CN111068742B - Catalyst for synthesizing low-carbon olefin by one-step method and application thereof - Google Patents
Catalyst for synthesizing low-carbon olefin by one-step method and application thereof Download PDFInfo
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- 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
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—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
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- 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
- B01J29/0341—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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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
- B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
- B01J29/045—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
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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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- 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
Abstract
The invention relates to a catalyst for synthesizing low-carbon olefin by a one-step method and application thereof, and mainly solves the problems of low CO conversion rate and low-carbon olefin selectivity in the reaction of synthesizing the low-carbon olefin by the one-step method in the prior art. The invention adopts a one-step method to synthesize a catalyst for low-carbon olefin, which comprises the following components in parts by weight: 5-40 parts of component a); 5-40 parts of component b); 1-30 parts of component c); 10 to 50 portions of component d); 5-40 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 VIIB or an oxide thereof; component c) comprises at least one element selected from group IIIB 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 sieves, better solves the problem and can be used for industrial production of synthesizing low-carbon olefin by a Fischer-Tropsch one-step method.
Description
Technical Field
The invention relates to a catalyst for synthesizing low-carbon olefin by a one-step method, and a preparation method 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 olefins mainly adopts a petrochemical route of cracking light hydrocarbons (ethane, naphtha and light diesel), and due to the gradual shortage of global petroleum resources and the long-term high-level operation of the price of crude oil, the development of a tubular cracking furnace process which only depends on the light hydrocarbons of petroleum as raw materials in the low carbon olefin industry encounters larger and larger raw material problems, and the production process and the raw materials of the low carbon olefins 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 preparing the low-carbon olefin by the synthesis gas one-step method originates from the traditional Fischer-Tropsch synthesis reaction, the carbon number distribution of the traditional Fischer-Tropsch synthesis product follows ASF distribution, and each hydrocarbon has the maximum theoretical selectivity, such as C 2 -C 4 The maximum selectivity of the fraction is 57%, the gasoline fraction (C) 5 -C 11 ) 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 alpha olefins on the catalyst. Fischer-Tropsch synthesis is a strongly exothermic reaction with a large amount of reactionsThe catalyst carbon deposition reaction is promoted to generate methane and low-carbon alkane more easily by heat, so that the selectivity of the low-carbon olefin 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-series catalyst, and can be subjected to physical and chemical modification 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 acid center of catalyst can inhibit secondary reaction of low carbon olefin and raise its selectivity. The catalyst performance can be obviously improved by the carrier effect of the catalyst carrier and the addition of some transition metal additives and alkali metal additives, and a novel Fischer-Tropsch synthesis catalyst with non-ASF (asymmetric catalytic shift) distribution of products and high activity and high selectivity for preparing low-carbon olefins is developed.
The Fischer-Tropsch synthesis of low-carbon olefin is one of the research hotspots for developing Fischer-Tropsch synthesis catalysts. In patent CN1083415A published by the institute of chemical and physical sciences of the Chinese academy of sciences, an iron-manganese catalyst system carried by alkali metal oxides of group IIA such as MgO or high-silicon zeolite molecular sieves (or phosphorus-aluminum zeolite) is used, strong base K or Cs ions are used as an auxiliary agent, and higher activity (90% of CO conversion rate) and selectivity (66% of low-carbon olefin selectivity) can be obtained under the reaction pressure of 1.0-5.0 MPa and the reaction temperature of 300-400 ℃ for preparing low-carbon olefin from synthesis gas. 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 number 01144691.9 filed by Beijing university of chemical industry, laser pyrolysis method is adopted in combination withPreparation of Fe by solid-phase reaction combined technology 3 The 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) 5 The 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 auxiliaries, the Fe/activated carbon catalyst is used for reaction for preparing low-carbon olefin from synthesis gas, under the condition of no circulation of raw material gas, the conversion rate of CO is 96%, and the selectivity of the low-carbon olefin in hydrocarbon is 68%. The iron salt and the auxiliary agent manganese salt used for preparing the catalyst are relatively expensive and relatively difficult-to-dissolve iron oxalate and manganese acetate, 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 number 200710063301.9, the catalyst is prepared from common medicines and reagents, iron salt is used as ferric nitrate, manganese salt is manganese nitrate, sylvite is 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 the low carbon olefin in the product in the technology of synthesizing the low carbon olefin by the one-step method in the prior art, and the catalyst for synthesizing the low carbon olefin by the one-step method is provided.
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 synthesizing the low-carbon olefin by the one-step method comprises the following components in parts by weight:
5-40 parts of component a); 5-40 parts of component b); 1-30 parts of component c); 10-50 parts of component d); 5 to 40 portions of component e);
component a) is selected from iron series elements or oxides thereof; component b) comprises at least one element selected from group VIIB or an oxide thereof; component c) comprises at least one element selected from group IIIB 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 above technical scheme, the content of the component a) is preferably 10 to 35 parts.
In the above technical scheme, the content of the component b) is preferably 10 to 35 parts.
In the above technical scheme, the content of the component c) is preferably 5 to 25 parts.
In the above technical scheme, the content of the component d) is preferably 20 to 45 parts.
In the above technical scheme, the content of the component e) is preferably 10 to 40 parts.
In the above technical solution, the component b) preferably further comprises a group IIIA element or an oxide thereof.
In the above technical solution, the group IIIA element preferably includes In or an oxide thereof.
