CN106607053A - Fe-Mn catalyst for directly preparing low-carbon olefins from synthesis gas and preparation method of Fe-Mn catalyst - Google Patents
Fe-Mn catalyst for directly preparing low-carbon olefins from synthesis gas and preparation method of Fe-Mn catalyst Download PDFInfo
- Publication number
- CN106607053A CN106607053A CN201510686093.2A CN201510686093A CN106607053A CN 106607053 A CN106607053 A CN 106607053A CN 201510686093 A CN201510686093 A CN 201510686093A CN 106607053 A CN106607053 A CN 106607053A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- synthesis gas
- weight
- low
- carbon alkene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a Fe-Mn catalyst for directly preparing low-carbon olefins from synthesis gas for a fluidized bed and a preparation method of the Fe-Mn catalyst. The catalyst is mainly used for solving the problems that the Fischer-Tropsch synthesis reaction is a strong exothermic reaction, so that when a static bed is used, heat removal in a reactor is difficult, temperature runaway is easy, a catalyst is prone to inactivation and the weight selectivity of low-carbon inactivation is low in the prior art. The adopted catalyst comprises, by weight, 10-70 parts of carriers and 30-90 parts of active components, wherein the carriers are selected from at least one of Si oxide and Al oxide, the active components contain the composition with the chemical formula being Fe100MnaBbCcOx in the atomic ratio, B is selected from one of Pd and Pt, and C is selected from one of alkaline-earth metals. Accordingly, the technical problems are well solved, and the Fe-Mn catalyst is used in industrial production for directly preparing low-carbon olefins from synthesis gas.
Description
Technical field
The present invention relates to a kind of directly prepare Fe-Mn series catalysts of low-carbon alkene and preparation method thereof for synthesis gas
Background technology
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 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.
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.
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
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 new synthesis gas is directly synthesized the Fe-series catalyst of low-carbon alkene.When the catalyst is directly synthesized low-carbon alkene for synthesis gas, 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 synthesis gas directly prepares the Fe-Mn catalyst of low-carbon alkene.The catalyst is in terms of parts by weight, including following components：A) 10～70 parts of carriers, carrier is at least one in the oxide of Si or Al；B) 30～90 parts of active components, active component contains with atomic ratio measuring chemical formula such as Fe100MnaBbCcOxCompositionss, at least one of the wherein B in the Pt or Pd, at least one of the C in alkaline-earth metal, the span of a is 2.5～250.0, the span of b for the span of 0.1～10.0, c be 0.5～20.0, x to meet catalyst in oxygen atom sum needed for each element quantivalence.
Catalyst formulation is preferably active component and also includes element D in above-mentioned technical proposal, D for Cl or Br at least one, the ratio of D and Fe is with atomic ratio measuring as Fe：D=100：The span of d, d is 0.01～2.
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 5～200.0, the value preferred scope of b is 0.03～1.75 for the value preferred scope of 1.0～18.0, d for the value preferred scope of 0.5～8.0, c.
It is as follows to solve above-mentioned technical problem the technical solution used in the present invention two：Synthesis gas directly prepares the preparation method of the Fe-Mn catalyst of low-carbon alkene, comprises the following steps that：
(1) Dissolvable Fe salt is made into solution with belit 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 Mn salt is soluble in water；
(3) solution II is mixed into peptization with mixed sediment I and obtains slurry III；
(4) will be selected from SiO2Or Al2O3In at least one colloidal sol and the hydroxide or saline solution of C classes and the compound solution of D be added in slurry III, mixing beating, while adding the pH value that acid-base modifier adjusts slurry to be 1～5 to obtain slurry IV, 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-Mn series catalysts.
The scope of inlet temperature 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 precious metals pt or Pd can improve the Hydrogenation of catalyst，So that the conversion ratio of catalyst is improved，But the effect of Mn can then suppress the further hydrogenation of alkene，So that the amount of alkene is far longer than the amount of alkane in product，And the poisoning of slight Cl or Br then can cooperate with to suppress the excessive carbonization of catalyst surface come so that catalyst can ensure that the long-play under high activity with precious metals pt or Pd，Special preparation method causes the duct of preformed catalyst to be more conducive to formation and the desorption of lower carbon number hydrocarbons，The active component of catalyst is caused to disperse as far as possible simultaneously，Reduce the reunion that active component causes because of area carbon，The catalyst is allowd to keep the selectivity of high conversion ratio and high low-carbon alkene for a long time，It is highly suitable for the commercial Application that synthesis gas is directly synthesized low-carbon alkene.
