CN106607058A - Iron-based catalyst for preparing low-carbon olefin directly from synthesis gas and preparation method of iron-based catalyst - Google Patents
Iron-based catalyst for preparing low-carbon olefin directly from synthesis gas and preparation method of iron-based catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 75
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 55
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 54
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 26
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title abstract description 43
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title abstract description 6
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 8
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 3
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims abstract description 3
- 239000002002 slurry Substances 0.000 claims description 88
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 52
- 239000007789 gas Substances 0.000 claims description 37
- 150000001336 alkenes Chemical class 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 18
- 238000010009 beating Methods 0.000 claims description 17
- 238000001935 peptisation Methods 0.000 claims description 17
- 239000002244 precipitate Substances 0.000 claims description 16
- 238000005245 sintering Methods 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 15
- 239000007921 spray Substances 0.000 claims description 6
- 239000002585 base Substances 0.000 claims description 4
- 238000007493 shaping process Methods 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- BCAARMUWIRURQS-UHFFFAOYSA-N dicalcium;oxocalcium;silicate Chemical compound [Ca+2].[Ca+2].[Ca]=O.[O-][Si]([O-])([O-])[O-] BCAARMUWIRURQS-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 239000003607 modifier Substances 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000004005 microsphere Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 18
- 239000000203 mixture Substances 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract 1
- 230000003068 static effect Effects 0.000 abstract 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 63
- 239000000243 solution Substances 0.000 description 58
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 46
- 229910021529 ammonia Inorganic materials 0.000 description 23
- 238000000034 method Methods 0.000 description 23
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 22
- 238000001556 precipitation Methods 0.000 description 20
- 239000012530 fluid Substances 0.000 description 18
- 239000010936 titanium Substances 0.000 description 18
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical class [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 15
- 238000005119 centrifugation Methods 0.000 description 13
- 239000000463 material Substances 0.000 description 13
- 238000004513 sizing Methods 0.000 description 13
- 238000001694 spray drying Methods 0.000 description 13
- 238000005507 spraying Methods 0.000 description 13
- 229910016874 Fe(NO3) Inorganic materials 0.000 description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 11
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 10
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical class Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 10
- 239000011259 mixed solution Substances 0.000 description 8
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 8
- 239000003921 oil Substances 0.000 description 7
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical class [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 description 7
- 239000013049 sediment Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 6
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 6
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical class [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000003245 coal Substances 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003034 coal gas Substances 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 230000003134 recirculating effect Effects 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000772415 Neovison vison Species 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- -1 ethylene, propylene Chemical group 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 235000003642 hunger Nutrition 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000037351 starvation Effects 0.000 description 1
- XIFFNSGJZPAYQJ-UHFFFAOYSA-N sulfuric acid;zirconium Chemical compound [Zr].OS(O)(=O)=O XIFFNSGJZPAYQJ-UHFFFAOYSA-N 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Classifications
-
- 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
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to an iron-based catalyst for preparing low-carbon olefin directly from synthesis gas and a preparation method for the iron-based catalyst, and mainly solves the problems in the prior art that Fischer-Tropsch synthesis reaction is strong exothermic reaction, so that when a static bed is used, heat removal is difficult and temperature runaway is easily caused in a reactor; the catalyst is easily inactivated; and the weight selectivity of the low-carbon olefin is low. The catalyst adopted in the invention comprises the following active components containing a composition with a chemical formula of Fe100AaBbOx in atomic ratio, wherein A is selected from one of Ti or Zr; and B is selected from one of alkali metals, so that the above problems are well solved. The iron-based catalyst can be applied to industrial production of preparing the low-carbon olefin directly from the synthesis gas.
Description
Technical field
The present invention relates to a kind of directly prepare catalyst of low-carbon alkene and preparation method thereof for synthesis gas
Background technology
The characteristics of China's energy is the few gas oil starvation of rich coal, the coal environmental pollution for causing of directly burning also is taken seriously increasingly, so exploitation is converted into the process of oil product by coal/natural gas ECDC into gas, can not only reduce to external dependence on the energy, and have great importance for the coal-fired problem of environmental pollution for causing is solved.
