CN101586036A - Method for preparing liquid olefin hydrocarbon by supercritical phase Fischer-Tropsch synthesis reaction - Google Patents
Method for preparing liquid olefin hydrocarbon by supercritical phase Fischer-Tropsch synthesis reaction Download PDFInfo
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- CN101586036A CN101586036A CNA2009100881963A CN200910088196A CN101586036A CN 101586036 A CN101586036 A CN 101586036A CN A2009100881963 A CNA2009100881963 A CN A2009100881963A CN 200910088196 A CN200910088196 A CN 200910088196A CN 101586036 A CN101586036 A CN 101586036A
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Abstract
The present invention provides a method for preparing liquid olefin hydrocarbon by supercritical phase Fischer-Tropsch synthesis reaction, the supercritical dissolvent and synthesis gas are together inputted into a Fischer-Tropsch synthesis reactor, the Fischer-Tropsch synthesis reaction can be performed under the supercritical state of the supercritical dissolvent using the advantage of the fast heat transferring of the supercritical fluid. The method overcomes the local overheating of the catalyst bed layer, prevents the carbon deposit of the catalyst, prolongs the service life of the catalyst. The conversion rate of CO of liquid state olefin hydrocarbon prepared by the invention can reach up to more than 90.72 %, the highest selectivity of the liquid phase product yield can reach up to 97.37 %, the content of the gaseous product yield is low about 2.63-23.47 %, wherein, the amounts of CO2 and CH4 are 0.39-10.21 % and 0.6-9.32 %. Moreover, the reaction temperature is reduced, the energy consumption is economized and the production cost is reduced because of the adding of supercritical dissolvent.
Description
Technical field
The invention provides a kind of technology that supercutical fluid is applied to Fischer-Tropsch synthesis.This technology is mainly used in synthetic gas CO+H
2Directly transform the high-quality clean fuel of system.
Background technology
Preparing in the method for clean fuel at present, can be divided into two big classes generally: the one, petroleum path; The 2nd, non-petroleum path.Since twice oil crisis of the outburst seventies in 20th century, countries in the world are devoted to research and develop the route of non-oil resource synthesis clean fuel one after another, and have obtained some great progress.
Nineteen twenty-three, F.Fischer and H.Tropsch have found with CO and H
2The method of mixture synthin product, and first under the condition of 150 normal atmosphere and 400 ℃-500 ℃, with cobalt catalyst with CO+H
2Conversion obtains the compound of carbon containing, hydrogen, oxygen.People call Fischer-Tropsch synthetic (it is synthetic to be called for short F-T) to this reaction:
The F-T synthetic is found to be and coal is converted into liquid hydrocarbon fuels a feasible approach is provided.It has abundant in coal and natural gas source for those and to lack the country of oil especially attractive.Especially twice oil crisis at the beginning of the seventies impels each major industrial country to greatly develop the research that non-oil resource is produced synthetic gasoline and chemical, develops competitive new synthetic technology, makes the synthetic research focus that becomes once more of F-T.
Among the patent CN101186550, under the Fischer-Tropsch synthesis condition, the synthetic product utilization cold high pressure separator that generates of Fischer-Tropsch progressively separates, and isolated unreacted unstripped gas recycles.This technical process is complicated, and cost is higher, and energy consumption is bigger.
Tang Haodong; Liu Huazhang; Lv Deyi; Yang Xiazhen. fused iron catalyst supercritical phase Fischer-Tropsch synthetic research .[J]. colleges and universities' chemical engineering journal; 2008; 22 (2); among the 259-264; in fixed-bed reactor, studied the Fischer-Tropsch synthesis on the fused iron catalyst under the supercritical phase condition; discovery is reactant and the easier diffusion of product in supercritical medium, has suppressed the deposition of catalyst surface carbon non-activated preferably, thereby has improved CO transformation efficiency and the olefine selective in the Fischer-Tropsch synthesis; increase the chainpropagation factor, reduced methane selectively.
