CN112588315B - Chromium-based metal oxide-molecular sieve catalyst and preparation method and application thereof - Google Patents
Chromium-based metal oxide-molecular sieve catalyst and preparation method and application thereof Download PDFInfo
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- 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
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- C07C2529/82—Phosphates
- C07C2529/84—Aluminophosphates containing other elements, e.g. metals, boron
- C07C2529/85—Silicoaluminophosphates (SAPO compounds)
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Abstract
The invention provides a chromium-based metal oxide-molecular sieve catalyst, which comprises a chromium-based metal oxide and an H-SAPO-34 molecular sieve; the chemical formula of the chromium-based metal oxide is CraMbOc(ii) a A to c represent the relative substance amount of each element, and the total valence of the chromium-based metal oxide is zero; and M is one or more of zinc, indium, aluminum and zirconium. The invention takes H-SAPO-34 molecular sieve as a matrix and takes chromium-based metal oxide as an active component to prepare the composite catalyst for CO2The hydrogenation is carried out to prepare the ethylene, and the selectivity of the ethylene can be obviously improved. The results of the examples show that the chromium-based metal oxide-molecular sieve catalyst provided by the present invention is used for CO2Hydrogenation to ethylene, CO2The conversion of (a) was 12.7%, the selectivity of total lower olefins was 95.9%, and the selectivity of ethylene was 66.4%.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a chromium-based metal oxide-molecular sieve catalyst and a preparation method and application thereof.
Background
The rapid consumption of fossil energy induces CO2Resulting in serious environmental problems and global warming. Introducing CO2The high value-added chemical raw materials such as methanol, formic acid, methane, low-carbon olefin, aromatic hydrocarbon and the like are prepared by conversion, and not only can the CO in the atmosphere be reduced2The content of the (D) also provides a new idea for the preparation of clean energy. It is composed ofMedium, low carbon olefin (C)2 ＝–C4 ＝) Including ethylene, propylene and butylene, as important basic raw materials in the chemical industry, have attracted the interest of a large number of researchers, while ethylene has a higher economic value than propylene and butylene and has a large market demand in the modern chemical industry. Thus, a sustainable direct conversion of CO was developed2The new route for preparing ethylene has important strategic significance.
In the prior art, CO2The preparation of the low-carbon olefin by hydrogenation mainly comprises two reaction routes: the Fischer-Tropsch synthesis (Fischer-Tropsch synthesis) route and the Methanol-based intermediate synthesis (Methanol-intermediate) route. In the Fischer-Tropsch synthesis route, Fe-based, Co-based or Rh-based catalysts are typically employed, although higher CO is exhibited2Conversion rate, but selectivity of low carbon olefin is generally lower than 58% due to limitation of Anderson-Schultz-Flory (ASF) rule, wherein C2The selectivity to hydrocarbons (including ethylene and ethane) is less than 30%. ZnZrO prepared based on methanol intermediate routex/SAPO-34、ZnAl2O4/SAPO-34、ZnGa2O4/SAPO-34、In2O3SAPO-34 and InZrOxSAPO-34, etc. bifunctional catalyst in CO2In the reaction of preparing olefin by hydrogenation, the ASF regulation limit can be effectively broken through, and the C is greatly improved2 ＝–C4 ＝Olefin selectivity, but the problem of low ethylene selectivity still remains. For example, there are studies (Gao P, Dang S, Li S, et al direct Production of lower alcohols from CO2conversion via bifunctional catalysis[J]ACSCatal, 2018, 8, 571-2O3CO catalyzed by/H-SAPO-34 composite catalyst2The selectivity of low-carbon olefin in total hydrocarbon can reach 80% through hydrogenation reaction, but the selectivity of ethylene is lower than 35%; study (Liu X, Wang M, Yin H, et al. tandem analysis for hydrogenation of CO and CO)2to lower olefins with bifunctional catalysts composed of spinel oxide and SAPO-34[J].ACS Catal，2020，10，8303-8314；Liu Xiaoliang，Wang Ye et al.Selective transformation of carbon dioxide into lower olefins with a bifunctional catalyst composed of ZnGa2O4and SAPO-34[J]Commun, 2018, 54, 140-2O4SAPO-34 and ZnGa2O4SAPO-34 two catalysts in CO2In the olefin preparation by hydrogenation, the selectivity of low-carbon olefin in total hydrocarbon reaches 80-87%, but the selectivity of ethylene is still lower than 30%.
Disclosure of Invention
The invention aims to provide a chromium-based metal oxide-molecular sieve catalyst, and a preparation method and application thereof2In the preparation of ethylene by hydrogenation, the selectivity of ethylene can be obviously improved.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a chromium-based metal oxide-molecular sieve catalyst, which comprises a chromium-based metal oxide and an H-SAPO-34 molecular sieve; the chemical formula of the chromium-based metal oxide is CraMbOc(ii) a A to c represent the relative substance amount of each element, and the total valence of the chromium-based metal oxide is zero; and M is one or more of zinc, indium, aluminum and zirconium.
Preferably, the ratio of the amounts of species of Cr and M in the chromium-based metal oxide, a: b is 1: (0 to 0.5).
Preferably, the mass ratio of the chromium-based metal oxide to the H-SAPO-34 molecular sieve is (0.2-5): 1.
preferably, the Si/Al ratio of the H-SAPO-34 molecular sieve is 0.01-0.5.