Using synthesis gas, (main component is CO and H2) Fischer-Tropsch (Fascher-Tropsch) building-up process of synthesis hydrocarbon in the presence of catalyst, it is an important channel of coal and natural gas indirect liquefaction.The method is to be invented by Germany scientist Frans Fischer and Hans Tropsch nineteen twenty-three, i.e. CO occurs heterogeneous catalysis hydrogenation on metallic catalyst, generates the process of the mixture based on linear paraffin and alkene.Germany has just carried out research and development in the twenties in last century, and realizes industrialization in 1936, closes because economically competing with petroleum industry after World War II；South Africa possesses abundant coal resources, but petroleum resources plaque is weary, and limited by international community's economy and political sanction for a long time, its development coal-to-oil industry technology is forced, and coal base F-T artificial oils factory (Sasol-1) that First production capacity is 25～400,000 tons of product/years has been built up in 1955.The world oil crisis twice of 1973 and 1979, cause world's crude oil price to fall and swing fluctuating, big rise and big fall, and based on the consideration that Strategic Technology is laid in, F-T synthetic technologys arouse the interest of industrialized country again.1980 and nineteen eighty-two, South Africa Sasol companies build up and have gone into operation Liang Zuomeiji artificial oils factory again in succession.But plummeting for World oil price in 1986, has postponed F-T synthetic technologys in other national heavy industrialization processes.Since twentieth century nineties, petroleum resources shortage and in poor quality increasingly, while coal and natural gas proved reserves are but continuously increased, fischer-tropsch technologies cause extensive concern, Fiscber-Tropscb synthesis technology also to obtain significant progress again.Current conventional fischer-tropsch catalysts, from active component for be divided into two big class：Ferrum-based catalyst and cobalt-base catalyst；And common synthesis technique is divided into two big class if classifying from synthesis condition angle：High temperature fischer-tropsch synthesis technique and Low Temperature Fischer Tropsch synthesis technique；Synthesis technique from using reactor difference being divided into three major types if classifying：Fixed bed fischer-tropsch synthesis process, fluid bed fischer-tropsch synthesis process (have early stage recirculating fluidized bed and developed on the basis of recirculating fluidized bed later it is fixed fluidized bed) and syrup state bed Fischer Tropsch synthesis technique.Fixed bed therein is generally used for low temperature fischer-tropsch process with slurry bed system, is used for the production of mink cell focus and wax, and fluid bed is then more suitable for producing the high temperature fischer-tropsch technique of the more hydro carbons of lightweight
What the fischer-tropsch catalysts of document and patent report were more in recent years applies to cryogenic high pressure paste state bed reactor to produce high-carbon long chain hydrocarbons, and general mostly is precipitated iron catalyst, or immersion-type Co catalysts.A kind of preparation method of the F- T synthesis precipitated iron catalyst suitable for paste state bed reactor is reported if Rentech companies of the U.S. are in patent USP5504118 and CN1113905A.The F- T synthesis of light hydrocarbon it is general it is many carry out in a fluidized bed reactor, be that reaction temperature is higher the characteristics of the technique, conversion ratio is higher, the difficulty that there is no solid-liquor separation.The currently reported mostly molten iron type catalyst for being applied to fluid bed F- T synthesis, occasionally has some type of precipitated iron catalyst.A kind of preparation of the molten iron type catalyst for F- T synthesis is referred to if in patent CN1704161A, a kind of precipitated iron catalyst for fluid bed in patent CN1695804A, is referred to.
Preparing low-carbon olefin has direct method and indirect method, is the high temperature fischer-tropsch synthesis under specific catalyst under so-called direct method i.e. specified conditions.Although there is some that fixed bed applications are used for the trial of low-carbon alkene production in high temperature fischer-tropsch at present, such as Rule of Germany, the DaLian, China Chemistry and Physics Institute, but as Fischer-Tropsch synthesis are strong exothermal reaction, during using fixed bed, hot difficulty, easy temperature runaway in reactor, are removed, catalyst is made easily to inactivate, these trials terminate in laboratory stage.Fluid bed can be very good to overcome these problems that fixed bed is present, but Fluidized Multicomponent Metallic Oxides Catalysts prepared by the catalyst that either prepared using molten iron method or the sedimentation method all have products distribution width, the low shortcoming of selectivity of light olefin at present.
The content of the invention
One of the technical problem to be solved is as Fischer-Tropsch synthesis are strong exothermal reaction present in prior art, during using fixed bed, hot difficulty is removed in reaction, easy temperature runaway, make the catalyst easily low problem of inactivation and low-carbon alkene weight selectivities, there is provided a kind of new synthesis gas is directly synthesized the catalyst of low-carbon alkene.When the catalyst is directly synthesized low-carbon alkene for synthesis gas, removes hot fast with reaction, be difficult the high advantage of temperature runaway and low-carbon alkene weight selectivities.
To solve above-mentioned technical problem, the technical solution used in the present invention one is as follows：The Fe-series catalyst of the direct producing light olefins of a kind of synthesis gas, comprising following components：Active component contains with atomic ratio measuring, chemical formula such as Fe100AaBbOxCompositionss, at least one of the wherein A in the Ti or Zr, at least one of the B in alkali metal, the span of a for 25.0～250.0, b span be 0.1～10.0, x in meet catalyst needed for each element quantivalence oxygen atom sum.
In above-mentioned technical proposal, catalyst formulation preferably active component also includes Elements C, and C is at least one of S or P, and the ratio of C and Fe is with atomic ratio measuring as Fe：C=100：The span of c, c is 0.01～2.
In above-mentioned technical proposal, the value preferred scope of a is 0.03～1.75 for the value preferred scope of 0.5～8.0, c for the value preferred scope of 50.0～200.0, b.
