CN111068742A - 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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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 selectivity of the low-carbon olefin synthesized 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 a component a); 5-40 parts of component b); 1-30 parts of component c); 10-50 parts of component d); 5-40 parts of a 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 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 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 conforms to ASF distribution, and each hydrocarbon has the maximum theoretical selectivity, such as C2-C4The maximum selectivity of the fraction is 57%, the gasoline fraction (C)5-C11) The selectivity of the Fischer-Tropsch synthesis product limits the selectivity of the synthesized low-carbon olefin, the catalysts for preparing the low-carbon olefin from the Fischer-Tropsch synthesis gas are mainly iron series catalysts, physical and chemical modification can be carried out on the Fischer-Tropsch synthesis catalyst for improving the selectivity of the synthesis gas for directly preparing the low-carbon olefin, for example, a pore structure suitable for a molecular sieve is utilized, the low-carbon olefin can be favorably diffused away from a metal active center in time, the secondary reaction of the olefin is inhibited, the dispersion of metal ions is improved, the selectivity of the low-carbon olefin and the selectivity of the low-carbon olefin are improved, the low-carbon metal ions and the low-carbon metal ions are also improved, the low-carbon metal ions and the low-carbon olefin adsorption effect are improved, the selectivity of the Fischer-Tropsch synthesis catalyst is improved, the low-carbon olefin and the low-carbon olefin adsorption effect of the low-carbon olefin are improved, the secondary adsorption effect of the low-carbon olefin is improved, the low-carbon-hydrocarbon selectivity of the low-carbon-olefin is improved, the low-carbon-olefin and the low-carbon-olefin can be improved, the secondary reaction of the low-carbon-olefin is improved, the low-carbon-olefin can be improved, the selectivity of the low-carbon-olefin and the low-carbon-olefin can be improved by the activity of the low-carbon-olefin can be improved by the addition of the low-carbon-olefin through the addition of the molecular sieve, the catalytic-carbon-The carrier effect and the addition of some transition metal auxiliary agents and alkali metal auxiliary agents can obviously improve the performance of the catalyst, and develop a novel Fischer-Tropsch synthesis catalyst with non-ASF distribution, high activity and high selectivity for preparing low-carbon olefin.
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 institute of chemical and physical sciences in the chinese academy of sciences, an iron-manganese catalyst system supported by an alkali metal oxide of group IIA such as MgO or a high-silicon zeolite molecular sieve (or a phospho-aluminum zeolite) is used, and strong base K or Cs ions are used as an auxiliary agent, so that high activity (90% of CO conversion) and high selectivity (66% of low-carbon olefin selectivity) can be obtained at a reaction temperature of 300-400 ℃ under a reaction pressure of 1.0-5.0 MPa 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 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 its patent application No. 200710063301.9, the catalyst is prepared by using common medicines and reagents, the used iron salt is ferric nitrate, manganese salt is manganese nitrate, potassium salt is potassium carbonate, and the activated carbon is coconut shell carbon, and the catalyst has to be roasted at high temperature and passivated under the protection of flowing nitrogen, special equipment is required, and the preparation process is carried outComplex and high cost. 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 synthesizing low carbon olefin by one-step method in the prior art, and the catalyst for synthesizing low carbon olefin by 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 a component a); 5-40 parts of component b); 1-30 parts of component c); 10-50 parts of component d); 5-40 parts of a 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 technical scheme, the content of the component a) is preferably 10-35 parts.
In the technical scheme, the content of the component b) is preferably 10-35 parts.
In the technical scheme, the content of the component c) is preferably 5-25 parts.
In the technical scheme, the content of the component d) is preferably 20-45 parts.
In the technical scheme, the content of the component e) is preferably 10-40 parts.
In the above technical solution, the component b) preferably further comprises a group IIIA element or an oxide thereof.
In the above technical solutions, 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, In or its oxide is In2O3And Mn or an oxide thereof In MnO, the In (or an oxide thereof), and Mn (or an oxide thereof) weight ratio may be, but 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, 1.71, 1.81, 2.01, 2.11, 2.21, 2.51, 3.01, and the like.
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 an oxide thereof, and in this case, Zr (or an oxide thereof) and Er (or an oxide thereof) have a synergistic effect in improving CO conversion and selectivity of low-carbon olefins in the product.
The ratio of Zr (or its oxide) to Er is not particularly limited, and Zr or its oxide is ZrO2And Er or its oxide in Er2O3In terms of weight ratio, the weight ratio of Zr (or oxide thereof) to Er (or oxide thereof) may be, but 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 solution, the modified MCM-41 molecular sieve preferably contains 1 to 16% by weight of the modifier, and more specifically, 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 the like.
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 La2O3And Cs or oxides thereof as Cs2The 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 scheme, the preferable range of the calcination temperature in step (iii) is 400-800 ℃.
In the above technical scheme, the preferable range of the roasting 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 technical scheme, the preferable range of the roasting temperature in the step (3) is 400-800 ℃.