In the above technical solution, VIIB element preferably includes Mn or its oxide, and In (or its oxide) and Mn (or its oxide) have a synergistic effect In improving CO conversion and selectivity of low-carbon olefin In the product.
The ratio of In (or its oxide) to Mn is not particularly limited, and In or its oxide is In 2 O 3 And Mn or an oxide thereof In MnO, the In (or an oxide thereof), and Mn (or an oxide thereof) weight ratio may be, but is not limited to, 0.51 to 3, and more specific, non-limiting weight ratios may be 0.61, 0.71, 0.81, 0.91, 1.01, 1.11, 1.21, 1.31, 1.41, 1.51, 1.61, 1.3171, 1.81, 2.01, 2.11, 2.21, 2.51, 3.01, etc.
In the above technical solution, the component c) preferably further comprises an IVB element or an oxide thereof.
In the above embodiment, the group IVB element preferably includes Zr or an oxide thereof.
In the above technical solution, the rare earth element preferably includes Er or its oxide, and in this case, the Zr (or its oxide) and Er (or its oxide) have a synergistic effect in improving the CO conversion rate and the selectivity of the low-carbon olefin in the product.
The ratio of Zr (or an oxide thereof) to Er is not particularly limited, and Zr or an oxide thereof is ZrO 2 And Er or its oxide in Er 2 O 3 In terms of weight ratio, the weight ratio of Zr (or oxide thereof) to Er (or oxide thereof) may be, but is not limited to, 0.11 to 3, and more specific non-limiting weight ratios may be 0.11, 0.21, 0.31, 0.41, 0.51, 0.61, 0.81, 1.01, 1.21, 1.41, 1.61, 1.81, 2.01, 2.21, 2.51, 3.01, and the like.
In the above technical solution, the MCM-41 type molecular sieve is preferably a MCM-41 molecular sieve modified with a modifier, and the modifier includes at least one element of rare earth elements or an oxide thereof.
In the above technical solution, the modifier preferably further comprises at least one element of IA or an oxide thereof.
In the above technical scheme, the modified MCM-41 molecular sieve preferably contains 1 to 16% by weight of the modifier, and more specific non-limiting values of the content are 2.1%, 3.1%, 4.1%, 5.1%, 6.1%, 7.1%, 8.1%, 9.1%, 10.1%, 12.1%, 14.1%, and so on.
In the above technical solution, the rare earth element preferably includes La or an oxide thereof.
In the above technical solution, the IA element preferably includes Cs or its oxide, and in this case, la (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 La (or its oxide) to Cs is not particularly limited, and La or its oxide is La 2 O 3 The counting is carried out on the basis of the number of the counter,and Cs or oxides thereof with Cs 2 The weight ratio of La (or its oxide), and Cs (or its oxide) calculated as O may be, but not limited to, 0.11 to 5, and more specific non-limiting weight ratios may be 0.11, 0.21, 0.31, 0.41, 0.51, 0.61, 0.81, 1.01, 1.21, 1.41, 1.51, 1.61, 1.81, 2.01, 2.21, 2.51, 3.01, 3.51, 4.01, 4.51, and the like.
In the technical scheme, the modified MCM-41 molecular sieve is prepared by a method comprising the following steps:
(i) Dissolving rare earth and/or IA element salt 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 solution, the preferable range of the calcination temperature in step (iii) is 400 to 800 ℃.
In the above-mentioned embodiment, the preferable range of the calcination time in the step (iii) is 2.0 to 8.0 hours.
To solve the second technical problem, the technical solution of the present invention is as follows: the preparation method of the catalyst for synthesizing the low-carbon olefin by the one-step method in one of the technical schemes of the technical problems comprises the following steps:
(1) Dissolving the corresponding salts of the components a), b) and c) in water to prepare a solution A;
(2) Mixing the solution A with titanium dioxide to obtain a mixture B;
(3) Drying and roasting the mixture B to obtain a mixture C;
(4) And mixing the mixture C and the MCM-41 type molecular sieve to obtain the required catalyst for synthesizing the low-carbon olefin by the one-step method.
In the above technical scheme, the preferable range of the roasting temperature in the step (3) is 400-800 ℃.
In the above technical solution, the preferable range of the calcination time in the step (3) is 4.0 to 8.0 hours.
In the above technical scheme, the mixing manner of the step (ii) and/or the step (2) is not particularly required, but the mixing effect is particularly good under vacuum. For example, but not limited to, the solution is impregnated with the corresponding solid component under a vacuum of 1 to 80 kPa.
In the technical scheme, the mixing mode in the step (4) is not particularly required, but the mixing mode is ground and mixed in a ball mill, then tabletting and forming are carried out, and the further crushing and screening effects are particularly good.
In order to solve the third technical problem, the technical scheme of the invention is as follows:
in one of the technical schemes of the technical problems, the catalyst for synthesizing the low-carbon olefin by the one-step method is used for preparing C by a Fischer-Tropsch method 2 ～C 4 To 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 one-step method for synthesizing C 2 ～C 4 The 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 material 2 ～C 4 The olefin of (1).
In the above technical scheme, H in the synthesis gas 2 The molar ratio of CO to CO is preferably 1 to 3.
In the above technical scheme, the reaction temperature is preferably 250 to 450 ℃.
In the above technical scheme, the reaction pressure is preferably 0.5 to 3.0MPa.
