CN111285382A - Method for preparing metal modified nano-crystalline SAPO-34 molecular sieve, product and application thereof - Google Patents

Method for preparing metal modified nano-crystalline SAPO-34 molecular sieve, product and application thereof Download PDF

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CN111285382A
CN111285382A CN202010085958.0A CN202010085958A CN111285382A CN 111285382 A CN111285382 A CN 111285382A CN 202010085958 A CN202010085958 A CN 202010085958A CN 111285382 A CN111285382 A CN 111285382A
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王亮
李科达
贺大威
谭成刚
姜淑杰
李世洪
韩国勇
赵全
纪天旭
张海旭
张德宇
冯延铠
何福正
焉德超
张铭
姜月
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Zhongke New Catalytic Technology Dalian Co ltd
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/30—Ion-exchange
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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Abstract

The invention provides a synthesis method of a metal modified nano-crystalline SAPO-34 molecular sieve, a product and application thereof, the invention comprises the steps of carrying out ion exchange on the SAPO-34 molecular sieve used as a raw material and a metal solution, and then crushing the ion exchanged SAPO-34 molecular sieve into particles with the particle size of 10-800 nm to obtain a low-crystallinity crystallization precursor containing target metal ions; mixing an organic amine template agent R, water and optional silicon source, aluminum source and phosphorus source to prepare a crystallization liquid; and mixing the crystallization precursor with crystallization liquid, performing hydrothermal crystallization, and finally separating to obtain the metal modified nano-crystalline SAPO-34 molecular sieve. The method not only can simply prepare the metal modified nano-crystalline SAPO-34 molecular sieve, but also can effectively improve the mass transfer capacity of the molecular sieve catalyst, obviously prolong the service life and obviously improve the selectivity in the reaction of preparing olefin from methanol.

Description

Method for preparing metal modified nano-crystalline SAPO-34 molecular sieve, product and application thereof
Technical Field
The invention belongs to the technical field of SAPO molecular sieves, and particularly relates to a method for preparing a metal modified nano-crystalline SAPO-34 molecular sieve, a product and application thereof.
Background
The low-carbon olefin represented by ethylene and propylene is the most basic raw material in the chemical industry, and the annual yield of the olefin can be measured by the chemical development level of a country. Therefore, the development of olefin production technology is of great significance to the entire chemical industry. The traditional low-carbon olefin production process mainly depends on petroleum catalytic cracking and combines the current situation of 'more coal, poor gas and less oil' in China, and the development of low-carbon olefins such as ethylene, propylene and the like produced by using coal or natural gas as a raw material through methanol has extremely important strategic significance.
The technology for preparing methanol from coal or natural gas is very perfect and industrialized, and the key content of the technology for preparing olefin from Methanol (MTO) lies in the development of a catalyst with high selectivity, carbon deposition resistance and strong regeneration capacity. Although researchers have made breakthrough progress so far, many problems still need to be solved. United states united carbides Corporation (Union Carbide Corporation) succeeded in developing a new silicoaluminophosphate series molecular sieve SAPO-n (n stands for structural model) in 1984. Among them, the excellent catalytic performance of SAPO-34 molecular sieve in MTO reaction is receiving wide attention. The SAPO-34 molecular sieve consists of four elements of silicon, aluminum, phosphorus and oxygen, the composition of the four elements can be changed within a certain range, and SiO4、PO4And AlO4The electronegative framework of the molecular sieve is formed, so that the molecular sieve has proton acidity. The crystal framework of the molecular sieve is Chabazite (CHA), and the molecular sieve has an elliptical spherical cage formed by eight-membered rings and a three-dimensional pore structure, and the pore diameter belongs to micropores. Therefore, the SAPO-34 molecular sieve has excellent catalytic activity in the MTO reaction. Researches show that the physicochemical properties influencing the catalytic performance of the SAPO-34 molecular sieve mainly comprise surface acidity, grain size, pore structure, chemical environment in pore channels and the like. Proper reduction of acid strength and density is beneficial to increase ethylene and propylene selectivity and can extend catalyst life.
