CN103421530A - Fischer tropsch synthesis method adopting fixed bed - Google Patents
Fischer tropsch synthesis method adopting fixed bed Download PDFInfo
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- CN103421530A CN103421530A CN2013103118941A CN201310311894A CN103421530A CN 103421530 A CN103421530 A CN 103421530A CN 2013103118941 A CN2013103118941 A CN 2013103118941A CN 201310311894 A CN201310311894 A CN 201310311894A CN 103421530 A CN103421530 A CN 103421530A
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Abstract
The invention provides a fischer tropsch synthesis method adopting fixed bed, which comprises the following steps: raw materials are put into a fixed bed fischer tropsch reactor, and are subjected to fischer tropsch synthesis reaction under the effect of the cobalt-based fischer tropsch synthesis catalyst; the substances flowing out of the reactor are subjected to condensation and separation so as to obtain heavy hydrocarbon substances, and the hydrocarbon substances and the feed gas are mixed and are put into the ischer tropsch reactor for further fischer tropsch synthesis reaction. According to the method provided by the invention, only the heavy hydrocarbon substances in the product subjected to fischer tropsch synthesis reaction are reused for controlling the temperature of the catalyst bed, so that the problems that in the prior art, as the liquid product returned to the inlet of the fischer tropsch reactor is a series of hydrocarbon mixture and has complex components, the evaporation capacity is difficult to control, the temperature of fischer tropsch synthesis catalyst bed is difficult to control and the like are solved.
Description
Technical field
The present invention relates to a kind of fixed bed Fischer-Tropsch synthesis method, belong to technical field of coal chemical industry.
Background technology
Fischer-Tropsch synthesis refers to containing H
2React the hydrocarbon mixture of generation different chain length and the reaction of oxygenatedchemicals with the synthetic gas of CO under the effect of solid catalyst, be the important reaction in the ICL for Indirect Coal Liquefaction process, become ICL for Indirect Coal Liquefaction at present and produced one of important method of various hydro carbons and oxygenatedchemicals.
Fixed bed Fischer-Tropsch synthesis method, due to its easy operation format, becomes one of main synthetic technology of each major oil companies' exploitation.But the temperature of fixed bed FischerTropsch synthesis catalyst bed is controlled and is had certain difficulty, if the bed excessive temperature differentials, product selectivity will variation, under extreme case, temperature control is improper can cause the beds temperature runaway, causes even sintering deactivation of catalyst performance degradation.Therefore, the control of reaction bed temperature is one of synthetic technological difficulties of fixed bed Fischer-Tropsch, and how reaction heat being shifted out in time is the key factor that guarantees the reaction process stable operation.At present, the main method of head it off has following several: the diameter that reduces the fixed bed reaction pipe; Increase the circulation gas flow; The suitable catalyzer of exploitation physico-chemical property.Although above method can solve reaction bed temperature problem more rambunctious to a certain extent, also there is technology drawback separately.For example: reducing reaction tube diameter can directly affect the loading amount of catalyzer, reduces the utilization ratio of reactor, increases the equipment making difficulty; Increase circulation gas flow can cause the rising of bed pressure drop increase and gas compression expense, in addition, is subject to the catalyst strength requirement, and the circulation gas flow 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 a non-technologic solution.
CN101747127A discloses a kind of fixed bed Fischer-Tropsch synthesis method, in the method, reactor effluent through step pressure reducing, cooling with separate after, the products such as gas, benzoline, intermediate oil, wax and water have been obtained, the benzoline obtained is partly turned back to Fischer-Tropsch synthesis device entrance, by the circulation of part benzoline, with this, control the temperature of beds.
CN101928194A discloses a kind of fixed bed Fischer-Tropsch synthesis method, in the method, reactor effluent through preliminary cooling with separate after, obtain carburet hydrogen series products, liquid hydrocarbon product and water, wherein liquid hydrocarbon product obtains benzoline, intermediate oil and heavy distillate after separating.The partially liq hydrocarbon products (heavy synthetic oil, light synthetic or the liquid product after the cut cutting) and the portion gas hydrocarbon products that obtain are returned to Fischer-Tropsch synthesis device entrance, also for the control to reaction bed temperature, thereby reduce the risk of beds temperature runaway.
