CN102863306B - Slurry bed ft synthesis method - Google Patents

Slurry bed ft synthesis method Download PDF

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Publication number
CN102863306B
CN102863306B CN201110184012.0A CN201110184012A CN102863306B CN 102863306 B CN102863306 B CN 102863306B CN 201110184012 A CN201110184012 A CN 201110184012A CN 102863306 B CN102863306 B CN 102863306B
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fischer
reaction
catalyst
tropsch
synthesis
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CN102863306A (en
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李�杰
袁长富
张舒冬
宋喜军
张喜文
倪向前
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/40—Ethylene production

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  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention relates to a slurry bed ft synthesis method, which is characterized in that a proper amount of a reduced ft synthesis catalyst and a reaction solvent are weighted and placed in a slurry bed reactor, after airtight and gas displacement, the temperature and pressure are increased to reach the ft synthesis reaction condition, the synthesis catalyst and the reaction solvent are sealed and stirred for 1-5 hours and then synthetic gas is switched for the ft synthesis reaction, and the reaction solvent comprises 1-5% of water or an oxygen-containing organic matter by weight. The oxygen-containing organic matter comprises one or more of methanol, ethanol, propanol, ethylene oxide, acetone and epoxypropane. The ft synthesis reaction condition is characterized in that the reaction pressure is 1.5-2.2 MPa, the reaction temperature is 180-230 DEG C, and the volume air speed of the synthetic gas is 500-2500h<-1>. The method is used for keeping the high activity during the stable period of a cobalt-based Fischer-Tropasch synthetic catalyst, and reducing the initial activity of the catalyst.