Above-mentioned catalyst is for the reaction of F- T synthesis low-carbon alkene, 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 10000 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】
Take five water platinum tetrachlorides of the Fe(NO3)39H2O and 16.0g wiring solution-forming soluble in water of 606.03g, 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 platinum oxide free from foreign meter after being washed with deionized three times；Add a certain amount of water to make solution II manganese nitrate of weight % of 13.45g 50, solution II is mixed into peptization with mixed sediment I and obtains colloidal slurry III；By the SiO that 49.5g weight contents are 40%2Colloidal sol is added in slurry III with the magnesium nitrate hexahydrate of 76.92g, mixing beating, it is subsequently adding the dilute hydrochloric acid of 0.11g5 weight %, the pH value for adjusting slurry with ammonia is 5, obtain colloidal sol shape to be uniformly dispersed and place the uniform sizing material IV (solid content 45%) that will not be layered for a long time, by the slurry spray drying forming, 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 low-carbon alkene ferrum-manganese series catalyzer, it is made and consists of (except special identifier all components ratio is atomic ratio)：
90 weight %Fe100Mn2.5Pt0.1Mg20.0Cl0.01Ox+ 10 weight %SiO2。
【Embodiment 2】：
Take the palladium chloride of the Fe(NO3)39H2O and 26.60g wiring solution-forming soluble in water of 606.03g, then centrifugation after the strong aqua ammonia cocurrent of the solution and weight % of 400g 25, obtains the mixed precipitation I of fresh pure hydrated ferric oxide. and Palladium monoxide after being washed with deionized three times；The manganese nitrate of 1345g50% is dissolved in the water and makes solution II, solution II is mixed into peptization with mixed sediment I and obtains colloidal slurry III；By the Al that 1016g weight contents are 25%2O3Colloidal sol is added in slurry III with 35.42g calcium nitrate tetrahydrates, mixing beating, it is subsequently adding the weight % dilute hydrobromic acids of 48.6g 5, the pH value for adjusting slurry is 1, obtain colloidal sol shape to be uniformly dispersed and place 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 low-carbon alkene ferrum-manganese series catalyzer, it is made and consists of (except special identifier all components ratio is atomic ratio)：
60 weight %Fe100Mn250.0Pd10.0Ca10.0Br2.0Ox+ 40 weight %Al2O3。
【Embodiment 3】：
Take five water platinum tetrachlorides of 367.43g ferric citrates and 160g wiring solution-forming soluble in water, then centrifugation after the strong aqua ammonia cocurrent of the solution and weight % of 400g 25, obtains the mixed precipitation I of fresh pure hydrated ferric oxide. and platinum oxide after being washed with deionized three times；Add a certain amount of water to make solution II manganese nitrate of weight % of 26.90g 50, solution I is mixed into beating with mixed sediment II and obtains colloidal slurry III；By the SiO of 435g weight contents 40%2Colloidal sol is added in slurry III with 63.49g strontium nitrates, mixing beating, it is subsequently adding the dilute hydrochloric acid of 0.33g5 weight %, the pH value for adjusting slurry is 3, obtain colloidal sol shape to be uniformly dispersed and place the uniform sizing material IV (solid content 35%) that will not be layered for a long time, by the slurry spray drying forming, 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 low-carbon alkene ferrum-manganese series catalyzer, it is made and consists of (except special identifier all components ratio is atomic ratio)：
50 weight %Fe100Mn5.0Pt1.0Sr20.0Cl0.03Ox+ 50 weight %SiO2
【Embodiment 4】：
Take the palladium chloride of the Fe(NO3)39H2O and 0.53g wiring solution-forming soluble in water of 606.03g, then centrifugation after the strong aqua ammonia cocurrent of the solution and weight % of 400g 25, obtains the mixed precipitation I of fresh pure hydrated ferric oxide. and Palladium monoxide after being washed with deionized three times；Add a certain amount of water to make solution II manganese nitrate of weight % of 1076g 50, solution I is mixed into beating with mixed sediment II and obtains colloidal slurry III；By the SiO that 1150g weight contents are 40%2Colloidal sol and the TiO that 1380g weight contents are 20%2Colloidal sol is added in slurry III with 3.92g barium nitrates, mixing beating, it is subsequently adding the dilute hydrochloric acid of 19.25g5 weight %, the pH value for adjusting slurry simultaneously is 2.5, obtain colloidal sol shape to be uniformly dispersed and place the uniform sizing material IV (solid content 30%) that will not be layered for a long time, by the slurry spray drying forming, 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, microspheroidal fluid bed synthesis gas must be obtained and directly prepare low-carbon alkene ferrum-manganese series catalyzer, it is made and consists of (except special identifier all components ratio is atomic ratio)：