It is as follows to solve above-mentioned technical problem the technical solution used in the present invention two：The preparation method of the Fe-series catalyst of the direct producing light olefins of synthesis gas, comprises the following steps that：
1) solution is made by solubility alite soluble in water；Then mixed sediment I is filtrated to get with after alkaline precipitating agent cocurrent；
(2) solution II is made by Fe salt soluble in water；
(3) solution II is mixed into peptization with mixed sediment I and obtains slurry III；
(4) compound solution of the hydroxide or saline solution and C of B classes is added in slurry III, mixing beating, while adding the pH value that acid-base modifier adjusts slurry to obtain slurry IV for 1～5, the solid content of slurry IV is 15～45 weight %；
(5) slurry IV is sent into into spray dryer spray shaping, then in 400～750 DEG C of roasting temperatures 0.15～6 hour, obtains micro-spherical catalyst.
In the slurry preparation process of catalyst described in such scheme, the condition of peptization is 40～100 DEG C, and the time is 0.5～24h.
The condition for mixing beating in the slurry preparation process of catalyst described in such scheme is 10～100 DEG C.
In the spray shaping condition of catalyst described in such scheme, the scope of inlet temperature is 200～380 DEG C, and the excellent scope of outlet temperature is 100～230 DEG C.
The preferred scope of catalyst sintering temperature described in such scheme is 450～700 DEG C, and the preferred scope of the catalyst roasting time is 0.5～5h.
The catalyst for according to said method obtaining, the addition of Ti/Zr and special Adding Way can both help host element Fe effectively to disperse, reduce the reunion that active component causes because of area carbon, the excessive hydrogenation of catalyst can be suppressed to a certain extent again so that the amount of alkene is far longer than the amount of alkane in product, and the poisoning of slight S or P can then suppress the excessive carbonization of catalyst surface to cause catalyst be highly suitable for the commercial Application that synthesis gas is directly synthesized low-carbon alkene with long-play.
Above-mentioned catalyst directly prepares low-carbon alkene reaction, with synthesis gas as unstripped gas, H for synthesis gas2It is 3 with CO mol ratios, is 1.5MPa in reaction pressure, reaction temperature is 350 DEG C, and reaction volume air speed is 10000 hours-1Under conditions of, unstripped gas is contacted with catalyst in a fluidized bed reactor, achieves preferable technique effect：The conversion ratio of CO, up to 97%, is singly C2 =-C4 =The weight selectivities of (ethylene, propylene and butylene) component are up to 73%.
Below by embodiment, the invention will be further elaborated.
Specific embodiment
【Embodiment 1】
Take 40.0g titanyl sulfates to be dissolved in the water of 1000ml, be made into the titanyl sulfate solution of 0.25mol/L, by centrifugation after ammonia parallel-flow precipitation of the solution with 5 weight % of 400g, after being washed with deionized three times, obtain fresh titanium oxide precipitate I；
The Fe(NO3)39H2O for taking 606.03g is dissolved in wiring solution-forming II in a certain amount of water；
Solution II is mixed with precipitate I, in 40 DEG C of water-bath, peptization 24h obtains the slurry III of colloidal；
The potassium hydroxide of 0.084g is dissolved in into 1.00g water and is made into potassium hydroxide solution
Slurry III is cooled to into 10 DEG C in 10 DEG C of water-bath, then above-mentioned potassium hydroxide is added in the slurry III after cooling, the mixing beating under conditions of 10 DEG C；
Then add the dilute sulfuric acid of 15 weight % of 0.098g in above-mentioned slurry；
It is 5 finally to adjust the pH value of slurry with ammonia, obtains colloidal sol shape and is uniformly dispersed and places the uniform sizing material IV (solid content 45%) that will not be layered for a long time；
By IV spray drying forming of slurry, spraying machine inlet temperature is 380 DEG C, 230 DEG C of outlet temperature；
Then roasting is carried out, 750 DEG C of sintering temperature, roasting time 6h obtain microspheroidal fluid bed synthesis gas and directly prepare light olefins catalyst, and which is made and consists of：
Fe100Ti25K0.1S0.01Ox
【Embodiment 2】：
Take five water zirconium nitrates of 1072g to be dissolved in the water of 2500ml, be made into the zirconium nitrate solution of 0.8mol/L, by centrifugation after ammonia parallel-flow precipitation of the solution with 25 weight % of 800g, after being washed with deionized three times, obtain fresh zirconium oxide precipitation I；
The Fe(NO3)39H2O for taking 606.03g is dissolved in wiring solution-forming II in a certain amount of water；
Solution II is mixed with precipitate I, in 100 DEG C of water-bath, peptization 0.5h obtains the slurry III of colloidal；
20.47g cesium nitrates are dissolved in 50.0g water and are made into cesium nitrate solution；