Preferably, the particle size of the chromium-based metal oxide-molecular sieve catalyst is 10-60 meshes.
The invention provides a preparation method of the chromium-based metal oxide-molecular sieve catalyst in the technical scheme, which comprises the following steps:
(1) mixing water-soluble chromium salt, water-soluble M salt and water to obtain chromium-based composite metal ion salt solution;
(2) mixing the chromium-based composite metal ion salt solution obtained in the step (1) with a complexing agent or a precipitating agent, and carrying out a complexing reaction or a precipitation reaction to obtain a chromium-based metal oxide precursor;
(3) roasting the chromium-based metal oxide precursor obtained in the step (2) to obtain chromium-based metal oxide;
(4) and (4) mixing the chromium-based metal oxide obtained in the step (3) with an H-SAPO-34 molecular sieve to obtain the chromium-based metal oxide-molecular sieve catalyst.
Preferably, the ratio of the total metal ions in the chromium-based composite metal ion salt solution in the step (2) to the amount of the complexing agent or precipitant is 1: (0.5-5).
Preferably, the temperature of the complexation reaction and the precipitation reaction in the step (2) is 60-90 ℃ independently, and the time of the complexation reaction and the precipitation reaction is 3-8 h independently.
Preferably, the roasting temperature in the step (3) is 350-700 ℃, and the roasting time is 4-10 h.
The invention also provides the chromium-based metal oxide-molecular sieve catalyst prepared by the technical scheme or the chromium-based metal oxide-molecular sieve catalyst prepared by the preparation method in the technical scheme in CO2Application in the preparation of ethylene by hydrogenation.
The invention provides a chromium-based metal oxide-molecular sieve catalyst, which comprises a chromium-based metal oxide and an H-SAPO-34 molecular sieve; the chemical formula of the chromium-based metal oxide is CraMbOc(ii) a A to c represent the relative substance amount of each element, and the total valence of the chromium-based metal oxide is zero; and M is one or more of zinc, indium, aluminum and zirconium. The invention takes H-SAPO-34 molecular sieve as a matrix and takes chromium-based metal oxide as an active component to prepare the composite catalyst for CO2The hydrogenation is used for preparing ethylene, so that the selectivity of the ethylene can be obviously improved; the H-SAPO-34 molecular sieve has an eight-membered ring pore structure, is favorable for limiting the generation of long-chain hydrocarbons, and can slow down secondary reactions such as methylation, hydrogenation and the like due to the lower acid strength, so that the selectivity of ethylene is improved; the chromium-based metal oxide is effective in promoting CO2The adsorption and activation of the catalyst can simultaneously form methanol and ethanol intermediates, which is beneficial to improving the selectivity of ethylene. The results of the examples show that the chromium-based metal oxide-molecular sieve catalyst provided by the present invention is used for CO2Hydrogenation to ethylene, CO2The conversion of (a) was 12.7%, the selectivity of total lower olefins was 95.9%, and the selectivity of ethylene was 66.4%.
The preparation method of the chromium-based metal oxide-molecular sieve catalyst provided by the invention is simple to operate, low in cost, free of secondary pollution and suitable for industrial production.
Drawings
FIG. 1 is an XRD spectrum of a chromium-based metal oxide prepared in example 1 of the present invention;
FIG. 2 shows the preparation of a chromium-based metal oxide-molecular sieve catalyst in CO according to example 1 of the present invention2CH in reaction for preparing ethylene by hydrogenation4、C2 0-C4 0、C2 ＝-C4 ＝、C5 +Selectivity of oxygenates and CO2Graph of the conversion over time;
FIG. 3 shows the preparation of a chromium-based metal oxide-molecular sieve catalyst in CO according to example 1 of the present invention2C in reaction of preparing ethylene by hydrogenation2 ＝～C5 ＝And C2 ＝/C3 ＝The ratio is plotted against time.
Detailed Description
The invention provides a chromium-based metal oxide-molecular sieve catalyst, which comprises a chromium-based metal oxide and an H-SAPO-34 molecular sieve; the chemical formula of the chromium-based metal oxide is CraMbOc(ii) a A to c represent the relative substance amount of each element, and the total valence of the chromium-based metal oxide is zero; and M is one or more of zinc, indium, aluminum and zirconium. The invention takes chromium-based metal oxide as an active component to form a chromium-based metal oxide-molecular sieve catalyst with H-SAPO-34 molecular sieve, and the catalyst is used for CO2Hydrogenation to ethylene reaction, canThe selectivity of ethylene is obviously improved.
The chromium-based metal oxide-molecular sieve catalyst provided by the invention comprises chromium-based metal oxide, wherein the chemical formula of the chromium-based metal oxide is CraMbOc(ii) a A to c represent the relative substance amount of each element, and the total valence of the chromium-based metal oxide is zero; and M is one or more of zinc, indium, aluminum and zirconium. The invention takes chromium-based metal oxide as an active component, and can effectively promote CO2The adsorption and activation of the catalyst can simultaneously form methanol and ethanol intermediates, which is beneficial to improving the selectivity of ethylene.
In the present invention, the Cr isaMbOcIn the conventional method for expressing the metal oxide component in the field, the relative amounts of the elements are expressed by a to c, so that the total valence of the chromium-based metal oxide is zero.
