CN109651030B - Method for directly preparing low-carbon olefin from synthesis gas - Google Patents

Method for directly preparing low-carbon olefin from synthesis gas Download PDF

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CN109651030B
CN109651030B CN201710934565.0A CN201710934565A CN109651030B CN 109651030 B CN109651030 B CN 109651030B CN 201710934565 A CN201710934565 A CN 201710934565A CN 109651030 B CN109651030 B CN 109651030B
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parts
low
synthesis gas
carbon olefin
catalyst
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CN109651030A (en
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李剑锋
陶跃武
宋卫林
庞颖聪
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
    • B01J29/0316—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing iron group metals, noble metals or copper
    • B01J29/0333—Iron group metals or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
    • B01J29/0341—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/03—Catalysts comprising molecular sieves not having base-exchange properties
    • 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 directly preparing low-carbon olefin from synthesis gas, which mainly solves the problems of low CO conversion rate and low-carbon olefin selectivity in the reaction of preparing low-carbon olefin from synthesis gas in the prior art. The invention relates to a method for directly preparing low-carbon olefin by using synthesis gas, which comprises the step of taking the 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 to 20 parts of at least one element of group IIB or an oxide thereof; c) 1-20 parts of at least one element in IVB group or oxide thereof; d) 10-40 parts of silicon dioxide; e) the technical scheme of 10-50 parts of SBA-15 type molecular sieve well solves the problem and can be used for industrial production of preparing low-carbon olefin from synthesis gas.

Description

Method for directly preparing low-carbon olefin from synthesis gas
Technical Field
The invention relates to a method for directly preparing low-carbon olefin from synthesis gas.
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; 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 low-carbon olefin from Fischer-Tropsch synthesis gas is mainly iron series catalyst, and can be physically and chemically modified for improving the selectivity of directly preparing low-carbon olefin from synthesis gasFor example, the proper pore channel structure of the molecular sieve is utilized, so that the low-carbon olefin can be conveniently diffused away from the 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 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 auxiliary agents for preparing low carbon from synthesis gasAnd (3) olefin reaction, wherein under the condition of no raw material gas circulation, the CO conversion rate is 96%, and the selectivity of the low-carbon olefin in the hydrocarbon is 68%. The iron salt and the auxiliary agent manganese salt used for preparing the catalyst are relatively expensive and relatively difficult to dissolve, 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
The invention aims to solve the technical 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 provides a method for directly preparing low-carbon olefin from synthesis gas.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a process for preparing low-carbon olefin directly from synthetic gas 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 to 20 parts of at least one element of group IIB or an oxide thereof;
c) 1-20 parts of at least one element in IVB group or oxide thereof;
d) 10-40 parts of silicon dioxide;
e) 10-50 parts of SBA-15 type molecular sieve.
In the above technical scheme, H in the synthesis gas2The molar ratio of the carbon to the CO is excellentThe selection is 1-3.
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. 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 5-15 parts.
In the technical scheme, the content of the component c) is preferably 5-15 parts.
In the technical scheme, the content of the component d) is preferably 15-35 parts.
In the technical scheme, the content of the component e) is preferably 15-45 parts.
In the above technical solution, the component b) preferably further comprises group IIA elements or oxides thereof.
In the above technical solution, the group IIB element preferably includes Zn or an oxide thereof.
In the above technical scheme, the IIA element preferably includes Mg or an oxide thereof, and in this case, Zn (or an oxide thereof) and Mg (or an oxide thereof) have a synergistic effect in improving the CO conversion rate and the selectivity of low-carbon olefins in the product.
The ratio of Zn (or its oxide) and Mg is not particularly limited, Zn or its oxide is calculated as ZnO, and Mg or its oxide is calculated as MgO, the weight ratio of Zn (or its oxide), and Mg (or its oxide) 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 component c) preferably further comprises a group VB 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 VB element preferably includes V or an oxide thereof, and in this case, Zr (or an oxide thereof) and V (or an oxide thereof) have a synergistic effect in improving the CO conversion rate and the selectivity of low-carbon olefins in the product.