Above-mentioned cesium nitrate solution is added in slurry III in 100 DEG C of water-bath, the mixing beating under conditions of 100 DEG C；
Then 15 weight % phosphoric acid,diluteds of 19.6g are added in above-mentioned slurry；
It is 1 finally to adjust the pH value of slurry with dust technology, obtains colloidal sol shape and is uniformly dispersed and places the uniform sizing material IV (solid content 15%) that will not be layered for a long time；
By the slurry spray drying forming, spraying machine inlet temperature is 200 DEG C, 100 DEG C of outlet temperature；
Then roasting is carried out, 450 DEG C of sintering temperature, roasting time 0.15h obtain microspheroidal fluid bed synthesis gas and directly prepare light olefins catalyst, and which is made and consists of：
Fe100Zr250.0Cs10.0P2.0Ox
【Embodiment 3】：
Take 80.0g titanyl sulfates to be dissolved in the water of 2000ml, be made into the titanyl sulfate solution of 0.25mol/L, by centrifugation after ammonia parallel-flow precipitation of the solution with 5 weight % of 800g, after being washed with deionized three times, obtain fresh titanium oxide precipitate I；
Take 367.43g ferric citrates and be dissolved in wiring solution-forming II in a certain amount of water；
Solution II is mixed with precipitate I, in 70 DEG C of water-bath, peptization 12h obtains the slurry III of colloidal；
4.8g sodium hydroxide is dissolved in into 10.00g water and is made into potassium hydroxide solution
Slurry III is cooled to into 40 DEG C in 40 DEG C of water-bath, then above-mentioned potassium hydroxide is added in the slurry III after cooling, the mixing beating under conditions of 40 DEG C；
The dilute sulfuric acid of 15 weight % of 0.294g is subsequently adding in above-mentioned slurry；
It is 3 finally to adjust the pH value of slurry with weak ammonia, obtains colloidal sol shape and is uniformly dispersed and places the uniform sizing material IV (solid content 35%) that will not be layered for a long time；
By IV spray drying forming of slurry, spraying machine inlet temperature is 230 DEG C, 140 DEG C of outlet temperature；
Then roasting is carried out, 400 DEG C of sintering temperature, roasting time 5h obtain microspheroidal fluid bed synthesis gas and directly prepare light olefins catalyst, and which is made and consists of：
Fe100Ti50Na8.0S0.03Ox
【Embodiment 4】：
Take 190.0g titanium tetrachlorides to be dissolved in the water of 4000ml, be made into the titanium tetrachloride solution of 0.25mol/L, by centrifugation after ammonia parallel-flow precipitation of the solution with 5 weight % of 1600g, after being washed with deionized three times, obtain fresh titanium oxide precipitate I；
The magnesium nitrate hexahydrate for taking the Fe(NO3)39H2O and 76.92g of 606.03g is dissolved in wiring solution-forming II in a certain amount of water；
Solution II is mixed with precipitate I, in 80 DEG C of water-bath, peptization 5h obtains the slurry III of colloidal；
0.77g rubidium hydroxides are dissolved in into 2.00g water and are made into rubidium hydroxide solution；
Slurry III is heated to into 90 DEG C in 90 DEG C of water-bath, then above-mentioned rubidium hydroxide is added in the slurry III after heating, the mixing beating under conditions of 90 DEG C；
Then 15 weight % phosphoric acid,diluteds of 7.35g are added in above-mentioned slurry；
It is 2.5 finally to adjust the pH value of slurry with weak ammonia, obtains colloidal sol shape and is uniformly dispersed and places the uniform sizing material IV (solid content 30%) that will not be layered for a long time；
By IV spray drying forming of slurry, spraying machine inlet temperature is 280 DEG C, 150 DEG C of outlet temperature；
Then roasting is carried out, 700 DEG C of sintering temperature, roasting time 0.5h obtain microspheroidal fluid bed synthesis gas and directly prepare light olefins catalyst, and which is made and consists of：
Fe100Ti100Mg20.0Rb0.5P1.75Ox
【Embodiment 5】：
Take 40.0g titanyl sulfates to be dissolved in the water of 1000ml, be made into the titanyl sulfate solution of 0.25mol/L；
Take 88.9g Disulfatozirconic acid .s to be dissolved in the water of 1000ml, be made into the sulphuric acid zirconium solution of 0.25mol/L；
Above-mentioned two solution is mixed to get into the mixing salt solution of titanium and zirconium, then centrifugation after the ammonia parallel-flow precipitation by the solution with 5 weight % of 800g, obtains fresh titanium oxide and zirconic mixed precipitation I after being washed with deionized three times；
The Fe(NO3)39H2O for taking 606.03g is dissolved in wiring solution-forming II in a certain amount of water；
Solution II is mixed with mixed sediment I, in 60 DEG C of water-bath, peptization 8h obtains the slurry III of colloidal；
The potassium hydroxide of 0.84g is dissolved in into 1.00g water and is made into potassium hydroxide solution
Slurry III is heated to into 70 DEG C in 70 DEG C of water-bath, then above-mentioned potassium hydroxide is added in the slurry III after heating, the mixing beating under conditions of 70 DEG C；
Then add the dilute sulfuric acid of 15 weight % of 0.98g in above-mentioned slurry；
