CN107790144A - Synthesis gas directly prepares catalyst of low-carbon alkene and preparation method thereof - Google Patents

Synthesis gas directly prepares catalyst of low-carbon alkene and preparation method thereof Download PDF

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CN107790144A
CN107790144A CN201610772494.4A CN201610772494A CN107790144A CN 107790144 A CN107790144 A CN 107790144A CN 201610772494 A CN201610772494 A CN 201610772494A CN 107790144 A CN107790144 A CN 107790144A
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catalyst
synthesis gas
slurry
low
fluid bed
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CN107790144B (en
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庞颖聪
陶跃武
戴毅敏
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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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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8872—Alkali or alkaline earth metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8892—Manganese
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
    • C07C1/0425—Catalysts; their physical properties
    • C07C1/043—Catalysts; their physical properties characterised by the composition
    • C07C1/0435—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof
    • C07C1/044—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof containing iron
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
    • C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
    • C10G2/332—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the iron-group
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous 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
    • 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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Abstract

Catalyst of low-carbon alkene and preparation method thereof is directly prepared the present invention relates to a kind of synthesis gas for fluid bed, mainly solve in the prior art because Fischer-Tropsch synthesis is strong exothermal reaction, during using fixed bed, hot difficulty is removed in reactor, easy temperature runaway, catalyst is set easily to inactivate and the problem of low-carbon alkene weight selectivities are low.The catalyst that the present invention uses is in terms of parts by weight, including following components：A) 0.5~5 part of structural promoter, the auxiliary agent are the carbon dust of graphite state；B) 95~99.5 parts of active components, active component contain with atomic ratio measuring, the following composition of chemical formula：Fe100AaBbCcOx, the one kind of A in Mn or Mo, B is selected from least one of Ti or Zr, the one kind of C in alkali metal；Preferably solve above mentioned problem, the industrial production of low-carbon alkene is directly prepared for synthesis gas.

Description

Synthesis gas directly prepares catalyst of low-carbon alkene and preparation method thereof
Technical field
Catalyst of low-carbon alkene and preparation method thereof is directly prepared with synthesis gas the present invention relates to a kind of fluid bed
Background technology
The characteristics of China's energy is the few gas oil starvation of rich coal, and environmental pollution caused by coal directly burns is also increasingly by weight Depending on so exploitation is converted into the process of oil product by coal/natural gas through synthesis gas, can not only reduce on the energy to foreign countries Rely on, and have great importance for problem of environmental pollution caused by solution fire coal.
Using synthesis gas, (main component is CO and H2) Fischer-Tropsch (Fascher- of synthesis hydrocarbon in the presence of catalyst Tropsch) building-up process, it is an important channel of coal and natural gas indirect liquefaction.This method is nineteen twenty-three by German science Family's Frans Fischer and Hans Tropsch inventions, i.e. heterogeneous catalysis hydrogenation occurs on metallic catalyst for CO, Generate 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 industrialization was realized in 1936, closed after World War II because can not economically be competed with petroleum industry；South Africa possesses abundant Coal resources, but petroleum resources plaque is weary, and is limited for a long time by international community's economy and political sanction, forces its Development of Coal Oils preparation industry technology, and built up coal base F-T artificial oil factory of the First production capacity for 25~400,000 tons of product/years in 1955 (Sasol-1).The world oil crisis twice of 1973 and 1979, cause world's crude oil price to fall and swing fluctuating, rise greatly greatly Fall, based on the consideration of Strategic Technology deposit, F-T synthetic technologys arouse the interest of industrialized country again.1980 and nineteen eighty-two, South Africa Sasol companies build up in succession again and Liang Zuomeiji artificial oils factory of having gone into operation.But plummeting for World oil price in 1986, is pushed away Late F-T synthetic technologys are in other national heavy industrialization processes.Since twentieth century nineties, petroleum resources are increasingly short Scarce and in poor quality, while coal and natural gas proved reserves are but continuously increased, fischer-tropsch technologies cause extensive concern, Fischer-Tropsch again Synthetic technology has also obtained significant progress.Currently used fischer-tropsch catalysts, from active component for be divided into two major classes：Iron Base catalyst and cobalt-base catalyst；And common synthesis technique is divided into two major classes if classifying from synthesis condition angle：High temperature Fischer-tropsch synthesis process and Low Temperature Fischer Tropsch synthesis technique；It is big that synthesis technique is divided into three if classifying from used reactor difference Class：Fixed bed fischer-tropsch synthesis process, fluid bed fischer-tropsch synthesis process (have the recirculating fluidized bed of early stage and later ciculation fluidized Developed on the basis of bed fixed fluidized bed) and syrup state bed Fischer Tropsch synthesis technique.Fixed bed therein and slurry bed system are general Applied to low temperature fischer-tropsch process, it is used for the production of mink cell focus and wax, and fluid bed is then more suitable for production more lightweight The high temperature fischer-tropsch technique of hydro carbons
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, general mostly is precipitated iron catalyst, or immersion-type Co catalysts.If Rentech companies of the U.S. are special A kind of F- T synthesis precipitated iron suitable for paste state bed reactor is just reported in sharp USP5504118 and CN1113905A to be catalyzed The preparation method of agent.The F- T synthesis of light hydrocarbon it is general it is more carries out in a fluidized bed reactor, be reaction temperature the characteristics of the technique Degree is higher, and conversion ratio is higher, in the absence of the difficulty of solid-liquor separation.Currently reported is applied to the more of fluid bed F- T synthesis For molten iron type catalyst, occasionally there is some type of precipitated iron catalyst.One kind is referred to if in patent CN1704161A to be used for The preparation of the molten iron type catalyst of F- T synthesis, a kind of precipitated iron for fluid bed is referred in patent CN1695804A and is catalyzed Agent.
