CN107913729A - Composite catalyst and preparation method thereof - Google Patents
Composite catalyst and preparation method thereof Download PDFInfo
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- CN107913729A CN107913729A CN201610880522.4A CN201610880522A CN107913729A CN 107913729 A CN107913729 A CN 107913729A CN 201610880522 A CN201610880522 A CN 201610880522A CN 107913729 A CN107913729 A CN 107913729A
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
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- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0425—Catalysts; their physical properties
- C07C1/043—Catalysts; their physical properties characterised by the composition
- C07C1/0435—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof
- C07C1/044—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof containing iron
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- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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- B01J2229/10—After treatment, characterised by the effect to be obtained
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Abstract
The present invention relates to the method for composite catalyst and preparation method thereof and synthesis gas production low-carbon alkene, mainly solve the problems, such as that CO conversion ratios are low low with selectivity of light olefin in one-step method from syngas reaction for preparing light olefins existing in the prior art.The present invention uses, composite catalyst, by weight percentage including following components：A) 1~20% ferro element or its oxide；B) 1~15% Ce elements or its oxide；C) at least one of magnesium and calcium element or its oxide are selected from 1~15%；D) 2~10% neodymium element or its oxide；E) 20~75% silica；F) technical solution of 20~40% 5 molecular sieve of modified ZSM-5, preferably solves the problems, such as this, the industrial production available for synthesis gas preparing low-carbon olefins.
Description
Technical field
The present invention relates to composite catalyst and its preparation method and application, more particularly to a kind of low-carbon alkene that produces
Composite catalyst and its preparation method and application.
Background technology
Low-carbon alkene refers to the alkene that carbon number is less than or equal to 4.Using ethene, propylene as representative low-carbon alkene right and wrong
Often important basic organic chemical industry raw material, with the rapid growth of China's economy, for a long time, low-carbon alkene market is not for should
Ask.At present, the petrochemical industry route that the production of low-carbon alkene is mainly cracked using lighter hydrocarbons (ethane, naphtha, light diesel fuel), due to
The long-term run at high level of growing lack and crude oil price of Global Oil resource, development low-carbon alkene industry rely solely on petroleum light hydrocarbon
Increasing raw material problem can be run into for the tube cracking furnace technique of raw material, low-carbon alkene production technology and raw material must be polynary
Change.The direct preparing low-carbon olefins of one-step method from syngas be exactly carbon monoxide and hydrogen under catalyst action, it is anti-by F- T synthesis
The process of low-carbon alkene of the carbon number less than or equal to 4 should directly be made, which need not be as indirect method technique from conjunction
Into gas through methanol or dimethyl ether, alkene is further prepared, simplification of flowsheet, greatly reduces investment.Petroleum resources are short at home
Lack, it is current that external dependence degree is higher and higher, international oil price constantly rises violently, selects synthesis gas producing olefinic hydrocarbons technique to widen former material
Expect source, synthesis gas will be produced by raw material of crude oil, natural gas, coal and recyclable materials, can be based on high cost feedstocks
As naphtha steam cracking technology in terms of provide alternative solution.The coal price of the abundant coal resources of China and relative moderate
Refined oil for Development of Coal and provide the good market opportunity using preparation of low carbon olefines by synthetic gas technique.And enriched in Natural Gas In China
Oil gas field near, if Gas Prices are cheap, and application preparation of low carbon olefines by synthetic gas technique fabulous opportunity.If energy
Using the coal and natural gas resource of China's abundant, pass through gas making producing synthesis gas (gaseous mixture of carbon monoxide and hydrogen), hair
The substitute energy source for petroleum technology of preparation of low carbon olefines by synthetic gas is opened up, will be of great significance to solving energy problem of China.
One-step method from syngas producing light olefins technology originates from traditional Fischer-Tropsch synthesis, traditional Fischer-Tropsch synthetic
Carbon number distribution defer to ASF distribution, each hydro carbons all have theoretical maximum selectivity, such as C2-C4The selectivity of cut 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 got over
Greatly.Once α values determine, the selectivity of whole synthetic product determines that, chain growth probability α values depend on catalyst composition,
Granularity and reaction condition etc..In recent years, it has been found that the alkene secondary counter caused by alhpa olefin adsorbing again on a catalyst
Should, product distribution is distributed away from ideal ASF.F- T synthesis is a kind of strong exothermal reaction, and substantial amounts of reaction heat will promote catalyst
Carbon deposit reaction is easier generation methane and low-carbon alkanes, causes selectivity of light olefin significantly to decline；Secondly, complicated power
It is unfavorable that factor is also caused to selectivity synthesis low-carbon alkene；The ASF distributions of Fischer-Tropsch synthetic limit synthesizing low-carbon alkene
Selectivity.The catalyst of F- T synthesis gas producing light olefins is mainly iron catalyst series, is directly made to improve synthesis gas
The selectivity of low-carbon alkene is taken, physics and chemical modification can be carried out to fischer-tropsch synthetic catalyst, as utilized molecular sieve suitable
Pore passage structure, is conducive to low-carbon alkene and diffuses out metal active centres in time, suppresses the secondary response of low-carbon alkene；Improve gold
Belong to ion dispersiveness, also there is preferable olefine selective；Support-metal strong interaction, which changes, can also improve low-carbon alkene choosing
Selecting property；Suitable transition metal is added, the bond energy of active component and carbon can be strengthened, suppresses methane generation, improves low-carbon alkene
Selectivity；Electronics accelerating auxiliaries are added, promote the heat increase of CO chemisorbeds, adsorbance also increases, and hydrogen adsorptive capacity reduces, as a result
Selectivity of light olefin increase；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 can obviously improve
Can, develop the fischer-tropsch synthetic catalyst with the non-ASF of the product novel high-activity high selectivity producing light olefins being distributed.