It is 3.5 that last weak ammonia adjusts the pH value of slurry, obtains colloidal sol shape and is uniformly dispersed and places the uniform sizing material IV (solid content 25%) that will not be layered for a long time；
By IV spray drying forming of slurry, spraying machine inlet temperature is 330 DEG C, 200 DEG C of outlet temperature；
Then roasting is carried out, 450 DEG C of sintering temperature, roasting time 3.4h obtain microspheroidal fluid bed synthesis gas and directly prepare light olefins catalyst, and which is made and consists of：
Fe100Ti25Zr25K1.0S0.1Ox
【Embodiment 6】：
Take 190.0g titanium tetrachlorides to be dissolved in the water of 4000ml, be made into the titanium tetrachloride solution of 0.25mol/L；
Take 233.2g Zirconium tetrachloride. to be dissolved in the water of 4000ml, be made into the Zirconium tetrachloride. solution of 0.25mol/L；
Above-mentioned two solution is mixed to get into the mixed solution of titanium and zirconates, then centrifugation after the ammonia parallel-flow precipitation by the mixed solution with 10 weight % of 1600g, obtains fresh titanium oxide and zirconic mixed precipitation I after being washed with deionized three times；
The Fe(NO3)39H2O for taking 606.03g is dissolved in wiring solution-forming II in a certain amount of water；
Solution II is mixed with mixed sediment I, in 90 DEG C of water-bath, peptization 2.5h obtains the slurry III of colloidal；
4.3g potassium hydroxide is dissolved in into 9.00g water and is made into potassium hydroxide solution；
Slurry III is heated to into 95 DEG C in 95 DEG C of water-bath, then above-mentioned rubidium hydroxide is added in the slurry III after heating, the mixing beating under conditions of 95 DEG C；
Then add the dilute sulfuric acid of 15 weight % of 17.15g in above-mentioned slurry；
It is 4.5 that last weak ammonia adjusts the pH value of slurry, obtains colloidal sol shape and is uniformly dispersed and places the uniform sizing material IV (solid content 20%) that will not be layered for a long time；
By IV spray drying forming of slurry, spraying machine inlet temperature is 360 DEG C, 220 DEG C of outlet temperature；
Then roasting is carried out, 550 DEG C of sintering temperature, roasting time 1.4h obtain microspheroidal fluid bed synthesis gas and directly prepare light olefins catalyst, and which is made and consists of：
Fe100Ti100Zr100K5.0S1.75Ox
【Embodiment 7】：
Take five water zirconium nitrates of 428.8g to be dissolved in the water of 1000ml, be made into the zirconium nitrate solution of 0.8mol/L, by centrifugation after ammonia parallel-flow precipitation of the solution with 10 weight % of 800g, after being washed with deionized three times, obtain fresh zirconium oxide precipitation I；
The Fe(NO3)39H2O for taking 606.03g is dissolved in wiring solution-forming II in a certain amount of water；
Solution II is mixed with precipitate I, in 90 DEG C of water-bath, peptization 0.5h obtains the slurry III of colloidal；
0.13g potassium hydroxide is dissolved in 1.0g water and is made into potassium hydroxide solution；
Above-mentioned potassium hydroxide solution is added in slurry III in 100 DEG C of water-bath, the mixing beating under conditions of 100 DEG C；
Then add the phosphoric acid,diluted of 15 weight % of dilute sulfuric acid and 0.126g of 15 weight % of 0.294g in above-mentioned slurry；
It is 3.5 finally to adjust the pH value of slurry with dust technology, obtains colloidal sol shape and is uniformly dispersed and places the uniform sizing material IV (solid content 25%) that will not be layered for a long time；
By the slurry spray drying forming, spraying machine inlet temperature is 260 DEG C, 130 DEG C of outlet temperature；
Then roasting is carried out, 550 DEG C of sintering temperature, roasting time 4h obtain microspheroidal fluid bed synthesis gas and directly prepare light olefins catalyst, and which is made and consists of：
Fe100Zr100K0.5S0.03P0.03Ox
【Embodiment 8】：
Take 95.0g titanium tetrachlorides to be dissolved in the water of 2000ml, be made into the titanium tetrachloride solution of 0.25mol/L；
Take 116.6.2g Zirconium tetrachloride. to be dissolved in the water of 2000ml, be made into the Zirconium tetrachloride. solution of 0.25mol/L；
Above-mentioned two solution is mixed to get into the mixed solution of titanium and zirconates, then centrifugation after the ammonia parallel-flow precipitation by the mixed solution with 10 weight % of 800g, obtains fresh titanium oxide and zirconic mixed precipitation I after being washed with deionized three times；
The Fe(NO3)39H2O for taking 606.03g is dissolved in wiring solution-forming II in a certain amount of water；
Solution II is mixed with mixed sediment I, in 90 DEG C of water-bath, peptization 1.0h obtains the slurry III of colloidal；
0.13g potassium hydroxide is dissolved in 1.0g water and is made into potassium hydroxide solution；
Above-mentioned potassium hydroxide solution is added in slurry III in 100 DEG C of water-bath, the mixing beating under conditions of 100 DEG C；
