# US 9,908,093 B2 · Process for converting a carbonaceous material to methane, methanol and/or dimethyl ether using microchannel process technology > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 9,908,093 B2 - Document ID: US9908093B2 - Status: Granted - Kind: B2 - Application number: 12/420,942 - Filed: 2009-04-09 - Published: 2009-10-15 - Granted: 2018-03-06 - Earliest claimed: 2008-04-09 - Assignees: Velocys, Inc. - Applicants: Wayne W. Simmons; Robert Dwayne Litt; Terry Mazanec; Anna Lee Tonkovich - Inventors: Wayne W. Simmons; Robert Dwayne Litt; Terry Mazanec; Anna Lee Tonkovich - Web page: https://patentgrep.com/patent/US9908093B2 ## CPC - B01J 19/0093: {Microreactors, e.g. miniaturised or microfabricated reactors (laboratory containers with capillary fluid transport in microfabricated channels or chambers B01L3/5027)} - C01B 3/22: by decomposition of gaseous or liquid organic compounds - C01B 3/32: by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air - C01B 3/501: by diffusion - C01B 3/52: by contacting with liquids; Regeneration of used liquids - C01B 3/56: by contacting with solids; Regeneration of used solids - C07C 1/04: from carbon monoxide with hydrogen - C07C 1/20: starting from organic compounds containing only oxygen atoms as heteroatoms - C07C 2/84: catalytic - C07C 9/06: Ethane - C07C 11/04: Ethene - C07C 29/152: characterised by the reactor used - C10J 3/00: Production of combustible gases containing carbon monoxide from solid carbonaceous fuels (destructive distillation processes C10B) - B01J 2219/00835: Comprising catalytically active material - B01J 2219/00846: comprising nanostructures, e.g. nanotubes - B01J 2219/0086: Dimensions of the flow channels - B01J 2219/00873: Heat exchange - B01J 2219/00918: by adsorption - B01J 2219/00921: by absorption - B01J 2219/00984: Residence time - C01B 2203/0205: containing a reforming step - C01B 2203/0266: containing a decomposition step - C01B 2203/0405: Purification by membrane separation - C01B 2203/0415: Purification by absorption in liquids - C01B 2203/042: Purification by adsorption on solids - C01B 2203/043: Regenerative adsorption process in two or more beds, one for adsorption, the other for regeneration - C01B 2203/0465: Composition of the impurity - C01B 2203/0475: the impurity being carbon dioxide - C01B 2203/0485: the impurity being a sulfur compound - C01B 2203/06: Integration with other chemical processes - C01B 2203/061: Methanol production - C01B 2203/062: Hydrocarbon production, e.g. Fischer-Tropsch process - C01B 2203/0838: by heat exchange with exothermic reactions, other than by combustion of fuel - C01B 2203/0883: by indirect heat exchange - C01B 2203/1217: Alcohols - C01B 2203/84: Energy production - C07C 2529/85: Silicoaluminophosphates (SAPO compounds) - C10J 2300/1662: to methane - C10J 2300/1665: to alcohols, e.g. methanol or ethanol - Y02E 50/10: Biofuels, e.g. bio-diesel - Y02E 50/30: Fuel from waste, e.g. synthetic alcohol or diesel - Y02P 30/20: using bio-feedstock - Y02P 30/40: Ethylene production - B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS - C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C} - C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS - 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 - 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 This invention relates to a process for converting a carbonaceous material to a desired product comprising methane, methanol and/or dimethyl ether, the process comprising: gasifying the carbonaceous material at a temperature in excess of about 700° C. to form synthesis gas; and flowing the synthesis gas through two or more reaction zones in a microchannel reactor to convert the synthesis gas to the desired product. ## Claims ### Claim 1 A process for converting a carbonaceous material to a desired product comprising methane, methanol or dimethyl ether, the carbonaceous material being selected from biomass and waste material, the process comprising: (A) gasifying the carbonaceous material in the presence of a gasification agent at a temperature of at least about 700° C. in a gasifier to form synthesis gas, the synthesis gas comprising H2 and CO, water, particulate solids, and contaminants, the contaminants being selected from sulfur, halogen, selenium, phosphorus and arsenic; and flowing the synthesis gas out of the gasifier and reducing the temperature of the synthesis gas flowing out of the gasifier; flowing the synthesis gas through one or more gas-liquid sorption devices, temperature swing adsorption devices, pressure swing adsorption devices, microchannel devices containing layers of nanofibers or nano-composite films, cyclones and/or condensers to reduce the level of water, particulate solids and contaminants in the synthesis gas; adding H2 to the synthesis gas to