CN104357078A - Fixed bed Fischer-Tropsch synthesis method - Google Patents
Fixed bed Fischer-Tropsch synthesis method Download PDFInfo
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- CN104357078A CN104357078A CN201410629420.6A CN201410629420A CN104357078A CN 104357078 A CN104357078 A CN 104357078A CN 201410629420 A CN201410629420 A CN 201410629420A CN 104357078 A CN104357078 A CN 104357078A
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- gas
- fischer
- reactor
- tropsch synthesis
- fixed bed
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
Abstract
The invention discloses a fixed bed Fischer-Tropsch synthesis method which comprises the following steps: by using natural gas, asphalt, coal and biomass resources containing carbon and hydrogen as raw materials, producing a synthesis gas; feeding the synthesis gas into a fixed bed Fischer-Tropsch synthesis reactor; carrying gout Fischer-Tropsch synthesis reaction under the effect of a Fischer-Tropsch synthesis catalyst; carrying out gas-liquid separation on a material flow flowing from the reaction into a thermal high-pressure separator; recovering the liquid as a coarse product of Fischer-Tropsch synthesis; discharging water; carrying out gas-liquid separation on gas entering into a cold high-pressure separator, wherein all or part of gas enters into the reactor and/or the reactor to recycle; and recovering a hydrocarbon therein. Therefore, the fixed bed Fischer-Tropsch synthesis method has obvious social and economic benefits.
Description
Technical field
The present invention relates to a kind of fixed bed Fischer-Tropsch synthesis method.
Background technology
The heat-eliminating medium after product, unconverted raw material and heating is extracted out from reactor part, another reactor part is rejoined to the raw material that major general is portion of non-converted, hydrocarbon product can be extracted out, preferably the water formed in Fischer-Tropsch reaction is removed, cooled under the condition of the heat production at the same time of the heat-eliminating medium after heating, and rejoin reactor part.Hydrogen is added in reaction reagent preferably between reactive moieties.The method is reactor used more, has separation system, cause complicated operation after each reactor.CN1662476A provides a kind of method preparing hydrocarbon.The method relates to the method preparing hydrocarbon and heat production at least two sections at high temperature under high pressure in the presence of a catalyst with H2 and CO.The method adopts at least two or more fixed-bed reactor being preferably high voidage to carry out F-T synthesis, the H2/CO charge ratio 1.6 ~ 0.4 of each section.Wherein reaction reagent and heat-eliminating medium add reactor part, and reaction reagent part is converted, and heat-eliminating medium directly absorbs the heat that Fischer-Tropsch reaction produces.
By catalyst strength requirement, circulating flow rate can not be excessive, otherwise too high bed pressure drop will cause catalyst breakage; The exploitation of the catalyzer that physico-chemical property is suitable is then the solution in a non-process.In current solution Fischer-Tropsch synthesis or F-T, the main method of technical problem has following several: (1) reduces the diameter of fixed bed reaction pipe; (2) circulating flow rate is increased; (3) the suitable catalyzer of physico-chemical property is developed.Although above method can solve reaction bed temperature problem more rambunctious to a certain extent, also there is respective technology drawback.Reduce the loading amount that reaction tube diameter directly affects catalyzer, reduce the utilization ratio of reactor; Increase circulating flow rate and will cause the rising of bed pressure drop increase and gas compression expense.
US4579986 discloses a kind of under the effect of cobalt-base catalyst, is produced the method for liquid hydrocarbon by F-T synthesis.C1 ~ C4 gas hydrocarbon selective described by this patented method in 18 % by weight ~ 28.5 % by weight, C5+ liquid hydrocarbon selectivity 71.5 % by weight ~ 82 % by weight.
CN1417291A discloses a kind of technological process optionally being prepared diesel oil distillate by F-T synthesis by synthetic gas.This production method adopts one-stage process, directly prepares based on the product of diesel oil distillate alkane by synthetic gas; Synthetic gas mainly consists of H2 and CO, and H2/CO volume ratio is 1.0-4.0; Fischer-tropsch synthetic catalyst is containing metal cobalt/carried by active carbon body catalyst; Fischer-Tropsch synthesis condition is: temperature of reaction is 120-400 DEG C, and reaction pressure is 0.05-10MPa, and synthetic gas air speed is 100-5000h-1.Utilize the method can obtain the diesel oil distillate of 180-380 DEG C, this cut at least contains the alkane of 95% by weight, and the ratio of its isomeric hydrocarbon and positive structure hydrocarbon is in 0.03 0.3 scope.The method uses paste state bed reactor optionally to prepare diesel oil distillate.