Much work has been done on the synthesis of highly active SAPO-34 molecular sieves. Wherein, after the SAPO-34 molecular sieve is synthesized, the acidity of the molecular sieve is regulated and controlled by modifying the SAPO-34 molecular sieve through metal ions, so that the catalyst has better selectivity of low-carbon olefin and longer service life. Chinese patent CN108097304A relates to a preparation method of a metallic copper modified SAPO-34 molecular sieve. The method comprises the steps of firstly synthesizing the SAPO-34 molecular sieve by a two-stage crystallization method, then filtering crystallization liquid to obtain filtrate and filter cakes, then adding oxidizing acid into the filter cakes to react, and simultaneously adding the oxidizing acid and cuprous salt into the filtrate to react. And finally, mixing the filter cake and the filtrate, and performing a first-line treatment to obtain the Cu-SAPO-34 molecular sieve catalyst with high activity, low cost and no pollution. Chinese patent CN104495870B reports that a metal modified SAPO-34 molecular sieve is obtained by ion exchange of metal salt and a synthesized SAPO-34 molecular sieve under the action of ammonium chloride. The catalyst prepared by the method has a regular pore structure and a larger specific surface area, and the acidity and the orifice of the molecular sieve are effectively regulated and controlled, so that the selectivity of ethylene and propylene in the reaction of preparing olefin from methanol is improved to 94 percent.
In addition, the synthesized nano-crystalline molecular sieve can also improve the catalytic capability of the catalyst. The microporous pore canals of the SAPO-34 molecular sieve generate limitation on the diffusion mass transfer of reactants or products, thereby causing rapid carbon deposition inactivation. Research finds that reducing the particle size of the molecular sieve is beneficial to eliminating the limitation of diffusion mass transfer and obtaining long catalytic life. Patent CN102275948B discloses a synthesis method of nano-crystalline silicoaluminophosphate molecular sieve SAPO-34, the volume median diameter of which is less than 800 nm. However, the method for synthesizing the metal modified nano-crystalline SAPO-34 molecular sieve simultaneously regulates and controls the acidity of the molecular sieve catalyst and improves the mass transfer capacity so as to enhance the catalytic performance of the catalyst in the preparation of olefin from methanol, and has not been reported.
Disclosure of Invention
Therefore, the invention starts from the finished product of the SAPO-34 molecular sieve, firstly, the commercial SAPO-34 molecular sieve is subjected to metal ion exchange, and then, the SAPO-34 subjected to ion exchange is subjected to crushing treatment, so that the enriched part of peripheral silicon is effectively reduced, and meanwhile, metal ions are introduced into a crystallization precursor. Then repairing the crystal structure of the SAPO-34 molecular sieve by secondary crystallization, dispersing metal ions in the crystal framework structure of the SAPO-34 molecular sieve, integrating the metal ions into the crystal structure, and effectively regulating and controlling the acidity and the pore opening of the nano crystal particles of the SAPO-34 molecular sieve by regulating the composition of a crystallization liquid and the crystallization conditions so as to achieve the purpose of improving the catalytic performance of the SAPO-34 molecular sieve. Therefore, the metal ion modified nano-crystalline SAPO-34 molecular sieve with high catalytic performance in the MTO reaction is prepared simply and conveniently at low cost. Accordingly, in one aspect, the present invention provides a method for preparing a metal ion modified nanocrystalline SAPO-34 molecular sieve, the method comprising the steps of:
(1) the SAPO-34 molecular sieve as the raw material is put into a metal salt water solution for ion exchange, and then centrifugal separation is carried out to obtain the SAPO-34 molecular sieve after ion exchange;
(2) crushing the SAPO-34 molecular sieve subjected to ion exchange into particles with the particle size of 10-800 nm to obtain a crystallization precursor with low crystallinity;
(3) and (3) mixing the crystallization precursor obtained in the step (2) with crystallization liquid, performing hydrothermal crystallization, and separating to obtain the metal-modified nano-crystalline SAPO-34 molecular sieve, wherein the crystallization liquid is one or more of an organic amine template agent R, water, a silicon source, an aluminum source and a phosphorus source.