form an upgraded synthesis gas with a molar ratio of H2 to CO in the range from about 1.5 to about 4; converting the upgraded synthesis gas to the desired product in a microchannel reactor, the microchannel reactor including a first reaction zone and another reaction zone and comprising a plurality of process microchannels and a plurality of heat exchange channels, the process microchannels having lengths in the range from about 0.2 to about 3 meters; the upgraded synthesis gas being converted to the desired product using the following exothermic equilibrium limited reaction process steps (B)(I) and (B)(II); wherein step (B)(I) comprises flowing the upgraded synthesis gas through a first reaction zone in the microchannel reactor at a first reaction temperature in contact with a first catalyst to form an intermediate product composition, the first catalyst being in the form of a fixed bed of particulate solids, the particulate solids of the first catalyst having a median particle diameter in the range from about 1 to about 1000 microns, the intermediate product composition comprising H2, CO and the desired product, the approach to equilibrium for conversion of the CO in the first reaction zone being at least about 5%; and step (B)(II) comprises flowing the intermediate product composition from the previous step through another reaction zone in the microchannel reactor at another reaction temperature in contact with another catalyst to form the desired product, the another catalyst being in the form of a fixed bed of particulate solids, the particulate solids of the another catalyst having a median particle diameter in the range from about 1 to about 1000 microns, the approach to equilibrium for conversion of the CO in the another reaction zone being at least about 5%, the another reaction temperature being at least about 5° C. less than the first reaction temperature; and flowing a heat exchange fluid in the heat exchange channels during steps (B)(I) and (B)(II), and transferring heat from the process microchannels to the heat exchange channels, wherein the heat exchange fluid used in the heat exchange channels during steps (B)(I) and (B)(II) comprises steam, liquid water and/or air, and at least part of the steam, liquid water and/or air used in the heat exchange channels during steps (B)(I) and (B)(II) flows from the heat exchange channels to the gasifier and is used as the gasification agent during step (A). ### Claim 2 (depends on 1) The process of claim 1 wherein nitrogen is separated from air in a nitrogen separator prior to step (A) to provide an oxygen enriched air or purified oxygen, and the carbonaceous material is gasified during step (A) in the presence of the oxygen enriched air or purified oxygen. ### Claim 3 (depends on 2) The process of claim 2 wherein the nitrogen is separated from the air in a microchannel separator using an ionic liquid as an absorbent liquid. ### Claim 4 (depends on 1) The process of claim 1 wherein the carbonaceous material is pyrolyzed prior to step (A) resulting in the formation of a pyrolytic oil, the pyrolytic oil being gasified during step (A). ### Claim 5 (depends on 1) The process of claim 1 wherein the level of sulfur contaminants in the synthesis gas is reduced using a ZnO guardbed. ### Claim 6 (depends on 1) The process of claim 1 wherein the carbonaceous material comprises municipal solid waste, hazardous waste, refuse derived fuel, tires, trash, sewage sludge, animal waste, petroleum coke, trash, garbage, agricultural waste, corn stover, switch grass, wood cuttings, timber, grass clippings, construction demolition materials, plastic material, cotton gin waste, or a mixture of two or more thereof. ### Claim 7 (depends on 1) The process of claim 1 wherein the ratio of H2 to CO for the upgraded synthesis gas is in the range from about 1.5 to about 2.5. ### Claim 8 (depends on 1) The process of claim 1 wherein subsequent to step (B)(I) but prior to step (B)(II) the intermediate product composition formed in step (B)(I) flows through an additional reaction zone in the microchannel reactor at an additional reaction temperature in contact with an additional catalyst to form another intermediate product composition, the additional catalyst being in the form of a fixed bed of particulate solids, the particulate solids of the additional catalyst having a median particle diameter in the range from about 1 to about 1000 microns, the another intermediate product composition comprising synthesis gas and the desired product, the approach to equilibrium for the conversion of the synthesis gas in the additional reaction zone being at least about 5%. ### Claim 9 (depends on 1) The process of claim 1 wherein the conversion of CO in the first reaction zone is in the range from about 5% to about 95%, and the conversion of CO