CN107282102B - Preparation method of metal-loaded molecular sieve catalyst - Google Patents
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- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
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Abstract
The invention provides a preparation method of a metal-loaded molecular sieve catalyst, which comprises the following steps: mixing a precursor compound for preparing the molecular sieve with a carbon template agent, and carrying out carbonization treatment to form a precursor xerogel containing porous carbon spheres; dipping a metal salt solution on the precursor xerogel to form porous carbon spheres carrying active metal and precursor microcrystals; adding a molecular sieve template agent, and carrying out hydrothermal reaction to form a molecular sieve structure; and roasting the molecular sieve structure to obtain the metal-loaded molecular sieve catalyst. The invention can realize the uniform distribution of the metal active center in the molecular sieve pore channel and improve the selectivity of the low-carbon olefin.
Description
Technical Field
The invention relates to the technical field of molecular sieve catalysts, in particular to a preparation method of a metal-loaded molecular sieve catalyst for directly preparing low-carbon olefin from high-selectivity synthesis gas.
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. The development of the technology for directly preparing ethylene and propylene from synthesis gas (which can be obtained by converting natural gas and coal) not only can reduce the dependence on petroleum resources, but also has important significance for the development of chemical industry in some gas-rich and oil-deficient areas. Compared with the indirect method, the process has the characteristics of simple process, less equipment investment and the like, and belongs to the F-T synthesis reaction substantially. The purpose of the F-T synthesis reaction is to synthesize liquid hydrocarbons for fuel from synthesis gas, and although 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 an auxiliary agent, the yield of the low-carbon olefins is still not high and is only 20-25%. A great deal of research is carried out on the process by a plurality of scientific research institutes and well-known enterprises at home and abroad, and the development of the high-efficiency catalyst, especially the development of the catalyst with high olefin selectivity, is considered as the key of the process.
The metal-loaded molecular sieve is an important catalyst for directly preparing low-carbon olefin from synthesis gas, and is a high-selectivity catalyst with a metal active center and an acid active center, wherein reducing metal is loaded in a pore structure of the molecular sieve. In the prior art, the catalyst is generally prepared by adopting an impregnation method or a microemulsion method in combination with a hydrothermal method, and in the process of introducing active metal into a molecular sieve, due to solid-liquid contact, osmotic pressure and the like, uneven distribution of metal in pore channels of the molecular sieve is easily caused, so that the catalytic performance of the catalyst is reduced, and the selectivity of low-carbon olefin is reduced.
Disclosure of Invention
In view of the above, the present invention provides a method for preparing a metal-supported molecular sieve catalyst, which can achieve uniform distribution of metal active centers in molecular sieve pores and improve the selectivity of low-carbon olefins.
The invention provides a preparation method of a metal-loaded molecular sieve catalyst, which comprises the following steps:
s1: mixing a precursor compound for preparing the molecular sieve with a carbon template agent, and carrying out carbonization treatment to form a precursor xerogel containing porous carbon spheres;
s2: dipping a metal salt solution on the precursor xerogel to form porous carbon spheres carrying active metal and precursor microcrystals;
s3: adding a molecular sieve template agent, and carrying out hydrothermal reaction to form a molecular sieve structure;
s4: roasting the molecular sieve structure to obtain a metal-loaded molecular sieve catalyst;
wherein the carbon template of step S1 has the following properties: (1) can be carbonized after heat treatment; (2) reducing groups (such as aldehyde groups) remain after carbonization. The preferred carbon templating agent is sucrose.
In the process, a carbon template agent can form a porous carbon sphere through carbonization, when a metal salt solution is soaked in a precursor xerogel containing the porous carbon sphere, because aldehyde group and other reducing groups are remained on the porous carbon sphere, metal ions in the solution are reduced into metal and loaded on the surface of the carbon sphere, precursor microcrystals of a molecular sieve are formed on the porous carbon sphere, after the molecular sieve template agent is added, the molecular sieve structure is formed and coated on the porous carbon sphere under hydrothermal conditions, and after other post-treatment processing such as roasting, the porous carbon sphere is removed, so that the uniformly mixed and coated metal-loaded molecular sieve catalyst is obtained.