The metal salt of the metal salt aqueous solution in the step (1) is one or a mixture of any more of inorganic salts and organic salts of copper, rhodium, cobalt, manganese, magnesium, iron, nickel and zinc. Further, the metal salt of the aqueous solution of metal salt in step (1) is one or a mixture of any of inorganic and organic salts of copper, cobalt, manganese, nickel and zinc.
In a preferred embodiment, the ion exchange temperature in the step (1) is 30-95 ℃, and the ion exchange time is 2-8 hours. Furthermore, in the step (1), the ion exchange temperature is 40-80 ℃, and the ion exchange time is 2-6 hours.
In a preferred embodiment, in the step (2), the ion-exchanged SAPO-34 molecular sieve is pulverized into particles with a particle size of 50 to 800nm, and further, is pulverized into particles with a particle size of 50 to 500 nm.
In a preferred embodiment, the silicon source used in step (3) is selected from one or more of ethyl orthosilicate, silica sol and white carbon black; the aluminum source is one or more selected from aluminum isopropoxide, pseudo-boehmite, aluminum sol and aluminum hydroxide; the phosphorus source is selected from one or more of phosphoric acid, phosphorous acid and phosphorus pentoxide; the organic amine template agent is selected from one or more of triethylamine, diethylamine, di-n-propylamine, morpholine, tetraethylammonium hydroxide, isopropylamine and diisopropanolamine.
In a preferred embodiment, the crystallization liquid in step (3) is a mixed liquid of an organic amine template agent R, water, a silicon source, an aluminum source and a phosphorus source, and the molar ratio of the aluminum source, the phosphorus source, the silicon source, the organic amine template agent R and the water in the crystallization liquid is Al2O3∶P2O5∶ SiO2∶R∶H2O is 0.1-30: 0.05-12: 1-300: 1000, preferably Al2O3∶P2O5∶SiO2∶ R∶H2O is 1-20: 1-10: 1-100: 1000. In the invention, the composition of the nanocrystalline SAPO-34 molecular sieve can be controlled by adjusting the composition of the crystallization liquid in the step (3) or regulating and controlling the crystallization temperature and time.
In a preferred embodiment, the mass ratio of the crystallization liquid to the crystallization precursor in the step (4) is 1-100: 1.
In a preferred embodiment, the hydrothermal crystallization in the step (4) is performed at a temperature of 80 to 240 ℃ for 0.5 to 72 hours.
In another aspect, the present invention provides a metal modified nanocrystalline SAPO-34 molecular sieve prepared by the above method, the crystal framework of which is doped with a quantity of metal ions, which may include metal ions such as copper, cobalt, manganese, nickel and zinc. The metal modified nano-crystalline SAPO-34 molecular sieve has the particle size of 10-800 nm, and the crystal morphology is a cubic or cubic accumulation body. Furthermore, the granularity of the metal modified nano-crystalline SAPO-34 molecular sieve is 50-500 nm.
In another aspect, the invention provides the use of the nanocrystalline SAPO-34 molecular sieve as a catalyst for acid-catalyzed reactions, especially for reactions for producing olefins by converting oxygenates, after being calcined in air at a temperature of 400-700 ℃.
The method has the beneficial effects that the SAPO-34 molecular sieve is subjected to metal ion exchange, and then the SAPO-34 subjected to ion exchange is crushed, so that the enriched silicon part on the periphery is effectively reduced, and metal ions are introduced into a crystallization precursor. Then repairing the crystal structure of the SAPO-34 molecular sieve by secondary crystallization, dispersing metal ions in the crystal framework structure of the SAPO-34 molecular sieve, and effectively regulating and controlling the acidity and the pore opening of the nano crystal grain of the SAPO-34 molecular sieve by regulating and controlling the composition of a crystallization liquid and the crystallization conditions so as to achieve the purpose of improving the catalytic performance of the SAPO-34 molecular sieve. The invention has low cost, is simple and convenient, and the prepared metal ion modified nanocrystalline SAPO-34 molecular sieve has high catalytic performance in MTO reaction, can effectively improve the mass transfer capability of the molecular sieve catalyst, obviously prolongs the service life in the reaction of preparing olefin from methanol, and obviously improves the selectivity. Therefore, the metal ion modified nano-crystalline SAPO-34 molecular sieve is prepared simply and conveniently at low cost.
