CN109651028B - Method for producing low-carbon olefin by fixed bed - Google Patents
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0425—Catalysts; their physical properties
- C07C1/043—Catalysts; their physical properties characterised by the composition
- C07C1/0435—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof
- C07C1/044—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof containing iron
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/85—Chromium, molybdenum or tungsten
- C07C2523/86—Chromium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/889—Manganese, technetium or rhenium
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention relates to a method for producing low-carbon olefin by a fixed bed, which mainly solves the problems of low CO conversion rate and low-carbon olefin selectivity in the reaction of preparing low-carbon olefin by synthesis gas in the prior art. The invention discloses a method for producing low-carbon olefin by adopting a fixed bed, which comprises the step of taking synthesis gas as a raw material, and carrying out contact reaction on the raw material and a catalyst to generate C-containing2～C4The catalyst comprises the following components in parts by weight: a)5 to 40 parts of an iron-based element or an oxide thereof; b) 1-30 parts of a composition comprising at least one element of group VIIB or an oxide thereof; c) the technical scheme of 40-90 parts of the mixture formed by sintering kaliophilite and at least one of magnesium oxide and aluminum oxide at high temperature better solves the problem and can be used for industrial production of low-carbon olefin by a fixed bed.
Description
Technical Field
The invention relates to a method for producing low-carbon olefin by a fixed bed.
Background
The lower olefin is 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 (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. The Fischer-Tropsch synthesis is a strong exothermic reaction, and a large amount of reaction heat promotes the carbon deposition reaction of the catalyst to generate methane and low-carbon alkane more easily, so that the selectivity of the low-carbon alkene is greatly reduced(ii) a Secondly, the complex kinetic factors also cause disadvantages for selectively synthesizing the low-carbon olefin; the ASF distribution of the Fischer-Tropsch synthesis product limits the selectivity of synthesizing low-carbon olefin. The catalyst for preparing the low-carbon olefin from the Fischer-Tropsch synthesis gas is mainly an iron catalyst, and can be used for carrying out physical and chemical modification on the Fischer-Tropsch synthesis catalyst in order to improve the selectivity of directly preparing the low-carbon olefin from the synthesis gas, for example, the proper pore channel structure of a molecular sieve is utilized, so that the low-carbon olefin can be conveniently diffused away from a metal active center in time, and the secondary reaction of the low-carbon olefin is inhibited; the metal ion dispersibility is improved, and the olefin selectivity is better; the selectivity of the low-carbon olefin can also be improved by changing the interaction between the metal and the carrier; proper transition metal is added, so that the bond energy of the active component and carbon can be enhanced, the generation of methane is inhibited, and the selectivity of low-carbon olefin is improved; the electron promoting assistant is added to promote the increase of CO chemical adsorption heat, the increase of adsorption quantity and the decrease of hydrogen adsorption quantity, so that the selectivity of the low-carbon olefin is increased; eliminating the acid center of the catalyst can inhibit the secondary reaction of the low-carbon olefin and improve the selectivity of the low-carbon olefin. The performance of the catalyst can be obviously improved by the carrier effect of the catalyst carrier and the addition of certain transition metal additives and alkali metal additives, and a novel Fischer-Tropsch synthesis catalyst with non-ASF distribution of products and high activity and high selectivity for preparing low-carbon olefin is developed.
The one-step method for producing low-carbon olefin by using synthesis gas becomes 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 with the C as the main component is applied to preparing low-carbon olefin by using synthesis gas,the method obtains good catalytic effect, the preparation process is relatively complicated due to the need of using a laser pyrolysis technology, and the raw materials adopt Fe (CO)5The catalyst cost is high, and industrialization is difficult. In patent ZL03109585.2 filed by Beijing university of chemical industry, a vacuum impregnation method is adopted to prepare a Fe/activated carbon catalyst taking manganese, copper, zinc, silicon, potassium and the like as additives for the reaction of preparing low-carbon olefin from synthesis gas, and under the condition of no circulation of raw material gas, the conversion rate of CO is 96 percent, and the selectivity of the low-carbon olefin in hydrocarbon is 68 percent. The iron salt and the auxiliary agent manganese salt used for preparing the catalyst are relatively expensive and relatively difficult to dissolve, and simultaneously, the ethanol is used as a solvent, so that the raw material cost and the operation cost in the catalyst preparation process are inevitably increased. In order to further reduce the cost of the catalyst, in the patent application No. 200710063301.9, the catalyst is prepared by using common medicines and reagents, iron salt is used as ferric nitrate, manganese salt is used as manganese nitrate, potassium salt is used as potassium carbonate, activated carbon is coconut shell carbon, the catalyst needs to be roasted at high temperature and passivated under the protection of flowing nitrogen, special equipment is needed, the preparation process is complex, and the cost is high. And the catalyst has lower CO conversion rate and lower selectivity of the low-carbon olefin in the reaction of preparing the low-carbon olefin from the synthesis gas.
Disclosure of Invention
One of the technical problems to be solved by the invention is the problems of low CO conversion rate and low selectivity of low-carbon olefin in the product in the technology of preparing low-carbon olefin from synthesis gas in the prior art, and the method for producing low-carbon olefin by using the fixed bed is provided.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a process for preparing low-carbon olefin by fixed bed includes such steps as contact reaction of synthetic gas with catalyst to generate C2～C4The catalyst comprises the following components in parts by weight:
a)5 to 40 parts of an iron-based element or an oxide thereof;
b) 1-30 parts of a composition comprising at least one element of group VIIB or an oxide thereof;
c) 40-90 parts of a mixture formed by sintering kaliophilite and at least one of magnesium oxide and aluminum oxide at high temperature.
In the above technical scheme, H in the synthesis gas2The molar ratio of CO to CO is preferably 1 to 3.