Wherein the precursor compound of the molecular sieve in the step S1 comprises precursor compounds of silicon, aluminum and phosphorus. The precursor compound of silicon can be one or more of silica gel, sodium silicate and ethyl orthosilicate, the precursor compound of aluminum can be one or more of alumina sol, pseudo-boehmite, sodium metaaluminate and aluminum isopropoxide, and the precursor compound of phosphorus can be one or more of phosphoric acid and phosphorous acid. The molar ratio of the precursor compounds of silicon, aluminum and phosphorus to the carbon template agent is respectively SiO2、Al2O3、PO4 3+、C12Measured as SiO2：Al2O3：PO4 3+：C12(0.01-5): 1, (0.01-5): 0.5-20), preferably SiO2：Al2O3：PO4 3+：C12＝(0.05～2):1:(0.05～2):(1～10)。
Wherein the carbonization treatment condition in the step S1 is 160-220 ℃ of carbonization temperature and 2-48 h of carbonization time, preferably 4-24 h. The proper carbonization condition is beneficial to rapid carbonization and the porous carbon spheres with proper porous structures can be obtained, and the pore channel structures (pore size, pore wall size and the like) of the porous carbon spheres can be controlled by properly adjusting the carbonization condition; meanwhile, the proper carbonization condition is beneficial to the formation of dry gel of the molecular sieve precursor, and preparation is made for the nucleation of the molecular sieve precursor microcrystal.
Wherein, the metal salt solution in the step S2 may be Cu2+、Mg2+、Fe3+、Cr3+、Zn2+、Zr4+、Ce3+One or more nitrates. The concentration of the metal salt solution is 0.1-5 mol/L, preferably 0.5-3 mol/L calculated by metal ions. The proper metal salt solution concentration provides metal ions which can sufficiently enter the porous carbon spheres and an osmotic driving effect in the dipping process, the metal ions can quickly enter pores under the dual actions of osmotic driving and pore adsorption of the carbon spheres and are reduced into metal by reducing groups on the surfaces of the porous carbon spheres, so that the metal ions are uniformly attached to the surfaces of the porous carbon spheres.
Wherein, the dipping condition in the step S2 is that the dipping temperature is 10-60 ℃ and the dipping time is 1-10 h. An equal volume impregnation or an over-volume impregnation is generally employed. The proper impregnation temperature can accelerate the impregnation speed and simultaneously promote the rapid formation of the molecular sieve precursor microcrystals.
In the step S2, the first drying treatment is further included after the dipping, and the preferable conditions are that the drying temperature is 80-160 ℃ and the drying time is 4-24 h. The drying process can remove residual immersion liquid on one hand and is beneficial to the stability of active metal and precursor microcrystal in the porous carbon sphere on the other hand.
Wherein, the molecular sieve template in step S3 is an organic template, preferably one or more of diethylamine, triethylamine, n-propylamine, n-butylamine, tetraethylammonium hydroxide, tetrapropylammonium hydroxide and tetrabutylammonium hydroxide. The molar ratio of the organic template to the precursor compound of the molecular sieve is N, SiO respectively2Counting as N: SiO 22The ratio is 0.2 to 10, preferably 1 to 5.
Wherein the hydrothermal reaction condition in the step S3 is 160-210 ℃.
Wherein, the roasting condition in the step S4 is that the roasting temperature is 400-800 ℃, preferably 450-650 ℃; the roasting time is 2-10 h, preferably 4-8 h; the baking atmosphere is a flowing atmosphere with an oxygen content of 50-100 vol%. The porous carbon spheres can be removed in the roasting process, and the molecular sieve catalyst with uniformly loaded metal active centers is obtained.