Summary of the invention
The purpose of this invention is to provide the technology that a kind of F-T building-up reactions that supercritical solvent is applied to prepares liquefied olefines.
General fischer-tropsch synthesizes in gas phase or liquid phase and carries out, because this building-up reactions is a strong exothermal reaction, though higher speed of reaction and rate of diffusion are arranged in the gas phase fixed bed reaction, beds can produce local superheating, cause methane selectively to increase catalyst deactivation.Though in liquid phase reaction, there is not the bed local superheating, but owing to be subjected to mass transfer limit, the wax in the product is filled in the catalyzer micropore easily, increases the probability of catalyst carbon deposit, on de-waxing and wax and catalyst separating, also have certain difficulty, and its speed of reaction is also low than gas-phase reaction.
Supercutical fluid be a kind of temperature and pressure be in stagnation point above, do not have liquid-gas interface and have the material phase of liquids and gases character concurrently, this fluid has the advantage of liquids and gases concurrently: viscosity is little, spread coefficient is big, density is big, have good dissolution characteristics and mass transfer, heat transfer characteristic, and responsive especially to temperature and pressure near stagnation point.Studies show that the Fischer-Tropsch under the super critical condition synthesizes many features: (1) reduces the product content of methane and carbonic acid gas; (2) because supercutical fluid has good dissolution characteristics, dissolving that can be very fast, the product that extraction surface gathers prevent carbon deposit; (3) diffusibility of product in the increase catalyzer aperture.
It is as follows that hydrocarbon by supercritical phase Fischer-Tropsch synthesis reaction prepares the clean fuel concrete steps;
A. in reactor, add the synthetic carrier free cobalt-base catalyst of Fischer-Tropsch;
B. reducing gas and supercritical solvent are fed in the described reactor of steps A, purge catalyzer 10～30min with reducing gas at normal temperatures earlier; Being warming up to 260 ℃～400 ℃, pressure again is that 6～8Mpa continued logical reducing gas reducing catalyst 2～24 hours;
C. reducing gas is switched to synthetic gas, be warmed up to the supercritical state of supercritical solvent, reacted 5 hours, collect through condenser and obtain liquid product.
The described catalyzer of steps A is Co/SiO
2, Co/SBA-15 or Co/Mn carrier free cobalt-base catalyst; More preferably the Co/Mn mol ratio is 2.0 carrier free cobalt-base catalyst.
The described reactor of step B is a reactor.Described reducing gas is CO, H
2Mixed gas with arbitrary proportion.Described supercritical state is 200～400 ℃ according to its supercritical temperature of different supercritical solvents, and pressure is 3.0～10.0MPa.Described supercritical solvent is butane, pentane, hexane, heptane, octane, nonane, decane, methyl alcohol, ethanol, benzene,toluene,xylene, CO
2Or in the nitrogen 1～2 kind.Preferably Skellysolve A, normal hexane, normal heptane, octane, positive nonane, n-decane or CO
2In 1～2 kind, more preferably normal hexane and CO
2Mixture.The add-on of supercritical solvent is decided according to the volume of reactor, is benchmark so that reaction can reach the supercritical temperature and the pressure of this solvent.
Synthetic gas described in the step C is H
2With the volume ratio of CO be 1～3 mixed gas.
In step C reaction process, gathered a product, and analyze, investigate the stability of catalyst activity in each time period every 1～2 hour.When reaction finishes gas-phase product is taken a sample through gas chromatographic analysis, by analyzing CO content wherein, the transformation efficiency that calculates CO is more than 90.72%; CO in the gas-phase product
2And CH
4Content is respectively 0.39～10.21% and 0.6～9.32%.Liquid product is measured each content and gross weight of forming of liquid product through gas-chromatography workstation off-line analysis.The liquid product selectivity reaches as high as 97.37%.
