151: Reduction of greenhouse gas [GHG] emissions, e.g. CO2
- Y02P 30/20: using bio-feedstock
- C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C}
- B01D: SEPARATION (separating solids from solids by wet methods B03B, B03D; by pneumatic jigs or tables B03B; by other dry methods B07; magnetic or electrostatic separation of solid materials from solid materials or fluids, separation by high-voltage electric fields B03C; centrifuges, vortex apparatus B04; presses per se for squeezing-out liquid from liquid-containing material B30B9/02; treatment of water C02F, e.g. softening by ion-exchange C02F1/42; {arrangements of air intake cleaners in gas turbine plants F02C7/05} ; arrangements or mounting of filters in air-conditioning, air-humidification or ventilation F24F13/28)
- C10G: CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION (cracking to hydrogen or synthesis gas C01B; cracking or pyrolysis of hydrocarbon gases to individual hydrocarbons or mixtures thereof of definite or specified constitution C07C; cracking to cokes C10B); RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10J: PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES (synthesis gas from liquid or gaseous hydrocarbons C01B; underground gasification of minerals E21B43/295); CARBURETTING AIR OR OTHER GASES
- C10K: PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

The invention relates to a method and apparatus for producing liquid hydro carbonaceous product (1) such as biofuel from solid biomass (2). The method comprises a gasifying step for gasifying solid biomass (2) in a gasifier (6) to produce raw synthesis gas (3), conditioning of the raw synthesis gas (3) to purify the raw synthesis gas (3) to obtain purified synthesis gas (4) having a molar ratio of hydrogen to carbon monoxide between 2.5 to 1 and 0.5 to 1, preferably to between 2.1 to 1 and 1.8 to 1, more preferably about 2 to 1, and subjecting purified synthesis gas (4) to a Fischer-Tropsch synthesis in a Fischer-Tropsch reactor (5) to produce liquid hydro carbonaceous product (1).

## Claims

### Claim 1

A method for producing liquid hydro carbonaceous product (1) such as biofuel from solid biomass (2), characterized by the method comprising:
a gasifying step for gasifying solid biomass (2) in a fluidized bed gasifier (6) at 750-850° C. to produce raw synthesis gas (3),
conditioning of the raw synthesis gas (3) to purify the raw synthesis gas (3) to obtain purified synthesis gas (4) having a molar ratio of hydrogen to carbon monoxide between 2.5 to 1 and 0.5 to 1, preferably to between 2.1 to 1 and 1.8 to 1, more preferably about 2 to 1, wherein one of the conditioning steps is a catalytic treatment in a reformer (18), one of the conditioning steps is a water-gas-shift reaction in a water-to-gas shift reactor (21) and the last conditioning step is sulfur removal in a guard bed and
subjecting purified synthesis gas (4) to a Fischer-Tropsch synthesis in a Fischer-Tropsch reactor (5) to produce liquid hydro carbonaceous product (1).

### Claim 2 (depends on 1)

The method according to claim 1, characterized
in that the gasification step includes gasifying of solid biomass (2) in a gasifier (6) comprising a fluidized bed reactor, and
in that oxygen (7) and steam (8) are used as fluidizing medium in the fluidized bed reactor.

### Claim 3 (depends on 2)

The method according to claim 2, characterized by using in addition tail gas (9) from the Fischer-Tropsch reactor (5) as gasification and fluidizing medium in the fluidized bed reactor.

### Claim 4 (depends on 1)

The method according to any of the claim 1, characterized by using a lock hopper (10) for feeding solid biomass (2) to the gasifier (6).

### Claim 5 (depends on 1)

The method according to any of the claim 1, characterized by feeding the raw synthesis gas (3) into a first particle separator (16) for performing a particle separation step for separating particles such as ash, char and bed material from the raw synthesis gas (3).

### Claim 6 (depends on 5)

The method according to claim 5, characterized by feeding the raw synthesis gas (3) from the first particle separator (16) to a second particle separator (17) for performing a dust separation step lowering the dust content in the raw synthesis gas (3).

