CN111068740B - Catalyst for producing low-carbon olefin by Fischer-Tropsch synthesis and application thereof - Google Patents

Catalyst for producing low-carbon olefin by Fischer-Tropsch synthesis and application thereof Download PDF

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CN111068740B
CN111068740B CN201811214080.5A CN201811214080A CN111068740B CN 111068740 B CN111068740 B CN 111068740B CN 201811214080 A CN201811214080 A CN 201811214080A CN 111068740 B CN111068740 B CN 111068740B
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CN111068740A (en
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李剑锋
陶跃武
宋卫林
庞颖聪
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Sinopec Shanghai Research Institute of Petrochemical Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
    • B01J29/0316—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing iron group metals, noble metals or copper
    • B01J29/0333—Iron group metals or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
    • B01J29/042—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 containing iron group metals, noble metals or copper
    • B01J29/044—Iron group metals or copper
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
    • C07C1/0425—Catalysts; their physical properties
    • C07C1/043—Catalysts; their physical properties characterised by the composition
    • C07C1/0435—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof
    • C07C1/044—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof containing iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

The invention relates to a catalyst for producing low-carbon olefin by Fischer-Tropsch synthesis and an application thereof, and mainly solves the problems of low CO conversion rate and low-carbon olefin selectivity in the reaction for producing the low-carbon olefin by Fischer-Tropsch synthesis in the prior art. The invention relates to a catalyst for producing low-carbon olefin by Fischer-Tropsch synthesis, which comprises the following components in parts by weight: 10-60 parts of a component a); 1-20 parts of component b); 1-20 parts of component c); 5-30 parts of component d); 10-60 parts of component e); component a) is selected from iron series elements or oxides thereof; component b) comprises at least one element selected from group IVA or an oxide thereof; component c) comprises at least one element selected from group IVB or an oxide thereof; component d) is selected from titanium dioxide; the component e) is selected from the technical scheme of MCM-41 type molecular sieve, so that the problem is solved well, and the method can be used for industrial production of low-carbon olefin by Fischer-Tropsch synthesis.

Description

Catalyst for producing low-carbon olefin by Fischer-Tropsch synthesis and application thereof
Technical Field
The invention relates to a catalyst for producing low-carbon olefin by Fischer-Tropsch synthesis and application thereof.
Background
The lower olefin means an olefin having 4 or less carbon atoms. The low-carbon olefin represented by ethylene and propylene is a very important basic organic chemical raw material, and the market of the low-carbon olefin is short in supply and demand for a long time along with the rapid growth of the economy of China. At present, the production of low-carbon olefin mainly adopts a petrochemical route of light hydrocarbon (ethane, naphtha and light diesel oil) cracking, and due to the gradual shortage of global petroleum resources and the long-term high-order running of the price of crude oil, the development of the tubular cracking furnace process which only depends on the light hydrocarbon as the raw material in the low-carbon olefin industry encounters larger and larger raw material problems, and the production process and the raw material of the low-carbon olefin need to be diversified. The one-step method for directly preparing the low-carbon olefin from the synthesis gas is a process for directly preparing the low-carbon olefin with the carbon atom number less than or equal to 4 by the Fischer-Tropsch synthesis reaction of carbon monoxide and hydrogen under the action of the catalyst, and the process does not need to further prepare the olefin from the synthesis gas through methanol or dimethyl ether like an indirect process, thereby simplifying the process flow and greatly reducing the investment. At present, the shortage of petroleum resources in China, higher and higher external dependence and the soaring international oil price, the process for preparing olefin by selecting synthesis gas can broaden the raw material sources, and the synthesis gas can be produced by taking crude oil, natural gas, coal and renewable materials as raw materials, so that a substitute scheme can be provided for the technical aspect of steam cracking based on high-cost raw materials such as naphtha. The abundant coal resources and the relatively low coal price in China provide good market opportunities for developing processes for refining coal and preparing low-carbon olefins by using synthesis gas. In the vicinity of the rich oil-gas field of natural gas in China, if the natural gas is low in price, the method is also an excellent opportunity for preparing low-carbon olefin by using the synthesis gas. If the abundant coal and natural gas resources in China can be utilized, the synthesis gas (the mixed gas of carbon monoxide and hydrogen) is prepared by gas making, and the development of the petroleum alternative energy technology for preparing low-carbon olefin from the synthesis gas is bound to have great significance for solving the energy problem in China.
The technology for directly synthesizing the low-carbon olefin from the synthesis gas originates from the traditional Fischer-Tropsch synthesis reaction, and the carbon number distribution of the traditional Fischer-Tropsch synthesis product conforms to the ASF (anaerobic-Filter) componentCloth, each hydrocarbon having the greatest theoretical selectivity, e.g. C2-C4The maximum selectivity of the fraction is 57%, the gasoline fraction (C)5-C11) The selectivity of (a) is at most 48%. The greater the value of the chain growth probability α, the greater the selectivity of the product heavy hydrocarbons. Once the alpha value is determined, the selectivity of the overall synthesis product is determined, and the chain growth probability alpha value depends on the catalyst composition, particle size, reaction conditions, and the like. In recent years, it has been found that the product distribution deviates from the ideal ASF distribution due to secondary reactions of olefins caused by re-adsorption of olefins on the catalyst. The Fischer-Tropsch synthesis is a strong exothermic reaction, and a large amount of reaction heat promotes the carbon deposition reaction of the catalyst to generate methane and low-carbon alkane more easily, so that the selectivity of the low-carbon alkene is greatly reduced; secondly, the complex kinetic factors also cause disadvantages for selectively synthesizing the low-carbon olefin; the ASF distribution of the Fischer-Tropsch synthesis product limits the selectivity of synthesizing low-carbon olefin. The catalyst for preparing the low-carbon olefin from the Fischer-Tropsch synthesis gas is mainly an iron catalyst, and can be used for carrying out physical and chemical modification on the Fischer-Tropsch synthesis catalyst in order to improve the selectivity of directly preparing the low-carbon olefin from the synthesis gas, for example, the proper pore channel structure of a molecular sieve is utilized, so that the low-carbon olefin can be conveniently diffused away from a metal active center in time, and the secondary reaction of the low-carbon olefin is inhibited; the metal ion dispersibility is improved, and the olefin selectivity is better; the selectivity of the low-carbon olefin can also be improved by changing the interaction between the metal and the carrier; proper transition metal is added, so that the bond energy of the active component and carbon can be enhanced, the generation of methane is inhibited, and the selectivity of low-carbon olefin is improved; the electron promoting assistant is added to promote the increase of CO chemical adsorption heat, the increase of adsorption quantity and the decrease of hydrogen adsorption quantity, so that the selectivity of the low-carbon olefin is increased; eliminating the acid center of the catalyst can inhibit the secondary reaction of the low-carbon olefin and improve the selectivity of the low-carbon olefin. The performance of the catalyst can be obviously improved by the carrier effect of the catalyst carrier and the addition of certain transition metal additives and alkali metal additives, and a novel Fischer-Tropsch synthesis catalyst with non-ASF distribution of products and high activity and high selectivity for preparing low-carbon olefin is developed.
