CN106607049A - Catalyst for preparing low-carbon olefins from synthesis gas and preparation method thereof - Google Patents

Catalyst for preparing low-carbon olefins from synthesis gas and preparation method thereof Download PDF

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CN106607049A
CN106607049A CN201510685593.4A CN201510685593A CN106607049A CN 106607049 A CN106607049 A CN 106607049A CN 201510685593 A CN201510685593 A CN 201510685593A CN 106607049 A CN106607049 A CN 106607049A
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catalyst
preparation
slurry
solution
low carbon
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CN106607049B (en
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庞颖聪
陶跃武
宋卫林
李剑锋
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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    • 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

Abstract

The invention relates to a catalyst for preparing low-carbon olefins from synthesis gas and a preparation method thereof. The catalyst for preparing the low-carbon olefins from the synthesis gas and the preparation method thereof mainly solve the problems that in the prior art, because the Fischer-Tropsch synthesis reaction is a strong exothermic reaction, in the process of using a fixed bed, heat is difficult to remove in a reactor, temperature runaway is easy, the catalyst tends to be inactive and the weight selectivity of the low-carbon olefins is low. According to the technical scheme, the catalyst adopted by the method comprises, in terms of atomic ratio, a composition with a chemical formula being Fe100MnaBbCcOx, wherein B is selected from at least one of Ga and In, and C is selected from at least one of Rh and Ir. The problems can be well solved through adopting the above technical scheme, and the catalyst can be applied to industrial production of preparing the low-carbon olefins from the synthesis gas through a one-step method.

Description

Catalyst of preparation of low carbon olefines by synthetic gas and preparation method thereof
Technical field
The present invention relates to a kind of catalyst for synthesis gas low-carbon alkene and preparation method thereof
Background technology
Fischer-Tropsch (Fascher-Tropsch) synthesis is that (main component is CO and H using synthesis gas2) 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 the research and development to F- T synthesis 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 in succession again.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 again extensive concern, Fiscber-Tropscb synthesis technology also to obtain significant progress.
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 is divided into three major types if classifying from the reactor difference for being used：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.
In recent years, it is to grow with each passing day to the demand of oil product with the fast development of China's economy.The characteristics of China's energy is the few gas oil starvation of rich coal, and the coal environmental pollution for causing of directly burning also is taken seriously increasingly.Exploitation is converted into the process of oil product by coal/natural gas ECDC into gas, not only can be reduced to external dependence on the energy, and is had great importance for the coal-fired problem of environmental pollution for causing is solved.
What in recent years the fischer-tropsch catalysts of document and patent report were more 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 there is 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 is referred in patent CN1695804A.
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 because Fischer-Tropsch synthesis are strong exothermal reaction, during using fixed bed, hot difficulty, easy temperature runaway are removed in reactor, catalyst is set 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 at present products distribution width, the low shortcoming of selectivity of light olefin.
The content of the invention
One of the technical problem to be solved is because 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 catalyst of the new direct producing light olefins of the step of synthesis gas one.When the catalyst is used for fluid bed synthesizing low-carbon alkene, remove hot fast with reaction, be difficult the high advantage of temperature runaway and low-carbon alkene weight selectivities.
It is as follows to solve above-mentioned technical problem the technical solution used in the present invention one：A kind of catalyst of preparation of low carbon olefines by synthetic gas.The catalytic component contains with atomic ratio measuring, chemical formula Fe100MnaBbCcOxCompositionss：At least one of the B selected from Ga or In, at least one of the C in Rh or Ir, the span of a is 0.5～20.0 for the span of 25.0～250.0, b, the span of c be 0.1～10.0, x to meet catalyst in oxygen atom sum needed for each element quantivalence.
Catalyst formulation is optimized for active component and also includes element D in above-mentioned technical proposal, and D is that alkali metal is a kind of, and the ratio of D and Fe is with atomic ratio measuring as Fe：D=100：The span of d, d is 0.05～5.0.
Carrier consumption preferred scope is by weight percentage the 15～65% of catalyst weight in above-mentioned technical proposal, the value preferred scope of a is 50～200.0, the value preferred scope of b is 0.1～4.5 for the value preferred scope of 0.5～8.0, d for the value preferred scope of 1.0～15.0, c.
