CN110639495B - Catalyst for synthesizing low-carbon olefin by synthesis gas and application of catalyst in synthesizing low-carbon olefin - Google Patents

Catalyst for synthesizing low-carbon olefin by synthesis gas and application of catalyst in synthesizing low-carbon olefin Download PDF

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CN110639495B
CN110639495B CN201810676245.4A CN201810676245A CN110639495B CN 110639495 B CN110639495 B CN 110639495B CN 201810676245 A CN201810676245 A CN 201810676245A CN 110639495 B CN110639495 B CN 110639495B
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catalyst
synthesis gas
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carbon olefin
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CN110639495A (en
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宋卫林
陶跃武
庞颖聪
李剑锋
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Sinopec Shanghai Research Institute of Petrochemical Technology
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Abstract

The invention relates to a catalyst for synthesizing low-carbon olefin from synthesis gas and application of the catalyst in synthesizing the low-carbon olefin, and mainly solves the problem of low selectivity of the catalyst in preparing the olefin from the synthesis gas. (1) 10-90% of active components containing V and Mg; (2) the technical scheme of 10-90% of the carrier well solves the problem and can be used for industrial application of preparing low-carbon olefin from synthesis gas.

Description

Catalyst for synthesizing low-carbon olefin from synthesis gas and application of catalyst in synthesizing low-carbon olefin
Technical Field
The invention relates to a catalyst for synthesizing low-carbon olefin by synthesis gas and application of the catalyst in synthesizing the low-carbon olefin.
Background
Low-carbon olefins (olefins with carbon atoms less than or equal to 4) represented by ethylene and propylene are basic raw materials in chemical industry, at present, the main raw materials of the low-carbon olefins in the world are petroleum hydrocarbons, wherein naphtha accounts for most of the raw materials, and alkane, hydrogenated diesel oil, part of heavy oil and the like also exist. Natural gas or light petroleum fractions are mostly used as raw materials at home and abroad, and low-carbon olefin is produced by adopting a steam cracking process in an ethylene combined device. Steam cracking is a large energy consuming device in petrochemical industry and is completely dependent on non-renewable petroleum resources. With the increasing shortage of petroleum resources, alternative resources are urgently needed to be searched. Therefore, the research work of producing olefin by replacing petroleum with natural gas is regarded as important, and some famous petroleum companies and scientific research institutes in the world carry out the research and development work and obtain the attractive results. Under the background of adjusting the structure of energy utilization at present to gradually reduce the dependence of national economic development on petroleum energy, natural gas resources rich in reserves in China are utilized to prepare synthesis gas (carbon monoxide and hydrogen mixed gas) through gas making, and then the synthesis gas is converted into C2-C4 olefin, so that the method has high strategic significance in the long run.
The method for converting the synthesis gas into the olefin comprises an indirect method and a direct method, wherein a process for preparing the low-carbon olefin MTO by cracking the methanol and a process for preparing the low-carbon olefin SDTO by the dimethyl ether from the formed gas comprise the steps of firstly synthesizing the methanol or the dimethyl ether from the synthesis gas and then converting the methanol or the dimethyl ether into the olefin.
Fischer-Tropsch synthesis utilizes synthesis gas (with major components being CO and H) 2 ) The process of synthesizing hydrocarbon under the action of catalyst is an important way for indirect liquefaction of coal and natural gas. The method is invented in 1923 by German scientists Frans Fischer and Hans Tropsh, namely a process of carrying out heterogeneous catalytic hydrogenation reaction on CO on a metal catalyst to generate a mixture mainly comprising straight-chain alkane and olefin. Research and development are carried out in the last 20 th century in germany, and industrialization is realized in 1936, and the two-war aftermath is closed because the economy cannot compete with the petroleum industry; south Africa has abundant coal resources, but oil resources are scarce, and are limited by international socioeconomic and political sanctions for a long time, so that the south Africa is forced to develop the coal-to-oil industrial technology, and a first coal-based F-T synthetic oil plant (Sasol-1) with the production capacity of 25-40 ten thousand tons of products per year is built in 1955. The two global oil crises in 1973 and 1979 caused the price of crude oil in the world to fall and rise greatly, and the F-T synthesis technology re-aroused interest in industrialized countries based on the consideration of strategic technical reserves. In 1980 and 1982, Sasol company in south Africa built and produced two coal-based synthetic oil plants in succession. But in 1986 the world oil price is greatly reducedThe large-scale industrialization process of the F-T synthesis technology in other countries is delayed. Since the 90 s of the twentieth century, petroleum resources are in shortage and deterioration, and the exploratory reserves of coal and natural gas are increasing, the fischer-tropsch technology attracts extensive attention again, and the fischer-tropsch synthesis technology is developed greatly. Currently, the fischer-tropsch catalysts commonly used are divided into two main groups in terms of active components: an iron-based catalyst and a cobalt-based catalyst; while the common synthesis processes are classified into two main categories from the viewpoint of synthesis conditions: a high temperature Fischer-Tropsch synthesis process and a low temperature Fischer-Tropsch synthesis process; the synthesis processes are classified into three main groups, depending on the reactor used: a fixed bed fischer-tropsch synthesis process, a fluidized bed fischer-tropsch synthesis process (with an earlier circulating fluidized bed and a later fixed fluidized bed developed on the basis of a circulating fluidized bed) and a slurry bed fischer-tropsch synthesis process. The fixed bed and the slurry bed are generally applied to the low-temperature Fischer-Tropsch process and are mostly used for producing heavy oil and wax, and the fluidized bed is more suitable for the high-temperature Fischer-Tropsch process for producing lighter hydrocarbons.