US6458857 discloses a kind of method of being produced more than 371 DEG C heavy hydrocarbons by F-T synthesis to greatest extent.Under the effect that Co is catalyst based, by reducing air speed, constantly shifting out catalyzer and the method for fresh makeup catalyst improves heavy hydrocarbon selectivity from reactor, its stable C 5+ selectivity higher (about 85 % by weight), but, the open defect of the method is, reduction because of air speed not only have impact on operation stability, treatment capacity is reduced simultaneously, constantly shift out catalyzer and fresh makeup catalyst and also make becoming of the method complicated.
US6765026B2 discloses the processing method that the catalyst based F-T synthesis of a kind of Co produces liquid hydrocarbon, and the C5+ liquid hydrocarbon selectivity that the method describes is 58 % by weight ~ 80 about % by weight.
Summary of the invention
Technical problem to be solved by this invention is that the temperature of fixed bed FischerTropsch synthesis catalyst bed controls difficulty, consequent bed excessive temperature differentials, the problem of product selectivity difference.The object of the invention is on the basis of existing technology, a kind of fixed bed Fischer-Tropsch synthesis method of one-stage process is provided.
A kind of fixed bed Fischer-Tropsch synthesis method, with the resource of Sweet natural gas, pitch, coal, biomass carbon containing and hydrogen for raw material production goes out synthetic gas, enter fixed bed Fischer-Tropsch synthesis device, Fischer-Tropsch synthesis is carried out under the effect of fischer-tropsch synthetic catalyst, enter high pressure hot separator from the material of reactor outflow and carry out gas-liquid separation, using the thick Product recycling of liquid wherein as F-T synthesis, discharge water wherein, the reaction conditions of reactor is: pressure is 0.5 ~ 6MPa, temperature is 150 ~ 350 DEG C, and gas hourly space velocity is 500 ~ 6000h
-1, H2/CO raw materials components mole ratio is 1 ~ 3; Gas enters cold high pressure separator and carries out gas-liquid separation, gas wherein all or part of enter reactor and/or reactor cycles, reclaim hydrocarbon product wherein.
Advantage of the present invention is:
(1) method provided by the invention is simple to operate, has good C 5+ selectivity good, is particularly suitable for the Fischer-Tropsch synthesis in producing, for the purpose of heavy paraffins.
(2) the present invention is one-stage process Fischer-Tropsch synthesis, and equipment is simple, simple to operate.
(3) target product selectivity of the present invention is high, and method beds axle provided by the present invention has a narrow range of temperature mutually, and monolith activity is not fully exerted, and liquid hydrocarbon selectivity is high, and improves intermediate oil yield.