It is as follows to solve above-mentioned technical problem the technical solution used in the present invention two：The preparation method of the catalyst of preparation of low carbon olefines by synthetic gas, comprises the following steps that：
(1) Dissolvable Fe salt is made into solution with celite is soluble in water；Then it is filtrated to get mixed sediment I with after alkaline precipitating agent cocurrent；
(2) solution II is made by soluble M n salt and belit are soluble in water；
(3) solution II is mixed into peptization with mixed sediment I and obtains slurry III；
(4) compound solution of D 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 microspheroidal Fe base catalyst.
Inlet temperature scope is 200～380 DEG C in the spray shaping condition of catalyst described in above-mentioned technical proposal, and the scope of outlet temperature is 100～230 DEG C.
The preferred scope of catalyst sintering temperature described in above-mentioned technical proposal is 450～700 DEG C, and the preferred scope of the catalyst roasting time is 0.5～5h.
By the catalyst for according to said method obtaining because the addition of noble metal Rh or Ir can improve the Hydrogenation of catalyst, so that the conversion ratio of catalyst is improved, simultaneously noble metal substantially increases the performance of the CO absorption of catalyst with Mn synergism so that the selectivity of alkene will be significantly larger than the selectivity of alkane.Special preparation method and component ratio cause to add extra inert component do carrier just can improve catalyst active component dispersion and the intensity of catalyst, the efficiency of raising catalyst that simultaneously can be higher, you can to use catalyst under higher air speed；Simultaneously good dispersion can reduce the reunion that active component causes because of area carbon so that the catalyst can for a long time keep the selectivity of high conversion ratio and high low-carbon alkene, be highly suitable for the commercial Application that synthesis gas is directly synthesized low-carbon alkene.
Above-mentioned catalyst first uses H for the reaction of F- T synthesis low-carbon alkene2With the synthesis gas that CO mol ratios are 0.25 in 1.5MPa, 450 DEG C, air speed is 1000 hours-1Lower reductase 12 4 hours, then with synthesis gas as unstripped gas, H2It is 3 with CO mol ratios, is 1.5MPa in reaction pressure, reaction temperature is 350 DEG C, and reaction volume air speed is 15000 hours-1Under conditions of, in a fluidized bed reactor unstripped gas is contacted with catalyst, 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】
1) rhodium chloride of the Fe(NO3)39H2O and 0.314g wiring solution-forming soluble in water of 606.03g is taken, then centrifugation after the strong aqua ammonia cocurrent of the solution and weight % of 400g 25, obtains the mixed precipitation I of fresh hydrated ferric oxide. and rhodium oxide after being washed with deionized three times；
2) manganese nitrate of weight % of 134.5g 50 and the nitric hydrate galliums of 3.13g nine are dissolved in the water and make solution II；
3) solution II is mixed into beating with mixed sediment I and obtains colloidal slurry III；
4) potassium hydroxide of 0.042g is dissolved in into water to be then added in slurry III, mixing beating, the pH value that slurry is adjusted with ammonia is 5, obtains colloidal sol shape and be uniformly dispersed and place the uniform sizing material IV (solid content 45%) that will not be layered for a long time；
5) by the spray drying forming of slurry IV, spraying machine inlet temperature is 380 DEG C, and then 230 DEG C of outlet temperature carries out roasting, 750 DEG C of sintering temperature, roasting time 6h；
The microspheric fluid bed ferrimanganic series catalysts that can be used for the direct producing light olefins of the step of synthesis gas one are obtained through above-mentioned steps, it is made and consists of (except special identifier all components ratio is atomic ratio)：
Fe100Mn25.0Ga0.5Rh0.1K0.05Ox
【Embodiment 2】：
1) iridous chloride of the Fe(NO3)39H2O and 44.79g wiring solution-forming soluble in water of 606.03g is taken, then centrifugation after the strong aqua ammonia cocurrent of the solution and weight % of 400g 25, obtains the mixed precipitation I of fresh hydrated ferric oxide. and yttrium oxide after being washed with deionized three times；