Drawings
FIG. 1 is an XRD diffraction pattern of samples 2 to 9 obtained in examples 2 to 9.
Detailed Description
The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
In the invention, the commercial SAPO-34 molecular sieve for crushing as the raw material is purchased from New technology of Chinese Clay and Convolvulus GmbH, and the particle size range is 1-10 μm.
Example 1: preparation of SAPO-34 molecular sieve samples (a) - (f) after ion exchange
Placing a commercial SAPO-34 molecular sieve purchased from the new catalysis technology of Chinese Clay and Connection, Inc. in a solution containing metal ions, stirring for 5 minutes, heating to an ion exchange temperature, carrying out ion exchange for a certain time, carrying out centrifugal separation to obtain a solid, washing for 3 times by deionized water, and drying at 80 ℃ to obtain an SAPO-34 molecular sieve sample (metal modified SAPO molecular sieve sample) after ion exchange, wherein the relations among the number of the obtained metal modified SAPO molecular sieve sample, the number of the adopted molecular sieve raw powder, the solution containing the metal ions, the solid-liquid mass ratio of the molecular sieve raw powder to the solution containing the metal ions, the ion exchange temperature and the ion exchange time are shown in Table 1.
TABLE 1 Metal modified SAPO molecular sieve samples
Figure BDA0002382044120000041
Examples 2 to 9: preparation of metal ion modified nano-crystalline SAPO-34 molecular sieve product
Taking SAPO-34 molecular sieve samples (a) - (f) subjected to ion exchange in example 1 as raw materials respectively, and crushing the raw materials into particles of 10-800 nm to obtain a crystallization precursor with small particle size and low crystallinity; then mixing an organic amine template agent R, water, a silicon source, an aluminum source and a phosphorus source according to a certain proportion to prepare a crystallization liquid; mixing the crystallization precursor and the crystallization liquid according to a certain proportion, and carrying out secondary crystallization at a certain temperature for a period of time; and (3) carrying out centrifugal separation, washing by deionized water and drying (in air at 120 ℃) to obtain the SAPO-34 molecular sieve with the nano crystal grains, representing the crystallinity by XRD, representing the product by XRF, measuring the particle size ranges of the precursor and the obtained product by a laser particle size method, and calculating the average value. Wherein, the SAPO-34 molecular sieve sample after ion exchange, the particle size range of the precursor, the used template agent, the raw materials, the composition (molar ratio) of the secondary crystallization liquid, the mass ratio of the secondary crystallization liquid to the precursor, the temperature and time of the secondary crystallization, the yield, and the particle size range and the average particle size of the obtained product are shown in the following table 2.
TABLE 2 Metal ion modified nanocrystalline SAPO-34 molecular sieve products
Figure BDA0002382044120000051
Example 10: XRD characterization and XRF elemental analysis of products 2-9
And (3) characterizing the products 2-9 obtained in the examples 2-9 by adopting X-ray powder diffraction phase analysis and X-ray fluorescence element analysis. The results show that the products 2-9 obtained in examples 2-9 all have standard XRD diffraction spectra (figure 1) similar to that of SAPO-34, namely, the peak positions of the diffraction peaks are the same, and the peak intensities are slightly different. The elemental composition of the products 2-9 obtained in examples 2-9 is shown in Table 3.