30 weight %Fe100Mn200.0Pd0.5Ba1.0Cl1.75Ox+ 30 weight %Al2O3+ 40 weight %SiO2
【Embodiment 5】：
Take the palladium chloride of the Fe(NO3)39H2O and 21.28g wiring solution-forming soluble in water of 606.03g, then centrifugation after the strong aqua ammonia cocurrent of the solution and weight % of 400g 25, obtains the mixed precipitation I of fresh pure hydrated ferric oxide. and Palladium monoxide after being washed with deionized three times；Add a certain amount of water to make solution II manganese nitrate of weight % of 26.90g 50, solution I is mixed into beating with mixed sediment II and obtains colloidal slurry III；By the SiO of 435g weight contents 40%2Colloidal sol is added in slurry III with the magnesium nitrate hexahydrate of 53.13g calcium nitrate tetrahydrates and 19.23g, mixing beating, it is subsequently adding the dilute hydrochloric acid of 0.33g5 weight %, the pH value for adjusting slurry with weak ammonia is 3.5, obtain colloidal sol shape to be uniformly dispersed and place 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 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 low-carbon alkene ferrum-manganese series catalyzer, it is made and consists of (except special identifier all components ratio is atomic ratio)：
50 weight %Fe100Mn5Pd8.0Ca15.0Mg5.0Cl0.03Ox+ 50 weight %SiO2
【Embodiment 6】：
The palladium chloride of the Fe(NO3)39H2O and 0.53g that take 606.03g 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 pure hydrated ferric oxide. and Palladium monoxide after being washed with deionized three times；The manganese nitrate of 53.8g50 weight % is dissolved in the water and makes solution II, solution II is mixed into beating with mixed sediment I and obtains colloidal slurry III；By the Al of 800g weight contents 25%2O3Colloidal sol is added in slurry III with the magnesium nitrate hexahydrate of 19.23g, mixing beating, it is subsequently adding the dilute hydrochloric acid of 19.25g5 weight %, the pH value for adjusting slurry is 4.5, obtain colloidal sol shape to be uniformly dispersed and place the uniform sizing material IV (solid content 20%) that will not be layered for a long time, by the slurry spray drying forming, 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 low-carbon alkene ferrum-manganese series catalyzer, it is made and consists of (except special identifier all components ratio is atomic ratio)：
45 weight %Fe100Mn10.0Pd0.2Mg5.0Cl1.75Ox+ 55 weight %Al2O3。
【Embodiment 7】：
Take the palladium chloride wiring solution-forming soluble in water of the Fe(NO3)39H2O 13.3g of 606.03g, then centrifugation after the strong aqua ammonia cocurrent of the solution and weight % of 400g 25, obtains the mixed precipitation I of fresh pure hydrated ferric oxide. and Palladium monoxide after being washed with deionized three times；The manganese nitrate of 53.8g50 weight % is dissolved in the water and makes solution II, solution II is mixed into beating with mixed sediment I and obtains colloidal slurry III；By the SiO of 41.35g weight contents 40%2Colloidal sol and 33.08g weight content 25%Al2O3It is added in slurry III with the magnesium nitrate hexahydrate of 76.92g, mixing beating, it is subsequently adding the dilute hydrochloric acid and the weight % dilute hydrobromic acids of 0.73g 5 of 0.33g5 weight %, the pH value for adjusting slurry is 3.5, obtain colloidal sol shape to be uniformly dispersed and place 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 low-carbon alkene ferrum-manganese series catalyzer, it is made and consists of (except special identifier all components ratio is atomic ratio)：
85 weight %Fe100Mn10.0Pd5.0Mg20.0Cl0.03Br0.03Ox+ 10 weight %SiO2+ 5 weight %Al2O3
【Embodiment 8】：