In the technical scheme, the reaction temperature is preferably 250-400 ℃.
In the technical scheme, the reaction pressure is preferably 1.0-3.0 MPa.
In the technical scheme, the volume space velocity of the raw material gas is preferably 500-5000 h-1。
In the above technical solution, the iron-based element is selected from at least one of iron, cobalt and nickel.
In the above technical solution, the iron oxide is preferably iron sesquioxide, and the cobalt oxide 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 5-25 parts.
In the technical scheme, the content of the component c) is preferably 50-80 parts.
In the above technical solution, the component b) preferably further comprises a group IIIB element or an oxide thereof.
In the above technical solution, the VIIB group element preferably includes Mn or an oxide thereof.
In the above technical solution, the group IIIB element preferably includes Y or an oxide thereof, and in this case, Mn (or an oxide thereof) and Y (or an oxide thereof) have a synergistic effect in increasing the CO conversion rate and the selectivity of low-carbon olefins in the product.
The ratio of Mn (or oxide thereof) to Y is not particularly limited, Mn or oxide thereof is in MnO, and Y or oxide thereof is in Y2O3In terms of the weight ratio of Mn (or an oxide thereof), and Y (or an oxide thereof) may be, but not limited to, 0.5 to 5, and more specific non-limiting weight ratios may be 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.5, 1.6, 1.7, 1.8, 2.0, 2.1, 2.2, 2.5, 3.0, 3.5, 4.0, 4.5, and the like.
In the above technical solution, the mixture is preferably kaliophilite and at least one of magnesium oxide and aluminum oxide.
In the above technical solution, the mixture is more preferably kaliophilite and at least two of magnesium oxide and aluminum oxide, and in this case, kaliophilite and magnesium oxide and aluminum oxide have synergistic effect between each other, namely, kaliophilite-magnesium oxide, magnesium oxide-aluminum oxide and aluminum oxide-kaliophilite, in the aspects of improving the CO conversion rate and the selectivity of low-carbon olefin in the product. The ratio between two is not particularly limited. For example, but not limited to, kaliophilite in KAlSiO4Magnesium oxide in MgO and aluminum oxide in Al2O3The weight ratio of kaliophilite to magnesium oxide can be 0.1-10, more specific ratio can be 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, etc.; the weight ratio of magnesium oxide to aluminum oxide can be 0.1 to 10, and more specific ratios can be, for example, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, and the like; the kaliophilite to alumina weight ratio can be 0.1 to 10, more specific ratios can be, for example, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, and the like.
In the above technical scheme, the mixture is prepared by a method comprising the following steps:
(i) mixing kaliophilite, at least one of magnesium oxide and aluminum oxide and a binder to obtain a powdery material A;
(ii) adding water into the material A, and kneading to obtain a material B;
(iii) extruding the material B into strips, forming and drying to obtain a material C;
(iv) and sintering the material C at a high temperature, cooling, crushing and screening to obtain a required mixture D.
In the above technical scheme, the binder and the amount used in step (i) are not particularly limited, and can be reasonably selected by one skilled in the art. For example, but not limited to, the binder may be hydroxypropyl methylcellulose powder, hydroxyethyl methylcellulose powder, carboxymethyl cellulose, starch, dextrin, polyethylene glycol, polyvinyl alcohol, and the like; the amount of the binder is, for example, but not limited to, 3-6% of the total weight of the raw materials of the mixture.
In the above technical solution, the amount of water used in step (ii) is not particularly limited, and is preferably such that the kneading and extruding degree can be achieved, and for this reason, a person skilled in the art can reasonably select and do not need to pay creative labor, for example, but not limited to, the amount of water used in step (ii) is preferably 5-15% of the total weight of the raw materials of the mixture in step (i).
In the above-mentioned embodiment, the process conditions for drying in step (iii) are not particularly limited, and the final degree of drying is not particularly limited. For example, but not limited to, the drying temperature is 100-150 ℃, and the drying time is more than 6 hours (e.g., 8 hours, 12 hours, 18 hours, 24 hours, etc.).
In the technical scheme, the preferable range of the high-temperature sintering temperature in the step (iv) is 1000-1500 ℃. Such as, but not limited to 1050 deg.C, 1100 deg.C, 1150 deg.C, 1200 deg.C, 1350 deg.C, 1450 deg.C, etc.
In the technical scheme, the high-temperature sintering time in the step (iv) is preferably 2-10 hours. Such as, but not limited to, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 9 hours, and the like.
In the above technical scheme, the mixing manner of step (i) has no special requirement, and all the steps can obtain comparable technical effects. However, those skilled in the art know that the effect of further crushing and sieving is particularly good when the mixture is formed by tabletting after being milled in a ball mill.
In the above technical scheme, the catalyst can be prepared by a method comprising the following steps:
(1) dissolving the corresponding salts of the components a) and b) in water to prepare a solution E;
(2) mixing the solution E with the mixture D to obtain a mixture F;
(3) and drying and roasting the mixture F to obtain the catalyst for producing the low-carbon olefin by the fixed bed.
In the above technical scheme, as non-limiting examples, the salts corresponding to the components a) and b) of step (1) may be nitrates, carboxylates (such as, but not limited to, acetates, carbonates, bicarbonates) and the like.
In the technical scheme, the mixing mode of the step (2) is not particularly required, but the mixing effect is particularly good under the vacuum condition. For example, but not limited to, the solution is impregnated with the corresponding solid component under a vacuum of 1 to 80 kPa.
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 400-500 ℃;
the reducing agent is H2And/or CO;
the pressure of reduction is normal pressure to 2MPa (measured by gauge pressure);
the volume space velocity of the reducing agent is 1500-6000 hr-1；
The reduction time is 6-24 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 6000 hours-1
Reducing gas H2
The reduction time was 12 hours.