Then add the phosphoric acid,diluted of 15 weight % of dilute sulfuric acid and 0.126g of 15 weight % of 0.294g in above-mentioned slurry；
It is 1.5 finally to adjust the pH value of slurry with dust technology, obtains colloidal sol shape and is uniformly dispersed and places the uniform sizing material IV (solid content 20%) that will not be layered for a long time；
By IV spray drying forming of slurry, spraying machine inlet temperature is 290 DEG C, 180 DEG C of outlet temperature；
Then roasting is carried out, 650 DEG C of sintering temperature, roasting time 3h obtain microspheroidal fluid bed synthesis gas and directly prepare light olefins catalyst, and which is made and consists of：
Fe100Ti50Zr50K0.5S0.03P0.03Ox
【Embodiment 9】：
Take 95.0g titanium tetrachlorides to be dissolved in the water of 2000ml, be made into the titanium tetrachloride solution of 0.25mol/L；
Take 116.6.2g Zirconium tetrachloride. to be dissolved in the water of 2000ml, be made into the Zirconium tetrachloride. solution of 0.25mol/L；
Above-mentioned two solution is mixed to get into the mixed solution of titanium and zirconates, then centrifugation after the ammonia parallel-flow precipitation by the mixed solution with 10 weight % of 800g, obtains fresh titanium oxide and zirconic mixed precipitation I after being washed with deionized three times；
The Fe(NO3)39H2O for taking 606.03g is dissolved in wiring solution-forming II in a certain amount of water；
Solution II is mixed with mixed sediment I, in 90 DEG C of water-bath, peptization 1.0h obtains the slurry III of colloidal；
0.084g potassium hydroxide is dissolved in 1.0g water and is made into potassium hydroxide solution；
10.64g cesium nitrates are dissolved in 23.0g water and are made into cesium nitrate solution；
Respectively above-mentioned potassium hydroxide solution and cesium nitrate solution are added in slurry III in 100 DEG C of water-bath, the mixing beating under conditions of 100 DEG C；
Then again the dilute sulfuric acid of 15 weight % of 17.15g is added in above-mentioned slurry；
It is 4.7 finally to adjust the pH value of slurry with ammonia, obtains colloidal sol shape and is uniformly dispersed and places the uniform sizing material IV (solid content 20%) that will not be layered for a long time；
By IV spray drying forming of slurry, spraying machine inlet temperature is 350 DEG C, 215 DEG C of outlet temperature；
Then roasting is carried out, 650 DEG C of sintering temperature, roasting time 5.2h obtain microspheroidal fluid bed synthesis gas and directly prepare light olefins catalyst, and which is made and consists of：
Fe100Ti50Zr50Cs5.2K0.1S1.75O
【Embodiment 10】
Take 95.0g titanium tetrachlorides to be dissolved in the water of 2000ml, be made into the titanium tetrachloride solution of 0.25mol/L；
Take 116.6.2g Zirconium tetrachloride. to be dissolved in the water of 2000ml, be made into the Zirconium tetrachloride. solution of 0.25mol/L；
Above-mentioned two solution is mixed to get into the mixed solution of titanium and zirconates, then centrifugation after the ammonia parallel-flow precipitation by the mixed solution with 10 weight % of 800g, obtains fresh titanium oxide and zirconic mixed precipitation I after being washed with deionized three times；
The Fe(NO3)39H2O for taking 606.03g is dissolved in wiring solution-forming II in a certain amount of water；
Solution II is mixed with mixed sediment I, in 90 DEG C of water-bath, peptization 1.0h obtains the slurry III of colloidal；
0.084g potassium hydroxide is dissolved in 1.0g water and is made into potassium hydroxide solution；
10.64g cesium nitrates are dissolved in 23.0g water and are made into cesium nitrate solution；
Respectively above-mentioned potassium hydroxide solution and cesium nitrate solution are added in slurry III in 100 DEG C of water-bath, the mixing beating under conditions of 100 DEG C；
Then add the phosphoric acid,diluted of 15 weight % of dilute sulfuric acid and 0.126g of 15 weight % of 0.294g in above-mentioned slurry；
It is 5 finally to adjust the pH value of slurry with ammonia, obtains colloidal sol shape and is uniformly dispersed and places the uniform sizing material IV (solid content 45%) that will not be layered for a long time；
By IV spray drying forming of slurry, spraying machine inlet temperature is 380 DEG C, 230 DEG C of outlet temperature；
Then roasting is carried out, 750 DEG C of sintering temperature, roasting time 6h obtain microspheroidal fluid bed synthesis gas and directly prepare light olefins catalyst, and which is made and consists of：
Fe100Ti50Zr50Cs5.2K0.1S0.03P0.03Ox
【Comparative example 1】
Take 20.0g titanyl sulfates to be dissolved in the water of 500ml, be made into the titanyl sulfate solution of 0.25mol/L, by centrifugation after ammonia parallel-flow precipitation of the solution with 5 weight % of 200g, after being washed with deionized three times, obtain fresh titanium oxide precipitate I；
The Fe(NO3)39H2O for taking 606.03g is dissolved in wiring solution-forming II in a certain amount of water；
Solution II is mixed with precipitate I, in 40 DEG C of water-bath, peptization 24h obtains the slurry III of colloidal；