Preparing low-carbon olefin has direct method and indirect method, is specific under so-called direct method i.e. specified conditions High temperature fischer-tropsch synthesis under catalyst.Although there are some that fixed bed applications are used for into low-carbon alkene production in high temperature fischer-tropsch at present Attempt, such as Rule of Germany, the DaLian, China Chemistry and Physics Institute, but because Fischer-Tropsch synthesis is strong exothermal reaction, use fixed bed When, hot difficulty is removed in reactor, easy temperature runaway, catalyst is easily inactivated, these trials terminate in laboratory stage.Fluid bed can To overcome these problems existing for fixed bed well, but prepared by the catalyst or the precipitation method that are either prepared using molten iron method Fluidized Multicomponent Metallic Oxides Catalysts the shortcomings that product distribution is wide, and selectivity of light olefin is low at present all be present.
The content of the invention
One of technical problems to be solved by the invention are because Fischer-Tropsch synthesis is to put by force present in prior art Thermal response, during using fixed bed, hot difficulty is removed in reaction, easy temperature runaway, catalyst is easily inactivated and the selection of low-carbon alkene weight A kind of the problem of property is low, there is provided Fe-series catalyst of the direct synthesizing low-carbon alkene of new synthesis gas.The catalyst is used for synthesis gas During direct synthesizing low-carbon alkene, there is reaction to remove hot fast, the advantages of being not easy temperature runaway and high low-carbon alkene weight selectivities.
It is as follows to solve above-mentioned technical problem the technical solution adopted by the present invention one：A kind of fluid bed is directly made with synthesis gas The catalyst of standby low-carbon alkene.The catalyst is in terms of parts by weight, including following components：A) 0.5~5 part of structural promoter, this is helped Agent is the nano-carbon powder of graphite state；B) 95~99.5 parts of active components, active component contain with atomic ratio measuring, and chemical formula is following Composition：Fe100AaBbCcOx, the one kind of wherein A in Mn or Mo, B is selected from least one of Ti or Zr, and C is selected from alkali gold At least one of category；The span that the span that a span is 2.5~250.0, b is 20~200.0, c is 0.1~10.0, x are to meet the oxygen atom sum in catalyst needed for each element chemical valence.
In above-mentioned technical proposal, most several granularities of graphite powder are 20~60nm；Most several granularities of graphite powder are preferably 30~ 50nm。
In above-mentioned technical proposal structural promoter dosage preferred scope by weight percentage for catalyst weight 0.8~ 4.5%, a value preferred scope are that 5~200.0, b value preferred scope is 25.0~180.0, c value preferred scope For 0.5~8.0, the granularity of structural promoter graphite state nano-carbon powder is between 10~100nm.
It is as follows to solve above-mentioned technical problem the technical solution adopted by the present invention two：Fluid bed is directly prepared low with synthesis gas The method for preparing catalyst of carbon olefin, is comprised the following steps that：
(1) by Dissolvable Fe salt with B salt is soluble in water that solution is made；Then be filtrated to get after alkaline precipitating agent cocurrent it is mixed Close sediment I；
(2) solution II is made by A ackd salt is soluble in water；
(3) solution II is mixed into peptization with mixed sediment I and obtains slurry III；
(4) solution of the hydroxide of C classes or salt is added in slurry III and be mixed with beating, then add nano level stone Black state carbon dust shearing or glue mill make its dispersed in the slurry, while the pH value for adding acid-base modifier regulation slurry is 1 ~5 obtain slurry IV, and the solid content of slurry IV is 15~45 weight %；
(5) slurry IV is sent into spray dryer spray shaping, it is then small in 350~550 DEG C of roasting temperatures 0.15~6 When, obtain microspheric catalyst.
Temperature maintains 40~80 DEG C in the honed journey of the catalyst pulp preparation steps peptization and shearing/glue.
In the spray shaping condition of the catalyst preferred scope of inlet temperature be 200~350 DEG C, outlet temperature it is excellent It is 100~230 DEG C to select scope, and the preferred scope of the catalyst sintering temperature is 400~500 DEG C.
The preferred scope of the catalyst roasting time is 0.5~5h.
