Gas-liquid-solid three-phase suspension bed reactor for fischer-tropsch synthesis and its applications
원문보기
IPC분류정보
국가/구분
United States(US) Patent
등록
국제특허분류(IPC7판)
C07C-027/06
B01J-008/08
출원번호
US-0527355
(2007-10-12)
등록번호
US-8506895
(2013-08-13)
우선권정보
CN-2007 1 0161575 (2007-09-29)
국제출원번호
PCT/CN2007/002941
(2007-10-12)
§371/§102 date
20100329
(20100329)
국제공개번호
WO2009/043201
(2009-04-09)
발명자
/ 주소
Wang, Jinsheng
Hao, Xu
Liu, Dongxun
Bai, Liang
Cao, Liren
Li, Yongwang
출원인 / 주소
Synfuels China Technology Co. Ltd.
대리인 / 주소
Seed IP Law Group PLLC
인용정보
피인용 횟수 :
2인용 특허 :
7
초록▼
A Fischer-Tropsch synthesis three-phase suspension bed reactor (“suspension bed” also called “slurry bed”) and its supplemental systems, may include: 1) structure and dimension design of F-T synthesis reactor, 2) a gas distributor located at the bottom of the reactor, 3) structure and arrangement of
A Fischer-Tropsch synthesis three-phase suspension bed reactor (“suspension bed” also called “slurry bed”) and its supplemental systems, may include: 1) structure and dimension design of F-T synthesis reactor, 2) a gas distributor located at the bottom of the reactor, 3) structure and arrangement of a heat exchanger members inside the reactor, 4) a liquid-solid filtration separation device inside reactor, 5) a flow guidance device inside reactor, 6) a condensate flux and separation member located in the gas phase space at the top of reactor, 7) a pressure stabilizer, a cleaning system for the separation device; an online cleaning system for the gas distributor; an ancillary system for slurry deposition and a pre-condensate and mist separation system located at the outlet of upper reactor. This reactor is suitable for industrial scale application of Fischer-Tropsch synthesis.
대표청구항▼
1. A gas-liquid-solid three phase suspension bed reactor for Fischer-Tropsch synthesis, which is used for F-T synthesis reaction of synthesis gas (CO+H2) to synthesize F-T fuel by low temperature slurry bed process or high temperature slurry bed process in the presence of catalyst; the reactor compr
1. A gas-liquid-solid three phase suspension bed reactor for Fischer-Tropsch synthesis, which is used for F-T synthesis reaction of synthesis gas (CO+H2) to synthesize F-T fuel by low temperature slurry bed process or high temperature slurry bed process in the presence of catalyst; the reactor comprising: a reactor main body having a vertical cylindrical body with a height of from about 25 meters to about 45 meters;a direct introduction type or a clapboard distribution type gas distributor located at a bottom of the reactor main body;a lower primary heat exchanger immersed in a three-phase reaction region and located in a lower portion of a reaction zone bounded by the reactor main body;an upper primary heat exchanger having a first portion immersed in the three-phase reaction region and a remaining portion extending above the level of the three-phase reaction region into a gas separation zone above the three-phase reaction region, the upper primary heat exchanger located in an upper portion of the reaction zone bounded by the reactor main body;an ancillary heat exchanger located above a the gas separation zone;a plurality of sets of solid catalyst-liquid heavy products separators disposed axially about at least a portion of the reactor main body;a plurality of groups of vertical flow guidance pipes, each group of the plurality of groups including at least one vertical flow guidance pipe to circulate a respective vertical portion of the three-phase reaction region and positioned axially about an inside of the reactor main body;a mist separation device located proximate a top of the reactor main body; andat least two supplemental systems, including an ancillary system proximate a bottom of the reactor main body to handle deposited slurry, and a pre-condensate and mist separation system located in a top of a reactor outlet. 