In step S4, before calcination, centrifugal water washing and a second drying treatment step are further included to separate the molecular sieve structure containing porous carbon spheres and prepare the molecular sieve structure before calcination.
Compared with the prior art, the carbon template agent is introduced in the preparation process, so that the molecular sieve carrier and the metal active component can be uniformly mixed and coated, no redundant impurities are generated, the obtained catalyst has good catalytic performance, and the catalyst is particularly suitable for catalytic reaction of directly preparing low-carbon olefin from synthesis gas, and the selectivity of the low-carbon olefin is greatly improved.
Detailed Description
The illustrative embodiments and descriptions of the present invention are provided to explain the present invention and not to limit the present invention unduly.
Example 1
Weighing raw materials according to a molar ratio of silica gel (30 mass percent), pseudo-boehmite, phosphoric acid and cane sugar of 0.2:1:0.1:3, uniformly mixing at room temperature, carbonizing at 220 ℃ for 4h in a hydrothermal kettle, and naturally cooling to room temperature to obtain the precursor porous carbon sphere xerogel. Preparing a metal salt solution with a molar ratio of copper nitrate, zinc nitrate and aluminum nitrate of 4.5:4.5:1, wherein the active component accounts for 30 percent (mass ratio) of the catalyst based on the metal, soaking the active component in the porous carbon sphere xerogel at room temperature in an equal volume manner, and drying the porous carbon sphere for 24 hours at 80 ℃ to obtain the porous carbon sphere containing the active component and precursor microcrystals. Adding the porous carbon spheres into a solution with the molar ratio of silica gel to tetraethylammonium hydroxide of 2.4:1, carrying out hydrothermal treatment at 180 ℃ for 4d, carrying out centrifugal washing, drying at 100 ℃ for 12h, and roasting at 600 ℃ for 4h in a pure oxygen atmosphere to obtain the catalyst.
Example 2
Weighing raw materials according to the molar ratio of sodium silicate to aluminum sulfate to phosphorous acid to sucrose of 0.6:1:0.4:7, uniformly mixing at room temperature, carbonizing at 160 ℃ for 24 hours in a hydrothermal kettle, and naturally cooling to room temperature to obtain the precursor porous carbon sphere xerogel. Preparing a metal salt solution with the molar ratio of ferric nitrate to chromium nitrate being 1:1, soaking the metal salt solution in the porous carbon sphere xerogel at the temperature of 25 ℃ in an overdose manner, wherein the concentration of the total metal salt solution is 5mol/L, the soaking time is 10h, and drying the metal salt solution at the temperature of 110 ℃ for 12h to obtain the porous carbon sphere containing active components and precursor microcrystals. Adding the porous carbon spheres into a solution with a molar ratio of sodium silicate to triethylamine being 1:1, carrying out hydrothermal treatment at 200 ℃ for 2d, washing with centrifugal water, drying at 120 ℃ for 6h, and roasting at 550 ℃ for 6h in an oxygen atmosphere of 80 vol% to obtain the catalyst.
Example 3
Weighing raw materials according to the molar ratio of ethyl orthosilicate to aluminum isopropoxide to phosphoric acid to cane sugar of 0.2:1:0.5:10, uniformly mixing at room temperature, carbonizing at 175 ℃ for 10h in a hydrothermal kettle, and naturally cooling to room temperature to obtain the precursor porous carbon sphere xerogel. Preparing a metal salt solution with the molar ratio of zinc nitrate to chromium nitrate being 1:1, soaking the metal salt solution in the porous carbon sphere xerogel at the temperature of 25 ℃ in an overdose manner for 10 hours at the concentration of 1.5mol/L of the total metal salt solution, and drying the metal salt solution at the temperature of 110 ℃ for 12 hours to obtain the porous carbon sphere containing active components and precursor microcrystals. Adding the porous carbon spheres into a solution with the molar ratio of ethyl orthosilicate to diethylamine to tetrapropylammonium hydroxide being 1:0.24:0.30, carrying out hydrothermal treatment at 190 ℃ for 3d, centrifugally washing, drying at 110 ℃ for 10h, and roasting at 650 ℃ for 4h in an oxygen atmosphere of 50 vol% to obtain the catalyst.
