WO2021087618A1 - Process for producing synthetic hydrocarbons from biomass - Google Patents
Process for producing synthetic hydrocarbons from biomass Download PDFInfo
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- WO2021087618A1 WO2021087618A1 PCT/CA2020/051510 CA2020051510W WO2021087618A1 WO 2021087618 A1 WO2021087618 A1 WO 2021087618A1 CA 2020051510 W CA2020051510 W CA 2020051510W WO 2021087618 A1 WO2021087618 A1 WO 2021087618A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- hydrogen
- biomass
- biomass feedstock
- generated
- syngas
- Prior art date
Links
- 239000002028 Biomass Substances 0.000 title claims abstract description 77
- 238000000034 method Methods 0.000 title claims abstract description 68
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 38
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 38
- 239000001257 hydrogen Substances 0.000 claims abstract description 67
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 67
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 61
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 16
- 239000001301 oxygen Substances 0.000 claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 6
- 239000007789 gas Substances 0.000 claims description 25
- 230000005611 electricity Effects 0.000 claims description 23
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 20
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 16
- 238000004064 recycling Methods 0.000 claims description 14
- 239000013589 supplement Substances 0.000 claims description 12
- 239000001569 carbon dioxide Substances 0.000 claims description 10
- 238000005194 fractionation Methods 0.000 claims description 8
- 238000004517 catalytic hydrocracking Methods 0.000 claims description 7
- 239000006227 byproduct Substances 0.000 claims description 6
- 239000002699 waste material Substances 0.000 claims description 6
- 239000002657 fibrous material Substances 0.000 claims description 4
- 238000006317 isomerization reaction Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000002916 wood waste Substances 0.000 claims description 3
- 239000002154 agricultural waste Substances 0.000 claims description 2
- 239000010865 sewage Substances 0.000 claims description 2
- 238000004227 thermal cracking Methods 0.000 claims description 2
- 239000002351 wastewater Substances 0.000 claims description 2
- 238000005868 electrolysis reaction Methods 0.000 abstract description 29
- 150000002431 hydrogen Chemical class 0.000 abstract description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 14
- 229910052799 carbon Inorganic materials 0.000 description 14
- 238000002309 gasification Methods 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 239000004215 Carbon black (E152) Substances 0.000 description 10
- 239000000446 fuel Substances 0.000 description 10
- 239000007788 liquid Substances 0.000 description 9
- 239000003345 natural gas Substances 0.000 description 8
- 238000004140 cleaning Methods 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000002803 fossil fuel Substances 0.000 description 4
- 238000010248 power generation Methods 0.000 description 4
- 239000002918 waste heat Substances 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000010354 integration Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000002407 reforming Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000002551 biofuel Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000011269 tar Substances 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 241001520808 Panicum virgatum Species 0.000 description 1
- 240000001398 Typha domingensis Species 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 description 1
- JPNWDVUTVSTKMV-UHFFFAOYSA-N cobalt tungsten Chemical compound [Co].[W] JPNWDVUTVSTKMV-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 239000010800 human waste Substances 0.000 description 1
- -1 hydrogen halides Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- MOWMLACGTDMJRV-UHFFFAOYSA-N nickel tungsten Chemical compound [Ni].[W] MOWMLACGTDMJRV-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000010908 plant waste Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/72—Other features
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/002—Removal of contaminants
- C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
- C10K1/005—Carbon dioxide
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
- C10K3/06—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by mixing with gases
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B15/00—Operating or servicing cells
- C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
- C25B15/081—Supplying products to non-electrochemical reactors that are combined with the electrochemical cell, e.g. Sabatier reactor
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0903—Feed preparation
- C10J2300/0909—Drying
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0913—Carbonaceous raw material
- C10J2300/0916—Biomass
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/16—Integration of gasification processes with another plant or parts within the plant
- C10J2300/164—Integration of gasification processes with another plant or parts within the plant with conversion of synthesis gas
- C10J2300/1656—Conversion of synthesis gas to chemicals
- C10J2300/1659—Conversion of synthesis gas to chemicals to liquid hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/16—Integration of gasification processes with another plant or parts within the plant
- C10J2300/1684—Integration of gasification processes with another plant or parts within the plant with electrolysis of water
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/141—Feedstock
- Y02P20/145—Feedstock the feedstock being materials of biological origin
Definitions
- the present invention pertains to the field of the production of synthetic hydrocarbons from renewable and/or low carbon sources.