The potassium hydroxide of 0.084g is dissolved in into 1.00g water and is made into potassium hydroxide solution
Slurry III is cooled to into 10 DEG C in 10 DEG C of water-bath, then above-mentioned potassium hydroxide is added in the slurry III after cooling, the mixing beating under conditions of 10 DEG C；
Then add the dilute sulfuric acid of 15 weight % of 0.098g in above-mentioned slurry；
It is 5 finally to adjust the pH value of slurry with ammonia, obtains colloidal sol shape and is uniformly dispersed and places the uniform sizing material IV (solid content 45%) that will not be layered for a long time；
By IV spray drying forming of slurry, spraying machine inlet temperature is 380 DEG C, 230 DEG C of outlet temperature；
Then roasting is carried out, 750 DEG C of sintering temperature, roasting time 6h obtain microspheroidal fluid bed synthesis gas and directly prepare light olefins catalyst, and which is made and consists of：
Fe100Ti12.5K0.1S0.01Ox
【Comparative example 2】
Take 40.0g titanyl sulfates to be dissolved in the water of 1000ml, be made into the titanyl sulfate solution of 0.25mol/L, by centrifugation after ammonia parallel-flow precipitation of the solution with 5 weight % of 400g, after being washed with deionized three times, obtain fresh titanium oxide precipitate I；
The Fe(NO3)39H2O for taking 606.03g is dissolved in wiring solution-forming II in a certain amount of water；
Solution II is mixed with precipitate I, in 40 DEG C of water-bath, peptization 24h obtains the slurry III of colloidal；
The potassium hydroxide of 0.0084g is dissolved in into 1.00g water and is made into potassium hydroxide solution
Slurry III is cooled to into 10 DEG C in 10 DEG C of water-bath, then above-mentioned potassium hydroxide is added in the slurry III after cooling, the mixing beating under conditions of 10 DEG C；
Then add the dilute sulfuric acid of 15 weight % of 0.098g in above-mentioned slurry；
It is 5 finally to adjust the pH value of slurry with ammonia, obtains colloidal sol shape and is uniformly dispersed and places the uniform sizing material IV (solid content 45%) that will not be layered for a long time；
By IV spray drying forming of slurry, spraying machine inlet temperature is 380 DEG C, 230 DEG C of outlet temperature；
Then roasting is carried out, 750 DEG C of sintering temperature, roasting time 6h obtain microspheroidal fluid bed synthesis gas and directly prepare light olefins catalyst, and which is made and consists of：
Fe100Ti25K0.01S0.01Ox
【Comparative example 3】：
Take 40.0g titanyl sulfates to be dissolved in the water of 1000ml, be made into the titanyl sulfate solution of 0.25mol/L, by centrifugation after ammonia parallel-flow precipitation of the solution with 5 weight % of 400g, after being washed with deionized three times, obtain fresh titanium oxide precipitate I；
The Fe(NO3)39H2O for taking 606.03g is dissolved in wiring solution-forming II in a certain amount of water；
Solution II is mixed with precipitate I, in 40 DEG C of water-bath, peptization 24h obtains the slurry III of colloidal；
The potassium hydroxide of 0.084g is dissolved in into 1.00g water and is made into potassium hydroxide solution；
Slurry III is cooled to into 10 DEG C in 10 DEG C of water-bath, then above-mentioned potassium hydroxide is added in the slurry III after cooling, the mixing beating under conditions of 10 DEG C；
Then add the dilute sulfuric acid of 15 weight % of 39.2g in above-mentioned slurry
It is 5 finally to adjust the pH value of slurry with ammonia, obtains colloidal sol shape and is uniformly dispersed and places the uniform sizing material IV (solid content 45%) that will not be layered for a long time；
By IV spray drying forming of slurry, spraying machine inlet temperature is 380 DEG C, 230 DEG C of outlet temperature；
Then roasting is carried out, 750 DEG C of sintering temperature, roasting time 6h obtain microspheroidal fluid bed synthesis gas and directly prepare light olefins catalyst, and which is made and consists of：
Fe100Ti25K0.1S4.0Ox
【Comparative example 4】
Fixed bed catalyst is prepared using the method described in CN 1395993A, its formula is identical with embodiment 3
Obtained above-mentioned catalyst carries out Fischer-Tropsch synthesis in addition to comparative example 4 under following reaction conditions, is as a result listed in table 1.
Reducing condition is：
450 DEG C of temperature
Pressure normal pressure
50 grams of loaded catalyst
Catalyst loading (reaction volume air speed) 2500 hours-1
Also Primordial Qi H2/ CO=0.25/1
24 hours recovery times
Reaction condition is：
38 millimeters of fluidized-bed reactors of φ
350 DEG C of reaction temperature
Reaction pressure 1.5MPa
50 grams of loaded catalyst
Catalyst loading (reaction volume air speed) 10000 hours-1
Proportioning raw materials (mole) H2/ CO=3/1
By comparative example 3, as described in patent CN 1395993A, in fixed bed, evaluation analysis result is listed in table
#The data being reacted to during 2000h
* the data of former patent are selected from.