By the catalyst according to said method obtained because Mn or Mo effect can suppress the further hydrogenation of alkene, so as to So that the amount of alkene is far longer than the amount of alkane in product, Ti/Zr addition and special Adding Way can help pivot Plain Fe effectively disperses, and reduces active component and reunites caused by area carbon, and the addition of structural promoter graphite state carbon dust is then On the one hand time and the temperature of activation of catalyst needs are reduced, on the other hand suppressing the excessive carbonization of catalyst surface makes Catalyst can ensure long-play under high activity, special preparation method causes the duct of preformed catalyst to be more conducive to The formation of lower carbon number hydrocarbons and desorption, while make it that the active component of catalyst is scattered as far as possible, active component is reduced because of surface area Reunite caused by carbon so that the catalyst can keep the selectivity of high conversion ratio and high low-carbon alkene for a long time, non- Often it is applied to the commercial Application of the direct synthesizing low-carbon alkene of synthesis gas.
Above-mentioned catalyst is used for the direct synthesizing low-carbon olefine reaction of synthesis gas, using synthesis gas as unstripped gas, H2With CO moles Than being 1.5MPa in reaction pressure, reaction temperature is 350 DEG C, and reaction volume air speed is 10000 hours for 3-1Under conditions of, Unstripped gas contacts with catalyst in fluidized-bed reactor, achieves preferable technique effect：CO conversion ratio is up to 97%, Dan Shi C2 =-C4 =The weight selectivities of (ethene, propylene and butylene) component are up to 73%.
Below by embodiment, the invention will be further elaborated.
Embodiment
【Embodiment 1】
Take the titanyl sulfate wiring solution-forming soluble in water of 606.03g Fe(NO3)39H2O and 40.0g, then the solution with Centrifuged after the weight % of 2665g 5 ammonia spirit cocurrent, be washed with deionized and obtain fresh iron hydroxide afterwards three times With the mixed precipitation I of titanium hydroxide；
Add a certain amount of water that solution II is made the weight % of 13.45g 50 manganese nitrate；
Solution II and mixed sediment I are blended in peptization in 40 DEG C of water-bath and obtain colloidal slurry III；
It is maintained in 40 DEG C of water-bath and 0.084g potassium hydroxide is added in slurry III, be mixed with beating, then adds grain Degree most several granularities between 10~100nm about cause graphite powder in 30nm or so graphite powder 7.73g, cutter THE ADIABATIC SHEAR IN It is dispersed in the slurry；
With ammoniacal liquor regulation slurry pH value be 5, obtain colloidal sol shape be uniformly dispersed and for a long time place will not be layered it is uniform Slurry IV (solid content 45%)；
By the slurry spray drying forming, spraying machine inlet temperature is 350 DEG C, 230 DEG C of outlet temperature；
Then it is calcined, 550 DEG C, roasting time 6h of sintering temperature, obtains microspheroidal fluid bed and directly made with synthesis gas Standby light olefins catalyst, it is (except special identifier all components ratio is atomic ratio) that composition, which is made, in it：
95 weight %Fe100Mn2.5Ti20K0.1Ox+ 5 weight %C.
【Embodiment 2】：
Take the titanyl sulfate wiring solution-forming soluble in water of 606.03g Fe(NO3)39H2O and 40.0g, then the solution with Centrifuged after the weight % of 2665g 5 ammonia spirit cocurrent, be washed with deionized and obtain fresh iron hydroxide afterwards three times With the mixed precipitation I of titanium hydroxide；
Add a certain amount of water that solution II is made the weight % of 13.45g 50 manganese nitrate；
Solution II and mixed sediment I are blended in peptization in 80 DEG C of water-bath and obtain colloidal slurry III；
It is maintained in 40 DEG C of water-bath and 0.084g potassium hydroxide is added in slurry III, be mixed with beating, then adds grain Degree most several granularities between 10~100nm about cause graphite powder in 50nm or so graphite powder 0.74g, cutter THE ADIABATIC SHEAR IN It is dispersed in the slurry；
With ammoniacal liquor regulation slurry pH value be 5, obtain colloidal sol shape be uniformly dispersed and for a long time place will not be layered it is uniform Slurry IV (solid content 15%)；
By the slurry spray drying forming, spraying machine inlet temperature is 350 DEG C, 230 DEG C of outlet temperature；
Then it is calcined, 350 DEG C, roasting time 0.15h of sintering temperature, it is direct obtains microspheroidal fluid bed synthesis gas Light olefins catalyst is prepared, it is (except special identifier all components ratio is atomic ratio) that composition, which is made, in it：
99.5 weight %Fe100Mn2.5Ti20K0.1Ox+ 0.5 weight %C.