In the technical scheme, the volume space velocity of the raw material gas is preferably 500-8000 h -1 。
As known to those skilled in the art, the catalyst of the present invention is used for preparing C from synthesis gas 2 ～C 4 Before 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 H 2 And/or CO;
the reduction pressure is normal pressure to 3MPa (measured by gauge pressure);
the volume space velocity of the reducing agent is 1500-8000 hr -1 ；
The reduction time is 6 to 48 hours.
For convenience of comparison, the reduction conditions in the examples of the present invention are as follows:
the temperature is 450 DEG C
Pressure and atmosphere
Catalyst loading 3ml
Volume space velocity of reducing agent is 5000 hours -1
Reducing gas H 2
The reduction time was 24 hours.
By adopting the catalyst, the CO conversion rate can reach 99.8 percent, which is improved by 3.8 percent compared with the prior art; the selectivity of the low-carbon olefin in hydrocarbon can reach 79.0 percent, which is improved by 11.0 percent compared with the prior art, and a better technical effect is achieved.
Detailed Description
[ example 1 ]
1. Preparation of modified MCM-41 molecular sieve
Weighing the corresponding 10 g of La 2 O 3 Dissolving lanthanum nitrate hexahydrate in 60 g of deionized water to prepare a solution D; under the condition of vacuum degree of 80kPa, dipping the solution D on 90 g of MCM-41 molecular sieve to obtain a mixture E; and drying the mixture E at 110 ℃, and then roasting at 500 ℃ for 6 hours to obtain the modified MCM-41 molecular sieve.
2. Preparation of the catalyst
Weighing the equivalent of 20.0 parts by weight of Fe 2 O 3 Corresponding to 20.0 parts by weight of In 2 O 3 Corresponding to 10.0 parts by weight of ZrO, of indium nitrate hydrate 2 Dissolving the pentahydrate zirconium nitrate into 30.0 g of deionized water to prepare a solution A; impregnating the solution A on 30.0 parts by weight of titanium dioxide under the condition of a vacuum degree of 80kPa to obtain a mixture B; and drying the impregnated mixture B at 110 ℃, and then roasting at 600 ℃ for 6 hours to obtain a mixture C.
Mixing 80 g of the mixture C with 20 g of the modified MCM-41 molecular sieve, milling and mixing in a ball mill, tabletting for molding, crushing and sieving to obtain particles of 40-80 meshes to obtain the catalyst.
The prepared catalyst comprises the following components in percentage by weight: 20% of Fe 2 O 3 ，20％In 2 O 3 ，10％ZrO 2 ，30％TiO 2 20% modified MCM-41 (containing La) 2 O 3 10％)。
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 330 DEG C
The reaction pressure is 1.0MPa
Catalyst loading 3ml
Catalyst loading 5000 hours -1
Raw material ratio (mol) H 2 /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 La equivalent to 10 g 2 O 3 Dissolving lanthanum nitrate hexahydrate in 60 g of deionized water to prepare a solution D; under the condition of vacuum degree of 80kPa, dipping the solution D on 90 g of MCM-41 molecular sieve to obtain a mixture E; and drying the mixture E at 110 ℃, and then roasting at 500 ℃ for 6 hours to obtain the modified MCM-41 molecular sieve.
2. Preparation of the catalyst
Weighing the equivalent of 20.0 parts by weight of Fe 2 O 3 Iron nitrate nonahydrate, 50% manganese nitrate solution corresponding to 20.0 parts by weight of MnO, zrO corresponding to 10.0 parts by weight 2 Dissolving the pentahydrate zirconium nitrate into 30.0 g of deionized water to prepare a solution A; immersing the solution A in 30.0 weight parts of titanium dioxide under the condition of 80kPa to obtainTo mixture B; and drying the impregnated mixture B at 110 ℃, and then roasting at 600 ℃ for 6 hours to obtain a mixture C.
And mixing 80 g of the mixture C and 20 g of the modified MCM-41 molecular sieve, milling and mixing in a ball mill, tabletting for forming, crushing and sieving particles of 40-80 meshes to obtain the catalyst.
The prepared catalyst comprises the following components in percentage by weight: 20% of Fe 2 O 3 ，20％MnO，10％ZrO 2 ，30％TiO 2 20% modified MCM-41 (containing La) 2 O 3 10％)。
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 330 DEG C
The reaction pressure is 1.0MPa
Catalyst loading 3ml
Catalyst loading 5000 hours -1
Raw material ratio (mol) H 2 /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 corresponding 10 g of La 2 O 3 Dissolving lanthanum nitrate hexahydrate in 60 g of deionized water to prepare a solution D; under the condition of vacuum degree of 80kPa, dipping the solution D on 90 g of MCM-41 molecular sieve to obtain a mixture E; and drying the mixture E at 110 ℃, and then roasting at 500 ℃ for 6 hours to obtain the modified MCM-41 molecular sieve.
2. Preparation of the catalyst
Weighing the equivalent of 20.0 parts by weight of Fe 2 O 3 Corresponding to 20.0 parts by weight of In 2 O 3 Corresponding to 10.0 parts by weight of Er 2 O 3 Dissolving erbium nitrate hexahydrate in 30.0 g of deionized water to prepare a solution A; under the condition of vacuum degree of 80kPa, the solution A is soaked on 30.0 weight parts of titanium dioxide to obtain a mixture B; and drying the impregnated mixture B at 110 ℃, and then roasting at 600 ℃ for 6 hours to obtain a mixture C.