2) manganese nitrate of weight % of 1345g 50 and the nitric hydrate indiums of 117.3g five are dissolved in the water and make solution II；
3) solution II is mixed into beating with mixed sediment I and obtains colloidal slurry III；
4) 4.20g potassium hydroxide is dissolved in into water to be then added in slurry III, mixing beating, the pH value that slurry is adjusted with dust technology is 1, obtains colloidal sol shape and be uniformly dispersed and place the uniform sizing material IV (solid content 15%) that will not be layered for a long time；
5) by the spray drying forming of slurry IV, spraying machine inlet temperature is 200 DEG C, and then 100 DEG C of outlet temperature carries out roasting, 450 DEG C of sintering temperature, roasting time 0.15h；
The microspheric fluid bed Iron-Manganese Catalyst that can be used for the direct producing light olefins of the step of synthesis gas one is obtained through above-mentioned steps, it is made and consists of (except special identifier all components ratio is atomic ratio)：
Fe100Mn250.0In20.0Ir10.0K5.0Ox
【Embodiment 3】：
1) rhodium chloride of 367.43g ferric citrates and 1.57g wiring solution-forming soluble in water is taken, then centrifugation after the strong aqua ammonia cocurrent of the solution and weight % of 400g 25, obtains the mixed precipitation I of fresh hydrated ferric oxide. and rhodium oxide after being washed with deionized three times；
2) manganese nitrate of weight % of 269.0g 50 and the nitric hydrate galliums of 125.2g nine are dissolved in the water and make solution II；
3) solution II is mixed into beating with mixed sediment I and obtains colloidal slurry III；
4) 1.05g sodium hydroxide is dissolved in into water to be then added in slurry III, mixing beating, while it is 3 to adjust the pH value of slurry with weak ammonia, obtains colloidal sol shape and be uniformly dispersed and place the uniform sizing material IV (solid content 35%) that will not be layered for a long time；
5) by the spray drying forming of slurry IV, spraying machine inlet temperature is 230 DEG C, and then 140 DEG C of outlet temperature carries out roasting, 400 DEG C of sintering temperature, roasting time 5h；
The microspheric fluid bed Iron-Manganese Catalyst for the direct producing light olefins of the step of synthesis gas one is obtained through above-mentioned steps, it is made and consists of (except special identifier all components ratio is atomic ratio)：
Fe100Mn50.0Ga20.0Rh0.5Na1.75Ox
【Embodiment 4】：
1) rhodium chloride of the Fe(NO3)39H2O and 25.12g wiring solution-forming soluble in water of 606.03g is taken, then centrifugation after the strong aqua ammonia cocurrent of the solution and weight % of 400g 25, obtains the mixed precipitation I of fresh hydrated ferric oxide. and rhodium oxide after being washed with deionized three times；
2) manganese nitrate of 1076g50 weight % and the nitric hydrate indiums of 58.7g five are dissolved in the water and make solution II；
3) solution II is mixed into beating with mixed sediment I and obtains colloidal slurry III；
4) 0.54g Lithium hydrates are dissolved in into water to be then added in slurry III, mixing beating, the pH value that slurry is adjusted with weak ammonia is 2.5, obtain colloidal sol shape and be uniformly dispersed and place the uniform sizing material IV (solid content 30%) that will not be layered for a long time；
5) by the spray drying forming of slurry IV, spraying machine inlet temperature is 280 DEG C, and then 150 DEG C of outlet temperature carries out roasting, 700 DEG C of sintering temperature, roasting time 0.5h；
The microspheric fluid bed Iron-Manganese Catalyst for the direct producing light olefins of the step of synthesis gas one is obtained through above-mentioned steps, it is made and consists of (except special identifier all components ratio is atomic ratio)：
Fe100Mn200.0In10.0Rh8.0Li1.5Ox
【Embodiment 5】：
1) iridous chloride of the Fe(NO3)39H2O and 2.24g wiring solution-forming soluble in water of 606.03g is taken, then centrifugation after the strong aqua ammonia cocurrent of the solution and weight % of 400g 25, obtains the mixed precipitation I of fresh hydrated ferric oxide. and yttrium oxide after being washed with deionized three times；