in the another reaction zone is in the range from about 5% to about 99%. ### Claim 10 (depends on 1) The process of claim 1 wherein the first catalyst in step (B)(I) has the same composition as the another catalyst in step (B)(II). ### Claim 11 (depends on 8) The process of claim 8 wherein the additional catalyst has the same composition as the first catalyst in step (B)(I), the another catalyst in step (B)(II), or both the first catalyst in step (B)(I) and the another catalyst in step (B)(II). ### Claim 12 (depends on 1) The process of claim 1 wherein the first catalyst in step (B)(I) has a different composition than the another catalyst in step (B)(II). ### Claim 13 (depends on 8) The process of claim 8 wherein the additional catalyst has a different composition than the first catalyst in step (B)(I), the another catalyst in step (B)(II), or both the first catalyst in step (B)(I) and the another catalyst in step (B)(II). ### Claim 14 (depends on 1) The process of claim 1 wherein the microchannel reactor comprises at least one manifold for flowing synthesis gas into the process microchannels, at least one manifold for flowing product out of the process microchannels, at least one manifold for flowing a heat exchange fluid into the heat exchange channels, and at least one manifold for flowing the heat exchange fluid out of the heat exchange channels. ### Claim 15 (depends on 1) The process of claim 1 wherein one or more microchannel reactors are used to form the desired product, the one or more microchannel reactors being positioned in a vessel. ### Claim 16 (depends on 15) The process of claim 15 wherein each microchannel reactor comprises from about 100 to about 50,000 process microchannels, and the vessel contains from 1 to about 1000 microchannel reactors. ### Claim 17 (depends on 15) The process of claim 15 wherein the vessel is a pressurized vessel. ### Claim 18 (depends on 1) The process of claim 1 wherein the process microchannels have an internal height of up to about 10 mm. ### Claim 19 (depends on 1) The process of claim 1 wherein the process microchannels and heat exchange channels are made of a material comprising: steel; aluminum; titanium; nickel; copper; an alloy of any of the foregoing metals; monel; inconel; brass; quartz; silicon; or a combination of two or more thereof. ### Claim 20 (depends on 1) The process of claim 1 wherein fluid flowing in the process microchannels contacts surface features in the process microchannels, the contacting of the surface features imparting a disruptive flow to the fluid. ### Claim 21 (depends on 1) The process of claim 1 wherein the heat exchange channels comprises microchannels. ### Claim 22 (depends on 1) The process of claim 1 wherein the process microchannels and the heat exchange channels have rectangular cross sections. ### Claim 23 (depends on 1) The process of claim 1 wherein the first catalyst and/or the another catalyst comprises a copper oxide, zinc oxide and/or an aluminum oxide. ### Claim 24 (depends on 23) The process of claim 23 wherein the first catalyst and/or the another catalyst further comprise an oxide of one or more rare earth elements, zirconium, yttrium, chromium, silver, gallium, vanadium, molybdenum, tungsten, titanium, or a mixture of two or more thereof. ### Claim 25 (depends on 1) The process of claim 1 wherein the first catalyst and/or the another catalyst comprise nickel, iron, cobalt, ruthenium, molybdenum, vanadium, titanium, an oxide of any of the foregoing metals, or a mixture of two or more of the foregoing metals and/or oxides. ### Claim 26 (depends on 1) The process of claim 1 wherein the first catalyst and/or another catalyst comprise vanadium and/or molybdenum in the form of a free metal, hydroxide, oxide and/or sulfide in combination with one or more salts, hydroxides, oxides or sulfides of one or more metals belonging to Group IA, IIA or IIIB from the Periodic Table. ### Claim 27 (depends on 1) The process of claim 1 wherein the process microchannels have at least one heat transfer wall, the heat flux for heat exchange within the microchannel reactor being in the range from about 0.01 to about 500 watts per square centimeter of surface area of the heat transfer wall. ### Claim 28 (depends on 1) The process of claim 1 wherein the pressure in the first reaction zone and/or the another reaction zone is in the range up to about 50 atmospheres. ### Claim 29 (depends on 1) The process of claim 1 wherein the average temperature in the first reaction zone is in the range from about 150 to about 400° C. ### Claim 30 (depends on 1) The process of claim 1 wherein the average temperature in the first reaction zone is in the range from about 250 to about 850° C. ### Claim 31 (depends on 1) The process of claim 1 wherein the contact time within the first reaction zone