Table 3 elemental composition of the products of the examples
Figure BDA0002382044120000061
Comparative example 1
10g of pseudo-boehmite (72.5 wt%), 40g of water, 16.4g of phosphoric acid (85 wt%), 4.3g of silica sol (30 wt%) were sequentially added into a synthesis kettle, and after stirring, 18.5g of N, N-dimethylcyclohexylamine was added, and the mixture was stirred under a seal for 2 hours to obtain a uniform initial synthesis gel. And transferring the gel into a stainless steel synthesis kettle, heating to 190 ℃, and dynamically crystallizing for 12 hours. Taking out the synthesis kettle and cooling. The solid product was centrifuged, washed to neutrality with deionized water, and dried in air at 100 ℃ to obtain 10.5g of raw powder with a solid yield of 47.1%. XRD analysis showed the resulting solid to be SAPO-34 molecular sieve. The XRD data are similar to those in table 2, i.e., the peak positions are the same, the intensities of each peak are lower than those of the sample of example 2, and the highest peak intensity is about 70% of that of the sample of example 2.
Comparative example 2
16.4g of phosphoric acid (85 wt%), 40g of water, 4.3g of silica sol (30 wt%) and 10g of pseudo-boehmite (72.5 wt%) were sequentially added to the synthesis kettle, and after stirring, 18.5g of N, N-dimethylcyclohexylamine was added, and the mixture was stirred under a seal for 2 hours to obtain a uniform initial synthesis gel. And transferring the gel into a stainless steel synthesis kettle, heating to 190 ℃, and dynamically crystallizing for 48 hours. Taking out the synthesis kettle and cooling. The solid product was centrifuged, washed to neutrality with deionized water, and dried in air at 100 ℃ to obtain 16.6g of raw powder with a solid yield of 75.7%. XRD analysis showed the resulting solid to be SAPO-34 molecular sieve. The XRD data are similar to those in table 2, i.e., the peak positions are the same, the intensities of each peak are lower than those of the sample of example 2, and the highest peak intensity is about 85% of that of the sample of example 2.
Example 10
The samples obtained in the example 2 and the comparative example 1 are introduced with air at 600 ℃ for roasting for 4 hours, and then are tabletted and crushed to 20-40 meshes. A1.0 g sample was weighed and charged into a fixed bed reactor to evaluate the MTO reaction. Activating for 1 hour at 550 ℃ by introducing nitrogen, and then cooling to 450 ℃ for reaction. The methanol is carried by nitrogen, the flow rate of the nitrogen is 40ml/min, and the weight space velocity of the methanol is 2.0h-1. The reaction products were analyzed by on-line gas chromatography (Varian3800, FID detector, capillary column PoraPLOTQ-HT) and the results are shown in Table 4. The comparison shows that the reaction life (196min) of the example 2 is longer than that of the comparative example 1(148min), and the diene selectivity (93.5%) is higher than that of the comparative example 1 (86.46%), so that the example 2 has more excellent catalytic activity.
Results of methanol to olefin reactions for samples in Table 4
Figure BDA0002382044120000071
While the invention has been described with reference to exemplary embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed, but that the invention will include all embodiments falling within the scope of the appended claims.

Claims (10)

1. A method for preparing a metal modified nano-crystalline SAPO-34 molecular sieve is characterized by comprising the following steps:
the method comprises the following steps:
(1) the SAPO-34 molecular sieve as the raw material is put into a metal salt water solution for ion exchange, and then centrifugal separation is carried out to obtain the SAPO-34 molecular sieve after ion exchange;
(2) crushing the SAPO-34 molecular sieve subjected to ion exchange in the step (1) into particles with the particle size of 10-800 nm to obtain a crystallization precursor with low crystallinity;
(3) and (3) mixing the crystallization precursor obtained in the step (2) with crystallization liquid, performing hydrothermal crystallization, and separating to obtain the metal-modified nano-crystalline SAPO-34 molecular sieve, wherein the crystallization liquid is one or more of an organic amine template agent R, water, a silicon source, an aluminum source and a phosphorus source.