Take five water platinum tetrachlorides of the Fe(NO3)39H2O and 80.0g wiring solution-forming soluble in water of 606.03g, then centrifugation after the strong aqua ammonia cocurrent of the solution and weight % of 400g 25, obtains the mixed precipitation I of fresh pure hydrated ferric oxide. and platinum oxide after being washed with deionized three times；The manganese nitrate of 53.8g50 weight % is dissolved in the water and makes solution II, solution II is mixed into beating with mixed sediment I and obtains colloidal slurry III；By the Al of 800g weight contents 25%2O3Colloidal sol is added in slurry III with the magnesium nitrate hexahydrate of 76.92g and the potassium hydroxide of 1.68g, mixing beating, it is subsequently adding the dilute hydrochloric acid of 19.25g5 weight %, the pH value for adjusting slurry is 1.5, obtain colloidal sol shape to be uniformly dispersed and place the uniform sizing material IV (solid content 20%) that will not be layered for a long time, by the slurry spray drying forming, 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 low-carbon alkene ferrum-manganese series catalyzer, it is made and consists of (except special identifier all components ratio is atomic ratio)：
45 weight %Fe100Mn10.0Pt0.5Mg20.0K2.0Cl1.75Ox+ 55 weight %Al2O3。
【Embodiment 9】：
Take the palladium chloride wiring solution-forming soluble in water of the Fe(NO3)39H2O of 606.03g and the five water platinum tetrachlorides of 80.0g and 1.33g, then centrifugation after the strong aqua ammonia cocurrent of the solution and weight % of 400g 25, obtains the mixed precipitation I of fresh pure hydrated ferric oxide. and platinum oxide and Palladium monoxide after being washed with deionized three times；The manganese nitrate of 269g 50% is dissolved in the water and makes solution II, solution II is mixed into beating with mixed sediment I and obtains colloidal slurry III；By the SiO that 440g weight contents are 40%2Colloidal sol is added in slurry III with the magnesium nitrate hexahydrate of 53.13g calcium nitrate tetrahydrates and 19.23g, mixing beating, it is subsequently adding the dilute hydrochloric acid of 19.25g5 weight %, the pH value for adjusting slurry is 4.7, obtain colloidal sol shape to be uniformly dispersed and place the uniform sizing material IV (solid content 20%) that will not be layered for a long time, by the slurry spray drying forming, 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 low-carbon alkene ferrum-manganese series catalyzer, it is made and consists of (except special identifier all components ratio is atomic ratio)：
50 weight %Fe100Mn50Pt0.5Pd0.5Ca15.0Mg5.0Cl1.75Ox+ 50 weight %SiO2
【Embodiment 10】
Take the palladium chloride wiring solution-forming soluble in water of the Fe(NO3)39H2O of 606.03g and the five water platinum tetrachlorides of 80.0g and 1.33g, then centrifugation after the strong aqua ammonia cocurrent of the solution and weight % of 400g 25, obtains the mixed precipitation I of fresh pure hydrated ferric oxide. and platinum oxide and Palladium monoxide after being washed with deionized three times；The manganese nitrate of 269g 50% is dissolved in the water and makes solution II, solution II is mixed into beating with mixed sediment I and obtains colloidal slurry III；By the SiO that 440g weight contents are 40%2The magnesium nitrate hexahydrate of colloidal sol and 19.23g is added in slurry III, mixing beating, it is subsequently adding the dilute hydrochloric acid of 19.25g5 weight %, the pH value for adjusting slurry is 5, obtain colloidal sol shape to be uniformly dispersed and place the uniform sizing material IV (solid content 45%) that will not be layered for a long time, by the slurry spray drying forming, 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 iron-base fischer-tropsch synthesis catalyst, it is made and consists of (except special identifier all components ratio is atomic ratio)：
50 weight %Fe100Mn50Pt0.5Pd0.5Mg5.0Cl1.75Ox+ 50 weight %SiO2
【Comparative example 1】