The invention has the beneficial effects as follows:
1. the present invention utilizes the good mass-and heat-transfer performance of supercutical fluid, reduced the growing amount of methane and carbonic acid gas in the F-T synthetic reaction process significantly, reduced the carbon distribution phenomenon of catalyzer, accelerated separating of catalyzer and macromole product, prolong the work-ing life of catalyzer, reduced the cost of F-T building-up reactions.
2. the transformation efficiency of CO of the present invention can reach more than 90.72%, and the selectivity of liquid product reaches as high as 97.37%, and the content of gaseous product is low to be about 2.63～23.47%, wherein CO
2And CH
4Amount still less, be respectively 0.39～10.21% and 0.6～9.32%.
3. the application of the supercutical fluid that the present invention relates in the F-T building-up reactions, on original single supercritical solvent basis, add the lower solubility promoter of supercritical temperature, the temperature of whole reaction system is reduced, save energy so on the one hand, the reduction owing to temperature has also suppressed CH on the other hand
4Generation.
Embodiment
Embodiment 1
Get 1g Co/Mn=2.0 carrier free Co based Fischer-Tropsch synthesis catalyst and put into reactor, and add the 35ml normal hexane,, use H under the 7MPa at 340 ℃
2Reduction 6h feeds synthetic gas then, and reaction pressure is 4.5Mpa, and temperature of reaction is 240 ℃, reacts 5 hours.Gas-phase product is through gas-chromatography workstation sampling analysis, and liquid product is collected through condenser, through gas-chromatography workstation off-line analysis.CO transformation efficiency 94.30%, gas-phase product content is 2.63% in the resultant, wherein CO
2Be 0.42%, CH
4Be 0.60%, C
2Be 1.23%, C
3Be 0.72%, C
4Be 1.40%; Liquid product content is 97.37%, wherein C
5～C
10Be 50.17%, C
11 +Be 47.20%.
Embodiment 2
Get 1g Co/Mn=2.0 carrier free Co based Fischer-Tropsch synthesis catalyst and put into reactor, and add the 35ml Skellysolve A,, use H under the 7MPa at 350 ℃
2Reduction 6h, drop to normal temperature, switch to synthetic gas then, reaction pressure is 5Mpa, temperature of reaction is 200 ℃, gas-phase product is through gas-chromatography workstation sampling analysis, and liquid product is collected through condenser, through gas-chromatography workstation off-line analysis, reaction was through 5 hours, CO transformation efficiency 93.11%, gas-phase product content is 5.62% in the resultant, wherein CO
2Be 0.39%, CH
4Be 0.61%, C
2Be 1.56%, C
3Be 1.36%, C
4Be 1.70%; Liquid product content is 94.38%, wherein C
5～C
10Be 49.48%, C
11 +Be 44.90%.
Embodiment 3
Get 1g Co/Mn=2.0 carrier free Co based Fischer-Tropsch synthesis catalyst and put into reactor, and add the 35ml normal heptane,, use H under the 7MPa at 350 ℃
2Reduction 6h drops to normal temperature, switches to synthetic gas, and reaction pressure is 4.1Mpa, and temperature of reaction is 280 ℃, and gas-phase product is through gas-chromatography workstation sampling analysis, and liquid product is collected through condenser, through gas-chromatography workstation off-line analysis.Reaction is through 5 hours, CO transformation efficiency 94.75%, and gas-phase product content is 11.92% in the resultant, wherein CO
2Be 4.21%, CH
4Be 3.99%, C
2Be 2.32%, C
3Be 0.88%, C
4Be 1.52%; Liquid product content is 88.08%, wherein C
5～C
10Be 46.77%, C
11+ be 41.30%.