- the carbon-based fossil fuels such as coal, oil and natural gas are non-renewable resources and of limited supply. Combustion of fossil fuel has caused a rise in atmospheric carbon dioxide concentrations, which are believed to contribute to global climate change. The concern for carbon emissions from fossil fuels has created an increased interest in the development of synthetic fuel sources.
- Biofuels are considered viable alternatives to fossil fuels for several reasons. Biofuels are renewable energy sources produced from biomass.
- One of the advantageous features of the biomass to fuel technology is that it presents a possibility to not only formulate a less carbon intensive product, but also make use of waste biomass materials, such as forestry by products, construction and other wood waste products, human waste products, or agriculture feedstocks, byproducts and waste products.
- the Fischer-Tropsch (FT) process converts hydrogen and carbon monoxide (commonly known as syngas) into liquid hydrocarbons, examples of which include synthetic diesel, naphtha, kerosene, aviation or jet fuel and paraffinic wax.
- syngas carbon monoxide
- the molar ratio of the H 2 :CO in the syngas is required to be approximately 2:1.
- Reforming of natural gas via SMR and/or ATR also requires heat addition for combustion of natural gas, a non-renewable resource.
- a Biomass to Liquids (BTL) process such as disclosed in WO2012106795 incorporates biomass gasification and natural gas reforming to provide hydrocarbon liquid products with lower carbon intensity (Cl) than petroleum fuels (reduction of over 40%).
- this process is also dependent upon non-renewable feedstock (i.e. natural gas).
- An object of the present invention is to provide a process for production of synthetic hydrocarbons from renewable and/or low carbon sources.
- a process for preparing synthetic hydrocarbons from a biomass feedstock which comprises: a) electrolyzing water in an electrolyzer to produce oxygen and hydrogen; b) feeding the 0 2 generated in step a), and the biomass feedstock into a gasifier, and gasifying the feedstock under partial oxidation reaction conditions to generate a hydrogen lean syngas having H 2 :CO ratio of about 1 :1 ; c) adding at least a portion of the H 2 generated in step a) to the hydrogen lean syngas generated in step b) to formulate hydrogen rich syngas having H 2 :CO ratio of about 2:1; d) reacting the hydrogen rich syngas in a Fischer Tropsch (FT) reactor to produce the synthetic hydrocarbons and water; e) recycling at least a portion of the water produced in step d) for use in step a).
- FT Fischer Tropsch
- Figure 1 depicts a flow diagram of a conventional biomass to liquids process
- Figure 2 depicts a flow diagram of a biomass to liquids process in accordance with an embodiment of the present invention.
- syngas is an abbreviation for “synthesis gas”, which is a mixture comprising hydrogen, carbon monoxide, and some carbon dioxide.
- hydroxan syngas refers to syngas having H 2 :CO molar ratio of about 1 :1 , such as 0.5: 1 to 1.2:1.
- hydroxane rich syngas refers to syngas having H 2 :CO molar ratio of about 2:1 , such as 1.8:1 to 2.2:1 , which is desired optimum ratio for use in Fischer-Tropsch reaction.
- electrolysis refers to the process of using electricity to split water into hydrogen and oxygen.
- the term “about” refers to a +/-10% variation from the nominal value. It is to be understood that such a variation is always included in a given value provided herein, whether or not it is specifically referred to.
- the present invention relates to a process for production of synthetic hydrocarbon from low carbon and/or renewable sources, i.e. biomass, water and ectricity.
- the present application provides an improved biomass to liquid process for preparing synthetic hydrocarbons, which utilizes low carbon and/or renewable energy to produce oxygen and hydrogen, wherein the oxygen is utilized for efficient operation of the biomass gasifier and the hydrogen is utilized for the production of a tar free hydrogen rich syngas suitable for Fischer Tropsch (FT) conversions to obtain synthetic hydrocarbons, including transportation fuels.
- FT Fischer Tropsch
- the process of the present application does not include the water gas shift reaction or natural gas reforming, thereby reducing the carbon foot print and dependence on nonrenewable feedstocks (e.g. natural gas).
- nonrenewable feedstocks e.g. natural gas.
- Low carbon renewable hydro/solar/wind sourced electricity which is plentiful and inexpensive in many regions
- low carbon nuclear electricity can be utilized to eliminate the need for a non-renewable source, such as natural gas.