【Embodiment 3】：
Take 367.43g ironic citrates 400.0g titanyl sulfate wiring solution-forming soluble in water, after the solution and 1467g 25 Centrifuged after weight % ammonia spirit cocurrent, be washed with deionized and obtain fresh iron hydroxide and hydroxide afterwards three times The mixed precipitation I of titanium；
Add a certain amount of water that solution II is made the weight % of 1345g 50 manganese nitrate；
It is maintained in 60 DEG C of water-bath and 8.4g potassium hydroxide is added in slurry III, be mixed with beating, then adds granularity Most several granularities about make it that graphite powder is equal in 40nm or so graphite powder 26.4g, cutter THE ADIABATIC SHEAR IN between 10~100nm It is even to disperse in the slurry；
The pH value that slurry is finally adjusted with dust technology is 1, obtains colloidal sol shape and is uniformly dispersed and places for a long time and will not be layered Uniform sizing material IV (solid content 25%)；
By the slurry spray drying forming, spraying machine inlet temperature is 200 DEG C, 100 DEG C of outlet temperature；
Then it is calcined, 400 DEG C, roasting time 1.0h of sintering temperature, it is direct obtains microspheroidal fluid bed synthesis gas Light olefins catalyst is prepared, it is (except special identifier all components ratio is atomic ratio) that composition, which is made, in it：
96 weight %Fe100Mn250Ti200K10Ox+ 4 weight %C
【Embodiment 4】：
Take 606.03g Fe(NO3)39H2O and 428.8g five water zirconium nitrate wiring solution-formings soluble in water, after the solution With being centrifuged after the weight % of 1067g 25 ammonia spirit cocurrent, it is washed with deionized and obtains fresh hydroxide afterwards three times The mixed precipitation I of iron and zirconium hydroxide；
Add a certain amount of water that solution II is made the weight % of 1345g 50 manganese nitrate；
It is maintained in 70 DEG C of water-bath and 0.84g potassium hydroxide is added in slurry III, be mixed with beating, then adds granularity Most several granularities about make it that graphite powder is equal in 30nm or so graphite powder 23.8g, cutter THE ADIABATIC SHEAR IN between 10~100nm It is even to disperse in the slurry；
The pH value that slurry is finally adjusted with dust technology is 2, obtains colloidal sol shape and is uniformly dispersed and places for a long time and will not be layered Uniform sizing material IV (solid content 40%)；
By the slurry spray drying forming, spraying machine inlet temperature is 320 DEG C, 180 DEG C of outlet temperature；
Then it is calcined, 500 DEG C, roasting time 0.5h of sintering temperature, it is direct obtains microspheroidal fluid bed synthesis gas Light olefins catalyst is prepared, it is (except special identifier all components ratio is atomic ratio) that composition, which is made, in it：
96 weight %Fe100Mn250Zr100K1.0Ox+ 4 weight %C
【Embodiment 5】：
Take 606.03g Fe(NO3)39H2O and 428.8g five water zirconium nitrate wiring solution-formings soluble in water, after the solution With being centrifuged after the weight % of 1067g 25 ammonia spirit cocurrent, it is washed with deionized and obtains fresh hydroxide afterwards three times The mixed precipitation I of iron and zirconium hydroxide；
Add a certain amount of water that solution II is made 665.1g five water nitric acid molybdenums；
It is maintained in 80 DEG C of water-bath and 0.84g potassium hydroxide is added in slurry III, be mixed with beating, then adds granularity Most several granularities about make it that graphite powder is equal in 30nm or so graphite powder 20.2g, cutter THE ADIABATIC SHEAR IN between 10~100nm It is even to disperse in the slurry；
The pH value that slurry is finally adjusted with weak aqua ammonia is 4.0, obtains colloidal sol shape and is uniformly dispersed and places for a long time and will not divide The uniform sizing material IV (solid content 40%) of layer；
By the slurry spray drying forming, spraying machine inlet temperature is 300 DEG C, 170 DEG C of outlet temperature；
Then it is calcined, 520 DEG C, roasting time 1.5h of sintering temperature, it is direct obtains microspheroidal fluid bed synthesis gas Light olefins catalyst is prepared, it is (except special identifier all components ratio is atomic ratio) that composition, which is made, in it：
96 weight %Fe100Mo100Zr100K1.0Ox+ 4 weight %C
【Embodiment 6】：
Take the titanyl sulfate wiring solution-forming soluble in water of 606.03g Fe(NO3)39H2O and 200.0g, after the solution with Centrifuged after the weight % of 1067g 25 ammonia spirit cocurrent, be washed with deionized and obtain fresh iron hydroxide afterwards three times With the mixed precipitation I of titanium hydroxide；
Add a certain amount of water that solution II is made the weight % of 538g 50 manganese nitrate；
It is maintained in 70 DEG C of water-bath and 3.5g sodium hydroxides is added in slurry III, be mixed with beating, then adds granularity Most several granularities cross colloid mill three times so that graphite powder is equal about in 35nm or so graphite powder 14.53g between 10~100nm It is even to disperse in the slurry；