Synthesis gas directly produces low-carbon alkene, it has also become one of research hotspot of fischer-tropsch synthetic catalyst exploitation.The Chinese Academy of Sciences
In patent CN1083415A disclosed in Dalian Chemical Physics Research Institute, with the Group IIA such as MgO alkali metal oxide or silica-rich zeolite point
Iron-Mn catalyst system that son sieve (or phosphorus aluminium zeolite) supports, makees auxiliary agent, in synthesis of gas produced low-carbon alkene with highly basic K or Cs ion
Hydrocarbon reaction pressure is 1.0~5.0MPa, at 300~400 DEG C of reaction temperature, can obtain higher activity (CO conversion ratios 90%) and
Selectivity (selectivity of light olefin 66%).But the catalyst preparation process is complicated, the particularly preparation of carrier zeolite molecular sieve
Forming process cost 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 combination solid phase reaction combination technique is used to be prepared for Fe3Fe base nano-catalysts based on C are applied to synthesis
Gas producing light olefins, and good catalytic effect is achieved, due to needing to use laser pyrolysis technology, preparation process is more numerous
Trivial, raw material uses Fe (CO)5, catalyst cost is very high, and industrialization is difficult.The patent that Beijing University of Chemical Technology is declared
In ZL03109585.2, use vacuum impregnation technology to prepare manganese, copper, zinc silicon, potassium etc. and be used to close for the Fe/ activated-carbon catalysts of auxiliary agent
Into gas reaction for preparing light olefins, under conditions of no unstripped gas circulates, CO conversion ratios 96%, low-carbon alkene is in hydrocarbon
Selectivity 68%.The molysite and auxiliary agent manganese salt that the catalyst preparation uses are more expensive and less soluble ferric oxalate and acetic acid
Manganese, while with the cost of material and running cost of ethanol as solvent, just inevitable increase catalyst preparation process.To be further
The cost of catalyst is reduced, in its number of patent application 200710063301.9, catalyst uses common medicine and reagent system
Standby, the molysite used is ferric nitrate, and manganese salt is manganese nitrate, and sylvite is potassium carbonate, and activated carbon is coconut husk charcoal, can catalyst must flow
Dynamic nitrogen protection is lower to carry out high-temperature roasting and Passivation Treatment, it is necessary to which special installation, preparation process is complicated, and cost is higher.It is and above-mentioned
CO conversion ratio and selectivity of light olefin of the catalyst in fixed bed reaction are relatively low.
The content of the invention
The first technical problem to be solved by the present invention is that synthesis gas produces in low-carbon alkene technology CO turns in the prior art
The problem of rate is low low with selectivity of light olefin in product, there is provided composite catalyst, the catalyst are produced for synthesis gas
When low-carbon alkene reacts, have the advantages that selectivity of light olefin is high in CO high conversion rates and product.
The second technical problem to be solved by the present invention is to provide the preparation method of the catalyst of one of above-mentioned technical problem.
The third technical problem to be solved by the present invention is to provide the synthesis gas of the catalyst using one of above-mentioned technical problem
The method for producing low-carbon alkene.
To solve one of above-mentioned technical problem, the technical solution adopted by the present invention is as follows：Composite catalyst, with weight hundred
Divide includes following components than meter：
A) 1~20% ferro element or its oxide；
B) 1~15% Ce elements or its oxide；
C) at least one of magnesium and calcium element or its oxide are selected from 1~15%；
D) 2~10% neodymium element or its oxide；
E) 20~75% silica；
F) 20~40% modified zsm-5 zeolite, including following components in terms of the parts by weight of modified zsm-5 zeolite
(1) 1~10% part of gallium element or its oxide；(2) 90~99% parts of ZSM-5 molecular sieves.
In above-mentioned technical proposal, the oxide of iron is preferably di-iron trioxide in catalyst.
In above-mentioned technical proposal, in terms of catalyst weight percent, the preferred scope of ferro element or its oxide content is 5
~15%.
In above-mentioned technical proposal, the oxide of Cerium in Catalysts is preferably ceria.
In above-mentioned technical proposal, in terms of catalyst weight percent, the preferred scope of Ce elements or its oxide content is 1
~10%.
In above-mentioned technical proposal, the oxide of magnesium and calcium is respectively magnesia and calcium oxide in catalyst.
In above-mentioned technical proposal, in terms of catalyst weight percent, at least one of magnesium and calcium element or its oxide
The preferred scope of content is 1~10%.
In above-mentioned technical proposal, the oxide of neodymium is neodymium oxide in catalyst.
In above-mentioned technical proposal, in terms of catalyst weight percent, the preferred scope of neodymium element or its oxide content is 2
~8%.
In above-mentioned technical proposal, the silica described in catalyst, in terms of catalyst weight percent, content it is preferred
Scope is 20~60%.
In above-mentioned technical proposal, the silica alumina ratio preferred scope of the ZSM-5 molecular sieve described in catalyst is 200~600.
To solve the two of above-mentioned technical problem, technical scheme is as follows：The technical side of one of above-mentioned technical problem
The preparation of the composite catalyst, comprises the following steps any one of case：
(1) it is soluble in water that mixed solution A is made by molysite, cerium salt, magnesium salts or calcium salt, neodymium salt；
(2) mixed solution A is mixed to obtain to catalyst precarsor B with silica；
(3) by catalyst precarsor B, roast after drying, obtain required Fischer-Tropsch synthetic iron-based catalyst C.
(4) solution D is made by gallium salt is soluble in water；
(5) solution D is mixed to obtain to catalyst precarsor E with ZSM-5 molecular sieve；
(6) by catalyst precarsor E, roast after drying, obtain required ZSM-5 Type Zeolites agent F.
(7) Fischer-Tropsch synthetic iron-based catalyst C and ZSM-5 Type Zeolites agent F are mixed to get required compound
Catalyst.
In above-mentioned technical proposal, the hybrid mode of step (2) and/or step (5) does not specially require, but in vacuum condition
Lower mixed effect is especially good.Solution is such as, but not limited to impregnated into corresponding solid constituent under the conditions of 1~80kPa of vacuum.
After in above-mentioned technical proposal, the hybrid mode of step (7) does not specially require, but mill is mixed in the ball mill, tabletting
Shaping, further crushing and screening effect are especially good.