The Fischer-Tropsch synthesis for producing the low-carbon olefin becomes one of the research hotspots for developing Fischer-Tropsch synthesis catalysts. Chemical compound of Chinese courtyardIn patent CN1083415A, the patent discloses by physical research discloses that an iron-manganese catalyst system supported by group IIA alkali metal oxides such as MgO or high-silicon zeolite molecular sieves (or phospho-aluminum zeolite) is used, and strong base K or Cs ions are used as an auxiliary agent, and under the reaction pressure of 1.0-5.0 MPa and the reaction temperature of 300-400 ℃, higher activity (90% of CO conversion) and selectivity (66% of low-carbon olefin selectivity) can be obtained. However, the preparation process of the catalyst is complex, and particularly, the preparation and forming process of the carrier zeolite molecular sieve has high cost and is not beneficial to industrial production. In the patent application No. 01144691.9 filed by Beijing university of chemical industry, the Fe is prepared by combining laser pyrolysis with solid phase reaction combined technology3The Fe-based nano catalyst mainly containing C is applied to preparing low-carbon olefin from synthesis gas, and obtains good catalytic effect, the preparation process is relatively complicated due to the need of using a laser pyrolysis technology, and the raw material adopts Fe (CO)5The catalyst cost is high, and industrialization is difficult. In patent ZL03109585.2 filed by Beijing university of chemical industry, a vacuum impregnation method is adopted to prepare a Fe/activated carbon catalyst taking manganese, copper, zinc, silicon, potassium and the like as additives for the reaction of preparing low-carbon olefin from synthesis gas, and under the condition of no circulation of raw material gas, the conversion rate of CO is 96 percent, and the selectivity of the low-carbon olefin in hydrocarbon is 68 percent. The iron salt and the auxiliary agent manganese salt used for preparing the catalyst are relatively expensive and relatively difficult to dissolve, and simultaneously, the ethanol is used as a solvent, so that the raw material cost and the operation cost in the catalyst preparation process are inevitably increased. In order to further reduce the cost of the catalyst, in the patent application No. 200710063301.9, the catalyst is prepared by using common medicines and reagents, iron salt is used as ferric nitrate, manganese salt is used as manganese nitrate, potassium salt is used as potassium carbonate, activated carbon is coconut shell carbon, the catalyst needs to be roasted at high temperature and passivated under the protection of flowing nitrogen, special equipment is needed, the preparation process is complex, and the cost is high. And the catalyst has lower CO conversion rate and lower selectivity of the low-carbon olefin in the reaction of preparing the low-carbon olefin from the synthesis gas.
Disclosure of Invention
One of the technical problems to be solved by the invention is the problems of low CO conversion rate and low selectivity of low carbon olefin in the product in the technology of producing low carbon olefin by Fischer-Tropsch synthesis in the prior art, and the invention provides a novel catalyst for producing low carbon olefin by Fischer-Tropsch synthesis, wherein the catalyst has the advantages of high CO conversion rate and high selectivity of low carbon olefin.
The second technical problem to be solved by the present invention is to provide a method for preparing a catalyst.
The present invention is also directed to a catalyst comprising one of the above-mentioned problems.
In order to solve one of the above technical problems, the technical scheme adopted by the invention is as follows:
the catalyst for producing the low-carbon olefin by Fischer-Tropsch synthesis comprises the following components in parts by weight:
10-60 parts of a component a); 1-20 parts of component b); 1-20 parts of component c); 5-30 parts of component d); 10-60 parts of component e);
component a) is selected from iron series elements or oxides thereof; component b) comprises at least one element selected from group IVA or an oxide thereof; component c) comprises at least one element selected from group IVB or an oxide thereof; component d) is selected from titanium dioxide; component e) is selected from molecular sieves of the MCM-41 type.
In the above technical solution, the iron-based element is selected from at least one of iron, cobalt and nickel. The oxide of iron is preferably iron sesquioxide and the oxide of cobalt is preferably cobaltosic oxide.
In the technical scheme, the content of the component a) is preferably 20-50 parts.
In the technical scheme, the content of the component b) is preferably 5-15 parts.
In the technical scheme, the content of the component c) is preferably 5-15 parts.
In the technical scheme, the content of the component d) is preferably 10-25 parts.
In the technical scheme, the content of the component e) is preferably 15-50 parts.
In the above technical scheme, the component b) preferably further comprises group IIB elements or oxides thereof.
In the above technical solution, the group IVA element preferably includes Ge or an oxide thereof.
In the above technical solution, the group IIB element preferably includes Zn or its oxide, and in this case, Ge (or its oxide) and Zn (or its oxide) have a synergistic effect in improving CO conversion and selectivity of low-carbon olefin in the product.
The ratio of Ge (or oxide thereof) to Zn is not particularly limited, and Ge or oxide thereof is GeO2And Zn or an oxide thereof in terms of ZnO, the weight ratio of Ge (or an oxide thereof), and Zn (or an oxide thereof) may be, but is not limited to, 0.5 to 3, and more specific non-limiting weight ratios may be 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 2.0, 2.1, 2.2, 2.5, 3.0, and so forth.
In the above technical solution, the component c) preferably further comprises a group IIA element or an oxide thereof.
In the above embodiment, the group IVB element preferably includes Zr or an oxide thereof.
In the above technical scheme, the IIA element preferably includes Sr or its oxide, and in this case, Zr (or its oxide) and Sr (or its oxide) have a synergistic effect in improving CO conversion and selectivity of low-carbon olefin in the product.
The ratio of Zr (or its oxide) to Sr is not particularly limited, and Zr or its oxide is ZrO2And Sr or an oxide thereof in terms of SrO, Zr (or an oxide thereof), and Sr (or an oxide thereof) may be, but not limited to, 0.1 to 5, and more specific, non-limiting weight ratios may be 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.8, 1.0, 1.2, 1.4, 1.5, 1.6, 1.8, 2.0, 2.2, 2.5, 3.0, 3.5, 4.0, 4.5, and so forth.
In the above technical solution, the MCM-41 type molecular sieve is preferably an MCM-41 molecular sieve modified with a modifier, and the modifier includes at least one element of VA elements or an oxide thereof.
In the above technical solution, the modifier further comprises at least one element of IA or an oxide thereof.
In the above technical solution, the modified MCM-41 molecular sieve preferably contains 1 to 15% by weight of the modifier, and more specifically, non-limiting values of the content are 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, and so on.
In the above embodiment, the group VA element preferably includes Bi or an oxide thereof.
In the above technical solution, the IA element preferably includes Cs or its oxide, and in this case, Bi (or its oxide) and Cs (or its oxide) have a synergistic effect in improving CO conversion and selectivity of low-carbon olefin in the product.
The ratio of Bi (or its oxide) to Cs is not particularly limited, and Bi or its oxide is Bi2O3And Cs or oxides thereof as Cs2The weight ratio of Bi (or oxide thereof) to Cs (or oxide thereof) in terms of O may be, but is not limited to, 0.1 to 5, and more specific non-limiting weight ratios may be 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.8, 1.0, 1.2, 1.4, 1.5, 1.6, 1.8, 2.0, 2.2, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, and the like.
To solve the second technical problem, the technical solution of the present invention is as follows: the preparation method of the catalyst for producing low-carbon olefins by Fischer-Tropsch synthesis, which is one of the technical problems, comprises the following steps:
(1) mixing corresponding oxides of the components a), b) and c), titanium dioxide of the component d) and a binder to obtain a powdery material A;
(2) adding water into the material A, and kneading to obtain a material B;
(3) extruding the material B into strips, forming and drying to obtain a material C;
(4) and sintering the material C at a high temperature, cooling, crushing and screening to obtain a required molten state mixture D.
(5) And mixing the molten mixture D with an MCM-41 type molecular sieve to obtain the required catalyst.