And mixing 80 g of the mixture C and 20 g of the modified MCM-41 molecular sieve, milling and mixing in a ball mill, tabletting for forming, crushing and sieving particles of 40-80 meshes to obtain the catalyst.
The prepared catalyst comprises the following components in percentage by weight: 20% of Fe 2 O 3 ，20％In 2 O 3 ，10％Er 2 O 3 ，30％TiO 2 20% modified MCM-41 (containing La) 2 O 3 10％)。
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 330 DEG C
The reaction pressure is 1.0MPa
Catalyst loading 3ml
Catalyst loading 5000 hours -1
Raw material ratio (mol) H 2 /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 La equivalent to 10 g 2 O 3 Dissolving lanthanum nitrate hexahydrate in 60 g of deionized water to prepare a solution D; under the condition of vacuum degree of 80kPa, dipping the solution D on 90 g of MCM-41 molecular sieve to obtain a mixture E; and drying the mixture E at 110 ℃, and then roasting at 500 ℃ for 6 hours to obtain the modified MCM-41 molecular sieve.
2. Preparation of the catalyst
Weighing the equivalent of 20.0 parts by weight of Fe 2 O 3 Iron nitrate nonahydrate, 50% manganese nitrate solution corresponding to 20.0 parts by weight of MnO, er corresponding to 10.0 parts by weight 2 O 3 Dissolving erbium nitrate hexahydrate in 30.0 g of deionized water to prepare a solution A; impregnating the solution A on 30.0 parts by weight of titanium dioxide under the condition of a vacuum degree of 80kPa to obtain a mixture B; and drying the impregnated mixture B at 110 ℃, and then roasting at 600 ℃ for 6 hours to obtain a mixture C.
And mixing 80 g of the mixture C and 20 g of the modified MCM-41 molecular sieve, milling and mixing in a ball mill, tabletting for forming, crushing and sieving particles of 40-80 meshes to obtain the catalyst.
The prepared catalyst comprises the following components in percentage by weight: 20% of Fe 2 O 3 ，20％MnO，10％Er 2 O 3 ，30％TiO 2 20% modified MCM-41 (containing La) 2 O 3 10％)。
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 330 DEG C
Reaction pressure 1.0MPa
Catalyst loading 3ml
Catalyst loading 5000 hours -1
Raw material ratio (mol) H 2 /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 corresponding 10 g of La 2 O 3 Dissolving lanthanum nitrate hexahydrate in 60 g of deionized water to prepare a solution D; under the condition of vacuum degree of 80kPa, dipping the solution D on 90 g of MCM-41 molecular sieve to obtain a mixture E; drying mixture E at 110 deg.CAnd then roasting at 500 ℃ for 6 hours to obtain the modified MCM-41 molecular sieve.
2. Preparation of the catalyst
Weighing the equivalent of 20.0 parts by weight of Fe 2 O 3 Iron nitrate nonahydrate (equivalent to 12.0 parts by weight of In) 2 O 3 Indium nitrate hydrate, a 50% manganese nitrate solution corresponding to 8.0 parts by weight of MnO, and ZrO corresponding to 10.0 parts by weight of 2 Dissolving the pentahydrate zirconium nitrate into 30.0 g of deionized water to prepare a solution A; under the condition of vacuum degree of 80kPa, the solution A is soaked on 30.0 weight parts of titanium dioxide to obtain a mixture B; and drying the impregnated mixture B at 110 ℃, and then roasting at 600 ℃ for 6 hours to obtain a mixture C.
And mixing 80 g of the mixture C and 20 g of the modified MCM-41 molecular sieve, milling and mixing in a ball mill, tabletting for forming, crushing and sieving particles of 40-80 meshes to obtain the catalyst.
The prepared catalyst comprises the following components in percentage by weight: 20% of Fe 2 O 3 ，12％In 2 O 3 ，8％MnO，10％ZrO 2 ，30％TiO 2 20% modified MCM-41 (containing La) 2 O 3 10％)。
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 330 DEG C
The reaction pressure is 1.0MPa
Catalyst loading 3ml
Catalyst loading 5000 hours -1
Raw material ratio (mol) H 2 /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 La equivalent to 10 g 2 O 3 Dissolving lanthanum nitrate hexahydrate in 60 g of deionized water to prepare a solution D; under the condition of vacuum degree of 80kPa, dipping the solution D on 90 g of MCM-41 molecular sieve to obtain a mixture E; and drying the mixture E at 110 ℃, and then roasting at 500 ℃ for 6 hours to obtain the modified MCM-41 molecular sieve.
2. Preparation of the catalyst
Weighing the equivalent of 20.0 parts by weight of Fe 2 O 3 Iron nitrate nonahydrate (equivalent to 12.0 parts by weight of In) 2 O 3 Indium nitrate hydrate, 50% manganese nitrate solution corresponding to 8.0 parts by weight of MnO, and Er corresponding to 10.0 parts by weight of 2 O 3 Erbium nitrate hexahydrate is dissolved in 30.0 g of deionized water to prepare a solution A; under the condition of vacuum degree of 80kPa, the solution A is soaked on 30.0 weight parts of titanium dioxide to obtain a mixture B; and drying the impregnated mixture B at 110 ℃, and then roasting at 600 ℃ for 6 hours to obtain a mixture C.