By adopting the method, the CO conversion rate can reach 99.6 percent, which is improved by 3.6 percent compared with the prior art; the selectivity of the low-carbon olefin in hydrocarbon can reach 78.9 percent, which is 10.9 percent higher than that of the prior art, and a better technical effect is achieved.
Detailed Description
[ example 1 ]
1. Preparation of the mixture
Weighing 100 parts by weight of kaliophilite (KAl)SiO4) Adding 4 wt% of hydroxypropyl methyl cellulose powder according to the total weight of the raw materials, and milling and mixing for 6 hours in a ball mill to obtain a material A; adding 7 wt% of deionized water into the milled and mixed material A according to the total amount of the raw materials, and kneading the mixture to be soft to obtain a material B; feeding the kneaded material B into a strip extruding machine to prepare a strip with the diameter of 5mm, cutting the strip into a column shape with the length of 20mm, naturally airing the strip, feeding the strip into drying equipment, and drying the strip for 12 hours at 110 ℃ to obtain a material C; and (3) feeding the dried material C into a high-temperature furnace, calcining for 6.0 hours at 1200 ℃, cooling, crushing, screening and screening particles of 40-80 meshes to obtain a mixture D.
2. Preparation of the catalyst
Weighing 25 parts by weight of Fe2O3Dissolving ferric nitrate nonahydrate and 40% manganese nitrate solution equivalent to 15 parts by weight of MnO in 30.0 g of deionized water to prepare solution E; immersing the solution E in 60 parts by weight of the mixture D under a vacuum degree of 80kPa to obtain a mixture F; and drying the impregnated mixture F at 120 ℃, and then roasting at 600 ℃ for 5 hours to obtain the catalyst.
The prepared catalyst comprises the following components in percentage by weight: 25% Fe2O3，15％MnO，60％KAlSiO4。
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 350 DEG C
The reaction pressure is 2.0MPa
Catalyst loading 3ml
Catalyst loading 6000 hours-1
Raw material ratio (mol) H2/CO＝1.5/1。
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 the mixture
Weighing 100 parts by weight of kaliophilite (KAlSiO)4) Adding 4 wt% of hydroxypropyl methyl cellulose powder according to the total weight of the raw materials, and milling and mixing for 6 hours in a ball mill to obtain a material A; adding 7 wt% of deionized water into the milled and mixed material A according to the total amount of the raw materials, and kneading the mixture to be soft to obtain a material B; feeding the kneaded material B into a strip extruding machine to prepare a strip with the diameter of 5mm, cutting the strip into a column shape with the length of 20mm, naturally airing the strip, feeding the strip into drying equipment, and drying the strip for 12 hours at 110 ℃ to obtain a material C; and (3) feeding the dried material C into a high-temperature furnace, calcining for 6.0 hours at 1200 ℃, cooling, crushing, screening and screening particles of 40-80 meshes to obtain a mixture D.
2. Preparation of the catalyst
Weighing 25 parts by weight of Fe2O3Of iron nitrate nonahydrate corresponding to 15 parts by weight of Y2O3Dissolving yttrium nitrate hexahydrate in 30.0 g of deionized water to prepare a solution E; immersing the solution E in 60 parts by weight of the mixture D under a vacuum degree of 80kPa to obtain a mixture F; and drying the impregnated mixture F at 120 ℃, and then roasting at 600 ℃ for 5 hours to obtain the catalyst.
The prepared catalyst comprises the following components in percentage by weight: 25% Fe2O3，15％Y2O3，60％KAlSiO4。
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 350 DEG C
The reaction pressure is 2.0MPa
Catalyst loading 3ml
Catalyst loading 6000 hours-1
Raw material ratio (mol) H2/CO＝1.5/1。
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 the mixture
Weighing magnesium carbonate equivalent to 100 parts by weight of MgO and hydroxypropyl methyl cellulose powder accounting for 4 percent of the total weight of the raw materials, and milling and mixing the mixture in a ball mill for 6 hours to obtain a material A; adding 7 wt% of deionized water into the milled and mixed material A according to the total amount of the raw materials, and kneading the mixture to be soft to obtain a material B; feeding the kneaded material B into a strip extruding machine to prepare a strip with the diameter of 5mm, cutting the strip into a column shape with the length of 20mm, naturally airing the strip, feeding the strip into drying equipment, and drying the strip for 12 hours at 110 ℃ to obtain a material C; and (3) feeding the dried material C into a high-temperature furnace, calcining for 6.0 hours at 1200 ℃, cooling, crushing, screening and screening particles of 40-80 meshes to obtain a mixture D.
2. Preparation of the catalyst
Weighing 25 parts by weight of Fe2O3Dissolving ferric nitrate nonahydrate and 40% manganese nitrate solution equivalent to 15 parts by weight of MnO in 30.0 g of deionized water to prepare solution E; immersing the solution E in 60 parts by weight of the mixture D under a vacuum degree of 80kPa to obtain a mixture F; and drying the impregnated mixture F at 120 ℃, and then roasting at 600 ℃ for 5 hours to obtain the catalyst.