The pH value that slurry is finally adjusted with dust technology is 1.5, obtains colloidal sol shape and is uniformly dispersed and places for a long time and will not divide The uniform sizing material IV (solid content 35%) of layer；
By the slurry spray drying forming, spraying machine inlet temperature is 280 DEG C, 160 DEG C of outlet temperature；
Then it is calcined, 450 DEG C, roasting time 3.0h of sintering temperature, it is direct obtains microspheroidal fluid bed synthesis gas Light olefins catalyst is prepared, it is (except special identifier all components ratio is atomic ratio) that composition, which is made, in it：
96 weight %Fe100Mn100Ti100Na5.0Ox+ 4 weight %C
【Embodiment 7】：
Take 367.43g ironic citrates and 200.0g titanyl sulfate wiring solution-forming soluble in water, after the solution and 1067g Centrifuged after 25 weight % ammonia spirit cocurrent, be washed with deionized and obtain fresh iron hydroxide and hydrogen-oxygen afterwards three times Change the mixed precipitation I of titanium；
Add a certain amount of water that solution II is made the weight % of 538g 50 manganese nitrate；
It is maintained in 80 DEG C of water-bath and 7.5g rubidium hydroxides is added in slurry III, be mixed with beating, then adds granularity Most several granularities cross colloid mill three times so that graphite powder is equal about in 45nm or so graphite powder 14.55g between 10~100nm It is even to disperse in the slurry；
The pH value that slurry is finally adjusted with dust technology is 1.5, obtains colloidal sol shape and is uniformly dispersed and places for a long time and will not divide The uniform sizing material IV (solid content 35%) of layer；
By the slurry spray drying forming, spraying machine inlet temperature is 280 DEG C, 160 DEG C of outlet temperature；
Then it is calcined, 450 DEG C, roasting time 3.0h of sintering temperature, it is direct obtains microspheroidal fluid bed synthesis gas Light olefins catalyst is prepared, it is (except special identifier all components ratio is atomic ratio) that composition, which is made, in it：
96 weight %Fe100Mn100Ti100Rb5.0Ox+ 4 weight %C
【Embodiment 8】：
606.03g Fe(NO3)39H2O and 200.0g titanyl sulfate and 428.8g five water zirconium nitrates are taken to be dissolved in water Middle wiring solution-forming, after the solution with being centrifuged after the weight % of 1467g 25 ammonia spirit cocurrent, be washed with deionized three The mixed precipitation I of fresh iron hydroxide and titanium hydroxide and zirconium hydroxide is obtained after secondary；
Add a certain amount of water that solution II is made the weight % of 538g 50 manganese nitrate；
It is maintained in 70 DEG C of water-bath and 4.2g potassium hydroxide is added in slurry III, be mixed with beating, then adds granularity Most several granularities cross colloid mill three times so that graphite powder is equal about in 35nm or so graphite powder 22.21g between 10~100nm It is even to disperse in the slurry；
The pH value that slurry is finally adjusted with dust technology is 1.5, obtains colloidal sol shape and is uniformly dispersed and places for a long time and will not divide The uniform sizing material IV (solid content 35%) of layer；
By the slurry spray drying forming, spraying machine inlet temperature is 280 DEG C, 160 DEG C of outlet temperature；
Then it is calcined, 450 DEG C, roasting time 3.0h of sintering temperature, it is direct obtains microspheroidal fluid bed synthesis gas Light olefins catalyst is prepared, it is (except special identifier all components ratio is atomic ratio) that composition, which is made, in it：
96 weight %Fe100Mn100Ti100Zr100K5.0Ox+ 4 weight %C
【Embodiment 9】：
Take 367.43g ironic citrates and 200.0g titanyl sulfate wiring solution-forming soluble in water, after the solution and 1067g Centrifuged after 25 weight % ammonia spirit cocurrent, be washed with deionized and obtain fresh iron hydroxide and hydrogen-oxygen afterwards three times Change the mixed precipitation I of titanium；
Add a certain amount of water that solution II is made the weight % of 538g 50 manganese nitrate；
It is maintained in 80 DEG C of water-bath and 7.5g rubidium hydroxides and 4.2g potassium hydroxide is added in slurry III, mixing is beaten Slurry, then add granularity most several granularities between 10~100nm and, about in 45nm or so graphite powder 14.55g, cross colloid mill three All over so that graphite powder is dispersed in the slurry；
The pH value that slurry is finally adjusted with dust technology is 1.5, obtains colloidal sol shape and is uniformly dispersed and places for a long time and will not divide The uniform sizing material IV (solid content 35%) of layer；
By the slurry spray drying forming, spraying machine inlet temperature is 280 DEG C, 160 DEG C of outlet temperature；
Then it is calcined, 450 DEG C, roasting time 3.0h of sintering temperature, it is direct obtains microspheroidal fluid bed synthesis gas Light olefins catalyst is prepared, it is (except special identifier all components ratio is atomic ratio) that composition, which is made, in it：
96 weight %Fe100Mn100Ti100Rb5.0K5.0Ox+ 4 weight %C
【Embodiment 10】
