CN106607048A - Method for producing low-carbon olefins by using fixed bed - Google Patents
Method for producing low-carbon olefins by using fixed bed Download PDFInfo
- Publication number
- CN106607048A CN106607048A CN201510685508.4A CN201510685508A CN106607048A CN 106607048 A CN106607048 A CN 106607048A CN 201510685508 A CN201510685508 A CN 201510685508A CN 106607048 A CN106607048 A CN 106607048A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- oxide
- ferrum
- grams
- fixed bed
- 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
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
Landscapes
- Catalysts (AREA)
Abstract
The invention relates to a method for producing low-carbon olefins by using a fixed bed. The method mainly solves the problems of a low conversion rate of CO and low selectivity of the low-carbon olefins in the reaction process of producing the low-carbon olefins from synthesis gas by using the fixed bed in the prior art. According to the technical scheme, a catalyst adopted by the method comprises the following components, by weight percentage, a) 10-50% of Fe or an oxide thereof, b) 1-5% of Rh or an oxide thereof, c) 9-30% of at least one element selected from Cu and Zn or at least one oxide thereof, d) 9-30% of at least one element selected from K and Cs or at least one oxide thereof, e) 1-5% of Pr or an oxide thereof, and f) 30-70% of a carrier which comprises the following components, based on the weight of the carrier, (1) 20-70 parts of titanium oxide, and (2) 30-80 parts of silicon dioxide. The problems can be well solved through the above technical scheme, and the method can be applied to industrial production of preparing the low-carbon olefins from the synthesis gas by using the fixed bed.
Description
Technical field
The present invention relates to a kind of method of fixed bed production low-carbon alkene.
Background technology
Low-carbon alkene refers to alkene of the carbon number less than or equal to 4.Low-carbon alkene with ethylene, propylene as representative is very important basic organic chemical industry raw material, and with the rapid growth of China's economy, for a long time, supply falls short of demand in low-carbon alkene market.At present, the production of low-carbon alkene is mainly using the petrochemical industry route of lighter hydrocarbons (ethane, Petroleum, light diesel fuel) cracking, due to the day by day shortage and the long-term run at high level of crude oil price of Global Oil resource, development low-carbon alkene industry relies solely on the tube cracking furnace technique that petroleum light hydrocarbon is raw material can run into an increasing raw material difficult problem, and low-carbon alkene production technology and raw material must diversification.The direct preparing low-carbon olefins of one-step method from syngas are exactly carbon monoxide and hydrogen under catalyst action, the process of low-carbon alkene of the carbon number less than or equal to 4 is directly obtained by Fischer-Tropsch synthesis, the technique need not be as indirect method technique from synthesis gas through methanol or dimethyl ether, further prepare alkene, simplification of flowsheet, greatly reduces investment.Petroleum resources shortage at home, it is current that external dependence degree more and more higher, international oil price constantly rise violently, raw material sources can be widened from synthesis gas producing olefinic hydrocarbons technique, will with crude oil, natural gas, coal and recyclable materials as raw material production synthesis gas, can for based on the steam cracking technology of high cost raw material such as Petroleum aspect replacement scheme is provided.The coal price of the abundant coal resources of China and relative moderate is refined oil for Development of Coal and provides the good market opportunity using preparation of low carbon olefines by synthetic gas technique.And be also using the fabulous opportunity of preparation of low carbon olefines by synthetic gas technique if Gas Prices are cheap near the oil gas field that Natural Gas In China enriches.If the coal and natural gas resource of China's abundant can be utilized, by gas making producing synthesis gas (gaseous mixture of carbon monoxide and hydrogen), the substitute energy source for petroleum technology of development preparation of low carbon olefines by synthetic gas, will be significant to solving energy problem of China.
One-step method from syngas producing light olefins technology originates from traditional Fischer-Tropsch synthesis, and the carbon number distribution of traditional Fischer-Tropsch synthetic defers to ASF distributions, and each hydro carbons all has theoretical maximum selectivity, such as C2-C4The selectivity of fraction is up to 57%, gasoline fraction (C5-C11) selectivity be up to 48%.Chain growth probability α values are bigger, and the selectivity of product heavy hydrocarbon is bigger.Once α values are determined, the selectivity of whole synthetic product is determined that, chain increases probability α values and depends on catalyst composition, granularity and reaction condition etc..In recent years, it has been found that due to the alkene secondary response that alhpa olefin adsorbing again on a catalyst causes, products distribution is distributed away from ideal ASF.F- T synthesis are a kind of strong exothermal reactions, and substantial amounts of reaction heat will promote catalyst carbon deposit reaction easily to generate methane and low-carbon alkanes, and cause selectivity of light olefin significantly to decline；Secondly, complicated kinetic factor also causes unfavorable to selectivity synthesis low-carbon alkene；The ASF distributions of Fischer-Tropsch synthetic limit the selectivity of synthesizing low-carbon alkene.The catalyst of F- T synthesis gas producing light olefins is mainly ferrum catalyst series, in order to improve the selectivity of the direct preparing low-carbon olefins of synthesis gas, physics and chemical modification can be carried out to fischer-tropsch synthetic catalyst, such as using the pore passage structure that molecular sieve is suitable, be conducive to low-carbon alkene to diffuse out metal active centres in time, suppress the secondary response of low-carbon alkene；Metal ion dispersibility is improved, also there is preferable olefine selective；Support-metal strong interaction changes can also improve selectivity of light olefin；The suitable transition metal of addition, can strengthen the bond energy of active component and carbon, suppress methane to generate, and improve selectivity of light olefin；Addition electronics accelerating auxiliaries, promote CO chemisorbeds heat to increase, and adsorbance also increases, and hydrogen adsorptive capacity reduces, and as a result selectivity of light olefin increases；Catalyst acid center is eliminated, the secondary response of low-carbon alkene can be suppressed, improve its selectivity.By the Support effect and some transition metal promoters of addition and alkali metal promoter of catalyst carrier, catalyst performance is can obviously improve, develop the fischer-tropsch synthetic catalyst of the novel high-activity high selectivity producing light olefins with the non-ASF distributions of product.