The prepared catalyst comprises the following components in percentage by weight: 25% Fe2O3，15％Bi2O3，60％MgO。
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 350 DEG C
The reaction pressure is 2.0MPa
Catalyst loading 3ml
Catalyst loading 6000 hours-1
Raw material ratio (mol) H2/CO＝1.5/1。
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 the mixture
Weighing magnesium carbonate equivalent to 100 parts by weight of MgO and hydroxypropyl methyl cellulose powder accounting for 4 percent of the total weight of the raw materials, and milling and mixing the mixture in a ball mill for 6 hours to obtain a material A; adding 7 wt% of deionized water into the milled and mixed material A according to the total amount of the raw materials, and kneading the mixture to be soft to obtain a material B; feeding the kneaded material B into a strip extruding machine to prepare a strip with the diameter of 5mm, cutting the strip into a column shape with the length of 20mm, naturally airing the strip, feeding the strip into drying equipment, and drying the strip for 12 hours at 110 ℃ to obtain a material C; and (3) feeding the dried material C into a high-temperature furnace, calcining for 6.0 hours at 1200 ℃, cooling, crushing, screening and screening particles of 40-80 meshes to obtain a mixture D.
2. Preparation of the catalyst
Weighing 25 parts by weight of Fe2O3Of iron nitrate nonahydrate corresponding to 15 parts by weight of Y2O3Dissolving yttrium nitrate hexahydrate in 30.0 g of deionized water to prepare a solution E; immersing the solution E in 60 parts by weight of the mixture D under a vacuum degree of 80kPa to obtain a mixture F; and drying the impregnated mixture F at 120 ℃, and then roasting at 600 ℃ for 5 hours to obtain the catalyst.
The prepared catalyst comprises the following components in percentage by weight: 25% Fe2O3，15％Y2O3，60％MgO。
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 350 DEG C
The reaction pressure is 2.0MPa
Catalyst loading 3ml
Catalyst loading 6000 hours-1
Raw material ratio (mol) H2/CO＝1.5/1。
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 the mixture
Weighing alumina (Al) equivalent to 100 weight parts2O3) Adding 4 wt% of hydroxypropyl methyl cellulose powder according to the total weight of the raw materials, and milling and mixing for 6 hours in a ball mill to obtain a material A; adding 7 wt% of deionized water into the milled and mixed material A according to the total amount of the raw materials, and kneading the mixture to be soft to obtain a material B; feeding the kneaded material B into a strip extruding machine to prepare a strip with the diameter of 5mm, cutting the strip into a column shape with the length of 20mm, naturally airing the strip, feeding the strip into drying equipment, and drying the strip for 12 hours at 110 ℃ to obtain a material C; and (3) feeding the dried material C into a high-temperature furnace, calcining for 6.0 hours at 1200 ℃, cooling, crushing, screening and screening particles of 40-80 meshes to obtain a mixture D.
2. Preparation of the catalyst
Weighing 25 parts by weight of Fe2O3Dissolving ferric nitrate nonahydrate and 40% manganese nitrate solution equivalent to 15 parts by weight of MnO in 30.0 g of deionized water to prepare solution E; immersing the solution E in 60 parts by weight of the mixture D under a vacuum degree of 80kPa to obtain a mixture F; and drying the impregnated mixture F at 120 ℃, and then roasting at 600 ℃ for 5 hours to obtain the catalyst.
The prepared catalyst comprises the following components in percentage by weight: 25% Fe2O3，15％MnO，60％Al2O3。
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 350 DEG C
The reaction pressure is 2.0MPa
Catalyst loading 3ml
Catalyst loading 6000 hours-1
Raw material ratio (mol) H2/CO＝1.5/1。
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 the mixture
Weighing alumina (Al) equivalent to 100 weight parts2O3) Adding 4 wt% of hydroxypropyl methyl cellulose powder according to the total weight of the raw materials, and milling and mixing for 6 hours in a ball mill to obtain a material A; adding 7 wt% of deionized water into the milled and mixed material A according to the total amount of the raw materials, and kneading the mixture to be soft to obtain a material B; feeding the kneaded material B into a strip extruding machine to prepare a strip with the diameter of 5mm, cutting the strip into a column shape with the length of 20mm, naturally airing the strip, feeding the strip into drying equipment, and drying the strip for 12 hours at 110 ℃ to obtain a material C; and (3) feeding the dried material C into a high-temperature furnace, calcining for 6.0 hours at 1200 ℃, cooling, crushing, screening and screening particles of 40-80 meshes to obtain a mixture D.
2. Preparation of the catalyst
Weighing 25 parts by weight of Fe2O3Of iron nitrate nonahydrate corresponding to 15 parts by weight of Y2O3Dissolving yttrium nitrate hexahydrate in 30.0 g of deionized water to prepare a solution E; immersing the solution E in 60 parts by weight of the mixture D under a vacuum degree of 80kPa to obtain a mixture F; and drying the impregnated mixture F at 120 ℃, and then roasting at 600 ℃ for 5 hours to obtain the catalyst.
The prepared catalyst comprises the following components in percentage by weight: 25% Fe2O3，15％Y2O3，60％Al2O3。
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 350 DEG C
The reaction pressure is 2.0MPa
Catalyst loading 3ml
Catalyst loading 6000 hours-1
Raw material ratio (mol) H2/CO＝1.5/1。
For convenience of comparison, the composition of the catalyst of the present invention and the evaluation results are shown in Table 1.
[ example 7 ]
1. Preparation of the mixture
Weighing kaliophilite (KAlSiO) equivalent to 100 weight parts4) Adding 4 wt% of hydroxypropyl methyl cellulose powder according to the total weight of the raw materials, and milling and mixing for 6 hours in a ball mill to obtain a material A; adding 7 wt% of deionized water into the milled and mixed material A according to the total amount of the raw materials, and kneading the mixture to be soft to obtain a material B; feeding the kneaded material B into a strip extruding machine to prepare a strip with the diameter of 5mm, cutting the strip into a column shape with the length of 20mm, naturally airing the strip, feeding the strip into drying equipment, and drying the strip for 12 hours at 110 ℃ to obtain a material C; and (3) feeding the dried material C into a high-temperature furnace, calcining for 6.0 hours at 1200 ℃, cooling, crushing, screening and screening particles of 40-80 meshes to obtain a mixture D.