- the process of the present invention involves electrolysis of water in an electrolyzer to produce oxygen and hydrogen.
- the oxygen generated via the water electrolysis is used for partial oxidation of a biomass feedstock in a gasifier to generate a hydrogen lean syngas.
- At least a portion of the hydrogen generated via the water electrolysis is added to the hydrogen lean syngas to formulate a hydrogen rich syngas.
- the hydrogen rich syngas is then reacted in a Fischer Tropsch (FT) reactor to produce synthetic hydrocarbons and water.
- FT Fischer Tropsch
- the water generated during the FT reaction is recycled to the electrolysis step, thereby reducing/minimizing the amount of water required from an external source, eventually using the recycled water as primary source for the electrolysis process.
- any suitable electrolyzer can be selected to conduct the electrolysis step.
- a suitable temperature and/or pressure for the electrolysis is selected as appropriate for the type of electrolyzer used.
- the electrolysis step can be carried out at a temperature from about 25 °C to about 1000 °C. In some embodiments, the electrolysis step is carried out at temperature about 50 °C to about 850 °C. In some embodiments, the electrolysis step is carried out at temperature about 75 °C to about 100 °C.
- the electrolysis step can be carried out a pressure up to 50 bar.
- the process comprises removing excess moisture from the biomass feedstock to achieve a desired water content level prior to feeding the feedstock to the gasfier. Excess moisture from the biomass feedstock can be removed by subjecting the initial feedstock to a biomass dryer.
- the Fischer-Tropsch (FT) reaction is a highly exothermic reaction. At least a portion of energy/heat from the FT reaction, typically in the form of steam, is used in the process described herein, to remove excess moisture from the biomass feedstock, and optionally to generate power/electricity.
- the process comprises feeding at least a portion of the steam generated during the FT reaction to recover heat, which is then used to remove excess moisture from the biomass feedstock.
- the process comprises feeding at least a portion of steam generated in the FT reaction to an electricity generator to produce electricity which can be used to supplement electricity for the electrolyzer, and the residual heat after power generation is used to remove excess moisture from the biomass feedstock.
- the refinery gas generated in the FT reaction is recycled to the biomass dryer for removing excess moisture from the biomass feedstock.
- electrolysis processes result in generation of heat, which can be recovered.
- the process comprises recycling at least a portion of the heat generated in the electrolysis step for removing excess moisture from the biomass feedstock.
- a portion of the heat generated in the electrolysis step can be used for generating power for the electrolyzer.
- Waste heat from the electrolysis step can be captured through organic Rankine cycle (ORC) and/or Sterling cycle generator technology.
- Gasification of biomass results in generation of hot raw syngas, which can be fed to a steam-generating heat exchanger to produce steam and a cooled raw syngas.
- the process comprises utilizing the steam generated in the heat exchanger to produce electricity to operate the electrolyzer, thereby reducing the amount of electricity from the external source.
- the process further comprises recycling/utilizing at least a portion of the excess heat generated during the gasification step for removing excess moisture from the biomass feedstock.
- the synthesized hydrocarbons formulated via the FT reaction can be fractionated to obtain a desired product, such as naphtha, diesel, jet fuel, etc.
- the refinery gas formed during fractionation process is recycled to the biomass dryer for removing excess moisture from the biomass feedstock.
- the heat from the FT reaction, heat from the gasification reaction and the refinery gas generated in the FT-reaction and/or the fractionation process are recycled to the biomass dryer for removing excess moisture from the biomass feedstock.
- the refinery gas from the FT reaction and/or fractionation process can be used in an internal combustion engine or micro-turbine to generate power for electrolyzer.
- the waste heat from the internal combustion engine can be captured via organic Rankine cycle technology.
- the hydrogen lean syngas obtained from the gasifier is subjected to cleaning operation(s) prior to use in the FT reaction to remove syngas contaminants, such as tars, nitrogen based compounds (NH 3 , HCN, etc.), sulfur based compounds (H 2 S, COS, etc.), hydrogen halides (HCI, HF, etc.) and trace metals (Na, K, etc.).
- cleaning operations involve scrubbing units and guard units known to those skilled in the art to create a relatively clean syngas suitable for use in a Fischer- Tropsch unit.