One-step method from syngas is directly produced low-carbon alkene, it has also become one of study hotspot of fischer-tropsch synthetic catalyst exploitation.In patent CN1083415A disclosed in Dalian Chemiclophysics Inst., Chinese Academy of Sciences, ferrum-Mn catalyst the system supported with the Group IIA such as MgO alkali metal oxide or silica-rich zeolite molecular sieve (or phosphorus aluminum zeolite), auxiliary agent is made with highly basic K or Cs ion, it is 1.0～5.0MPa in preparation of low carbon olefines by synthetic gas reaction pressure, at 300～400 DEG C of reaction temperature, higher activity (CO conversion ratios 90%) and selectivity (selectivity of light olefin 66%) can be obtained.But the catalyst preparation process is complicated, the preparation molding process cost of particularly carrier zeolite molecular sieve is higher, is unfavorable for industrialized production.In the number of patent application 01144691.9 that Beijing University of Chemical Technology is declared, laser pyrolysis processes are adopted to be prepared for Fe with reference to solid state reaction combination technique3Fe base nano-catalysts based on C are applied to preparation of low carbon olefines by synthetic gas, and achieve good catalytic effect, and due to needing to use laser pyrolysis technology, preparation technology is comparatively laborious, and raw material adopts Fe (CO)5, catalyst cost is very high, and industrialization is difficult.In patent ZL03109585.2 that Beijing University of Chemical Technology is declared, adopt vacuum impregnation technology to prepare manganese, copper, zinc silicon, potassium etc. and react for preparation of low carbon olefines by synthetic gas for the Fe/ activated-carbon catalysts of auxiliary agent, under conditions of circulating without unstripped gas, CO conversion ratios 96%, selectivity 68% of the low-carbon alkene in Hydrocarbon.The iron salt and auxiliary agent manganese salt that the catalyst preparation is used is more expensive and less soluble ferric oxalate and manganese acetate, while with ethanol as solvent, just unavoidably increasing the cost of material and running cost of catalyst preparation process.For the cost for further reducing catalyst; in its number of patent application 200710063301.9; catalyst is prepared using common medicine and reagent, and the iron salt for using is ferric nitrate, and manganese salt is manganese nitrate; potassium salt is potassium carbonate; activated carbon is coconut husk charcoal, can catalyst must flowing nitrogen protection under carry out high-temperature roasting and Passivation Treatment, need special installation; preparation process is complicated, relatively costly.And CO conversion ratio and selectivity of light olefin of the above-mentioned catalyst in fixed bed reaction is relatively low.
The content of the invention
The technical problem to be solved be that CO conversion ratios are low in fixed bed production low-carbon alkene technology in prior art and product in the low problem of selectivity of light olefin, a kind of method of new fixed bed production low-carbon alkene is provided, the method uses new fixed bed producing light olefins ferrum-based catalyst, has the advantages that selectivity of light olefin is high in CO high conversion rates and product.
To solve above-mentioned technical problem, the technical solution used in the present invention is as follows：A kind of method of fixed bed production low-carbon alkene, with H2Synthesis gas with CO compositions is raw material, and under certain reaction condition, unstripped gas is contacted with ferrum-based catalyst, generates and mainly contain C2-C4Alkene.Catalyst wherein used, by weight percentage including following components：
A) 10～50% ferrum element or its oxide；
B) 1～5% rhodium element or its oxide；
C) 9～30% at least one element in copper and zinc or its oxide；
D) 9～30% at least one element in potassium and caesium or its oxide；
E) 1～5% praseodymium element or its oxide；
F) 30～70% carrier, in terms of vehicle weight number, including (1) 20～70 part of titanium dioxide of following components；(2) 30～80 parts of silicon dioxide.
In above-mentioned technical proposal, the preferred version of the oxide of ferrum is iron sesquioxide, and by weight percentage the preferred scope of content is 10～40 parts；The preferred version of the oxide of rhodium is rhodium sesquioxide, and by weight percentage the preferred scope of content is 1～4 part；The preferred version of the oxide of copper and zinc is respectively copper oxide and Zinc Oxide, and by weight percentage the preferred scope of content is 10～25 parts；The preferred version of the oxide of potassium and caesium is respectively potassium oxide and Cs2O, and by weight percentage the preferred scope of content is 10～25 parts；The preferred version of the oxide of praseodymium is 11 six praseodymiums of oxidation, and by weight percentage the preferred scope of content is 1～4 part.
In above-mentioned technical proposal, complex carrier is prepared by titanium dioxide and silicon dioxide mixed-forming, and with the calculating of vehicle weight number, the preferred scope of content of titanium dioxide is 20～70 parts；The preferred scope of dioxide-containing silica is 30～80 parts.
In above-mentioned technical proposal, the ferrum-based catalyst of described fixed bed production low-carbon alkene is comprised the following steps：
(1) nano titanium dioxide powder is added in nano grade silica particles, then carries out ball milling mixing, add water molding and drying, in 700～1000 DEG C of high-temperature roastings 1～6 hour after drying, to prepare complex carrier H stand-by for crushing and screening after cooling；
(2) by iron salt, rhodium salt, mantoquita or zinc salt, potassium salt or cesium salt, and praseodymium salt, it is dissolved in deionized water and makes mixed solution I；
(3) under the conditions of 1～80kPa of vacuum, above-mentioned mixed solution I be impregnated in on the complex carrier H handled well in (1) step to obtain catalyst precarsor J；
(4) by catalyst precarsor J, roasting after drying obtains required catalyst.
In above-mentioned technical proposal, the preferred scope of the sintering temperature in step (1) is 700～900 DEG C, and the preferred scope of roasting time is 1.0～4.0 hours；The preferred scope of the sintering temperature in step (4) is 400～800 DEG C, and the preferred scope of roasting time is 2.0～6.0 hours.
In above-mentioned technical proposal, the method for the fixed bed production low-carbon alkene, with synthesis gas as raw material, H2It is 1～3 with the mol ratio of CO, is 250～400 DEG C in reaction temperature, reaction pressure is 1.0～3.0Mpa, feed gas volume air speed is 500～5000h-1Under conditions of, unstripped gas is generated with the catalyst haptoreaction and contains C2～C4Alkene.