In above-mentioned two kinds of disclosed fixed bed Fischer-Tropsch synthesis methods, although propose the liquid Fischer-Tropsch synthetic of a part is back to the Fischer-Tropsch synthesis device, absorb to evaporate in beds by the partially liq hydrocarbon products amount of heat that Fischer-Tropsch synthesis is emitted, thereby make fixed bed Fischer-Tropsch synthesis device reaction bed temperature steady.But, the partially liq hydrocarbon products that is back to the Fischer-Tropsch synthesis device comprises high-boiling hydrocarbons and lower boiling hydro carbons, after the unstripped gas with Fischer-Tropsch synthesis device entrance mixes, be subject to the impact of vapor liquid equilibrium, lower boiling hydrocarbon products can evaporate the absorption heat and make the gas flow temperature that enters fixed bed Fischer-Tropsch synthesis device beds reduce, even be reduced to the minimum temperature of fischer-tropsch synthetic catalyst requirement (, the light-off temperature of catalyzer) below, thereby cause Fischer-Tropsch synthesis to stop.Due to the liquid Fischer-Tropsch synthetic that is back to the Fischer-Tropsch synthesis device mixture that is a series of hydro carbons, complicated component, the steam output of hydro carbons is difficult to control, and makes the temperature of fischer-tropsch synthetic catalyst bed be difficult to controlled.
Summary of the invention
Technical problem solved by the invention is to control difficulty for the temperature of beds in fixed bed Fischer-Tropsch building-up process, the bed excessive temperature differentials produced therefrom, easily produce the problem of reaction focus, a kind of fixed bed Fischer-Tropsch synthesis method that is easy to control reaction bed temperature is provided.
The invention provides a kind of fixed bed Fischer-Tropsch synthesis method, comprising: unstripped gas is sent into to the fixed bed fischer-tropsch reactor, carry out Fischer-Tropsch synthesis under the effect of Co based Fischer-Tropsch synthesis catalyst; The heavy hydrocarbon material that reactor effluent is obtained after condensation, separation further participates in Fischer-Tropsch synthesis after mixing in the Fischer-Tropsch synthesis device with described unstripped gas.
In the present invention, heavy hydrocarbon material in fixed bed fischer-tropsch reaction resultant is turned back to fixed bed fischer-tropsch reactor entrance to be mixed with unstripped gas, because heavy hydrocarbon material (annotate: the heavy hydrocarbon that the present invention refers to is the hydrocarbons of carbonatoms >=10) has higher boiling point, after mixing with unstripped gas, steam output is less, can guarantee that the mixed temperature of heavy hydrocarbon material and unstripped gas meets the requirement of fixed bed FischerTropsch synthesis catalyst bed temperature.Simultaneously, carrying out along with Fischer-Tropsch synthesis, the a large amount of reaction heat that discharge, can evaporate and remove in time by beds the time by the heavy hydrocarbon material, make fixed bed fischer-tropsch reactor reaction bed temperature steady, both can avoid the bed temperature runaway, and can guarantee that again bed temperature can not be reduced to below the catalyzer light-off temperature, Fischer-Tropsch synthesis is normally carried out.
Further, controlling the fischer-tropsch reaction condition is: working pressure 1.0-8.0MPa; Temperature of reaction 150-300 ℃.
Further, the hydrocarbons that described heavy hydrocarbon material is carbonatoms >=10.
Further, control the condensing temperature of reactor effluent between 150-200 ℃, by the control to condensing temperature, can obtain needed carbonatoms >=10 heavy hydrocarbon materials, also can adjust the condensation number of heavy hydrocarbon material simultaneously.