Embodiment
Embodiment 1
A kind of fixed bed Fischer-Tropsch synthesis method, with the resource of Sweet natural gas, pitch, coal, biomass carbon containing and hydrogen for raw material production goes out synthetic gas, enter fixed bed Fischer-Tropsch synthesis device, Fischer-Tropsch synthesis is carried out under the effect of fischer-tropsch synthetic catalyst, enter high pressure hot separator from the material of reactor outflow and carry out gas-liquid separation, using the thick Product recycling of liquid wherein as F-T synthesis, discharge water wherein, the reaction conditions of reactor is: pressure is 6MPa, temperature is 350 DEG C, and gas hourly space velocity is 6000h
-1, H2/CO raw materials components mole ratio is 3; Gas enters cold high pressure separator and carries out gas-liquid separation, gas wherein all or part of enter reactor and/or reactor cycles, reclaim hydrocarbon product wherein
Embodiment 2
A kind of fixed bed Fischer-Tropsch synthesis method, with the resource of Sweet natural gas, pitch, coal, biomass carbon containing and hydrogen for raw material production goes out synthetic gas, enter fixed bed Fischer-Tropsch synthesis device, Fischer-Tropsch synthesis is carried out under the effect of fischer-tropsch synthetic catalyst, enter high pressure hot separator from the material of reactor outflow and carry out gas-liquid separation, using the thick Product recycling of liquid wherein as F-T synthesis, discharge water wherein, the reaction conditions of reactor is: pressure is 0.5MPa, temperature is 150 DEG C, and gas hourly space velocity is 500h
-1, H2/CO raw materials components mole ratio is 1; Gas enters cold high pressure separator and carries out gas-liquid separation, gas wherein all or part of enter reactor and/or reactor cycles, reclaim hydrocarbon product wherein
Embodiment 3
A kind of fixed bed Fischer-Tropsch synthesis method, with the resource of Sweet natural gas, pitch, coal, biomass carbon containing and hydrogen for raw material production goes out synthetic gas, enter fixed bed Fischer-Tropsch synthesis device, Fischer-Tropsch synthesis is carried out under the effect of fischer-tropsch synthetic catalyst, enter high pressure hot separator from the material of reactor outflow and carry out gas-liquid separation, using the thick Product recycling of liquid wherein as F-T synthesis, discharge water wherein, the reaction conditions of reactor is: pressure is 1MPa, temperature is 200 DEG C, and gas hourly space velocity is 5000h
-1, H2/CO raw materials components mole ratio is 1; Gas enters cold high pressure separator and carries out gas-liquid separation, gas wherein all or part of enter reactor and/or reactor cycles, reclaim hydrocarbon product wherein
Embodiment 4
A kind of fixed bed Fischer-Tropsch synthesis method, with the resource of Sweet natural gas, pitch, coal, biomass carbon containing and hydrogen for raw material production goes out synthetic gas, enter fixed bed Fischer-Tropsch synthesis device, Fischer-Tropsch synthesis is carried out under the effect of fischer-tropsch synthetic catalyst, enter high pressure hot separator from the material of reactor outflow and carry out gas-liquid separation, using the thick Product recycling of liquid wherein as F-T synthesis, discharge water wherein, the reaction conditions of reactor is: pressure is 16MPa, temperature is 1501 DEG C, and gas hourly space velocity is 6000h
-1, H2/CO raw materials components mole ratio is 1; Gas enters cold high pressure separator and carries out gas-liquid separation, gas wherein all or part of enter reactor and/or reactor cycles, reclaim hydrocarbon product wherein
Embodiment 5
A kind of fixed bed Fischer-Tropsch synthesis method, with the resource of Sweet natural gas, pitch, coal, biomass carbon containing and hydrogen for raw material production goes out synthetic gas, enter fixed bed Fischer-Tropsch synthesis device, Fischer-Tropsch synthesis is carried out under the effect of fischer-tropsch synthetic catalyst, enter high pressure hot separator from the material of reactor outflow and carry out gas-liquid separation, using the thick Product recycling of liquid wherein as F-T synthesis, discharge water wherein, the reaction conditions of reactor is: pressure is 4MPa, temperature is 250 DEG C, and gas hourly space velocity is 4000h
-1, H2/CO raw materials components mole ratio is 2; Gas enters cold high pressure separator and carries out gas-liquid separation, gas wherein all or part of enter reactor and/or reactor cycles, reclaim hydrocarbon product wherein
Embodiment 6
A kind of fixed bed Fischer-Tropsch synthesis method, with the resource of Sweet natural gas, pitch, coal, biomass carbon containing and hydrogen for raw material production goes out synthetic gas, enter fixed bed Fischer-Tropsch synthesis device, Fischer-Tropsch synthesis is carried out under the effect of fischer-tropsch synthetic catalyst, enter high pressure hot separator from the material of reactor outflow and carry out gas-liquid separation, using the thick Product recycling of liquid wherein as F-T synthesis, discharge water wherein, the reaction conditions of reactor is: pressure is 3MPa, temperature is 180 DEG C, and gas hourly space velocity is 5500h
-1, H2/CO raw materials components mole ratio is 2; Gas enters cold high pressure separator and carries out gas-liquid separation, gas wherein all or part of enter reactor and/or reactor cycles, reclaim hydrocarbon product wherein.