The catalyst that the inventive method is adopted is prepared by vacuum impregnation technology, and active component and auxiliary agent high uniformity can be made to be scattered in complex carrier surface, and increase is exposed to the quantity of the active sites of carrier surface, improves the conversion ratio of CO.
Transition metal Rh is introduced in the ferrum-based catalyst that the inventive method is adopted, transition metal Cu or Zn, and alkali metal K or Cs is used as catalyst promoter, can be with the electron valence state of main active component Fe of modulation, so as to be conducive to improving the CO conversion ratios of catalyst and the selectivity of low-carbon alkene.Particularly when Rh and Pr is added, due to the synergism between Rh and Pr and other active components and auxiliary agent, the activity of catalyst can be effectively discharged, improve the conversion ratio of CO and the selectivity of low-carbon alkene, achieve good technique effect.
The ferrum-based catalyst that the inventive method is adopted adopts TiO2And SiO2Complex carrier, not only can modulation active component electron valence state, and strengthen the interaction strength of catalyst activity component, auxiliary agent and carrier, so as to be conducive to improving the selectivity of light olefin of catalyst, strengthen anti-carbon effect simultaneously, reduce area carbon and generate.
The reaction condition of fixed bed production low-carbon alkene is as follows：With H2With CO composition synthesis gas be raw material, H2It is 1～3 with the mol ratio of CO, is 250～400 DEG C in reaction temperature, reaction pressure is 1.0～3.0Mpa, feed gas volume air speed is 500～5000h-1Under conditions of, unstripped gas is contacted with above-mentioned catalyst, achieves preferable technique effect：CO conversion ratios improve 3.5% up to 99.5% than prior art；Selectivity of the low-carbon alkene in Hydrocarbon improves 10.0% up to 78.0% than prior art, and more detailed result sees attached list.
The present invention is described further for the following examples, and protection scope of the present invention is not limited to these embodiments restrictions.
Specific embodiment
【Embodiment 1】
Weigh 60.0 grams of nano titanium oxide (TiO2) powder and 40.0 grams of nano silicon (SiO2) powder mix homogeneously, grind mixed 3 hours in ball mill, make compound G stand-by；Deionized water is added in the mixed compound G of above-mentioned mill, kneading extrusion molding is carried out；After drying at a temperature of 800 DEG C roasting 3 hours, crushing and screening prepares complex carrier H into 20～40 mesh after cooling；101.2 grams of Fe(NO3)39H2Os, 6.8 grams of rhodium nitrates, 45.6 grams of Gerhardites, 32.2 grams of potassium nitrate, 4.0 gram of six nitric hydrate praseodymium are dissolved in 40.0 grams of deionized waters and make mixed solution I；Under conditions of vacuum 80kPa, above-mentioned mixed solution I be impregnated in on 45.0 grams of complex carrier H for having prepared to obtain catalyst precarsor J；The catalyst precarsor J for having impregnated is dried under the conditions of 110 DEG C, then carries out roasting, 600 DEG C of sintering temperature, roasting time 4h, that is, the ferrum-based catalyst of the fixed bed production low-carbon alkene needed for obtaining.Prepared catalyst by weight percentage, comprising following components：20%Fe2O3, 3%Rh2O3, 15%CuO, 15%K2O, 2%Pr6O11, 27%TiO2, 18%SiO2；Made ferrum-based catalyst is fixed under certain condition bed production low-carbon alkene reaction, and experimental result is listed in table 1.
【Embodiment 2】
Weigh 70.0 grams of nano titanium oxide (TiO2) powder and 30.0 grams of nano silicon (SiO2) powder mix homogeneously, grind mixed 3 hours in ball mill, make compound G stand-by；Deionized water is added in the mixed compound G of above-mentioned mill, kneading extrusion molding is carried out；After drying at a temperature of 700 DEG C roasting 6 hours, crushing and screening prepares complex carrier H into 20～40 mesh after cooling；253.0 grams of Fe(NO3)39H2Os, 2.3 grams of rhodium nitrates, 27.3 grams of Gerhardites, 19.3 grams of potassium nitrate, 2.0 gram of six nitric hydrate praseodymium are dissolved in 40.0 grams of deionized waters and make mixed solution I；Under conditions of vacuum 80kPa, above-mentioned mixed solution I be impregnated in on 30.0 grams of complex carrier H for having prepared to obtain catalyst precarsor J；The catalyst precarsor J for having impregnated is dried under the conditions of 110 DEG C, then carries out roasting, 600 DEG C of sintering temperature, roasting time 4h, that is, the ferrum-based catalyst of the fixed bed production low-carbon alkene needed for obtaining.Prepared catalyst by weight percentage, comprising following components：50%Fe2O3, 1%Rh2O3, 9%CuO, 9%K2O, 1%Pr6O11, 21%TiO2, 9%SiO2；Made ferrum-based catalyst is fixed under certain condition bed production low-carbon alkene reaction, and experimental result is listed in table 1.
【Embodiment 3】
Weigh 20.0 grams of nano titanium oxide (TiO2) powder and 80.0 grams of nano silicon (SiO2) powder mix homogeneously, grind mixed 3 hours in ball mill, make compound G stand-by；Deionized water is added in the mixed compound G of above-mentioned mill, kneading extrusion molding is carried out；After drying at a temperature of 1000 DEG C roasting 1 hour, crushing and screening prepares complex carrier H into 20～40 mesh after cooling；50.6 grams of Fe(NO3)39H2Os, 2.3 grams of rhodium nitrates, 27.3 grams of Gerhardites, 19.3 grams of potassium nitrate, 2.0 gram of six nitric hydrate praseodymium are dissolved in 50.0 grams of deionized waters and make mixed solution I；Under conditions of vacuum 80kPa, above-mentioned mixed solution I be impregnated in on 70.0 grams of complex carrier H for having prepared to obtain catalyst precarsor J；The catalyst precarsor J for having impregnated is dried under the conditions of 110 DEG C, then carries out roasting, 600 DEG C of sintering temperature, roasting time 4h, that is, the ferrum-based catalyst of the fixed bed production low-carbon alkene needed for obtaining.Prepared catalyst by weight percentage, comprising following components：10%Fe2O3, 1%Rh2O3, 9%CuO, 9%K2O, 1%Pr6O11, 14%TiO2, 56%SiO2；Made ferrum-based catalyst is fixed under certain condition bed production low-carbon alkene reaction, and experimental result is listed in table 1.