The purpose of the present carbon-chemical synthesis of hydrocarbons is to convert them into lower olefins as basic chemical raw materials, of which ethylene and propylene are currently the most valuable materials. Moreover, the synthesis gas is directly used for preparing the low-carbon olefin to be a target product generated by one-step reaction, the process flow is simpler than that of an indirect method, and the economic evaluation is more economical. In the last decade, direct synthesis of lower olefins from synthesis gas has begun to attract attention.
The synthesis gas is directly converted into the low-carbon olefin through Fischer-Tropsch synthesis, and besides the influence of reaction process conditions, thermodynamics and kinetics, the catalyst is one of the most important influencing factors. Franz Fisher and Hans Tropsch, German scientists, in 1923, discovered reactions for the catalytic conversion of synthesis gas to hydrocarbons, and the process for the preparation of hydrocarbons from synthesis gas reactions was therefore known as the Fischer-Tropsch (F-T) synthesis process, i.e., the synthesis of hydrocarbons from CO and H 2 Producing hydrocarbons, by-product water and CO by reaction 2 . In 1955, a large fixed bed F-T synthesis plant using Coal as raw material was built by SASOL (south Africa Coal and Gas corporation), and then a circulating fluidized bed technology was developed, mostFixed fluidized bed and slurry bed technologies have recently been developed. Today, the annual coal handling capacity of SASOL has reached 5000 ten thousand and the annual production of oils and chemicals has reached 760 ten thousand tons. Although the conventional Fischer-Tropsch synthesis reaction aims at synthesizing liquid hydrocarbons for fuel from synthesis gas, the yield of low-carbon olefins (C2-C4 olefins) is improved to a certain extent by using a fluidized bed technology, an iron-based catalyst and adding auxiliaries, but the yield of the low-carbon olefins is still not high and is only 20-25%.
At present, the catalytic systems for preparing low-carbon olefins from synthesis gas mainly comprise the following systems. (1) The modified F-T catalyst Dent et al found that the cobalt-based catalyst can be used for synthesizing low-carbon olefins with high selectivity, such as: Co-Cu/Al 2 O 3 、 Co-Fe/SiO 2 、Fe-Co/C、Co-Ni/MnO 2 And Fe-Co alloy systems. Among these, the improved FT catalyst developed by the luer chemical company gave better results in Fe-ZnO-K 2 Mn or Ti and other components are added on the O catalyst, and high-speed gas circulation is adopted, so that the conversion rate of CO is 80%, and the selectivity of low-carbon olefin is 70%; (2) the superfine particle catalyst Venter et al obtains the active carbon supported high-dispersion K-Fe-Mn catalyst by carbonyl complex decomposition method, the catalyst has high activity, C in the product 2 -C 4 Olefins account for 85-90% and methane is the only other product detected. Cupta et al, using laser pyrolysis, produce catalytically active Fe x Si y C z Equal powder CO conversion of 40%, C 2 ＝ -C 4 ＝ The selectivity reaches 87%, and only a small amount of methane is needed. Shanxi coal chemical industry cloguan, etc. successfully develops and develops a novel and practical ultrafine particle Fe/Mn catalyst by adopting a degradation method of an organic salt compound, the CO conversion rate is more than 95 percent, and C is 2 ＝ -C 4 ＝ /C 2 -C 4 Is more than 80 percent. The highly dispersed amorphous superfine iron powder and carbon powder are prepared by laser pyrolysis method and are successfully prepared into a new F-T synthetic active species Fe through solid-phase reaction 3 C. Preparation of Fe 3 The C is a main body of Fe-C, Fe-C-Mn, Fe-C-Mn-K and other nano catalysts, the CO conversion rate reaches 90 percent, and the olefin selectivity reaches more than 80 percent; (3) amorphous synthesis catalyst Yokoyama et al use amorphous Fe 40 Ni 40 P 16 B 4 Compound, CO conversion 50%, C 2 -C 5 The hydrocarbon selectivity was 65% while the crystalline catalyst produced predominantly methane; (4) the zeolite catalyst represents a system comprising Co-A, Co-Y, Fe-Y and other catalysts, the zeolite-supported high-dispersion iron catalyst prepared by Ballivet-Tketchenko and other people has quite high selectivity of low-carbon olefin, and 88-98 percent of the low-carbon olefin is in C 2 -C 4 Within this range, other iron catalysts such as ZSM-5, mordenite, supported on zeolite 13X also showed similar behavior.