In the above technical scheme, the binder and the amount used in step (1) are not particularly limited, and may be reasonably selected by those skilled in the art. For example, but not limited to, the binder may be hydroxypropyl methylcellulose powder, hydroxyethyl methylcellulose powder, carboxymethyl cellulose, starch, dextrin, polyethylene glycol, polyvinyl alcohol, and the like; the binder is used in an amount such as, but not limited to, 3 to 7% of the total weight of components a), b), c) and d).
In the above technical solution, the amount of water used in step (2) is not particularly limited, and is preferably such that the kneading and extruding degree can be achieved, and for this reason, a person skilled in the art can reasonably select and does not need to pay creative labor, for example, but not limited to, the amount of water used in step (2) is preferably 5 to 15% of the total weight of all components a), b), c) and d) in step (1).
In the above-mentioned technical means, the process conditions for drying in the step (3) are not particularly limited, and the final degree of drying is not particularly limited. For example, but not limited to, the drying temperature is 100-150 ℃, and the drying time is more than 6 hours (e.g., 8 hours, 12 hours, 18 hours, 24 hours, etc.).
In the technical scheme, the preferable range of the high-temperature sintering temperature in the step (4) is 1200-1700 ℃. Such as but not limited to 1200 deg.C, 1250 deg.C, 1300 deg.C, 1350 deg.C, 1400 deg.C, 1450 deg.C, 1500 deg.C, 1550 deg.C, 1600 deg.C, 1650 deg.C, etc.
In the technical scheme, the high-temperature sintering time in the step (4) is preferably 4-10 hours. Such as but not limited to 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, and the like.
In the technical scheme, the mixing mode of the step (5) has no special requirement, and all the technical effects can be obtained. However, those skilled in the art know that the effect of further crushing and sieving is particularly good when the mixture is formed by tabletting after being milled in a ball mill.
In the technical scheme, the modified MCM-41 molecular sieve is prepared by a method comprising the following steps:
(i) dissolving salt of VA and/or IA element in water to prepare solution D;
(ii) mixing the solution D with an MCM-41 molecular sieve to obtain a mixture E;
(iii) and roasting the mixture E to obtain the required modified MCM-41 molecular sieve.
In the above technical scheme, the preferable range of the calcination temperature in the step (iii) is 300-800 ℃.
In the above technical scheme, the preferable range of the calcination time in the step (iii) is 4.0 to 10.0 hours.
In order to solve the third technical problem, the technical scheme of the invention is as follows:
in one of the technical schemes, the catalyst for producing low-carbon olefin by Fischer-Tropsch synthesis is used for producing C by Fischer-Tropsch synthesis2～C4To olefins according to (1).
The technical key of the invention is the selection of the catalyst, and the technical conditions of the specific application can be reasonably selected by a person skilled in the art without creative labor. For example, the specific application conditions may be:
Fischer-Tropsch synthesis production C2～C4The method comprises the step of contacting and reacting the raw material with the catalyst in one of the technical schemes of the technical problems to generate the C-containing catalyst by taking the synthesis gas as the raw material2～C4The olefin of (1).
In the above technical scheme, H in the synthesis gas2The molar ratio of CO to CO is preferably 1 to 3.
In the technical scheme, the reaction temperature is preferably 250-400 ℃.
In the technical scheme, the reaction pressure is preferably 1.0-3.0 MPa.
In the technical scheme, the volume space velocity of the raw material gas is preferably 500-8000 h-1。
As will be appreciated by those skilled in the art, the catalysts of the present invention are useful in the Fischer-Tropsch synthesis of C2～C4Before the reaction of the olefin(s) in (b), it is preferable to carry out an on-line reduction treatment step, and the specific reduction conditions can be reasonably selected by those skilled in the art without any inventive step, such as but not limited to the following:
the reduction temperature is 400-600 ℃;
the reducing agent is H2And/or CO;
the pressure of reduction is normal pressure to 2MPa (measured by gauge pressure);
the volume space velocity of the reducing agent is 1500-8000 hr-1；
The reduction time is 6-48 hours.
For convenience of comparison, the reduction conditions in the examples of the present invention are:
the temperature is 500 DEG C
Pressure and atmosphere
Catalyst loading 3ml
Volume space velocity of reducing agent 6000 hours-1
Reducing gas H2
The reduction time was 36 hours.
By adopting the catalyst, the CO conversion rate can reach 99.6 percent, which is improved by 3.6 percent compared with the prior art; the selectivity of the low-carbon olefin in hydrocarbon can reach 78.9 percent, which is 10.9 percent higher than that of the prior art, and a better technical effect is achieved.
Detailed Description
[ example 1 ]
1. Preparation of modified MCM-41 molecular sieve
Weighing the equivalent of 9 g of Bi2O3Dissolving bismuth nitrate pentahydrate in 70 g of deionized water to prepare a solution D; under the condition of vacuum degree of 80kPa, dipping the solution D on 91 g of MCM-41 molecular sieve to obtain a mixture E; and drying the mixture E at 110 ℃, and then roasting at 550 ℃ for 8 hours to obtain the modified MCM-41 molecular sieve.
2. Preparation of the catalyst
30.0 parts by weight of iron (Fe) oxide2O3) 10.0 parts by weight of germanium oxide (GeO)2) 10.0 parts by weight of zirconium oxide (ZrO)2) 20.0 parts by weight of titanium dioxide (TiO)2) Grinding and mixing the four raw materials and 5 weight percent of hydroxypropyl methyl cellulose powder in a ball mill for 4 hours according to the total weight of the four raw materials to obtain a material A; adding deionized water accounting for 8 percent of the total weight of the four raw materials into the milled and mixed material A, and kneading the mixture to be soft to obtain a material B; feeding the kneaded material B into a strip extruding machine to prepare a strip with the diameter of 5mm, cutting the strip into a column shape with the length of 20mm, naturally airing the strip, feeding the strip into drying equipment, and drying the strip for 12 hours at 110 ℃ to obtain a material C; and (3) putting the dried material C into a high-temperature furnace, calcining for 8.0 hours at 1300 ℃, cooling and crushing, and taking particles which pass through a 120-mesh standard sieve to obtain a molten mixture D.
Mixing 70G of the molten mixture D and 30G of the modified MCM-41 molecular sieve G, grinding and mixing in a ball mill, tabletting for molding, crushing and sieving particles of 40-80 meshes to obtain the catalyst.
The prepared catalyst comprises the following components in percentage by weight: 30% Fe2O3，10％GeO2，10％ZrO2，20％TiO230% modified MCM-41 (containing Bi)2O3 9％)。
3. Catalyst evaluation
The evaluation conditions of the catalyst were:
the reaction conditions are as follows:
phi 8 mm fixed bed reactor
The reaction temperature is 360 DEG C
The reaction pressure is 1.5MPa
Catalyst loading 3ml
Catalyst loading 5000 hours-1
Raw material ratio (mol) H2/CO＝2.0/1。
For convenience of comparison, the composition of the catalyst of the present invention and the evaluation results are shown in Table 1.
[ example 2 ]
1. Preparation of modified MCM-41 molecular sieve
Weighing the equivalent of 9 g of Bi2O3Dissolving bismuth nitrate pentahydrate in 70 g of deionized water to prepare a solution D; under the condition of vacuum degree of 80kPa, dipping the solution D on 91 g of MCM-41 molecular sieve to obtain a mixture E; and drying the mixture E at 110 ℃, and then roasting at 550 ℃ for 8 hours to obtain the modified MCM-41 molecular sieve.