Example 4
Weighing raw materials according to a molar ratio of silica sol (30 mass percent), aluminum sol, phosphorous acid and cane sugar of 1.5:1:0.3:20, uniformly mixing at room temperature, carbonizing at 180 ℃ for 10h in a hydrothermal kettle, and naturally cooling to room temperature to obtain the precursor porous carbon sphere xerogel. Preparing a metal salt solution with the molar ratio of ferric nitrate to magnesium nitrate being 1:1, soaking the metal salt solution in the porous carbon sphere xerogel at the temperature of 40 ℃ in an overdose manner, wherein the concentration of the total metal salt solution is 2.5mol/L, the soaking time is 6h, and drying the metal salt solution at the temperature of 95 ℃ for 20h to obtain the porous carbon sphere containing active components and precursor microcrystals. Adding the porous carbon spheres into a solution with the molar ratio of silica sol to n-butylamine to tetraethylammonium hydroxide being 1:0.20:0.20, carrying out hydrothermal treatment at 195 ℃ for 2d, washing with centrifugal water, drying at 110 ℃ for 10h, and roasting at 450 ℃ for 8h in an oxygen atmosphere of 50 vol% to obtain the catalyst.
Example 5
Weighing raw materials according to the molar ratio of sodium silicate to aluminum isopropoxide to phosphoric acid to sucrose of 0.4:1:0.4:1, uniformly mixing at room temperature, carbonizing at 170 ℃ for 24 hours in a hydrothermal kettle, and naturally cooling to room temperature to obtain the precursor porous carbon sphere xerogel. Preparing a metal salt solution with the molar ratio of ferric nitrate to cerium nitrate being 8:1, soaking the metal salt solution in the porous carbon sphere xerogel at the temperature of 30 ℃ in an overdose manner, wherein the concentration of the total metal salt solution is 1.0mol/L, the soaking time is 9h, and drying the metal salt solution for 20h at the temperature of 100 ℃ to obtain the porous carbon sphere containing the active component and the precursor microcrystal. Adding the porous carbon spheres into a solution with the molar ratio of sodium silicate to triethylamine to tetraethylammonium hydroxide being 1:0.35:0.20, carrying out hydrothermal treatment at 160 ℃ for 5d, washing with centrifugal water, drying at 100 ℃ for 24h, and roasting at 580 ℃ for 5h in 70 vol% oxygen atmosphere to obtain the catalyst.
Example 6
Weighing raw materials according to the molar ratio of ethyl orthosilicate to sodium metaaluminate to phosphorous acid to sucrose of 0.7:1:0.5:5, uniformly mixing at room temperature, carbonizing at 185 ℃ for 7 hours in a hydrothermal kettle, and naturally cooling to room temperature to obtain the precursor porous carbon sphere xerogel. Preparing a metal salt solution with the molar ratio of zinc nitrate to zirconium nitrate being 3:1, wherein the active component accounts for 24 percent (mass ratio) of the catalyst according to the metal, soaking the active component and the zirconium nitrate in the porous carbon sphere xerogel at room temperature in an equal volume manner to obtain the porous carbon sphere containing the active component and the precursor microcrystal. Adding the porous carbon spheres into a solution with the molar ratio of ethyl orthosilicate to n-butylamine to tetrapropylammonium hydroxide being 1:0.18:0.24, carrying out hydrothermal treatment at 210 ℃ for 1d, carrying out centrifugal water washing, drying at 90 ℃ for 20h, and roasting at 500 ℃ for 8h in an oxygen atmosphere of 80 vol% to obtain the catalyst.