In above-mentioned technical proposal, the preferred scope of the calcination temperature in step (3) is 700~900 DEG C, roasting time it is excellent
Select scope for 2.0~8.0 it is small when；The preferred scope of calcination temperature in step (6) be 400~600 DEG C, roasting time it is preferred
When scope is 2.0~6.0 small.
To solve the three of above-mentioned technical problem, technical scheme is as follows：The method that synthesis gas produces low-carbon alkene,
Using synthesis gas as raw material, H2Be 1~3 with the molar ratio of CO, be 250~400 DEG C in reaction temperature, reaction pressure for 1.0~
3.0Mpa, feed gas volume air speed are 500~5000h-1Under conditions of, the technical solution of one of unstripped gas and above-mentioned technical problem
Any one of composite catalyst haptoreaction generation C2~C4Alkene.
The method of the present invention use Fischer-Tropsch synthetic iron-based catalyst prepared by vacuum impregnation technology, can make active component and
Auxiliary agent high uniformity is scattered in carrier surface, and increase is exposed to the quantity of the active sites of carrier surface, improves the conversion ratio of CO；Subtract
The particle diameter of small active component and auxiliary agent, improves selectivity of light olefin.The gallium modified zsm-5 zeolite of use passes through vacuum impregnation
Prepared by method, be conducive to gallium element in the dispersed of ZSM-5 molecular sieve channel surfaces, reduces the surface acidity of ZSM-5 molecular sieve.
Transition metal Ce, alkaline-earth metal Mg or Ca are introduced in the Fischer-Tropsch synthetic iron-based catalyst that the method for the present invention uses, with
And rare earth metal Nd is conducive to improve the CO conversion ratios of catalyst and the selectivity of low-carbon alkene as catalyst promoter.Especially
It is to introduce rare earth metal Nd, due to the interaction between Nd and active component and auxiliary agent, can effectively discharges the activity of catalyst,
Improve the conversion ratio of CO and the selectivity of low-carbon alkene.
The method of the present invention is mixed with compound catalysis using Fischer-Tropsch synthetic iron-based catalyst and modified zsm-5 zeolite
Agent, on the one hand produces low-carbon alkene using fischer-tropsch synthetic catalyst high-activity high-selectivity, on the other hand utilizes modified ZSM-5 point
The splitting action of son sieve, by the long chain hydrocarbons catalytic pyrolysis of fischer-tropsch reaction generation into small molecule low-carbon alkene, further improves low-carbon
Olefine selective.
The use condition of the catalyst is as follows：With H2Synthesis gas with CO compositions is raw material, H2With the molar ratio of CO for 1~
3, it is 250~400 DEG C in reaction temperature, reaction pressure is 1.0~3.0Mpa, and feed gas volume air speed is 500~2500h-1's
Under the conditions of, unstripped gas is contacted with catalyst, achieves preferable technique effect：CO conversion ratios compare the prior art up to 99.7%
Improve 3.7%；Selectivity of the low-carbon alkene in hydrocarbon improves 10.1% up to 78.1%, than the prior art, more in detail
Thin result is seen attached list.
The present invention is described further for the following examples, protection scope of the present invention and from these embodiments
Limitation.
Embodiment
【Embodiment 1】
Weigh 50.6 grams of Fe(NO3)39H2Os, 17.7 gram of six nitric hydrate cerium, 50.9 grams of magnesium nitrate hexahydrates, 13.0 gram six
Nitric hydrate neodymium, is dissolved in 30.0 grams of deionized waters and mixed solution A is made；Under conditions of vacuum 80kPa, by above-mentioned mixing
Solution A is impregnated in 40.0 grams of SiO2Catalyst precarsor B is obtained on carrier；The catalyst precarsor B impregnated is done under the conditions of 120 DEG C
It is dry, then roasted, 800 DEG C of calcination temperature, roasting time 5h, that is, obtain Fischer-Tropsch synthetic iron-based catalyst C.Weigh 6.7 grams
Nine nitric hydrate galliums, are dissolved in 10.0 grams of deionized waters and solution D are made；Under conditions of vacuum 80kPa, by above-mentioned solution D
It is impregnated on the ZSM-5 molecular sieve that 28.5 grams of silica alumina ratios are 400 and obtains catalyst precarsor E；The catalyst precarsor E impregnated is 120
It is dry under the conditions of DEG C, then roasted, 500 DEG C of calcination temperature, roasting time 4h, that is, obtain ZSM-5 Type Zeolites
Agent F.After Fischer-Tropsch synthetic iron-based catalyst C and ZSM-5 Type Zeolites agent F is mixed, after mill is mixed in the ball mill, tabletting
Shaping, crushing and screening obtain required composite catalyst.Obtained composite catalyst by weight percentage, comprising with the following group
Point：10%Fe2O3, 7%CeO2, 8%MgO, 5%Nd2O3, 40%SiO2, 1.5%Ga2O3, 28.5%ZSM-5；Made is compound
Type catalyst carries out synthesis gas production low-carbon alkene reaction under certain condition, and experimental result is listed in table 1.
【Embodiment 2】
Weigh 5.1 grams of Fe(NO3)39H2Os, 2.5 gram of six nitric hydrate cerium, 6.4 grams of magnesium nitrate hexahydrates, 5.2 gram of six hydration
Neodymium nitrate, is dissolved in 30.0 grams of deionized waters and mixed solution A is made；Under conditions of vacuum 80kPa, by above-mentioned mixed solution
A is impregnated in 75.0 grams of SiO2Catalyst precarsor B is obtained on carrier；The catalyst precarsor B impregnated is dry under the conditions of 120 DEG C, so
After roasted, 700 DEG C of calcination temperature, roasting time 8h, that is, obtain Fischer-Tropsch synthetic iron-based catalyst C.Weigh 4.5 gram of nine hydration
Gallium nitrate, is dissolved in 10.0 grams of deionized waters and solution D is made；Under conditions of vacuum 80kPa, above-mentioned solution D is impregnated in
Catalyst precarsor E is obtained on the ZSM-5 molecular sieve that 19.0 grams of silica alumina ratios are 400；The catalyst precarsor E impregnated is in 120 DEG C of conditions
Lower drying, is then roasted, and 500 DEG C, roasting time 4h of calcination temperature, that is, obtain ZSM-5 Type Zeolites agent F.Will
After Fischer-Tropsch synthetic iron-based catalyst C and ZSM-5 Type Zeolites agent F mixing, after mill is mixed in the ball mill, compression molding,
Crushing and screening obtains required composite catalyst.Obtained composite catalyst by weight percentage, includes following components：
1%Fe2O3, 1%CeO2, 1%MgO, 2%Nd2O3, 75%SiO2, 1.0%Ga2O3, 19.0%ZSM-5；It is made compound to urge
Agent carries out synthesis gas production low-carbon alkene reaction under certain condition, and experimental result is listed in table 1.