606.03g Fe(NO3)39H2O and 200.0g titanyl sulfate and 428.8g five water zirconium nitrates are taken to be dissolved in water Middle wiring solution-forming, after the solution with being centrifuged after the weight % of 1467g 25 ammonia spirit cocurrent, be washed with deionized three The mixed precipitation I of fresh iron hydroxide and titanium hydroxide and zirconium hydroxide is obtained after secondary；
Add a certain amount of water that solution II is made the weight % of 538g 50 manganese nitrate；
It is maintained in 70 DEG C of water-bath and 7.5g rubidium hydroxides and 4.2g potassium hydroxide is added in slurry III, mixing is beaten Slurry, then add granularity most several granularities between 10~100nm and, about in 35nm or so graphite powder 22.21g, cross colloid mill three All over so that graphite powder is dispersed in the slurry；
The pH value that slurry is finally adjusted with dust technology is 1.5, obtains colloidal sol shape and is uniformly dispersed and places for a long time and will not divide The uniform sizing material IV (solid content 35%) of layer；
By the slurry spray drying forming, spraying machine inlet temperature is 280 DEG C, 160 DEG C of outlet temperature；
Then it is calcined, 450 DEG C, roasting time 3.0h of sintering temperature, it is direct obtains microspheroidal fluid bed synthesis gas Light olefins catalyst is prepared, it is (except special identifier all components ratio is atomic ratio) that composition, which is made, in it：
96 weight %Fe100Mn100Ti100Zr100Rb5.0K5.0Ox+ 4 weight %C
【Embodiment 11】
606.03g Fe(NO3)39H2O and 200.0g titanyl sulfate and 428.8g five water zirconium nitrates are taken to be dissolved in water Middle wiring solution-forming, after the solution with being centrifuged after the weight % of 1467g 25 ammonia spirit cocurrent, be washed with deionized three The mixed precipitation I of fresh iron hydroxide and titanium hydroxide and zirconium hydroxide is obtained after secondary；
Add a certain amount of water that solution II is made the weight % of 538g 50 manganese nitrate；
It is maintained in 70 DEG C of water-bath and 7.5g rubidium hydroxides and 4.2g potassium hydroxide is added in slurry III, mixing is beaten Slurry, then add granularity most several granularities between 10~100nm and, about in 10nm or so graphite powder 22.21g, cross colloid mill three All over so that graphite powder is dispersed in the slurry；
The pH value that slurry is finally adjusted with dust technology is 1.5, obtains colloidal sol shape and is uniformly dispersed and places for a long time and will not divide The uniform sizing material IV (solid content 35%) of layer；
By the slurry spray drying forming, spraying machine inlet temperature is 280 DEG C, 160 DEG C of outlet temperature；
Then it is calcined, 450 DEG C, roasting time 3.0h of sintering temperature, it is direct obtains microspheroidal fluid bed synthesis gas Light olefins catalyst is prepared, it is (except special identifier all components ratio is atomic ratio) that composition, which is made, in it：
96 weight %Fe100Mn100Ti100Zr100Rb5.0K5.0Ox+ 4 weight %C
【Embodiment 12】
606.03g Fe(NO3)39H2O and 200.0g titanyl sulfate and 428.8g five water zirconium nitrates are taken to be dissolved in water Middle wiring solution-forming, after the solution with being centrifuged after the weight % of 1467g 25 ammonia spirit cocurrent, be washed with deionized three The mixed precipitation I of fresh iron hydroxide and titanium hydroxide and zirconium hydroxide is obtained after secondary；
Add a certain amount of water that solution II is made the weight % of 538g 50 manganese nitrate；
It is maintained in 70 DEG C of water-bath and 7.5g rubidium hydroxides and 4.2g potassium hydroxide is added in slurry III, mixing is beaten Slurry, then add granularity most several granularities between 10~100nm and, about in 70nm or so graphite powder 22.21g, cross colloid mill three All over so that graphite powder is dispersed in the slurry；
The pH value that slurry is finally adjusted with dust technology is 1.5, obtains colloidal sol shape and is uniformly dispersed and places for a long time and will not divide The uniform sizing material IV (solid content 35%) of layer；
By the slurry spray drying forming, spraying machine inlet temperature is 280 DEG C, 160 DEG C of outlet temperature；
Then it is calcined, 450 DEG C, roasting time 3.0h of sintering temperature, it is direct obtains microspheroidal fluid bed synthesis gas Light olefins catalyst is prepared, it is (except special identifier all components ratio is atomic ratio) that composition, which is made, in it：
96 weight %Fe100Mn100Ti100Zr100Rb5.0K5.0Ox+ 4 weight %C
【Comparative example 1】
Take 367.43g ironic citrates and 200.0g titanyl sulfate wiring solution-forming soluble in water, after the solution and 1067g Centrifuged after 25 weight % ammonia spirit cocurrent, be washed with deionized and obtain fresh iron hydroxide and hydrogen-oxygen afterwards three times Change the mixed precipitation I of titanium；
Add a certain amount of water that solution II is made the weight % of 538g 50 manganese nitrate；
It is maintained in 80 DEG C of water-bath and 7.5g rubidium hydroxides is added in slurry III, is mixed with beating；
