IPC분류정보
국가/구분 |
United States(US) Patent
등록
|
국제특허분류(IPC7판) |
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출원번호 |
US-0675629
(2012-11-13)
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등록번호 |
US-8557105
(2013-10-15)
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발명자
/ 주소 |
- Lott, Roger K.
- Chang, Yu-Hwa
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출원인 / 주소 |
- Headwaters Technology Innovation, LLC
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대리인 / 주소 |
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인용정보 |
피인용 횟수 :
2 인용 특허 :
185 |
초록
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Methods for hydrocracking a heavy hydrocarbon feedstock (e.g., heavy oil and/or coal resid) employ a catalyst composed of well dispersed metal sulfide catalyst particles (e.g., colloidally or molecularly dispersed catalyst particles, such as molybdenum sulfide), which provide an increased concentrat
Methods for hydrocracking a heavy hydrocarbon feedstock (e.g., heavy oil and/or coal resid) employ a catalyst composed of well dispersed metal sulfide catalyst particles (e.g., colloidally or molecularly dispersed catalyst particles, such as molybdenum sulfide), which provide an increased concentration of metal sulfide catalyst particles within lower quality materials requiring additional hydrocracking. In addition to increased metal sulfide catalyst concentration, the systems and methods provide increased reactor throughput, increased reaction rate, and higher conversion of asphaltenes and lower quality materials. Increased conversion of asphaltenes and lower quality materials also reduces equipment fouling, enables processing of a wider range of lower quality feedstocks, and leads to more efficient use of a supported catalyst if used in combination with the well dispersed metal sulfide catalyst particles.
대표청구항
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1. A method of hydrocracking a heavy hydrocarbon feedstock using well dispersed metal sulfide catalyst particles, the method comprising: providing a heavy hydrocarbon feedstock that includes a significant fraction of hydrocarbons having a boiling point above 343° C. and/or asphaltenes;blending a cat
1. A method of hydrocracking a heavy hydrocarbon feedstock using well dispersed metal sulfide catalyst particles, the method comprising: providing a heavy hydrocarbon feedstock that includes a significant fraction of hydrocarbons having a boiling point above 343° C. and/or asphaltenes;blending a catalyst precursor with the heavy hydrocarbon feedstock at a temperature below a decomposition temperature of the catalyst precursor to form a conditioned feedstock composition that is thereafter heated to above the decomposition temperature to form well dispersed metal sulfide catalyst particles in situ within the heavy hydrocarbon feedstock;introducing into a first hydrocracking reactor, hydrogen (H2) gas and the heavy hydrocarbon feedstock including the well dispersed metal sulfide catalyst particles already formed in situ within the heavy hydrocarbon feedstock and/or the conditioned feedstock composition to form the well dispersed metal sulfide catalyst particles in situ within the heavy hydrocarbon feedstock when heated to above the decomposition temperature of the catalyst precursor, the first hydrocracking reactor including a first gas-liquid two or more phase hydrocracking reactor having a first concentration of well dispersed metal sulfide catalyst particles that, together with the hydrogen gas, facilitate beneficial upgrading reactions within the heavy hydrocarbon feedstock;separating an effluent from the first hydrocracking reactor into a lower boiling volatile gaseous vapor fraction and a higher boiling liquid fraction in a manner so that the metal sulfide catalyst particles remain in the higher boiling liquid fraction and have increased concentration compared to a concentration of the well dispersed metal sulfide catalyst particles within the first hydrocracking reactor; andintroducing at least a portion of the higher boiling liquid fraction containing the increased concentration of the metal sulfide catalyst particles and additional hydrogen (H2) gas into a second gas-liquid two or more phase hydrocracking reactor, wherein the increased concentration of metal sulfide catalyst particles within the second hydrocracking reactor provides increased conversion and/or reaction rate and/or throughput. 2. A method as recited in claim 1, wherein substantially all of said higher boiling liquid fraction is introduced into said second hydrocracking reactor. 3. A method as recited in claim 1, wherein separating the effluent produced from the first hydrocracking reactor is achieved by introducing the effluent into a pressure differential interstage separator which induces a significant pressure drop so as to separate the lower boiling volatile gaseous vapor fraction from the higher boiling liquid fraction, wherein the pressure drop is determined at least in part by a difference between a first higher pressure at which the first hydrocracking reactor operates and a second lower pressure at which the second hydrocracking reactor operates. 4. A method as recited in claim 3, further comprising: introducing an effluent from said second hydrocracking reactor into a second interstage pressure differential separator which induces a second pressure drop so as to separate a second lower boiling volatile gaseous vapor fraction from a second higher boiling liquid fraction; andintroducing at least a portion of said second higher boiling liquid fraction and additional hydrogen (H2) gas into a third gas-liquid two or more phase hydrocracking reactor and wherein said second higher boiling liquid fraction has a third concentration of metal sulfide catalyst particles that is greater than said second concentration of metal sulfide catalyst particles within said second hydrocracking reactor. 5. A method as recited in claim 3, wherein the pressure drop is between about 100 psi and about 1000 psi. 6. A method as recited in claim 3, wherein the pressure drop is between about 200 psi and about 700 psi. 7. A method as recited in claim 1, wherein said well dispersed metal sulfide catalyst particles comprise molybdenum sulfide and wherein said molybdenum sulfide has a concentration within said higher boiling liquid fraction introduced into said second hydrocracking reactor that is at least about 10 percent higher than a molybdenum sulfide concentration within said first hydrocracking reactor. 8. A method as recited in claim 7, wherein said molybdenum sulfide has a concentration within said higher boiling liquid fraction introduced into said second hydrocracking reactor that is at least about 25 percent higher than a molybdenum sulfide concentration within said first hydrocracking reactor. 9. A method as recited in claim 7, wherein said molybdenum sulfide has a concentration within said higher boiling liquid fraction introduced into said second hydrocracking reactor that is at least about 30 percent higher than a molybdenum sulfide concentration within said first hydrocracking reactor. 10. A method as recited in claim 1, wherein the first hydrocracking reactor is operated at a first pressure and the second hydrocracking reactor is operated at a second pressure, wherein the first pressure is between about 100 psi and about 1000 psi higher than the second pressure and at least partially corresponds to a pressure drop induced by a pressure differential interstage separator that separates the effluent from the first hydrocracking reactor into the lower boiling volatile gaseous vapor fraction and the higher boiling liquid fraction. 11. A method as recited in claim 10, wherein the first pressure is between about 200 psi and about 700 psi higher than the second pressure. 12. A method as recited in claim 10, wherein the first pressure is between about 300 psi and about 500 psi higher than the second pressure. 13. A method as recited in claim 1, wherein the well dispersed metal sulfide catalyst particles are colloidally or molecularly dispersed and have a particle size less than about 100 nm. 14. A method as recited in claim 1, wherein at least one of the first or second gas-liquid two or more phase hydrocracking reactors comprises a three-phase gas-liquid-solid hydrocracking reactor comprising a solid supported catalyst. 15. A method as recited in claim 1, wherein at least one of the first or second gas-liquid two or more phase hydrocracking reactors comprises an ebullated bed reactor. 16. A method as recited in claim 1, wherein at least one of the first or second gas-liquid two or more phase hydrocracking reactors comprises a fixed bed reactor. 17. A method as recited in claim 1, wherein the heavy hydrocarbon feedstock comprises at least one member selected from the group consisting of heavy crude, oils sands bitumen, bottom of the barrel and resid left over from refinery processes, visbreaker bottoms, coal resid, Lloydminster heavy oil, Cold Lake bitumen, Athabasca bitumen, atmospheric tower bottoms, vacuum tower bottoms, residuum, resid pitch, vacuum residue, and higher-boiling liquid fractions that remain after subjecting crude oil, bitumen from tar sands, liquefied coal, or coal tar feedstocks to distillation or hot separation. 18. A method as recited in claim 1, wherein the metal sulfide catalyst particles comprise colloidal or molecular catalyst particles having a particle size of less than 1 micron. 19. A method as recited in claim 18, wherein the metal sulfide catalyst particles further comprise micron-sized or larger catalyst particles in addition to the colloidal or molecular catalyst particles. 20. A method of hydrocracking a heavy hydrocarbon feedstock using well dispersed metal sulfide catalyst particles, the method comprising: providing a heavy hydrocarbon feedstock that includes a significant fraction of hydrocarbons having a boiling point above 343° C. and/or asphaltenes;blending a catalyst precursor with the heavy hydrocarbon feedstock at a temperature below a decomposition temperature of the catalyst precursor to form a conditioned heavy hydrocarbon feedstock composition;introducing the conditioned heavy hydrocarbon feedstock composition into a first gas-liquid two or more phase hydrocracking reactor and heating the conditioned heavy hydrocarbon feedstock composition within the first hydrocracking reactor to convert the catalyst precursor into well dispersed metal sulfide catalyst particles in situ within the heavy hydrocarbon feedstock, the first gas-liquid two or more phase hydrocracking reactor having a first concentration of metal sulfide catalyst particles, operating at a first pressure, and producing an effluent;introducing the effluent produced from the first hydrocracking reactor into a pressure differential interstage separator which induces a significant pressure drop so as to separate the effluent into a lower boiling volatile gaseous vapor fraction and a higher boiling liquid fraction; andintroducing at least a portion of the higher boiling liquid fraction into a second gas-liquid two or more phase hydrocracking reactor having a second concentration of metal sulfide catalyst particles that is greater than the first concentration of metal sulfide catalyst particles within the first hydrocracking reactor and operating at a second pressure that is less than the first pressure, wherein the pressure drop of the pressure differential interstage separator is determined at least in part by a difference between the first and second pressures. 