In the invention, M is one or more of zinc, indium, aluminum and zirconium, preferably one or more of zinc, indium and zirconium.
In the present invention, the ratio of the amounts of substances of Cr and M in the chromium-based metal oxide, a: b is preferably 1: (0 to 0.5), more preferably 1: (0 to 0.1). In the present invention, the ratio of the amounts of the Cr and M is controlled within the above range, which is advantageous for improving the activity of the catalyst.
In the present invention, the Cr isaMbOcPreferably Cr2O3、Cr2.0Zn0.2O3.2、Cr2.0In0.2O3.3、Cr2.0Al0.2O3.3Or Cr2.0Zr0.2O3.4More preferably Cr2O3、Cr2.0Zn0.2O3.2、Cr2.0In0.2O3.3Or Cr2.0Zr0.2O3.4Most preferably Cr2O3。
The chromium-based metal oxide-molecular sieve catalyst provided by the invention also comprises an H-SAPO-34 molecular sieve. The source of the H-SAPO-34 molecular sieve is not particularly limited in the invention, and commercially available products well known to those skilled in the art can be used. The H-SAPO-34 molecular sieve is used as a matrix material, has an eight-membered ring pore structure, is favorable for limiting the generation of long-chain hydrocarbons, and can slow down secondary reactions such as methylation and hydrogenation due to low acid strength, thereby being favorable for improving the selectivity of ethylene.
In the invention, the mass ratio of the chromium-based metal oxide to the H-SAPO-34 molecular sieve is preferably (0.2-5): 1, more preferably (0.25-4): 1, and most preferably (0.5-2): 1. The invention controls the mass ratio of the chromium-based metal oxide to the H-SAPO-34 molecular sieve in the range, is favorable for improving the activity of the catalyst, and the mass of the chromium-based metal oxide is too low, so that the catalyst activates CO2The capability is reduced, and CO is reduced2The conversion rate and the quality of the molecular sieve are too low, the number of acid sites is reduced, and the conversion of a methanol intermediate to generate olefin is not facilitated.
In the invention, the Si/Al ratio of the H-SAPO-34 molecular sieve is preferably 0.01-0.5, and more preferably 0.02-0.2. In the invention, the silica-alumina ratio of the H-SAPO-34 molecular sieve is too low, the acid content is less, and the conversion of a methanol intermediate to generate olefin is not facilitated; and the H-SAPO-34 molecular sieve has too high silica-alumina ratio and too much acid, which can cause secondary reactions such as methylation, cracking, hydrogenation and the like, and reduce the selectivity of a target product.
In the invention, the particle size of the chromium-based metal oxide-molecular sieve catalyst is preferably 10-60 meshes, more preferably 20-50 meshes, and most preferably 30-40 meshes. In the present invention, the particle size of the catalyst is preferably controlled within the above range, which is advantageous for the full exertion of the catalytic performance of the catalyst.
The chromium-based metal oxide-molecular sieve catalyst provided by the invention takes H-SAPO-34 molecular sieve as a matrix and chromium-based metal oxide as an active component, and is used for CO2The hydrogenation is carried out to prepare the ethylene, and the selectivity of the ethylene can be obviously improved.
The invention provides a preparation method of the chromium-based metal oxide-molecular sieve catalyst in the technical scheme, which comprises the following steps:
(1) mixing water-soluble chromium salt, water-soluble M salt and water to obtain chromium-based composite metal ion salt solution;
(2) mixing the chromium-based composite metal ion salt solution obtained in the step (1) with a complexing agent or a precipitating agent, and carrying out a complexing reaction or a precipitation reaction to obtain a chromium-based metal oxide precursor;
(3) roasting the chromium-based metal oxide precursor obtained in the step (2) to obtain chromium-based metal oxide;
(4) and (4) mixing the chromium-based metal oxide obtained in the step (3) with an H-SAPO-34 molecular sieve to obtain the chromium-based metal oxide-molecular sieve catalyst.
The invention mixes water-soluble chromium salt, water-soluble M salt and water to obtain chromium-based composite metal ion salt solution.
In the present invention, the water-soluble metal chromium salt preferably includes chromium nitrate, chromium chloride or chromium sulfate, more preferably chromium nitrate; the water-soluble M salt preferably comprises one or more of water-soluble zinc salt, water-soluble indium salt, water-soluble aluminum salt and water-soluble zirconium salt, and more preferably comprises one or more of water-soluble zinc salt, water-soluble indium salt and water-soluble zirconium salt.
In the present invention, the water-soluble zinc salt preferably includes zinc nitrate, zinc chloride or zinc sulfate, more preferably zinc nitrate; the water-soluble indium salt preferably comprises indium nitrate, indium chloride or indium sulfate, more preferably indium nitrate; the water-soluble aluminum salt preferably comprises aluminum nitrate, aluminum chloride or aluminum sulfate, more preferably aluminum nitrate; the water-soluble zirconium salt preferably comprises zirconium nitrate, zirconium chloride or zirconium sulfate, more preferably zirconium nitrate.
In the present invention, the water is preferably deionized water.
The operation of mixing the water-soluble chromium salt, the water-soluble M salt and water is not particularly limited in the invention, and the technical scheme for preparing the mixed solution, which is well known to those skilled in the art, can be adopted.