These catalysts were developed on the basis of the original fischer-tropsch catalysts, with Fe, Co or Ni as the active component. Such catalysts must be reductively activated, i.e., in the metallic state, before use. In order to obtain a low-carbon product in the process of preparing the low-carbon olefin from the synthesis gas, the operation temperature is generally high, and the active metal components can be subjected to structural change. The metal Fe can be carbonized to form iron carbide in the reaction process, and although the formation of the iron carbide does not influence the activity and is even beneficial to the selectivity, the change of the catalyst structure can cause the phenomena of carbon deposition, crushing and pulverization of the catalyst, so the stability of the catalyst is poor. Co catalysts are not suitable for use at high temperatures because the formation of cobalt carbide can lead to catalyst deactivation; the Ni catalyst is easy to deposit carbon at high temperature, and the main product is methane, so that the selectivity of the low-carbon olefin is low.
Disclosure of Invention
One of the technical problems solved by the invention is the problem of low selectivity of the catalyst for preparing low-carbon olefin (C2-C4 olefin) from synthesis gas in the prior art, and the invention provides the catalyst for synthesizing the low-carbon olefin from the synthesis gas, which is used for preparing the low-carbon olefin from the synthesis gas and has better low-carbon olefin selectivity.
The second technical problem to be solved by the invention is the preparation method of the catalyst.
The third technical problem to be solved by the invention is the application of the catalyst.
In order to solve one of the technical problems, the technical scheme adopted by the invention is as follows:
the catalyst for synthesizing the low-carbon olefin by the synthesis gas comprises the following components in percentage by weight:
(1) 10-90% of active components containing V and Mg;
(2) 10-90% of carrier.
In the above technical solution, the support is not particularly limited, and those commonly used in the art may be used, for example, but not limited to, the support is at least one selected from the group consisting of alumina, silica, titania and zirconia. More preferably, the support comprises a mixture of alumina and zirconia, the alumina and zirconia having a synergistic effect in increasing the selectivity to lower olefins.
In the above technical scheme, the amount of the carrier used in the catalyst is not particularly limited, and may be reasonably selected by those skilled in the art, for example, but not limited to, the weight content of the carrier is preferably 40-70%.
The catalyst component of the present invention is free of group VIII elements such as, but not limited to, Fe, Co, Ni, etc.
In the above technical scheme, the V-containing active ingredient is preferably represented by the following general formula in terms of atomic ratio: v b Mg c A a O x
Wherein A is at least one selected from Mn, Cu, Zn and Ce;
the value range of a is as follows: 0 to 200 parts by weight; preferably a is greater than 0 and 200 or less;
b ranges from 60 to 90 and b + c is 100;
x is the total number of oxygen atoms required to satisfy the valences of the other elements.
V and A have a synergistic effect on the aspect of improving the selectivity of the low-carbon olefin.
In the above technical solution, as one of the preferable technical solutions, at this time, the following two elements have a synergistic effect in improving the selectivity of the low-carbon olefin:
a includes both Cu and Mn, and the mutual ratio of the two elements is not particularly limited, for example, but not limited to, the atomic ratio of Mn to Cu is 1 to 10, and the numerical value therebetween as a non-limiting specific atomic ratio may be, for example, 2, 3, 4, 5, 6, 7, 8, 9.
Or A comprises both Zn and Mn, the mutual ratio of the two elements is not particularly limited, for example but not limited to, the atomic ratio of Mn to Zn is 1 to 10, and the numerical value therebetween as a non-limiting specific atomic ratio may be, for example, 2, 3, 4, 5, 6, 7, 8, 9.
Or A comprises both Zn and Ce, the mutual ratio of the two elements is not particularly limited, for example but not limited to the atomic ratio of Zn to Ce is 1-10, and the numerical value of the non-limiting specific atomic ratio therebetween can be, for example, 2, 3, 4, 5, 6, 7, 8, 9.
As the most preferable technical solution, a includes Cu, Zn and Mn at the same time, and the mutual ratio of the three elements is not particularly limited, for example, but not limited to, Mn: cu: the atomic ratio of Zn is (2-5): 1-4): 1.
At the moment, the three elements have obvious synergistic effect on the aspect of improving the selectivity of the low-carbon olefin.
In the above technical scheme, the value range of a is preferably 5-150; the range of a is more preferably 20 to 120.
To solve the second technical problem, the technical solution of the present invention is:
the preparation method of the catalyst according to any of the above technical solutions comprises the following steps:
(1) preparing a compound containing active component elements into a solution I;
(2) mixing the solution I with a carrier;
(3) and (4) roasting.
In the above-mentioned embodiments, the compound containing an active ingredient element is not particularly limited as long as it contains the active ingredient element. Such as but not limited to nitrates, ammonium salts, acetates, and the like.
In the above technical solution, the calcination step of step (3) of the present invention is necessary, and in addition to this necessary step, those skilled in the art know that a drying step may be further included after step (2) and before step (3) in order to obtain more uniform distribution of the active component and higher strength of the obtained catalyst.