And mixing 80 g of the mixture C and 20 g of the modified MCM-41 molecular sieve, milling and mixing in a ball mill, tabletting for forming, crushing and sieving particles of 40-80 meshes to obtain the catalyst.
The prepared catalyst comprises the following components in percentage by weight: 20% of Fe 2 O 3 ，12％In 2 O 3 ，8％MnO，10％Er 2 O 3 ，30％TiO 2 20% modified MCM-41 (containing La) 2 O 3 10％)。
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 330 DEG C
The reaction pressure is 1.0MPa
Catalyst loading 3ml
Catalyst loading 5000 hours -1
Raw material ratio (mol) H 2 /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 example 5 In comparison with example 6 and examples 1 to 4, it can be seen that In (or its oxide) and Mn (or its oxide) have a synergistic effect In increasing CO conversion and low carbon olefin selectivity In the product.
[ example 7 ]
1. Preparation of modified MCM-41 molecular sieve
Weighing the corresponding 10 g of La 2 O 3 Dissolving lanthanum nitrate hexahydrate in 60 g of deionized water to prepare a solution D; under the condition of vacuum degree of 80kPa, dipping the solution D on 90 g of MCM-41 molecular sieve to obtain a mixture E; and drying the mixture E at 110 ℃, and then roasting at 500 ℃ for 6 hours to obtain the modified MCM-41 molecular sieve.
2. Preparation of the catalyst
Weighing the equivalent of 20.0 parts by weight of Fe 2 O 3 Corresponding to 20.0 parts by weight of In 2 O 3 Indium nitrate hydrate of (1), corresponding to 4.0 parts by weight of ZrO 2 Corresponding to 6.0 parts by weight of Er 2 O 3 Erbium nitrate hexahydrate is dissolved in 30.0 g of deionized water to prepare a solution A; under the condition of vacuum degree of 80kPa, the solution A is soaked on 30.0 weight parts of titanium dioxide to obtain a mixture B; and drying the impregnated mixture B at 110 ℃, and then roasting at 600 ℃ for 6 hours to obtain a mixture C.
And mixing 80 g of the mixture C and 20 g of the modified MCM-41 molecular sieve, milling and mixing in a ball mill, tabletting for forming, crushing and sieving particles of 40-80 meshes to obtain the catalyst.
The prepared catalyst comprises the following components in percentage by weight: 20% of Fe 2 O 3 ，20％In 2 O 3 ，4％ZrO 2 ，6％Er 2 O 3 ，30％TiO 2 20% modified MCM-41 (containing La) 2 O 3 10％)。
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 330 DEG C
The reaction pressure is 1.0MPa
Catalyst loading 3ml
Catalyst loading 5000 hours -1
Raw material ratio (mol) H 2 /CO＝2.0/1。
For the sake 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 La equivalent to 10 g 2 O 3 Dissolving lanthanum nitrate hexahydrate in 60 g of deionized water to prepare a solution D; under the condition of vacuum degree of 80kPa, dipping the solution D on 90 g of MCM-41 molecular sieve to obtain a mixture E; and drying the mixture E at 110 ℃, and then roasting at 500 ℃ for 6 hours to obtain the modified MCM-41 molecular sieve.
2. Preparation of the catalyst
Weighing the equivalent of 20.0 parts by weight of Fe 2 O 3 Iron nitrate nonahydrate, 50% manganese nitrate solution corresponding to 20.0 parts by weight of MnO, zrO corresponding to 4.0 parts by weight 2 Corresponding to 6.0 parts by weight of Er 2 O 3 Dissolving erbium nitrate hexahydrate in 30.0 g of deionized water to prepare a solution A; under the condition of vacuum degree of 80kPa, the solution A is soaked on 30.0 weight parts of titanium dioxide to obtain a mixture B; and drying the impregnated mixture B at 110 ℃, and then roasting at 600 ℃ for 6 hours to obtain a mixture C.
And mixing 80 g of the mixture C and 20 g of the modified MCM-41 molecular sieve, milling and mixing in a ball mill, tabletting for forming, crushing and sieving particles of 40-80 meshes to obtain the catalyst.
The prepared catalyst comprises the following components in percentage by weight：20％Fe 2 O 3 ，20％MnO，4％ZrO 2 ，6％Er 2 O 3 ，30％TiO 2 20% modified MCM-41 (containing La) 2 O 3 10％)。
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 was 330 deg.C
The reaction pressure is 1.0MPa
Catalyst loading 3ml
Catalyst loading 5000 hours -1
Raw material ratio (mol) H 2 /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 the equivalent of 10 g Cs 2 O cesium nitrate, dissolved in 60 g deionized water to make solution D; under the condition of vacuum degree of 80kPa, dipping the solution D on 90 g of MCM-41 molecular sieve to obtain a mixture E; and drying the mixture E at 110 ℃, and then roasting at 500 ℃ for 6 hours to obtain the modified MCM-41 molecular sieve.
2. Preparation of the catalyst
Weighing the equivalent of 20.0 parts by weight of Fe 2 O 3 Corresponding to 12.0 parts by weight of In 2 O 3 Indium nitrate hydrate, a 50% manganese nitrate solution corresponding to 8.0 parts by weight of MnO, and ZrO corresponding to 10.0 parts by weight of 2 Dissolving the pentahydrate zirconium nitrate into 30.0 g of deionized water to prepare a solution A; impregnating the solution A on 30.0 parts by weight of titanium dioxide under the condition of a vacuum degree of 80kPa to obtain a mixture B; and drying the impregnated mixture B at 110 ℃, and then roasting at 600 ℃ for 6 hours to obtain a mixture C.
