Two stage process for the conversion of synthesis gas using a cobalt catalyst in the first stage and a supported ruthenium catalyst in the second stage
원문보기
IPC분류정보
국가/구분
United States(US) Patent
등록
국제특허분류(IPC7판)
C07C-027/00
C10G-002/00
C07C-001/04
출원번호
US-0521923
(2010-12-16)
등록번호
US-8859631
(2014-10-14)
우선권정보
GB-1000971.0 (2010-01-21)
국제출원번호
PCT/GB2010/052116
(2010-12-16)
§371/§102 date
20130104
(20130104)
국제공개번호
WO2011/089377
(2011-07-28)
발명자
/ 주소
McKenna, Mark
출원인 / 주소
Johnson Matthey PLC
대리인 / 주소
RatnerPrestia
인용정보
피인용 횟수 :
0인용 특허 :
2
초록▼
A process is described for the conversion of synthesis gas into hydrocarbons including the steps of; (i) passing a synthesis gas comprising hydrogen and carbon monoxide over a cobalt catalyst at elevated temperature and pressure to produce a first reaction product mixture comprising hydrocarbons, st
A process is described for the conversion of synthesis gas into hydrocarbons including the steps of; (i) passing a synthesis gas comprising hydrogen and carbon monoxide over a cobalt catalyst at elevated temperature and pressure to produce a first reaction product mixture comprising hydrocarbons, steam, carbon monoxide and hydrogen,(ii) condensing and separating water from the first reaction product mixture to produce a de-watered first reaction product mixture,(iii) passing the de-watered first reaction product mixture over a supported ruthenium catalyst at elevated temperature and pressure to produce a second reaction product mixture containing hydrocarbons, and(iv) recovering the hydrocarbons from the second reaction product mixture.
대표청구항▼
1. A process for the conversion of synthesis gas into hydrocarbons comprising the steps of; (i) passing a synthesis gas comprising hydrogen and carbon monoxide over a cobalt catalyst at a temperature in the range 210-225° C. to produce a first reaction product mixture comprising hydrocarbons, steam,
1. A process for the conversion of synthesis gas into hydrocarbons comprising the steps of; (i) passing a synthesis gas comprising hydrogen and carbon monoxide over a cobalt catalyst at a temperature in the range 210-225° C. to produce a first reaction product mixture comprising hydrocarbons, steam, carbon monoxide and hydrogen of a first reaction stage,(ii) condensing and separating water from the first reaction product mixture to produce a de-watered first reaction product mixture,(iii) passing the de-watered first reaction product mixture over a supported ruthenium catalyst at a temperature in the range 230-265° C. and a pressure in the range 35-55 bar abs, to produce a second reaction product mixture containing hydrocarbons of a second reaction stage, and(iv) recovering the hydrocarbons from the second reaction product mixturewherein the pressure of the second reaction stage is higher than that of the first reaction stage, and the pressure of the first reactor stage is at least 5 bar abs. 2. A process according to claim 1, wherein the cobalt catalyst comprises cobalt supported on an oxidic support or silicon carbide support. 3. A process according to claim 2, wherein the oxidic support is selected from the group consisting of alumina, silica, titanic, zirconia, zinc oxide, and a mixture thereof. 4. A process according to claim 2, wherein the oxidic support is selected from the group consisting of alpha alumina, a transition alumina, a hydrated alumina, an alpha alumina coated in a layer of metal aluminate, and a transition alumina coated in a layer of metal aluminate. 5. A process according to claim 1, wherein the cobalt catalyst comprises an intimate mixture of cobalt and oxidic compounds. 6. A process according to claim 5, wherein the oxidic compounds comprise cobalt-aluminium oxide or cobalt-zinc oxide compounds. 7. A process according to claim 1, wherein the cobalt catalyst is free of precious metal promoters. 8. A process according to claim 1, wherein the cobalt content of the cobalt catalyst is in the range 5-45% by weight. 9. A process according to claim 1, wherein the cobalt catalyst is in a form selected from the group consisting of a powder with a volume-median diameter in the range 1 to 200 micrometers, a shaped unit with a particle size in the range 1-25 mm, and a coating on a metal or ceramic support. 