Embodiment 4
Get 1g Co/Mn=2.0 carrier free Co based Fischer-Tropsch synthesis catalyst and put into reactor, and add the positive nonane of 35ml,, use H under the 7MPa at 350 ℃
2Reduction 6h drops to normal temperature, switches to synthetic gas, and reaction pressure is 3.9Mpa, temperature of reaction is 330 ℃, carries out 1,2,3.5 in reaction, gas-phase product is through gas-chromatography workstation sampling analysis in the time of 5 hours, and liquid product is collected through condenser, through gas-chromatography workstation off-line analysis.Reaction is through 5 hours, catalyst performance stabilised, and CO transformation efficiency 95.01%, gas-phase product content is 23.47% in the resultant, wherein CO
2Be 10.21%, CH
4Be 9.32%, C
2Be 1.16%, C
3Be 1.03%, C
4Be 1.79%; Liquid product content is 76.53%, wherein C
5～C
10Be 38.01%, C
11 +Be 38.52%.
Embodiment 5
Get 1gCo/Mn=2.0 carrier free Co based Fischer-Tropsch synthesis catalyst and put into reactor, and add the 35ml normal hexane,, use H under the 7MPa at 350 ℃
2Reduction 6h drops to normal temperature, switches to synthetic gas, and adds the CO of 0.5Mpa at normal temperatures
2As cosolvent, reaction pressure is 4.5Mpa, and temperature of reaction is 232 ℃, and gas-phase product is through gas-chromatography workstation sampling analysis, and liquid product is collected through condenser, through gas-chromatography workstation off-line analysis.Reaction is through 5 hours, catalyst performance stabilised, and CO transformation efficiency 92.78%, gas-phase product content is 15.00% in the resultant, wherein CO
2Be 2.4%, CH
4Be 2.18%, C
2～C
4Be 10.42%; Liquid product content is 85.00%, wherein C
5～C
10Be 23.39%, C
11 +Be 61.61%.
Embodiment 6
Get 1g Co/Mn=2.0 carrier free Co based Fischer-Tropsch synthesis catalyst and put into reactor, and add the 35ml normal hexane,, use H under the 7MPa at 350 ℃
2Reduction 6h drops to normal temperature, switches to synthetic gas, and adds the CO of 1.0Mpa at normal temperatures
2As cosolvent, reaction pressure is 5Mpa, and temperature of reaction is 220 ℃, and gas-phase product is through gas-chromatography workstation sampling analysis, and liquid product is collected through condenser, through gas-chromatography workstation off-line analysis.Reaction is through 5 hours, catalyst performance stabilised, and CO transformation efficiency 92.43%, gas-phase product content is 11.00% in the resultant, wherein CO
2Be 1.78%, CH
4Be 1.18%, C
2～C
4Be 8.04%; Liquid product content is 89.00%, wherein C
5～C
10Be 26.85%, C
11 +Be 62.15%.
Embodiment 7
Get 1g Co/SiO
2Catalyzer is put into reactor, and adds the 35ml normal hexane, at 350 ℃, uses H under the 7MPa
2Reduction 6h drops to normal temperature, switches to synthetic gas, and adds the CO of 1.0Mpa at normal temperatures
2As cosolvent, reaction pressure is 5Mpa, and temperature of reaction is 220 ℃, and gas-phase product is through gas-chromatography workstation sampling analysis, and liquid product is collected through condenser, through gas-chromatography workstation off-line analysis.Reaction is through 5 hours, catalyst performance stabilised, and CO transformation efficiency 90.33%, gas-phase product content is 18.00% in the resultant, wherein CO
2Be 2.93%, CH
4Be 2.19%, C
2～C
4Be 10.22%; Liquid product content is 82.00%, wherein C
5～C
10Be 40.22%, C
11 +Be 41.78%.
Embodiment 8
Get the 1gCo/SBA-15 catalyzer and put into reactor, and add the 35ml normal hexane,, use H under the 7MPa at 350 ℃
2Reduction 6h drops to normal temperature, switches to synthetic gas, and adds the CO of 1.0Mpa at normal temperatures
2As cosolvent, reaction pressure is 5Mpa, and temperature of reaction is 220 ℃, and gas-phase product is through gas-chromatography workstation sampling analysis, and liquid product is collected through condenser, through gas-chromatography workstation off-line analysis.Reaction is through 5 hours, catalyst performance stabilised, and CO transformation efficiency 90.72%, gas-phase product content is 15.24% in the resultant, wherein CO
2Be 1.99%, CH
4Be 3.48%, C
2～C
4Be 9.34%; Liquid product content is 84.76%, wherein C
5～C
10Be 48.13%, C
11 +Be 36.63%.