In the invention, the concentration of chromium ions in the chromium-based composite metal ion salt solution is preferably 0.01-1.5 mol/L, more preferably 0.1-0.8 mol/L, and most preferably 0.2-0.5 mol/L; the concentration of M ions in the chromium-based composite metal ion salt solution is preferably 0-0.2 mol/L, more preferably 0-0.1 mol/L, and most preferably 0-0.05 mol/L.
After the chromium-based composite metal ion salt solution is obtained, the chromium-based composite metal ion salt solution is mixed with a complexing agent or a precipitating agent to carry out a complexing reaction or a precipitation reaction, so as to obtain a chromium-based metal oxide precursor.
In the present invention, the complexing agent preferably includes one or more of glucose, citric acid, tartaric acid, salicylic acid and adipic acid, and more preferably glucose. When the number of the complexing agents is two or more, the mass ratio of the complexing agents is not particularly limited, and the complexing agents can be added in any proportion.
In the present invention, the precipitant preferably includes one or more of a water-soluble carbonate and a water-soluble bicarbonate. In the present invention, the water-soluble carbonate preferably includes one or more of ammonium carbonate, sodium carbonate, lithium carbonate and potassium carbonate, more preferably ammonium carbonate; the water-soluble bicarbonate preferably comprises one or more of ammonium bicarbonate, sodium bicarbonate, lithium bicarbonate and potassium bicarbonate, and more preferably ammonium bicarbonate. When the number of the precipitating agents is two or more, the mass ratio of the precipitating agents is not particularly limited, and the precipitating agents may be added in any ratio.
In the present invention, the precipitant is preferably added in the form of an aqueous precipitant solution. In the invention, the concentration of the precipitant aqueous solution is preferably 0.4-6.0 mol/L, and more preferably 0.5-3.0 mol/L.
In the present invention, the ratio of the total metal ions in the chromium-based composite metal ion salt solution to the amount of the substance of the complexing agent or the precipitating agent is preferably 1: (0.5 to 5), more preferably 1: (2-4). The invention preferably controls the ratio of the total metal ions in the chromium-based composite metal ion salt solution to the amount of the complexing agent or the precipitating agent within the range, thereby ensuring the full reaction and not wasting raw materials.
In the invention, the temperature of the complexation reaction and the precipitation reaction is preferably 60-90 ℃ independently, and more preferably 65-85 ℃; the time of the complexation reaction and the precipitation reaction is preferably 3-8 h independently, and more preferably 4-7 h independently.
After the complex reaction is completed, the invention preferably dries the product obtained after the complex reaction is completed to obtain the chromium-based metal oxide precursor. In the invention, the drying temperature is preferably 80-120 ℃, more preferably 90-110 ℃, and most preferably 100 ℃; the drying time is preferably 3-12 h, more preferably 4-10 h, and most preferably 5-8 h; the means for drying is preferably an oven.
After the precipitation reaction is finished, the invention preferably washes, centrifuges and dries the product obtained after the precipitation reaction is finished in sequence to obtain the chromium-based metal oxide precursor. The washing, centrifuging and drying operations are not particularly limited in the present invention, and washing, centrifuging and drying techniques well known to those skilled in the art may be used. In the present invention, the washing detergent is preferably water; the number of washing is preferably 3 to 6, more preferably 4 to 5. In the invention, the drying temperature is preferably 80-120 ℃, more preferably 90-110 ℃, and most preferably 100 ℃; the drying time is preferably 3-12 h, more preferably 4-10 h, and most preferably 5-8 h.
After obtaining the chromium-based metal oxide precursor, the invention roasts the chromium-based metal oxide precursor to obtain the chromium-based metal oxide.
In the invention, the roasting temperature is preferably 350-700 ℃, more preferably 400-650 ℃, and most preferably 500-600 ℃; the roasting time is preferably 4-10 hours, more preferably 5-9 hours, and most preferably 6-8 hours; the roasting atmosphere is preferably air; the means for calcining is preferably a muffle furnace.
After the chromium-based metal oxide is obtained, the chromium-based metal oxide is mixed with the H-SAPO-34 molecular sieve to obtain the chromium-based metal oxide-molecular sieve catalyst.
In the invention, the mass ratio of the chromium-based metal oxide to the H-SAPO-34 molecular sieve is preferably (0.2-5): 1, more preferably (0.25-4): 1, and most preferably (0.5-2): 1.
In the present invention, the mixing manner of the chromium-based metal oxide and the H-SAPO-34 molecular sieve is preferably grinding. The grinding mode is not particularly limited in the present invention, and the grinding method known to those skilled in the art can be used. In an embodiment of the invention, the grinding is preferably mechanical grinding.
After the chromium-based metal oxide and the H-SAPO-34 molecular sieve are mixed, the mixed product is preferably subjected to tabletting, crushing and screening in sequence to obtain the chromium-based metal oxide-molecular sieve catalyst. The tabletting, crushing and sieving operations are not particularly limited in the present invention, and the technical solutions of tabletting, crushing and sieving known to those skilled in the art can be adopted. In the present invention, the pressure of the tablet is preferably 15.0 MPa.
The preparation method of the chromium-based metal oxide-molecular sieve catalyst provided by the invention is simple to operate, has no secondary pollution, and is suitable for industrial production.