10. A process according to claim 1, wherein the ruthenium catalyst comprises ruthenium supported on an oxidic support, graphite, or silicon carbide support. 11. A process according to claim 10, wherein the oxidic support is selected from the group consisting of alumina, silica, titanic, zirconia, zinc oxide, and a mixture thereof. 12. A process according to claim 10, wherein the oxidic support is selected from the group consisting of an alpha alumina, a transition alumina, a hydrated alumina, and an alumina coated in a layer of metal aluminate. 13. A process according to claim 1, wherein the ruthenium catalyst is free of cobalt. 14. A process according to claim 1, wherein the ruthenium content of the ruthenium catalyst is in the range 0.1-10% by weight. 15. A process according to claim 1, wherein the ruthenium catalyst is a powder with a volume-median diameter in the range 1 to 200 micrometers, a shaped unit with a particle size in the range 1-25 mm, and a coating on a metal or ceramic support. 16. A process according to claim 1, wherein the first reaction stage is performed by passing the synthesis gas mixture through a fixed bed of the cobalt catalyst or through a slurry of the cobalt catalyst in a hydrocarbon liquid medium. 17. A process according to claim 1, wherein the second reaction stage is performed by passing the synthesis gas mixture through a fixed bed of the ruthenium catalyst or through a slurry of the ruthenium catalyst in a hydrocarbon liquid medium. 18. A process according to claim 1, wherein the temperature of the first reaction product mixture is adjusted by heat exchange before the second reaction stage. 19. A process according to claim 1, wherein the composition of the first stage reaction mixture is adjusted by addition of synthesis gas, hydrogen, carbon monoxide, or an inert gas or by the removal of hydrocarbon or steam. 20. A process according to claim 1, wherein >50% of the conversion of the synthesis gas occurs over the ruthenium catalyst. 21. A process according claim 1, operated under conditions such that the conversion of the synthesis gas to hydrocarbons in the second stage reaction mixture is ≧90% on a molar basis. 22. A process according to claim 1, wherein the recovery of hydrocarbons from the second stage reaction product mixture creates a tail gas comprising hydrogen, carbon monoxide, carbon dioxide, and methane, and at least a portion of the tail gas is recycled to one or more of an upstream synthesis gas generation stage, the synthesis gas fed to the cobalt catalyst, the first stage reaction product mixture fed to the ruthenium catalyst, or a separation stage that provides one or more gases enriched in hydrogen, carbon monoxide, carbon dioxide, or methane. 23. A process according to claim 22, wherein at least a portion of the tail gas is recycled to the ruthenium-catalysed stage. 24. A process according to claim 22, wherein at least a portion of one or more of the gasses recovered in the separation stage is recycled to one or more of an upstream synthesis gas generation stage, the synthesis gas fed to the cobalt catalyst, the first stage reaction product mixture fed to the ruthenium catalyst, or a downstream hydrocarbon processing stage. 25. A process according to claim 24, wherein CO2 formed in the first and second stage reaction is recovered from the tail gas. 26. A process according to claim 1, wherein the recovery of hydrocarbons from the first or second stage reaction product mixture creates a co-produced water stream comprising water and oxygenated hydrocarbons and at least a portion of the co-produced water is recycled to an upstream synthesis gas generation stage or a separation stage that provides a stream enriched in oxygenates. 27. A process according to claim 26, wherein at least a portion of the oxygenates from the separation stage is recycled to an upstream synthesis gas generation stage.
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이 특허에 인용된 특허 (2)
Kim Chang J. (Bedminster NJ) Fiato Rocco A. (Scotch Plains NJ), Multi-stage Fischer-Tropsch process.
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