The synthetic method of fixed bed Fischer-Tropsch of the present invention can be selected fixed-bed reactor commonly used, also can adopt the fixed-bed reactor with following structure to carry out Fischer-Tropsch synthesis:
A kind of fixed-bed reactor synthetic for Fischer-Tropsch comprise: housing and be arranged on spray equipment, upper tubesheet, lower tubesheet, reaction tubes, spiral coil cooling tube, the porous plate in this housing, wherein,
Be filled with catalyzer in described reaction tubes;
Described housing is connected with described upper tubesheet, lower tubesheet, and described upper tubesheet and described lower tubesheet are provided with through hole;
Described reaction tubes is vertically installed between described upper tubesheet and lower tubesheet, and the two ends of described reaction tubes are connected with described through hole is airtight respectively;
Described spray equipment is arranged at described upper tubesheet top, and is connected with the phlegma entrance;
Described spiral coil cooling tube is arranged between described lower tubesheet and described porous plate;
Described porous plate below is formed with phlegma and accumulates district.
In above-mentioned fixed-bed reactor, described housing top and bottom are respectively arranged with unstripped gas entrance and condensate outlet; Housing sidewall at the described spiral coil cooling tube of correspondence is provided with heat-eliminating medium entrance, heat-eliminating medium outlet; Housing sidewall at the described reaction tubes of correspondence is provided with heat-eliminating medium entrance and heat-eliminating medium outlet; The housing sidewall of accumulating district at the described phlegma of correspondence is provided with liquidometer and syngas outlet
In above-mentioned fixed-bed reactor, be equipped with successively the ceramic fire resistant ball that particle diameter is respectively Φ 25mm and Φ 50mm below described spiral coil cooling tube.
Than prior art, the present invention has following beneficial effect:
1, fixed bed Fischer-Tropsch synthesis method of the present invention, heavy hydrocarbon material cycle in the Fischer-Tropsch synthesis product is used in the temperature of beds is controlled, solved in the prior art and caused the sharply decline of fixed bed fischer-tropsch reactor reaction bed temperature due to a large amount of evaporations of benzoline, the problem that may cause fischer-tropsch reaction to stop.
2, fixed bed Fischer-Tropsch synthesis method of the present invention, to condensation, the separation of heavy hydrocarbons, and with the mixing of unstripped gas, all can be integrated in cobalt-based fixed bed Fischer-Tropsch synthesis device, effectively reduce the number of devices used in building-up process, also simplified operating process simultaneously.
The accompanying drawing explanation
The fixed bed Fischer-Tropsch synthesis method schema that Fig. 1 is the embodiment of the present invention 1.
The fixed bed Fischer-Tropsch synthesis method schema that Fig. 2 is the embodiment of the present invention 2.
Embodiment
For making the purpose, technical solutions and advantages of the present invention clearer, in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described, obviously, described embodiment is the present invention's part embodiment, rather than whole embodiment.Embodiment based in the present invention, those of ordinary skills, not making under the creative work prerequisite the every other embodiment obtained, belong to the scope of protection of the invention.
Embodiment 1
The fixed bed Fischer-Tropsch synthesis method schema that Fig. 1 is embodiment 1, idiographic flow is as follows:
Shown in Fig. 1, unstripped gas (H
2/ CO) 1 with isolated heavy hydrocarbon material 8 after mixing tank 2 mixes, the mixture 3 be mixed to get is sent into to fixed bed fischer-tropsch reactor 4, carry out Fischer-Tropsch synthesis under the effect of Co based Fischer-Tropsch synthesis catalyst, wherein, the condition of controlling Fischer-Tropsch synthesis is: working pressure 5.0MPa, 200 ℃ of temperature of reaction;
After reaction, the effluent 5 of fixed bed fischer-tropsch reactor 4 bottoms enters condenser 6, is to carry out condensation under 150-200 ℃ in condensing temperature, then isolates through condensed heavy hydrocarbon material 8 by separator 7, and uncooled effluent 10 is sent to subsequent processing;
Will be by condenser 6 with separator 7 condensations, separate the heavy hydrocarbon material 8 that obtains and send back in mixing tank 2 and unstripped gas (H through recycle pump 9
2And CO), after 1 mixing, send into fixed bed fischer-tropsch reactor 4 and further participate in Fischer-Tropsch synthesis.