The invention also provides the technical scheme that the chromium-based metal oxide-molecular sieve catalyst is applied to CO2Application in the preparation of ethylene by hydrogenation.
In the present invention, the chromium-based metal oxide-molecular sieve catalyst is applied to CO as a catalyst2In the preparation of ethylene by hydrogenation. In the present invention, the chromium-based metal oxide-molecular sieve catalyst is used in CO2The use in the hydrogenation of ethylene preferably comprises the following steps: reducing the chromium-based metal oxide-molecular sieve catalyst, and mixing the reduced chromium-based metal oxide-molecular sieve catalyst with CO2、H2Mixing, and carrying out hydrogenation reaction to obtain the low-carbon olefin.
In the invention, the temperature of the reduction treatment is preferably 350-450 ℃, and more preferably 400 ℃; the time of the reduction treatment is preferably 1-4 h, and more preferably 2-3 h; the reducing agent for the reduction treatment is preferably hydrogen gas.
In the present invention, said H2And CO2The volume ratio of (1-8): 1 is preferable, the ratio of (2-4): 1 is more preferable, and the ratio of (3): 1 is most preferable. In the present invention, said H2And CO2The space velocity of the mixed gas (c) is preferably 800 to 10000 mL/(h.g), more preferably 1200 to 5000 mL/(h.g), and most preferably 2000 to E4000mL/(h·g)。
In the invention, the temperature of the hydrogenation reaction is preferably 300-400 ℃, more preferably 340-380 ℃, and most preferably 350-370 ℃; the pressure of the hydrogenation reaction is preferably 0.1-3 MPa; more preferably 0.3 to 1.0MPa, most preferably 0.5 to 0.8 MPa; the time of the hydrogenation reaction is preferably 10-800 h; more preferably 30 to 200 hours, and most preferably 50 to 150 hours.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
60.0150g of chromium nitrate is dissolved in 1500mL of deionized water to obtain a chromium nitrate solution; mixing the chromium nitrate solution with 89.1765g of glucose (the mass ratio of chromium ions in the chromium nitrate solution to glucose is 1: 3, the concentration of the chromium ions is 0.1mol/L), carrying out complex reaction at 80 ℃, obtaining a chromium-based metal oxide precursor after 8h, drying in an oven at 100 ℃ for 10h, then transferring to a muffle furnace, roasting at 500 ℃ for 3h in the air atmosphere, and naturally cooling to obtain the chromium-based metal oxide Cr2O3；
The chromium-based metal oxide Cr is2O3And grinding and mixing the H-SAPO-34 molecular sieve with the H-SAPO-34 molecular sieve according to the mass ratio of 0.5:1 (the silica-alumina ratio of the H-SAPO-34 molecular sieve is 0.025), then tabletting under 15.0MPa, and finally crushing and sieving to obtain the chromium-based metal oxide-molecular sieve catalyst with the granularity of 20-40 meshes.
FIG. 1 shows a chromium-based metal oxide Cr prepared in this example2O3XRD spectrum of (1). As can be seen, the chromium-based metal oxide Cr prepared in this example2O3Exhibits a hexagonal crystal form and has high crystallinity.
FIG. 2 shows the preparation of a chromium-based metal oxide-molecular sieve catalyst at CO2CH in reaction for preparing ethylene by hydrogenation4、C2 0-C4 0、C2 ＝-C4 ＝、C5 +Selectivity of oxygenates and CO2In which the oxygen-containing compounds are represented by oxydases, CH4、C5 +Substantially coinciding with the time-dependent curve of the selectivity for the oxygenate. It can be seen that the chromium-based metal oxide-molecular sieve catalyst prepared in this example was used for CO2Total lower olefins (C) in the hydrogenation to ethylene reaction2 ＝-C4 ＝) The selectivity can reach 95.9 percent at most.
FIG. 3 shows the preparation of a chromium-based metal oxide-molecular sieve catalyst in CO2C in reaction of preparing ethylene by hydrogenation2 ＝～C5 ＝And C2 ＝/C3 ＝The ratio is plotted against time. It can be seen that the chromium-based metal oxide-molecular sieve catalyst prepared in this example was used for CO2In the reaction of preparing ethylene by hydrogenation, the highest selectivity of ethylene can reach 66.4%, and the highest ratio of ethylene/propylene can reach 2.63.
Example 2
80.0200g of chromium nitrate and 5.9498g of zinc nitrate are dissolved in 1500mL of deionized water to obtain a chromium-based composite metal ion salt solution; mixing the chromium-based composite metal ion salt solution with 130.7922g of glucose (the mass ratio of chromium nitrate to zinc nitrate is 10: 1, the mass ratio of total metal ions in the chromium-based composite metal ion salt solution to glucose is 1: 3, the concentration of chromium ions is 0.133mol/L, and the concentration of zinc ions is 0.0133mol/L), carrying out complex reaction at 80 ℃, obtaining a chromium-based metal oxide precursor after 8 hours, drying in an oven at 100 ℃ for 10 hours, transferring to a muffle furnace, roasting in an air atmosphere at 500 ℃ for 3 hours, and naturally cooling to obtain the chromium-based metal oxide Cr2.0Zn0.2O3.2；
The chromium-based metal oxide Cr is2.0Zn0.2O3.2And grinding and mixing the H-SAPO-34 molecular sieve with the H-SAPO-34 molecular sieve according to the mass ratio of 0.5:1 (the silica-alumina ratio of the H-SAPO-34 molecular sieve is 0.025), then tabletting under 15.0MPa, and finally crushing and sieving to obtain the chromium-based metal oxide-molecular sieve catalyst with the granularity of 20-40 meshes.
