CN112694102B - Method for acid treatment of molecular sieves - Google Patents

Method for acid treatment of molecular sieves Download PDF

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CN112694102B
CN112694102B CN201911009059.6A CN201911009059A CN112694102B CN 112694102 B CN112694102 B CN 112694102B CN 201911009059 A CN201911009059 A CN 201911009059A CN 112694102 B CN112694102 B CN 112694102B
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molecular sieve
acid
pore
treating
sapo
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CN112694102A (en
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任淑
邹薇
吴江
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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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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/54—Phosphates, e.g. APO or SAPO compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
    • C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
    • C01B37/08—Silicoaluminophosphates [SAPO compounds], e.g. CoSAPO
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/16—Pore diameter
    • C01P2006/17—Pore diameter distribution

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  • Silicates, Zeolites, And Molecular Sieves (AREA)
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Abstract

The invention provides a preparation method of a hierarchical pore structure silicon-aluminum element-containing molecular sieve catalyst. The invention mainly solves the problem that the distribution of the hierarchical pore molecular sieve pore channels obtained after the existing post-treatment Al removal is uncontrollable. The invention mainly utilizes macromolecular acid chelating agent to carry out post-treatment. Roasting the raw zeolite powder, adding the roasted zeolite powder into an acid chelating agent solution, stirring, washing and drying to obtain the multistage pore zeolite. The invention can solve the problem that the distribution of the hierarchical pore canal after Al removal is uncontrollable, thereby leading the distribution of the zeolite pore canal structure to be controllable.

Description

Method for acid treatment of molecular sieves
Technical Field
The invention relates to preparation of a catalyst, in particular to preparation of a hierarchical pore structure silicon-aluminum element-containing molecular sieve catalyst.
Background
The molecular sieve material is a crystalline microporous silicate, and has wide application in the fields of catalysis, adsorption, separation and ion exchange due to the complex pore structure, adjustable acidity, high thermal stability, high hydrothermal stability and the like.
However, due to the single pore structure and smaller pore size of the molecular sieve, the diffusion resistance of large-size molecules in the pore is increased, and the application of the molecular sieve in the catalytic reaction participated by the large molecules is further limited. In recent years, many researches show that the introduction of mesoporous or macroporous construction of a multistage porous molecular sieve into a silicon-aluminum molecular sieve can improve the catalytic performance of the molecular sieve catalyst. The existing methods for synthesizing the hierarchical pore molecular sieve comprise a soft template method, a hard template method, an attached crystal growth method, a nano assembly method and the like, but the industrialization process is seriously affected by the problems of complex synthesis process, high raw material cost, high energy consumption and the like. Post-treatment is a relatively widely used process in industry, including steam treatment, acid treatment and alkali treatment. The acidity of the molecular sieve can be regulated, the active site can be increased, and hierarchical pore channels can be generated by the post-treatment method, so that the catalytic performance is improved.
In patent CN 104525250A, the conventional microporous SAPO-34 molecular sieve is treated with organic base, and SAPO-34 molecular sieve with micropores, mesopores and macropores is obtained by optimizing the treatment conditions, but the patent focuses on treating SAPO-34 molecular sieve with various organic bases to obtain a multi-stage porous molecular sieve, and the influence of treatment with chemical acid is not involved. Because the alkali treatment process involves Si removal to produce mesopores and the acid post-treatment is to remove Al to produce multi-stage pores, the difference in the mesoporous mode of the two processes will affect the low carbon olefin selectivity and catalyst life in the MTO process.
The patent CN106629766A and the patent CN107285342A respectively obtain the multistage pore molecular sieve with better crystallinity and excellent catalytic performance through solid phase alkali, acid post-treatment ZSM-5 and SAPO-34, but the uniformity of the solid phase post-treatment is not easy to control.
CN 109626390 AEU-1 molecular sieve is first treated in acid solution, then treated in alkali solution, and finally treated in controlled roasting temperature and acid treatment, and finally combined post-treatment of desilication and CTAB assisted secondary crystallization is carried out to prepare the multistage pore molecular sieve, so that the whole post-treatment process is complicated.
