CN109092292B - Catalyst for preparing low-carbon olefin by CO hydrogenation - Google Patents

Catalyst for preparing low-carbon olefin by CO hydrogenation Download PDF

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CN109092292B
CN109092292B CN201710478219.6A CN201710478219A CN109092292B CN 109092292 B CN109092292 B CN 109092292B CN 201710478219 A CN201710478219 A CN 201710478219A CN 109092292 B CN109092292 B CN 109092292B
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catalyst
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carbon olefin
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CN109092292A (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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    • 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
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/28—Molybdenum
    • 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
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/32—Manganese, technetium or rhenium
    • B01J23/34—Manganese
    • 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
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/885—Molybdenum and 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
    • 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
    • B01J23/8898—Manganese, technetium or rhenium containing also molybdenum
    • 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
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • 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 catalyst for preparing low-carbon olefin by CO hydrogenation, which mainly solves the problem of low catalyst selectivity in the preparation of olefin by CO hydrogenation. (1) 20-80% of Mo-containing active component; (2) the technical scheme of 20-80% of the carrier well solves the problem, and can be used for industrial application of preparing low-carbon olefin by CO hydrogenation.

Description

Catalyst for preparing low-carbon olefin by CO hydrogenation
Technical Field
The invention relates to a catalyst for preparing low-carbon olefin by CO hydrogenation and a using method thereof.
Background
The 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 the majority, and alkane, hydrogenated diesel oil, part of heavy oil and the like are also used. 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 uses synthesis gas (with the 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. However, the great reduction of the oil price in the world in 1986 postpones the large-scale industrialization process of the F-T synthesis technology in other countries. 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 synthetic processes are classified into two main categories from the viewpoint of synthetic conditions: a high temperature Fischer-Tropsch synthesis process and a low temperature Fischer-Tropsch synthesis process; the synthesis processes being classified differently from the reactor usedThe words fall into three main categories: fixed bed fischer-tropsch synthesis processes, fluidised bed fischer-tropsch synthesis processes (with an earlier circulating fluidised bed and a later fixed fluidised bed developed on the basis of a circulating fluidised bed) and slurry bed fischer-tropsch synthesis processes. The fixed bed and the slurry bed are generally applied to a low-temperature Fischer-Tropsch process and are mainly used for producing heavy oil and wax, and the fluidized bed is more suitable for a 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 become a concern.
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 H2Reaction for producing hydrocarbons, by-product water and CO2The SASO L (South Africa Coal and Gas Corporation) in South Africa in 1955 is built into a large fixed bed F-T synthesis device taking Coal as raw material, then a circulating fluidized bed technology is developed, and a fixed fluidized bed and a slurry bed technology are developed recently, nowadays, the annual treatment capacity of Coal of SASO L reaches 5000 ten thousand, the annual capacity of oil products and chemicals reaches 760 ten thousand tons, the past Fischer-Tropsch synthesis reaction aims at synthesizing liquid hydrocarbons for fuel from synthesis Gas, although the yield of low carbon olefins (C2-C4 olefins) is improved to a certain extent by the fluidized bed technology, the use of iron-based catalysts and the addition of auxiliaries, the yield of the low carbon olefins is still 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) Improved fischer-tropsch catalyst Dent et al found cobalt-based catalystsCan be used for synthesizing low-carbon olefin with high selectivity, such as: Co-Cu/Al2O3、Co-Fe/SiO2、Fe-Co/C、Co-Ni/MnO2And Fe-Co alloy systems. Among these, the improved FT catalyst developed by the luer chemical company gave better results in Fe-ZnO-K2Mn 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 and the like obtain the activated carbon supported high-dispersion K-Fe-Mn catalyst by a carbonyl complex decomposition method, the catalyst has high activity, and C in the product2-C4Olefins account for 85-90% and methane is the only other product detected. Cupta et al, using laser pyrolysis, produce catalytically active FexSiyCzEqual powder CO conversion of 40%, C2 ＝-C4 ＝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 is2 ＝-C4 ＝/C2-C4Greater than 80%. 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 reaction3C. Preparation of Fe3The 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 synthetic catalyst Yokoyama et al uses amorphous Fe40Ni40P16B4Compound, CO conversion 50%, C2-C5The hydrocarbon selectivity was 65%, while the crystalline catalyst produced predominantly methane; (4) the zeolite catalyst is represented by Co-A, Co-Y, Fe-Y and other catalysts, the high-dispersion iron catalyst carried by the zeolite prepared by Ballvet-Tketchenko et al has quite high selectivity of low-carbon olefin, and 88-98 percent of the low-carbon olefin is in C2-C4Other iron catalysts such as ZSM-5, mordenite, zeolite 13X supported iron catalysts also showed similar behavior in the range.