2. Preparation of the catalyst
30.0 parts by weight of iron (Fe) oxide2O3) 10.0 parts by weight of zinc oxide (ZnO), 10.0 parts by weight of zirconium oxide (ZrO)2) 20.0 parts by weight of titanium dioxide (TiO)2) Grinding and mixing the four raw materials and 5 weight percent of hydroxypropyl methyl cellulose powder in a ball mill for 4 hours according to the total weight of the four raw materials to obtain a material A;adding deionized water accounting for 8 percent of the total weight of the four raw materials into the milled and mixed material A, and kneading the mixture to be soft to obtain a material B; feeding the kneaded material B into a strip extruding machine to prepare a strip with the diameter of 5mm, cutting the strip into a column shape with the length of 20mm, naturally airing the strip, feeding the strip into drying equipment, and drying the strip for 12 hours at 110 ℃ to obtain a material C; and (3) putting the dried material C into a high-temperature furnace, calcining for 8.0 hours at 1300 ℃, cooling and crushing, and taking particles which pass through a 120-mesh standard sieve to obtain a molten mixture D.
Mixing 70G of the molten mixture D and 30G of the modified MCM-41 molecular sieve G, grinding and mixing in a ball mill, tabletting for molding, crushing and sieving particles of 40-80 meshes to obtain the catalyst.
The prepared catalyst comprises the following components in percentage by weight: 30% Fe2O3，10％ZnO，10％ZrO2，20％TiO230% modified MCM-41 (containing Bi)2O3 9％)。
3. Catalyst evaluation
The evaluation conditions of the catalyst were:
the reaction conditions are as follows:
phi 8 mm fixed bed reactor
The reaction temperature is 360 DEG C
The reaction pressure is 1.5MPa
Catalyst loading 3ml
Catalyst loading 5000 hours-1
Raw material ratio (mol) H2/CO＝2.0/1。
For convenience of comparison, the composition of the catalyst of the present invention and the evaluation results are shown in Table 1.
[ example 3 ]
1. Preparation of modified MCM-41 molecular sieve
Weighing the equivalent of 9 g of Bi2O3Dissolving bismuth nitrate pentahydrate in 70 g of deionized water to prepare a solution D; under the condition of vacuum degree of 80kPa, dipping the solution D on 91 g of MCM-41 molecular sieve to obtain a mixture E; the mixture E is dried at the temperature of 110 ℃ and then is roasted,the roasting temperature is 550 ℃, and the roasting time is 8 hours, thus obtaining the modified MCM-41 molecular sieve.
2. Preparation of the catalyst
30.0 parts by weight of iron (Fe) oxide2O3) 10.0 parts by weight of germanium oxide (GeO)2) 10.0 parts by weight of strontium oxide (SrO), 20.0 parts by weight of titanium dioxide (TiO)2) Grinding and mixing the four raw materials and 5 weight percent of hydroxypropyl methyl cellulose powder in a ball mill for 4 hours according to the total weight of the four raw materials to obtain a material A; adding deionized water accounting for 8 percent of the total weight of the four raw materials into the milled and mixed material A, and kneading the mixture to be soft to obtain a material B; feeding the kneaded material B into a strip extruding machine to prepare a strip with the diameter of 5mm, cutting the strip into a column shape with the length of 20mm, naturally airing the strip, feeding the strip into drying equipment, and drying the strip for 12 hours at 110 ℃ to obtain a material C; and (3) putting the dried material C into a high-temperature furnace, calcining for 8.0 hours at 1300 ℃, cooling and crushing, and taking particles which pass through a 120-mesh standard sieve to obtain a molten mixture D.
Mixing 70G of the molten mixture D and 30G of the modified MCM-41 molecular sieve G, grinding and mixing in a ball mill, tabletting for molding, crushing and sieving particles of 40-80 meshes to obtain the catalyst.
The prepared catalyst comprises the following components in percentage by weight: 30% Fe2O3，10％GeO2，10％SrO，20％TiO230% modified MCM-41 (containing Bi)2O3 9％)。
3. Catalyst evaluation
The evaluation conditions of the catalyst were:
the reaction conditions are as follows:
phi 8 mm fixed bed reactor
The reaction temperature is 360 DEG C
The reaction pressure is 1.5MPa
Catalyst loading 3ml
Catalyst loading 5000 hours-1
Raw material ratio (mol) H2/CO＝2.0/1。
For convenience of comparison, the composition of the catalyst of the present invention and the evaluation results are shown in Table 1.
[ example 4 ]
1. Preparation of modified MCM-41 molecular sieve
Weighing the equivalent of 9 g of Bi2O3Dissolving bismuth nitrate pentahydrate in 70 g of deionized water to prepare a solution D; under the condition of vacuum degree of 80kPa, dipping the solution D on 91 g of MCM-41 molecular sieve to obtain a mixture E; and drying the mixture E at 110 ℃, and then roasting at 550 ℃ for 8 hours to obtain the modified MCM-41 molecular sieve.
2. Preparation of the catalyst
30.0 parts by weight of iron (Fe) oxide2O3) 10.0 parts by weight of zinc oxide (ZnO), 10.0 parts by weight of strontium oxide (SrO), and 20.0 parts by weight of titanium dioxide (TiO)2) Grinding and mixing the four raw materials and 5 weight percent of hydroxypropyl methyl cellulose powder in a ball mill for 4 hours according to the total weight of the four raw materials to obtain a material A; adding deionized water accounting for 8 percent of the total weight of the four raw materials into the milled and mixed material A, and kneading the mixture to be soft to obtain a material B; feeding the kneaded material B into a strip extruding machine to prepare a strip with the diameter of 5mm, cutting the strip into a column shape with the length of 20mm, naturally airing the strip, feeding the strip into drying equipment, and drying the strip for 12 hours at 110 ℃ to obtain a material C; and (3) putting the dried material C into a high-temperature furnace, calcining for 8.0 hours at 1300 ℃, cooling and crushing, and taking particles which pass through a 120-mesh standard sieve to obtain a molten mixture D.
Mixing 70G of the molten mixture D and 30G of the modified MCM-41 molecular sieve G, grinding and mixing in a ball mill, tabletting for molding, crushing and sieving particles of 40-80 meshes to obtain the catalyst.
The prepared catalyst comprises the following components in percentage by weight: 30% Fe2O3，10％ZnO，10％SrO，20％TiO230% modified MCM-41 (containing Bi)2O3 9％)。
3. Catalyst evaluation
The evaluation conditions of the catalyst were:
the reaction conditions are as follows:
phi 8 mm fixed bed reactor
The reaction temperature is 360 DEG C
The reaction pressure is 1.5MPa
Catalyst loading 3ml
Catalyst loading 5000 hours-1
Raw material ratio (mol) H2/CO＝2.0/1。
For convenience of comparison, the composition of the catalyst of the present invention and the evaluation results are shown in Table 1.
[ example 5 ]
1. Preparation of modified MCM-41 molecular sieve
Weighing the equivalent of 9 g of Bi2O3Dissolving bismuth nitrate pentahydrate in 70 g of deionized water to prepare a solution D; under the condition of vacuum degree of 80kPa, dipping the solution D on 91 g of MCM-41 molecular sieve to obtain a mixture E; and drying the mixture E at 110 ℃, and then roasting at 550 ℃ for 8 hours to obtain the modified MCM-41 molecular sieve.