In the above technical solution, a person skilled in the art can reasonably determine whether to include an evaporation step before drying, but when the material obtained after the operation of step (2) has a visible liquid material, evaporation is preferably performed before drying. The temperature for evaporation is not particularly limited, and those skilled in the art can select the temperature as appropriate, for example, but not limited to, from 60 ℃ to boiling point of the material, and further non-limiting examples of the temperature range include 70 ℃, 80 ℃, 90 ℃ and the like.
In the above technical scheme, the drying conditions are not particularly limited, and can be reasonably determined by those skilled in the art. The drying temperature is, for example, but not limited to, 80-150 ℃. Specific non-limiting examples of the temperature range include 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃ and the like.
In the above technical solution, the drying time is not particularly limited, for example, but not limited to, 4 to 12 hours, and non-limiting examples in this interval may be 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, and the like.
In the above-mentioned technical means, the atmosphere for calcination is not particularly limited, but an oxygen-containing atmosphere is usually used, and for economic reasons, air is usually used as the atmosphere for calcination.
In the technical scheme, the roasting temperature is preferably 450-650 ℃. Non-limiting specific examples within this interval may be 500 ℃, 550 ℃, 600 ℃ and the like.
In the technical scheme, the roasting time is preferably 2-12 hours. Non-limiting specific examples in this interval may be 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, and the like.
In the above technical solution, the compound of the active component element V may be at least one selected from ammonium metavanadate and ammonium vanadate.
In the technical scheme, the compound of the active component element Mg can be selected from magnesium nitrate and/or magnesium acetate.
In the above technical scheme, the compound of the active component element Cu can be selected from copper nitrate and/or copper acetate.
In the technical scheme, the compound of the active component element Mn can be selected from manganese nitrate and/or manganese acetate.
In the above technical scheme, the compound of the active component element Zn can be selected from zinc nitrate and/or zinc acetate.
In the above technical scheme, the compound of the active component element Ce may be selected from cerium nitrate and/or cerium acetate.
In order to solve the third technical problem, the technical scheme of the invention is as follows:
the application of the catalyst in the reaction of preparing the low-carbon olefin by using the synthesis gas is disclosed in one of the technical problems.
The specific application method can be as follows:
the reaction method for preparing the low-carbon olefin from the synthesis gas comprises the step of carrying out contact reaction on the synthesis gas and the catalyst in any one of the technical schemes of the technical problems to generate the low-carbon olefin.
In the above technical scheme, the reaction temperature is preferably 300-450 ℃, and non-limiting examples in this range can be 350 ℃, 400 ℃ and the like.
In the above technical solution, the reaction pressure is preferably 0.5 to 2.5MPa, and non-limiting examples within this range may be 1MPa, 1.5MPa, 2MPa, and the like. Unless otherwise indicated, all pressures referred to in the present specification are gauge pressures.
In the above technical scheme, the space velocity of the synthesis gas is preferably 1000-4000h -1 A non-limiting example in this range may be 1500h -1 、2000h -1 、2500h -1 、3000h -1 、3500h -1 And so on.
In the above technical scheme, H in the synthesis gas 2 The volume ratio to CO is preferably 0.5 to 3, and non-limiting examples within this range may be 1, 1.5, 2, 2.5, and the like.
The catalyst does not need to be reduced to a metal state, the oxidation state of the catalyst has CO hydrogenation activation capability, and in the using process of the catalyst, the metal oxide can not be reduced to metal, the oxidation state can be maintained, and the process of converting the metal into carbide is avoided, so that the problems of unstable structure, inactivation and the like of the traditional Fischer-Tropsch catalyst are solved. Meanwhile, due to the structural stability of the oxide, the catalyst can be used at a higher temperature, so that more low-carbon products can be obtained, and the selectivity of low-carbon olefin is improved.
The evaluation method of the catalyst of the present invention is as follows:
a reactor: a fixed bed reactor with an inner diameter of 10 mm;
catalyst loading: 2.0 g;
h in synthesis gas 2 The volume ratio of CO is 1.5;
synthetic gas hourly space velocity of 2000h -1 ；
The reaction temperature is 350 ℃;
the reaction pressure was 1.5 MPa.
C 2 -C 4 The olefin selectivity calculation is as follows:
Figure BDA0001709279710000071
the catalyst prepared by the method has the advantages of 300-450 ℃, 0.5-2.5MPa, and 1000-4000h of volume space velocity -1 Under the conditions of (1), CO conversion>50％，C 2 -C 4 Olefin selectivity>65%, and a better technical effect is achieved.
The invention is further illustrated by the following examples.
Detailed Description
[ example 1 ] A method for producing a polycarbonate
Weighing the equivalent of 50 g of V 2 O 5 And dissolving ammonium metavanadate and magnesium nitrate hexahydrate (wherein the atomic ratio of V to Mg is 80: 20) of MgO in water to obtain 100 g of impregnation liquid, mixing the impregnation liquid with 50 g of alumina (20-60 meshes), steaming at 80 ℃ under stirring until no visible liquid exists, drying at 120 ℃ for 12 hours, and roasting at 550 ℃ for 5 hours to obtain the catalyst.