2) manganese nitrate of weight % of 538.0g 50 and the nitric hydrate galliums of 62.6g nine and the nitric hydrate indiums of 58.7g five are dissolved in the water and make solution II；
3) solution II is mixed into beating with mixed sediment I and obtains colloidal slurry III；
4) 3.31g rubidium nitrates are dissolved in into water to be added in slurry III, mixing beating, it is 3.5 then to adjust the pH value of slurry with dust technology, obtain colloidal sol shape and be uniformly dispersed and place the uniform sizing material IV (solid content 25%) that will not be layered for a long time；
5) by the slurry spray drying forming, spraying machine inlet temperature is 330 DEG C, and then 200 DEG C of outlet temperature carries out roasting, 450 DEG C of sintering temperature, roasting time 3.4h；
The microspheric fluid bed Iron-Manganese Catalyst for the direct producing light olefins of the step of synthesis gas one is obtained through above-mentioned steps, it is made and consists of (except special identifier all components ratio is atomic ratio)：
Fe100Mn100.0Ga10.0In10.0Ir0.5Rb0.5Ox
【Embodiment 6】：
1) rhodium chloride for taking the Fe(NO3)39H2O of 606.03g and the iridous chloride of 2.24g and 0.63g is dissolved in water wiring solution-forming, then centrifugation after the strong aqua ammonia cocurrent of the solution and weight % of 400g 25, obtains the mixed precipitation I of fresh hydrated ferric oxide. and yttrium oxide and rhodium oxide after being washed with deionized three times；
2) manganese nitrate of 1076g50 weight % and the nitric hydrate indiums of 58.7g five are dissolved in the water and make solution II；
3) solution II is mixed into beating with mixed sediment I and obtains colloidal slurry III；
4) 1.59g strontium nitrates are dissolved in into water to be then added in slurry III, mixing beating, while it is 4.5 to adjust the pH value of slurry with weak ammonia, obtains colloidal sol shape and be uniformly dispersed and place the uniform sizing material IV (solid content 20%) that will not be layered for a long time；
5) by the spray drying forming of slurry IV, spraying machine inlet temperature is 360 DEG C, and then 220 DEG C of outlet temperature carries out roasting, 550 DEG C of sintering temperature, roasting time 1.4h；
The microspheric fluid bed Iron-Manganese Catalyst for the direct producing light olefins of the step of synthesis gas one is obtained through above-mentioned steps, it is made and consists of (except special identifier all components ratio is atomic ratio)：
Fe100Mn200.0In10.0Rh0.2Ir0.5Sr0.5Ox
【Embodiment 7】：
1) rhodium chloride for taking the Fe(NO3)39H2O of 606.03g and the iridous chloride of 2.24g and 0.63g is dissolved in water wiring solution-forming, then centrifugation after the strong aqua ammonia cocurrent of the solution and weight % of 400g 25, obtains the mixed precipitation I of fresh hydrated ferric oxide. and yttrium oxide and rhodium oxide after being washed with deionized three times；
2) manganese nitrate of 1076g50 weight % and the nitric hydrate indiums of 58.7g five are dissolved in the water and make solution II；
3) solution II is mixed into beating with mixed sediment I and obtains colloidal slurry III；
4) 4.5g Cesium hydrate. is dissolved in into water to be then added in slurry III, mixing beating, the pH value that slurry is adjusted with dust technology is 3.5, obtains colloidal sol shape and be uniformly dispersed and place the uniform sizing material IV (solid content 25%) that will not be layered for a long time；
5) by the spray drying forming of slurry IV, spraying machine inlet temperature is 260 DEG C, and then 130 DEG C of outlet temperature carries out roasting, 550 DEG C of sintering temperature, roasting time 4h；
The microspheric fluid bed Iron-Manganese Catalyst for the direct producing light olefins of the step of synthesis gas one is obtained through above-mentioned steps, it is made and consists of (except special identifier all components ratio is atomic ratio)：
Fe100Mn200.0In10.0Rh0.2Ir0.5Cs2.0Ox
【Embodiment 8】：