Claims (10)
1. a kind of catalyst that low-carbon alkene is directly prepared for synthesis gas, including following components：
Active component contains with atomic ratio measuring, the following compositionss of chemical formula：Fe100AaBbOx
At least one of the A in Ti or Zr；
At least one of the B in alkali metal；
The span of a is 25.0～250.0；
The span of b is 0.1～10.0；
Oxygen atom sums of the x in meet catalyst needed for each element quantivalence.
2. the catalyst that low-carbon alkene is directly prepared for synthesis gas according to claim 1, its active component also include Elements C, at least one of the C for S or P, and the ratio of C and Fe is with atomic ratio measuring as Fe：C=100：The span of c, c is 0.01～2.
3. the catalyst that low-carbon alkene is directly prepared for synthesis gas according to claim 1 and 2, it is characterised in that the span of a is 50.0～200.0.
4. the catalyst that low-carbon alkene is directly prepared for synthesis gas according to claim 1 and 2, it is characterised in that the span of b is 0.5～8.0.
5. the catalyst that low-carbon alkene is directly prepared for synthesis gas according to claim 2, it is characterised in that the span of c is 0.03～1.75.
6. the catalyst that low-carbon alkene is directly prepared for synthesis gas described in claim 1 or 2, comprises the following steps that：
(1) solution is made by solubility alite soluble in water；Then precipitate I is filtrated to get with after alkaline precipitating agent cocurrent；
(2) Fe salt is dissolved in into water and makes solution II；
(3) solution II is mixed into peptization with precipitate I and obtains slurry III；
(4) compound solution of the hydroxide or saline solution and C of B classes is added in slurry III, mixing beating, while adding the pH value that acid-base modifier adjusts slurry to obtain slurry IV for 1～5, the solid content of slurry IV is 15～45 weight %；
(5) slurry IV is sent into into spray dryer spray shaping, then in 400～750 DEG C of roasting temperatures 0.15～6 hour, obtains microspheric catalyst.
7. the preparation method that light olefins catalyst is directly prepared for synthesis gas according to claim 6, it is characterised in that the condition of peptization is 40～100 DEG C, the time is 0.5～24h.
8. the preparation method that light olefins catalyst is directly prepared for synthesis gas according to claim 6, it is characterised in that the condition of mixing beating is 10～100 DEG C.
9. the preparation method that light olefins catalyst is directly prepared for synthesis gas according to claim 6, it is characterised in that the spray shaping condition of catalyst is 200～380 DEG C of inlet temperature, 100～230 DEG C of outlet temperature.
10. the preparation method that light olefins catalyst is directly prepared for synthesis gas according to claim 6, it is characterised in that sintering temperature is 450～700 DEG C, roasting time is 0.5～5 hour.
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| CN109912373A (en) * | 2017-12-13 | 2019-06-21 | 中国石油化工股份有限公司 | For preparation of low carbon olefines by synthetic gas catalyst and preparation method thereof |
| CN112619651A (en) * | 2019-09-24 | 2021-04-09 | 中国石油化工股份有限公司 | Preparation method of catalyst for preparing low-carbon olefin from synthesis gas |
| CN112619650A (en) * | 2019-09-24 | 2021-04-09 | 中国石油化工股份有限公司 | Catalyst for preparing light olefin from synthesis gas and preparation method thereof |
| CN114425385A (en) * | 2020-10-15 | 2022-05-03 | 中国石油化工股份有限公司 | Catalyst for preparing low-carbon olefin by Fischer-Tropsch synthesis and preparation method and application thereof |
| CN117324010A (en) * | 2022-06-24 | 2024-01-02 | 中国石油化工股份有限公司 | A catalyst for directly producing olefins from synthesis gas and its preparation method and application |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109912373A (en) * | 2017-12-13 | 2019-06-21 | 中国石油化工股份有限公司 | For preparation of low carbon olefines by synthetic gas catalyst and preparation method thereof |
| CN109912373B (en) * | 2017-12-13 | 2022-03-08 | 中国石油化工股份有限公司 | Catalyst for preparing low-carbon olefin from synthesis gas and preparation method thereof |
| CN112619651A (en) * | 2019-09-24 | 2021-04-09 | 中国石油化工股份有限公司 | Preparation method of catalyst for preparing low-carbon olefin from synthesis gas |
| CN112619650A (en) * | 2019-09-24 | 2021-04-09 | 中国石油化工股份有限公司 | Catalyst for preparing light olefin from synthesis gas and preparation method thereof |
| CN112619650B (en) * | 2019-09-24 | 2023-05-02 | 中国石油化工股份有限公司 | Catalyst for preparing light olefin from synthesis gas and preparation method thereof |
| CN114425385A (en) * | 2020-10-15 | 2022-05-03 | 中国石油化工股份有限公司 | Catalyst for preparing low-carbon olefin by Fischer-Tropsch synthesis and preparation method and application thereof |
| CN114425385B (en) * | 2020-10-15 | 2024-02-02 | 中国石油化工股份有限公司 | Catalyst for preparing low-carbon olefin by Fischer-Tropsch synthesis, and preparation method and application thereof |
| CN117324010A (en) * | 2022-06-24 | 2024-01-02 | 中国石油化工股份有限公司 | A catalyst for directly producing olefins from synthesis gas and its preparation method and application |
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