Embodiment 7
A kind of fixed bed Fischer-Tropsch synthesis method, with the resource of Sweet natural gas, pitch, coal, biomass carbon containing and hydrogen for raw material production goes out synthetic gas, enter fixed bed Fischer-Tropsch synthesis device, Fischer-Tropsch synthesis is carried out under the effect of fischer-tropsch synthetic catalyst, enter high pressure hot separator from the material of reactor outflow and carry out gas-liquid separation, using the thick Product recycling of liquid wherein as F-T synthesis, discharge water wherein, the reaction conditions of reactor is: pressure is 6MPa, temperature is 200 DEG C, and gas hourly space velocity is 560h
-1, H2/CO raw materials components mole ratio is 1; Gas enters cold high pressure separator and carries out gas-liquid separation, gas wherein all or part of enter reactor and/or reactor cycles, reclaim hydrocarbon product wherein.
Claims (1)
1. a fixed bed Fischer-Tropsch synthesis method, it is characterized in that: with the resource of Sweet natural gas, pitch, coal, biomass carbon containing and hydrogen for raw material production goes out synthetic gas, enter fixed bed Fischer-Tropsch synthesis device, Fischer-Tropsch synthesis is carried out under the effect of fischer-tropsch synthetic catalyst, enter high pressure hot separator from the material of reactor outflow and carry out gas-liquid separation, using the thick Product recycling of liquid wherein as F-T synthesis, discharge water wherein, the reaction conditions of reactor is: pressure is 0.5 ~ 6MPa, temperature is 150 ~ 350 DEG C, and gas hourly space velocity is 500 ~ 6000h
-1, H2/CO raw materials components mole ratio is 1 ~ 3; Gas enters cold high pressure separator and carries out gas-liquid separation, gas wherein all or part of enter reactor and/or reactor cycles, reclaim hydrocarbon product wherein.
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| CN201410629420.6A CN104357078A (en) | 2014-11-10 | 2014-11-10 | Fixed bed Fischer-Tropsch synthesis method |
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| CN201410629420.6A CN104357078A (en) | 2014-11-10 | 2014-11-10 | Fixed bed Fischer-Tropsch synthesis method |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105219420B (en) * | 2015-10-20 | 2016-12-07 | 天津大学 | A kind of biomass full constituent prepares the device of automobile-used bio-fuel-oil |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103289723A (en) * | 2013-05-16 | 2013-09-11 | 赵淮光 | Cage-type sphere fixed bed Fischer-Tropsch synthesis method |
| CN103396826A (en) * | 2013-08-14 | 2013-11-20 | 神华集团有限责任公司 | Two-stage series-connected Fischer-Tropsch synthesis system and process thereof |
| CN103965935A (en) * | 2013-01-31 | 2014-08-06 | 中国科学院上海高等研究院 | Method for Fischer-Tropsch synthesis reaction |
| EP2865731A1 (en) * | 2012-06-26 | 2015-04-29 | Wuhan Kaidi Engineering Technology Research Institute Co., Ltd. | Method for fischer-tropsch synthesis and for utilizing exhaust |
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- 2014-11-10 CN CN201410629420.6A patent/CN104357078A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2865731A1 (en) * | 2012-06-26 | 2015-04-29 | Wuhan Kaidi Engineering Technology Research Institute Co., Ltd. | Method for fischer-tropsch synthesis and for utilizing exhaust |
| CN103965935A (en) * | 2013-01-31 | 2014-08-06 | 中国科学院上海高等研究院 | Method for Fischer-Tropsch synthesis reaction |
| CN103289723A (en) * | 2013-05-16 | 2013-09-11 | 赵淮光 | Cage-type sphere fixed bed Fischer-Tropsch synthesis method |
| CN103396826A (en) * | 2013-08-14 | 2013-11-20 | 神华集团有限责任公司 | Two-stage series-connected Fischer-Tropsch synthesis system and process thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105219420B (en) * | 2015-10-20 | 2016-12-07 | 天津大学 | A kind of biomass full constituent prepares the device of automobile-used bio-fuel-oil |
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Application publication date: 20150218 |