【Embodiment 3】
Weigh 101.2 grams of Fe(NO3)39H2Os, 25.2 gram of six nitric hydrate cerium, 29.3 grams of calcium nitrate, 26.1 gram of six hydration
Neodymium nitrate, is dissolved in 30.0 grams of deionized waters and mixed solution A is made；Under conditions of vacuum 80kPa, by above-mentioned mixed solution
A is impregnated in 20.0 grams of SiO2Catalyst precarsor B is obtained on carrier；The catalyst precarsor B impregnated is dry under the conditions of 120 DEG C, so
After roasted, 900 DEG C of calcination temperature, roasting time 2h, that is, obtain Fischer-Tropsch synthetic iron-based catalyst C.Weigh 6.7 gram of nine hydration
Gallium nitrate, is dissolved in 10.0 grams of deionized waters and solution D is made；Under conditions of vacuum 80kPa, above-mentioned solution D is impregnated in
Catalyst precarsor E is obtained on the ZSM-5 molecular sieve that 28.5 grams of silica alumina ratios are 400；The catalyst precarsor E impregnated is in 120 DEG C of conditions
Lower drying, is then roasted, and 500 DEG C, roasting time 4h of calcination temperature, that is, obtain ZSM-5 Type Zeolites agent F.Will
After Fischer-Tropsch synthetic iron-based catalyst C and ZSM-5 Type Zeolites agent F mixing, after mill is mixed in the ball mill, compression molding,
Crushing and screening obtains required composite catalyst.Obtained composite catalyst by weight percentage, includes following components：
20%Fe2O3, 10%CeO2, 10%CaO, 10%Nd2O3, 20%SiO2, 1.5%Ga2O3, 28.5%ZSM-5；Made is compound
Type catalyst carries out synthesis gas production low-carbon alkene reaction under certain condition, and experimental result is listed in table 1.
【Embodiment 4】
Weigh 25.3 grams of Fe(NO3)39H2Os, 37.8 gram of six nitric hydrate cerium, 95.4 grams of magnesium nitrate hexahydrates, 26.1 gram six
Nitric hydrate neodymium, is dissolved in 30.0 grams of deionized waters and mixed solution A is made；Under conditions of vacuum 80kPa, by above-mentioned mixing
Solution A is impregnated in 35.0 grams of SiO2Catalyst precarsor B is obtained on carrier；The catalyst precarsor B impregnated is done under the conditions of 120 DEG C
It is dry, then roasted, 800 DEG C of calcination temperature, roasting time 5h, that is, obtain Fischer-Tropsch synthetic iron-based catalyst C.Weigh 4.5 grams
Nine nitric hydrate galliums, are dissolved in 10.0 grams of deionized waters and solution D are made；Under conditions of vacuum 80kPa, by above-mentioned solution D
It is impregnated on the ZSM-5 molecular sieve that 19.0 grams of silica alumina ratios are 400 and obtains catalyst precarsor E；The catalyst precarsor E impregnated is 120
It is dry under the conditions of DEG C, then roasted, 400 DEG C of calcination temperature, roasting time 6h, that is, obtain ZSM-5 Type Zeolites
Agent F.After Fischer-Tropsch synthetic iron-based catalyst C and ZSM-5 Type Zeolites agent F is mixed, after mill is mixed in the ball mill, tabletting
Shaping, crushing and screening obtain required composite catalyst.Obtained composite catalyst by weight percentage, comprising with the following group
Point：5%Fe2O3, 15%CeO2, 15%MgO, 10%Nd2O3, 35%SiO2, 1.0%Ga2O3, 19.0%ZSM-5；Made answers
Mould assembly catalyst carries out synthesis gas production low-carbon alkene reaction under certain condition, and experimental result is listed in table 1.
【Embodiment 5】
Weigh 75.9 grams of Fe(NO3)39H2Os, 2.5 gram of six nitric hydrate cerium, 2.9 grams of calcium nitrate, 5.2 gram of six nitric hydrate
Neodymium, is dissolved in 30.0 grams of deionized waters and mixed solution A is made；Under conditions of vacuum 80kPa, above-mentioned mixed solution A is soaked
Stain is in 41.0 grams of SiO2Catalyst precarsor B is obtained on carrier；The catalyst precarsor B impregnated is dry under the conditions of 120 DEG C, Ran Houjin
Row roasting, 800 DEG C of calcination temperature, roasting time 5h, that is, obtain Fischer-Tropsch synthetic iron-based catalyst C.Weigh 8.9 gram of nine nitric hydrate
Gallium, is dissolved in 10.0 grams of deionized waters and solution D is made；Under conditions of vacuum 80kPa, above-mentioned solution D is impregnated in 38.0
Gram silica alumina ratio be on 400 ZSM-5 molecular sieve catalyst precarsor E；The catalyst precarsor E impregnated is done under the conditions of 120 DEG C
It is dry, then roasted, 600 DEG C, roasting time 2h of calcination temperature, that is, obtain ZSM-5 Type Zeolites agent F.By Fischer-Tropsch
After synthesis iron base catalyst C and ZSM-5 Type Zeolites agent F mixing, after mill is mixed in the ball mill, compression molding, crushes
Screening obtains required composite catalyst.Obtained composite catalyst by weight percentage, includes following components：15%
Fe2O3, 1%CeO2, 1%CaO, 2%Nd2O3, 41%SiO2, 1.5%Ga2O3, 28.5%ZSM-5；Made composite catalyst
Synthesis gas production low-carbon alkene reaction is carried out under certain condition, and experimental result is listed in table 1.