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, 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, and therefore, 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) by CO hydrogenation in the prior art, and the catalyst for preparing low-carbon olefin by CO hydrogenation is provided and has good low-carbon olefin selectivity when used for preparing low-carbon olefin by CO hydrogenation.
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 above technical problems, the technical scheme adopted by the invention is as follows: the catalyst for preparing the low-carbon olefin by CO hydrogenation comprises the following components in percentage by weight:
(1) 10-90% of Mo-containing active component;
(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.
In the above technical solution, the carrier more preferably comprises a mixture of alumina and zirconia, and the alumina and zirconia have a synergistic effect in improving the selectivity of the low-carbon olefin.
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, but the content of the carrier is preferably 40 to 70%.
The catalyst component of the present invention is free of group VIII elements such as, but not limited to, Fe, Co, Ni, and the like.
In the above technical solution, preferably, the Mo-containing active component may be represented by the following general formula in terms of atomic ratio: mo100AaOx。
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;
x is the total number of oxygen atoms required to satisfy the valences of the other elements.
In the technical scheme, a is preferably more than 0 and less than 200, and the value range of a is more preferably 5-150; most preferably, the value range of a is 20-120. Mo 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 preferable technical solutions, at this time, the following two elements have a synergistic effect in improving the selectivity of the low-carbon olefin:
a simultaneously comprises Cu and Mn, the mutual proportion of the two elements is not particularly limited, for example but not limited to, the atomic ratio of Mn to Cu 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;
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.
Of the above-mentioned embodiments, a is the most preferable embodiment, and includes Cu, Zn and Mn at the same time, and the mutual ratio of these 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.
To solve the second technical problem of the present invention, the technical solution of the present invention is as follows:
the method for preparing the catalyst according to any of the preceding technical solutions, 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.
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 compound that can be used to provide the active component element Mo may be, for example, but not limited to, ammonium paramolybdate, ammonium molybdate, molybdenum acetate, and the like.
In the above technical solution, the compound that can be used to provide the active component element Cu can be, for example, but not limited to, copper nitrate, copper acetate, and the like.
In the above technical solution, the compound that can be used to provide the active component element Mn may be, for example, but not limited to, manganese nitrate, manganese acetate, and the like.
In the above technical solution, the compound that can be used to provide the active component element Zn may be, for example, but not limited to, zinc nitrate, zinc acetate, and the like.
In the above technical solution, the compound that can be used to provide the active component element Ce may be, for example, but not limited to, cerium nitrate, cerium acetate, and the like.
In the above technical solutions, the solvent used for the solution is not particularly limited as long as it can dissolve the compound containing the active ingredient element to obtain the solution, and a person skilled in the art can reasonably select the solvent according to the dissolution property of the compound containing the active ingredient element. However, water is preferred as the solvent from the viewpoint of economy and safety.
In the above technical solution, the specific manner of mixing the solution I and the carrier in the step (2) is not particularly limited, the volume ratio between the solution I and the carrier is also not particularly limited, and the geometric shape and size of the carrier are not particularly limited, and can be reasonably selected by those skilled in the art, and all the solutions can achieve comparable technical effects of the present invention. Such as but not limited to dipping, rotary evaporation, spraying, sol-gel, and the like.
In the above technical solutions, 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 in order to obtain a more uniform distribution of the active components and a higher strength of the obtained catalyst, a drying step may be performed before calcination.
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.
In the above technical solutions, the temperature for evaporation is not particularly limited, and those skilled in the art can reasonably select the temperature, for example, but not limited to, from 60 ℃ to below the boiling temperature 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 to 150 ℃, and specific non-limiting examples of the temperature range include 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, and the like. The drying time is, for example, but not limited to, 4 to 12 hours, and non-limiting examples thereof include 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, and the like.
In the above-mentioned embodiment, although the atmosphere for calcination is not particularly limited, an atmosphere containing oxygen is usually used, and for economic reasons, air is usually used as the atmosphere for calcination.
In the above technical solution, the baking temperature is preferably 450 to 650 ℃, and non-limiting specific examples in this interval may be 500 ℃, 550 ℃, 600 ℃, and the like.
In the above technical solution, the time for the calcination is preferably 2 to 12 hours, and 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.
To solve the third technical problem, the technical scheme of the invention is as follows:
the application of the catalyst in the technical scheme of one of the technical problems in the reaction for preparing the low-carbon olefin by CO hydrogenation.
The specific application method can be as follows:
the reaction method for preparing the low-carbon olefin by CO hydrogenation comprises the step of carrying out contact reaction on 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 scheme, the reaction pressure is preferably 0.5 to 2.5MPa, and non-limiting examples in the range can 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 total gas volume space velocity of CO and hydrogen is preferably 1000-4000h-1A non-limiting example in this range may be 1500h-1、2000h-1、2500h-1、3000h-1、3500h-1And so on.
In the above technical scheme, H in the synthesis gas2The 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
H2The volume ratio of CO is 1.5;
total gas volume space velocity of CO and hydrogen of 2000h-1；
The reaction temperature is 350 ℃;
the reaction pressure was 1.5 MPa.
C2-C4The olefin selectivity calculation is as follows:
Figure BDA0001327649370000071
the catalyst prepared by the method has the advantages of 300-450 ℃, 0.5-2.5MPa, and 1000-4000h of volume space velocity-1Under the conditions of (1), CO conversion>50％，C2-C4Olefin selectivity>55%, and a better technical effect is achieved.
The invention is further illustrated by the following examples.
Detailed Description
[ example 1 ]
Weighing an amount of 50 g of MoO3Dissolving ammonium paramolybdate 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 composition and the evaluation results are shown in Table 1.
[ example 2 ]
Weighing an amount of 50 g of MoO3And MnO2Ammonium paramolybdate and manganese nitrate (wherein the atomic ratio of Mo to Mn is 100:70)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 ℃ in air atmosphere for 5 hours to obtain the catalyst.
The catalyst composition and the evaluation results are shown in Table 1.
[ COMPARATIVE EXAMPLE 1 ]
Weighing the equivalent of 50 g MnO2Dissolving 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 composition and the evaluation results are shown in Table 1.
[ example 3 ]
Weighing an amount of 50 g of MoO3And CuO ammonium paramolybdate and copper nitrate hexahydrate (wherein the atomic ratio of Mo to Cu 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 evaporated at 80 ℃ until no liquid is visible, 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 composition and the evaluation results are shown in Table 1.
[ COMPARATIVE EXAMPLE 2 ]
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 composition and the evaluation results are shown in Table 1.
[ example 4 ]
Weighing an amount of 50 g of MoO3And dissolving ammonium paramolybdate of ZnO and zinc nitrate hexahydrate (wherein the atomic ratio of Mo to Zn is 100:70) in water to obtain 100 g of impregnation liquid, mixing the impregnation liquid and 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 composition and the evaluation results are shown in Table 1.
[ COMPARATIVE EXAMPLE 3 ]
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 composition and the evaluation results are shown in Table 1.
[ example 5 ]
Weighing an amount of 50 g of MoO3CuO and MnO2Dissolving ammonium paramolybdate, copper nitrate hexahydrate and manganese nitrate (wherein the atomic ratio of Mo to Cu to Mn is 100:30:40) in water to obtain 100 g of impregnation liquid, mixing the impregnation liquid and 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 composition and the evaluation results are shown in Table 1.
[ example 6 ]
Weighing an amount of 50 g of MoO3ZnO and MnO2Dissolving ammonium paramolybdate, zinc nitrate hexahydrate and manganese nitrate (wherein the atomic ratio of Mo to Zn to Mn is 100:20:50) in water to obtain 100 g of impregnation liquid, mixing the impregnation liquid and 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 composition and the evaluation results are shown in Table 1.
[ example 7 ]
Weighing an amount of 50 g of MoO3ZnO and Ce2O3Dissolving ammonium paramolybdate, zinc nitrate hexahydrate and cerium nitrate hexahydrate (wherein the atomic ratio of Mo to Cu to Ce is 100:50:20) in water to obtain 100 g of impregnation liquid, mixing the impregnation liquid and 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 composition and the evaluation results are shown in Table 1.
[ example 8 ]
Weighing an amount of 50 g of MoO3And Ce2O3Dissolving ammonium paramolybdate and cerous nitrate hexahydrate (wherein the atomic ratio of Mo to Ce is 100:70) in water to obtain 100 g of impregnation liquid, mixing the impregnation liquid and 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 composition and the evaluation results are shown in Table 1.
[ COMPARATIVE EXAMPLE 4 ]
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 composition and the evaluation results are shown in Table 1.
[ example 9 ]
Weighing an amount of 50 g of MoO3CuO, ZnO and MnO2Dissolving ammonium paramolybdate, copper nitrate hexahydrate, zinc nitrate hexahydrate and manganese nitrate (wherein the atomic ratio of Mo: Cu: Zn: Mn is 100:10:25:35) in water to obtain 100 g of impregnation liquid, mixing the impregnation liquid and 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 composition and the evaluation results are shown in Table 1.
[ example 10 ]
Weighing an amount of 50 g of MoO3CuO, ZnO and MnO2Dissolving ammonium paramolybdate, copper nitrate hexahydrate, zinc nitrate hexahydrate and manganese nitrate (wherein the atomic ratio of Mo: Cu: Zn: 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 composition and the evaluation results are shown in Table 1.
[ example 11 ]
Weighing an amount of 50 g of MoO3CuO, ZnO and MnO2Dissolving ammonium paramolybdate, copper nitrate hexahydrate, zinc nitrate hexahydrate and manganese nitrate (wherein the atomic ratio of Mo: Cu: Zn: Mn is 100:10:25:35) in water to obtain 100 g of impregnation liquid, and mixing the impregnation liquid with 50 g of alumina and mixture zirconia (20-60 meshes, wherein Al is contained in the mixture)2O3：ZrO2The 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 composition and the evaluation results are shown in Table 1.
TABLE 1
Figure BDA0001327649370000111