2. Preparation of the catalyst
30.0 parts by weight of iron (Fe) oxide2O3) 5.0 parts by weight of germanium oxide (GeO)2) 5.0 parts by weight of zinc oxide (ZnO), 10.0 parts by weight of zirconium oxide (ZrO)2) 20.0 parts by weight of titanium dioxide (TiO)2) Grinding and mixing five raw materials and hydroxypropyl methyl cellulose powder accounting for 5 percent of the total weight of the five raw materials in a ball mill for 4 hours to obtain a material A; adding deionized water accounting for 8 percent of the total weight of the five raw materials into the milled and mixed material A, and kneading the mixture to be soft to obtain a material B; feeding the kneaded material B into a strip extruding machine to prepare a strip with the diameter of 5mm, cutting the strip into a column shape with the length of 20mm, naturally airing the strip, feeding the strip into drying equipment, and drying the strip for 12 hours at 110 ℃ to obtain a material C; and (3) putting the dried material C into a high-temperature furnace, calcining for 8.0 hours at 1300 ℃, cooling and crushing, and taking particles which pass through a 120-mesh standard sieve to obtain a molten mixture D.
Mixing 70G of the molten mixture D and 30G of the modified MCM-41 molecular sieve G, grinding and mixing in a ball mill, tabletting for molding, crushing and sieving particles of 40-80 meshes to obtain the catalyst.
The prepared catalyst comprises the following components in percentage by weight: 30% Fe2O3，5％GeO2，5％ZnO，10％ZrO2，20％TiO230% modified MCM-41 (containing Bi)2O3 9％)。
3. Catalyst evaluation
The evaluation conditions of the catalyst were:
the reaction conditions are as follows:
phi 8 mm fixed bed reactor
The reaction temperature is 360 DEG C
The reaction pressure is 1.5MPa
Catalyst loading 3ml
Catalyst loading 5000 hours-1
Raw material ratio (mol) H2/CO＝2.0/1。
For convenience of comparison, the composition of the catalyst of the present invention and the evaluation results are shown in Table 1.
[ example 6 ]
1. Preparation of modified MCM-41 molecular sieve
Weighing the equivalent of 9 g of Bi2O3Dissolving bismuth nitrate pentahydrate in 70 g of deionized water to prepare a solution D; under the condition of vacuum degree of 80kPa, dipping the solution D on 91 g of MCM-41 molecular sieve to obtain a mixture E; and drying the mixture E at 110 ℃, and then roasting at 550 ℃ for 8 hours to obtain the modified MCM-41 molecular sieve.
2. Preparation of the catalyst
30.0 parts by weight of iron (Fe) oxide2O3) 5.0 parts by weight of germanium oxide (GeO)2) 5.0 parts by weight of zinc oxide (ZnO), 10.0 parts by weight of strontium oxide (SrO), and 20.0 parts by weight of titanium dioxide (TiO)2) Five raw materials and hydroxypropyl methyl cellulose powder with the weight percentage of 5 percent based on the total weight of the five raw materials are ground and mixed for 4 hours in a ball millThen, obtaining a material A; adding deionized water accounting for 8 percent of the total weight of the five raw materials into the milled and mixed material A, and kneading the mixture to be soft to obtain a material B; feeding the kneaded material B into a strip extruding machine to prepare a strip with the diameter of 5mm, cutting the strip into a column shape with the length of 20mm, naturally airing the strip, feeding the strip into drying equipment, and drying the strip for 12 hours at 110 ℃ to obtain a material C; and (3) putting the dried material C into a high-temperature furnace, calcining for 8.0 hours at 1300 ℃, cooling and crushing, and taking particles which pass through a 120-mesh standard sieve to obtain a molten mixture D.
Mixing 70G of the molten mixture D and 30G of the modified MCM-41 molecular sieve G, grinding and mixing in a ball mill, tabletting for molding, crushing and sieving particles of 40-80 meshes to obtain the catalyst.
The prepared catalyst comprises the following components in percentage by weight: 30% Fe2O3，5％GeO2，5％ZnO，10％SrO，20％TiO230% modified MCM-41 (containing Bi)2O3 9％)。
3. Catalyst evaluation
The evaluation conditions of the catalyst were:
the reaction conditions are as follows:
phi 8 mm fixed bed reactor
The reaction temperature is 360 DEG C
The reaction pressure is 1.5MPa
Catalyst loading 3ml
Catalyst loading 5000 hours-1
Raw material ratio (mol) H2/CO＝2.0/1。
For convenience of comparison, the composition of the catalyst of the present invention and the evaluation results are shown in Table 1.
As shown in the same ratio of example 5 to example 6 and examples 1-4, the synergy between Ge (or oxide thereof) and Zn (or oxide thereof) in improving the CO conversion rate and the selectivity of the low-carbon olefin in the product is realized.
[ example 7 ]
1. Preparation of modified MCM-41 molecular sieve
Weigh out an amount equivalent to 9 gBi2O3Dissolving bismuth nitrate pentahydrate in 70 g of deionized water to prepare a solution D; under the condition of vacuum degree of 80kPa, dipping the solution D on 91 g of MCM-41 molecular sieve to obtain a mixture E; and drying the mixture E at 110 ℃, and then roasting at 550 ℃ for 8 hours to obtain the modified MCM-41 molecular sieve.
2. Preparation of the catalyst
30.0 parts by weight of iron (Fe) oxide2O3) 10.0 parts by weight of germanium oxide (GeO)2) 6.0 parts by weight of zirconium oxide (ZrO)2) 4.0 parts by weight of strontium oxide (SrO) and 20.0 parts by weight of titanium dioxide (TiO)2) Grinding and mixing the four raw materials and 5 weight percent of hydroxypropyl methyl cellulose powder in a ball mill for 4 hours according to the total weight of the four raw materials to obtain a material A; adding deionized water accounting for 8 percent of the total weight of the four raw materials into the milled and mixed material A, and kneading the mixture to be soft to obtain a material B; feeding the kneaded material B into a strip extruding machine to prepare a strip with the diameter of 5mm, cutting the strip into a column shape with the length of 20mm, naturally airing the strip, feeding the strip into drying equipment, and drying the strip for 12 hours at 110 ℃ to obtain a material C; and (3) putting the dried material C into a high-temperature furnace, calcining for 8.0 hours at 1300 ℃, cooling and crushing, and taking particles which pass through a 120-mesh standard sieve to obtain a molten mixture D.
Mixing 70G of the molten mixture D and 30G of the modified MCM-41 molecular sieve G, grinding and mixing in a ball mill, tabletting for molding, crushing and sieving particles of 40-80 meshes to obtain the catalyst.
The prepared catalyst comprises the following components in percentage by weight: 30% Fe2O3，10％GeO2，6％ZrO2，4％SrO，20％TiO230% modified MCM-41 (containing Bi)2O3 9％)。
3. Catalyst evaluation
The evaluation conditions of the catalyst were:
the reaction conditions are as follows:
phi 8 mm fixed bed reactor
The reaction temperature is 360 DEG C
The reaction pressure is 1.5MPa
Catalyst loading 3ml
Catalyst loading 5000 hours-1
Raw material ratio (mol) H2/CO＝2.0/1。
For convenience of comparison, the composition of the catalyst of the present invention and the evaluation results are shown in Table 1.
[ example 8 ]
1. Preparation of modified MCM-41 molecular sieve
Weighing the equivalent of 9 g of Bi2O3Dissolving bismuth nitrate pentahydrate in 70 g of deionized water to prepare a solution D; under the condition of vacuum degree of 80kPa, dipping the solution D on 91 g of MCM-41 molecular sieve to obtain a mixture E; and drying the mixture E at 110 ℃, and then roasting at 550 ℃ for 8 hours to obtain the modified MCM-41 molecular sieve.