Example 3
80.0200g of chromium nitrate and 6.3766g of indium nitrate are dissolved in 1500mL of deionized water to obtain a chromium-based composite metal ion salt solution; mixing the chromium-based composite metal ion salt solution with 130.7922g of glucose (the mass ratio of chromium nitrate to indium nitrate is 10: 1, the mass ratio of total metal ions in the chromium-based composite metal ion salt solution to glucose is 1: 3, the concentration of chromium ions is 0.133mol/L, and the concentration of indium ions is 0.0133mol/L), carrying out complex reaction at 80 ℃, obtaining a chromium-based metal oxide precursor after 8 hours, drying in an oven at 100 ℃ for 10 hours, transferring to a muffle furnace, roasting in an air atmosphere at 500 ℃ for 3 hours, and naturally cooling to obtain the chromium-based metal oxide Cr2.0In0.2O3.3；
The chromium-based metal oxide Cr is2.0In0.2O3.3And grinding and mixing the H-SAPO-34 molecular sieve with the H-SAPO-34 molecular sieve according to the mass ratio of 0.5:1 (the silica-alumina ratio of the H-SAPO-34 molecular sieve is 0.025), then tabletting under 15.0MPa, and finally crushing and sieving to obtain the chromium-based metal oxide-molecular sieve catalyst with the granularity of 20-40 meshes.
Example 4
80.0200g of chromium nitrate and 7.5026g of aluminum nitrate are dissolved in 1500mL of deionized water to obtain a chromium-based composite metal ion salt solution; mixing the chromium-based composite metal ion salt solution with 130.7922g of glucose (the mass ratio of chromium nitrate to aluminum nitrate is 10: 1, the mass ratio of total metal ions in the chromium-based composite metal ion salt solution to glucose is 1: 3, the concentration of chromium ions is 0.133mol/L, and the concentration of aluminum ions is 0.0133mol/L), carrying out complex reaction at 80 ℃, obtaining a chromium-based metal oxide precursor after 8 hours, drying in an oven at 100 ℃ for 10 hours, transferring to a muffle furnace, roasting in an air atmosphere at 500 ℃ for 3 hours, and naturally cooling to obtain the chromium-based metal oxide Cr2.0Al0.2O3.3；
The chromium-based metal oxide Cr is2.0Al0.2O3.3And grinding and mixing the H-SAPO-34 molecular sieve with the H-SAPO-34 molecular sieve according to the mass ratio of 0.5:1 (the silica-alumina ratio of the H-SAPO-34 molecular sieve is 0.025), then tabletting under 15.0MPa, and finally crushing and sieving to obtain the chromium-based metal oxide-molecular sieve catalyst with the granularity of 20-40 meshes.
Example 5
80.0200g of chromium nitrate and 8.5864g of zirconium nitrate are dissolved in 1500mL of deionized water to obtain a chromium-based composite metal ion salt solution; mixing the chromium-based composite metal ion salt solution with 130.7922g of glucose (the mass ratio of chromium nitrate to zirconium nitrate is 10: 1, the mass ratio of total metal ions in the chromium-based composite metal ion salt solution to glucose is 1: 3, the concentration of chromium ions is 0.133mol/L, and the concentration of zirconium ions is 0.0133mol/L), carrying out complex reaction at 80 ℃, obtaining a chromium-based metal oxide precursor after 8 hours, drying in an oven at 100 ℃ for 10 hours, transferring to a muffle furnace, roasting in an air atmosphere at 500 ℃ for 3 hours, and naturally cooling to obtain the chromium-based metal oxide Cr2.0Zr0.2O3.4；
The chromium-based metal oxide Cr is2.0Zr0.2O3.4And grinding and mixing the H-SAPO-34 molecular sieve with the H-SAPO-34 molecular sieve according to the mass ratio of 0.5:1 (the silica-alumina ratio of the H-SAPO-34 molecular sieve is 0.025), then tabletting under 15.0MPa, and finally crushing and sieving to obtain the chromium-based metal oxide-molecular sieve catalyst with the granularity of 20-40 meshes.
Example 6
60.0150g of chromium nitrate is dissolved in 1500mL of deionized water to obtain a chromium nitrate solution; mixing the chromium nitrate solution with 89.1765g of glucose (the mass ratio of chromium ions in the chromium nitrate solution to glucose is 1: 3, the concentration of the chromium ions is 0.1mol/L), carrying out complex reaction at 80 ℃, obtaining a chromium-based metal oxide precursor after 8h, drying in an oven at 100 ℃ for 10h, then transferring to a muffle furnace, roasting at 500 ℃ for 3h in the air atmosphere, and naturally cooling to obtain the chromium-based metal oxide Cr2O3；
The chromium-based metal oxide Cr is2O3And grinding and mixing the H-SAPO-34 molecular sieve with the H-SAPO-34 molecular sieve according to the mass ratio of 0.5:1 (the silica-alumina ratio of the H-SAPO-34 molecular sieve is 0.075), then tabletting under 15.0MPa, and finally crushing and sieving to obtain the chromium-based metal oxide-molecular sieve catalyst with the granularity of 20-40 meshes.