### Claim 7 (depends on 1)

The method according to any of the claim 1, characterized by the catalytic treatment of the raw synthesis gas (3) in the reformer (18) for converting tar and methane present in the raw synthesis gas (3) into carbon monoxide and hydrogen.

### Claim 8 (depends on 1)

The method according claim 1, characterized by the conditioning includes lowering the temperature of the raw synthesis gas (3) to about 250° C. in a cooler (19).

### Claim 9 (depends on 1)

The method according claim 1, characterized by the conditioning of the raw synthesis gas (3) including a filtering step for filtering the raw synthesis gas (3) in a filter (20) to remove particles such as ash, entrained bed material, and soot from the raw synthesis gas (3).

### Claim 10 (depends on 1)

The method according to claim 1, characterized by the conditioning of the raw synthesis gas (3) including subjecting the raw synthesis gas (3) to a water-gas-shift reaction in a water-to-gas shift reactor (21) for adjusting the molar ratio of hydrogen and carbon monoxide to between 2.5 to 1 and 0.5 to 1, preferably to between 2.1 to 1 and 1.8 to 1, more preferably to about 2 to 1.

### Claim 11 (depends on 1)

The method according to claim 1, characterized by the conditioning of the raw synthesis gas (3) including a scrubbing step for scrubbing the raw synthesis gas (3) to remove solids and tar components from the raw synthesis gas (3).

### Claim 12 (depends on 1)

The method according to claim 1, characterized by the conditioning of the raw synthesis gas (3) including a ultra purification step for removing sulfur components, CO2 (carbon dioxide), H2O (water), HCN (hydrogen cyanide), CH3Cl (methyl chloride), carbonyls, Cl (chloride) and NOx (nitrogen oxide) from the raw synthesis gas (3).

### Claim 13 (depends on 12)

The method according to claim 12, characterized in that the ultra purification step includes a physical cleaning process in which methanol or dimethyl ether is used as a solvent at a pressure of about 30 to 40 bar such as about 35 bar and at a temperature of about −25° C. to −60° C.

### Claim 14 (depends on 13)

The method according to claim 13, characterized by the conditioning includes lowering the temperature of the raw synthesis gas (3) to about 250° C. in a cooler (19).

### Claim 15 (depends on 12)

The method according to claim 12, characterized in that the ultra purification step includes a chemical cleaning process in which amine is used.

### Claim 16 (depends on 1)

The method according to claim 1, characterized by the method includes leading the raw synthesis gas (3) through at least one guard bed reactor (25) comprising zinc oxide catalysts and active carbon for removing sulfur species from the raw synthesis gas (3).

### Claim 17 (depends on 1)

The method according to any of the claim 1, characterized by using several gasifiers (6) for producing raw synthesis gas (3) of which at least one is a gasifier (6) for producing raw synthesis gas (3) from solid biomass (2) and of which at least one is a gasifier (6a) for producing raw synthesis gas (3a) from liquid solid biomass.

### Claim 18 (depends on 1)

The method of claim 1, wherein the catalytic treatment in a reformer (18) is the only catalytic treatment in a reformer of the method.

### Claim 19

An apparatus for producing liquid hydro carbonaceous product (1) such as biofuel from solid biomass (2), characterized in that the apparatus comprises
a fluidized bed gasifier (6) operating at 750-850° C. for gasifying solid biomass (2) to produce raw synthesis gas (3),
means for conditioning of the raw synthesis gas (3) to obtain purified synthesis gas (4) having a molar ratio of hydrogen to carbon monoxide between 2.5 to 1 and 0.5 to 1, preferably to between 2.1 to 1 and 1.8 to 1, more preferably about 2 to 1, comprising catalytic treatment of the raw synthesis gas in a reformer (18), adjusting the molar ratio of hydrogen and carbon monoxide in a water-gas-shift reactor (21) and as a last conditioning step sulfur removal in a guard bed and
a Fischer-Tropsch reactor (5) for subjecting the purified synthesis gas (4) to a Fischer-Tropsch synthesis to produce liquid hydro carbonaceous product (1) of the purified synthesis gas (4).