Example 7
Weighing raw materials according to a molar ratio of silica sol, aluminum isopropoxide, phosphoric acid and cane sugar of 0.3:1:0.5:9, uniformly mixing at room temperature, carbonizing at 210 ℃ for 3h in a hydrothermal kettle, and naturally cooling to room temperature to obtain the precursor porous carbon sphere xerogel. Preparing a metal salt solution with the molar ratio of zinc nitrate to cerium nitrate to zirconium nitrate being 1:2:2, soaking the metal salt solution in the porous carbon sphere xerogel at the temperature of 60 ℃ in an overdose manner, wherein the concentration of the total metal salt solution is 2mol/L, the soaking time is 2h, and the porous carbon sphere containing the active component and the precursor microcrystal is obtained after drying at the temperature of 120 ℃ for 6 h. Adding the porous carbon spheres into a solution with the molar ratio of silica sol to n-propylamine to tetrabutylammonium hydroxide being 1:0.50:0.30, carrying out hydrothermal treatment at 200 ℃ for 3d, centrifugally washing, drying at 120 ℃ for 6h, and roasting at 600 ℃ for 5h under 60 vol% oxygen atmosphere to obtain the catalyst.
Comparative example 1
The Cu-Zn-Al oxide catalyst and the SAPO-34 molecular sieve are uniformly mixed according to the proportion of the example 1, and are ball-milled in a micro ball mill for 30min at 15Hz and then are sieved to the required granularity, so that the catalyst is obtained.
Comparative example 2
The Zn-Cr oxide catalyst and the SAPO-34 molecular sieve are uniformly mixed according to the mixture ratio of the embodiment 3, and 10 mass percent of alumina sol (mass fraction is 20%) is added for spray granulation to obtain the catalyst.
The catalytic reaction for directly preparing the low-carbon olefin from the synthesis gas by using the catalyst is verified. The fixed bed reaction is exemplified, but the method is also applicable to a fluidized bed and a moving bed reactor. Screening the catalyst in the embodiment or the comparative example to 20-40 meshes, weighing 1.6g, diluting with quartz sand with the mass ratio of 1:8, filling into a fixed bed reactor, and purifying at normal pressureReducing for 3 hours at the temperature of 300-350 ℃ by using hydrogen. Switching the synthesis gas (H) after cooling in a nitrogen atmosphere2/CO＝2/1，N210 vol%) were reacted. The reaction effluent is collected by a hot trap and a cold trap respectively. The reaction conditions are that the reaction temperature is 260 ℃ and 450 ℃, and the space velocity is 1000h-1The reaction pressure is 2.5 MPa. The product is detected and analyzed by on-line chromatography. The results of the reaction evaluation are shown in Table 1. The result shows that the selectivity of the catalyst prepared by the method of the invention in low-carbon olefin is greatly improved.
TABLE 1
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and should not be taken as limiting the invention, so that any modifications, equivalents, improvements and the like, which are within the spirit and principle of the present invention, should be included in the scope of the present invention.
Claims (20)
1. A preparation method of a metal-loaded molecular sieve catalyst for preparing low-carbon olefin from synthesis gas comprises the following steps:
s1: mixing a precursor compound for preparing the molecular sieve with a carbon template agent, and carrying out carbonization treatment to form a precursor xerogel containing porous carbon spheres;
s2: dipping a metal salt solution on the precursor xerogel to form porous carbon spheres carrying active metal and precursor microcrystals;
s3: adding a molecular sieve template agent, and carrying out hydrothermal reaction to form a molecular sieve structure;
s4: roasting the molecular sieve structure to obtain a metal-loaded molecular sieve catalyst;
wherein the carbon template of step S1 has the following properties: (1) can be carbonized after heat treatment; (2) reducing groups remain after carbonization;
the precursor compounds of the molecular sieve in the step S1 comprise precursor compounds of silicon, aluminum and phosphorus; the molar ratio of the precursor compounds of silicon, aluminum and phosphorus to the carbon template agent is respectively SiO2、Al2O3、PO4 3-、C12Measured as SiO2：Al2O3：PO4 3-：C12=（0.01~5） : 1 : （0.01~5） : （0.5~20）。
2. The method of claim 1, wherein the residual reducing group after the carbonization of the carbon template is an aldehyde group.