In the technical scheme, the preferable range of the roasting time in the step (3) is 4.0-8.0 hours.
In the above technical solution, the mixing manner in step (ii) and/or 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) has no special requirement, but the tablet forming and further crushing and screening effects are particularly good after the mixing in the ball mill.
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 method2～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 one-step method for synthesizing 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 250-450 ℃.
In the technical scheme, the reaction pressure is preferably 0.5-3.0 MPa.
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 in the preparation of C from synthesis gas2～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 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 6-48 hours.
For convenience of comparison, the reduction conditions in the examples of the present invention are:
the temperature is 450 DEG C
Pressure and atmosphere
Catalyst loading 3ml
Volume space velocity of reducing agent is 5000 hours-1
Reducing gas H2
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 La equivalent to 10 g2O3Dissolving 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 Fe2O3Corresponding to 20.0 parts by weight of In2O3Corresponding to 10.0 parts by weight of ZrO, of indium nitrate hydrate2Dissolving 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, grinding 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% Fe2O3，20％In2O3，10％ZrO2，30％TiO220% modified MCM-41 (containing La)2O310％)。
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) 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 La equivalent to 10 g2O3Dissolving 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 Fe2O3Iron nitrate nonahydrate, 50% manganese nitrate solution corresponding to 20.0 parts by weight of MnO, ZrO corresponding to 10.0 parts by weight2Dissolving 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, grinding 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% Fe2O3，20％MnO，10％ZrO2，30％TiO220% modified MCM-41 (containing La)2O310％)。
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) 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 La equivalent to 10 g2O3Dissolving 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 Fe2O3Corresponding to 20.0 parts by weight of In2O3Corresponding to 10.0 parts by weight of Er2O3Dissolving 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, grinding 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% Fe2O3，20％In2O3，10％Er2O3，30％TiO220% modified MCM-41 (containing La)2O310％)。
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) 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 La equivalent to 10 g2O3Dissolving 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 Fe2O3Iron nitrate nonahydrate, 50% manganese nitrate solution corresponding to 20.0 parts by weight of MnO, Er corresponding to 10.0 parts by weight2O3Dissolving 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, grinding 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% Fe2O3，20％MnO，10％Er2O3，30％TiO220% modified MCM-41 (containing La)2O310％)。
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) 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 La equivalent to 10 g2O3Dissolving 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 Fe2O3Iron nitrate nonahydrate (equivalent to 12.0 parts by weight of In)2O3Indium 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 of2Dissolving 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, grinding 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% Fe2O3，12％In2O3，8％MnO，10％ZrO2，30％TiO220% modified MCM-41 (containing La)2O310％)。
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) 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 La equivalent to 10 g2O3Dissolving 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 Fe2O3Iron nitrate nonahydrate (equivalent to 12.0 parts by weight of In)2O3Indium nitrate hydrate, 50% manganese nitrate solution corresponding to 8.0 parts by weight of MnO, and Er corresponding to 10.0 parts by weight of2O3Dissolving 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, grinding 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% Fe2O3，12％In2O3，8％MnO，10％Er2O3，30％TiO220% modified MCM-41 (containing La)2O310％)。
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) 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 can be seen from the comparison between example 5 and examples 6 and examples 1-4, In (or oxide thereof) and Mn (or oxide thereof) have synergistic effect In improving CO conversion rate and selectivity of low-carbon olefin In the product.
[ example 7 ]
1. Preparation of modified MCM-41 molecular sieve
Weighing the La equivalent to 10 g2O3Dissolving 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 Fe2O3Corresponding to 20.0 parts by weight of In2O3Indium nitrate hydrate of (1), corresponding to 4.0 parts by weight of ZrO2Five water ofZirconium nitrate and 6.0 parts by weight of Er2O3Dissolving 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, grinding 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% Fe2O3，20％In2O3，4％ZrO2，6％Er2O3，30％TiO220% modified MCM-41 (containing La)2O310％)。
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) 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 La equivalent to 10 g2O3Dissolving 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 Fe2O3Iron nitrate nonahydrate, 50% manganese nitrate solution corresponding to 20.0 parts by weight of MnO, ZrO corresponding to 4.0 parts by weight2Corresponding to 6.0 parts by weight of Er2O3Dissolving 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, grinding 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% Fe2O3，20％MnO，4％ZrO2，6％Er2O3，30％TiO220% modified MCM-41 (containing La)2O310％)。