The method for synthesizing the hierarchical porous molecular sieve by adopting the acidic chelating agent with milder acidity after-treatment simplifies the process flow, and the macromolecular chelating agent can introduce a large amount of mesopores while maintaining the inherent property of zeolite. It maintains crystallinity to a greater extent than simple mineral acids. The macromolecular chelating agent can effectively protect the pore channel structure in the post-treatment process, so that the pore channel structure after dealumination in the acid treatment process is controllable, and the pore channel distribution of the obtained multistage pore molecular sieve catalyst is in ten-fold regular. And the acidity of the acid chelating agent is relatively mild, the crystallinity is hardly reduced after treatment, and the yield of the molecular sieve is improved.
Disclosure of Invention
The key technical problem to be solved by the invention is that zeolite pore channels obtained by a direct synthesis method and an acid aftertreatment method for obtaining the multistage pore molecular sieve in the prior art are uncontrollable. The invention provides a convenient preparation method of a hierarchical porous silicon-aluminum element-containing molecular sieve, which combines the advantages of mild acidity of an acidic chelating agent and the protection effect of macromolecules on pore channels, the pore channel structure formed after dealumination of the obtained molecular sieve is controllable, and the preparation process of the hierarchical porous molecular sieve is greatly simplified.
To achieve the above and other related objects, the present invention provides a synthesis method of acidic chelator solution aftertreatment of a hierarchical pore molecular sieve, the synthesis method comprising the steps of:
a method of acid treating a molecular sieve comprising the steps of:
(1) Adding a molecular sieve to be treated into a solution containing an acid chelating agent, and mixing under heating to obtain a mixture;
(2) The mixture is treated at 60-180 ℃ to obtain the hierarchical porous molecular sieve.
In the above technical scheme, preferably, the weight ratio of the molecular sieve to be treated in the step (1) to the acidic chelating agent-containing solution is 1: (1 to 50), preferably 1: (2-20).
In the above technical solution, preferably, the acid chelating agent is selected from one or at least one of ethylenediamine tetraacetic acid (EDTA), diethylenetriamine pentaacetic acid (DTPA), aminotrimethylene phosphonic Acid (ATMP), aminotrimethylene phosphonic Acid (ATP), gluconic acid and Maleic Acid (MAO).
In the above technical scheme, preferably, the molecular sieve is selected from a silicon-aluminum-containing molecular sieve, preferably from a SAPO molecular sieve and/or a ZSM-5 molecular sieve; more preferably from at least one of SAPO-11, SAPO-5, SAPO-34, SAPO-44, and AlPO-34.
In the above technical scheme, preferably, the relative crystallinity of the molecular sieve after the acid treatment is kept unchanged or increased.
The invention also relates to a molecular sieve, which is characterized in that the molecular sieve to be treated is obtained after the treatment by the method, and the molecular sieve to be treated is selected from the molecular sieves containing silicon-aluminum elements.
In the technical scheme, preferably, the molecular sieve contains microporous, mesoporous and macroporous tertiary pore structures, and the large pore size distribution is 400nm and 1100nm respectively; and/or BET specific surface area of 300 to 700m 2 /g，
In the above technical scheme, preferably, the crystallinity of the molecular sieve after treatment and the molecular sieve to be treated is greater than or equal to 1; preferably less than 1.1.
As a preferable scheme of the synthesis method of the multistage pore molecular sieve, the SAPO-34 molecular sieve crystal grain is cubic, the surface of the obtained multistage pore molecular sieve is provided with multistage pore channels which are regularly distributed, the pore diameter distribution is between 0.3 and 1100nm, and the BET specific surface area is300～700m 2 /g。
As a preferable scheme of the synthesis method of the hierarchical pore molecular sieve, in the step 3), the reaction temperature of the post-treatment is 60-180 ℃ and the reaction time is 30 min-12 h.
As a preferable scheme of the multistage pore molecular sieve synthesis method, in the step 1), the mass concentration of the acid chelating agent is 1-10%.