The pH value that slurry is finally adjusted with dust technology is 1.5, obtains colloidal sol shape and is uniformly dispersed and places for a long time and will not divide The uniform sizing material IV (solid content 35%) of layer；
By the slurry spray drying forming, spraying machine inlet temperature is 280 DEG C, 160 DEG C of outlet temperature；
Then it is calcined, 450 DEG C, roasting time 3.0h of sintering temperature, it is direct obtains microspheroidal fluid bed synthesis gas Light olefins catalyst is prepared, it is (except special identifier all components ratio is atomic ratio) that composition, which is made, in it：
Fe100Mn100Ti100Rb5.0Ox
【Comparative example 2】
Take the titanyl sulfate wiring solution-forming soluble in water of 606.03g Fe(NO3)39H2O and 40.0g, then the solution with Centrifuged after the weight % of 2665g 5 ammonia spirit cocurrent, be washed with deionized and obtain fresh iron hydroxide afterwards three times With the mixed precipitation I of titanium hydroxide；
Add a certain amount of water that solution II is made the weight % of 13.45g 50 manganese nitrate；
Solution II and mixed sediment I are blended in peptization in 40 DEG C of water-bath and obtain colloidal slurry III；
It is maintained in 40 DEG C of water-bath and 0.084g potassium hydroxide is added in slurry III, be mixed with beating, then adds grain Degree most several granularities between 10~100nm about cause graphite powder in 30nm or so graphite powder 17.2g, cutter THE ADIABATIC SHEAR IN It is dispersed in the slurry；
With ammoniacal liquor regulation slurry pH value be 5, obtain colloidal sol shape be uniformly dispersed and for a long time place will not be layered it is uniform Slurry IV (solid content 45%)；
By the slurry spray drying forming, spraying machine inlet temperature is 350 DEG C, 230 DEG C of outlet temperature；
Then it is calcined, 550 DEG C, roasting time 6h of sintering temperature, obtains microspheroidal fluid bed and directly made with synthesis gas Standby light olefins catalyst, it is (except special identifier all components ratio is atomic ratio) that composition, which is made, in it：
90 weight %Fe100Mn2.5Ti20K0.1Ox+ 10 weight %C.
【Comparative example 3】：
606.03g Fe(NO3)39H2O wiring solution-forming soluble in water is taken, then the ammonia of the solution and the weight % of 2665g 5 Centrifuged after aqueous solution cocurrent, be washed with deionized and obtain fresh iron hydroxide afterwards three times and the mixing of titanium hydroxide is sunk Shallow lake I；
Add a certain amount of water that solution II is made the weight % of 13.45g 50 manganese nitrate；
Solution II and mixed sediment I are blended in peptization in 40 DEG C of water-bath and obtain colloidal slurry III；
It is maintained in 40 DEG C of water-bath and 0.084g potassium hydroxide is added in slurry III, be mixed with beating, then adds grain Degree most several granularities between 10~100nm about cause graphite powder in 30nm or so graphite powder 6.43g, cutter THE ADIABATIC SHEAR IN It is dispersed in the slurry；
With ammoniacal liquor regulation slurry pH value be 5, obtain colloidal sol shape be uniformly dispersed and for a long time place will not be layered it is uniform Slurry IV (solid content 45%)；
By the slurry spray drying forming, spraying machine inlet temperature is 350 DEG C, 230 DEG C of outlet temperature；
Then it is calcined, 550 DEG C, roasting time 6h of sintering temperature, obtains microspheroidal fluid bed and directly made with synthesis gas Standby light olefins catalyst, it is (except special identifier all components ratio is atomic ratio) that composition, which is made, in it：
95 weight %Fe100Mn2.5K0.1Ox+ 5 weight %C.
【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：
250 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
10 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
Raw material proportioning (mole) H2/ CO=3/1
By comparative example 3, the evaluation analysis result in fixed bed as described in patent CN 1395993A is listed in table 1.
Table 1
#It is reacted to data during 2000h
* the data of former patent are selected from

Claims (10)

1. a kind of synthesis gas for fluid bed directly prepares the catalyst of low-carbon alkene, catalyst in terms of parts by weight, including Following components：
A) 0.5~5 part of structural promoter, the auxiliary agent are the nano-carbon powder of graphite state；
B) 95~99.5 parts of active components, active component contain with atomic ratio measuring, the following composition of chemical formula：Fe100AaBbCcOx
The one kind of A in Mn or Mo
B is selected from least one of Ti or Zr；
C is selected from least one of alkali metal；
A span is 2.5~250.0；
B span is 20~200.0；
C span is 0.1~10.0；
X is to meet the oxygen atom sum in catalyst needed for each element chemical valence.
2. the synthesis gas according to claim 1 for fluid bed directly prepares the catalyst of low-carbon alkene, its feature exists In a span be 5~200.0.
3. the synthesis gas according to claim 1 for fluid bed directly prepares the catalyst of low-carbon alkene, its feature exists In b span be 25~180.0.