2. A gas-liquid-solid three phase suspension bed reactor according to claim 1, wherein said direct introduction type gas distributor is located on a surface of a bottom shell of the reactor main body, and said direct introduction type gas distributor includes multiple groups of ring structures, spaced 10-200 mm from a downward side surface of said direct introduction gas distributor to an internal surface of the bottom shell of the reactor main body, each ring structure of the direct introduction gas distributor equipped with a number of pipe fittings each with a number of gas sparger openings pointing downward, the gas sparger openings having a diameter in the range of 1.0 millimeters (mm) to 8.0 mm, the sparger openings which can flush the internal surface of the bottom shell of the reactor main body with a gas at a velocity of 20 meters per second (m/s) to 100 m/s; said direct introduction gas distributor includes also includes a number of ring shaped flow guidance baffle plates between the ring structures, which ring shaped flow guidance baffle plates are connected to the internal surface of the reactor shell in parallel to a reactor axis, a height of each of the ring shaped flow guidance baffle plates being 10 millimeters (mm) to 300 mm to assure a final upward gas flow vertically, the and the ring shaped flow guidance baffle plates arranged in a circular or pie sliced region and connected with a gas inlet pipe via several conduits to form a group of gas distributors. 3. A gas-liquid-solid three phase suspension bed reactor according to claim 1, wherein said ancillary system for handling the deposited slurry equipped for the reactor includes: a connecting tube located at a lowest part of a distributing and gathering pipe that extends outside the reactor main body and which is fluidly connected to at least one of a liquid receiving container, which is adjusted and controlled by a liquid level control system or a space formed by the bottom shell cover that serves as a liquid receiving container and which is equipped with a liquid accumulation level indication and control system so that accumulated liquid can be discharged via automatic control or manual control system. 4. A gas-liquid-solid three phase suspension bed reactor according to claim 1, wherein the vertical cylindrical body height of said main body of F-T synthesis three-phase suspension bed reactor is 28 meters to 40 meters, to achieve a maximum superficial gas velocity of 0.50 meters per second (m/s), and a reactor internal diameter of 2 meters to 15 meters, suitable to achieve a superficial gas velocity of 0.35 meters per second (m/s) to 0.45 m/s, a reactor internal diameter of 4 meters to 12 meters, where a reactor productivity based on C3+ hydrocarbons is 16 tons/hour to 25 ton/hr for a 5 meter reactor internal diameter, 45 tons per hour (tons/hr) to 70 ton/hr for an 8 meter reactor internal diameter, 70 tons per hour (ton/hr) to 100 ton/hr for a 10 meter reactor internal diameter, or 90 tons per hour (ton/hr) to 140 ton/hr for a 12 meter reactor internal diameter. 5. A gas-liquid-solid three phase suspension bed reactor according to claim 1, further comprising: at least one of a one-stage or a two-stage primary heat exchanger which includes at least one of a number of U-tube tube heat exchange components or a central annular tube with rising tube as heat exchange components;a number of groups of heat exchange modules that includes several groups of heat exchange components via a group of main headers equipped with one or more supporting components, which are located at both ends of the main headers and mounted on a number of supporting members of a wall of the reactor to form hanging-up structure, and wherein a lower end of the primary heat exchanger proximate a lower part of the reactor main body is positioned 0.1 meter to 3 meters above the gas distributor. 6. A gas-liquid-solid three phase suspension bed reactor according to claim 5, further comprising: a number of liquid-solid filtration separation devices to separate a solid catalyst and a liquid heavy wax and to remove heavy wax products, the liquid-solid filtration separation devices located vertically in a middle-upper portion of the reactor main body; and where there is only one primary heat exchanger, the filtration separation devices located above the primary heat exchanger; and where there are two primary heat exchangers, the liquid-solid filtration separation devices located between two primary heat exchangers, andeach of the number of liquid-solid filtration separation devices includes multiple filtering elements which comprise of from 12 to 60 filtering pipes; both ends of each filtering pipe connected to a pipe assembly and extending outside the reactor main body via intermediate an delivery pipe following fluid uniform distribution principle; a lower end of the delivery pipe connected to an external wax discharge and a pressure stabilizing system to remove filtered wax liquid, an upper end of the delivery pipe connected to a cleaning system for on-line cleaning of the filtering pipe, the filtering pipes consisting of metal filtering pipes which can be back blown; a filtration media contained in the filtering pipes, the filtering media having a pore size of from about 1 micrometer (μm) to about 50 μm and a length of from about 0.3 meters to about 3.0 meters to reduce a catalyst content in a filtered liquid wax to less than 100 parts per million (ppm). 