The ratio of Zr (or its oxide) and V is not particularly limited, and Zr or its oxide is ZrO2And V or an oxide thereof with V2O5In terms of weight ratio, the weight ratio of Zr (or its oxide), and V (or its oxide) may be, but not limited to, 0.1 to 5, and more specific non-limiting weight ratios may be 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.8, 1.0, 1.2, 1.4, 1.6, 1.8, 2.0, 2.2, 2.5, 3.0, 3.5, 4.0, 4.5, and the like.
In the above technical scheme, the SBA-15 type molecular sieve preferably adopts an SBA-15 molecular sieve modified by using at least one element of rare earth elements or an oxide thereof as a modifier.
In the above technical scheme, the SBA-15 type molecular sieve preferably adopts an SBA-15 molecular sieve modified by at least one element of IA element or oxide thereof as a modifier.
In the above technical solution, the modified SBA-15 molecular sieve preferably contains 1 to 15% by weight of a modifier, and more specifically, non-limiting content values are 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 12%, 14%, and the like.
In the above technical solution, the rare earth element preferably includes Nd or an oxide thereof.
In the above technical solution, the IA element preferably includes Cs or its oxide, and in this case, the Nd (or its oxide) and Cs (or its oxide) have a synergistic effect in improving the CO conversion rate and the selectivity of the low-carbon olefin in the product.
The ratio of Nd (or its oxide) to Cs is not particularly limited, and Nd or its oxide is Nd2O3And Cs or oxides thereof as Cs2The weight ratio of Nd (or oxide thereof) to Cs (or oxide thereof) calculated as O may be, but is not limited to, 0.1 to 5, and more specific non-limiting weight ratios may be 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.8, 1.0, 1.2, 1.4, 1.6,1.8, 2.0, 2.2, 2.5, 3.0, 3.5, 4.0, 4.5, etc.
In the technical scheme, the modified SBA-15 molecular sieve is prepared by a method comprising the following steps:
(i) dissolving salt of rare earth element and/or IA element in water to prepare solution D;
(ii) mixing the solution D with an SBA-15 molecular sieve to obtain a mixture E;
(iii) and roasting the mixture E to obtain the required modified SBA 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.
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), b) and c) in water to prepare a solution A;
(2) mixing the solution A with silicon 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 modified SBA molecular sieve to obtain the required synthesis gas to directly prepare the catalyst of the low-carbon olefin.
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.
Those skilled in the art will recognize that the catalysis of the present inventionApplication of the agent in 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 pressure of reduction is normal pressure to 2MPa (measured by gauge pressure);
the volume space velocity of the reducing agent is 1500-10000 hr-1；
The reduction time is 6-72 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 24 hours.
By adopting the catalyst, the CO conversion rate can reach 99.7 percent, which is improved by 3.7 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 SBA-15 molecular sieve
Corresponding to 8 g of Nd was weighed out2O3Dissolving neodymium nitrate hexahydrate in 50 g of deionized water to prepare a solution D; under the condition of vacuum degree of 80kPa, soaking the solution D on 92 g of SBA-15 molecular sieve to obtain a mixture E; and drying the mixture E at 110 ℃, and then roasting at 550 ℃ for 4 hours to obtain the modified SBA-15 molecular sieve.
2. Preparation of the catalyst
Weighing phaseWhen the content is 25 parts by weight of Fe2O3Iron nitrate nonahydrate, zinc nitrate hexahydrate corresponding to 10 parts by weight of ZnO, ZrO 10 parts by weight2Dissolving the pentahydrate zirconium nitrate into 20.0 g of deionized water to prepare a solution A; under the condition of vacuum degree of 80kPa, the solution A is soaked on 25.0 g of silicon dioxide carrier to obtain a mixture B; and drying the impregnated mixture B at 110 ℃, and then roasting at 500 ℃ for 6 hours to obtain a mixture C.
And mixing 70 g of the mixture C and 30 g of the modified SBA-15 molecular sieve, grinding and mixing in a ball mill, tabletting for forming, crushing and sieving to obtain particles of 40-80 meshes to obtain the catalyst.