Description

A kind of method for synthesizing Fischer Tropsch of slurry bed
Technical field
The present invention relates to a kind of method for synthesizing Fischer Tropsch of slurry bed.
Background technology
F-T synthesis refers to synthetic gas (CO+H 2) catalyze and synthesize the reaction of liquid hydrocarbon fuel on a catalyst.Along with the exhaustion day by day of petroleum resources, prepare with Fischer-Tropsch synthesis the attention that liquid fuel receives countries in the world more.
Technique for F-T synthesis successively has fixed-bed process, Circulating Fluidized Bed Process, fixed fluidized bed technique and slurry bed system technique.Fixed-bed reactor have the shortcomings such as focus, blocking and throughput are low, and the fluid mapper process of circulating fluidized bed is restive, the low serious wear of catalyst utilization, and throughput is still on the low side.Fixed fluidized bed is the improved form of circulating fluidized bed, and not only structure simply easily operates, also solves the problem of the low and wearing and tearing of catalyst utilization, and throughput improves greatly.The development of natural gas liquefaction facilitates the development of paste state bed reactor, and particularly in recent years, syrup state bed Fischer Tropsch synthetic technology is greatly developed.
It is mostly catalyzer after the outer prereduction of device that syrup state bed Fischer Tropsch synthesizes catalyzer used, if this is because syrup state bed Fischer Tropsch synthesis technique carries out reducing in device in the process gone into operation, due to the existence of reaction solvent, affect the mass transfer of hydrogen, cause the reduction effect of catalyzer often not reach the requirement of use.
The reduction process of typical catalyzer is in the presence of hydrogen gas, and oxidation state precursor is activated by the high temperature reduction of hydrogen.In order to the activity pursuing reduction effect and then raising catalyzer is main purpose in the process of reduction.The disclosed method by reducing/oxidizing/reduction cyclic activation cobalt catalyst of US4492774, US4585798, US4088671, US4670414 and EP0253924, can improve the activity of F-T building-up reactions.All oxidation/reduction/the oxidations described in above-mentioned patent or reducing/oxidizing/reduction circulation use oxygen-containing gas at high temperature process solid catalyst and carry out mostly, may cause the oxide compound such as Co forming most stable 3o 4generation, reduce active ingredient content in the catalyst, in addition, also want the exothermicity of strict controlled oxidization reaction also to guarantee water partial pressure low between reduction period in order to avoid the sintering of cobalt.
European patent EP 0533228 discloses a kind of Co/Zr/Al 2o 3(SiO 2or TiO 2) method of reducing of catalyzer.Be specially under pressure is the condition of 1-10mbar and temperature 100 ~ 350 DEG C, with hydrogen-containing gas (0 ~ 70%H 2/ rare gas element, V/V) reducing catalyst, H in hydrogen-containing gas during reduction 2concentration and air speed progressively or increase continuously to ensure H 2the dividing potential drop of O is lower than 200mbar.
For F-T synthesis load type cobalt-base catalyst, although the activity of catalyzer can be improved by different method of reducing, but inevitably in the process of an initial reaction stage ubiquity rapid catalyst deactivation, then reach active stabilization period, the higher initial activity of activity is also high often.Fischer-Tropsch synthesis reaction pressure is within the scope of 0.5-4MPa, and pressure increase is favourable to F-T synthesis, so the reaction pressure adopted is mostly at more than 2.0MPa, and the pressure of system relies on the dividing potential drop of synthetic gas to maintain mostly, the rapid deactivation at the activity that catalyzer is too high in the early stage and initial stage, very disadvantageous to industrial operation, and the conversion of the synthetic gas that the initial stage is too high, cause a large amount of generations of product water, and be difficult to be pulled away rapidly, thus cause the increase of system water partial pressure, accelerate the inactivation of catalyzer.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of method for synthesizing Fischer Tropsch of slurry bed.Adopt the method can reduce the initial activity of catalyzer while keeping Co based Fischer-Tropsch synthesis catalyst high-activity stable stationary phase.
A kind of method for synthesizing Fischer Tropsch of slurry bed, take the fischer-tropsch synthetic catalyst after appropriate reduction and reaction solvent puts into paste state bed reactor, after airtight and hydrogen exchange, increasing temperature and pressure is to Fischer-Tropsch synthesis condition, after 1-5h is stirred in sealing, switching and merging gas carries out Fischer-Tropsch synthesis, and described reaction solvent by weight content meter contains water or the oxygen-bearing organic matter of 1-5%.
Oxygen-bearing organic matter described in the inventive method comprises one or more in methyl alcohol, ethanol, propyl alcohol, oxyethane, acetone, propylene oxide, particular methanol.
Fischer-Tropsch synthesis condition described in the inventive method is H in synthetic gas 2the mol ratio of/CO is 1.0 ~ 4.0; Temperature of reaction is 180 ~ 350 DEG C, and reaction pressure is 0.5 ~ 10MPa, and the volume space velocity of synthetic gas is 500 ~ 5000h -1, stirring velocity is 500-1200r/min.
Reaction solvent described in the inventive method is paraffin, and the volume ratio of paraffin and fischer-tropsch synthetic catalyst is 4-5.
Fischer-tropsch synthetic catalyst described in the inventive method is the fischer-tropsch synthetic catalyst after reduction of this area routine.Preferred fischer-tropsch synthetic catalyst is take Co as active ingredient, with one or more in Zr, Hf, Ce and Th, Pt, Ru, Ni, Mo and W for auxiliary agent, with ZrO 2, TiO 2, SiO 2and Al 2o 3one or more are mixed into carrier.
Compared with prior art, a kind of method for synthesizing Fischer Tropsch of slurry bed tool of the present invention has the following advantages:
1, in Fischer-Tropsch synthesis process, the initial activity of catalyzer is high, easily cause the fluctuation of the reaction conditions such as temperature, pressure, make reaction restive, sintering of catalyst even can be made to lose activity, the inventive method adds a small amount of weak oxidant (water or oxygen-bearing organic matter) in reaction solvent, can reduce the initial activity of catalyzer, and reaction process is steadily carried out;
2, the inventive method water or oxygen-bearing organic matter in temperature-rise period becomes steam, whole system is made to have certain steam partial pressure or oxygen-bearing organic matter partial vapor pressure, to the oxide treatment that catalyzer relaxes, simultaneously due to the existence of hydrogen, only reduce the initial activity of catalyzer, can not have an impact to other performance of catalyzer, and be easy to separate from reaction system;
3, the inventive method is before carrying out Fischer-Tropsch synthesis, the mixed air containing water vapor or oxygen-bearing organic matter steam and hydrogen is passed in paste state bed reactor, particularly under the condition passing into water vapour, reaction system can be impelled to carry out hydro-thermal reaction, that suppresses in Fischer-Tropsch synthesis process is hydrothermal, improve the stability of catalyzer, reduce the selectivity of methane.
Embodiment
Process and the effect of the inventive method is further illustrated below in conjunction with embodiment.
Example 1
Take the 20%Co0.8%Pt3%Zr/SiO after appropriate reduction 2(Wt.) fischer-tropsch synthetic catalyst and paraffin, containing massfraction in paraffin is the water of 2.5%, and catalyzer and paraffin volume ratio are 1:4, put into paste state bed reactor, after airtight and hydrogen exchange, increasing temperature and pressure to 220 DEG C, 2.0 MPa, 800r/min sealing switch H after stirring 2.5h 2/ CO=2(mol ratio) synthetic gas carry out Fischer-Tropsch synthesis, synthetic gas volume space velocity is 1500h -1.Reaction effluent is collected by hot trap, cold-trap respectively.The transformation efficiency of catalyzer, the results are shown in Table 1 for methane selectively and stability test.
Example 2
Take the 20%Co1%Ni3%Zr/TiO after appropriate reduction 2(Wt.) fischer-tropsch synthetic catalyst and paraffin, containing massfraction in paraffin is the acetone of 1%, and catalyzer and paraffin volume ratio are 1:5, put into paste state bed reactor, after airtight and hydrogen exchange, increasing temperature and pressure to 240 DEG C, 2.5 MPa, 600r/min sealing switch H after stirring 1h 2/ CO=2(mol ratio) synthetic gas carry out Fischer-Tropsch synthesis, synthetic gas volume space velocity is 2000h -1.Reaction effluent is collected by hot trap, cold-trap respectively.The transformation efficiency of catalyzer, the results are shown in Table 1 for methane selectively and stability test.
Example 3
Take the 20%Co0.05%Ru3%Zr/Al after appropriate reduction 2o 3(Wt.) fischer-tropsch synthetic catalyst and paraffin, containing massfraction in paraffin is the methyl alcohol of 5%, and catalyzer and paraffin volume ratio are 1:5, put into paste state bed reactor, after airtight and hydrogen exchange, increasing temperature and pressure to 220 DEG C, 2.0 MPa, 800r/min sealing switch H after stirring 5h 2/ CO=2(mol ratio) synthetic gas carry out Fischer-Tropsch synthesis, synthetic gas volume space velocity is 1500h -1.。Reaction effluent is collected by hot trap, cold-trap respectively.The transformation efficiency of catalyzer, the results are shown in Table 1 for methane selectively and stability test.
The reactivity worth of table 1 catalyzer.
Catalyzer Initial activity and selectivity, CO transformation efficiency (%) Initial activity and selectivity, CH 4Selectivity (wt%) 100h, CO transformation efficiency (%) 100h ,CH 4Selectivity (wt%) 200h, CO transformation efficiency (%) 200h ,CH 4Selectivity (wt%)
Embodiment 1 75.5 7.5 69.8 8.5 67.8 9.5
Embodiment 2 79.2 7.2 70.5 8.2 68.5 9.8
Embodiment 3 72.6 7.7 67.7 8.7 65.7 9.1
Comparative example 86.4 8.1 66.3 9.8 64.2 10.2
Comparative example:
Take the 20%Co0.05%Ru3%Zr/Al after appropriate reduction 2o 3(Wt.) fischer-tropsch synthetic catalyst and paraffin, catalyzer and paraffin volume ratio are 1:5, put into paste state bed reactor, pass into hydrogen and open whipping appts after airtight and gas displacement in reactor, be warming up to 220 DEG C, control pressure is 2.0 MPa, switch H 2/ CO=2(mol ratio) synthetic gas carry out Fischer-Tropsch synthesis, synthetic gas volume space velocity is 1500h -1, stirring velocity is 800r/min.Reaction effluent is collected by hot trap, cold-trap respectively.The transformation efficiency of catalyzer, the results are shown in Table 1 for methane selectively and stability test.