Take five water platinum tetrachlorides of the Fe(NO3)39H2O and 16.0g wiring solution-forming soluble in water of 606.03g, 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 platinum oxide free from foreign meter after being washed with deionized three times；Add a certain amount of water to make solution II manganese nitrate of weight % of 13.45g 50, solution II is mixed into peptization with mixed sediment I and obtains colloidal slurry III；By the SiO that 8442.3g weight contents are 40%2Colloidal sol is added in slurry III with the magnesium nitrate hexahydrate of 19.23g, mixing beating, it is subsequently adding the dilute hydrochloric acid of 0.11g5 weight %, the pH value for adjusting slurry is 5, obtain colloidal sol shape to be uniformly dispersed and place the uniform sizing material IV (solid content 45%) that will not be layered for a long time, by the slurry spray drying forming, 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 low-carbon alkene ferrum-manganese series catalyzer, it is made and consists of (except special identifier all components ratio is atomic ratio)：
5 weight %Fe100Mn2.5Pt0.1Mg20.0Cl0.01Ox+ 95 weight %SiO2。
【Comparative example 2】
Take five water platinum tetrachlorides of the Fe(NO3)39H2O and 16.0g wiring solution-forming soluble in water of 606.03g, 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 platinum oxide free from foreign meter after being washed with deionized three times；By the SiO that 49.5g weight contents are 40%2Colloidal sol is added in slurry III with the magnesium nitrate hexahydrate of 76.92g, mixing beating, it is subsequently adding the dilute hydrochloric acid of 0.11g5 weight %, the pH value for adjusting slurry is 5, obtain colloidal sol shape to be uniformly dispersed and place the uniform sizing material IV (solid content 45%) that will not be layered for a long time, by the slurry spray drying forming, 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 low-carbon alkene ferrum-manganese series catalyzer, it is made and consists of (except special identifier all components ratio is atomic ratio)：
90 weight %Fe100Pt0.1Mg20.0Cl0.01Ox+ 10 weight %SiO2。
【Comparative example 3】：
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 fresh pure ferric hydroxide precipitate I after being washed with deionized three times；The manganese nitrate of 269g 50% is dissolved in the water and makes solution II, solution II is mixed into beating with mixed sediment I and obtains colloidal slurry III；By the SiO that 440g weight contents are 40%2Colloidal sol is added in slurry III with 53.13g calcium nitrate tetrahydrates, mixing beating, the pH value for adjusting slurry is 4.7, obtain colloidal sol shape to be uniformly dispersed and place the uniform sizing material IV (solid content 20%) that will not be layered for a long time, by the slurry spray drying forming, 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, obtains microspheroidal fluid bed synthesis gas and directly prepares low-carbon alkene ferrum-manganese series catalyzer, and it is made and consists of (except special identifier all components ratio is atomic ratio)：
50 weight %Fe100Mn50Ca15.0Ox+ 50 weight %SiO2
【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 4, 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 (10)
1. a kind of Fe-Mn series catalysts that low-carbon alkene is directly prepared for synthesis gas, catalyst in terms of parts by weight,
Including following components：
A) 10～70 parts of carriers, carrier is at least one in the oxide of Si or Al；
B) 30～90 parts of active components, active component contains with atomic ratio measuring, the following compositionss of chemical formula：
Fe100MnaBbCcOx
At least one of the B in Pd or Pt；
At least one of the C in alkaline-earth metal；
The span of a is 2.5～250.0；
The span of b is 0.1～10.0；
The span of c is 0.5～20.0；
X to meet catalyst in oxygen atom sum needed for each element quantivalence.
2. Fe-Mn series catalysts that low-carbon alkene is directly prepared for synthesis gas according to claim 1, its
Active component also includes element D, and D is at least one of Cl or Br, and the ratio of D and Fe is with atomic ratio measuring
For Fe：D=100：The span of d, d is 0.01～2.
3. Fe-Mn series catalysts that low-carbon alkene is directly prepared for synthesis gas according to claim 1 and 2,
It is characterized in that the span of a is 5～200.0.
4. Fe-Mn series catalysts that low-carbon alkene is directly prepared for synthesis gas according to claim 1 and 2,
It is characterized in that the span of b is 0.5～8.0.
5. Fe-Mn series catalysts that low-carbon alkene is directly prepared for synthesis gas according to claim 1 and 2,
It is characterized in that the span of c is 1.0～18.0.
6. Fe-Mn series catalysts that low-carbon alkene is directly prepared for synthesis gas according to claim 1 and 2,
It is characterized in that carrier consumption is to be by weight percentage the 15～65% of catalyst weight.