2. Preparation of the catalyst
30.0 parts by weight of iron (Fe) oxide2O3) 10.0 parts by weight of zinc oxide (ZnO), 6.0 parts by weight of zirconium oxide (ZrO)2) 4.0 parts by weight of strontium oxide (SrO) and 20.0 parts by weight of titanium dioxide (TiO)2) Grinding and mixing the four raw materials and 5 weight percent of hydroxypropyl methyl cellulose powder in a ball mill for 4 hours according to the total weight of the four raw materials to obtain a material A; adding deionized water accounting for 8 percent of the total weight of the four raw materials into the milled and mixed material A, and kneading the mixture to be soft to obtain a material B; feeding the kneaded material B into a strip extruding machine to prepare a strip with the diameter of 5mm, cutting the strip into a column shape with the length of 20mm, naturally airing the strip, feeding the strip into drying equipment, and drying the strip for 12 hours at 110 ℃ to obtain a material C; and (3) putting the dried material C into a high-temperature furnace, calcining for 8.0 hours at 1300 ℃, cooling and crushing, and taking particles which pass through a 120-mesh standard sieve to obtain a molten mixture D.
Mixing 70G of the molten mixture D and 30G of the modified MCM-41 molecular sieve G, grinding and mixing in a ball mill, tabletting for molding, crushing and sieving particles of 40-80 meshes to obtain the catalyst.
The prepared catalyst comprises the following components in percentage by weight: 30% Fe2O3，10％ZnO，6％ZrO2，4％SrO，20％TiO230% modified MCM-41 (containing Bi)2O3 9％)。
3. Catalyst evaluation
The evaluation conditions of the catalyst were:
the reaction conditions are as follows:
phi 8 mm fixed bed reactor
The reaction temperature is 360 DEG C
The reaction pressure is 1.5MPa
Catalyst loading 3ml
Catalyst loading 5000 hours-1
Raw material ratio (mol) H2/CO＝2.0/1。
For convenience of comparison, the composition of the catalyst of the present invention and the evaluation results are shown in Table 1.
[ example 9 ]
1. Preparation of modified MCM-41 molecular sieve
Weighing an amount equivalent to 9 g of Cs2O cesium nitrate, dissolved in 70 g deionized water to make solution D; under the condition of vacuum degree of 80kPa, dipping the solution D on 91 g of MCM-41 molecular sieve to obtain a mixture E; and drying the mixture E at 110 ℃, and then roasting at 550 ℃ for 8 hours to obtain the modified MCM-41 molecular sieve.
2. Preparation of the catalyst
30.0 parts by weight of iron (Fe) oxide2O3) 5.0 parts by weight of germanium oxide (GeO)2) 5.0 parts by weight of zinc oxide (ZnO), 10.0 parts by weight of zirconium oxide (ZrO)2) 20.0 parts by weight of titanium dioxide (TiO)2) Grinding and mixing five raw materials and hydroxypropyl methyl cellulose powder accounting for 5 percent of the total weight of the five raw materials in a ball mill for 4 hours to obtain a material A; adding deionized water accounting for 8 percent of the total weight of the five raw materials into the milled and mixed material A, and kneading the mixture to be soft to obtain a material B; the kneaded material B is sent into a bar extruding machine,making into strips with the diameter of 5mm, cutting into columns with the length of 20mm, naturally drying, feeding into drying equipment, and drying at 110 ℃ for 12 hours to obtain a material C; and (3) putting the dried material C into a high-temperature furnace, calcining for 8.0 hours at 1300 ℃, cooling and crushing, and taking particles which pass through a 120-mesh standard sieve to obtain a molten mixture D.
Mixing 70G of the molten mixture D and 30G of the modified MCM-41 molecular sieve G, grinding and mixing in a ball mill, tabletting for molding, crushing and sieving particles of 40-80 meshes to obtain the catalyst.
The prepared catalyst comprises the following components in percentage by weight: 30% Fe2O3，5％GeO2，5％ZnO，10％ZrO2，20％TiO230% modified MCM-41 (containing Cs)2O 9％)。
3. Catalyst evaluation
The evaluation conditions of the catalyst were:
the reaction conditions are as follows:
phi 8 mm fixed bed reactor
The reaction temperature is 360 DEG C
The reaction pressure is 1.5MPa
Catalyst loading 3ml
Catalyst loading 5000 hours-1
Raw material ratio (mol) H2/CO＝2.0/1。
For convenience of comparison, the composition of the catalyst of the present invention and the evaluation results are shown in Table 1.
[ example 10 ]
1. Preparation of modified MCM-41 molecular sieve
Weighing an amount equivalent to 9 g of Cs2O cesium nitrate, dissolved in 70 g deionized water to make solution D; under the condition of vacuum degree of 80kPa, dipping the solution D on 91 g of MCM-41 molecular sieve to obtain a mixture E; and drying the mixture E at 110 ℃, and then roasting at 550 ℃ for 8 hours to obtain the modified MCM-41 molecular sieve.
2. Preparation of the catalyst
Weighing 30.0 parts by weight of trioxaneDi-iron (Fe)2O3) 5.0 parts by weight of germanium oxide (GeO)2) 5.0 parts by weight of zinc oxide (ZnO), 10.0 parts by weight of strontium oxide (SrO), and 20.0 parts by weight of titanium dioxide (TiO)2) Grinding and mixing five raw materials and hydroxypropyl methyl cellulose powder accounting for 5 percent of the total weight of the five raw materials in a ball mill for 4 hours to obtain a material A; adding deionized water accounting for 8 percent of the total weight of the five raw materials into the milled and mixed material A, and kneading the mixture to be soft to obtain a material B; feeding the kneaded material B into a strip extruding machine to prepare a strip with the diameter of 5mm, cutting the strip into a column shape with the length of 20mm, naturally airing the strip, feeding the strip into drying equipment, and drying the strip for 12 hours at 110 ℃ to obtain a material C; and (3) putting the dried material C into a high-temperature furnace, calcining for 8.0 hours at 1300 ℃, cooling and crushing, and taking particles which pass through a 120-mesh standard sieve to obtain a molten mixture D.
Mixing 70G of the molten mixture D and 30G of the modified MCM-41 molecular sieve G, grinding and mixing in a ball mill, tabletting for molding, crushing and sieving particles of 40-80 meshes to obtain the catalyst.
The prepared catalyst comprises the following components in percentage by weight: 30% Fe2O3，5％GeO2，5％ZnO，10％SrO，20％TiO230% modified MCM-41 (containing Cs)2O 9％)。
3. Catalyst evaluation
The evaluation conditions of the catalyst were:
the reaction conditions are as follows:
phi 8 mm fixed bed reactor
The reaction temperature is 360 DEG C
The reaction pressure is 1.5MPa
Catalyst loading 3ml
Catalyst loading 5000 hours-1
Raw material ratio (mol) H2/CO＝2.0/1。
For convenience of comparison, the composition of the catalyst of the present invention and the evaluation results are shown in Table 1.
[ example 11 ]
1. Preparation of modified MCM-41 molecular sieve
Weighing an amount equivalent to 9 g of Cs2O cesium nitrate, dissolved in 70 g deionized water to make solution D; under the condition of vacuum degree of 80kPa, dipping the solution D on 91 g of MCM-41 molecular sieve to obtain a mixture E; and drying the mixture E at 110 ℃, and then roasting at 550 ℃ for 8 hours to obtain the modified MCM-41 molecular sieve.