The fixed bed Fischer-Tropsch synthesis method schema that Fig. 2 is embodiment 2, idiographic flow is as follows:
Shown in Fig. 2, the present embodiment discloses a kind of fixed-bed reactor synthetic for Fischer-Tropsch, comprise: housing 2 and be arranged on spray equipment 1, upper tubesheet 5, lower tubesheet 5, reaction tubes 3, spiral coil cooling tube 6, the porous plate 8 in this housing wherein, is filled with catalyzer 4 in described reaction tubes 3; Described housing 2 is connected with described upper tubesheet 5, lower tubesheet 5, and described upper tubesheet 5 is provided with through hole with lower tubesheet 5; Described reaction tubes 3 is vertically installed between described upper tubesheet 5 and lower tubesheet 5, and the two ends of described reaction tubes 3 are connected with described through hole is airtight respectively; Described spray equipment 1 is arranged at described upper tubesheet 5 tops, and is connected with phlegma entrance N4; Described spiral coil cooling tube 6 is arranged between described lower tubesheet 5 and described porous plate 8; Described porous plate 8 belows are formed with phlegma and accumulate district.
In the present embodiment, described housing 2 tops and bottom are respectively arranged with unstripped gas entrance N1 and condensate outlet N3; Housing 2 sidewalls at the described spray equipment 1 of correspondence are provided with manhole M1; Housing 2 sidewalls at the described spiral coil cooling tube 6 of correspondence are provided with heat-eliminating medium entrance N5, heat-eliminating medium outlet N6 and manhole M2; Housing 2 sidewalls at the described reaction tubes 3 of correspondence are provided with feedwater entrance N7 and vapour-water mixed liquid outlet N8; Housing 2 sidewalls that accumulate district at the described phlegma of correspondence are provided with liquidometer 9 and syngas outlet N2.
In the present embodiment, be equipped with successively the ceramic fire resistant ball 7 that particle diameter is respectively Φ 25mm and Φ 50mm below described spiral coil cooling tube 6.The refractory ball that to be laid on the upper strata particle diameter be Φ 25mm is in order to prevent that catalyzer from falling in the refractory ball layer, be laid on lower floor's particle diameter that the refractory ball that is Φ 50mm is in order to reduce the gas flow resistance.
Adopting the present embodiment is example for the synthetic fixed-bed reactor of Fischer-Tropsch, shown in Fig. 2, illustrate above-mentioned for Fischer-Tropsch the using method of synthetic fixed-bed reactor:
Unstripped gas (CO, H
2) enter the upper space of housing 2 from the unstripped gas entrance N1 on housing 2 tops, and enter with the phlegma from housing 2 bottoms the reaction tubes 3 that catalyzer 4 is housed by spray equipment 1 after the upper space of housing 2 mixes, and carry out Fischer-Tropsch synthesis under the effect of catalyzer 4.
Through reacted Fischer-Tropsch synthetic gas, from the lower end of reaction tubes 3, flow out, carry out partial condensation through spiral coil cooling tube 6, synthetic gas with partial condensation liquid flows out from the hole of porous plate 8 through ceramic fire resistant ball 7, phlegma below porous plate 8 accumulates district and carries out gas-liquid separation, the phlegma of separating flows out from the condensate outlet N3 of the lower end of reactor, send the spray equipment 1 on housing 2 tops back to for recycling through high-pressure pump again, can play elimination " focus ", the effect of conditioned reaction pipe temperature.Uncooled gas accumulates the syngas outlet N2 outflow of housing 2 sidewalls in district from the described phlegma of correspondence, carry out the processing of next step operation.The liquid level of phlegma can be controlled its height by observing liquidometer 9, can play sealing function, prevents the bottom N3 effusion of uncooled Fischer-Tropsch synthesis gas from housing 2.