1) rhodium chloride for taking the Fe(NO3)39H2O of 606.03g and the iridous chloride of 2.24g and 0.63g is dissolved in water wiring solution-forming, then centrifugation after the strong aqua ammonia cocurrent of the solution and weight % of 400g 25, obtains the mixed precipitation I of fresh hydrated ferric oxide. and yttrium oxide and rhodium oxide after being washed with deionized three times；
2) manganese nitrate of 1076g50 weight % and the nitric hydrate indiums of 58.7g five and the nitric hydrate galliums of 62.6g nine are dissolved in the water and make solution II；
3) solution II is mixed into beating with mixed sediment I and obtains colloidal slurry III；
4) take 1.68g potassium hydroxide and be dissolved in water and be then added in slurry III, mixing beating, the pH value that slurry is adjusted with dust technology is 1.5, 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；
5) by the spray drying forming of slurry IV, spraying machine inlet temperature is 290 DEG C, and then 180 DEG C of outlet temperature carries out roasting, 650 DEG C of sintering temperature, roasting time 3h；
The microspheric fluid bed Iron-Manganese Catalyst for the direct producing light olefins of the step of synthesis gas one is obtained through above-mentioned steps, it is made and consists of (except special identifier all components ratio is atomic ratio)：
Fe100Mn200.0In10.0Ga10.0Rh0.2Ir0.5K2Ox
【Embodiment 9】：
1) rhodium chloride of the Fe(NO3)39H2O and 0.314g wiring solution-forming soluble in water of 606.03g is taken, then centrifugation after the strong aqua ammonia cocurrent of the solution and weight % of 400g 25, obtains the mixed precipitation I of fresh hydrated ferric oxide. and rhodium oxide after being washed with deionized three times；
2) manganese nitrate of weight % of 134.5g 50 and the nitric hydrate galliums of 3.13g nine are dissolved in the water and make solution II；
3) solution II is mixed into beating with mixed sediment I and obtains colloidal slurry III；
4) by the SiO of 1530g weight contents 40%2Colloidal sol is added in slurry III, is subsequently adding the potassium hydroxide of 0.042g, mixing beating, and the pH value that slurry is adjusted with ammonia is 4.7, is obtained 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；
5) by the spray drying forming of slurry IV, spraying machine inlet temperature is 350 DEG C, and then 215 DEG C of outlet temperature carries out roasting, 650 DEG C of sintering temperature, roasting time 5.2h；
The microspheric fluid bed Iron-Manganese Catalyst for the direct producing light olefins of the step of synthesis gas one is obtained through above-mentioned steps, it is made and consists of (except special identifier all components ratio is atomic ratio)：
35 weight %Fe100Cu0.5Mg20.0Rh0.1K0.05Ox+ 65 weight %SiO2
【Embodiment 10】
1) rhodium chloride for taking the Fe(NO3)39H2O of 606.03g and the iridous chloride of 2.24g and 0.63g is dissolved in water wiring solution-forming, then centrifugation after the strong aqua ammonia cocurrent of the solution and weight % of 400g 25, obtains the mixed precipitation I of fresh hydrated ferric oxide. and yttrium oxide and rhodium oxide after being washed with deionized three times；
2) manganese nitrate of 1076g50 weight % and the nitric hydrate indiums of 58.7g five and the nitric hydrate galliums of 62.6g nine are dissolved in the water and make solution II；
3) solution II is mixed into beating with mixed sediment I and obtains colloidal slurry III；
4) by the SiO of 1530g weight contents 40%2Colloidal sol is added in slurry III, is subsequently adding 1.68g potassium hydroxide, mixing beating, and the pH value that slurry is adjusted with dust technology is 1.5, is obtained 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；
5) by the spray drying forming of slurry IV, spraying machine inlet temperature is 290 DEG C, and then 180 DEG C of outlet temperature carries out roasting, 650 DEG C of sintering temperature, roasting time 3h；
The microspheric fluid bed Iron-Manganese Catalyst for the direct producing light olefins of the step of synthesis gas one is obtained through above-mentioned steps, it is made and consists of (except special identifier all components ratio is atomic ratio)：
Fe100Mn200.0In10.0Ga10.0Rh0.2Ir0.5K2Ox+ 65 weight %SiO2
【Comparative example 1】