### Claim 20 (depends on 19)

The apparatus according to claim 19, characterized
in that the gasifier (6) includes a fluidized bed reactor, and
in that the gasifier (6) includes means for feeding oxygen (7) and steam (8) into the gasifier (6) for using oxygen (7) and steam (8) as fluidizing medium in the fluidized bubbling bed reactor.

### Claim 21 (depends on 20)

The apparatus according to claim 20, characterized in that the apparatus includes means for feeding tail gas from the Fischer-Tropsch reactor (5) into the gasifier (6) for using gas from the Fischer-Tropsch reactor (5) as fluidizing medium in the fluidized bed reactor.

### Claim 22 (depends on 19)

The apparatus according to claim 19, characterized by comprising a lock hopper (10) for feeding solid biomass (2) to the gasifier.

### Claim 23 (depends on 19)

The apparatus according to claim 19, characterized by comprising solid biomass pre-treatment means (31) for drying the solid biomass (2) to a moisture content under 20% and/or for fine-dividing the solid biomass (2) to feedstock being less than 50 mm in particle size.

### Claim 24 (depends on 19)

The apparatus according to claim 19, characterized by a first particle separator (16) for separating particles such as ash, char and bed material particles from the raw synthesis gas (3).

### Claim 25 (depends on 19)

The apparatus according to claim 19, characterized by a second particle separator (17) for separating dust from the raw synthesis gas (3).

### Claim 26 (depends on 19)

The apparatus according to claim 19, characterized by the reformer (18) for catalytic treatment of the raw synthesis gas (3) for converting tar and methane present in the raw synthesis gas (3) into carbon monoxide and hydrogen.

### Claim 27 (depends on 19)

The apparatus according to claim 19, characterized by a cooler (19) for lowering the temperature of the raw synthesis gas (3) to about 250° C.

### Claim 28 (depends on 19)

The apparatus according to claim 19, characterized by a filter (20) for filtering ash, entrained bed material and/or soot from the raw synthesis gas (3).

### Claim 29 (depends on 19)

The apparatus according to claim 19, characterized by a water-gas-shift reactor (21) for adjusting the molar ratio of hydrogen and carbon monoxide in the raw synthesis gas (3) to between 2.5 to 1 and 0.5 to 1, preferably to between 2.1 to 1 and 1.8 to 1, more preferably to about 2 to 1.

### Claim 30 (depends on 19)

The apparatus according to claim 19, characterized by a scrubber (22) for removing solids and tar components from the raw synthesis gas (3).

### Claim 31 (depends on 19)

The apparatus according to claim 19, characterized by ultra purification means (23) for removing sulfur components, CO2 (carbon dioxide), H2O (water), HCN (hydrogen cyanide), CH3Cl (methyl chloride), carbonyls, Cl (chloride) and NOx (nitrogen oxide) from the raw synthesis gas (3).

### Claim 32 (depends on 31)

The apparatus according to claim 31, characterized by a compressor (24) for raising the pressure of the raw synthesis gas (3) to about 30 to 40 bar such as about 35 bar pressure before leading the raw synthesis gas (3) into the ultra purification means (23).

### Claim 33 (depends on 19)

The apparatus according to claim 19, characterized by a guard bed reactor (25) for removing sulfur species.

### Claim 34 (depends on 19)

The apparatus according to claim 19, characterized by several gasifiers (6) for producing raw synthesis gas (3) of which at least one is a gasifier (6) for producing raw synthesis gas (3) of solid biomass (2) and of which at least one is a gasifier (6a) for producing raw synthesis gas (3a) of liquid solid biomass.

### Claim 35 (depends on 19)

The apparatus of claim 19, wherein the reformer (18) is the only reformer of the apparatus.