7. A gas-liquid-solid three phase suspension bed reactor according to claim 6, wherein said liquid-solid filtration separation devices are located in a ring shaped region close to the wall in the reactor; each group of the filtration separation device is a filtration element that includes twenty (20) to fifty (50) filtration pipes, a length of a filtration section of the filtration pipes is from about 0.5 meters to about 2.5 meters; the filtration pipes being sintered/wound metal wire filtration pipes or sintered porous metal/ceramic filtration pipes, having a pore size of from about 10 micrometers (μm) to about 30 μm in diameter; and a minimum distance between adjacent filtration pipes of from about 20 millimeters (mm) to about 50 millimeters. 8. A gas-liquid-solid three phase suspension bed reactor according to claim 1, wherein at least one of the plurality of groups of flow guidance pipes can be located at a position inside the three-phase suspension bed and close to wall of the reactor, which is used for heat integration of the two-staged heat exchangers and for increasing the recycle volume of the suspension liquid to improve the catalyst distribution axially along the reactor. 9. A gas-liquid-solid three phase suspension bed reactor according to claim 1, wherein said mist separation device includes a primary mist separation device located in upper portion of the reactor main body and a secondary mist separation device external to the reactor main body, the secondary mist separation device being a cylinder condenser connected to the reactor outlet pipe, the cylinder condenser including a cylinder structure formed by one to eight layers of compactly arranged heat exchanging pipes equipped with a cone-shaped collector at a bottom of the condenser; whenever the mist entrained gas flow passes the heat exchanging pipe spaces, condensation and collisions occur, and the mist particles are grown and captured at the heat exchanging pipe wall which forms into a liquid film and flows into a bottom cone-shaped collector, then which flows downward through a back flux delivery pipe located at the bottom of the cone to the upper space above a primary baffle plate at least a portion of which includes a main header for the upper primary heat exchanger, to form liquid back flux and improve separation efficiency, to provide a first condensate product having a catalyst content of less than 2 parts per million (ppm). 10. A gas-liquid-solid three phase suspension bed reactor according to claim 1, wherein said pre-condensate mist separation system located at the reactor outlet includes a pre-condenser, a gas-liquid separator, a small liquid receptor and a number of automatic valves; the pre-condensate mist separation system to reduce a temperature of a gas flow from about 5° C. to about 10° C., and to provide a solids content of less than 2 parts per million (ppm) in a condensate formed at least partially by the gas flow. 11. A gas-liquid-solid three phase suspension bed reactor according to claim 1, wherein said F-T synthesis catalyst is at least one of: an iron-based catalyst of low temperature slurry bed process at reaction temperature of about 240° C. to about 250° C., with performance reaching about 0.3 kilograms of C3+ hydrocarbons per kilogram-hour (kg C3+/kg h) to about 0.6 kg C3+/kg h, methane selectivity of from about 2.0 weight percent (wt %) to about 5 wt %, and C2-C4 selectivity of from about 4.0 wt % to about 12.0 wt %; or an iron based catalyst used for high temperature slurry bed process of reaction temperature from about 250° C. to about 290° C., with performance reaching about 0.4 kg C3+/kg h to about 0.9 kgC3+/kg h, methane selectivity of from about 2.0 wt % to about 4.0 wt %, and C2-C4 selectivity of from about 3.0 wt % to about 10.0 wt %. 