# US 10,865,107 B2 · Novel, highly efficient, eco-friendly processes for converting CO2 or co-rich streams to liquid fuels and chemicals

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- Number: US 10,865,107 B2
- Document ID: US10865107B2
- Status: Granted
- Kind: B2
- Application number: 16/334,220
- Filed: 2017-09-10
- Published: 2019-07-25
- Granted: 2020-12-15
- Earliest claimed: 2016-09-19
- Assignees: B.G. Negev Technologies and Applications Ltd., At Ben-Gurion University
- Applicants: B.G. Negev Technologies & Applications Ltd., at Ben-Gurion University
- Inventors: Mordechay Herskowitz; Tomy Hos
- Web page: https://patentgrep.com/patent/US10865107B2

## CPC

- C01B 3/12: by reaction of water vapour with carbon monoxide
- B01J 21/04: Alumina
- B01J 21/063: {Titanium; Oxides or hydroxides thereof}
- B01J 23/52: Gold
- B01J 23/745: Iron
- B01J 23/755: Nickel
- B01J 35/613: {10-100 m2/g}
- B01J 35/615: {100-500 m2/g}
- B01J 35/633: {less than 0.5 ml/g}
- B01J 35/647: {2-50 nm}
- B01J 37/0009: {Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst}
- B01J 37/0036: {Grinding}
- B01J 37/0201: {Impregnation}
- B01J 37/031: {Precipitation}
- C01B 3/38: using catalysts
- C01B 3/501: by diffusion
- C10G 2/32: {with the use of catalysts}
- C10G 2/33: {characterised by the catalyst used}
- C10G 3/00: Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids (production from non-melting solid oxygen-containing carbonaceous materials C10G1/00)
- C10G 50/00: Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
- C10K 3/026: {Increasing the carbon monoxide content, e.g. reverse water-gas shift [RWGS]}
- C25B 1/00: Electrolytic production of inorganic compounds or non-metals
- C25B 1/01: Products
- C25B 15/08: Supplying or removing reactants or electrolytes; Regeneration of electrolytes
- C25B 15/083: {Separating products}
- C01B 2203/0238: the reforming step being a carbon dioxide reforming step
- C01B 2203/0405: Purification by membrane separation
- C01B 2203/065: using hydrotreating, e.g. hydrogenation, hydrodesulfurisation
- C01B 2203/1241: Natural gas or methane
- Y02P 20/00: Technologies relating to chemical industry
- Y02P 20/52: using catalysts, e.g. selective catalysts
- Y02P 30/20: using bio-feedstock
- C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C}
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- C10K: PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C25B: ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR (anodic or cathodic protection C23F13/00; single-crystal growth C30B)
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

The invention provides a process for preparing liquid fuels and chemicals, which process comprises feeding carbon monoxide and hydrogen to a hydrogenation reactor, wherein the molar ratio CO:H2 is in the range of 1:0.5 to 1:0.9, catalytically hydrogenating said carbon monoxide in said hydrogenation reactor, condensing the effluent of said hydrogenation reactor to recover one or more organic liquid(s) and an aqueous solution, feeding a non-condensable component of said effluent into an oligomerization reactor; condensing an effluent discharged from the oligomerization reactor to obtain an additional organic liquid and an additional gaseous stream, separating said additional organic liquid, and either combusting said additional gaseous stream to produce heat and electricity, or processing same to obtain recyclable gaseous streams utilizable in said process.

## Claims

### Claim 1

A process for preparing liquid fuels and chemicals, which process comprises feeding carbon monoxide and hydrogen to a hydrogenation reactor, wherein the molar ratio CO:H2 is in the range of 1:0.5 to 1:0.9, catalytically hydrogenating said carbon monoxide in said hydrogenation reactor to produce a hydrogenation effluent, condensing the effluent of said hydrogenation reactor to recover one or more organic liquid(s) and an aqueous solution, feeding a non-condensable component of said effluent into an oligomerization reactor; condensing an effluent discharged from the oligomerization reactor to obtain an additional organic liquid and an additional gaseous stream, separating said additional organic liquid, and either combusting said additional gaseous stream to produce heat and electricity, or processing said additional gaseous stream to obtain recyclable gaseous streams utilizable in said process, wherein the carbon monoxide and hydrogen feedstock is supplied by dry reforming carbon dioxide with natural gas or co-electrolysis of carbon dioxide and steam, wherein the process further comprises splitting the additional gaseous component generated in the oligomerization reaction into a carbon monoxide stream and carbon monoxide-depleted, carbon dioxide-rich stream, recycling said carbon monoxide stream to the hydrogenation reactor; dividing said carbon monoxide-depleted, carbon dioxide-rich stream into two subsidiary streams, wherein one subsidiary CO2-containing stream is used to supply CO2 to said dry reforming reaction or said co-electrolysis, and the other CO2-containing stream is reacted with hydrogen in reverse water gas shift reactor to produce CO and water, following which the effluent of said RWGS reactor is separated into water and CO-containing stream which is used to supply CO to the hydrogenation reaction.