4. the synthesis gas according to claim 1 for fluid bed directly prepares the catalyst of low-carbon alkene, its feature exists In c span be 0.5~8.0.
5. the synthesis gas according to claim 1 for fluid bed directly prepares the catalyst of low-carbon alkene, its feature exists It is by weight percentage the 0.8~4.5% of catalyst weight to be in structural promoter dosage.
6. the synthesis gas according to claim 1 for fluid bed directly prepares the catalyst of low-carbon alkene, its feature exists In structural promoter graphite state nano-carbon powder granularity between 10~100nm.
7. the synthesis gas according to claim 1 for fluid bed directly prepares the catalyst of low-carbon alkene, its preparation side Method comprises the following steps that：
(1) by Dissolvable Fe salt with B salt is soluble in water that solution is made；Then sunk with being filtrated to get to mix after alkaline precipitating agent cocurrent Starch I；
(2) solution II is made by A ackd salt is soluble in water；
(3) solution II is mixed into peptization with mixed sediment I and obtains slurry III；
(4) solution of the hydroxide of C classes or salt is added in slurry III and be mixed with beating, then add nano level graphite state Carbon dust is sheared or glue mill makes its dispersed in the slurry, while the pH value for adding acid-base modifier regulation slurry obtains for 1~5 To slurry IV, the solid content of slurry IV is 15~45 weight %；
(5) slurry IV is sent into spray dryer spray shaping, then in 350~550 DEG C of roasting temperatures 0.15~6 hour, Obtain microspheric catalyst.
8. fluid bed according to claim 7 directly prepares the preparation method of light olefins catalyst with synthesis gas, it is special Sign is that peptization and the temperature of the honed journey of shearing/glue maintain 40~80 DEG C.
9. fluid bed according to claim 7 directly prepares the preparation method of light olefins catalyst with synthesis gas, it is special Sign is that the spray shaping condition of catalyst is 200~350 DEG C of inlet temperature, 100~230 DEG C of outlet temperature.
10. fluid bed according to claim 7 directly prepares the preparation method of light olefins catalyst with synthesis gas, it is special Sign is that sintering temperature is 400~500 DEG C, and roasting time is 0.5~5 hour.
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Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1704161A (en) * 2004-05-28 2005-12-07 上海兖矿能源科技研发有限公司 Sintered iron catalyst for Fischer-Tropsch Synthesis and preparation method and application thereof
CN103962148A (en) * 2013-01-29 2014-08-06 中国石油化工股份有限公司 Fluidized bed catalyst for directly preparing low-carbon olefins from synthesis gas and producing method thereof
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
CN104275189A (en) * 2013-07-09 2015-01-14 中国石油化工股份有限公司 High-temperature sintering type catalyst for preparing light olefins from synthetic gas and preparation method thereof
CN104289226A (en) * 2014-09-08 2015-01-21 赵锦玲 Multifunctional solid catalyst
CN104801304A (en) * 2014-01-28 2015-07-29 中国科学院大连化学物理研究所 Iron-based catalyst for preparation of low carbon olefin from synthetic gas, and preparation method and application thereof
CN105195189A (en) * 2015-10-29 2015-12-30 江南大学 Catalyst facilitating direct preparation of light olefins from syngas as well as preparation and application of catalyst
CN105597776A (en) * 2016-02-22 2016-05-25 神华集团有限责任公司 Catalyst for Fischer-Tropsch synthesis and preparing method thereof
CN105854886A (en) * 2016-04-14 2016-08-17 宁夏大学 Catalyst for preparing low-carbon olefin through one-step conversion of synthesis gas and preparing method and application thereof

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1704161A (en) * 2004-05-28 2005-12-07 上海兖矿能源科技研发有限公司 Sintered iron catalyst for Fischer-Tropsch Synthesis and preparation method and application thereof
CN103962148A (en) * 2013-01-29 2014-08-06 中国石油化工股份有限公司 Fluidized bed catalyst for directly preparing low-carbon olefins from synthesis gas and producing method thereof
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
CN104275189A (en) * 2013-07-09 2015-01-14 中国石油化工股份有限公司 High-temperature sintering type catalyst for preparing light olefins from synthetic gas and preparation method thereof
CN104801304A (en) * 2014-01-28 2015-07-29 中国科学院大连化学物理研究所 Iron-based catalyst for preparation of low carbon olefin from synthetic gas, and preparation method and application thereof
CN104289226A (en) * 2014-09-08 2015-01-21 赵锦玲 Multifunctional solid catalyst
CN105195189A (en) * 2015-10-29 2015-12-30 江南大学 Catalyst facilitating direct preparation of light olefins from syngas as well as preparation and application of catalyst
CN105597776A (en) * 2016-02-22 2016-05-25 神华集团有限责任公司 Catalyst for Fischer-Tropsch synthesis and preparing method thereof
CN105854886A (en) * 2016-04-14 2016-08-17 宁夏大学 Catalyst for preparing low-carbon olefin through one-step conversion of synthesis gas and preparing method and application thereof

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