【Embodiment 6】
Weigh 101.2 grams of Fe(NO3)39H2Os, 37.8 gram of six nitric hydrate cerium, 95.4 grams of magnesium nitrate hexahydrates, 18.2 grams
Six nitric hydrate neodymiums, are dissolved in 30.0 grams of deionized waters and mixed solution A are made；, will be above-mentioned mixed under conditions of vacuum 80kPa
Close solution A and be impregnated in 20.0 grams of SiO2Catalyst precarsor B is obtained on carrier；The catalyst precarsor B impregnated is done under the conditions of 120 DEG C
It is dry, then roasted, 800 DEG C of calcination temperature, roasting time 5h, that is, obtain Fischer-Tropsch synthetic iron-based catalyst C.Weigh 5.4 grams
Nine nitric hydrate galliums, are dissolved in 10.0 grams of deionized waters and solution D are made；Under conditions of vacuum 80kPa, by above-mentioned solution D
It is impregnated on the ZSM-5 molecular sieve that 21.8 grams of silica alumina ratios are 200 and obtains catalyst precarsor E；The catalyst precarsor E impregnated is 120
It is dry under the conditions of DEG C, then roasted, 500 DEG C of calcination temperature, roasting time 4h, that is, obtain ZSM-5 Type Zeolites
Agent F.After Fischer-Tropsch synthetic iron-based catalyst C and ZSM-5 Type Zeolites agent F is mixed, after mill is mixed in the ball mill, tabletting
Shaping, crushing and screening obtain required composite catalyst.Obtained composite catalyst by weight percentage, comprising with the following group
Point：20%Fe2O3, 15%CeO2, 15%MgO, 7%Nd2O3, 20%SiO2, 1.2%Ga2O3, 21.8%ZSM-5；Made answers
Mould assembly catalyst carries out synthesis gas production low-carbon alkene reaction under certain condition, and experimental result is listed in table 1.
【Embodiment 7】
Weigh 5.1 grams of Fe(NO3)39H2Os, 12.6 gram of six nitric hydrate cerium, 14.6 grams of calcium nitrate, 5.2 gram of six nitric hydrate
Neodymium, is dissolved in 30.0 grams of deionized waters and mixed solution A is made；Under conditions of vacuum 80kPa, above-mentioned mixed solution A is soaked
Stain is in 60.0 grams of SiO2Catalyst precarsor B is obtained on carrier；The catalyst precarsor B impregnated is dry under the conditions of 120 DEG C, Ran Houjin
Row roasting, 800 DEG C of calcination temperature, roasting time 5h, that is, obtain Fischer-Tropsch synthetic iron-based catalyst C.Weigh 6.2 gram of nine nitric hydrate
Gallium, is dissolved in 10.0 grams of deionized waters and solution D is made；Under conditions of vacuum 80kPa, above-mentioned solution D is impregnated in 25.6
Gram silica alumina ratio be on 600 ZSM-5 molecular sieve catalyst precarsor E；The catalyst precarsor E impregnated is done under the conditions of 120 DEG C
It is dry, then roasted, 500 DEG C, roasting time 4h of calcination temperature, that is, obtain ZSM-5 Type Zeolites agent F.By Fischer-Tropsch
After synthesis iron base catalyst C and ZSM-5 Type Zeolites agent F mixing, after mill is mixed in the ball mill, compression molding, crushes
Screening obtains required composite catalyst.Obtained composite catalyst by weight percentage, includes following components：1%
Fe2O3, 5%CeO2, 5%CaO, 2%Nd2O3, 60%SiO2, 1.4%Ga2O3, 25.6%ZSM-5；Made composite catalyst
Synthesis gas production low-carbon alkene reaction is carried out under certain condition, and experimental result is listed in table 1.
【Embodiment 8】
Weigh 50.6 grams of Fe(NO3)39H2Os, 17.7 gram of six nitric hydrate cerium, 23.4 grams of calcium nitrate, 13.0 gram of six hydration nitre
Sour neodymium, is dissolved in 30.0 grams of deionized waters and mixed solution A is made；Under conditions of vacuum 80kPa, by above-mentioned mixed solution A
It is impregnated in 40.0 grams of SiO2Catalyst precarsor B is obtained on carrier；The catalyst precarsor B impregnated is dry under the conditions of 120 DEG C, then
Roasted, 800 DEG C of calcination temperature, roasting time 5h, that is, obtain Fischer-Tropsch synthetic iron-based catalyst C.Weigh 6.7 gram of nine hydration nitre
Sour gallium, is dissolved in 10.0 grams of deionized waters and solution D is made；Under conditions of vacuum 80kPa, above-mentioned solution D is impregnated in
Catalyst precarsor E is obtained on the ZSM-5 molecular sieve that 28.5 grams of silica alumina ratios are 300；The catalyst precarsor E impregnated is in 120 DEG C of conditions
Lower drying, is then roasted, and 500 DEG C, roasting time 4h of calcination temperature, that is, obtain ZSM-5 Type Zeolites agent F.Will
After Fischer-Tropsch synthetic iron-based catalyst C and ZSM-5 Type Zeolites agent F mixing, after mill is mixed in the ball mill, compression molding,
Crushing and screening obtains required composite catalyst.Obtained composite catalyst by weight percentage, includes following components：
10%Fe2O3, 7%CeO2, 8%CaO, 5%Nd2O3, 40%SiO2, 1.5%Ga2O3, 28.5%ZSM-5；It is made compound to urge
Agent carries out synthesis gas production low-carbon alkene reaction under certain condition, and experimental result is listed in table 1.