2. Preparation of the catalyst
Weighing 25 parts by weight of Fe2O3Iron nitrate nonahydrate, 40% manganese nitrate solution corresponding to 8 parts by weight of MnO, and Y corresponding to 7 parts by weight of2O3Dissolving yttrium nitrate hexahydrate in 30.0 g of deionized water to prepare a solution E; immersing the solution E in 60 parts by weight of the mixture D under a vacuum degree of 80kPa to obtain a mixture F; and drying the impregnated mixture F at 120 ℃, and then roasting at 600 ℃ for 5 hours to obtain the catalyst.
The prepared catalyst comprises the following components in percentage by weight: 25% Fe2O3，8％MnO，7％Y2O3，60％KAlSiO4。
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 350 DEG C
The reaction pressure is 2.0MPa
Catalyst loading 3ml
Catalyst loading 6000 hours-1
Raw material ratio (mol) H2/CO＝1.5/1。
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 the mixture
Weighing magnesium carbonate equivalent to 100 parts by weight of MgO and hydroxypropyl methyl cellulose powder accounting for 4 percent of the total weight of the raw materials, and milling and mixing the mixture in a ball mill for 6 hours to obtain a material A; adding 7 wt% of deionized water into the milled and mixed material A according to the total amount of the raw materials, and kneading the mixture to be soft to obtain a material B; feeding the kneaded material B into a strip extruding machine to prepare a strip with the diameter of 5mm, cutting the strip into a column shape with the length of 20mm, naturally airing the strip, feeding the strip into drying equipment, and drying the strip for 12 hours at 110 ℃ to obtain a material C; and (3) feeding the dried material C into a high-temperature furnace, calcining for 6.0 hours at 1200 ℃, cooling, crushing, screening and screening particles of 40-80 meshes to obtain a mixture D.
2. Preparation of the catalyst
Weighing 25 parts by weight of Fe2O3Iron nitrate nonahydrate, 40% manganese nitrate solution corresponding to 8 parts by weight of MnO, and Y corresponding to 7 parts by weight of2O3Dissolving yttrium nitrate hexahydrate in 30.0 g of deionized water to prepare a solution E; the solution E was immersed in a vacuum of 80kPaObtaining a mixture F on 60 parts by weight of the mixture D; and drying the impregnated mixture F at 120 ℃, and then roasting at 600 ℃ for 5 hours to obtain the catalyst.
The prepared catalyst comprises the following components in percentage by weight: 25% Fe2O3，8％MnO，7％Y2O3，60％MgO。
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 350 DEG C
The reaction pressure is 2.0MPa
Catalyst loading 3ml
Catalyst loading 6000 hours-1
Raw material ratio (mol) H2/CO＝1.5/1。
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 the mixture
Weighing alumina (Al) equivalent to 100 weight parts2O3) Adding 4 wt% of hydroxypropyl methyl cellulose powder according to the total weight of the raw materials, and milling and mixing for 6 hours in a ball mill to obtain a material A; adding 7 wt% of deionized water into the milled and mixed material A according to the total amount of the raw materials, and kneading the mixture to be soft to obtain a material B; feeding the kneaded material B into a strip extruding machine to prepare a strip with the diameter of 5mm, cutting the strip into a column shape with the length of 20mm, naturally airing the strip, feeding the strip into drying equipment, and drying the strip for 12 hours at 110 ℃ to obtain a material C; and (3) feeding the dried material C into a high-temperature furnace, calcining for 6.0 hours at 1200 ℃, cooling, crushing, screening and screening particles of 40-80 meshes to obtain a mixture D.
2. Preparation of the catalyst
Weighing 25 parts by weight of Fe2O3Of iron nitrate nonahydrate phaseWhen the manganese nitrate solution is 40% in MnO 8 parts by weight, the manganese nitrate solution is equivalent to Y7 parts by weight2O3Dissolving yttrium nitrate hexahydrate in 30.0 g of deionized water to prepare a solution E; immersing the solution E in 60 parts by weight of the mixture D under a vacuum degree of 80kPa to obtain a mixture F; and drying the impregnated mixture F at 120 ℃, and then roasting at 600 ℃ for 5 hours to obtain the catalyst.
The prepared catalyst comprises the following components in percentage by weight: 25% Fe2O3，8％MnO，7％Y2O3，60％Al2O3。
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 350 DEG C
The reaction pressure is 2.0MPa
Catalyst loading 3ml
Catalyst loading 6000 hours-1
Raw material ratio (mol) H2/CO＝1.5/1。
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 the mixture
Weighing 50 parts by weight of kaliophilite (KAlSiO)4) Adding magnesium carbonate equivalent to 50 parts by weight of MgO and hydroxypropyl methyl cellulose powder accounting for 4 percent of the total weight of the raw materials, and milling and mixing for 6 hours in a ball mill to obtain a material A; adding 7 wt% of deionized water into the milled and mixed material A according to the total amount of the raw materials, and kneading the mixture to be soft to obtain a material B; feeding the kneaded material B into a strip extruding machine to prepare a strip with the diameter of 5mm, cutting the strip into a column shape with the length of 20mm, naturally airing the strip, feeding the strip into drying equipment, and drying the strip for 12 hours at 110 ℃ to obtain a material C; the dried material C is sent into a high-temperature furnace at 1200 DEG CCalcining for 6.0 hours, cooling, crushing, screening and screening particles of 40-80 meshes to obtain a mixture D.
2. Preparation of the catalyst
Weighing 25 parts by weight of Fe2O3Dissolving ferric nitrate nonahydrate and 40% manganese nitrate solution equivalent to 15 parts by weight of MnO in 30.0 g of deionized water to prepare solution E; immersing the solution E in 60 parts by weight of the mixture D under a vacuum degree of 80kPa to obtain a mixture F; and drying the impregnated mixture F at 120 ℃, and then roasting at 600 ℃ for 5 hours to obtain the catalyst.