The catalyst evaluation conditions were as follows:
a reactor: a fixed bed reactor with an inner diameter of 10 mm;
catalyst loading: 2.0 g;
h in synthesis gas 2 CO volume ratio is 1.5;
synthetic gas volumetric space velocity of 2000h -1 ；
The reaction temperature is 350 ℃;
the reaction pressure was 1.5 MPa.
The catalyst composition and the evaluation results are shown in Table 1.
[ example 2 ]
Weighing the equivalent of 50 g of V 2 O 5 Dissolving ammonium metavanadate in water to obtain 100 g of impregnation liquid, mixing the impregnation liquid with 50 g of alumina (20-60 meshes), steaming at 80 ℃ under stirring until no visible liquid exists, drying at 120 ℃ for 12 hours, and roasting at 550 ℃ in an air atmosphere for 5 hours to obtain the catalyst.
The catalyst evaluation conditions were as follows:
a reactor: a fixed bed reactor with an inner diameter of 10 mm;
catalyst loading: 2.0 g;
h in synthesis gas 2 The volume ratio of CO is 1.5;
synthetic gas hourly space velocity of 2000h -1 ；
The reaction temperature is 350 ℃;
the reaction pressure was 1.5 MPa.
The catalyst composition and the evaluation results are shown in Table 1.
[ example 3 ]
Weighing magnesium nitrate hexahydrate equivalent to 50 g of Mg, dissolving the magnesium nitrate hexahydrate in water to obtain 100 g of impregnation liquid, mixing the impregnation liquid with 50 g of alumina (20-60 meshes), steaming at 80 ℃ under stirring till no visible liquid exists, drying at 120 ℃ for 12 hours, and roasting at 550 ℃ in air atmosphere for 5 hours to obtain the catalyst.
The catalyst evaluation conditions were as follows:
a reactor: a fixed bed reactor with an inner diameter of 10 mm;
catalyst loading: 2.0 g;
h in synthesis gas 2 The volume ratio of CO is 1.5;
synthetic gas volumetric space velocity of 2000h -1 ；
The reaction temperature is 350 ℃;
the reaction pressure was 1.5 MPa.
The catalyst composition and the evaluation results are shown in Table 1.
[ example 4 ] A method for producing a polycarbonate
Weighing the equivalent of 50 g of V 2 O 5 MgO and MnO 2 The ammonium metavanadate, the magnesium nitrate hexahydrate and the manganese nitrate (wherein the atomic ratio of V to Mg is 80: 20, the atomic ratio of the sum of the atomic numbers of V and Mg to Mn is 100:70) are dissolved in water to obtain 100 g of impregnation liquid, the impregnation liquid and 50 g of alumina (20-60 meshes) are mixed, the mixture is stirred and steamed at 80 ℃ until no visible liquid exists, the mixture is dried at 120 ℃ for 12 hours, and the mixture is roasted at 550 ℃ for 5 hours to obtain the catalyst.
The catalyst was evaluated under the following conditions:
a reactor: a fixed bed reactor with an inner diameter of 10 mm;
catalyst loading: 2.0 g;
h in synthesis gas 2 The volume ratio of CO is 1.5;
synthetic gas hourly space velocity of 2000h -1 ；
The reaction temperature is 350 ℃;
the reaction pressure was 1.5 MPa.
The catalyst composition and the evaluation results are shown in Table 1.
[ example 5 ] A method for producing a polycarbonate
Weighing the equivalent of 50 g MnO 2 Dissolving the manganese nitrate in water to obtain 100 g of impregnation liquid, mixing the impregnation liquid with 50 g of alumina (20-60 meshes), steaming at 80 ℃ under stirring until no visible liquid exists, drying at 120 ℃ for 12 hours, and roasting at 550 ℃ in an air atmosphere for 5 hours to obtain the catalyst.
The catalyst was evaluated under the following conditions:
a reactor: a fixed bed reactor with an inner diameter of 10 mm;
catalyst loading: 2.0 g;
h in synthesis gas 2 CO volume ratio is 1.5;
synthetic gas volumetric space velocity of 2000h -1 ；
The reaction temperature is 350 ℃;
the reaction pressure was 1.5 MPa.
The catalyst composition and the evaluation results are shown in Table 1.
[ example 6 ]
Weighing the equivalent of 50 g of V 2 O 5 And ammonium metavanadate, magnesium nitrate hexahydrate and copper nitrate hexahydrate (wherein the atomic ratio of V to Mg is 80: 20, and the atomic ratio of the sum of the atomic numbers of V and Mg to Cu is 100:70) of MgO and Cu are dissolved in water to obtain 100 g of impregnation liquid, the impregnation liquid and 50 g of alumina (20-60 meshes) are mixed, the mixture is stirred and evaporated at 80 ℃ until no visible liquid exists, the mixture is dried at 120 ℃ for 12 hours, and the mixture is roasted at 550 ℃ for 5 hours to obtain the catalyst.
The catalyst was evaluated under the following conditions:
a reactor: a fixed bed reactor with an inner diameter of 10 mm;
catalyst loading: 2.0 g;
h in synthesis gas 2 The volume ratio of CO is 1.5;
synthetic gas hourly space velocity of 2000h -1 ；
The reaction temperature is 350 ℃;
the reaction pressure was 1.5 MPa.