And mixing 80 g of the mixture C and 20 g of the modified MCM-41 molecular sieve, milling and mixing in a ball mill, tabletting for forming, crushing and sieving particles of 40-80 meshes to obtain the catalyst.
The prepared catalyst comprises the following components in percentage by weight: 20% of Fe 2 O 3 ，12％In 2 O 3 ，8％MnO，10％ZrO 2 ，30％TiO 2 20% modified MCM-41 (containing Cs) 2 O 10％)。
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 was 330 deg.C
Reaction pressure 1.0MPa
Catalyst loading 3ml
Catalyst loading 5000 hours -1
Raw material ratio (mol) H 2 /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 the equivalent of 10 g Cs 2 O cesium nitrate, dissolved in 60 g deionized water to make solution D; under the condition of vacuum degree of 80kPa, dipping the solution D on 90 g of MCM-41 molecular sieve to obtain a mixture E; and drying the mixture E at 110 ℃, and then roasting at 500 ℃ for 6 hours to obtain the modified MCM-41 molecular sieve.
2. Preparation of the catalyst
Weighing the equivalent of 20.0 parts by weight of Fe 2 O 3 Iron nitrate nonahydrate (equivalent to 12.0 parts by weight of In) 2 O 3 Indium nitrate hydrate, 50% manganese nitrate solution corresponding to 8.0 parts by weight of MnO, and Er corresponding to 10.0 parts by weight of 2 O 3 Dissolving erbium nitrate hexahydrate in 30.0 g of deionized water to prepare a solution A; the solution A was immersed in 30.0 parts by weight of titanium dioxide under a vacuum of 80kPaThereby obtaining a mixture B; and drying the impregnated mixture B at 110 ℃, and then roasting at 600 ℃ for 6 hours to obtain a mixture C.
And mixing 80 g of the mixture C and 20 g of the modified MCM-41 molecular sieve, milling and mixing in a ball mill, tabletting for forming, crushing and sieving particles of 40-80 meshes to obtain the catalyst.
The prepared catalyst comprises the following components in percentage by weight: 20% of Fe 2 O 3 ，12％In 2 O 3 ，8％MnO，10％Er 2 O 3 ，30％TiO 2 20% modified MCM-41 (containing Cs) 2 O 10％)。
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 330 DEG C
The reaction pressure is 1.0MPa
Catalyst loading 3ml
Catalyst loading 5000 hours -1
Raw material ratio (mol) H 2 /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 the equivalent of 10 g Cs 2 O cesium nitrate, dissolved in 60 g deionized water to make solution D; under the condition of vacuum degree of 80kPa, dipping the solution D on 90 g of MCM-41 molecular sieve to obtain a mixture E; and drying the mixture E at 110 ℃, and then roasting at 500 ℃ for 6 hours to obtain the modified MCM-41 molecular sieve.
2. Preparation of the catalyst
Weighing the equivalent of 20.0 parts by weight of Fe 2 O 3 Corresponding to 20.0 parts by weight of In 2 O 3 Corresponding to 4.0% by weight of indium nitrate hydratePartial ZrO 2 Corresponding to 6.0 parts by weight of Er 2 O 3 Dissolving erbium nitrate hexahydrate in 30.0 g of deionized water to prepare a solution A; impregnating the solution A on 30.0 parts by weight of titanium dioxide under the condition of a vacuum degree of 80kPa to obtain a mixture B; and drying the impregnated mixture B at 110 ℃, and then roasting at 600 ℃ for 6 hours to obtain a mixture C.
And mixing 80 g of the mixture C and 20 g of the modified MCM-41 molecular sieve, milling and mixing in a ball mill, tabletting for forming, crushing and sieving particles of 40-80 meshes to obtain the catalyst.
The prepared catalyst comprises the following components in percentage by weight: 20% of Fe 2 O 3 ，20％In 2 O 3 ，4％ZrO 2 ，6％Er 2 O 3 ，30％TiO 2 20% modified MCM-41 (containing Cs) 2 O 10％)。
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 330 DEG C
The reaction pressure is 1.0MPa
Catalyst loading 3ml
Catalyst loading 5000 hours -1
Raw material ratio (mol) H 2 /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 the equivalent of 10 g Cs 2 O cesium nitrate, dissolved in 60 g deionized water to make solution D; under the condition of vacuum degree of 80kPa, dipping the solution D on 90 g of MCM-41 molecular sieve to obtain a mixture E; and drying the mixture E at 110 ℃, and then roasting at 500 ℃ for 6 hours to obtain the modified MCM-41 molecular sieve.
2. Preparation of the catalyst
Weighing the equivalent of 20.0 parts by weight of Fe 2 O 3 Iron nitrate nonahydrate, 50% manganese nitrate solution corresponding to 20.0 parts by weight of MnO, zrO corresponding to 4.0 parts by weight 2 Corresponding to 6.0 parts by weight of Er 2 O 3 Erbium nitrate hexahydrate is dissolved in 30.0 g of deionized water to prepare a solution A; under the condition of vacuum degree of 80kPa, the solution A is soaked on 30.0 weight parts of titanium dioxide to obtain a mixture B; and drying the impregnated mixture B at 110 ℃, and then roasting at 600 ℃ for 6 hours to obtain a mixture C.