### Claim 2

A process for preparing liquid fuels and chemicals, which process comprises feeding carbon monoxide and hydrogen to a hydrogenation reactor, wherein the molar ratio CO:H2 is in the range of 1:0.5 to 1:0.9, catalytically hydrogenating said carbon monoxide in said hydrogenation reactor to produce a hydrogenation effluent, condensing the effluent of said hydrogenation reactor to recover one or more organic liquid(s) and an aqueous solution, feeding a non-condensable component of said effluent into an oligomerization reactor; condensing an effluent discharged from the oligomerization reactor to obtain an additional organic liquid and an additional gaseous stream, separating said additional organic liquid, and either combusting said additional gaseous stream to produce heat and electricity, or processing said additional gaseous stream to obtain recyclable gaseous streams utilizable in said process, comprising producing a mixture of carbon monoxide and hydrogen either by means of dry reforming carbon dioxide or co-electrolysis of carbon dioxide and steam, separating hydrogen in part from said mixture, to form syngas feedstock, feeding said syngas—wherein the molar ratio CO:H2 is in the range of 1:0.5 to 1:0.9 to a hydrogenation reactor, catalytically hydrogenating said carbon monoxide in said hydrogenation reactor to produce a hydrogenation effluent, condensing the effluent of said hydrogenation reactor at a first temperature to obtain a first organic liquid and a first gaseous stream, separating said first organic liquid and collecting same; condensing said first gaseous stream at a second temperature to obtain a second liquid, which consists of an organic phase and an aqueous phase, and a second gaseous stream; separating said second liquid into a second organic liquid and an aqueous phase; feeding said second gaseous stream into the oligomerization reactor; condensing the effluent discharged from the oligomerization reactor to obtain a third organic liquid and a third gaseous stream, separating and collecting third organic liquid, splitting said third gaseous component into a carbon monoxide stream and carbon monoxide-depleted, carbon dioxide-rich stream, recycling said carbon monoxide stream to said hydrogenation reactor; dividing said carbon monoxide-depleted, carbon dioxide-rich stream into two subsidiary streams, wherein one subsidiary CO2-containing stream is used to supply CO2 to said dry reforming reaction or said co-electrolysis, and the other CO2-containing stream is reacted with hydrogen in reverse water gas shift (RWGS) reactor to produce CO and water, following which the effluent of said RWGS reactor is separated into water and CO-containing stream which is used to supply CO to said hydrogenation reaction, hydrotreating one or more organic products collected in the process to form premium liquid fuels, and converting oxygenates in the aqueous solution into olefins which are fed to the oligomerization reactor.

### Claim 3

A process for preparing liquid fuels and chemicals, which process comprises feeding carbon monoxide and hydrogen to a hydrogenation reactor, wherein the molar ratio CO:H2 is in the range of 1:0.5 to 1:0.9, catalytically hydrogenating said carbon monoxide in said hydrogenation reactor to produce a hydrogenation effluent, condensing the effluent of said hydrogenation reactor to recover one or more organic liquid(s) and an aqueous solution, feeding a non-condensable component of said effluent into an oligomerization reactor; condensing an effluent discharged from the oligomerization reactor to obtain an additional organic liquid and an additional gaseous stream, separating said additional organic liquid, and either combusting said additional gaseous stream to produce heat and electricity, or processing said additional gaseous stream to obtain recyclable gaseous streams utilizable in said process, wherein the carbon monoxide and hydrogen feedstock is supplied from waste gases characterized by having H2/CO molar ratio of <0.5, the process comprises subjecting said waste gas to water gas shift (WGS) reaction to convert part of the CO so that the H2/CO molar ratio increases, and separating excess hydrogen in a membrane so that the H2/CO molar ratio of the stream fed to CO hydrogenation reactor is adjusted to about 0.6-0.8, and hydrogenating the product of said WGS reaction.

### Claim 4

A process for preparing liquid fuels and chemicals, which process comprises feeding carbon monoxide and hydrogen to a hydrogenation reactor, wherein the molar ratio CO:H2 is in the range of 1:0.5 to 1:0.9, catalytically hydrogenating said carbon monoxide in said hydrogenation reactor, to produce a hydrogenation effluent, condensing the effluent of said hydrogenation reactor to recover one or more organic liquid(s) and an aqueous solution, feeding a non-condensable component of said effluent into an oligomerization reactor; condensing an effluent discharged from the oligomerization reactor to obtain an additional organic liquid and an additional gaseous stream, separating said additional organic liquid, and either combusting said additional gaseous stream to produce heat and electricity, or processing said additional gaseous stream to obtain recyclable gaseous streams utilizable in said process, wherein the carbon monoxide and hydrogen feedstock is supplied from waste gases characterized by having H2/CO molar ratio of >0.9, the process comprises subjecting said waste gas to RWGS reaction, condensing the product of the RWGS reaction to obtain water and non-condensable component, separating water from the gaseous component and separating hydrogen therefrom, and directing the gaseous stream to the hydrogenation reaction.