【Embodiment 4】
Weigh 60.0 grams of nano titanium oxide (TiO2) powder and 40.0 grams of nano silicon (SiO2) powder mix homogeneously, grind mixed 3 hours in ball mill, make compound G stand-by；Deionized water is added in the mixed compound G of above-mentioned mill, kneading extrusion molding is carried out；After drying at a temperature of 800 DEG C roasting 3 hours, crushing and screening prepares complex carrier H into 20～40 mesh after cooling；50.6 grams of Fe(NO3)39H2Os, 11.4 grams of rhodium nitrates, 30.4 grams of Gerhardites, 64.4 grams of potassium nitrate, 2.0 gram of six nitric hydrate praseodymium are dissolved in 40.0 grams of deionized waters and make mixed solution I；Under conditions of vacuum 80kPa, above-mentioned mixed solution I be impregnated in on 44.0 grams of complex carrier H for having prepared to obtain catalyst precarsor J；The catalyst precarsor J for having impregnated is dried under the conditions of 110 DEG C, then carries out roasting, 400 DEG C of sintering temperature, roasting time 6h, that is, the ferrum-based catalyst of the fixed bed production low-carbon alkene needed for obtaining.Prepared catalyst by weight percentage, comprising following components：10%Fe2O3, 5%Rh2O3, 10%CuO, 30%K2O, 1%Pr6O11, 26.4%TiO2, 17.6%SiO2；Made ferrum-based catalyst is fixed under certain condition bed production low-carbon alkene reaction, and experimental result is listed in table 1.
【Embodiment 5】
Weigh 50.0 grams of nano titanium oxide (TiO2) powder and 50.0 grams of nano silicon (SiO2) powder mix homogeneously, grind mixed 3 hours in ball mill, make compound G stand-by；Deionized water is added in the mixed compound G of above-mentioned mill, kneading extrusion molding is carried out；After drying at a temperature of 800 DEG C roasting 3 hours, crushing and screening prepares complex carrier H into 20～40 mesh after cooling；70.8 grams of Fe(NO3)39H2Os, 2.3 grams of rhodium nitrates, 91.1 grams of Gerhardites, 21.5 grams of potassium nitrate, 10.0 gram of six nitric hydrate praseodymium are dissolved in 40.0 grams of deionized waters and make mixed solution I；Under conditions of vacuum 80kPa, above-mentioned mixed solution I be impregnated in on 40.0 grams of complex carrier H for having prepared to obtain catalyst precarsor J；The catalyst precarsor J for having impregnated is dried under the conditions of 110 DEG C, then carries out roasting, 800 DEG C of sintering temperature, roasting time 2h, that is, the ferrum-based catalyst of the fixed bed production low-carbon alkene needed for obtaining.Prepared catalyst by weight percentage, comprising following components：14%Fe2O3, 1%Rh2O3, 30%CuO, 10%K2O, 5%Pr6O11, 20%TiO2, 20%SiO2；Made ferrum-based catalyst is fixed under certain condition bed production low-carbon alkene reaction, and experimental result is listed in table 1.
【Embodiment 6】
Weigh 60.0 grams of nano titanium oxide (TiO2) powder and 40.0 grams of nano silicon (SiO2) powder mix homogeneously, grind mixed 3 hours in ball mill, make compound G stand-by；Deionized water is added in the mixed compound G of above-mentioned mill, kneading extrusion molding is carried out；After drying at a temperature of 900 DEG C roasting 4 hours, crushing and screening prepares complex carrier H into 20～40 mesh after cooling；202.4 grams of Fe(NO3)39H2Os, 9.1 grams of rhodium nitrates, 30.4 grams of Gerhardites, 21.5 grams of potassium nitrate, 8.0 gram of six nitric hydrate praseodymium are dissolved in 40.0 grams of deionized waters and make mixed solution I；Under conditions of vacuum 80kPa, above-mentioned mixed solution I be impregnated in on 32.0 grams of complex carrier H for having prepared to obtain catalyst precarsor J；The catalyst precarsor J for having impregnated is dried under the conditions of 110 DEG C, then carries out roasting, 600 DEG C of sintering temperature, roasting time 4h, that is, the ferrum-based catalyst of the fixed bed production low-carbon alkene needed for obtaining.Prepared catalyst by weight percentage, comprising following components：40%Fe2O3, 4%Rh2O3, 10%CuO, 10%K2O, 4%Pr6O11, 19.2%TiO2, 12.8%SiO2；Made ferrum-based catalyst is fixed under certain condition bed production low-carbon alkene reaction, and experimental result is listed in table 1.
【Embodiment 7】
Weigh 60.0 grams of nano titanium oxide (TiO2) powder and 40.0 grams of nano silicon (SiO2) powder mix homogeneously, grind mixed 3 hours in ball mill, make compound G stand-by；Deionized water is added in the mixed compound G of above-mentioned mill, kneading extrusion molding is carried out；After drying at a temperature of 800 DEG C roasting 3 hours, crushing and screening prepares complex carrier H into 20～40 mesh after cooling；101.2 grams of Fe(NO3)39H2Os, 9.1 grams of rhodium nitrates, 30.4 grams of Gerhardites, 53.7 grams of potassium nitrate, 10.0 gram of six nitric hydrate praseodymium are dissolved in 40.0 grams of deionized waters and make mixed solution I；Under conditions of vacuum 80kPa, above-mentioned mixed solution I be impregnated in on 36.0 grams of complex carrier H for having prepared to obtain catalyst precarsor J；The catalyst precarsor J for having impregnated is dried under the conditions of 110 DEG C, then carries out roasting, 600 DEG C of sintering temperature, roasting time 4h, that is, the ferrum-based catalyst of the fixed bed production low-carbon alkene needed for obtaining.Prepared catalyst by weight percentage, comprising following components：20%Fe2O3, 4%Rh2O3, 10%CuO, 25%K2O, 5%Pr6O11, 21.6%TiO2, 14.4%SiO2；Made ferrum-based catalyst is fixed under certain condition bed production low-carbon alkene reaction, and experimental result is listed in table 1.