And mixing 80 g of the mixture C and 20 g of the modified MCM-41 molecular sieve, milling and mixing in a ball mill, tabletting for forming, crushing and sieving particles of 40-80 meshes to obtain the catalyst.
The prepared catalyst comprises the following components in percentage by weight: 20% of Fe 2 O 3 ，20％MnO，4％ZrO 2 ，6％Er 2 O 3 ，30％TiO 2 20% modified MCM-41 (containing Cs) 2 O 10％)。
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 330 DEG C
The reaction pressure is 1.0MPa
Catalyst loading 3ml
Catalyst loading 5000 hours -1
Raw material ratio (mol) H 2 /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 corresponding 10 g of La 2 O 3 Dissolving lanthanum nitrate hexahydrate in 60 g of deionized water to prepare a solution D;under the condition of vacuum degree of 80kPa, dipping the solution D on 90 g of MCM-41 molecular sieve to obtain a mixture E; and drying the mixture E at 110 ℃, and then roasting at 500 ℃ for 6 hours to obtain the modified MCM-41 molecular sieve.
2. Preparation of the catalyst
Weighing the equivalent of 20.0 parts by weight of Fe 2 O 3 Corresponding to 12.0 parts by weight of In 2 O 3 Indium nitrate hydrate, a 50% manganese nitrate solution corresponding to 8.0 parts by weight of MnO, and 4.0 parts by weight of ZrO 2 Corresponding to 6.0 parts by weight of Er 2 O 3 Dissolving erbium nitrate hexahydrate in 30.0 g of deionized water to prepare a solution A; under the condition of vacuum degree of 80kPa, the solution A is soaked on 30.0 weight parts of titanium dioxide to obtain a mixture B; and drying the impregnated mixture B at 110 ℃, and then roasting at 600 ℃ for 6 hours to obtain a mixture C.
And mixing 80 g of the mixture C and 20 g of the modified MCM-41 molecular sieve, milling and mixing in a ball mill, tabletting for forming, crushing and sieving particles of 40-80 meshes to obtain the catalyst.
The prepared catalyst comprises the following components in percentage by weight: 20% of Fe 2 O 3 ，12％In 2 O 3 ，8％MnO，4％ZrO 2 ，6％Er 2 O 3 ，30％TiO 2 20% modified MCM-41 (containing La) 2 O 3 10％)。
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 330 DEG C
The reaction pressure is 1.0MPa
Catalyst loading 3ml
Catalyst loading 5000 hours -1
Raw material ratio (mol) H 2 /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 the equivalent of 10 g Cs 2 O cesium nitrate, dissolved in 60 g deionized water to make solution D; under the condition of vacuum degree of 80kPa, dipping the solution D on 90 g of MCM-41 molecular sieve to obtain a mixture E; and drying the mixture E at 110 ℃, and then roasting at 500 ℃ for 6 hours to obtain the modified MCM-41 molecular sieve.
2. Preparation of the catalyst
Weighing the equivalent of 20.0 parts by weight of Fe 2 O 3 Iron nitrate nonahydrate (equivalent to 12.0 parts by weight of In) 2 O 3 Indium nitrate hydrate, a 50% manganese nitrate solution corresponding to 8.0 parts by weight of MnO, and ZrO corresponding to 4.0 parts by weight of 2 Corresponding to 6.0 parts by weight of Er 2 O 3 Dissolving erbium nitrate hexahydrate in 30.0 g of deionized water to prepare a solution A; under the condition of vacuum degree of 80kPa, the solution A is soaked on 30.0 weight parts of titanium dioxide to obtain a mixture B; and drying the impregnated mixture B at 110 ℃, and then roasting at 600 ℃ for 6 hours to obtain a mixture C.
And mixing 80 g of the mixture C and 20 g of the modified MCM-41 molecular sieve, milling and mixing in a ball mill, tabletting for forming, crushing and sieving particles of 40-80 meshes to obtain the catalyst.
The prepared catalyst comprises the following components in percentage by weight: 20% of Fe 2 O 3 ，12％In 2 O 3 ，8％MnO，4％ZrO 2 ，6％Er 2 O 3 ，30％TiO 2 20% modified MCM-41 (containing Cs) 2 O 10％)。
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 330 DEG C
The reaction pressure is 1.0MPa
Catalyst loading 3ml
Catalyst loading 5000 hours -1
Raw material ratio (mol) H 2 /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 example 13 in comparison with example 14 and examples 5 to 12, it is seen that Zr (or an oxide thereof) and Er (or an oxide thereof) have a synergistic effect in improving CO conversion and selectivity to lower olefins.
[ example 15 ]
1. Preparation of modified MCM-41 molecular sieve
Weighing the La equivalent to 6 g 2 O 3 Lanthanum nitrate hexahydrate and equivalent to 4 grams of Cs 2 O cesium nitrate, dissolved in 60 g deionized water to make solution D; under the condition of vacuum degree of 80kPa, dipping the solution D on 90 g of MCM-41 molecular sieve to obtain a mixture E; and drying the mixture E at 110 ℃, and then roasting at 500 ℃ for 6 hours to obtain the modified MCM-41 molecular sieve.