- the raw hydrogen lean syngas obtained directly from the gasification of biomass feedstock or after the cleaning operation is treated to a carbon dioxide removal operation prior to reaction in the FT-reactor.
- the separated carbon dioxide is fed to the gasifier as blanket/sealing gas to prevent air ingress.
- Synthetic hydrocarbons obtained from the FT reaction can be subjected to hydroprocessing operation(s) to further upgrade the products.
- the hydroprocessing operation(s) include operations such as hydrocracking, thermal cracking, hydrotreating, isomerization or combinations thereof.
- a portion of the hydrogen generated in the electrolysis step is fed to the hydroprocessing operation.
- hydrocarbons recovered from the hydroprocessing operation(s) can be further fractionated to obtain products such as naphtha, diesel, kerosene, jet fuel, lube oil, and wax.
- the combined unit comprising hydroprocessor and hydrocarbon fractionator is commonly known as the hydrocarbon upgrader.
- hydrocarbon upgrader As is known by those skilled in the art, several hydrocarbon treatment methods can form part of an upgrader unit depending on the desired refined products, which are essentially free of sulfur.
- the resulting diesel may be used to produce environmentally friendly, sulfur-free fuel and/or blending stock for fuels by using as is or blending with higher sulfur fuels created from petroleum sources.
- Off gases generated during hydroprocessing operation(s) can be used in power generation.
- a suitable biomass feedstock for the process of the present invention includes, but is not limited to, municipal waste, wood waste, forestry waste material, waste water biomass, municipal sludge, biomass crops such as switchgrass, cattails, and short rotation crops, sewage biomass, agricultural waste (crop residues, livestock byproducts, etc.), agricultural by-products, industrial fibrous material, harvested fibrous material or any mixture thereof.
- the process of the present invention can incorporate any gasifier known in the relevant art, such as disclosed in U.S. Patent No. 7,776,114.
- the process of the present invention involves use of the gasifier described in Applicant’s PCT Publication No. WO 2018/058252, which is incorporated herein in its entirety.
- FT reactors include fixed bed reactors and slurry-bubble reactors, such as tubular reactors, and multiphase reactors with a stationary catalyst phase.
- hydrocracking refers to the splitting of an organic molecule and adding hydrogen to the resulting molecular fragments to form multiple smaller hydrocarbons (e.g., C 10 H 22 + H 2 CH 10 and skeletal isomers + C 6 H 14 ) ⁇ Since a hydrocracking catalyst may be active in hydroisomerization, skeletal isomerization can occur during the hydrocracking step. Accordingly, isomers of the smaller hydrocarbons may be formed.
- Hydrocracking a hydrocarbon stream derived from Fischer-Tropsch synthesis preferably takes place over a hydrocracking catalyst comprising a noble metal or at least one base metal, such as cobalt, platinum, cobalt- molybdenum, cobalt-tungsten, nickel-molybdenum, or nickel-tungsten, at a temperature of from about 550°F to about 750°F (from about 288°C to about 400°C) and at a hydrogen partial pressure of about 500 psia to about 1 ,500 psia (about 3,400 kPa to about 10,400 kPa).
- a noble metal or at least one base metal such as cobalt, platinum, cobalt- molybdenum, cobalt-tungsten, nickel-molybdenum, or nickel-tungsten
- FIG. 1 shown is a process flow diagram of a circuit for prior art gasifying biomass.
- the process is generally denoted by numeral 10 and begins with a biomass feedstock 12.
- the biomass is then treated in a gasifier 14 to which oxygen 16 is added as required.
- the gasifier generates a hydrogen lean/deficient synthesis gas (syngas) 18 having H 2 :Co molar ratio about 1 :1 , which is optionally subjected to cleaning operations 20 with subsequent water gas shift reaction in unit 22 to form hydrogen rich syngas 24 and carbon dioxide 26, which is rejected to atmosphere or collected.
- syngas hydrogen lean/deficient synthesis gas
- the hydrogen rich syngas 24 is then transferred to a Fischer-Tropsch reactor 28 to produce the hydrocarbons/ FT liquids 30 and water 32.
- the resulting hydrocarbons are then passed on to a hydrocarbon cracking stage (not shown) to obtain the desired hydrocarbon products, such as naphtha, diesel etc.
- the diesel formulated in this process is commonly known as synthetic diesel.
- an external source of hydrogen is supplemented to the Fischer- Tropsch unit (not shown) and the hydrocarbon cracking unit.