Example 7
60.0150g of chromium nitrate is dissolved in 1500mL of deionized water to obtain a chromium nitrate solution; mixing the chromium nitrate solution with 59.4510g of glucose (the mass ratio of chromium ions in the chromium nitrate solution to glucose is 1: 2, the concentration of the chromium ions is 0.1mol/L), carrying out a complex reaction at 70 ℃, obtaining a chromium-based metal oxide precursor after 9h, drying in an oven at 100 ℃ for 10h, then transferring to a muffle furnace, roasting at 600 ℃ for 3h in the air atmosphere, and naturally cooling to obtain a chromium-based metal oxide Cr2O3；
The chromium-based metal oxide Cr is2O3And grinding and mixing the H-SAPO-34 molecular sieve with the H-SAPO-34 molecular sieve according to the mass ratio of 0.5:1 (the silica-alumina ratio of the H-SAPO-34 molecular sieve is 0.025), then tabletting under 15.0MPa, and finally crushing and sieving to obtain the chromium-based metal oxide-molecular sieve catalyst with the granularity of 20-40 meshes.
Example 8
80.0200g of chromium nitrate is dissolved in 150mL of deionized water to obtain a chromium nitrate solution; 117.8250g of ammonium carbonate is dissolved in 200mL of deionized water to obtain an ammonium carbonate aqueous solution (the mass ratio of chromium ions to ammonium carbonate in the chromium nitrate solution is 2: 3, the concentration of the chromium ions is 1.33mol/L, and the concentration of the ammonium carbonate aqueous solution is 1.5 mol/L); mixing the chromium nitrate solution, the ammonium carbonate aqueous solution and 1000mL of deionized water, adjusting the pH value to 7, carrying out precipitation reaction at 80 ℃ for 3 hours to obtain a chromium-based metal oxide precursor, washing with deionized water for 4 times, centrifuging, drying in a 100 ℃ oven for 12 hours, transferring to a muffle furnace, roasting at 500 ℃ in an air atmosphere for 3 hours, and naturally cooling to obtain a chromium-based metal oxide Cr2O3；
Mixing the above chromium-based metal oxideCr2O3And grinding and mixing the H-SAPO-34 molecular sieve with the H-SAPO-34 molecular sieve according to the mass ratio of 0.5:1 (the silica-alumina ratio of the H-SAPO-34 molecular sieve is 0.025), then tabletting under 15.0MPa, and finally crushing and sieving to obtain the chromium-based metal oxide-molecular sieve catalyst with the granularity of 20-40 meshes.
Comparative example 1
8.9247g of zinc nitrate and 85.8640g of zirconium nitrate are dissolved in 1500mL of deionized water, then mixed with 136.7373g of glucose, the mixture is subjected to complexation reaction for 8 hours at 80 ℃, then a metal oxide precursor obtained by the complexation reaction is transferred to a 100 ℃ oven to be dried for 10 hours, then the dried metal oxide precursor is transferred to a muffle furnace to be roasted for 3 hours at 500 ℃ in air atmosphere, and the metal oxide Zn is obtained by natural cooling0.3Zr2.0O4.3；
The above metal oxide Zn is added0.3Zr2.0O4.3And grinding and mixing the H-SAPO-34 molecular sieve with the H-SAPO-34 molecular sieve according to the mass ratio of 0.5:1 (the silica-alumina ratio of the H-SAPO-34 molecular sieve is 0.025), tabletting under 15.0MPa, and finally crushing and sieving to obtain the metal oxide-molecular sieve catalyst with the granularity of 20-40 meshes.
Comparative example 2
47.8245g of indium nitrate and 8.5864g of zirconium nitrate are dissolved In 1500mL of deionized water, then mixed with 136.7373g of glucose, the mixture is subjected to complexation reaction for 8h at 80 ℃, then a metal oxide precursor obtained by the complexation reaction is transferred to a 100 ℃ oven to be dried for 10h, then the dried metal oxide precursor is transferred to a muffle furnace to be roasted for 3h at 500 ℃ In the air atmosphere, and the obtained product is naturally cooled to obtain the metal oxide In1.5Zr0.2O2.65；
In the above metal oxide1.5Zr0.2O2.65And grinding and mixing the H-SAPO-34 molecular sieve with the H-SAPO-34 molecular sieve according to the mass ratio of 0.5:1 (the silica-alumina ratio of the H-SAPO-34 molecular sieve is 0.025), tabletting under 15.0MPa, and finally crushing and sieving to obtain the metal oxide-molecular sieve catalyst with the granularity of 20-40 meshes.
Comparative example 3
8.9247g of zinc nitrate, 77.2776g of zirconium nitrate and 8.6844g of cerium nitrate were dissolved in 1500mL of deionized water, followed by reaction with136.7373g of glucose are mixed, the complexation reaction is carried out for 8h at the temperature of 80 ℃, then the metal oxide precursor obtained by the complexation reaction is transferred to a baking oven at the temperature of 100 ℃ for drying for 10h, then the metal oxide precursor is transferred to a muffle furnace, the metal oxide precursor is baked for 3h at the temperature of 500 ℃ in the air atmosphere, and the metal oxide Zn is obtained after natural cooling0.3Zr1.8Ce0.2O4.3；
The above metal oxide Zn is added0.3Zr1.8Ce0.2O4.3And grinding and mixing the H-SAPO-34 molecular sieve with the H-SAPO-34 molecular sieve according to the mass ratio of 0.5:1 (the silica-alumina ratio of the H-SAPO-34 molecular sieve is 0.025), tabletting under 15.0MPa, and finally crushing and sieving to obtain the metal oxide-molecular sieve catalyst with the granularity of 20-40 meshes.