The catalyst composition and the evaluation results are shown in Table 1.
[ example 7 ]
Weighing copper nitrate hexahydrate corresponding to 50 g of CuO, dissolving the copper nitrate hexahydrate in water to obtain 100 g of impregnation liquid, mixing the impregnation liquid with 50 g of alumina (20-60 meshes), steaming at 80 ℃ under stirring until no visible liquid exists, drying at 120 ℃ for 12 hours, and roasting at 550 ℃ for 5 hours in an air atmosphere to obtain the catalyst.
The catalyst evaluation conditions were as follows:
a reactor: a fixed bed reactor with an inner diameter of 10 mm;
catalyst loading: 2.0 g;
h in synthesis gas 2 The volume ratio of CO is 1.5;
synthetic gas hourly space velocity of 2000h -1 ；
The reaction temperature is 350 ℃;
the reaction pressure was 1.5 MPa.
The catalyst composition and the evaluation results are shown in Table 1.
[ example 8 ]
Weighing the equivalent of 50 g of V 2 O 5 And ammonium metavanadate, magnesium nitrate hexahydrate and zinc nitrate hexahydrate of MgO and ZnO (wherein the atomic ratio of V to Mg is 80: 20, and the atomic ratio of the sum of the atomic numbers of V and Mg to Zn is 100:70) are dissolved in water to obtain 100 g of impregnation liquid, the impregnation liquid and 50 g of alumina (20-60 meshes) are mixed, the mixture is stirred and steamed at 80 ℃ until no visible liquid exists, the mixture is dried at 120 ℃ for 12 hours, and the mixture is roasted at 550 ℃ for 5 hours to obtain the catalyst.
The catalyst evaluation conditions were as follows:
a reactor: a fixed bed reactor with an inner diameter of 10 mm;
catalyst loading: 2.0 g;
h in synthesis gas 2 The volume ratio of CO is 1.5;
synthetic gas volumetric space velocity of 2000h -1 ；
The reaction temperature is 350 ℃;
the reaction pressure was 1.5 MPa.
The catalyst composition and the evaluation results are shown in Table 1.
[ example 9 ]
Weighing zinc nitrate hexahydrate corresponding to 50 g of ZnO, dissolving in water to obtain 100 g of impregnation liquid, mixing the impregnation liquid with 50 g of aluminum oxide (20-60 meshes), steaming at 80 ℃ under stirring until no visible liquid exists, drying at 120 ℃ for 12 hours, and roasting at 550 ℃ for 5 hours in an air atmosphere to obtain the catalyst.
The catalyst was evaluated under the following conditions:
a reactor: a fixed bed reactor with an inner diameter of 10 mm;
catalyst loading: 2.0 g;
h in synthesis gas 2 The volume ratio of CO is 1.5;
synthetic gas hourly space velocity of 2000h -1 ；
The reaction temperature is 350 ℃;
the reaction pressure was 1.5 MPa.
The catalyst composition and the evaluation results are shown in Table 1.
[ example 10 ]
Weighing the equivalent of 50 g of V 2 O 5 MgO, CuO and MnO 2 Dissolving ammonium metavanadate, magnesium nitrate hexahydrate, copper nitrate hexahydrate and manganese nitrate (wherein the atomic ratio of V to Mg is 80: 20, the atomic ratio of the sum of the atomic numbers of V and Mg to the atomic ratio of Cu to Mn is 100:30:40) in water to obtain 100 g of impregnation liquid, mixing the impregnation liquid with 50 g of alumina (20-60 meshes), steaming at 80 ℃ under stirring until no visible liquid exists, drying at 120 ℃ for 12 hours, and roasting at 550 ℃ in an air atmosphere for 5 hours to obtain the catalyst.
The catalyst was evaluated under the following conditions:
a reactor: a fixed bed reactor with an inner diameter of 10 mm;
catalyst loading: 2.0 g;
h in synthesis gas 2 The volume ratio of CO is 1.5;
synthetic gas volumetric space velocity of 2000h -1 ；
The reaction temperature is 350 ℃;
the reaction pressure was 1.5 MPa.
The catalyst composition and the evaluation results are shown in Table 1.
[ example 11 ]
Weighing the equivalent of 50 g of V 2 O 5 MgO, ZnO and MnO 2 Dissolving ammonium metavanadate, magnesium nitrate hexahydrate, zinc nitrate hexahydrate and manganese nitrate (wherein the atomic ratio of V to Mg is 80: 20, the atomic ratio of the sum of the atomic numbers of V and Mg to the atomic ratio of Zn to Mn is 100:20:50) in water to obtain 100 g of impregnation liquid, mixing the impregnation liquid with 50 g of alumina (20-60 meshes), steaming at 80 ℃ under stirring until no visible liquid exists, drying at 120 ℃ for 12 hours, and roasting at 550 ℃ in an air atmosphere for 5 hours to obtain the catalyst.