1) rhodium chloride of the Fe(NO3)39H2O and 0.314g wiring solution-forming soluble in water of 606.03g is taken, then centrifugation after the strong aqua ammonia cocurrent of the solution and weight % of 400g 25, obtains the mixed precipitation I of fresh hydrated ferric oxide. and rhodium oxide after being washed with deionized three times；
2) manganese nitrate of weight % of 134.5g 50 is dissolved in the water and makes solution II；
3) solution II is mixed into beating with mixed sediment I and obtains colloidal slurry III；
4) potassium hydroxide of 0.042g is dissolved in into water to be then added in slurry III, mixing beating, the pH value that slurry is adjusted with ammonia is 5, obtains colloidal sol shape and be uniformly dispersed and place the uniform sizing material IV (solid content 45%) that will not be layered for a long time；
5) by the spray drying forming of slurry IV, spraying machine inlet temperature is 380 DEG C, and then 230 DEG C of outlet temperature carries out roasting, 750 DEG C of sintering temperature, roasting time 6h；
The microspheric fluid bed ferrimanganic series catalysts that can be used for the direct producing light olefins of the step of synthesis gas one are obtained through above-mentioned steps, it is made and consists of (except special identifier all components ratio is atomic ratio)：
Fe100Mn25.0Rh0.1K0.05Ox
【Comparative example 2】
1) the Fe(NO3)39H2O wiring solution-forming soluble in water of 606.03g is taken, then centrifugation after the strong aqua ammonia cocurrent of the solution and weight % of 400g 25, obtains the mixed precipitation I of fresh hydrated ferric oxide. and rhodium oxide after being washed with deionized three times；
2) manganese nitrate of weight % of 134.5g 50 and the nitric hydrate galliums of 3.13g nine are dissolved in the water and make solution II；
3) solution II is mixed into beating with mixed sediment I and obtains colloidal slurry III；
4) potassium hydroxide of 0.042g is dissolved in into water to be then added in slurry III, mixing beating, the pH value that slurry is adjusted with ammonia is 5, obtains colloidal sol shape and be uniformly dispersed and place the uniform sizing material IV (solid content 45%) that will not be layered for a long time；
5) by the spray drying forming of slurry IV, spraying machine inlet temperature is 380 DEG C, and then 230 DEG C of outlet temperature carries out roasting, 750 DEG C of sintering temperature, roasting time 6h；
The microspheric fluid bed ferrimanganic series catalysts that can be used for the direct producing light olefins of the step of synthesis gas one are obtained through above-mentioned steps, it is made and consists of (except special identifier all components ratio is atomic ratio)：
Fe100Mn25.0Ga0.5K0.05Ox
【Comparative example 3】：
1) rhodium chloride of the Fe(NO3)39H2O and 0.314g wiring solution-forming soluble in water of 606.03g is taken, then centrifugation after the strong aqua ammonia cocurrent of the solution and weight % of 400g 25, obtains the mixed precipitation I of fresh hydrated ferric oxide. and rhodium oxide after being washed with deionized three times；
2) the nitric hydrate galliums of 13.13g nine are dissolved in the water and make solution II；
3) solution II is mixed into beating with mixed sediment I and obtains slurry III；
4) potassium hydroxide of 0.042g is dissolved in into water to be then added in slurry III, mixing beating, the pH value that slurry is adjusted with dust technology is 5, obtains colloidal sol shape and be uniformly dispersed and place the uniform sizing material IV (solid content 45%) that will not be layered for a long time；
5) by the spray drying forming of slurry IV, spraying machine inlet temperature is 380 DEG C, and then 230 DEG C of outlet temperature carries out roasting, 750 DEG C of sintering temperature, roasting time 6h；
The microspheric fluid bed Fe-series catalyst that can be used for the direct producing light olefins of the step of synthesis gas one is obtained through above-mentioned steps, it is made and consists of (except special identifier all components ratio is atomic ratio)：
Fe100Ga0.5Rh0.1K0.05Ox
【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 3 under following reaction conditions, is as a result listed in table 1.