【Embodiment 8】
Weigh 60.0 grams of nano titanium oxide (TiO2) powder and 40.0 grams of nano silicon (SiO2) powder mix homogeneously, grind mixed 3 hours in ball mill, make compound G stand-by；Deionized water is added in the mixed compound G of above-mentioned mill, kneading extrusion molding is carried out；After drying at a temperature of 800 DEG C roasting 3 hours, crushing and screening prepares complex carrier H into 20～40 mesh after cooling；131.6 grams of Fe(NO3)39H2Os, 11.4 grams of rhodium nitrates, 75.9 grams of Gerhardites, 21.5 grams of potassium nitrate, 8.0 gram of six nitric hydrate praseodymium are dissolved in 40.0 grams of deionized waters and make mixed solution I；Under conditions of vacuum 80kPa, above-mentioned mixed solution I be impregnated in on 30.0 grams of complex carrier H for having prepared to obtain catalyst precarsor J；The catalyst precarsor J for having impregnated is dried under the conditions of 110 DEG C, then carries out roasting, 600 DEG C of sintering temperature, roasting time 4h, that is, the ferrum-based catalyst of the fixed bed production low-carbon alkene needed for obtaining.Prepared catalyst by weight percentage, comprising following components：26%Fe2O3, 5%Rh2O3, 25%CuO, 10%K2O, 4%Pr6O11, 18%TiO2, 12%SiO2；Made ferrum-based catalyst is fixed under certain condition bed production low-carbon alkene reaction, and experimental result is listed in table 1.
【Embodiment 9】
Weigh 60.0 grams of nano titanium oxide (TiO2) powder and 40.0 grams of nano silicon (SiO2) powder mix homogeneously, grind mixed 3 hours in ball mill, make compound G stand-by；Deionized water is added in the mixed compound G of above-mentioned mill, kneading extrusion molding is carried out；After drying at a temperature of 800 DEG C roasting 3 hours, crushing and screening prepares complex carrier H into 20～40 mesh after cooling；101.2 grams of Fe(NO3)39H2Os, 6.8 grams of rhodium nitrates, 54.8 grams of zinc nitrate hexahydrates, 32.2 grams of potassium nitrate, 4.0 gram of six nitric hydrate praseodymium are dissolved in 40.0 grams of deionized waters and make mixed solution I；Under conditions of vacuum 80kPa, above-mentioned mixed solution I be impregnated in on 45.0 grams of complex carrier H for having prepared to obtain catalyst precarsor J；The catalyst precarsor J for having impregnated is dried under the conditions of 110 DEG C, then carries out roasting, 600 DEG C of sintering temperature, roasting time 4h, that is, the ferrum-based catalyst of the fixed bed production low-carbon alkene needed for obtaining.Prepared catalyst by weight percentage, comprising following components：20%Fe2O3, 3%Rh2O3, 15%ZnO, 15%K2O, 2%Pr6O11, 27%TiO2, 18%SiO2；Made ferrum-based catalyst is fixed under certain condition bed production low-carbon alkene reaction, and experimental result is listed in table 1.
【Embodiment 10】
Weigh 60.0 grams of nano titanium oxide (TiO2) powder and 40.0 grams of nano silicon (SiO2) powder mix homogeneously, grind mixed 3 hours in ball mill, make compound G stand-by；Deionized water is added in the mixed compound G of above-mentioned mill, kneading extrusion molding is carried out；After drying at a temperature of 800 DEG C roasting 3 hours, crushing and screening prepares complex carrier H into 20～40 mesh after cooling；101.2 grams of Fe(NO3)39H2Os, 6.8 grams of rhodium nitrates, 45.6 grams of Gerhardites, 20.7 grams of cesium nitrates, 4.0 gram of six nitric hydrate praseodymium are dissolved in 40.0 grams of deionized waters and make mixed solution I；Under conditions of vacuum 80kPa, above-mentioned mixed solution I be impregnated in on 45.0 grams of complex carrier H for having prepared to obtain catalyst precarsor J；The catalyst precarsor J for having impregnated is dried under the conditions of 110 DEG C, then carries out roasting, 600 DEG C of sintering temperature, roasting time 4h, that is, the ferrum-based catalyst of the fixed bed production low-carbon alkene needed for obtaining.Prepared catalyst by weight percentage, comprising following components：20%Fe2O3, 3%Rh2O3, 15%CuO, 15%Cs2O, 2%Pr6O11, 27%TiO2, 18%SiO2；Made ferrum-based catalyst is fixed under certain condition bed production low-carbon alkene reaction, and experimental result is listed in table 1.
【Embodiment 11】
Weigh 60.0 grams of nano titanium oxide (TiO2) powder and 40.0 grams of nano silicon (SiO2) powder mix homogeneously, grind mixed 3 hours in ball mill, make compound G stand-by；Deionized water is added in the mixed compound G of above-mentioned mill, kneading extrusion molding is carried out；After drying at a temperature of 800 DEG C roasting 3 hours, crushing and screening prepares complex carrier H into 20～40 mesh after cooling；101.2 grams of Fe(NO3)39H2Os, 6.8 grams of rhodium nitrates, 54.8 grams of zinc nitrate hexahydrates, 20.7 grams of cesium nitrates, 4.0 gram of six nitric hydrate praseodymium are dissolved in 40.0 grams of deionized waters and make mixed solution I；Under conditions of vacuum 80kPa, above-mentioned mixed solution I be impregnated in on 45.0 grams of complex carrier H for having prepared to obtain catalyst precarsor J；The catalyst precarsor J for having impregnated is dried under the conditions of 110 DEG C, then carries out roasting, 600 DEG C of sintering temperature, roasting time 4h, that is, the ferrum-based catalyst of the fixed bed production low-carbon alkene needed for obtaining.Prepared catalyst by weight percentage, comprising following components：20%Fe2O3, 3%Rh2O3, 15%ZnO, 15%Cs2O, 2%Pr6O11, 27%TiO2, 18%SiO2；Made ferrum-based catalyst is fixed under certain condition bed production low-carbon alkene reaction, and experimental result is listed in table 1.