Claims (4)

1. a method for synthesizing Fischer Tropsch of slurry bed, it is characterized in that: take the fischer-tropsch synthetic catalyst after reduction and reaction solvent puts into paste state bed reactor, increasing temperature and pressure to 180 ~ 350 DEG C, 0.5 ~ 10MPa after airtight and hydrogen exchange, after 1-5h is stirred in sealing, switching and merging gas carries out Fischer-Tropsch synthesis, described reaction solvent by weight content meter contains the oxygen-bearing organic matter of 1-5%, and described oxygen-bearing organic matter is one or more in methyl alcohol, ethanol, propyl alcohol, oxyethane, acetone, propylene oxide.
2. method according to claim 1, is characterized in that: Fischer-Tropsch synthesis condition is H in synthetic gas 2the mol ratio of/CO is 1.0 ~ 4.0; Temperature of reaction is 180 ~ 350 DEG C, and reaction pressure is 0.5 ~ 10MPa, and the volume space velocity of synthetic gas is 500 ~ 5000h -1.
3. method according to claim 1, is characterized in that: described reaction solvent is paraffin, and the volume ratio of paraffin and fischer-tropsch synthetic catalyst is 4:1-5:1.
4. method according to claim 1, is characterized in that: described fischer-tropsch synthetic catalyst for being active ingredient with Co, with one or more in Zr, Hf, Ce, Th, Pt, Ru, Ni, Mo, W for auxiliary agent, with ZrO 2, TiO 2, SiO 2, Al 2o 3in one or more be mixed into the Co based Fischer-Tropsch synthesis catalyst of carrier.
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JP6774411B2 (en) * 2014-12-12 2020-10-21 ビーピー ピー・エル・シー・ Fischer-Tropsch method using a reduction-activated cobalt catalyst
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CN1121259C (en) * 1997-10-07 2003-09-17 萨索尔技术(控股)有限公司 Process for producing liquid and, optionally, gaseous products from gaseous reactants

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CN1121259C (en) * 1997-10-07 2003-09-17 萨索尔技术(控股)有限公司 Process for producing liquid and, optionally, gaseous products from gaseous reactants

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