The prepared catalyst comprises the following components in percentage by weight: 25% Fe2O3，10％ZnO，10％ZrO2，25％SiO230% modified SBA-15 (containing Nd)2O3 8％)。
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 1.5MPa
Catalyst loading 3ml
Catalyst loading 6000 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 SBA-15 molecular sieve
Corresponding to 8 g of Nd was weighed out2O3Dissolving neodymium nitrate hexahydrate in 50 g of deionized water to prepare a solution D; under the condition of vacuum degree of 80kPa, soaking the solution D on 92 g of SBA-15 molecular sieve to obtain a mixture E; drying the mixture E at 110 ℃, then roasting at 550 ℃, and roastingAnd (4) burning for 4h to obtain the modified SBA-15 molecular sieve.
2. Preparation of the catalyst
Weighing 25 parts by weight of Fe2O3Iron nitrate nonahydrate, magnesium nitrate hexahydrate corresponding to 10 parts by weight of MgO, and ZrO corresponding to 10 parts by weight of ZrO2Dissolving the pentahydrate zirconium nitrate into 20.0 g of deionized water to prepare a solution A; under the condition of vacuum degree of 80kPa, the solution A is soaked on 25.0 g of silicon dioxide carrier to obtain a mixture B; and drying the impregnated mixture B at 110 ℃, and then roasting at 500 ℃ for 6 hours to obtain a mixture C.
And mixing 70 g of the mixture C and 30 g of the modified SBA-15 molecular sieve, grinding and mixing in a ball mill, tabletting for forming, crushing and sieving to obtain particles of 40-80 meshes to obtain the catalyst.
The prepared catalyst comprises the following components in percentage by weight: 25% Fe2O3，10％MgO，10％ZrO2，25％SiO230% modified SBA-15 (containing Nd)2O3 8％)。
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 1.5MPa
Catalyst loading 3ml
Catalyst loading 6000 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 SBA-15 molecular sieve
Corresponding to 8 g of Nd was weighed out2O3Dissolving neodymium nitrate hexahydrate in 50 g of deionized water to prepare a solution D; under the condition of vacuum degree of 80kPa,soaking the solution D on 92 g of SBA-15 molecular sieve to obtain a mixture E; and drying the mixture E at 110 ℃, and then roasting at 550 ℃ for 4 hours to obtain the modified SBA-15 molecular sieve.
2. Preparation of the catalyst
Weighing 25 parts by weight of Fe2O3Iron nitrate nonahydrate, zinc nitrate hexahydrate corresponding to 6 parts by weight of ZnO, magnesium nitrate hexahydrate corresponding to 4 parts by weight of MgO, and ZrO 10 parts by weight2Dissolving the pentahydrate zirconium nitrate into 20.0 g of deionized water to prepare a solution A; under the condition of vacuum degree of 80kPa, the solution A is soaked on 25.0 g of silicon dioxide carrier to obtain a mixture B; and drying the impregnated mixture B at 110 ℃, and then roasting at 500 ℃ for 6 hours to obtain a mixture C.
And mixing 70 g of the mixture C and 30 g of the modified SBA-15 molecular sieve, grinding and mixing in a ball mill, tabletting for forming, crushing and sieving to obtain particles of 40-80 meshes to obtain the catalyst.
The prepared catalyst comprises the following components in percentage by weight: 25% Fe2O3，6％ZnO，4％MgO，10％ZrO2，25％SiO230% modified SBA-15 (containing Nd)2O3 8％)。
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 1.5MPa
Catalyst loading 3ml
Catalyst loading 6000 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 example 3 in comparison with examples 1 and 2, it can be seen that there is a synergistic effect between Zn (or its oxide) and Mg (or its oxide) in increasing CO conversion and low carbon olefin selectivity in the product.
[ example 4 ]
1. Preparation of modified SBA-15 molecular sieve
Corresponding to 8 g of Nd was weighed out2O3Dissolving neodymium nitrate hexahydrate in 50 g of deionized water to prepare a solution D; under the condition of vacuum degree of 80kPa, soaking the solution D on 92 g of SBA-15 molecular sieve to obtain a mixture E; and drying the mixture E at 110 ℃, and then roasting at 550 ℃ for 4 hours to obtain the modified SBA-15 molecular sieve.
2. Preparation of the catalyst
Weighing 25 parts by weight of Fe2O3Iron nitrate nonahydrate, zinc nitrate hexahydrate corresponding to 6 parts by weight of ZnO, magnesium nitrate hexahydrate corresponding to 4 parts by weight of MgO, and V corresponding to 10 parts by weight2O5Dissolving ammonium metavanadate in 20.0 g of deionized water to prepare a solution A; under the condition of vacuum degree of 80kPa, the solution A is soaked on 25.0 g of silicon dioxide carrier to obtain a mixture B; and drying the impregnated mixture B at 110 ℃, and then roasting at 500 ℃ for 6 hours to obtain a mixture C.