【Embodiment 12】
Catalyst obtained in Example 1, other are constant, only change reaction condition, carry out preparation of low carbon olefines by synthetic gas, and experimental result is listed in table 2.
【Comparative example 1】
Weigh 60.0 grams of nano titanium oxide (TiO2) powder and 40.0 grams of nano silicon (SiO2) powder mix homogeneously, grind mixed 3 hours in ball mill, make compound G stand-by；Deionized water is added in the mixed compound G of above-mentioned mill, kneading extrusion molding is carried out；After drying at a temperature of 800 DEG C roasting 3 hours, crushing and screening prepares complex carrier H into 20～40 mesh after cooling；By 101.2 grams of Fe(NO3)39H2Os, 45.6 grams of Gerhardites, 32.2 grams of potassium nitrate, 4.0 gram of six nitric hydrate praseodymium, it is dissolved in 40.0 grams of deionized waters and makes mixed solution I；Under conditions of vacuum 80kPa, above-mentioned mixed solution I be impregnated in on 48.0 grams of complex carrier H for having prepared to obtain catalyst precarsor J；The catalyst precarsor J for having impregnated is dried under the conditions of 110 DEG C, then carries out roasting, 600 DEG C of sintering temperature, roasting time 4h, that is, the ferrum-based catalyst of the fixed bed production low-carbon alkene needed for obtaining.Prepared catalyst by weight percentage, comprising following components：20%Fe2O3, 0%Rh2O3, 15%CuO, 15%K2O, 2%Pr6O11, 28.2%TiO2, 19.2%SiO2；Made ferrum-based catalyst is fixed under certain condition bed production low-carbon alkene reaction, and experimental result is listed in table 1.
【Comparative example 2】
Weigh 60.0 grams of nano titanium oxide (TiO2) powder and 40.0 grams of nano silicon (SiO2) powder mix homogeneously, grind mixed 3 hours in ball mill, make compound G stand-by；Deionized water is added in the mixed compound G of above-mentioned mill, kneading extrusion molding is carried out；After drying at a temperature of 800 DEG C roasting 3 hours, crushing and screening prepares complex carrier H into 20～40 mesh after cooling；101.2 grams of Fe(NO3)39H2Os, 13.7 grams of rhodium nitrates, 45.6 grams of Gerhardites, 32.2 grams of potassium nitrate, 4.0 gram of six nitric hydrate praseodymium are dissolved in 40.0 grams of deionized waters and make mixed solution I；Under conditions of vacuum 80kPa, above-mentioned mixed solution I be impregnated in on 42.0 grams of complex carrier H for having prepared to obtain catalyst precarsor J；The catalyst precarsor J for having impregnated is dried under the conditions of 110 DEG C, then carries out roasting, 600 DEG C of sintering temperature, roasting time 4h, that is, the ferrum-based catalyst of the fixed bed production low-carbon alkene needed for obtaining.Prepared catalyst by weight percentage, comprising following components：20%Fe2O3, 6%Rh2O3, 15%CuO, 15%K2O, 2%Pr6O11, 25.2%TiO2, 16.8%SiO2；Made ferrum-based catalyst is fixed under certain condition bed production low-carbon alkene reaction, and experimental result is listed in table 1.
【Comparative example 3】
Weigh 60.0 grams of nano titanium oxide (TiO2) powder and 40.0 grams of nano silicon (SiO2) powder mix homogeneously, grind mixed 3 hours in ball mill, make compound G stand-by；Deionized water is added in the mixed compound G of above-mentioned mill, kneading extrusion molding is carried out；After drying at a temperature of 800 DEG C roasting 3 hours, crushing and screening prepares complex carrier H into 20～40 mesh after cooling；101.2 grams of Fe(NO3)39H2Os, 6.8 grams of rhodium nitrates, 45.6 grams of Gerhardites, 32.2 grams of potassium nitrate are dissolved in 40.0 grams of deionized waters and make mixed solution I；Under conditions of vacuum 80kPa, above-mentioned mixed solution I be impregnated in on 47.0 grams of complex carrier H for having prepared to obtain catalyst precarsor J；The catalyst precarsor J for having impregnated is dried under the conditions of 110 DEG C, then carries out roasting, 600 DEG C of sintering temperature, roasting time 4h, that is, the ferrum-based catalyst of the fixed bed production low-carbon alkene needed for obtaining.Prepared catalyst by weight percentage, comprising following components：20%Fe2O3, 3%Rh2O3, 15%CuO, 15%K2O, 0%Pr6O11, 28.2%TiO2, 18.8%SiO2；Made ferrum-based catalyst is fixed under certain condition bed production low-carbon alkene reaction, and experimental result is listed in table 1.
【Comparative example 4】
Weigh 60.0 grams of nano titanium oxide (TiO2) powder and 40.0 grams of nano silicon (SiO2) powder mix homogeneously, grind mixed 3 hours in ball mill, make compound G stand-by；Deionized water is added in the mixed compound G of above-mentioned mill, kneading extrusion molding is carried out；After drying at a temperature of 800 DEG C roasting 3 hours, crushing and screening prepares complex carrier H into 20～40 mesh after cooling；101.2 grams of Fe(NO3)39H2Os, 6.8 grams of rhodium nitrates, 45.6 grams of Gerhardites, 32.2 grams of potassium nitrate, 4.0 gram of six nitric hydrate praseodymium are dissolved in 40.0 grams of deionized waters and make mixed solution I；Under conditions of vacuum 80kPa, above-mentioned mixed solution I be impregnated in on 41.0 grams of complex carrier H for having prepared to obtain catalyst precarsor J；The catalyst precarsor J for having impregnated is dried under the conditions of 110 DEG C, then carries out roasting, 600 DEG C of sintering temperature, roasting time 4h, that is, the ferrum-based catalyst of the fixed bed production low-carbon alkene needed for obtaining.Prepared catalyst by weight percentage, comprising following components：20%Fe2O3, 3%Rh2O3, 15%CuO, 15%K2O, 6%Pr6O11, 24.6%TiO2, 16.4%SiO2；Made ferrum-based catalyst is fixed under certain condition bed production low-carbon alkene reaction, and experimental result is listed in table 1.