【Embodiment 9】
Weigh 50.6 grams of Fe(NO3)39H2Os, 17.7 gram of six nitric hydrate cerium, 50.9 grams of magnesium nitrate hexahydrates, 13.0 gram six
Nitric hydrate neodymium, is dissolved in 30.0 grams of deionized waters and mixed solution A is made；Under conditions of vacuum 80kPa, by above-mentioned mixing
Solution A is impregnated in 40.0 grams of SiO2Catalyst precarsor B is obtained on carrier；The catalyst precarsor B impregnated is done under the conditions of 120 DEG C
It is dry, then roasted, 800 DEG C of calcination temperature, roasting time 5h, that is, obtain Fischer-Tropsch synthetic iron-based catalyst C.Weigh 1.3 grams
Nine nitric hydrate galliums, are dissolved in 10.0 grams of deionized waters and solution D are made；Under conditions of vacuum 80kPa, by above-mentioned solution D
It is impregnated on the ZSM-5 molecular sieve that 29.7 grams of silica alumina ratios are 500 and obtains catalyst precarsor E；The catalyst precarsor E impregnated is 120
It is dry under the conditions of DEG C, then roasted, 500 DEG C of calcination temperature, roasting time 4h, that is, obtain ZSM-5 Type Zeolites
Agent F.After Fischer-Tropsch synthetic iron-based catalyst C and ZSM-5 Type Zeolites agent F is mixed, after mill is mixed in the ball mill, tabletting
Shaping, crushing and screening obtain required composite catalyst.Obtained composite catalyst by weight percentage, comprising with the following group
Point：10%Fe2O3, 7%CeO2, 8%MgO, 5%Nd2O3, 40%SiO2, 0.3%Ga2O3, 29.7%ZSM-5；Made is compound
Type catalyst carries out synthesis gas production low-carbon alkene reaction under certain condition, and experimental result is listed in table 1.
【Embodiment 10】
Weigh 50.6 grams of Fe(NO3)39H2Os, 17.7 gram of six nitric hydrate cerium, 50.9 grams of magnesium nitrate hexahydrates, 13.0 gram six
Nitric hydrate neodymium, is dissolved in 30.0 grams of deionized waters and mixed solution A is made；Under conditions of vacuum 80kPa, by above-mentioned mixing
Solution A is impregnated in 40.0 grams of SiO2Catalyst precarsor B is obtained on carrier；The catalyst precarsor B impregnated is done under the conditions of 120 DEG C
It is dry, then roasted, 800 DEG C of calcination temperature, roasting time 5h, that is, obtain Fischer-Tropsch synthetic iron-based catalyst C.Weigh 9.4 grams
Nine nitric hydrate galliums, are dissolved in 10.0 grams of deionized waters and solution D are made；Under conditions of vacuum 80kPa, by above-mentioned solution D
It is impregnated on the ZSM-5 molecular sieve that 27.9 grams of silica alumina ratios are 400 and obtains catalyst precarsor E；The catalyst precarsor E impregnated is 120
It is dry under the conditions of DEG C, then roasted, 500 DEG C of calcination temperature, roasting time 4h, that is, obtain ZSM-5 Type Zeolites
Agent F.After Fischer-Tropsch synthetic iron-based catalyst C and ZSM-5 Type Zeolites agent F is mixed, after mill is mixed in the ball mill, tabletting
Shaping, crushing and screening obtain required composite catalyst.Obtained composite catalyst by weight percentage, comprising with the following group
Point：10%Fe2O3, 7%CeO2, 8%MgO, 5%Nd2O3, 40%SiO2, 2.1%Ga2O3, 27.9%ZSM-5；Made is compound
Type catalyst carries out synthesis gas production low-carbon alkene reaction under certain condition, and experimental result is listed in table 1.
【Embodiment 11】
Weigh 50.6 grams of Fe(NO3)39H2Os, 17.7 gram of six nitric hydrate cerium, 50.9 grams of magnesium nitrate hexahydrates, 13.0 gram six
Nitric hydrate neodymium, is dissolved in 30.0 grams of deionized waters and mixed solution A is made；Under conditions of vacuum 80kPa, by above-mentioned mixing
Solution A is impregnated in 40.0 grams of SiO2Catalyst precarsor B is obtained on carrier；The catalyst precarsor B impregnated is done under the conditions of 120 DEG C
It is dry, then roasted, 800 DEG C of calcination temperature, roasting time 5h, that is, obtain Fischer-Tropsch synthetic iron-based catalyst C.Weigh 13.4 grams
Nine nitric hydrate galliums, are dissolved in 10.0 grams of deionized waters and solution D are made；Under conditions of vacuum 80kPa, by above-mentioned solution D
It is impregnated on the ZSM-5 molecular sieve that 27.0 grams of silica alumina ratios are 400 and obtains catalyst precarsor E；The catalyst precarsor E impregnated is 120
It is dry under the conditions of DEG C, then roasted, 500 DEG C of calcination temperature, roasting time 4h, that is, obtain ZSM-5 Type Zeolites
Agent F.After Fischer-Tropsch synthetic iron-based catalyst C and ZSM-5 Type Zeolites agent F is mixed, after mill is mixed in the ball mill, tabletting
Shaping, crushing and screening obtain required composite catalyst.Obtained composite catalyst by weight percentage, comprising with the following group
Point：10%Fe2O3, 7%CeO2, 8%MgO, 5%Nd2O3, 40%SiO2, 3.0%Ga2O3, 27.0%ZSM-5；Made is compound
Type catalyst carries out synthesis gas production low-carbon alkene reaction under certain condition, and experimental result is listed in table 1.
【Embodiment 12】
Catalyst made from Example 1, other are constant, only change reaction condition, carry out synthesis gas production low-carbon alkene,
Experimental result is listed in table 2.