And mixing 70 g of the mixture C and 30 g of the modified SBA-15 molecular sieve, grinding and mixing in a ball mill, tabletting for forming, crushing and sieving to obtain particles of 40-80 meshes to obtain the catalyst.
The prepared catalyst comprises the following components in percentage by weight: 25% Fe2O3，6％ZnO，4％MgO，10％V2O5，25％SiO230% modified SBA-15 (containing Nd)2O3 8％)。
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 1.5MPa
Catalyst loading 3ml
Catalyst loading 6000 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 SBA-15 molecular sieve
Corresponding to 8 g of Nd was weighed out2O3Dissolving neodymium nitrate hexahydrate in 50 g of deionized water to prepare a solution D; under the condition of vacuum degree of 80kPa, soaking the solution D on 92 g of SBA-15 molecular sieve to obtain a mixture E; and drying the mixture E at 110 ℃, and then roasting at 550 ℃ for 4 hours to obtain the modified SBA-15 molecular sieve.
2. Preparation of the catalyst
Weighing 25 parts by weight of Fe2O3Iron nitrate nonahydrate, zinc nitrate hexahydrate corresponding to 6 parts by weight of ZnO, magnesium nitrate hexahydrate corresponding to 4 parts by weight of MgO, and ZrO 4 parts by weight2Corresponding to 6 parts by weight of V, of zirconium nitrate pentahydrate2O5Dissolving ammonium metavanadate in 20.0 g of deionized water to prepare a solution A; under the condition of vacuum degree of 80kPa, the solution A is soaked on 25.0 g of silicon dioxide carrier to obtain a mixture B; and drying the impregnated mixture B at 110 ℃, and then roasting at 500 ℃ for 6 hours to obtain a mixture C.
And mixing 70 g of the mixture C and 30 g of the modified SBA-15 molecular sieve, grinding and mixing in a ball mill, tabletting for forming, crushing and sieving to obtain particles of 40-80 meshes to obtain the catalyst.
The prepared catalyst comprises the following components in percentage by weight: 25% Fe2O3，6％ZnO，4％MgO、4％ZrO2，6％V2O5，25％SiO230% modified SBA-15 (containing Nd)2O3 8％)。
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 1.5MPa
Catalyst loading 3ml
Catalyst loading 6000 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 example 5 in comparison with examples 3 and 4, it is seen that Zr (or its oxide) and V (or its oxide) have a synergistic effect in increasing CO conversion and selectivity to lower olefins.
[ example 6 ]
1. Preparation of modified SBA-15 molecular sieve
Weighing the equivalent of 8 g of Cs2O cesium nitrate, dissolved in 50 grams of deionized water to make solution D; under the condition of vacuum degree of 80kPa, soaking the solution D on 92 g of SBA-15 molecular sieve to obtain a mixture E; and drying the mixture E at 110 ℃, and then roasting at 550 ℃ for 4 hours to obtain the modified SBA-15 molecular sieve.
2. Preparation of the catalyst
Weighing 25 parts by weight of Fe2O3Iron nitrate nonahydrate, zinc nitrate hexahydrate corresponding to 6 parts by weight of ZnO, magnesium nitrate hexahydrate corresponding to 4 parts by weight of MgO, and ZrO 4 parts by weight2Corresponding to 6 parts by weight of V, of zirconium nitrate pentahydrate2O5Dissolving ammonium metavanadate in 20.0 g of deionized water to prepare a solution A; under the condition of vacuum degree of 80kPa, the solution A is soaked on 25.0 g of silicon dioxide carrier to obtain a mixture B; and drying the impregnated mixture B at 110 ℃, and then roasting at 500 ℃ for 6 hours to obtain a mixture C.
And mixing 70 g of the mixture C and 30 g of the modified SBA-15 molecular sieve, grinding and mixing in a ball mill, tabletting for forming, crushing and sieving to obtain particles of 40-80 meshes to obtain the catalyst.