The catalyst evaluation conditions were as follows:
a reactor: a fixed bed reactor with an inner diameter of 10 mm;
catalyst loading: 2.0 g;
h in synthesis gas 2 The volume ratio of CO is 1.5;
synthetic gas volumetric space velocity of 2000h -1 ；
The reaction temperature is 350 ℃;
the reaction pressure was 1.5 MPa.
The catalyst composition and the evaluation results are shown in Table 1.
[ example 12 ]
Weighing the equivalent of 50 g of V 2 O 5 MgO, ZnO and Ce 2 O 3 Dissolving ammonium metavanadate, magnesium nitrate hexahydrate, zinc nitrate hexahydrate and cerium nitrate hexahydrate (wherein the atomic ratio of V to Mg is 80: 20, and the atomic ratio of the sum of the atomic numbers of V and Mg to Cu and Ce is 100:50:20) in water to obtain 100 g of impregnation liquid, mixing the impregnation liquid with 50 g of alumina (20-60 meshes), steaming at 80 ℃ under stirring until no visible liquid exists, drying at 120 ℃ for 12 hours, and roasting at 550 ℃ in an air atmosphere for 5 hours to obtain the catalyst.
The catalyst was evaluated under the following conditions:
a reactor: a fixed bed reactor with an inner diameter of 10 mm;
catalyst loading: 2.0 g;
h in synthesis gas 2 CO volume ratio is 1.5;
synthetic gas hourly space velocity of 2000h -1 ；
The reaction temperature is 350 ℃;
the reaction pressure was 1.5 MPa.
The catalyst composition and the evaluation results are shown in Table 1.
[ example 13 ]
Weighing the equivalent of 50 g of V 2 O 5 MgO, and Ce 2 O 3 The ammonium metavanadate, the magnesium nitrate hexahydrate and the cerium nitrate hexahydrate (wherein the atomic ratio of V to Mg is 80: 20, the atomic ratio of the sum of the atomic numbers of V and Mg to Ce is 100:70) are dissolved in water to obtain 100 g of impregnation liquid, the impregnation liquid is mixed with 50 g of alumina (20-60 meshes), the mixture is stirred and steamed at 80 ℃ until no visible liquid exists, the mixture is dried at 120 ℃ for 12 hours, and the mixture is roasted at 550 ℃ for 5 hours to obtain the catalyst.
The catalyst evaluation conditions were as follows:
a reactor: a fixed bed reactor with an inner diameter of 10 mm;
catalyst loading: 2.0 g;
h in synthesis gas 2 CO volume ratio is 1.5;
synthetic gas hourly space velocity of 2000h -1 ；
The reaction temperature is 350 ℃;
the reaction pressure was 1.5 MPa.
The catalyst composition and the evaluation results are shown in Table 1.
[ example 14 ]
Weighing cerous nitrate hexahydrate equivalent to 50 g of CeO, dissolving in water to obtain 100 g of impregnation liquid, mixing the impregnation liquid with 50 g of alumina (20-60 meshes), steaming at 80 ℃ under stirring until no visible liquid exists, drying at 120 ℃ for 12 hours, and roasting at 550 ℃ for 5 hours in an air atmosphere to obtain the catalyst.
The catalyst evaluation conditions were as follows:
a reactor: a fixed bed reactor with an inner diameter of 10 mm;
catalyst loading: 2.0 g;
h in synthesis gas 2 CO volume ratio is 1.5;
synthetic gas volumetric space velocity of 2000h -1 ；
The reaction temperature is 350 ℃;
the reaction pressure was 1.5 MPa.
The catalyst composition and the evaluation results are shown in Table 1.
[ example 15 ] A method for producing a polycarbonate
Weighing the equivalent of 50 g of V 2 O 5 MgO, CuO, ZnO and MnO 2 Dissolving ammonium metavanadate, magnesium nitrate hexahydrate, copper nitrate hexahydrate, zinc nitrate hexahydrate and manganese nitrate (wherein the atomic ratio of V to Mg is 80: 20, and the atomic ratio of the sum of the atomic numbers of V and Mg to Cu, Zn and Mn is 100:10:25:35) in water to obtain 100 g of impregnation liquid, mixing the impregnation liquid with 50 g of alumina (20-60 meshes), steaming at 80 ℃ under stirring until no visible liquid exists, drying at 120 ℃ for 12 hours, and roasting at 550 ℃ in an air atmosphere for 5 hours to obtain the catalyst.
The catalyst evaluation conditions were as follows:
a reactor: a fixed bed reactor with an inner diameter of 10 mm;
catalyst loading: 2.0 g;
h in synthesis gas 2 CO volume ratio is 1.5;
synthetic gas volumetric space velocity of 2000h -1 ；
The reaction temperature is 350 ℃;
the reaction pressure was 1.5 MPa.
The catalyst composition and the evaluation results are shown in Table 1.