The prepared catalyst comprises the following components in percentage by weight: 25% Fe2O3，15％MnO，30％KAlSiO4，30％MgO。
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 350 DEG C
The reaction pressure is 2.0MPa
Catalyst loading 3ml
Catalyst loading 6000 hours-1
Raw material ratio (mol) H2/CO＝1.5/1。
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 the mixture
Weighing 50 parts by weight of kaliophilite (KAlSiO)4) Adding magnesium carbonate equivalent to 50 parts by weight of MgO and hydroxypropyl methyl cellulose powder accounting for 4 percent of the total weight of the raw materials, and milling and mixing for 6 hours in a ball mill to obtain a material A; adding 7 wt% of deionized water into the milled and mixed material A according to the total amount of the raw materials, and kneading the mixture to be soft to obtain a material B; feeding the kneaded material B into a strip extruder, making into strips with diameter of 5mm, and cuttingForming into a column with the length of 20mm, naturally drying, sending into drying equipment, and drying at 110 ℃ for 12 hours to obtain a material C; and (3) feeding the dried material C into a high-temperature furnace, calcining for 6.0 hours at 1200 ℃, cooling, crushing, screening and screening particles of 40-80 meshes to obtain a mixture D.
2. Preparation of the catalyst
Weighing 25 parts by weight of Fe2O3Of iron nitrate nonahydrate corresponding to 15 parts by weight of Y2O3Dissolving yttrium nitrate hexahydrate in 30.0 g of deionized water to prepare a solution E; immersing the solution E in 60 parts by weight of the mixture D under a vacuum degree of 80kPa to obtain a mixture F; and drying the impregnated mixture F at 120 ℃, and then roasting at 600 ℃ for 5 hours to obtain the catalyst.
The prepared catalyst comprises the following components in percentage by weight: 25% Fe2O3，15％Y2O3，30％KAlSiO4，30％MgO。
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 350 DEG C
The reaction pressure is 2.0MPa
Catalyst loading 3ml
Catalyst loading 6000 hours-1
Raw material ratio (mol) H2/CO＝1.5/1。
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 the mixture
Weighing 50 parts by weight of kaliophilite (KAlSiO)4) Equivalent to 50 parts by weight of alumina (Al)2O3) And adding 4 wt% of hydroxypropyl methyl cellulose powder based on the total amount of the raw materials, and milling and mixing for 6 hours in a ball millObtaining a material A; adding 7 wt% of deionized water into the milled and mixed material A according to the total amount of the raw materials, and kneading the mixture to be soft to obtain a material B; feeding the kneaded material B into a strip extruding machine to prepare a strip with the diameter of 5mm, cutting the strip into a column shape with the length of 20mm, naturally airing the strip, feeding the strip into drying equipment, and drying the strip for 12 hours at 110 ℃ to obtain a material C; and (3) feeding the dried material C into a high-temperature furnace, calcining for 6.0 hours at 1200 ℃, cooling, crushing, screening and screening particles of 40-80 meshes to obtain a mixture D.
2. Preparation of the catalyst
Weighing 25 parts by weight of Fe2O3Dissolving ferric nitrate nonahydrate and 40% manganese nitrate solution equivalent to 15 parts by weight of MnO in 30.0 g of deionized water to prepare solution E; immersing the solution E in 60 parts by weight of the mixture D under a vacuum degree of 80kPa to obtain a mixture F; and drying the impregnated mixture F at 120 ℃, and then roasting at 600 ℃ for 5 hours to obtain the catalyst.
The prepared catalyst comprises the following components in percentage by weight: 20% Fe2O3，15％MnO，30％KAlSiO4，30％Al2O3。
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 350 DEG C
The reaction pressure is 2.0MPa
Catalyst loading 3ml
Catalyst loading 6000 hours-1
Raw material ratio (mol) H2/CO＝1.5/1。
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 the mixture
Weighing 50 parts by weight of the totalKaliophilite (KAlSiO)4) Equivalent to 50 parts by weight of alumina (Al)2O3) Adding 4 wt% of hydroxypropyl methyl cellulose powder according to the total weight of the raw materials, and milling and mixing for 6 hours in a ball mill to obtain a material A; adding 7 wt% of deionized water into the milled and mixed material A according to the total amount of the raw materials, and kneading the mixture to be soft to obtain a material B; feeding the kneaded material B into a strip extruding machine to prepare a strip with the diameter of 5mm, cutting the strip into a column shape with the length of 20mm, naturally airing the strip, feeding the strip into drying equipment, and drying the strip for 12 hours at 110 ℃ to obtain a material C; and (3) feeding the dried material C into a high-temperature furnace, calcining for 6.0 hours at 1200 ℃, cooling, crushing, screening and screening particles of 40-80 meshes to obtain a mixture D.
2. Preparation of the catalyst
Weighing 25 parts by weight of Fe2O3Of iron nitrate nonahydrate corresponding to 15 parts by weight of Y2O3Dissolving yttrium nitrate hexahydrate in 30.0 g of deionized water to prepare a solution E; immersing the solution E in 60 parts by weight of the mixture D under a vacuum degree of 80kPa to obtain a mixture F; and drying the impregnated mixture F at 120 ℃, and then roasting at 600 ℃ for 5 hours to obtain the catalyst.