2. Preparation of the catalyst
30.0 parts by weight of iron (Fe) oxide2O3) 10.0 parts by weight of germanium oxide (GeO)2) 6.0 parts by weight of zirconium oxide (ZrO)2) 4.0 parts by weight of strontium oxide (SrO) and 20.0 parts by weight of titanium dioxide (TiO)2) Grinding and mixing the four raw materials and 5 weight percent of hydroxypropyl methyl cellulose powder in a ball mill for 4 hours according to the total weight of the four raw materials to obtain a material A; adding deionized water accounting for 8 percent of the total weight of the four raw materials into the milled and mixed material A, and kneading the mixture to be soft to obtain a material B; feeding the kneaded material B into a strip extruding machine to prepare a strip with the diameter of 5mm, cutting the strip into a column shape with the length of 20mm, naturally airing the strip, feeding the strip into drying equipment, and drying the strip for 12 hours at 110 ℃ to obtain a material C; and (3) putting the dried material C into a high-temperature furnace, calcining for 8.0 hours at 1300 ℃, cooling and crushing, and taking particles which pass through a 120-mesh standard sieve to obtain a molten mixture D.
Mixing 70G of the molten mixture D and 30G of the modified MCM-41 molecular sieve G, grinding and mixing in a ball mill, tabletting for molding, crushing and sieving particles of 40-80 meshes to obtain the catalyst.
The prepared catalyst comprises the following components in percentage by weight: 30% Fe2O3，10％GeO2，6％ZrO2，4％SrO，20％TiO230% modified MCM-41 (containing Cs)2O 9％)。
3. Catalyst evaluation
The evaluation conditions of the catalyst were:
the reaction conditions are as follows:
phi 8 mm fixed bed reactor
The reaction temperature is 360 DEG C
The reaction pressure is 1.5MPa
Catalyst loading 3ml
Catalyst loading 5000 hours-1
Raw material ratio (mol) H2/CO＝2.0/1。
For convenience of comparison, the composition of the catalyst of the present invention and the evaluation results are shown in Table 1.
[ example 12 ]
1. Preparation of modified MCM-41 molecular sieve
Weighing an amount equivalent to 9 g of Cs2O cesium nitrate, dissolved in 70 g deionized water to make solution D; under the condition of vacuum degree of 80kPa, dipping the solution D on 91 g of MCM-41 molecular sieve to obtain a mixture E; and drying the mixture E at 110 ℃, and then roasting at 550 ℃ for 8 hours to obtain the modified MCM-41 molecular sieve.
2. Preparation of the catalyst
30.0 parts by weight of iron (Fe) oxide2O3) 10.0 parts by weight of zinc oxide (ZnO), 6.0 parts by weight of zirconium oxide (ZrO)2) 4.0 parts by weight of strontium oxide (SrO) and 20.0 parts by weight of titanium dioxide (TiO)2) Grinding and mixing the four raw materials and 5 weight percent of hydroxypropyl methyl cellulose powder in a ball mill for 4 hours according to the total weight of the four raw materials to obtain a material A; adding deionized water accounting for 8 percent of the total weight of the four raw materials into the milled and mixed material A, and kneading the mixture to be soft to obtain a material B; feeding the kneaded material B into a strip extruding machine to prepare a strip with the diameter of 5mm, cutting the strip into a column shape with the length of 20mm, naturally airing the strip, feeding the strip into drying equipment, and drying the strip for 12 hours at 110 ℃ to obtain a material C; and (3) putting the dried material C into a high-temperature furnace, calcining for 8.0 hours at 1300 ℃, cooling and crushing, and taking particles which pass through a 120-mesh standard sieve to obtain a molten mixture D.
Mixing 70G of the molten mixture D and 30G of the modified MCM-41 molecular sieve G, grinding and mixing in a ball mill, tabletting for molding, crushing and sieving particles of 40-80 meshes to obtain the catalyst.
The prepared catalyst comprises the following components in percentage by weight: 30% Fe2O3，10％ZnO，6％ZrO2，4％SrO，20％TiO230% modified MCM-41 (containing Cs)2O 9％)。
3. Catalyst evaluation
The evaluation conditions of the catalyst were:
the reaction conditions are as follows:
phi 8 mm fixed bed reactor
The reaction temperature is 360 DEG C
The reaction pressure is 1.5MPa
Catalyst loading 3ml
Catalyst loading 5000 hours-1
Raw material ratio (mol) H2/CO＝2.0/1。
For convenience of comparison, the composition of the catalyst of the present invention and the evaluation results are shown in Table 1.
[ example 13 ]
1. Preparation of modified MCM-41 molecular sieve
Weighing the equivalent of 9 g of Bi2O3Dissolving bismuth nitrate pentahydrate in 70 g of deionized water to prepare a solution D; under the condition of vacuum degree of 80kPa, dipping the solution D on 91 g of MCM-41 molecular sieve to obtain a mixture E; and drying the mixture E at 110 ℃, and then roasting at 550 ℃ for 8 hours to obtain the modified MCM-41 molecular sieve.
2. Preparation of the catalyst
30.0 parts by weight of iron (Fe) oxide2O3) 5.0 parts by weight of germanium oxide (GeO)2) 5.0 parts by weight of zinc oxide (ZnO), 6.0 parts by weight of zirconium oxide (ZrO)2) 4.0 parts by weight of strontium oxide (SrO) and 20.0 parts by weight of titanium dioxide (TiO)2) Grinding and mixing six raw materials and hydroxypropyl methyl cellulose powder accounting for 5 percent of the total weight of the six raw materials in a ball mill for 4 hours to obtain a material A; adding deionized water with weight percentage of 8% into the milled and mixed material A according to the total weight of the six raw materials, and kneading untilSoftening to obtain a material B; feeding the kneaded material B into a strip extruding machine to prepare a strip with the diameter of 5mm, cutting the strip into a column shape with the length of 20mm, naturally airing the strip, feeding the strip into drying equipment, and drying the strip for 12 hours at 110 ℃ to obtain a material C; and (3) putting the dried material C into a high-temperature furnace, calcining for 8.0 hours at 1300 ℃, cooling and crushing, and taking particles which pass through a 120-mesh standard sieve to obtain a molten mixture D.
Mixing 70G of the molten mixture D and 30G of the modified MCM-41 molecular sieve G, grinding and mixing in a ball mill, tabletting for molding, crushing and sieving particles of 40-80 meshes to obtain the catalyst.
The prepared catalyst comprises the following components in percentage by weight: 30% Fe2O3，5％GeO2，5％ZnO，6％ZrO2，4％SrO，20％TiO230% modified MCM-41 (containing Bi)2O3 9％)。
3. Catalyst evaluation
The evaluation conditions of the catalyst were:
the reaction conditions are as follows:
phi 8 mm fixed bed reactor
The reaction temperature is 360 DEG C
The reaction pressure is 1.5MPa
Catalyst loading 3ml
Catalyst loading 5000 hours-1
Raw material ratio (mol) H2/CO＝2.0/1。
For convenience of comparison, the composition of the catalyst of the present invention and the evaluation results are shown in Table 1.
[ example 14 ]
1. Preparation of modified MCM-41 molecular sieve
Weighing an amount equivalent to 9 g of Cs2O cesium nitrate, dissolved in 70 g deionized water to make solution D; under the condition of vacuum degree of 80kPa, dipping the solution D on 91 g of MCM-41 molecular sieve to obtain a mixture E; and drying the mixture E at 110 ℃, and then roasting at 550 ℃ for 8 hours to obtain the modified MCM-41 molecular sieve.