7. Fe-Mn series catalysts that low-carbon alkene is directly prepared for synthesis gas according to claim 2, its
The span for being characterised by d is 0.03～1.75.
8. the Fe-Mn series catalysts for directly preparing low-carbon alkene for synthesis gas described in claim 1 or 2, wrap
Include following processing step：
(1) Dissolvable Fe salt is made into solution with belit is soluble in water；Then with alkaline precipitating agent cocurrent after
It is filtrated to get mixed sediment I；
(2) solution II is made by Mn salt is soluble in water；
(3) solution II is mixed into peptization with mixed sediment I and obtains slurry III；
(4) will be selected from SiO2Or Al2O3In at least one colloidal sol and C classes hydroxide or saline solution
And the compound solution of D is added in slurry III, mixing beating, while adding acid-base modifier to adjust slurry
The pH value of material obtains slurry IV for 1～5, and 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 hours, obtain microspheroidal Fe-Mn series catalysts.
9. the system of the Fe-Mn series catalysts that low-carbon alkene is directly prepared for synthesis gas according to claim 8
Preparation Method, it is characterised in that the spray shaping condition of catalyst be 200～380 DEG C of inlet temperature, outlet temperature
100～230 DEG C.
10. Fe-Mn series catalysts that low-carbon alkene is directly prepared for synthesis gas according to claim 8
Preparation method, it is characterised in that sintering temperature is 450～700 DEG C, roasting time is 0.5～5 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510686093.2A CN106607053B (en) | 2015-10-21 | 2015-10-21 | Synthesis gas directly prepares Fe-Mn series catalysts of low-carbon alkene and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510686093.2A CN106607053B (en) | 2015-10-21 | 2015-10-21 | Synthesis gas directly prepares Fe-Mn series catalysts of low-carbon alkene and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106607053A true CN106607053A (en) | 2017-05-03 |
| CN106607053B CN106607053B (en) | 2019-06-11 |
Family
ID=58610952
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510686093.2A Active CN106607053B (en) | 2015-10-21 | 2015-10-21 | Synthesis gas directly prepares Fe-Mn series catalysts of low-carbon alkene and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106607053B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109092322A (en) * | 2017-06-21 | 2018-12-28 | 中国石油化工股份有限公司 | The catalyst system of the direct producing light olefins of synthesis gas |
| CN111068690A (en) * | 2018-10-18 | 2020-04-28 | 中国石油化工股份有限公司 | Catalyst for directly preparing low-carbon olefin from synthesis gas and application thereof |
| CN111068703A (en) * | 2018-10-18 | 2020-04-28 | 中国石油化工股份有限公司 | Catalyst for directly preparing low-carbon olefin from synthesis gas and application thereof |
| CN112619652A (en) * | 2019-09-24 | 2021-04-09 | 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 |
| CN112705218A (en) * | 2019-10-24 | 2021-04-27 | 中国石油化工股份有限公司 | Catalyst for preparing low-carbon olefin from synthesis gas, preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101745414A (en) * | 2008-12-12 | 2010-06-23 | 北京化工大学 | Catalyst for producing light olefins through methanol and preparation method thereof |
| CN103249481A (en) * | 2010-08-09 | 2013-08-14 | Gtl.F1公司 | Fischer-tropsch catalysts |
| CN103657676A (en) * | 2012-09-05 | 2014-03-26 | 中国石油化工股份有限公司 | Microspheric Fischer-Tropsch synthesis catalyst and preparation method and application of microspheric Fischer-Tropsch synthesis catalyst |
| 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 |
-
2015
- 2015-10-21 CN CN201510686093.2A patent/CN106607053B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101745414A (en) * | 2008-12-12 | 2010-06-23 | 北京化工大学 | Catalyst for producing light olefins through methanol and preparation method thereof |
| CN103249481A (en) * | 2010-08-09 | 2013-08-14 | Gtl.F1公司 | Fischer-tropsch catalysts |
| CN103657676A (en) * | 2012-09-05 | 2014-03-26 | 中国石油化工股份有限公司 | Microspheric Fischer-Tropsch synthesis catalyst and preparation method and application of microspheric Fischer-Tropsch synthesis catalyst |