The prepared catalyst comprises the following components in percentage by weight: 25% Fe2O3，15％Y2O3，30％KAlSiO4，30％Al2O3。
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 350 DEG C
The reaction pressure is 2.0MPa
Catalyst loading 3ml
Catalyst loading 6000 hours-1
Raw material ratio (mol) H2/CO＝1.5/1。
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 the mixture
Magnesium carbonate corresponding to 50 parts by weight of MgO and alumina (Al) corresponding to 50 parts by weight of MgO were weighed out2O3) Adding 4 wt% of hydroxypropyl methyl cellulose powder according to the total weight of the raw materials, and milling and mixing for 6 hours in a ball mill to obtain a material A; adding 7 wt% of deionized water into the milled and mixed material A according to the total amount of the raw materials, and kneading the mixture to be soft to obtain a material B; feeding the kneaded material B into a strip extruding machine to prepare a strip with the diameter of 5mm, cutting the strip into a column shape with the length of 20mm, naturally airing the strip, feeding the strip into drying equipment, and drying the strip for 12 hours at 110 ℃ to obtain a material C; and (3) feeding the dried material C into a high-temperature furnace, calcining for 6.0 hours at 1200 ℃, cooling, crushing, screening and screening particles of 40-80 meshes to obtain a mixture D.
2. Preparation of the catalyst
Weighing 25 parts by weight of Fe2O3Dissolving ferric nitrate nonahydrate and 40% manganese nitrate solution equivalent to 15 parts by weight of MnO in 30.0 g of deionized water to prepare solution E; immersing the solution E in 60 parts by weight of the mixture D under a vacuum degree of 80kPa to obtain a mixture F; and drying the impregnated mixture F at 120 ℃, and then roasting at 600 ℃ for 5 hours to obtain the catalyst.
The prepared catalyst comprises the following components in percentage by weight: 25% Fe2O3，15％MnO，30％MgO，30％Al2O3。
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 350 DEG C
The reaction pressure is 2.0MPa
Catalyst loading 3ml
Catalyst loading 6000 hours-1
Raw material ratio (mol) H2/CO＝1.5/1。
For convenience of comparison, the composition of the catalyst of the present invention and the evaluation results are shown in Table 1.
[ example 15 ]
1. Preparation of the mixture
Magnesium carbonate corresponding to 50 parts by weight of MgO and alumina (Al) corresponding to 50 parts by weight of MgO were weighed out2O3) Adding 4 wt% of hydroxypropyl methyl cellulose powder according to the total weight of the raw materials, and milling and mixing for 6 hours in a ball mill to obtain a material A; adding 7 wt% of deionized water into the milled and mixed material A according to the total amount of the raw materials, and kneading the mixture to be soft to obtain a material B; feeding the kneaded material B into a strip extruding machine to prepare a strip with the diameter of 5mm, cutting the strip into a column shape with the length of 20mm, naturally airing the strip, feeding the strip into drying equipment, and drying the strip for 12 hours at 110 ℃ to obtain a material C; and (3) feeding the dried material C into a high-temperature furnace, calcining for 6.0 hours at 1200 ℃, cooling, crushing, screening and screening particles of 40-80 meshes to obtain a mixture D.
2. Preparation of the catalyst
Weighing 25 parts by weight of Fe2O3Of iron nitrate nonahydrate corresponding to 15 parts by weight of Y2O3Dissolving yttrium nitrate hexahydrate in 30.0 g of deionized water to prepare a solution E; immersing the solution E in 60 parts by weight of the mixture D under a vacuum degree of 80kPa to obtain a mixture F; and drying the impregnated mixture F at 120 ℃, and then roasting at 600 ℃ for 5 hours to obtain the catalyst.
The prepared catalyst comprises the following components in percentage by weight: 25% Fe2O3，15％Y2O3，30％MgO，30％Al2O3。
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 350 DEG C
The reaction pressure is 2.0MPa
Catalyst loading 3ml
Catalyst loading 6000 hours-1
Raw material ratio (mol) H2/CO＝1.5/1。
For convenience of comparison, the composition of the catalyst of the present invention and the evaluation results are shown in Table 1.
[ example 16 ]
1. Preparation of the mixture
Weighing 50 parts by weight of kaliophilite (KAlSiO)4) Adding magnesium carbonate equivalent to 50 parts by weight of MgO and hydroxypropyl methyl cellulose powder accounting for 4 percent of the total weight of the raw materials, and milling and mixing for 6 hours in a ball mill to obtain a material A; adding 7 wt% of deionized water into the milled and mixed material A according to the total amount of the raw materials, and kneading the mixture to be soft to obtain a material B; feeding the kneaded material B into a strip extruding machine to prepare a strip with the diameter of 5mm, cutting the strip into a column shape with the length of 20mm, naturally airing the strip, feeding the strip into drying equipment, and drying the strip for 12 hours at 110 ℃ to obtain a material C; and (3) feeding the dried material C into a high-temperature furnace, calcining for 6.0 hours at 1200 ℃, cooling, crushing, screening and screening particles of 40-80 meshes to obtain a mixture D.
2. Preparation of the catalyst
Weighing 25 parts by weight of Fe2O3Iron nitrate nonahydrate, 40% manganese nitrate solution corresponding to 8 parts by weight of MnO, and Y corresponding to 7 parts by weight of2O3Dissolving yttrium nitrate hexahydrate in 30.0 g of deionized water to prepare a solution E; immersing the solution E in 60 parts by weight of the mixture D under a vacuum degree of 80kPa to obtain a mixture F; and drying the impregnated mixture F at 120 ℃, and then roasting at 600 ℃ for 5 hours to obtain the catalyst.
The prepared catalyst comprises the following components in percentage by weight: 25% Fe2O3，8％MnO，7％Y2O3，30％KAlSiO4，30％MgO。
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 350 DEG C
The reaction pressure is 2.0MPa
Catalyst loading 3ml
Catalyst loading 6000 hours-1
Raw material ratio (mol) H2/CO＝1.5/1。
For convenience of comparison, the composition of the catalyst of the present invention and the evaluation results are shown in Table 1.