21. A method as recited in claim 20, wherein both the pressure drop induced by the pressure differential interstage separator and the difference between the first and second pressures are between about 100 psi and about 1000 psi. 22. A method as recited in claim 20, wherein both the pressure drop induced by the pressure differential interstage separator and the difference between the first and second pressures are between about 200 psi to about 700 psi. 23. A method as recited in claim 20, wherein the second hydrocracking reactor has a concentration of metal sulfide catalyst particles that is at least about 25 percent higher than a concentration of metal sulfide catalyst particles within the first hydrocracking reactor. 24. A method as recited in claim 20, wherein at least one of the first or second gas-liquid two or more phase hydrocracking reactors comprises a three-phase gas-liquid-solid hydrocracking reactor comprising a solid supported catalyst. 25. A method as recited in claim 20, wherein at least one of the first or second gas-liquid two or more phase hydrocracking reactors comprises an ebullated bed reactor. 26. A method as recited in claim 20, wherein at least one of the first or second gas-liquid two or more phase hydrocracking reactors comprises a fixed bed reactor. 27. A method as recited in claim 20, wherein the well dispersed metal sulfide catalyst particles have a particle size less than about 100 nm. 28. A method of hydrocracking a heavy hydrocarbon feedstock using well dispersed metal sulfide catalyst particles, the method comprising: mixing a catalyst precursor into a heavy hydrocarbon feedstock to yield a conditioned heavy hydrocarbon feedstock composition comprised of the heavy hydrocarbon and the catalyst precursor;heating the conditioned heavy hydrocarbon feedstock composition to yield a heavy hydrocarbon feedstock that includes well dispersed metal sulfide catalyst particles formed in situ within the heavy hydrocarbon feedstock;introducing the heavy hydrocarbon feedstock and well dispersed metal sulfide catalyst particles into a first gas-liquid two or more phase hydrocracking reactor, the first gas-liquid two or more phase hydrocracking reactor having a first concentration of metal sulfide catalyst particles, operating at a first pressure, and producing an effluent;introducing the effluent produced from said first hydrocracking reactor into a pressure differential interstage separator which induces a significant pressure drop so as to separate the effluent into a lower boiling volatile gaseous vapor fraction and a higher boiling liquid fraction; andintroducing at least a portion of the higher boiling liquid fraction into a second gas-liquid two or more phase hydrocracking reactor having a second concentration of metal sulfide catalyst particles that is greater than the first concentration of metal sulfide catalyst particles within the first hydrocracking reactor and operating at a second pressure that is less than the first pressure, wherein the pressure drop of the pressure differential interstage separator is determined at least in part by a difference between the first and second pressures. 29. A method as recited in claim 28, wherein both the pressure drop induced by the pressure differential interstage separator and the difference between the first and second pressures are between about 100 psi and about 1000 psi. 30. A method as recited in claim 28, wherein both the pressure drop induced by the pressure differential interstage separator and the difference between the first and second pressures are between about 200 psi to about 700 psi. 31. A method as recited in claim 28, wherein the second hydrocracking reactor has a concentration of metal sulfide catalyst particles that is at least about 30 percent higher than a concentration of metal sulfide catalyst particles within the first hydrocracking reactor. 32. A method as recited in claim 28, wherein at least one of the first or second gas-liquid two or more phase hydrocracking reactors comprises a three-phase gas-liquid-solid hydrocracking reactor comprising a solid supported catalyst. 33. A method as recited in claim 28, wherein at least one of the first or second gas-liquid two or more phase hydrocracking reactors comprises an ebullated bed reactor. 34. A method as recited in claim 28, wherein at least one of the first or second gas-liquid two or more phase hydrocracking reactors comprises a fixed bed reactor. 35. A method as recited in claim 28, wherein the well dispersed metal sulfide catalyst particles are colloidally or molecularly dispersed and have a particle size less than about 100 nm.
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