3. The method of claim 1, wherein the carbon templating agent is sucrose.
4. The method for preparing a metal-supported molecular sieve catalyst according to claim 1, wherein the precursor compound of silicon is one or more of silica gel, sodium silicate and ethyl orthosilicate, the precursor compound of aluminum is one or more of alumina sol, pseudo-boehmite, sodium metaaluminate and aluminum isopropoxide, and the precursor compound of phosphorus is one or more of phosphoric acid and phosphorous acid.
5. The method of claim 1, wherein the molar ratio of the precursor compounds of silicon, aluminum and phosphorus to the carbon template is SiO2、Al2O3、PO4 3-、C12Measured as SiO2：Al2O3：PO4 3-：C12=（0.05~2） : 1: （0.05~2） : （1~10）。
6. The method for preparing the metal-supported molecular sieve catalyst according to claim 1, wherein the carbonization treatment conditions in the step S1 are 160-220 ℃ and 2-48 h.
7. The method for preparing the metal-supported molecular sieve catalyst according to claim 6, wherein the carbonization time in step S1 is 4-24 h.
8. The method for preparing a metal-supported molecular sieve catalyst according to claim 1, wherein the metal salt solution in the step S2 is Cu2+、Mg2+、Fe3+、Cr3+、Zn2+、Zr4+、Ce3+One or more nitrates.
9. The method for preparing the metal-supported molecular sieve catalyst according to claim 1, wherein the concentration of the metal salt solution is 0.1 to 5mol/L in terms of metal ions.
10. The method for preparing the metal-supported molecular sieve catalyst according to claim 1, wherein the concentration of the metal salt solution is 0.5 to 3mol/L in terms of metal ions.
11. The method for preparing the metal-supported molecular sieve catalyst according to claim 1, wherein the impregnation in the step S2 is carried out at an impregnation temperature of 10-60 ℃ for 1-10 h.
12. The method for preparing the metal-supported molecular sieve catalyst according to claim 1, wherein the step S2 further comprises a first drying treatment after the impregnation, wherein the drying temperature is 80-160 ℃, and the drying time is 4-24 hours.
13. The method of claim 1, wherein the molecular sieve template in step S3 is an organic template.
14. The method of claim 1, wherein the molecular sieve template in step S3 is one or more selected from diethylamine, triethylamine, n-propylamine, n-butylamine, tetraethylammonium hydroxide, tetrapropylammonium hydroxide and tetrabutylammonium hydroxide.
15. The method of claim 13, wherein the molar ratio of the organic template to the precursor compound of the molecular sieve is N, SiO2Counting as N: SiO 22=0.2~10。
16. The method of claim 13, wherein the molar ratio of the organic template to the precursor compound of the molecular sieve is N, SiO2Counting as N: SiO 22=1~5。
17. The method for preparing the metal-supported molecular sieve catalyst according to claim 1, wherein the hydrothermal reaction condition in the step S3 is 160-210 ℃.
18. The method for preparing the metal-supported molecular sieve catalyst according to claim 1, wherein the calcination condition in the step S4 is a calcination temperature of 400-800 ℃; the roasting time is 2-10 h; the baking atmosphere is a flowing atmosphere with an oxygen content of 50-100 vol%.
19. The method for preparing the metal-supported molecular sieve catalyst according to claim 18, wherein the calcination condition in the step S4 is that the calcination temperature is 450 to 650 ℃; the roasting time is 4-8 h.
20. The method of claim 1, wherein the step S4 further comprises a centrifugal water washing step and a second drying step before calcination.
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