Claims (3)
1. the method for a preparing liquid olefin hydrocarbon by supercritical phase Fischer-Tropsch synthesis reaction, concrete steps are as follows:
A. in reactor, add the synthetic carrier free cobalt-base catalyst of Fischer-Tropsch;
B. reducing gas and supercritical solvent are fed in the described reactor of steps A, purge catalyzer 10～30min with reducing gas at normal temperatures earlier; Being warming up to 260 ℃～400 ℃, pressure again is that 6～8Mpa continued logical reducing gas reducing catalyst 2～24 hours;
Described supercritical solvent is butane, pentane, hexane, heptane, octane, nonane, decane, methyl alcohol, ethanol, benzene,toluene,xylene, CO
2Or in the nitrogen 1～2 kind; Described reducing gas is CO, H
2Mixed gas with arbitrary proportion; The add-on of supercritical solvent is decided according to the volume of reactor, is benchmark so that reaction can reach the supercritical temperature and the pressure of this solvent.
C. reducing gas being switched to synthetic gas, be warmed up to the supercritical state of supercritical solvent, is 200～400 ℃ in critical temperature, and pressure is that 3.0～10.0MPa reacted 5 hours down, collects through condenser and obtains liquid product.
2. the method for preparing liquid olefin hydrocarbon by supercritical phase Fischer-Tropsch synthesis reaction according to claim 1 is characterized in that:
Catalyzer described in the steps A is for being Co/SiO
2, Co/SBA-15 or Co/Mn carrier cobalt-base catalyst;
The described reactor of step B is a reactor; Described supercritical solvent is Skellysolve A, normal hexane, normal heptane, octane, positive nonane, n-decane or CO
2In 1～2 kind;
The described synthetic gas of step C is H
2With the volume ratio of CO be 1～3 mixed gas.
3. the method for preparing liquid olefin hydrocarbon by supercritical phase Fischer-Tropsch synthesis reaction according to claim 1 is characterized in that catalyzer described in the steps A is is that the Co/Mn mol ratio is 2.0 carrier free cobalt-base catalyst; The described supercritical solvent of step B is normal hexane and CO
2Mixture.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102174594A (en) * | 2011-03-16 | 2011-09-07 | 中国科学院广州能源研究所 | Efficient enzyme hydrolysis method of lignocellulose biomass |
| CN104312613A (en) * | 2014-11-10 | 2015-01-28 | 华玉叶 | Method for preparing liquid olefin by utilizing thermal high-pressure separator |
| CN105498798A (en) * | 2015-12-11 | 2016-04-20 | 中国科学院上海高等研究院 | Catalyst for directly converting synthesis gas into long-chain alkene by one-step method |
| CN105087042B (en) * | 2014-05-09 | 2018-04-13 | 中国石油化工股份有限公司 | A kind of method of F- T synthesis |
-
2009
- 2009-07-13 CN CNA2009100881963A patent/CN101586036A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102174594A (en) * | 2011-03-16 | 2011-09-07 | 中国科学院广州能源研究所 | Efficient enzyme hydrolysis method of lignocellulose biomass |
| CN105087042B (en) * | 2014-05-09 | 2018-04-13 | 中国石油化工股份有限公司 | A kind of method of F- T synthesis |
| CN104312613A (en) * | 2014-11-10 | 2015-01-28 | 华玉叶 | Method for preparing liquid olefin by utilizing thermal high-pressure separator |
| CN105498798A (en) * | 2015-12-11 | 2016-04-20 | 中国科学院上海高等研究院 | Catalyst for directly converting synthesis gas into long-chain alkene by one-step method |
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Application publication date: 20091125 |