Reducing condition is：
450 DEG C of temperature
Pressure 1.5MPa
50 grams of loaded catalyst
Catalyst loading (reaction volume air speed) 1000 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) 15000 hours-1
Proportioning raw materials (mole) H2/ CO=3/1
By comparative example 3, evaluation analysis result is listed in table in fixed bed as described in patent CN 1395993A
#The data being reacted to during 2000h
* the data of former patent are selected from.

Claims (9)

1. a kind of catalyst for preparation of low carbon olefines by synthetic gas, catalyst contains with atomic ratio measuring, the following compositionss of chemical formula：
Fe100MnaBbCcOx
At least one of the B selected from Ga or In；
At least one of the C in Rh or Ir；
The span of a is 25～250.0；
The span of b is 0.5～20.0；
The span of c is 0.1～10.0；
X to meet catalyst in oxygen atom sum needed for each element quantivalence.
2. the catalyst for preparation of low carbon olefines by synthetic gas according to claim 1, its active component also includes element D, D A kind of for alkali metal, the ratio of D and Fe is with atomic ratio measuring as Fe：D=100：The span of d, d is 0.05～5.0.
3. the catalyst for preparation of low carbon olefines by synthetic gas according to claim 1 and 2, it is characterised in that the value model of a Enclose for 50～200.0.
4. the catalyst for preparation of low carbon olefines by synthetic gas according to claim 1 and 2, it is characterised in that the value model of b Enclose for 1.0～15.0.
5. the catalyst for preparation of low carbon olefines by synthetic gas according to claim 1 and 2, it is characterised in that the value model of c Enclose for 0.5～8.0.
6. the catalyst for preparation of low carbon olefines by synthetic gas according to claim 2, it is characterised in that the span of d is 0.1～4.5.
7. the catalyst for preparation of low carbon olefines by synthetic gas described in claim 1 or 2, comprises the following steps that：
(1) Dissolvable Fe salt is made into solution with celite is soluble in water；Then with alkaline precipitating agent cocurrent after be filtrated to get it is mixed Close precipitate I；
(2) solution II is made by soluble M n salt and belit are soluble in water；
(3) solution II is mixed into peptization with mixed sediment I and obtains slurry III；
(4) compound solution of D is added in slurry III, mixing beating, while adding acid-base modifier to adjust slurry PH value 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, Obtain micro-spherical catalyst granule.
8. the catalyst for preparation of low carbon olefines by synthetic gas according to claim 8, it is characterised in that the spraying of catalyst into Type condition be 200～380 DEG C of inlet temperature, 100～230 DEG C of outlet temperature.
9. the catalyst for preparation of low carbon olefines by synthetic gas according to claim 8, it is characterised in that sintering temperature is 450～700 DEG C, roasting time is 0.5～5 hour.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111068687A (en) * 2018-10-18 2020-04-28 中国石油化工股份有限公司 Catalyst for preparing low-carbon olefin by synthesis gas one-step method and application thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104096564A (en) * 2013-04-02 2014-10-15 北京化工大学 Fischer-Tropsch synthesis iron-based catalyst, preparation method and application thereof
CN104226329A (en) * 2013-06-17 2014-12-24 中国石油化工股份有限公司 Catalyst for direct preparation of low carbon olefin from synthesis gas and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104096564A (en) * 2013-04-02 2014-10-15 北京化工大学 Fischer-Tropsch synthesis iron-based catalyst, preparation method and application thereof
CN104226329A (en) * 2013-06-17 2014-12-24 中国石油化工股份有限公司 Catalyst for direct preparation of low carbon olefin from synthesis gas and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111068687A (en) * 2018-10-18 2020-04-28 中国石油化工股份有限公司 Catalyst for preparing low-carbon olefin by synthesis gas one-step method and application thereof
CN111068687B (en) * 2018-10-18 2022-12-09 中国石油化工股份有限公司 Catalyst for preparing low-carbon olefin by synthesis gas one-step method and application thereof

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