【Comparative example 1】
50.6 grams of Fe(NO3)39H2Os, 25.2 gram of six nitric hydrate cerium are weighed, 63.6 grams of magnesium nitrate hexahydrates, are dissolved in 30.0
Mixed solution A is made in gram deionized water；Under conditions of vacuum 80kPa, above-mentioned mixed solution A is impregnated in 40.0 grams
SiO2Catalyst precarsor B is obtained on carrier；The catalyst precarsor B impregnated is dry under the conditions of 120 DEG C, is then roasted, and roasts
800 DEG C of temperature is burnt, roasting time 5h, that is, obtain Fischer-Tropsch synthetic iron-based catalyst C.6.7 gram of nine nitric hydrate gallium is weighed, is dissolved in
Solution D is made in 10.0 grams of deionized waters；Under conditions of vacuum 80kPa, above-mentioned solution D is impregnated in 28.5 grams of silica alumina ratios
To obtain catalyst precarsor E on 400 ZSM-5 molecular sieve；The catalyst precarsor E impregnated is dry under the conditions of 120 DEG C, Ran Houjin
Row roasting, 500 DEG C, roasting time 4h of calcination temperature, that is, obtain ZSM-5 Type Zeolites agent F.Urged Fischer-Tropsch synthetic iron-based
After agent C and ZSM-5 Type Zeolites agent F mixing, after mill is mixed in the ball mill, compression molding, crushing and screening obtains institute
The composite catalyst needed.Obtained composite catalyst by weight percentage, includes following components：10%Fe2O3, 10%
CeO2, 10%MgO, 40%SiO2, 1.5%Ga2O3, 28.5%ZSM-5；Made composite catalyst under certain condition into
The production low-carbon alkene reaction of row synthesis gas, experimental result are listed in table 1.
【Comparative example 2】
Weigh 50.6 grams of Fe(NO3)39H2Os, 10.1 gram of six nitric hydrate cerium, 25.4 grams of magnesium nitrate hexahydrates, 31.3 gram six
Nitric hydrate neodymium, is dissolved in 30.0 grams of deionized waters and mixed solution A is made；Under conditions of vacuum 80kPa, by above-mentioned mixing
Solution A is impregnated in 40.0 grams of SiO2Catalyst precarsor B is obtained on carrier；The catalyst precarsor B impregnated is done under the conditions of 120 DEG C
It is dry, then roasted, 800 DEG C of calcination temperature, roasting time 5h, that is, obtain Fischer-Tropsch synthetic iron-based catalyst C.Weigh 6.7 grams
Nine nitric hydrate galliums, are dissolved in 10.0 grams of deionized waters and solution D are made；Under conditions of vacuum 80kPa, by above-mentioned solution D
It is impregnated on the ZSM-5 molecular sieve that 28.5 grams of silica alumina ratios are 400 and obtains catalyst precarsor E；The catalyst precarsor E impregnated is 120
It is dry under the conditions of DEG C, then roasted, 500 DEG C of calcination temperature, roasting time 4h, that is, obtain ZSM-5 Type Zeolites
Agent F.After Fischer-Tropsch synthetic iron-based catalyst C and ZSM-5 Type Zeolites agent F is mixed, after mill is mixed in the ball mill, tabletting
Shaping, crushing and screening obtain required composite catalyst.Obtained composite catalyst by weight percentage, comprising with the following group
Point：10%Fe2O3, 4%CeO2, 4%MgO, 12%Nd2O3, 40%SiO2, 1.5%Ga2O3, 28.5%ZSM-5；Made is compound
Type catalyst carries out synthesis gas production low-carbon alkene reaction under certain condition, and experimental result is listed in table 1.
【Comparative example 3】
Weigh 50.6 grams of Fe(NO3)39H2Os, 17.7 gram of six nitric hydrate cerium, 50.9 grams of magnesium nitrate hexahydrates, 13.0 gram six
Nitric hydrate neodymium, is dissolved in 30.0 grams of deionized waters and mixed solution A is made；Under conditions of vacuum 80kPa, by above-mentioned mixing
Solution A is impregnated in 40.0 grams of SiO2Catalyst precarsor B is obtained on carrier；The catalyst precarsor B impregnated is done under the conditions of 120 DEG C
It is dry, then roasted, 800 DEG C of calcination temperature, roasting time 5h, that is, obtain Fischer-Tropsch synthetic iron-based catalyst C.Weigh 30 grams of silicon
Aluminium drying under the conditions of 120 DEG C than the ZSM-5 molecular sieve for 400, is then roasted, 500 DEG C of calcination temperature, roasting time
4h.By Fischer-Tropsch synthetic iron-based catalyst C and after the mixing of modified ZSM-5 molecular sieve, after mill is mixed in the ball mill, tabletting into
Type, crushing and screening obtain required composite catalyst.Obtained composite catalyst by weight percentage, comprising with the following group
Point：10%Fe2O3, 7%CeO2, 8%MgO, 5%Nd2O3, 40%SiO2, 30%ZSM-5；Made composite catalyst is one
Synthesis gas production low-carbon alkene reaction is carried out under fixed condition, experimental result is listed in table 1.
【Comparative example 4】
Weigh 50.6 grams of Fe(NO3)39H2Os, 17.7 gram of six nitric hydrate cerium, 50.9 grams of magnesium nitrate hexahydrates, 13.0 gram six
Nitric hydrate neodymium, is dissolved in 30.0 grams of deionized waters and mixed solution A is made；Under conditions of vacuum 80kPa, by above-mentioned mixing
Solution A is impregnated in 40.0 grams of SiO2Catalyst precarsor B is obtained on carrier；The catalyst precarsor B impregnated is done under the conditions of 120 DEG C
It is dry, then roasted, 800 DEG C of calcination temperature, roasting time 5h, that is, obtain Fischer-Tropsch synthetic iron-based catalyst C.Weigh 16.1 grams
Nine nitric hydrate galliums, are dissolved in 10.0 grams of deionized waters and solution D are made；Under conditions of vacuum 80kPa, by above-mentioned solution D
It is impregnated on the ZSM-5 molecular sieve that 26.4 grams of silica alumina ratios are 400 and obtains catalyst precarsor E；The catalyst precarsor E impregnated is 120
It is dry under the conditions of DEG C, then roasted, 500 DEG C of calcination temperature, roasting time 4h, that is, obtain ZSM-5 Type Zeolites
Agent F.After Fischer-Tropsch synthetic iron-based catalyst C and ZSM-5 Type Zeolites agent F is mixed, after mill is mixed in the ball mill, tabletting
Shaping, crushing and screening obtain required composite catalyst.Obtained composite catalyst by weight percentage, comprising with the following group
Point：10%Fe2O3, 7%CeO2, 8%MgO, 5%Nd2O3, 40%SiO2, 3.6%Ga2O3, 26.4%ZSM-5；Made is compound
Type catalyst carries out synthesis gas production low-carbon alkene reaction under certain condition, and experimental result is listed in table 1.