- FIG. 2 depicts a flow diagram of an embodiment of the process of the present invention.
- the process is generally denoted by numeral 100 and begins with electrolysing water 112 in water electrolyzer 114 to generate oxygen 116 and hydrogen 118, and feeding a biomass feedstock 120 to a biomass dryer 124 to remove excess moisture to obtain a drier biomass feedstock 126 having water content about 15%.
- the biomass feedstock 126 and oxygen 116 are then fed to gasifier 128, and the feedstock is gasified under partial oxidation conditions to generate a hydrogen lean syngas 130 having H 2 :CO molar ratio about 1 :1.
- the hydrogen lean syngas 130 is optionally subjected to cleaning operations 132 and/or carbon dioxide removal operation 134 to remove C0 2 135.
- the C0 2 135 is optionally fed to the gasifier 128 to be used as blanket/sealing gas.
- At least a portion of hydrogen 118 generated via water electrolysis 114 is added to the hydrogen lean syngas 130 after the cleaning operations via line 133, and/or after carbon dioxide removal operation via line 136, to form hydrogen rich syngas 137.
- the hydrogen rich syngas 137 is then reacted in a Fischer-Tropsch reactor 138 to produce hydrocarbons 140 and water 142.
- Hydrocarbons 140 are then subjected to hydroprocessing operation(s) 144, followed by product fractionation 146 to obtain the desired hydrocarbon products, such as naphtha, diesel etc.
- Water 142 is recycled to the electrolyzer 114, and is used as primary water source for electrolysis.
- Energy/heat from the FT reactor 138 is then used to remove excess moisture from the biomass feedstock and/or to generate electricity for the electrolyzer.
- the steam 162 is passed through heat exchanger 156 to recover heat which is directed via line 160 to the biomass dryer 124 to supplement the heat used in the excess moisture.
- steam from the FT reactor 138 is directed via line 162 to power generator 152 to produce electricity 154 to supplement electricity for the electrolyzer 114, and a portion of the residual steam after power generation is passed through the heat exchanger 156 to obtain residual heat which is directed via line 160 to the biomass dryer 124 to supplement the heat used in the excess moisture removal process, and recovery water which is directed via line 168 to water electrolyzer 114.
- At least a portion of heat generated during the electrolysis process is optionally directed via line 148 to the biomass dryer 124 to supplement the heat used in the excess moisture removal process.
- a portion of excess steam generated in the gasifier 128 is optionally directed via line 150 to power generator 152 to produce electricity 154 to supplement electricity for the electrolyzer 114, and a portion of the residual steam after power generation is passed through a heat exchanger 156 to obtain residual heat which is directed via line 160 to the biomass dryer 124 to supplement the heat used in the excess moisture removal process, and recovery water which is directed via line 168 to water electrolyzer 114.
- refinery gases 164 and 166 generated during FT reaction and product fractionation respectively, are used to fire duct burner 158 for biomass dryer 124, thereby using them for removing excess moisture from the biomass feedstock.
- a portion of waste heat from the electrolysis step is captured through Organic Rankine Cycle (ORC) and/or Sterling cycle generator 170 to produce electricity 154 to supplement electricity for the electrolyzer 114.
- ORC Organic Rankine Cycle
- Sterling cycle generator 170 to produce electricity 154 to supplement electricity for the electrolyzer 114.
- the refinery gas 164 from the FT reaction and/or the refinery gas 166 from the fractionation process is used in an internal combustion engine or micro-turbine 172 to generate power for electrolyzer.
- the waste heat from the internal combustion engine is captured via ORC technology and/or Sterling cycle generator to produce additional electricity.