and/or the second reaction zone is up to about 2000 milliseconds. ### Claim 32 (depends on 1) The process of claim 1 wherein the process microchannels have fluid flowing in them in one direction, and the heat exchange channels have fluid flow in a direction that is co-current or counter-current to the flow of fluid in the process microchannels. ### Claim 33 (depends on 1) The process of claim 1 wherein the process microchannels have fluid flowing in them in one direction, and the heat exchange channels have fluid flowing in them in a direction that is cross-current to the flow of fluid in the process microchannels. ### Claim 34 (depends on 1) The process of claim 1 wherein the length of the process microchannels and the length of the heat exchange channels are about the same. ### Claim 35 (depends on 1) The process of claim 1 wherein the first catalyst and/or another catalyst comprise a graded catalyst. ### Claim 36 (depends on 1) The process of claim 1 wherein the Quality Index Factor for the microchannel reactor is less than about 50%. ### Claim 37 (depends on 1) The process of claim 1 wherein the superficial velocity for fluid flowing in the process microchannels is at least about 0.01 m/s. ### Claim 38 (depends on 1) The process of claim 1 wherein the space velocity for fluid flowing in the process microchannels is at least about 1000 hr−1. ### Claim 39 (depends on 1) The process of claim 1 wherein the pressure drop for fluid flowing in the process microchannels is up to about 10 atmospheres per meter. ### Claim 40 (depends on 1) The process of claim 1 wherein the Reynolds number for the flow of fluid in the process microchannels is in the range from about 10 to about 4000. ### Claim 41 (depends on 1) The process of claim 1 wherein the process microchannels are formed by positioning a waveform between planar sheets. ### Claim 42 (depends on 1) The process of claim 1 wherein the heat exchange channels are formed by positioning a waveform between planar sheets. ### Claim 43 (depends on 1) The process of claim 1 wherein the desired product comprises methanol, and the methanol is converted to one or more olefins. ### Claim 44 (depends on 43) The process of claim 43 wherein the methanol is converted to one or more olefins in a microchannel reactor. ### Claim 45 (depends on 43) The process of claim 43 wherein the methanol is converted to one or more olefins in the presence of a silico-alumino-phosphate catalyst. ### Claim 46 (depends on 1) The process of claim 1 wherein the desired product comprises methane, and the methane is converted to ethane, ethylene, or a mixture thereof. ### Claim 47 (depends on 46) The process of claim 46 wherein the methane is converted to ethane, ethylene, or a mixture thereof, in a microchannel reactor. ### Claim 48 (depends on 46) The process of claim 46 wherein the methane is converted to ethane, ethylene, or a mixture thereof, in the presence of an oxidative coupling catalyst. ### Claim 49 (depends on 1) The process of claim 1 wherein the product comprises dimethyl ether and CO2, the process further comprising reacting the CO2 with methane to form a mixture of CO and H2. ### Claim 50 (depends on 49) The process of claim 49 wherein the reaction of CO2 with methane is conducted in a microchannel reactor. ### Claim 51 (depends on 1) The process of claim 1 wherein the microchannel reactor is constructed of stainless steel with one or more copper or aluminum waveforms being used for forming the process microchannels. ### Claim 52 (depends on 1) The process of claim 1 wherein at least part of the desired product is separated from the intermediate product composition subsequent to or during step (B)(I) but prior to step (B)(II). ### Claim 53 (depends on 1) The process of claim 1, wherein the carbonaceous material is gasified in a counter-current fixed bed gasifier to form the synthesis gas. ### Claim 54 (depends on 1) The process of claim 1, wherein the carbonaceous material is gasified in a co-current fixed bed gasifier to form the synthesis gas. ### Claim 55 (depends on 1) The process of claim 1, wherein the carbonaceous material is gasified in a plasma based gasification system to form the synthesis gas. ### Claim 56 (depends on 4) The process of claim 4, wherein liquid hydrocarbons are separated from the synthesis gas prior to step (B)(I) and are combined with the carbonaceous material prior to being pyrolyzed. ### Claim 57 (depends on 1) The process of claim 1, wherein the carbonaceous material is gasified in a fluidized bed gasifier. ### Claim 58 (depends on 1) The process of claim 1, wherein the carbonaceous material is gasified in an entrained flow gasifier. ### Claim 59 (depends on 1) The process of claim 1 wherein the particulate solids are separated from the synthesis gas by flowing the synthesis gas through a cyclone.