[ example 16 ]
Weighing the equivalent of 50 g of V 2 O 5 MgO, CuO, ZnO and MnO 2 Dissolving ammonium metavanadate, magnesium nitrate hexahydrate, copper nitrate hexahydrate, zinc nitrate hexahydrate and manganese nitrate (wherein the atomic ratio of V to Mg is 80: 20, and the atomic ratio of the sum of the atomic numbers of V and Mg to Cu, Zn and Mn is 100:10:25:35) in water to obtain 100 g of impregnation liquid, mixing the impregnation liquid and 50 g of zirconium oxide (20-60 meshes), steaming at 80 ℃ under stirring until no visible liquid exists, drying at 120 ℃ for 12 hours, and roasting at 550 ℃ in an air atmosphere for 5 hours to obtain the catalyst.
The catalyst was evaluated under the following conditions:
a reactor: a fixed bed reactor with an inner diameter of 10 mm;
catalyst loading: 2.0 g;
h in synthesis gas 2 The volume ratio of CO is 1.5;
synthetic gas volumetric space velocity of 2000h -1 ；
The reaction temperature is 350 ℃;
the reaction pressure was 1.5 MPa.
The catalyst composition and the evaluation results are shown in Table 1.
[ example 17 ]
Weighing the equivalent of 50 g of V 2 O 5 MgO, CuO, ZnO and MnO 2 Dissolving ammonium metavanadate, magnesium nitrate hexahydrate, copper nitrate hexahydrate, zinc nitrate hexahydrate and manganese nitrate (wherein the atomic ratio of V to Mg is 80: 20, and the atomic ratio of the sum of the atomic numbers of V and Mg to Cu, Zn and Mn is 100:10:25:35) in water to obtain 100 g of impregnation liquid, and mixing the impregnation liquid with 50 g of aluminum oxide and mixed zirconium oxide (20-60) meshes, wherein Al is contained in the impregnation liquid, and the mixture is mixed with zirconium oxide (20-60) meshes 2 O 3 ：ZrO 2 The weight ratio of (1) to (3) under stirring, steaming at 80 ℃ until no visible liquid exists, drying at 120 ℃ for 12 hours, and roasting at 550 ℃ for 5 hours in an air atmosphere to obtain the catalyst.
The catalyst evaluation conditions were as follows:
a reactor: a fixed bed reactor with an inner diameter of 10 mm;
catalyst loading: 2.0 g;
h in synthesis gas 2 The volume ratio of CO is 1.5;
synthetic gas volumetric space velocity of 2000h -1 ；
The reaction temperature is 350 ℃;
the reaction pressure was 1.5 MPa.
The catalyst composition and the evaluation results are shown in Table 1.
TABLE 1
Figure BDA0001709279710000161

Claims (18)

1. The catalyst for synthesizing the low-carbon olefin by the synthesis gas comprises the following components in percentage by weight:
(1) 10-90% of active components containing V and Mg;
(2) 10-90% of a carrier;
the V-containing active component is represented by the following general formula in terms of atomic ratio: v b Mg c A a O x
Wherein A is at least one selected from Mn, Cu, Zn and Ce;
the value range of a is as follows: 0 to 200 parts by weight;
the value range of b is 60-90 and b + c = 100;
x is the total number of oxygen atoms required to satisfy the valences of the other elements.
2. The catalyst for synthesizing low-carbon olefin by synthesis gas according to claim 1, wherein the carrier is at least one selected from the group consisting of alumina, silica, titania and zirconia.
3. The catalyst for synthesizing light olefins from synthesis gas according to claim 1, wherein the weight content of the carrier is 40-70%.
4. The catalyst for synthesizing light olefins according to claim 1, wherein a has a value ranging from 5 to 150.
5. The catalyst for synthesizing light olefins according to claim 1, wherein a has a value ranging from 20 to 120.
6. A process for preparing a catalyst as claimed in any one of claims 1 to 5, comprising the steps of:
(1) preparing a compound containing active component elements into a solution I;
(2) mixing the solution I with a carrier;
(3) and (4) roasting.
7. The method according to claim 6, wherein a drying step is included after the step (2) and before the step (3).
8. The method according to claim 7, wherein the drying temperature is 80 to 150 ℃.
9. The method according to claim 7, wherein the drying time is 4 to 12 hours.
10. The method according to claim 6, wherein the calcination temperature is 450 to 650 ℃.
11. The method according to claim 6, wherein the calcination is carried out for 2 to 12 hours.
12. The method according to claim 6, wherein the compound of the active component element V is at least one selected from the group consisting of ammonium metavanadate and ammonium vanadate.
13. The preparation process as claimed in claim 6, wherein the compound of the active component element Mg is magnesium nitrate and/or magnesium acetate.
14. The method according to claim 6, wherein the active component element Cu compound is copper nitrate and/or copper acetate.
15. The process according to claim 6, wherein the compound of Mn as an active ingredient is manganese nitrate and/or manganese acetate.
16. The preparation process as claimed in claim 6, wherein the compound of the active component element Zn is zinc nitrate and/or zinc acetate.
17. The method according to claim 6, wherein the compound of Ce is cerium nitrate and/or cerium acetate.
18. The application of the catalyst of any one of claims 1-5 in the reaction of preparing low-carbon olefin from synthesis gas.
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