The prepared catalyst comprises the following components in percentage by weight: 25% Fe2O3，6％ZnO，4％MgO、4％ZrO2，6％V2O5，25％SiO230% modified SBA-15 (containing Cs)2O 8％)。
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 1.5MPa
Catalyst loading 3ml
Catalyst loading 6000 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 7 ]
1. Preparation of modified SBA-15 molecular sieve
Weighing the equivalent of 4 g of Nd2O3Neodymium nitrate hexahydrate corresponding to 4 grams of Cs2O cesium nitrate, dissolved in 50 grams of deionized water to make solution D; under the condition of vacuum degree of 80kPa, soaking the solution D on 92 g of SBA-15 molecular sieve to obtain a mixture E; and drying the mixture E at 110 ℃, and then roasting at 550 ℃ for 4 hours to obtain the modified SBA-15 molecular sieve.
2. Preparation of the catalyst
Weighing 25 parts by weight of Fe2O3Iron nitrate nonahydrate, zinc nitrate hexahydrate corresponding to 6 parts by weight of ZnO, magnesium nitrate hexahydrate corresponding to 4 parts by weight of MgO, and ZrO 4 parts by weight2Corresponding to 6 parts by weight of V, of zirconium nitrate pentahydrate2O5Dissolved in 20.0 g of ammonium metavanadatePreparing solution A in deionized water; under the condition of vacuum degree of 80kPa, the solution A is soaked on 25.0 g of silicon dioxide carrier to obtain a mixture B; and drying the impregnated mixture B at 110 ℃, and then roasting at 500 ℃ for 6 hours to obtain a mixture C.
And mixing 70 g of the mixture C and 30 g of the modified SBA-15 molecular sieve, grinding and mixing in a ball mill, tabletting for forming, crushing and sieving to obtain particles of 40-80 meshes to obtain the catalyst.
The prepared catalyst comprises the following components in percentage by weight: 25% Fe2O3，6％ZnO，4％MgO、4％ZrO2，6％V2O5，25％SiO230% modified SBA-15 (containing Nd)2O3 4％，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 350 DEG C
The reaction pressure is 1.5MPa
Catalyst loading 3ml
Catalyst loading 6000 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 7 and examples 5 and 6, it is clear that Nd (or its oxide) and Cs (or its oxide) have a synergistic effect in increasing the CO conversion and the selectivity of lower olefins. TABLE 1
Figure BDA0001429501330000131

Claims (10)

1. A process for preparing low-carbon olefin directly from synthetic gas includes such steps as preparing raw materialThe material reacts 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 to 20 parts of at least one element of group IIB or an oxide thereof;
c) 1-20 parts of Zr or an oxide thereof and V or an oxide thereof;
d) 10-40 parts of silicon dioxide;
e) 10-50 parts of SBA-15 type molecular sieve;
zr or oxides thereof with ZrO2In terms of V or oxides thereof, V is2O5The weight ratio of Zr or its oxide to V or its oxide is 0.1-5.
2. The method for directly preparing the low-carbon olefin by the synthesis gas according to claim 1, wherein H in the synthesis gas2And CO in a molar ratio of 1 to 3.
3. The method for directly preparing the low-carbon olefin from the synthesis gas according to claim 1, wherein the reaction temperature is 250-400 ℃.
4. The method for directly preparing the low-carbon olefin from the synthesis gas according to claim 1, wherein the reaction pressure is 1.0-3.0 MPa.
5. The method for directly preparing low-carbon olefins from synthesis gas according to claim 1, wherein the volume space velocity of the raw material gas is 500-5000 h-1。
6. The method for directly preparing the low-carbon olefin from the synthesis gas as claimed in claim 1, wherein the content of the component a) is 10-35 parts.
7. The method for directly preparing the low-carbon olefin from the synthesis gas as claimed in claim 1, wherein the content of the component b) is 5-15 parts.
8. The method for directly preparing the low-carbon olefin from the synthesis gas as claimed in claim 1, wherein the content of the component c) is 5-15 parts.
9. The method for directly preparing the low-carbon olefin from the synthesis gas as claimed in claim 1, wherein the content of the component d) is 15-35 parts.
10. The method for directly preparing the low-carbon olefin from the synthesis gas as claimed in claim 1, wherein the content of the component e) is 15-45 parts.
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