Removal of sulphur compounds from hydrocarbon streams using adsorbents and regeneration of the loaded adsorbents
원문보기
IPC분류정보
국가/구분
United States(US) Patent
등록
국제특허분류(IPC7판)
C10L-003/10
C10L-003/00
C10G-025/12
C10G-025/00
B01D-053/04
B01D-053/14
출원번호
UP-0533172
(2003-10-29)
등록번호
US-7517389
(2009-07-01)
우선권정보
EP-02257483(2002-10-29)
국제출원번호
PCT/EP03/050765
(2003-10-29)
§371/§102 date
20050429
(20050429)
국제공개번호
WO04/039926
(2004-05-13)
발명자
/ 주소
Van De Graaf, Jolinde Machteld
Last, Thijme
출원인 / 주소
Shell Oil Company
대리인 / 주소
Stewart, Charles W.
인용정보
피인용 횟수 :
3인용 특허 :
9
초록▼
The invention concerns a process for the removal of sulphur compounds from a hydrocarbon stream, especially a gaseous hydrocarbon gas stream, comprising said sulphur compounds, which process comprises contacting said gas stream with an adsorbent comprising a zeolite having a pore diameter of at leas
The invention concerns a process for the removal of sulphur compounds from a hydrocarbon stream, especially a gaseous hydrocarbon gas stream, comprising said sulphur compounds, which process comprises contacting said gas stream with an adsorbent comprising a zeolite having a pore diameter of at least 5 Å to adsorb the sulphur compounds thereon, the adsorption process followed by a regeneration process of used, loaded adsorbent by contacting the said loaded adsorbent with a regeneration gas stream having a relative water humidity less than 100%, especially less than 80%. Suitably the regeneration is followed by a dry regeneration treatment. The invention further relates to a process for the regeneration of adsorbent comprising a zeolite having a pore diameter of at least 5 Å loaded with sulphur compounds by contacting the adsorbent with a regeneration gas stream having a relative water humidity less than 100%, especially less than 80%. Suitably the regeneration is followed by a dry regeneration treatment.
대표청구항▼
The invention claimed is: 1. A process for removing water and sulfur compounds from a hydrocarbon stream containing water and sulfur compounds selected from the group consisting of hydrogen sulfide, carbonyl sulfides, mercaptans, especially C1-C6 mercaptans, organic disulfides, especially di-C1-C4-
The invention claimed is: 1. A process for removing water and sulfur compounds from a hydrocarbon stream containing water and sulfur compounds selected from the group consisting of hydrogen sulfide, carbonyl sulfides, mercaptans, especially C1-C6 mercaptans, organic disulfides, especially di-C1-C4-alkyl sulphides, organic disulfides, especially di-C1-C4-alkyl disulfides, thiophene compounds, aromatic mercaptans, especially phenyl mercaptan, and mixtures thereof, wherein the total amount of said sulfur compounds contained in the hydrocarbon stream is up to 3 vol %, based on total hydrocarbon stream, by adsorbing at least 60 wt % of the water contained in said hydrocarbon stream therefrom onto a first zeolite having a pore diameter of less than 5 Å; and thereafter, contacting said hydrocarbon stream with an adsorbent comprising a second zeolite having a pore diameter of at least 5 Å to adsorb the sulfur compounds thereon to thereby provide a loaded adsorbent, followed by a regeneration of said loaded adsorbent in the presence of water by contacting said loaded adsorbent with a regeneration gas stream comprising an inert gas or an inert gas mixture having a relative humidity of between 5% and 60%, said regeneration being conducted at a temperature of between 200 and 400° C. and a pressure between 30 and 120 bara, whereby an absorbent having significantly reduced degradation/ageing is obtained. 2. A process according to claim 1, in which the hydrocarbon stream is a gaseous stream and also comprises hydrogen sulfide and optionally carbon dioxide and up to 2 vol % hydrogen sulfide, with the hydrogen sulfide and part of the carbon dioxide being removed by means of washing the hydrocarbon stream with a chemical solvent. 3. A process according to claim 2, in which the temperature of the zeolite adsorption process is between 10 and 60° C., the pressure is between 10 and 150 bara, and the superficial gas velocity is between 0.03 and 0.6 m/s. 4. A process for the regeneration of an adsorbent, wherein said process comprises: providing one or more vessels having a first adsorbent bed comprising a first zeolite having a pore diameter of 5 Å or less and a second adsorbent bed comprising a second zeolite having a pore diameter of more than 5 Å; using said one or more vessels in the removal of sulfur compounds from a hydrocarbon stream to provide said second zeolite that is loaded with sulfur compounds; and regenerating said second zeolite that is loaded with sulfur compounds by contacting the adsorbent with a regeneration gas stream having a relative water humidity of between 5% and 60% at a temperature of between 200 and 400° C. and a pressure between 30 and 120 bara, whereby a second zeolite having a significantly reduced degradation/ageing is obtained. 