[ example 17 ]
1. Preparation of the mixture
Weighing 50 parts by weight of kaliophilite (KAlSiO)4) Equivalent to 50 parts by weight of alumina (Al)2O3) Adding 4 wt% of hydroxypropyl methyl cellulose powder according to the total weight of the raw materials, and milling and mixing for 6 hours in a ball mill to obtain a material A; adding 7 wt% of deionized water into the milled and mixed material A according to the total amount of the raw materials, and kneading the mixture to be soft to obtain a material B; feeding the kneaded material B into a strip extruding machine to prepare a strip with the diameter of 5mm, cutting the strip into a column shape with the length of 20mm, naturally airing the strip, feeding the strip into drying equipment, and drying the strip for 12 hours at 110 ℃ to obtain a material C; and (3) feeding the dried material C into a high-temperature furnace, calcining for 6.0 hours at 1200 ℃, cooling, crushing, screening and screening particles of 40-80 meshes to obtain a mixture D.
2. Preparation of the catalyst
Weighing 25 parts by weight of Fe2O3Iron nitrate nonahydrate, 40% manganese nitrate solution corresponding to 8 parts by weight of MnO, and Y corresponding to 7 parts by weight of2O3Dissolving yttrium nitrate hexahydrate in 30.0 g of deionized water to prepare a solution E; the solution E was immersed in 60 parts by weight of a solvent and mixed under a vacuum of 80kPaObtaining a mixture F on the substance D; and drying the impregnated mixture F at 120 ℃, and then roasting at 600 ℃ for 5 hours to obtain the catalyst.
The prepared catalyst comprises the following components in percentage by weight: 25% Fe2O3，8％MnO，7％Y2O3，30％KAlSiO4，30％Al2O3。
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 350 DEG C
The reaction pressure is 2.0MPa
Catalyst loading 3ml
Catalyst loading 6000 hours-1
Raw material ratio (mol) H2/CO＝1.5/1。
For convenience of comparison, the composition of the catalyst of the present invention and the evaluation results are shown in Table 1.
[ example 18 ]
1. Preparation of the mixture
Magnesium carbonate corresponding to 50 parts by weight of MgO and alumina (Al) corresponding to 50 parts by weight of MgO were weighed out2O3) Adding 4 wt% of hydroxypropyl methyl cellulose powder according to the total weight of the raw materials, and milling and mixing for 6 hours in a ball mill to obtain a material A; adding 7 wt% of deionized water into the milled and mixed material A according to the total amount of the raw materials, and kneading the mixture to be soft to obtain a material B; feeding the kneaded material B into a strip extruding machine to prepare a strip with the diameter of 5mm, cutting the strip into a column shape with the length of 20mm, naturally airing the strip, feeding the strip into drying equipment, and drying the strip for 12 hours at 110 ℃ to obtain a material C; and (3) feeding the dried material C into a high-temperature furnace, calcining for 6.0 hours at 1200 ℃, cooling, crushing, screening and screening particles of 40-80 meshes to obtain a mixture D.
2. Preparation of the catalyst
Weighing is equivalent to25 parts by weight of Fe2O3Iron nitrate nonahydrate, 40% manganese nitrate solution corresponding to 8 parts by weight of MnO, and Y corresponding to 7 parts by weight of2O3Dissolving yttrium nitrate hexahydrate in 30.0 g of deionized water to prepare a solution E; immersing the solution E in 60 parts by weight of the mixture D under a vacuum degree of 80kPa to obtain a mixture F; and drying the impregnated mixture F at 120 ℃, and then roasting at 600 ℃ for 5 hours to obtain the catalyst.
The prepared catalyst comprises the following components in percentage by weight: 25% Fe2O3，8％MnO，7％Y2O3，30％MgO，30％Al2O3。
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 350 DEG C
The reaction pressure is 2.0MPa
Catalyst loading 3ml
Catalyst loading 6000 hours-1
Raw material ratio (mol) H2/CO＝1.5/1。
For convenience of comparison, the composition of the catalyst of the present invention and the evaluation results are shown in Table 1.
TABLE 1
Claims (8)
1. A process for preparing low-carbon olefin by fixed bed includes such steps as contact reaction of synthetic gas with catalyst to generate C2～C4The catalyst comprises the following components in parts by weight:
a) 5-40 parts of iron element or oxide thereof;
b) 1-30 parts of Mn or its oxide and Y or its oxide;
c) 40-90 parts of a mixture formed by sintering kaliophilite and at least one of magnesium oxide and aluminum oxide at high temperature;
mn or its oxide in MnO and Y or its oxide in Y2O3The weight ratio of Mn or its oxide to Y or its oxide is 0.5-5.
2. The fixed bed method for producing light olefins according to claim 1, wherein H in the synthesis gas is2And CO in a molar ratio of 1 to 3.
3. The method for producing the low-carbon olefin by the fixed bed according to claim 1, wherein the reaction temperature is 250-400 ℃.
4. The method for producing the low-carbon olefin by the fixed bed according to claim 1, wherein the reaction pressure is 1.0-3.0 MPa.
5. The method for producing low-carbon olefins by using the fixed bed according to claim 1, wherein the volume space velocity of the raw material gas is 500-5000 h-1。
6. The method for producing the low-carbon olefin by the fixed bed according to claim 1, wherein the content of the component a) is 10-35 parts.
7. The method for producing the low-carbon olefin by the fixed bed according to claim 1, wherein the content of the component b) is 5-25 parts.
8. The method for producing low-carbon olefins by using the fixed bed according to claim 1, wherein the content of the component c) is 50-80 parts.
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