Application example
Catalysts prepared in examples 1-8 and comparative examples 1-3 were respectively added to H2Reducing at 400 deg.C for 2h in atmosphere, and applying to CO2Hydrogenation to prepare ethylene;
wherein, the reaction conditions of the catalysts prepared in examples 1 to 6 and 8 and comparative examples 1 to 3 are as follows: the reaction temperature is 370 ℃, the reaction pressure is 0.5MPa, H2With CO2The volume ratio of (A) to (B) is 3:1, and the space velocity is 4000 mL/(h.g);
the reaction conditions for the catalyst prepared in example 7 were: the reaction temperature is 370 ℃, the reaction pressure is 1.0MPa, H2With CO2The volume ratio of (A) to (B) is 3:1, and the space velocity is 4000 mL/(h.g); after the reaction was completed, the catalysts prepared in examples 1 to 8 and comparative examples 1 to 3 were tested for their catalytic performance, and the results are shown in tables 1 and 2.
TABLE 1 catalytic Performance of catalysts prepared in examples 1-8 and comparative examples 1-3
TABLE 2 catalytic Properties of catalysts prepared in examples 1 to 8 and comparative examples 1 to 3
Wherein, C2 ＝Represents ethylene, C3 ＝Represents propylene, C4 ＝Represents butene, C5 ＝Represents pentene, C2 ＝-C4 ＝C represents C2-4 olefins (i.e., ethylene, propylene and butylene)2 0-C4 0C represents C2-4 alkane (i.e. ethane, propane and butane)5 +Is C is alkane and olefin with carbon number of 5 or more, oxygen-containing compound including methanol, dimethyl ether and ethanol2 ＝/C3 ＝The ratio indicates the ethylene/propylene ratio.
As can be seen from tables 1 and 2, the chromium-based metal oxide-molecular sieve catalyst provided by the present invention has excellent CO2Catalytic performance of hydrogenation to prepare ethylene and total low-carbon olefin (C)2 ＝-C4 ＝) The selectivity of the catalyst is 84.5-95.9%, wherein the selectivity of ethylene is 51.1-66.4%, and the ratio of ethylene/propylene is 1.71-2.63. Compared with comparative examples 1 to 3, other metal oxides such as Zn are used0.3Zr2.0O4.3、Zn0.3Zr1.8Ce0.2O4.3Or In1.5Zr0.2O2.65The catalyst formed by the catalyst and the H-SAPO-34 molecular sieve has the ethylene selectivity of only 35.1-38.6 percent, and the ethylene/propylene ratio is reduced to 0.77-1.03.
As can be seen from the above examples, the chromium-based metal oxide-molecular sieve catalyst provided by the present invention is used for catalyzing CO2The reaction for preparing ethylene by hydrogenation has the performances of high ethylene selectivity and high ethylene/propylene ratio.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (8)
1. Chromium-based metal oxide-molecular sieve catalyst in CO2The application of hydrogenation to ethylene preparation is characterized in that the chromium-based metal oxide-molecular sieve catalyst consists of chromium-based metal oxide and H-SAPO-34 molecular sieve; the chromium-based metal oxide is Cr2O3。
2. The use according to claim 1, wherein the mass ratio of the chromium-based metal oxide to the H-SAPO-34 molecular sieve is (0.2-5): 1.
3. the use of claim 1, wherein the H-SAPO-34 molecular sieve has a silica to alumina ratio of 0.01 to 0.5.
4. The use of claim 1, wherein the chromium-based metal oxide-molecular sieve catalyst has a particle size of 10 to 60 mesh.
5. The use according to claim 1, wherein the preparation of the chromium-based metal oxide-molecular sieve catalyst comprises the steps of:
(1) mixing water-soluble chromium salt with water to obtain a chromium-based metal ion salt solution;
(2) mixing the chromium-based metal ion salt solution obtained in the step (1) with a complexing agent or a precipitating agent, and carrying out a complexing reaction or a precipitation reaction to obtain a chromium-based metal oxide precursor;
(3) roasting the chromium-based metal oxide precursor obtained in the step (2) to obtain chromium-based metal oxide;
(4) and (4) mixing the chromium-based metal oxide obtained in the step (3) with an H-SAPO-34 molecular sieve to obtain the chromium-based metal oxide-molecular sieve catalyst.
6. Use according to claim 5, wherein the ratio of the total metal ions in the chromium-based metal ion salt solution in step (2) to the amount of complexing or precipitating agent is 1: (0.5-5).
7. The use according to claim 5, wherein the temperature of the complexation reaction and the precipitation reaction in step (2) is 60-90 ℃ independently, and the time of the complexation reaction and the precipitation reaction is 3-8 h independently.
8. The use of claim 5, wherein the roasting temperature in the step (3) is 350-700 ℃ and the roasting time is 4-10 h.
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