Above-described embodiment is with the reducing condition of comparative example：
450 DEG C of temperature
Pressure normal pressure
Loaded catalyst 3ml
Catalyst loading 1000 hours-1
Also Primordial Qi H2
8 hours recovery times
Reaction condition is：
8 millimeters of fixed bed reactors of φ
330 DEG C of reaction temperature
Reaction pressure 1.5MPa
Loaded catalyst 3ml
Catalyst loading 1000 hours-1
Proportioning raw materials (mole) H2/ CO=1.5/1
Table 1
Table 2
* compared with the condition described in table 1 change appreciation condition.
Claims (10)
1. a kind of ferrum-based catalyst of fixed bed production low-carbon alkene, by weight percentage including following components：
A) 10～50% ferrum element or its oxide；
B) 1～5% rhodium element or its oxide；
C) 9～30% at least one element in copper and zinc or its oxide；
D) 9～30% at least one element in potassium and caesium or its oxide；
E) 1～5% praseodymium element or its oxide；
F) 30～70% carrier, in terms of vehicle weight number, including (1) 20～70 part of titanium dioxide of following components；(2)
30～80 parts of silicon dioxide.
2. the ferrum-based catalyst of a kind of fixed bed production low-carbon alkene according to claim 1, it is characterised in that described
Catalyst in ferrum oxide be iron sesquioxide, in terms of catalyst weight percent, content be 10～40%.
3. the ferrum-based catalyst of a kind of fixed bed production low-carbon alkene according to claim 1, it is characterised in that described
Catalyst in rhodium oxide be rhodium sesquioxide, in terms of catalyst weight percent, content be 1～4%.
4. the ferrum-based catalyst of a kind of fixed bed production low-carbon alkene according to claim 1, it is characterised in that described
Catalyst in the oxide of copper and zinc be respectively copper oxide and Zinc Oxide, in terms of catalyst weight percent, content is 10～
25%.
5. the ferrum-based catalyst of a kind of fixed bed production low-carbon alkene according to claim 1, it is characterised in that described
Catalyst in the oxide of potassium and caesium be respectively potassium oxide and Cs2O, in terms of catalyst weight percent, content is 10～
25%.
6. the ferrum-based catalyst of a kind of fixed bed production low-carbon alkene according to claim 1, it is characterised in that described
Catalyst in praseodymium oxide be 11 oxidation six praseodymiums, in terms of catalyst weight percent, content be 1～4%.
7. the ferrum-based catalyst of a kind of fixed bed production low-carbon alkene according to claim 1, the carrier is by dioxy
Change titanium and be prepared by silicon dioxide mixed-forming.
8. a kind of ferrum-based catalyst of the fixed bed production low-carbon alkene described in any one of claim 1～7, including following step
Suddenly：
(1) in nano titanium dioxide powder addition nano grade silica particles, ball milling mixing will then be carried out, add water molding
And drying, in 700～1000 DEG C of high temperature sinterings 1～6 hour after drying, to prepare complex carrier H stand-by for crushing and screening after cooling；
(2) by iron salt, rhodium salt, mantoquita or zinc salt, potassium salt or cesium salt, and praseodymium salt, be dissolved in deionized water make it is mixed
Close solution I；
(3) under the conditions of 1～80kPa of vacuum, above-mentioned mixed solution I impregnated in handle well in (1) step compound
On carrier H catalyst precarsor J；
(4) by catalyst precarsor J, roasting after drying obtains required catalyst.
9. the preparation method of the ferrum-based catalyst of fixed bed production low-carbon alkene according to claim 8, its feature exists
In catalyst precarsor sintering temperature be 400～800 DEG C, roasting time 2.0～6.0 hours.