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- Oil, Petroleum & Natural Gas (AREA)
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Abstract
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Priority Applications (6)
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CA3156190A CA3156190C (en) | 2019-11-08 | 2020-11-06 | Process for producing synthetic hydrocarbons from biomass |
US17/774,689 US11753597B2 (en) | 2019-11-08 | 2020-11-06 | Process for producing synthetic hydrocarbons from biomass |
BR112022008806A BR112022008806A2 (en) | 2019-11-08 | 2020-11-06 | PROCESS FOR PRODUCTION OF SYNTHETIC HYDROCARBONS FROM BIOMASS |
EP20885362.2A EP4055119A4 (en) | 2019-11-08 | 2020-11-06 | Process for producing synthetic hydrocarbons from biomass |
AU2020380421A AU2020380421A1 (en) | 2019-11-08 | 2020-11-06 | Process for producing synthetic hydrocarbons from biomass |
MX2022005578A MX2022005578A (en) | 2019-11-08 | 2020-11-06 | Process for producing synthetic hydrocarbons from biomass. |
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US201962933015P | 2019-11-08 | 2019-11-08 | |
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US (1) | US11753597B2 (en) |
EP (1) | EP4055119A4 (en) |
AU (1) | AU2020380421A1 (en) |
BR (1) | BR112022008806A2 (en) |
CA (1) | CA3156190C (en) |
CL (1) | CL2022001205A1 (en) |
CZ (1) | CZ2022233A3 (en) |
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WO2023064089A1 (en) * | 2021-10-15 | 2023-04-20 | DG Fuels, LLC | Processes and systems for producing hydrocarbon fuels having high carbon conversion efficiency |
WO2024017651A1 (en) * | 2022-07-20 | 2024-01-25 | IFP Energies Nouvelles | Improved method for converting a feedstock containing a biomass fraction for the production of hydrocarbons by means of fischer-tropsch synthesis |
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US20150275112A1 (en) * | 2012-10-31 | 2015-10-01 | IFP Energies Nouvelles | Improved process for the conversion of a feed containing biomass for the production of hydrocarbons, by fischer-tropsch synthesis |
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CA2357527C (en) | 2001-10-01 | 2009-12-01 | Technology Convergence Inc. | Methanol recycle stream |
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WO2008033812A2 (en) * | 2006-09-11 | 2008-03-20 | Purdue Research Foundation | System and process for producing synthetic liquid hydrocarbon |
US20100175320A1 (en) * | 2006-12-29 | 2010-07-15 | Pacific Renewable Fuels Llc | Energy efficient system and process for the continuous production of fuels and energy from syngas |
EP2166064A1 (en) | 2008-09-19 | 2010-03-24 | Siemens Aktiengesellschaft | A chemical product providing system and method for providing a chemical product |
DE102010028181A1 (en) * | 2010-04-26 | 2011-10-27 | Siemens Aktiengesellschaft | Production plant for chemical raw materials or fuels and a method for operating such a production plant |
FR2989366B1 (en) * | 2012-04-13 | 2015-08-14 | Commissariat Energie Atomique | DIHYDROGEN PRODUCTION BY HEAD GAS TRANSFORMATION FROM A SYNTHESIS |
DE102013012661A1 (en) | 2013-07-30 | 2015-02-05 | Linde Aktiengesellschaft | Process and installation for enriching a synthesis gas generated by gasification with hydrogen |
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US20130345325A1 (en) * | 2011-02-22 | 2013-12-26 | Areva | Method for producing methanol or hydrocarbons from a carbon material, including a reforming step, the operating conditions of which are selectively adjusted |
US20150275112A1 (en) * | 2012-10-31 | 2015-10-01 | IFP Energies Nouvelles | Improved process for the conversion of a feed containing biomass for the production of hydrocarbons, by fischer-tropsch synthesis |
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WO2023064089A1 (en) * | 2021-10-15 | 2023-04-20 | DG Fuels, LLC | Processes and systems for producing hydrocarbon fuels having high carbon conversion efficiency |
WO2024017651A1 (en) * | 2022-07-20 | 2024-01-25 | IFP Energies Nouvelles | Improved method for converting a feedstock containing a biomass fraction for the production of hydrocarbons by means of fischer-tropsch synthesis |
FR3138142A1 (en) * | 2022-07-20 | 2024-01-26 | IFP Energies Nouvelles | IMPROVED PROCESS FOR CONVERTING A FEED CONTAINING A BIOMASS FRACTION FOR THE PRODUCTION OF FISCHER-TROPSCH SYNTHETIC HYDROCARBONS. |
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CL2022001205A1 (en) | 2023-02-24 |
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CA3156190A1 (en) | 2021-05-14 |
AU2020380421A1 (en) | 2022-06-09 |
US11753597B2 (en) | 2023-09-12 |
EP4055119A1 (en) | 2022-09-14 |
US20220396743A1 (en) | 2022-12-15 |
CA3156190C (en) | 2023-12-12 |
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BR112022008806A2 (en) | 2022-07-26 |
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