5. A process according to claim 4, in which the adsorbent in said second adsorbent bed comprises zeolite dispersed in a binder and the relative water humidity of said regeneration gas stream is between 10% and 30%. 6. A process according to claim 4, in which the regeneration is carried out at a pressure between 50 and 90 bara, a temperature between 230 and 350° C., and a superficial gas velocity of less than 0.20 m/s. 7. A process according to claim 6, in which the regeneration gas stream is a gas stream obtained by saturating the stream at a temperature below the regeneration temperature. 8. A process according claim 7, in which the regeneration gas stream has a relative humidity between 10 and 30%. 9. A process for the removal of sulfur compounds from a hydrocarbon stream, wherein said hydrocarbon stream is a gaseous stream and contains a sulfur compound selected from the group consisting of hydrogen sulfide, carbonyl sulfide, mercaptans, organic sulfides, organic disulfides, thiophene compounds, aromatic mercaptans and mixtures thereof, said process comprises: treating said hydrocarbon stream to remove water therefrom followed by contacting said hydrocarbon stream with an adsorbent comprising a zeolite having a pore diameter of at least 5 Å to absorb said sulfur compound thereon to thereby provide a sulfur loaded adsorbent; and contacting said sulfur loaded adsorbent with a regeneration gas stream having a relative humidity between 10 and 30%, wherein the regeneration gas comprises an inert gas, whereby a regenerated adsorbent is obtained having significantly reduced degradation/ageing is obtained. 10. A process according to claim 9, wherein said mercaptans include C1-C6 mercaptans, said organic sulfides include di-C1-C4-alkyl sulfides, organic disulfides include di-C1-C4 alkyl disulfides, said aromatic mercaptans include phenyl mercaptan, and the total amount of said sulfur compounds contained in said hydrocarbon stream is up to 3 vol % based on total gas stream. 11. A process according to claim 10, in which said hydrocarbon stream prior to contacting with said adsorbent, comprises hydrogen sulfide in the range up to 2 vol % hydrogen sulfide, and a part thereof is removed by means of washing with a chemical solvent. 12. A process according to claim 11, in which the temperature of the step of contacting said hydrocarbon stream with said adsorbent is between 10 and 60° C., the pressure is between 10 and 150 bara, and the superficial gas velocity is between 0.03 and 0.6 m/s. 13. A process for the regeneration of an adsorbent, which is loaded with a sulfur compound, by contacting the adsorbent with a regeneration gas stream having a relative water humidity of between 5 and 60% at a temperature of between 200 and 400° C. and a pressure between 30 and 120 bara, wherein said adsorbent is contained in at least two beds, with one bed comprising a first zeolite having a pore diameter of up to 5 Å, and with a second bed comprising a second zeolite having a pore diameter of more than 5 Å, whereby said regenerated absorbent has significantly reduced degradation/ageing. 14. A process according to claim 13, wherein said adsorbent of said second bed further comprises said second zeolite dispersed in a binder. 15. A process according to claim 14, in which the contacting step is carried out at a pressure between 50 and 90 bara, a temperature between 230 and 350° C. and a superficial gas velocity of less than 0.20 m/s. 16. A process according to claim 15, in which said regeneration gas stream is a gas stream obtained by saturating the stream at a temperature below the regeneration temperature. 17. A process according to claim 16, in which said regeneration gas stream has a relative humidity between 10 and 30%.
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이 특허에 인용된 특허 (9)
Grover Bhadra S. (Pound Ridge NY) Nagji Moez M. (Stamford CT), Gas treatment process.
Sherman John D. (Chappaqua NY) Katsaros Arthur T. (Macungie PA), Suppression of COS formation in molecular sieve purification of hydrocarbon gas streams.
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