10. a kind of method of fixed bed production low-carbon alkene, with synthesis gas as raw material, H2It is 1～3 with the mol ratio of CO,
It it is 250～400 DEG C in reaction temperature, reaction pressure is 1.0～3.0Mpa, feed gas volume air speed is 500～5000h-1Condition
Under, unstripped gas is generated with the ferrum-based catalyst haptoreaction of the fixed bed production low-carbon alkene described in any one of claim 1～9
Containing C2～C4Alkene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510685508.4A CN106607048B (en) | 2015-10-21 | 2015-10-21 | The method of fixed bed production low-carbon alkene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510685508.4A CN106607048B (en) | 2015-10-21 | 2015-10-21 | The method of fixed bed production low-carbon alkene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106607048A true CN106607048A (en) | 2017-05-03 |
| CN106607048B CN106607048B (en) | 2019-06-11 |
Family
ID=58610342
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510685508.4A Active CN106607048B (en) | 2015-10-21 | 2015-10-21 | The method of fixed bed production low-carbon alkene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106607048B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109651031A (en) * | 2017-10-10 | 2019-04-19 | 中国石油化工股份有限公司 | The method that synthesis gas directly produces low-carbon alkene |
| CN109865516A (en) * | 2017-12-04 | 2019-06-11 | 中国科学院大连化学物理研究所 | A kind of ferrum-based catalyst and its preparation method and application |
| 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 (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050096215A1 (en) * | 2003-10-31 | 2005-05-05 | Conocophillips Company | Process for producing synthesis gas using stabilized composite catalyst |
| CN102219628A (en) * | 2010-04-15 | 2011-10-19 | 中国石油化工股份有限公司 | Method for preparing low-carbon hydrocarbon by using synthesis gas |
| CN103521239A (en) * | 2012-07-03 | 2014-01-22 | 中国石油化工股份有限公司 | Catalyst for preparing low-carbon olefin through Fischer-Tropsch synthesis and preparation method of catalyst |
| CN103657674A (en) * | 2012-09-05 | 2014-03-26 | 中国石油化工股份有限公司 | Iron-based catalyst for preparing olefin from synthesis gas, as well as method and application of catalyst |
| CN103933989A (en) * | 2013-01-23 | 2014-07-23 | 中国石油化工股份有限公司 | Catalyst for synthesis of low carbon olefins and its preparation method |
| CN104148106A (en) * | 2013-05-16 | 2014-11-19 | 中国石油化工股份有限公司 | Catalyst for producing low-carbon olefin by using synthesis gas and preparation method of catalyst |
| CN104549296A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Catalyst for directly preparing low-carbon olefin from microspherical synthesis gas, as well as preparation method thereof |
| CN104888838A (en) * | 2015-06-03 | 2015-09-09 | 中国科学院山西煤炭化学研究所 | Catalyst for directly manufacturing low-carbon olefin through nuclear shell type synthesis gas and preparation method and application |
-
2015
- 2015-10-21 CN CN201510685508.4A patent/CN106607048B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050096215A1 (en) * | 2003-10-31 | 2005-05-05 | Conocophillips Company | Process for producing synthesis gas using stabilized composite catalyst |
| CN102219628A (en) * | 2010-04-15 | 2011-10-19 | 中国石油化工股份有限公司 | Method for preparing low-carbon hydrocarbon by using synthesis gas |
| CN103521239A (en) * | 2012-07-03 | 2014-01-22 | 中国石油化工股份有限公司 | Catalyst for preparing low-carbon olefin through Fischer-Tropsch synthesis and preparation method of catalyst |
| CN103657674A (en) * | 2012-09-05 | 2014-03-26 | 中国石油化工股份有限公司 | Iron-based catalyst for preparing olefin from synthesis gas, as well as method and application of catalyst |
| CN103933989A (en) * | 2013-01-23 | 2014-07-23 | 中国石油化工股份有限公司 | Catalyst for synthesis of low carbon olefins and its preparation method |
| CN104148106A (en) * | 2013-05-16 | 2014-11-19 | 中国石油化工股份有限公司 | Catalyst for producing low-carbon olefin by using synthesis gas and preparation method of catalyst |
| CN104549296A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Catalyst for directly preparing low-carbon olefin from microspherical synthesis gas, as well as preparation method thereof |
| CN104888838A (en) * | 2015-06-03 | 2015-09-09 | 中国科学院山西煤炭化学研究所 | Catalyst for directly manufacturing low-carbon olefin through nuclear shell type synthesis gas and preparation method and application |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109651031A (en) * | 2017-10-10 | 2019-04-19 | 中国石油化工股份有限公司 | The method that synthesis gas directly produces low-carbon alkene |
| CN109651031B (en) * | 2017-10-10 | 2021-08-03 | 中国石油化工股份有限公司 | Method for directly producing low-carbon olefin by using synthesis gas |
| CN109865516A (en) * | 2017-12-04 | 2019-06-11 | 中国科学院大连化学物理研究所 | A kind of ferrum-based catalyst and its preparation method and application |
| 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 |
|---|---|
| CN106607048B (en) | 2019-06-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104148106B (en) | Synthesis gas produces catalyst of low-carbon alkene and preparation method thereof | |
| CN106607043B (en) | Ferrum-based catalyst and its preparation method and application | |
| CN104549325B (en) | Catalyst for preparing low-carbon olefin from synthesis gas by one-step method, preparation method and application of catalyst | |
| CN104437532B (en) | Fixed bed producing light olefins catalyst, preparation method and its usage | |
| CN104437511B (en) | Catalyst for producing light olefins by fixed bed and preparation method for catalyst for producing light olefins by fixed bed | |
| CN104549352B (en) | The catalyst and its application method of synthesis gas production low-carbon alkene | |
| CN107913729B (en) | Composite catalyst and preparation method thereof | |
| CN104549342B (en) | Preparation of low carbon olefines by synthetic gas iron catalyst and preparation method thereof | |
| CN105435801B (en) | Load typed iron catalyst and its preparation method and application | |
| CN105562026B (en) | Ferrum-based catalyst of sulfur-bearing and its preparation method and application | |
| CN106607048A (en) | Method for producing low-carbon olefins by using fixed bed | |
| CN106607047A (en) | Iron-based catalyst for preparing low-carbon olefins from synthesis gas and application of iron-based catalyst | |
| CN105582936B (en) | Slug type preparation of low carbon olefines by synthetic gas catalyst and preparation method thereof | |
| CN104437524B (en) | Iron-based catalyst for preparing low-carbon alkane as well as preparation method and using method of iron-based catalyst for preparing low-carbon alkane | |
| CN107913718A (en) | The ferrum-based catalyst of the direct synthesizing low-carbon alkene of synthesis gas | |
| CN104275189B (en) | Catalyst of high temperature sintering type preparation of low carbon olefines by synthetic gas and preparation method thereof | |
| CN109304216B (en) | Catalyst for producing low-carbon olefin by synthesis gas one-step method | |
| CN109304218A (en) | The catalyst of synthesis gas production low-carbon alkene | |
| CN109305870B (en) | Method for preparing low-carbon olefin by synthesis gas one-step method | |
| CN109304215B (en) | Catalyst for preparing low-carbon olefin by synthesis gas one-step method | |
| CN106607052B (en) | Sulfur-bearing iron-based catalyst of high temperature sintering type and preparation method thereof | |
| CN109647492A (en) | Synthesis gas directly produces the catalyst of low-carbon alkene | |
| CN109304220A (en) | The catalyst of preparing low-carbon olefin | |
| CN109651030B (en) | Method for directly preparing low-carbon olefin from synthesis gas | |
| CN109305871B (en) | Method for producing low-carbon olefin by synthesis gas one-step method |
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 |