As a preferable scheme of the multi-level porous molecular sieve, the multi-level porous molecular sieve is provided with three-level composite pore canals of macropores, mesopores and micropores.
Compared with the prior art, the method for synthesizing the acidic chelating agent of the multi-stage pore molecular sieve by post-treatment has the advantages that the process flow is simplified, the molecular sieve yield is improved, in the post-treatment process, the chelating agent is mild in acidity, and the macromolecular acidic chelating agent can effectively protect the pore channel structure, so that the removal of aluminum element in the acid treatment process is controllable, the obtained multi-stage pore molecular sieve is compounded in multi-stage pore channels, the crystallinity is good, the catalyst performance is greatly improved, and the potential economic value and the social value are realized.
Drawings
Figure 1 shows the XRD pattern of the hierarchical pore molecular sieve prepared in example 1 of the present invention.
Figure 2 shows the XRD pattern of the hierarchical pore molecular sieve prepared in example 2 of the present invention.
FIG. 3 is a scanning electron micrograph showing a hierarchical pore molecular sieve prepared in example 2 of the present invention.
Fig. 4 shows nitrogen adsorption and desorption isotherms of the multi-stage pore molecular sieve prepared in example 7 of the present invention.
FIG. 5 shows a scanning electron micrograph of a hierarchical pore molecular sieve prepared in example 9 of the present invention.
FIG. 6 shows a scanning electron micrograph of a hierarchical pore molecular sieve prepared in example 11 of the present invention.
Fig. 7 shows an XRD spectrum of the hierarchical pore molecular sieve prepared in comparative example 1 of the present invention.
FIG. 8 is a scanning electron micrograph showing the hierarchical pore molecular sieve prepared in comparative example 1 of the present invention.
FIG. 9 is a scanning electron micrograph showing the hierarchical pore molecular sieve prepared in comparative example 1 of the present invention.
FIG. 10 is a scanning electron micrograph showing a hierarchical pore molecular sieve prepared in comparative example 2 of the present invention.
Detailed Description
The invention is further illustrated by the following examples.
The invention is further illustrated with respect to SAPO-34 molecular sieves in conjunction with the examples, but is not limited to SAPO-34 and the invention is not limited to the examples:
example 1
20g of commercial SAPO-34 molecular sieve and 100g of 2% Ethylene Diamine Tetraacetic Acid (EDTA) solution are weighed, stirred at 90 ℃ for 6 hours, and the separated solid is subjected to conventional washing, drying and roasting to obtain the SAPO-34 molecular sieve catalyst with a multi-level pore structure.
FIG. 1 is a representation of XRD of a product showing that the product is a typical CHA structure with an increase in relative crystallinity due to washing out of amorphous components during treatment with an acidic chelator solution.
Example 2
20g of commercial SAPO-34 molecular sieve and 100g of 1% ethylenediamine tetraacetic acid (EDTA) solution are weighed, stirred at 90 ℃ for 6 hours, and the separated solid is subjected to conventional washing, drying and roasting to obtain the SAPO-34 molecular sieve catalyst with a multi-level pore structure.
Figure 2 is a representation of XRD of the product, showing that the product is a typical CHA structure with an increase in relative crystallinity due to washing out of amorphous components during treatment with the acid chelator solution.
Fig. 3 is an SEM scanning electron microscope photograph of the product, and it can be seen that the particles of the product are cubic crystals of about 1-4 μm, and the original smooth cubic surface becomes rough.
Example 3
20g of commercial SAPO-34 molecular sieve and 100g of 2% Diethyl Triamine Pentaacetic Acid (DTPA) solution are weighed, stirred at 90 ℃ for 2 hours, and the separated solid is subjected to conventional washing, drying and roasting to obtain the SAPO-34 molecular sieve catalyst with a multi-level pore structure.
Example 4
20g of commercial SAPO-34 molecular sieve and 200g of 2% Ethylene Diamine Tetraacetic Acid (EDTA) solution are weighed, stirred at 90 ℃ for 12 hours, and the separated solid is subjected to conventional washing, drying and roasting to obtain the SAPO-34 molecular sieve catalyst with a multi-level pore structure.