Claims (4)

  1. The reaction method for preparing the low-carbon olefin by CO hydrogenation comprises the following steps of carrying out contact reaction on synthesis gas and a catalyst for preparing the low-carbon olefin by CO hydrogenation to generate the low-carbon olefin, wherein the catalyst for preparing the low-carbon olefin by CO hydrogenation comprises the following components in percentage by weight:
    (1) 10-90% of Mo-containing active component;
    (2) 10-90% of a carrier, wherein the Mo-containing active component is represented by the following general formula in terms of atomic ratio: mo100AaOx
    Wherein A is at least one selected from Mn, Cu, Zn and Ce;
    the value range of a is as follows: 20-120;
    x is the total number of oxygen atoms required to satisfy the valences of the other elements.
  2. 2. The reaction method according to claim 1, wherein the support is at least one selected from the group consisting of alumina, silica, titania and zirconia.
  3. 3. The reaction process of claim 1, wherein the carrier is present in an amount of 40 to 70% by weight.
  4. 4. The reaction method of any one of claims 1 to 3, wherein the preparation method of the catalyst for preparing the low-carbon olefin by CO hydrogenation 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.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1314206A (en) * 2000-03-22 2001-09-26 中国科学院大连化学物理研究所 Metal oxide catalyst for clearing halogenated aromatic through catalytic oxidation
CN1522178A (en) * 2001-05-08 2004-08-18 �յ�-��ѧ��˾ High surface area, small crystallite size catalyst for fischer-tropsch synthesis
CN104549343A (en) * 2013-10-28 2015-04-29 中国石油化工股份有限公司 Catalyst for preparing low-carbon olefin from synthesis gas as well as preparation method and application of catalyst

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1314206A (en) * 2000-03-22 2001-09-26 中国科学院大连化学物理研究所 Metal oxide catalyst for clearing halogenated aromatic through catalytic oxidation
CN1522178A (en) * 2001-05-08 2004-08-18 �յ�-��ѧ��˾ High surface area, small crystallite size catalyst for fischer-tropsch synthesis
CN104549343A (en) * 2013-10-28 2015-04-29 中国石油化工股份有限公司 Catalyst for preparing low-carbon olefin from synthesis gas as well as preparation method and application of catalyst

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