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) 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 the equivalent of 10 g Cs2O cesium nitrate, dissolved in 60 g deionized water to make solution D; in trueUnder the condition of the void 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 Fe2O3Iron nitrate nonahydrate (equivalent to 12.0 parts by weight of In)2O3Indium 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 of2Dissolving 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, grinding 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% Fe2O3，12％In2O3，8％MnO，10％ZrO2，30％TiO220% modified MCM-41 (containing Cs)2O 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) 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 the equivalent of 10 g Cs2O 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 Fe2O3Iron nitrate nonahydrate (equivalent to 12.0 parts by weight of In)2O3Indium nitrate hydrate, 50% manganese nitrate solution corresponding to 8.0 parts by weight of MnO, and Er corresponding to 10.0 parts by weight of2O3Dissolving 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, grinding 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% Fe2O3，12％In2O3，8％MnO，10％Er2O3，30％TiO220% modified MCM-41 (containing Cs)2O 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) 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 the equivalent of 10 g Cs2O 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 Fe2O3Corresponding to 20.0 parts by weight of In2O3Indium nitrate hydrate of (1), corresponding to 4.0 parts by weight of ZrO2Corresponding to 6.0 parts by weight of Er2O3Dissolving 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, grinding 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% Fe2O3，20％In2O3，4％ZrO2，6％Er2O3，30％TiO220% modified MCM-41 (containing Cs)2O 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) 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 the equivalent of 10 g Cs2O 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 Fe2O3Iron nitrate nonahydrate, 50% manganese nitrate solution corresponding to 20.0 parts by weight of MnO, ZrO corresponding to 4.0 parts by weight2Corresponding to 6.0 parts by weight of Er2O3Dissolving 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, grinding 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% Fe2O3，20％MnO，4％ZrO2，6％Er2O3，30％TiO220% modified MCM-41 (containing Cs)2O 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) 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 La equivalent to 10 g2O3Dissolving 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 Fe2O3Iron nitrate nonahydrate (equivalent to 12.0 parts by weight of In)2O3Indium nitrate hydrate, a 50% manganese nitrate solution corresponding to 8.0 parts by weight of MnO, and 4.0 parts by weight of ZrO2Corresponding to 6.0 parts by weight of Er2O3Dissolving 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, grinding 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% Fe2O3，12％In2O3，8％MnO，4％ZrO2，6％Er2O3，30％TiO220% modified MCM-41 (containing La)2O310％)。
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) 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 the equivalent of 10 g Cs2O 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 Fe2O3Iron nitrate nonahydrate (equivalent to 12.0 parts by weight of In)2O3Indium nitrate hydrate, a 50% manganese nitrate solution corresponding to 8.0 parts by weight of MnO, and 4.0 parts by weight of ZrO2Corresponding to 6.0 parts by weight of Er2O3Dissolving erbium nitrate hexahydrate in 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, grinding 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% Fe2O3，12％In2O3，8％MnO，4％ZrO2，6％Er2O3，30％TiO220% modified MCM-41 (containing Cs)2O 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) 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 13 and examples 14 and 5 to 12, it is clear that Zr (or its oxide) and Er (or its oxide) have a synergistic effect in increasing the CO conversion and the selectivity of lower olefins.
[ example 15 ]
1. Preparation of modified MCM-41 molecular sieve
Weighing the La equivalent to 6 g2O3Lanthanum nitrate hexahydrate and equivalent to 4 grams of Cs2O 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; drying the mixture E at 110 ℃, and then roasting at 500 ℃ for 6h, namelyObtaining the modified MCM-41 molecular sieve.
2. Preparation of the catalyst
Weighing the equivalent of 20.0 parts by weight of Fe2O3Iron nitrate nonahydrate (equivalent to 12.0 parts by weight of In)2O3Indium nitrate hydrate, a 50% manganese nitrate solution corresponding to 8.0 parts by weight of MnO, and 4.0 parts by weight of ZrO2Corresponding to 6.0 parts by weight of Er2O3Dissolving 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, grinding 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% Fe2O3，12％In2O3，8％MnO，4％ZrO2，6％Er2O3，30％TiO220% modified MCM-41 (containing La)2O36％，Cs2O 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) 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 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 (10)
1. 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 a component a); 5-40 parts of component b); 1-30 parts of component c); 10-50 parts of component d); 5-40 parts of a 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.
2. The catalyst for synthesizing light olefins 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 synthesizing the low-carbon olefin by the one-step method according to claim 1, wherein the content of the component a) is 10-35 parts.
4. The catalyst for synthesizing the low-carbon olefin by the one-step method according to claim 1, wherein the content of the component b) is 10-35 parts.
5. The catalyst for synthesizing the low-carbon olefin by the one-step method according to claim 1, wherein the content of the component c) is 5-25 parts.
6. The catalyst for synthesizing the low-carbon olefin by the one-step method according to claim 1, wherein the content of the component d) is 20-45 parts.
7. The catalyst for synthesizing the low-carbon olefin by the one-step method according to claim 1, wherein the content of the component e) is 10-40 parts.
8. The catalyst for synthesizing the light olefins by the one-step method according to claim 1, wherein the MCM-41 type molecular sieve is a modifier modified MCM-41 molecular sieve, and the modifier comprises at least one element of rare earth elements or an oxide thereof.
9. The preparation method of the catalyst for synthesizing the low-carbon olefin by the one-step method, which is disclosed by any one of claims 1 to 8, comprises the following steps of:
(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.
10. The method for preparing C by using the catalyst for synthesizing the low-carbon olefin by the one-step method in the Fischer-Tropsch process according to any one of claims 1 to 82～C4To olefins according to (1).
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