12. A gas-liquid-solid three phase suspension bed reactor according to claim 1, further comprising: a plurality of groups of solid catalyst-liquid heavy products separators distributed in an annular region close to a wall of the reactor main body. 13. A gas-liquid-solid three phase suspension bed reactor according to claim 12, further comprising a number of external supplemental devices that include at least one of: a filtered wax receptor and filtration pressure stabilization system for efficient operation of at least a portion of the plurality of groups of solid catalyst-liquid heavy products separators; anda cleaning system for at least a portion of the plurality of groups of solid catalyst-liquid heavy products separators;wherein the filtered wax receptor and filtration pressure stabilization system comprises a liquid wax receptor and its liquid level control system, a gas pressure buffer tank, a pressure stabilization tank and a precision pressure control system;wherein the cleaning system comprises a gas cleaning system and/or a liquid cleaning system;wherein the gas cleaning system includes a gas compressor, a gas heater and a thermally insulated gas buffer tank; and wherein at least one of: a synthesis gas, nitrogen, or a synthesis gas from the F-T synthesis process provides at least a portion of a cleaning medium;wherein the liquid cleaning system includes a heated, thermally insulated, hot oil pump and cleaning liquid metering pump. 14. A gas-liquid-solid three phase suspension bed reactor according to claim 1, wherein the gas-liquid-solid three-phase suspension reactor includes from one to eight groups of the gas distributors, which are formed into a single uniformly distributed gas distributor proximate a bottom shell of the reactor main body; a downward side surface of the ring structures of the gas distributor is spaced about 30 millimeters (mm) to about 150 mm from an internal surface of the bottom shell of the reactor main body; each of a number of gas sparger openings in the gas distributor having a diameter of from about 1.5 mm to about 5 mm such that the gas sparger openings can flush the internal surface of the bottom shell with a gas having a velocity of from about 30 meters per second (m/s) to about 90 m/s. 15. A gas-liquid-solid three phase suspension bed reactor according to claim 1, wherein the clapboard type gas distributor is includes: clapboards positioned above a welding line between the lower portion of the reaction zone to separate the reaction zone from a free space proximate a bottom shell of the reactor main body; a number of distributor pipe fittings located on an upper side of the clapboard and closely connected to the clapboards via a number of downwardly facing intermediate pipes, each of the number of distributor pipe fittings connected to the free space through the clapboard, and a number of inlet gas conduits that enter the free space and are pointing downward toward an internal surface of the bottom shell of the reactor main body. 16. A gas-liquid-solid three phase suspension bed reactor according to claim 12, wherein the plurality of groups of a solid catalyst-liquid heavy products separator are located above the lower primary heat exchanger or between two stages of at least one of: the lower primary heat exchanger or the upper primary heat exchanger. 17. A gas-liquid-solid three phase suspension bed reactor according to claim 12 wherein the ancillary heat exchanger is located at an upper part of a separator zone that includes at least one group of solid catalyst-liquid heavy products separators, and extends into a space existent between each of the solid catalyst-liquid heavy products separators in the at least one group of solid catalyst-liquid heavy products separators. 18. A gas-liquid-solid three phase suspension bed reactor according to claim 12 wherein the pre-condensate and mist separation system includes a secondary mist separator at the upper outlet of the reactor main body. 19. The gas-liquid-solid three phase suspension bed reactor according to claim 13 wherein a cleaning medium used by the a heated, thermally insulated, hot oil pump and cleaning liquid metering pump includes a dehydrogenated F-T distillate oil having a boiling point of from about 300° C. to about 380° C. 20. A gas-liquid-solid three phase suspension bed reactor according to claim 12 wherein the mist separation device includes a primary condensing type mist separation device combined with at least one of an upper primary heat exchanger or at least one of a number of ancillary main header pipes.
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