Be full of the feedwater from drum between the pipe of reaction tubes 3, its feedwater enters from the feedwater entrance N7 of housing 2 sidewalls of the described reaction tubes 3 of correspondence, when taking away Fischer-Tropsch synthesis heat, a feedwater part is vaporized, and steam-water mixture flows out from the vapour of housing 2 sidewalls of the described reaction tubes 3 of correspondence-water mixed liquid outlet N8.
Finally it should be noted that: above embodiment only, in order to technical scheme of the present invention to be described, is not intended to limit; Although with reference to previous embodiment, the present invention is had been described in detail, those of ordinary skill in the art is to be understood that: its technical scheme that still can put down in writing aforementioned each embodiment is modified, or part technical characterictic wherein is equal to replacement; And these modifications or replacement do not make the essence of appropriate technical solution break away from the spirit and scope of various embodiments of the present invention technical scheme.
Claims (4)
1. a fixed bed Fischer-Tropsch synthesis method, is characterized in that, comprising:
Unstripped gas is sent into to the fixed bed fischer-tropsch reactor, carry out Fischer-Tropsch synthesis under the effect of Co based Fischer-Tropsch synthesis catalyst;
The heavy hydrocarbon material that reactor effluent is obtained after condensation, separation further participates in Fischer-Tropsch synthesis after mixing in the Fischer-Tropsch synthesis device with described unstripped gas.
2. fixed bed Fischer-Tropsch synthesis method according to claim 1, is characterized in that, the condition of controlling fischer-tropsch reaction is: working pressure 1.0-8.0MPa; Temperature of reaction 150-300 ℃.
3. fixed bed Fischer-Tropsch synthesis method according to claim 1, is characterized in that, the hydrocarbons that described heavy hydrocarbon material is carbonatoms >=10.
4. fixed bed Fischer-Tropsch synthesis method according to claim 1, is characterized in that, controls the condensing temperature of reactor effluent between 150-200 ℃.
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| CN2013103118941A CN103421530A (en) | 2013-07-23 | 2013-07-23 | Fischer tropsch synthesis method adopting fixed bed |
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| CN2013103118941A CN103421530A (en) | 2013-07-23 | 2013-07-23 | Fischer tropsch synthesis method adopting fixed bed |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105498643A (en) * | 2016-01-12 | 2016-04-20 | 天津市鹏翔科技有限公司 | Efficient forced circulating tube type fluidization reaction device |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6486220B1 (en) * | 1999-11-17 | 2002-11-26 | Conoco Inc. | Regeneration procedure for Fischer-Tropsch catalyst |
| CN101747127A (en) * | 2008-12-18 | 2010-06-23 | 中国石油化工股份有限公司 | Fischer-Tropsch synthesis method for fixed bed |
| CN101928194A (en) * | 2009-06-18 | 2010-12-29 | 中国石油化工股份有限公司 | Tropsch synthesis method of fixed bed |
-
2013
- 2013-07-23 CN CN2013103118941A patent/CN103421530A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6486220B1 (en) * | 1999-11-17 | 2002-11-26 | Conoco Inc. | Regeneration procedure for Fischer-Tropsch catalyst |
| CN101747127A (en) * | 2008-12-18 | 2010-06-23 | 中国石油化工股份有限公司 | Fischer-Tropsch synthesis method for fixed bed |
| CN101928194A (en) * | 2009-06-18 | 2010-12-29 | 中国石油化工股份有限公司 | Tropsch synthesis method of fixed bed |
Non-Patent Citations (1)
| Title |
|---|
| 孙启文: "《煤炭间接液化》", 30 September 2012 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105498643A (en) * | 2016-01-12 | 2016-04-20 | 天津市鹏翔科技有限公司 | Efficient forced circulating tube type fluidization reaction device |
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Application publication date: 20131204 |