2. Preparation of the catalyst
Weighing the equivalent of 20.0 parts by weight of Fe 2 O 3 Iron nitrate nonahydrate (equivalent to 12.0 parts by weight of In) 2 O 3 Indium nitrate hydrate, a 50% manganese nitrate solution corresponding to 8.0 parts by weight of MnO, and 4.0 parts by weight of ZrO 2 Corresponding to 6.0 parts by weight of Er 2 O 3 Erbium nitrate hexahydrate is dissolved in 30.0 g of deionized water to prepare a solution A; under the condition of vacuum degree of 80kPa, the solution A is soaked on 30.0 weight parts of titanium dioxide to obtain a mixture B; and drying the impregnated mixture B at 110 ℃, and then roasting at 600 ℃ for 6 hours to obtain a mixture C.
And mixing 80 g of the mixture C and 20 g of the modified MCM-41 molecular sieve, milling and mixing in a ball mill, tabletting for forming, crushing and sieving particles of 40-80 meshes to obtain the catalyst.
The prepared catalyst comprises the following components in percentage by weight: 20% of Fe 2 O 3 ，12％In 2 O 3 ，8％MnO，4％ZrO 2 ，6％Er 2 O 3 ，30％TiO 2 20% modified MCM-41 (containing La) 2 O 3 6％，Cs 2 O 4％)。
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 330 DEG C
The reaction pressure is 1.0MPa
Catalyst loading 3ml
Catalyst loading 5000 hours -1
Raw material ratio (mol) H 2 /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 La (or its oxide) and Cs (or its oxide) have a synergistic effect in increasing CO conversion and selectivity to lower olefins.
TABLE 1
Claims (12)
1. The catalyst for synthesizing the low-carbon olefin by the one-step method is characterized in that: the paint comprises the following components in parts by weight:
5-40 parts of component a); 5-40 parts of component b); 1-30 parts of component c); 10 to 50 portions of component d); 5-40 parts of component e);
component a) at least one element selected from the group consisting of iron-based elements or oxides thereof; component b) comprises at least one element selected from group VIIB elements and group IIIA elements or an oxide thereof; component c) comprises at least one element selected from group IIIB elements and group IVB elements or an oxide thereof; component d) is selected from titanium dioxide; component e) is selected from MCM-41 type molecular sieves;
the component b) comprises Mn or an oxide thereof and In or an oxide thereof;
the MCM-41 type molecular sieve is a modifier modified MCM-41 molecular sieve, and the modifier comprises at least one element or an oxide of rare earth elements and IA group elements.
2. The catalyst for synthesizing light olefins by one-step method according to claim 1, wherein the component c) comprises Zr or its oxide; or, said component c) comprises Er or an oxide thereof.
3. The catalyst for synthesizing the low-carbon olefin by the one-step method according to claim 1, wherein the modifier comprises La or an oxide thereof.
4. The catalyst for synthesizing low carbon olefins according to the one-step method of claim 3, wherein the modifier comprises Cs or an oxide thereof.
5. The catalyst for synthesizing light olefins by one-step process according to any of claims 1 to 4, wherein the content of the component a) is 10 to 35 parts.
6. The catalyst for synthesizing low carbon olefin by one-step method according to any one of claims 1 to 4, wherein the content of the component b) is 10 to 35 parts.
7. The catalyst for synthesizing light olefins by one-step process according to any of claims 1 to 4, wherein the content of the component c) is 5 to 25 parts.
8. The catalyst for synthesizing light olefins by one-step process according to any of claims 1 to 4, wherein the content of the component d) is 20 to 45 parts.
9. The catalyst for synthesizing the low-carbon olefin by the one-step method according to any one of claims 1 to 4, wherein the content of the component e) is 10 to 40 parts.
10. The preparation method of the catalyst for synthesizing low-carbon olefin by the one-step method according to any one of claims 1 to 9, which is characterized by comprising the following steps: the method comprises the following steps:
(1) Dissolving the corresponding salts of the components a), b) and c) in water to prepare a solution A;
(2) Mixing the solution A with titanium dioxide to obtain a mixture B;
(3) Drying and roasting the mixture B to obtain a mixture C;
(4) And mixing the mixture C and the MCM-41 type molecular sieve to obtain the required catalyst for synthesizing the low-carbon olefin by the one-step method.
11. The method for preparing a catalyst for synthesizing light olefins according to claim 10, wherein the calcination temperature in step (3) is in the range of 400-800 ℃, and/or the calcination time in step (3) is in the range of 4.0-8.0 hours.
12. The method for preparing C by the Fischer-Tropsch process by using the catalyst for synthesizing the low-carbon olefin by the one-step method in any one of claims 1 to 9 2 ～C 4 To olefins according to (1).
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| CN104148106B (en) * | 2013-05-16 | 2016-08-03 | 中国石油化工股份有限公司 | Synthesis gas produces catalyst of low-carbon alkene and preparation method thereof |
| CN104874417B (en) * | 2014-02-28 | 2018-08-10 | 中国科学院青岛生物能源与过程研究所 | Co based Fischer-Tropsch synthesis catalyst of composite carrier load and its preparation method and application |
| CN106311317B (en) * | 2015-07-02 | 2019-04-16 | 中国科学院大连化学物理研究所 | A kind of catalyst and the method that low-carbon alkene is directly prepared by one-step method from syngas |
| CN107638883B (en) * | 2017-09-28 | 2020-09-08 | 江苏迈川工程技术研究院有限公司 | Catalyst for directly synthesizing low-carbon olefin by Fischer-Tropsch synthesis, preparation and application |
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