2. Preparation of the catalyst
30.0 parts by weight of iron (Fe) oxide2O3) 5.0 parts by weight of germanium oxide (GeO)2) 5.0 parts by weight of zinc oxide (ZnO), 6.0 parts by weight of zirconium oxide (ZrO)2) 4.0 parts by weight of strontium oxide (SrO) and 20.0 parts by weight of titanium dioxide (TiO)2) Grinding and mixing six raw materials and hydroxypropyl methyl cellulose powder accounting for 5 percent of the total weight of the six raw materials in a ball mill for 4 hours to obtain a material A; adding deionized water accounting for 8 percent of the total weight of the six raw materials into the milled and mixed material A, and kneading the mixture to be soft to obtain a material B; feeding the kneaded material B into a strip extruding machine to prepare a strip with the diameter of 5mm, cutting the strip into a column shape with the length of 20mm, naturally airing the strip, feeding the strip into drying equipment, and drying the strip for 12 hours at 110 ℃ to obtain a material C; and (3) putting the dried material C into a high-temperature furnace, calcining for 8.0 hours at 1300 ℃, cooling and crushing, and taking particles which pass through a 120-mesh standard sieve to obtain a molten mixture D.
Mixing 70G of the molten mixture D and 30G of the modified MCM-41 molecular sieve G, grinding and mixing in a ball mill, tabletting for molding, crushing and sieving particles of 40-80 meshes to obtain the catalyst.
The prepared catalyst comprises the following components in percentage by weight: 30% Fe2O3，5％GeO2，5％ZnO，6％ZrO2，4％SrO，20％TiO230% modified MCM-41 (containing Cs)2O 9％)。
3. Catalyst evaluation
The evaluation conditions of the catalyst were:
the reaction conditions are as follows:
phi 8 mm fixed bed reactor
The reaction temperature is 360 DEG C
The reaction pressure is 1.5MPa
Catalyst loading 3ml
Catalyst loading 5000 hours-1
Raw material ratio (mol) H2/CO＝2.0/1。
For convenience of comparison, the composition of the catalyst of the present invention and the evaluation results are shown in Table 1.
As seen from the comparison between example 13 and examples 14 and 5 to 12, Zr (or an oxide thereof) and Sr (or an oxide thereof) have a synergistic effect in increasing the CO conversion rate and the selectivity of the lower olefins.
[ example 15 ]
1. Preparation of modified MCM-41 molecular sieve
Weighing the equivalent of 6 g of Bi2O3Bismuth nitrate pentahydrate and 3 g Cs2O cesium nitrate, dissolved in 70 g deionized water to make solution D; under the condition of vacuum degree of 80kPa, dipping the solution D on 91 g of MCM-41 molecular sieve to obtain a mixture E; and drying the mixture E at 110 ℃, and then roasting at 550 ℃ for 8 hours to obtain the modified MCM-41 molecular sieve.
2. Preparation of the catalyst
30.0 parts by weight of iron (Fe) oxide2O3) 5.0 parts by weight of germanium oxide (GeO)2) 5.0 parts by weight of zinc oxide (ZnO), 6.0 parts by weight of zirconium oxide (ZrO)2) 4.0 parts by weight of strontium oxide (SrO) and 20.0 parts by weight of titanium dioxide (TiO)2) Grinding and mixing six raw materials and hydroxypropyl methyl cellulose powder accounting for 5 percent of the total weight of the six raw materials in a ball mill for 4 hours to obtain a material A; adding deionized water accounting for 8 percent of the total weight of the six raw materials into the milled and mixed material A, and kneading the mixture to be soft to obtain a material B; feeding the kneaded material B into a strip extruding machine to prepare a strip with the diameter of 5mm, cutting the strip into a column shape with the length of 20mm, naturally airing the strip, feeding the strip into drying equipment, and drying the strip for 12 hours at 110 ℃ to obtain a material C; and (3) putting the dried material C into a high-temperature furnace, calcining for 8.0 hours at 1300 ℃, cooling and crushing, and taking particles which pass through a 120-mesh standard sieve to obtain a molten mixture D.
Mixing 70G of the molten mixture D and 30G of the modified MCM-41 molecular sieve G, grinding and mixing in a ball mill, tabletting for molding, crushing and sieving particles of 40-80 meshes to obtain the catalyst.
To obtain the catalystComprises the following components in percentage by weight: 30% Fe2O3，5％GeO2，5％ZnO，6％ZrO2，4％SrO，20％TiO230% modified MCM-41 (containing Bi)2O3 6％，Cs2O 3％)。
3. Catalyst evaluation
The evaluation conditions of the catalyst were:
the reaction conditions are as follows:
phi 8 mm fixed bed reactor
The reaction temperature is 360 DEG C
The reaction pressure is 1.5MPa
Catalyst loading 3ml
Catalyst loading 5000 hours-1
Raw material ratio (mol) H2/CO＝2.0/1。
For convenience of comparison, the composition of the catalyst of the present invention and the evaluation results are shown in Table 1.
From the comparison between example 15 and examples 13 and 14, it is clear that Bi (or its oxide) and Cs (or its oxide) have a synergistic effect in increasing CO conversion and selectivity to lower olefins.
TABLE 1
Figure BDA0001833110180000221

Claims (9)

1. The catalyst for producing the low-carbon olefin by Fischer-Tropsch synthesis comprises the following components in parts by weight:
10-60 parts of a component a); 1-20 parts of component b); 1-20 parts of component c); 5-30 parts of component d); 10-60 parts of component e);
component a) is selected from iron series elements or oxides thereof; component b) comprises at least one element selected from group IVA or an oxide thereof; component c) comprises at least one element selected from group IVB or an oxide thereof; component d) is selected from titanium dioxide; component e) is selected from MCM-41 type molecular sieves;
the MCM-41 type molecular sieve is a modifier modified MCM-41 molecular sieve, and the modifier comprises at least one element in VA elements or an oxide thereof.
2. The catalyst for producing light olefins by Fischer-Tropsch synthesis according to claim 1, wherein the iron-based element is at least one selected from the group consisting of iron, cobalt and nickel.
3. The catalyst for producing low-carbon olefin by Fischer-Tropsch synthesis according to claim 1, wherein the content of the component a) is 20-50 parts.
4. The catalyst for producing low-carbon olefin by Fischer-Tropsch synthesis according to claim 1, wherein the content of the component b) is 5-15 parts.
5. The catalyst for producing low-carbon olefin by Fischer-Tropsch synthesis according to claim 1, wherein the content of the component c) is 5-15 parts.
6. The catalyst for producing low-carbon olefin by Fischer-Tropsch synthesis according to claim 1, wherein the content of the component d) is 10-25 parts.
7. The catalyst for producing low-carbon olefins by Fischer-Tropsch synthesis according to claim 1, wherein the content of the component e) is 15-50 parts.
8. The preparation method of the catalyst for producing low-carbon olefin by Fischer-Tropsch synthesis according to any one of claims 1 to 7, comprising the following steps:
(1) mixing corresponding oxides of the components a), b) and c), titanium dioxide of the component d) and a binder to obtain a powdery material A;
(2) adding water into the material A, and kneading to obtain a material B;
(3) extruding the material B into strips, forming and drying to obtain a material C;
(4) sintering the material C at a high temperature, cooling, crushing and screening to obtain a required molten state mixture D;
(5) and mixing the molten mixture D with an MCM-41 type molecular sieve to obtain the required catalyst.
9. The catalyst for producing low-carbon olefin by Fischer-Tropsch synthesis according to any one of claims 1 to 7 in Fischer-Tropsch synthesis production C2～C4To olefins according to (1).
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