Example 5
20g of commercial SAPO-34 molecular sieve and 40g of 2% Ethylene Diamine Tetraacetic Acid (EDTA) solution are taken, stirred at 60 ℃ for 12 hours, and the separated solid is subjected to conventional washing, drying and roasting to obtain the SAPO-34 molecular sieve catalyst with a multi-level pore structure.
Example 6
10g of commercial SAPO-34 molecular sieve and 200g of 2% Ethylene Diamine Tetraacetic Acid (EDTA) solution are taken, stirred at 120 ℃ for 3 hours, and the separated solid is subjected to conventional washing, drying and roasting to obtain the SAPO-34 molecular sieve catalyst with a multi-level pore structure.
Example 7
20g of commercial SAPO-34 molecular sieve and 160g of 2% Ethylene Diamine Tetraacetic Acid (EDTA) solution are weighed, stirred at 90 ℃ for 6 hours, and the separated solid is subjected to conventional washing, drying and roasting to obtain the SAPO-34 molecular sieve catalyst with a multi-level pore structure.
FIG. 4 shows the adsorption and desorption isotherms of nitrogen in the product, and can be seen that the sample is at P/P 0 There is an obvious lifting and hysteresis at the position of =0.8-1.0, which proves the existence of mesopores in the molecular sieve.
Example 8
20g of commercial SAPO-34 molecular sieve and 100g of 2% Maleic Acid (MAO) solution are taken, stirred at 150 ℃ for 10 hours, and the separated solid is subjected to conventional washing, drying and roasting to obtain the SAPO-34 molecular sieve catalyst with a multi-level pore structure.
Example 9
Weighing 20g of commercial SAPO-34 molecular sieve and 100g of 4% ethylenediamine tetraacetic acid (EDTA) solution, stirring at 90 ℃ for 6 hours, separating the obtained solid, and performing conventional washing, drying and roasting to obtain the SAPO-34 molecular sieve catalyst with a multi-level pore structure
Fig. 5 is mercury intrusion test run data for the product, from which it can be seen that the acid chelating agent treated sample produced macropores at 400 and 1100 nm.
Example 10
20g of commercial SAPO-34 molecular sieve and 100g of 10% Diethyl Triamine Pentaacetic Acid (DTPA) solution are weighed, stirred at 60 ℃ for 30min, and the separated solid is subjected to conventional washing, drying and roasting to obtain the SAPO-34 molecular sieve catalyst with a multi-level pore structure.
Example 11
20g of commercial SAPO-34 molecular sieve and 100g of 2% concentration amino trimethylene phosphonic Acid (ATP) solution are weighed, stirred at 90 ℃ for 6 hours, and the separated solid is subjected to conventional washing, drying and roasting to obtain the SAPO-34 molecular sieve catalyst with a multi-level pore structure.
Fig. 6 is an SEM scanning electron microscope photograph, and it can be seen that the particles of the product are cubic crystals with a particle size of about 1-4 μm, and the pore canal structure with butterfly spot appearance on the surface of the original smooth cube can be seen in the figure.
Example 12
20g of commercial SAPO-34 molecular sieve and 100g of 2% concentration gluconic acid solution are taken, stirred at 160 ℃ for 8 hours, and the separated solid is washed, dried and roasted conventionally to obtain the SAPO-34 molecular sieve catalyst with a multi-level pore structure.
Example 13
20g of commercial SAPO-34 molecular sieve and 100g of 2% ethylene diamine tetraacetic acid solution are taken, stirred at 60 ℃ for 8 hours, and the separated solid is subjected to conventional washing, drying and roasting to obtain the SAPO-34 molecular sieve catalyst with a multi-level pore structure.
Example 14
20g of commercial SAPO-34 molecular sieve and 100g of 1% ethylene diamine tetraacetic acid solution are taken, stirred at 180 ℃ for 30min, and the separated solid is subjected to conventional washing, drying and roasting to obtain the SAPO-34 molecular sieve catalyst with a multi-level pore structure.
Comparative example 1
The same conditions as in example 1 were used to change the ethylenediamine tetraacetic acid solution to a nitric acid solution of the same mass concentration, to obtain the final product.
Fig. 7 is a graph of the XRD pattern of the treated product versus the raw powder, showing a significant decrease in the relative crystallinity of the sample after nitric acid treatment.
Fig. 8 is an SEM image of the product, and it can be seen that the sample is broken more severely and the crystallization of the sample is significantly reduced. The result shows that the loss of crystallinity is relatively large and the yield is relatively low in the nitric acid aftertreatment.
Comparative example 2
The post-treatment temperature was changed to 30℃using the same conditions as in example 1, to obtain a final product. The SEM of the sample of FIG. 9 was not significantly modified from the original powder, and the surface was not roughened or channels with a butterfly spot morphology were present.
Comparative example 3
The mass concentration of ethylenediamine tetraacetic acid added was changed to 40% by using the same conditions as in example 1, to obtain the final product. FIG. 10 is an SEM image of the sample showing significant breakage.
The acidic chelating agent post-treatment method provided by the invention synthesizes the multi-stage pore molecular sieve, simplifies the process flow, improves the molecular sieve yield, and the obtained multi-stage pore canal is not only compounded, but also controllable after dealumination.
The above embodiments are merely illustrative of the principles of the present invention and its effectiveness, and are not intended to limit the invention. Modifications and variations may be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is intended that all equivalent modifications and variations of the invention be covered by the claims, which are within the ordinary skill of the art, be within the spirit and scope of the present disclosure.

Claims (11)

1. A method of acid treating a molecular sieve comprising the steps of: (1) Adding a molecular sieve to be treated into a solution containing an acid chelating agent, and mixing under heating to obtain a mixture, wherein the molecular sieve is selected from at least one of SAPO-11, SAPO-5, SAPO-34, SAPO-44 and AlPO-34; (2) The mixture is treated at 60-180 ℃ to obtain a multi-level pore molecular sieve, wherein the molecular sieve contains a microporous, mesoporous and macroporous tertiary pore canal structure, and the large pore diameter distribution is 400nm and 1100nm respectively; and/or BET specific surface area of 300 to 700m 2 /g。
2. The method for acid-treating a molecular sieve according to claim 1, wherein the weight ratio of the molecular sieve to be treated and the acidic chelating agent-containing solution in step (1) is 1 (1) to (50).
3. The method for acid-treating a molecular sieve according to claim 1 or 2, wherein the weight ratio of the molecular sieve to be treated and the acidic chelating agent-containing solution in step (1) is 1 (2 to 20).
4. The method of acid treating a molecular sieve according to claim 1, wherein the treatment time in step (2) is at least 20 minutes.
5. The method for acid treating a molecular sieve according to claim 1 or 4, wherein the treatment time in step (2) is at least 30min to 12h.
6. The method of acid treating a molecular sieve according to claim 1, wherein the acid chelating agent is present in the solution in an amount of 1% to 30% by weight.
7. The method of acid treating a molecular sieve according to claim 1 or 6, wherein the acid chelating agent is present in the solution in an amount of 1% to 10% by weight.
8. The method of acid treating a molecular sieve according to claim 1, wherein the acid chelating agent is selected from one or at least one of ethylenediamine tetraacetic acid (EDTA), diethylenetriamine pentaacetic acid (DTPA), aminotrimethylene phosphonic Acid (ATMP), aminotrimethylene phosphonic Acid (ATP), gluconic acid and Maleic Acid (MAO).
9. The method of acid treating a molecular sieve according to claim 1, wherein the relative crystallinity of the molecular sieve after acid treatment is maintained or increased.
10. The method for acid-treating a molecular sieve according to claim 9, characterized in that the crystallinity of the molecular sieve after treatment and the molecular sieve to be treated is 1 or more.
11. The method of acid treating a molecular sieve according to claim 10, characterized in that the crystallinity of the molecular sieve after treatment and the molecular sieve to be treated is less than 1.1.
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