2. The method for preparing a metal modified nanocrystalline SAPO-34 molecular sieve according to claim 1, characterized in that: the metal salt of the metal salt solution in the step (1) is one or a mixture of any more of inorganic salts and organic salts of copper, rhodium, cobalt, manganese, magnesium, iron, nickel and zinc.
3. The method for preparing a metal modified nanocrystalline SAPO-34 molecular sieve according to claim 1, characterized in that: the ion exchange temperature in the step (1) is 30-95 ℃, and the ion exchange time is 2-8 hours.
4. The method for preparing a metal modified nanocrystalline SAPO-34 molecular sieve according to claim 1, characterized in that: and (3) crushing the SAPO-34 molecular sieve subjected to ion exchange into particles with the particle size of 50-800 nm in the step (2).
5. The method for preparing a metal modified nanocrystalline SAPO-34 molecular sieve according to claim 1, characterized in that: the silicon source used in the step (3) is one or more selected from ethyl orthosilicate, silica sol and white carbon black; the aluminum source is one or more selected from aluminum isopropoxide, pseudo-boehmite, aluminum sol and aluminum hydroxide; the phosphorus source is selected from one or more of phosphoric acid, phosphorous acid and phosphorus pentoxide; the organic amine template agent R is selected from one or more of triethylamine, diethylamine, di-n-propylamine, morpholine, tetraethylammonium hydroxide, isopropylamine and diisopropanolamine.
6. The method of claim 1, wherein the method is used for preparing the metal modified nano-crystalline SAPO-34 molecular sieve,the method is characterized in that: the crystallization liquid in the step (3) is a mixed liquid of an organic amine template agent R, water, a silicon source, an aluminum source and a phosphorus source, and the molar ratio of the aluminum source, the phosphorus source, the silicon source, the organic amine template agent R and the water in the crystallization liquid is Al2O3:P2O5:SiO2:R:H2O＝0.1～30:0.1～30:0.05～12:1～300:1000。
7. The method for preparing a metal modified nanocrystalline SAPO-34 molecular sieve according to claim 1, characterized in that: the mass ratio of the crystallization liquid to the crystallization precursor in the step (3) is 1-100: 1.
8. The metal modified nano-crystalline SAPO-34 molecular sieve prepared by the method of any one of claims 1 to 7, wherein the metal modified nano-crystalline SAPO-34 molecular sieve has a particle size of 10 to 800nm, a cubic or cubic stack of crystals, and a crystal framework doped with metal ions.
9. Use of the metal modified nano-crystalline SAPO-34 molecular sieve of claim 8 as a catalyst for acid-catalyzed reactions after calcination in air at 400-700 ℃.
10. The use of the metal modified nano-crystalline SAPO-34 molecular sieve of claim 8 as a catalyst for olefin production by oxygenate conversion after calcination in 500-700 ℃ air.
CN202010085958.0A 2020-02-11 2020-02-11 Method for preparing metal modified nano-crystalline SAPO-34 molecular sieve, product and application thereof Withdrawn CN111285382A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115805097A (en) * 2022-12-01 2023-03-17 中触媒新材料股份有限公司 Large-grain Zn @ Silicalite-1 low-carbon alkane dehydrogenation catalyst and preparation method thereof
CN115920947A (en) * 2022-12-27 2023-04-07 中触媒新材料股份有限公司 Co @ Silicalite-1 low-carbon alkane dehydrogenation catalyst and preparation method and application thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115805097A (en) * 2022-12-01 2023-03-17 中触媒新材料股份有限公司 Large-grain Zn @ Silicalite-1 low-carbon alkane dehydrogenation catalyst and preparation method thereof
CN115805097B (en) * 2022-12-01 2024-03-01 中触媒新材料股份有限公司 Large-grain Zn@Silicalite-1 low-carbon alkane dehydrogenation catalyst and preparation method thereof
CN115920947A (en) * 2022-12-27 2023-04-07 中触媒新材料股份有限公司 Co @ Silicalite-1 low-carbon alkane dehydrogenation catalyst and preparation method and application thereof

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Application publication date: 20200616