The reducing condition of above-described embodiment and comparative example is：
450 DEG C of temperature
Pressure normal pressure
Loaded catalyst 3ml
When catalyst loading 2000 is small-1
Also Primordial Qi H2
When recovery time 12 is small
Reaction condition is：
8 millimeters of fixed bed reactors of φ
330 DEG C of reaction temperature
Reaction pressure 1.5MPa
Loaded catalyst 3ml
When catalyst loading 2000 is small-1
Raw material proportioning (mole) H2/ CO=2.5/1
Table 1
Table 2
* the appreciation condition changed compared with the condition described in table 1.
Claims (9)
1. composite catalyst, by weight percentage including following components：
A) 1~20% ferro element or its oxide；
B) 1~15% Ce elements or its oxide；
C) at least one of magnesium and calcium element or its oxide are selected from 1~15%；
D) 2~10% neodymium element or its oxide；
E) 20~75% silica；
F) 20~40% modified zsm-5 zeolite, including following components (1) 1 in terms of the parts by weight of modified zsm-5 zeolite
~10% part of gallium element or its oxide；(2) 90~99% parts of ZSM-5 molecular sieves.
2. composite catalyst according to claim 1, it is characterised in that the oxide of iron is three in the catalyst
Aoxidize two iron.
3. composite catalyst according to claim 1, it is characterised in that the oxide of the Cerium in Catalysts is two
Cerium oxide.
4. composite catalyst according to claim 1, it is characterised in that the oxide of magnesium and calcium in the catalyst
Respectively magnesia and calcium oxide.
5. composite catalyst according to claim 1, it is characterised in that the oxide of neodymium is three in the catalyst
Aoxidize two neodymiums.
6. composite catalyst according to claim 1, it is characterised in that silica in the catalyst, with catalysis
Agent percentage by weight meter, content are 20~60%.
7. composite catalyst according to claim 1, it is characterised in that the silicon of ZSM-5 molecular sieve in the catalyst
Aluminium ratio is 200~600.
8. the preparation method of claim 1~7 any one of them composite catalyst, comprises the following steps：
(1) it is soluble in water that solution A is made by molysite, cerium salt, magnesium salts or calcium salt, neodymium salt；
(2) mixed solution A is mixed to obtain to catalyst precarsor B with silica；
(3) by catalyst precarsor B, roast after drying, obtain required Fischer-Tropsch synthetic iron-based catalyst C.
(4) solution D is made by gallium salt is soluble in water；
(5) solution D is mixed to obtain to catalyst precarsor E with ZSM-5 molecular sieve；
(6) by catalyst precarsor E, roast after drying, obtain required ZSM-5 Type Zeolites agent F.
(7) Fischer-Tropsch synthetic iron-based catalyst C and ZSM-5 Type Zeolites agent F are mixed to get required compound catalysis
Agent.
9. the method that synthesis gas produces low-carbon alkene, using synthesis gas as raw material, H2Molar ratio with CO is 1~3, in reaction temperature
For 250~400 DEG C, reaction pressure is 1.0~3.0Mpa, and feed gas volume air speed is 500~5000h-1Under conditions of, unstripped gas
C is generated with claim 1~7 any one of them composite catalyst haptoreaction2~C4Alkene.
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Cited By (4)
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| CN109939725A (en) * | 2019-03-15 | 2019-06-28 | 武汉科技大学 | A kind of synthesis gas directly converts the catalyst and preparation method thereof of isoparaffin processed |
| CN111068741A (en) * | 2018-10-18 | 2020-04-28 | 中国石油化工股份有限公司 | Catalyst for synthesizing low-carbon olefin by one-step method and application thereof |
| CN112619691A (en) * | 2019-10-09 | 2021-04-09 | 中国石油化工股份有限公司 | Catalyst for directly producing low-carbon olefin by Fischer-Tropsch synthesis and preparation method and application thereof |
| CN114369002A (en) * | 2020-10-14 | 2022-04-19 | 中国石油天然气股份有限公司 | Method for synthesizing linear alpha-olefin by synthesis gas |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111068741A (en) * | 2018-10-18 | 2020-04-28 | 中国石油化工股份有限公司 | Catalyst for synthesizing low-carbon olefin by one-step method and application thereof |
| CN111068741B (en) * | 2018-10-18 | 2023-04-07 | 中国石油化工股份有限公司 | Catalyst for synthesizing low-carbon olefin by one-step method and application thereof |
| CN109939725A (en) * | 2019-03-15 | 2019-06-28 | 武汉科技大学 | A kind of synthesis gas directly converts the catalyst and preparation method thereof of isoparaffin processed |
| CN109939725B (en) * | 2019-03-15 | 2021-12-14 | 武汉科技大学 | Catalyst for preparing isoparaffin by directly converting synthesis gas and preparation method thereof |
| CN112619691A (en) * | 2019-10-09 | 2021-04-09 | 中国石油化工股份有限公司 | Catalyst for directly producing low-carbon olefin by Fischer-Tropsch synthesis and preparation method and application thereof |
| CN112619691B (en) * | 2019-10-09 | 2022-08-12 | 中国石油化工股份有限公司 | Catalyst for directly producing low-carbon olefin by Fischer-Tropsch synthesis and preparation method and application thereof |
| CN114369002A (en) * | 2020-10-14 | 2022-04-19 | 中国石油天然气股份有限公司 | Method for synthesizing linear alpha-olefin by synthesis gas |
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