| 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 |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109092322A (en) * | 2017-06-21 | 2018-12-28 | 中国石油化工股份有限公司 | The catalyst system of the direct producing light olefins of synthesis gas |
| CN109092322B (en) * | 2017-06-21 | 2021-05-11 | 中国石油化工股份有限公司 | Catalyst system for directly preparing low-carbon olefin from synthesis gas |
| CN111068690A (en) * | 2018-10-18 | 2020-04-28 | 中国石油化工股份有限公司 | Catalyst for directly preparing low-carbon olefin from synthesis gas and application thereof |
| CN111068703A (en) * | 2018-10-18 | 2020-04-28 | 中国石油化工股份有限公司 | Catalyst for directly preparing low-carbon olefin from synthesis gas and application thereof |
| CN112619652A (en) * | 2019-09-24 | 2021-04-09 | 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 |
| CN112619652B (en) * | 2019-09-24 | 2023-08-08 | 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 |
| CN112705218A (en) * | 2019-10-24 | 2021-04-27 | 中国石油化工股份有限公司 | Catalyst for preparing low-carbon olefin from synthesis gas, preparation method and application thereof |
| CN112705218B (en) * | 2019-10-24 | 2023-11-28 | 中国石油化工股份有限公司 | Catalyst for preparing low-carbon olefin from synthesis gas, preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106607053B (en) | 2019-06-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104226329B (en) | Catalyst for direct preparation of low carbon olefin from synthesis gas and preparation method thereof | |
| CN106607037B (en) | GTO catalyst for fluid bed and preparation method thereof | |
| CN106607053B (en) | Synthesis gas directly prepares Fe-Mn series catalysts of low-carbon alkene and preparation method thereof | |
| CN104549296A (en) | Catalyst for directly preparing low-carbon olefin from microspherical synthesis gas, as well as preparation method thereof | |
| CN102371155B (en) | Iron-based catalyst for Fischer-Tropsch synthesis of heavy hydrocarbon and its preparation method | |
| CN101993707B (en) | Fischer-Tropsch synthesis method for heavy hydrocarbon | |
| CN103933989B (en) | For the synthesis of the Catalysts and its preparation method of low-carbon alkene | |
| CN102453492B (en) | Fischer-Tropsch synthesis method for heavy hydrocarbons | |
| CN106607061A (en) | Fluidized bed catalyst for preparing low-carbon olefin from synthetic gas through one step method and preparation method of fluidized bed catalyst | |
| CN106607051B (en) | The catalyst and preparation method thereof of one step producing light olefins of synthesis gas | |
| CN106607050B (en) | The fluid catalyst and preparation method thereof of one-step method from syngas producing light olefins | |
| CN104107699B (en) | Ferrum-based catalyst for synthesizing low-carbon alkene and preparation method thereof | |
| CN105363463A (en) | Catalyst for synthesizing gas light hydrocarbon and preparation method of catalyst | |
| CN105363458A (en) | Catalyst for synthesizing light hydrocarbon and preparation method of catalyst | |
| CN106607058A (en) | Iron-based catalyst for preparing low-carbon olefin directly from synthesis gas and preparation method of iron-based catalyst | |
| CN102041021B (en) | Method for synthesizing heavy hydrocarbon by fischer-tropsch | |
| CN102039135B (en) | Fe-based fluidized bed catalyst for Fischer-Tropsch synthesis and preparation method thereof | |
| CN109092321A (en) | The catalyst system of one-step method from syngas producing light olefins | |
| CN106607059A (en) | Fe-Mn-based catalyst for preparing low-carbon olefin directly from synthesis gas and preparation method of Fe-Mn-based catalyst | |
| CN111068687B (en) | Catalyst for preparing low-carbon olefin by synthesis gas one-step method and application thereof | |
| CN103418393B (en) | The Catalysts and its preparation method of Fischer-Tropsch synthesis of heavy hydrocarbon | |
| CN106607049B (en) | Catalyst of preparation of low carbon olefines by synthetic gas and preparation method thereof | |
| CN103666517A (en) | Method for producing heavy hydrocarbons through Fischer-Tropsch synthesis | |
| CN103657676B (en) | Microspherical Fischer-Tropsch catalyst and its preparation method and application | |
| CN109647428A (en) | The ferrum-based catalyst of one-step method from syngas producing light olefins |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |