CN110407230B - Method for synthesizing CHA structure molecular sieve and CHA structure molecular sieve - Google Patents

Method for synthesizing CHA structure molecular sieve and CHA structure molecular sieve Download PDF

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CN110407230B
CN110407230B CN201810402770.7A CN201810402770A CN110407230B CN 110407230 B CN110407230 B CN 110407230B CN 201810402770 A CN201810402770 A CN 201810402770A CN 110407230 B CN110407230 B CN 110407230B
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刘建强
李明罡
罗一斌
舒兴田
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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Abstract

The present disclosure relates to a method for synthesizing a CHA structure molecular sieveA method and a CHA structure molecular sieve, the method comprising the steps of: a. mixing an organic template agent, an aluminum source, a silicon source and optional water to obtain a mixture to be crystallized, wherein the ratio of R: SiO 22：Al2O3＝(1‑100)：(10‑500)：1，H2O：SiO2(5-100): 1, wherein R represents the mole number of the organic template in the mixture to be crystallized; b. b, crystallizing the mixture to be crystallized obtained in the step a, and recovering a solid product; wherein the organic template agent is 5,6,7, 8-tetrahydronaphthalene-2-yl-trimethyl ammonium hydroxide and/or p-vinyl phenyl-N, N, N-trimethyl ammonium hydroxide. The method adopts the novel template agent to synthesize the CHA structure molecular sieve, saves the alkali metal ion exchange process in the prior art, has simple synthesis steps, low production cost, no COD wastewater discharge and no pollution to the environment.

Description

Method for synthesizing CHA structure molecular sieve and CHA structure molecular sieve
Technical Field
The disclosure relates to a method for synthesizing a CHA-structured molecular sieve and the CHA-structured molecular sieve.
Background
The CHA structure silicon-aluminum molecular sieve is a zeolite material with eight-membered ring windows and three-dimensional cross channel structures, has a channel structure with specific size and shape, has good adsorption performance and shape selection performance, has larger specific surface area and adjustable acid property, and is widely applied to gas separation and catalytic reaction.
U.S. Pat. No. 4,544,538 discloses a method for synthesizing a CHA structure silicon-aluminum molecular sieve, which comprises the steps of uniformly mixing a template agent, a silicon source, an aluminum source, an alkali metal salt and water by taking expensive and toxic adamantane quaternary ammonium ions as the template agent, and performing hydrothermal crystallization at 100-235 ℃ for more than 3 days to obtain the CHA structure silicon-aluminum molecular sieve. The obtained product is exchanged with an ammonium-containing solution, and then the hydrogen-type CHA-structure silicon-aluminum molecular sieve can be obtained by roasting, but a large amount of nitrogen-containing wastewater is generated in the exchange process, and the environmental protection pressure of enterprises is huge.
Disclosure of Invention
It is an object of the present disclosure to provide a method of synthesizing a CHA-structured molecular sieve and a CHA-structured molecular sieve, which method is capable of avoiding the use of expensive and toxic organic templating agents.
To achieve the above object, a first aspect of the present disclosure: there is provided a method of synthesizing a CHA structured molecular sieve, the method comprising the steps of:
a. mixing an organic template agent, an aluminum source, a silicon source and optional water to obtain a mixture to be crystallized, wherein the ratio of R: SiO 22：Al2O3＝(1-100)：(10-500)：1，H2O：SiO2(5-100): 1, wherein R represents the mole number of the organic template in the mixture to be crystallized;
b. b, crystallizing the mixture to be crystallized obtained in the step a, and recovering a solid product;
wherein the organic template agent is 5,6,7, 8-tetrahydronaphthalene-2-yl-trimethyl ammonium hydroxide and/or p-vinyl phenyl-N, N, N-trimethyl ammonium hydroxide.
Optionally, the method further comprises: in the step a, the organic template agent and an aluminum source are mixed, and are processed for 0.5 to 50 hours at the temperature of between 45 and 190 ℃ under a closed condition to obtain an aluminum-containing colloid, and then the aluminum-containing colloid is mixed with a silicon source and optional water to obtain a mixture to be crystallized.
Optionally, the method further comprises: in the step a, the mixture to be crystallized also contains a seed crystal, the seed crystal is a CHA structure silicon-aluminum molecular sieve, and the weight ratio of the seed crystal to the silicon source calculated by silicon oxide is (1-20): 100.
alternatively, the seed crystal has a silica to alumina molar ratio of 10 to 40 on an oxide basis.
Optionally, the method further comprises: in the step a, firstly, mixing an organic template agent and an aluminum source, and processing for 0.5-50 hours at 45-190 ℃ under a closed condition to obtain an aluminum-containing colloid, and then mixing the aluminum-containing colloid with seed crystals, a silicon source and optional water to obtain a mixture to be crystallized.
Optionally, in step a, the aluminum source is at least one selected from the group consisting of aluminum, boehmite, pseudoboehmite, gibbsite, aluminum hydroxide, alumina and aluminum alcoholate.
Optionally, in step a, the silicon source is at least one selected from the group consisting of silicate, silica, silicic acid, silica gel, clay, and ethyl silicate.
Optionally, in step a, the content of alkali metal in the mixture to be crystallized is not higher than 1000ppm based on the total weight of the mixture to be crystallized.
Optionally, the method further comprises: and collecting crystallization mother liquor obtained by the crystallization treatment, and returning the crystallization mother liquor to be used for preparing the mixture to be crystallized.
Optionally, in step b, the conditions of the crystallization treatment are as follows: the temperature is 120 ℃ and 190 ℃, and the time is 1-10 days.
Optionally, the method further comprises: and recovering the solid product, and then drying and roasting.
Optionally, the drying conditions are: the temperature is 50-120 ℃, and the time is 4-24 hours;
the roasting conditions are as follows: the temperature is 300 ℃ and 700 ℃ and the time is 1-10 hours.
In a second aspect of the present disclosure: there is provided a CHA structured molecular sieve synthesized by the method of the first aspect of the disclosure.
Through the technical scheme, the CHA structure molecular sieve is synthesized by adopting the novel template agent, the use of expensive and toxic N, N, N-trimethyl-adamantyl ammonium hydroxide is avoided, the alkali metal ion exchange process in the prior art is omitted, the synthesis step is simple, the production cost is low, COD (chemical oxygen demand) wastewater discharge is avoided, and the environment pollution is avoided. The CHA structure molecular sieve prepared by the method can reach higher silicon-aluminum ratio and has higher relative crystallinity.
Additional features and advantages of the disclosure will be set forth in the detailed description which follows.
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The accompanying drawings, which are included to provide a further understanding of the disclosure and are incorporated in and constitute a part of this specification, illustrate embodiments of the disclosure and together with the description serve to explain the disclosure without limiting the disclosure. In the drawings:
FIG. 1 is an X-ray diffraction pattern of the CHA structure molecular sieve prepared in example 1.
Fig. 2 is a scanning electron micrograph of the CHA structured molecular sieve prepared in example 1.
Detailed Description
The following detailed description of specific embodiments of the present disclosure is provided in connection with the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the present disclosure, are given by way of illustration and explanation only, not limitation.
The first aspect of the disclosure: there is provided a method of synthesizing a CHA structured molecular sieve, the method comprising the steps of:
a. mixing an organic template agent, an aluminum source, a silicon source and optional water to obtain a mixture to be crystallized, wherein the ratio of R: SiO 22：Al2O3＝(1-100)：(10-500)：1，H2O：SiO2(5-100): 1, wherein R represents the mole number of the organic template in the mixture to be crystallized;
b. b, crystallizing the mixture to be crystallized obtained in the step a, and recovering a solid product;
wherein the organic template agent is 5,6,7, 8-tetrahydronaphthalene-2-yl-trimethyl ammonium hydroxide and/or p-vinyl phenyl-N, N, N-trimethyl ammonium hydroxide.
The CHA structure molecular sieve is synthesized by adopting the novel template agent, the use of expensive and toxic N, N, N-trimethyl-adamantyl ammonium hydroxide is avoided, the alkali metal ion exchange procedure in the prior art is omitted, the synthesis step is simple, the production cost is low, COD wastewater discharge is avoided, and the environmental pollution is avoided.
According to the present disclosure, the 5,6,7, 8-tetrahydronaphthalen-2-yl-trimethylammonium hydroxide has the formula C13H20NOH, structural formula:
Figure BDA0001646118560000041
the chemical formula of the p-vinyl phenyl-N, N, N-trimethyl ammonium hydroxide is C11H16NOH, structural formula:
Figure BDA0001646118560000042
according to the present disclosure, the organic templating agent is preferably 5,6,7, 8-tetrahydronaphthalen-2-yl-trimethylammonium hydroxide. The 5,6,7, 8-tetrahydronaphthalen-2-yl-trimethylammonium hydroxide and/or p-vinylphenyl-N, N, N-trimethylammonium hydroxide may be prepared by methods known in the art. The organic template may be in the form of an aqueous solution, and the concentration of the aqueous solution is not particularly limited in the present disclosure.
According to the present disclosure, the method may further comprise: in the step a, the organic template agent and an aluminum source are mixed, and are processed for 0.5 to 50 hours at the temperature of between 45 and 190 ℃ under a closed condition to obtain an aluminum-containing colloid, and then the aluminum-containing colloid is mixed with a silicon source and optional water to obtain a mixture to be crystallized. Preferably, the treatment time is 2 to 45 hours. Thus, the organic template and the aluminum source are treated firstly, so that the aluminum can be completely dissolved, and the crystallization treatment is favorably carried out. The dosage of the organic template and the aluminum source is within the range of the mixture ratio for the composition of the mixture to be crystallized, namely, the organic template and Al are used2O3The molar ratio of the aluminum source is (1-100): 1, preferably (2-60): 1.
to facilitate the crystallization process, in one embodiment of the present disclosure, the method may further include: in the step a, the mixture to be crystallized also contains seed crystals. The seed crystal is a CHA structure aluminosilicate molecular sieve, and can be prepared by adopting the existing method for preparing the CHA structure aluminosilicate molecular sieve, such as the method disclosed in patent US 4859442. The seed crystal may have a silica to alumina molar ratio, calculated as oxide, of 10 to 40, preferably 15 to 35. The seed crystal may be used in a small amount to achieve the above object, for example, the weight ratio of the seed crystal to the silicon source in terms of silicon oxide may be (1-20): 100, preferably (5-15): 1. in this embodiment, the method may further comprise: in the step a, firstly, mixing an organic template agent and an aluminum source, and processing for 0.5-50 hours at 45-190 ℃ under a closed condition to obtain an aluminum-containing colloid, and then mixing the aluminum-containing colloid with seed crystals, a silicon source and optional water to obtain a mixture to be crystallized. Preferably, the treatment time is 2 to 45 hours.
According to the present disclosure, preferably, in the mixture to be crystallized R: SiO 22：Al2O3＝(2-60)：(15-450)：1，H2O：SiO2(6-70): 1, wherein R represents the number of moles of organic templating agent in the mixture to be crystallized. It should be noted that the water in the mixture to be crystallized may be derived from an organic template, a silicon source or an aluminum source, and when the water content is insufficient, water may be additionally added, so long as the water-silicon ratio satisfies the range of the present disclosure.
According to the present disclosure, in order to make the content of alkali metal in the synthesized CHA structure molecular sieve low, the content of alkali metal in the mixture to be crystallized in step a may be not higher than 1000ppm, preferably not higher than 500ppm, based on the total weight of the mixture to be crystallized.
In accordance with the present disclosure, the aluminum source and the silicon source may be those conventionally used in the art, and in order to make the alkali metal content in the mixture to be crystallized low, the aluminum source and the silicon source of the present disclosure preferably do not contain alkali metal. For example, in the step a, the aluminum source may be at least one selected from the group consisting of aluminum, boehmite, pseudoboehmite, gibbsite, aluminum hydroxide, alumina and aluminum alcoholate. The silicon source can be at least one selected from silicate, silicon dioxide, silicic acid, silica gel, clay and ethyl silicate, and the silicon dioxide can be any form of silicon dioxide, such as fumed silica and/or precipitated silica; the silicon source is preferably at least one selected from silica gel, fumed silica, precipitated silica and ethyl silicate.
According to the disclosure, after the crystallization treatment is completed, the mixture obtained by the crystallization treatment is subjected to solid-liquid separation to obtain a solid product and a crystallization mother liquor, and in order to fully utilize the crystallization mother liquor, the method may further include: and collecting crystallization mother liquor obtained by the crystallization treatment, and returning the crystallization mother liquor to be used for preparing the mixture to be crystallized. The crystallization mother liquor can be used as make-up water to be returned for preparing the mixture to be crystallized, so that the discharge of waste water containing COD is avoided.
The conditions of the crystallization process may be conventional crystallization conditions in the art for synthesizing CHA structured molecular sieves, in accordance with the present disclosure. For example, in step b, the crystallization conditions may be: the temperature is 120-190 ℃, and preferably 160-170 ℃; the time period is 1 to 10 days, preferably 2 to 8 days, and more preferably 2.5 to 4 days. The crystallization treatment is carried out under a closed condition.
According to the present disclosure, the method may further comprise: and recovering the solid product, and then drying and roasting. The drying and calcination are conventional procedures for synthesizing molecular sieves in the art, and the conditions thereof are not particularly limited in the present disclosure. For example, the drying conditions may be: the temperature is 50-120 ℃ and the time is 4-24 hours. The roasting conditions can be as follows: the temperature is 300 ℃ and 700 ℃ and the time is 1-10 hours.
In a second aspect of the present disclosure: there is provided a CHA structured molecular sieve synthesized by the method of the first aspect of the disclosure. The molecular sieve with the CHA structure synthesized by the method of the first aspect of the disclosure has a specific surface area of 500-710m2/g，SiO2/Al2O3The molar ratio may be 10 to 500, and may have an alkali metal content, particularly a sodium content, of 1000ppm or less, preferably 500ppm or less, and the relative crystallinity may be 80% or more, and the crystal grain diameter may be 0.1 to 5 μm.
The present disclosure is further illustrated by the following examples, but is not limited thereto.
In the examples, the chemical composition of the molecular sieve was determined by X-ray fluorescence, which is described in "synthesis of ZSM11 molecular sieve and characterization thereof using EU-1 molecular sieve as a seed", gunn morning et al, petroleum refining and chemical industry, 2011, 7.
The content of alkali metals (for the determination of lithium, sodium and potassium) in the mixture to be crystallized is determined by the method of the national standard method GBT 15337-2008.
The relative crystallinity described in the examples is expressed as a ratio, in percent, of the sum of the peak areas of five characteristic diffraction peaks, at 9.5 °, 14.0 °, 16.1 °, 17.8 °, 20.5 °, in terms of 2 θ, of the product prepared by the process of the present disclosure and the X-ray diffraction (XRD) pattern of a CHA structured molecular sieve standard. XRD was measured on a SIMENS D5005 model X-ray diffractometer with CuK α radiation, 44 kv, 40 ma and a scan speed of 2 °/min. The CHA structured molecular sieve synthesized by the method of example 5 of patent US4859442 is used as a standard and its crystallinity is defined as 100%.
The specific surface area of the molecular sieve was measured using AS-3, AS-6 static nitrogen adsorption apparatus manufactured by Quantachrome instruments. The instrument parameters are as follows: the sample was placed in a sample handling system and evacuated to 1.33X 10 at 300 deg.C-2Pa, keeping the temperature and the pressure for 4h, and purifying the sample. Testing the purified samples at different specific pressures P/P at a liquid nitrogen temperature of-196 DEG C0The adsorption quantity and the desorption quantity of the nitrogen under the condition are obtained to obtain N2Adsorption-desorption isotherm curve. The specific surface area is then calculated using the two parameter BET formula.
In the examples, 5,6,7, 8-tetrahydronaphthalen-2-yl-trimethylammonium hydroxide or p-vinylbenzene-N, N-trimethylammonium hydroxide was prepared by: iodomethylation of 5,6,7, 8-tetrahydronaphthalen-2-yl-amine (or p-vinylphenylamine) to give the corresponding 5,6,7, 8-tetrahydronaphthalen-2-yl-trimethylammonium iodide (or p-vinylphenyl-N, N-trimethylammonium iodide), which is then reacted with sodium hydroxide to give the corresponding 5,6,7, 8-tetrahydronaphthalen-2-yl-trimethylammonium hydroxide (or p-vinylphenyl-N, N-trimethylammonium hydroxide); a process for the preparation of a seeded CHA structured aluminosilicate molecular sieve is disclosed in US 4859442.
Examples 1-16 are presented to illustrate the methods provided by the present disclosure for synthesizing CHA structured molecular sieves.
Example 1
0.50g of pseudoboehmite (Changling catalyst works, Al) was weighed out2O375% by weight) was mixed with 185.69g of 5,6,7, 8-tetrahydronaphthalen-2-yl-trimethylammonium hydroxide (25% by weight aqueous solution), placed in a polytetrafluoroethylene-lined reaction vessel, reacted at 100 ℃ for 41 hours under a sealed condition, cooled to room temperature, and then mixed with 6.73g of silica gel (Qingdao ocean chemical Co., Ltd., SiO)2Content 98.4% by weight) and 19.44g of water, to obtain a mixture to be crystallized having a molar composition R: SiO 22：Al2O3＝61：30：1，H2O：SiO280: 1, alkali metal content 416 ppm. And (3) crystallizing the mixture to be crystallized in a high-pressure reaction kettle at 160 ℃ for 96 hours, filtering and washing after crystallization, drying at 120 ℃ for 4 hours, and roasting at 550 ℃ for 6 hours to obtain the hydrogen-type CHA structure molecular sieve C-1.
The XRD spectrum of molecular sieve C-1 is shown in figure 1, and as can be seen from figure 1, molecular sieve C-1 has characteristic peaks at 9.5 °, 14.0 °, 16.1 °, 17.8 ° and 20.5 °, which proves that it is a CHA structure molecular sieve. The scanning electron microscope image is shown in FIG. 2. The grain size, relative crystallinity, etc. are shown in Table 1.
Example 2
9.71g of aluminum hydroxide (Beijing chemical product, analytical pure, Al) was weighed2 O 335% by weight) was mixed with 119.28g of p-vinylbenzene-N, N, N-trimethylammonium hydroxide (25% by weight aqueous solution), placed in a polytetrafluoroethylene-lined reaction vessel, reacted at 128 ℃ under a closed condition for 30 hours, cooled to room temperature, and then mixed with 81.26g of silica gel (Qingdao ocean chemical Co., Ltd., SiO)2Content 98.4% by weight) and 46.86g of water, to obtain a mixture to be crystallized having a molar composition R: SiO 22：Al2O3＝5：40：1，H2O：SiO26: 1, alkali metal content 368 ppm. Crystallizing the mixture at 175 deg.C for 48 hr in high-pressure reactor, filtering, washing, and oven drying at 120 deg.C for 14 hrThen, roasting for 6h at 550 ℃ to obtain the hydrogen-type CHA structure molecular sieve C-2.
The XRD spectrum of the molecular sieve C-2 is similar to that of figure 1, the molecular sieve product does not agglomerate, and the dispersity is similar to that of figure 2. The grain size, relative crystallinity, etc. are shown in Table 1.
Example 3
0.10g of alumina (Changling catalyst works, Al) was weighed out2O3Content 98 wt%), was mixed with 39.78g of 5,6,7, 8-tetrahydronaphthalen-2-yl-trimethylammonium hydroxide (25 wt% aqueous solution), placed in a polytetrafluoroethylene-lined reaction vessel, reacted at 150 ℃ for 10 hours under a sealed condition, cooled to room temperature, and then mixed with 11.48g of silica gel (Qingdao ocean chemical Co., Ltd., SiO)2Content 98.4% by weight) and 10.65g of water, to obtain a mixture to be crystallized having a molar composition R: SiO 22：Al2O3＝50：196：1，H2O：SiO212: 1, the alkali metal content was 238 ppm. And (3) crystallizing the mixture to be crystallized at 165 ℃ for 96 hours in a high-pressure reaction kettle, filtering and washing after crystallization, drying for 20 hours at 120 ℃, and roasting for 6 hours at 550 ℃ to obtain the hydrogen-type CHA structure molecular sieve C-3.
The XRD spectrum of the molecular sieve C-3 is similar to that of figure 1, the molecular sieve product does not agglomerate, and the dispersity is similar to that of figure 2. The grain size, relative crystallinity, etc. are shown in Table 1.
Example 4
0.36g of pseudoboehmite (Changling catalyst plant, Al) was weighed out2O375% by weight) was mixed with 122.74g of 5,6,7, 8-tetrahydronaphthalen-2-yl-trimethylammonium hydroxide (25% by weight aqueous solution), placed in a polytetrafluoroethylene-lined reaction vessel, reacted at 185 ℃ for 0.5 hour under a closed condition, cooled to room temperature, and then mixed with 64.97g of fumed silica (Shenyang chemical Co., Ltd., SiO)2Content 99% by weight) and 215.94g of water, to give a mixture to be crystallized having the molar composition R: SiO 22：Al2O3＝56：405：1，H2O：SiO216: 1, the alkali metal content is 411 ppm. Crystallizing the mixture to be crystallized in a high-pressure reaction kettle at 180 ℃ for 170 hours, and passing through a crystallizerFiltering, returning the filtrate, namely crystallization mother liquor, to be used for preparing a mixture to be crystallized, washing a filter cake, drying at 120 ℃ for 20 hours, and roasting at 550 ℃ for 6 hours to obtain the hydrogen-type CHA structure molecular sieve C-4.
The XRD spectrum of the molecular sieve C-4 is similar to that of figure 1, the molecular sieve product does not agglomerate, and the dispersity is similar to that of figure 2. The grain size, relative crystallinity, etc. are shown in Table 1.
Example 5
0.15g of pseudoboehmite (Changling catalyst works, Al) was weighed out2O3Content 75 wt.%), 80g of the crystallization mother liquor of example 4, 70.32g of organic template 5,6,7, 8-tetrahydronaphthalen-2-yl-trimethylammonium hydroxide (25 wt.% aqueous solution), placing in a reaction vessel containing a polytetrafluoroethylene liner, reacting at 120 ℃ under a closed condition for 22 hours, cooling to room temperature, and then mixing with 7.42g of fumed silica (Shenyang chemical Co., Ltd., SiO)2Content 99% by weight) and 76.50g of water to obtain a mixture to be crystallized having a molar composition R: SiO 22：Al2O3＝77：111：1，H2O：SiO295: 1, the alkali metal content was 352 ppm. And (3) crystallizing the mixture to be crystallized in a high-pressure reaction kettle at 135 ℃ for 90 hours, filtering and washing after crystallization, drying at 120 ℃ for 20 hours, and roasting at 550 ℃ for 6 hours to obtain the hydrogen-type CHA structure molecular sieve C-5.
The XRD spectrum of the molecular sieve C-5 is similar to that of figure 1, the molecular sieve product does not agglomerate, and the dispersity is similar to that of figure 2. The grain size, relative crystallinity, etc. are shown in Table 1.
Example 6
0.12g of alumina (Changling catalyst works, Al) was weighed out2O398 wt%), was mixed with 23.11g of p-vinylbenzene-N, N, N-trimethylammonium hydroxide (25 wt% aqueous solution), placed in a polytetrafluoroethylene-lined reaction vessel, reacted at 145 ℃ under a closed condition for 24 hours, cooled to room temperature, and then mixed with 29.30g of precipitated silica (SiO, Jiang chemical Co., Ltd., Zhejiang)2Content 93% by weight) and 144.11g of water, to give a mixture to be crystallized having a molar composition R: SiO 22：Al2O3＝28：394：1，H2O：SiO220: 1, the alkali metal content was 117 ppm. And (3) crystallizing the mixture to be crystallized in a high-pressure reaction kettle at 160 ℃ for 60 hours, filtering and washing after crystallization, drying at 120 ℃ for 24 hours, and roasting at 550 ℃ for 6 hours to obtain the hydrogen-type CHA structure molecular sieve C-6.
The XRD spectrum of the molecular sieve C-6 is similar to that of figure 1, the molecular sieve product does not agglomerate, and the dispersity is similar to that of figure 2. The grain size, relative crystallinity, etc. are shown in Table 1.
Example 7
0.19g of alumina (Changling catalyst works, Al) was weighed out2O3Content 98 wt%), was mixed with 84.64g of 5,6,7, 8-tetrahydronaphthalen-2-yl-trimethylammonium hydroxide (25 wt% aqueous solution), placed in a polytetrafluoroethylene-lined reaction vessel, reacted at 180 ℃ under closed conditions for 0.6 hour, cooled to room temperature, and then mixed with 27.94g of ethyl silicate (having a content of 98 wt% or more, from yokohama new chemistry ltd.) and 91.74g of water to obtain a mixture to be crystallized having a molar composition of R: SiO 22：Al2O3＝56：72：1，H2O：SiO265: 1, alkali metal content 371 ppm. And (3) crystallizing the mixture to be crystallized in a high-pressure reaction kettle at 170 ℃ for 96 hours, filtering and washing after crystallization, drying at 120 ℃ for 24 hours, and roasting at 550 ℃ for 6 hours to obtain the hydrogen-type CHA structure molecular sieve C-7.
The XRD spectrum of molecular sieve C-7 is similar to that of figure 1, the molecular sieve product does not agglomerate, and the dispersity is similar to that of figure 2. The grain size, relative crystallinity, etc. are shown in Table 1.
Example 8
0.50g of pseudoboehmite (Changling catalyst works, Al) was weighed out2O375 wt%), and 185.69g of 5,6,7, 8-tetrahydronaphthalen-2-yl-trimethylammonium hydroxide (25 wt% aqueous solution), placing the mixture in a polytetrafluoroethylene-lined reaction kettle, reacting at 100 ℃ for 41 hours in a sealed environment, cooling to room temperature, and mixing with 0.1g of seed crystal (CHA-structured silica-alumina molecular sieve, silica-alumina molar ratio of 11) and 6.73g of silica gel (Qingdao ocean chemical Co., Ltd., SiO)2Content 98.4 wt.%) and 19.44g of water, the weight of the seed and the silicon source, calculated as silicaThe quantity ratio is 1.5: 100, obtaining a mixture to be crystallized, wherein the molar composition is R: SiO 22：Al2O3＝61：30：1，H2O：SiO280: 1, alkali metal content 416 ppm. And (3) crystallizing the mixture to be crystallized in a high-pressure reaction kettle at 160 ℃ for 96 hours, filtering and washing after crystallization, drying at 120 ℃ for 4 hours, and roasting at 550 ℃ for 6 hours to obtain the hydrogen-type CHA structure molecular sieve C-8.
The XRD spectrum of the molecular sieve C-8 is similar to that of figure 1, the molecular sieve product does not agglomerate, and the dispersity is similar to that of figure 2. The grain size, relative crystallinity, etc. are shown in Table 1.
Example 9
9.71g of aluminum hydroxide (Beijing chemical product, analytical pure, Al) was weighed2 O 335% by weight) of the above-mentioned polymer was mixed with 119.28g of p-vinylbenzene-N, N, N-trimethylammonium hydroxide (25% by weight of an aqueous solution), the mixture was placed in a polytetrafluoroethylene-lined reaction vessel, reacted at 128 ℃ for 30 hours under a sealed condition, cooled to room temperature, and then mixed with 6.40g of a seed crystal (a CHA-structured silica-alumina molecular sieve having a silica-alumina molar ratio of 20) and 81.26g of silica gel (Qingdao ocean chemical Co., Ltd., SiO)2Content 98.4 wt.%) and 46.86g of water, the weight ratio of seed to silicon source, calculated as silica, being 8: 100, obtaining a mixture to be crystallized, wherein the molar composition is R: SiO 22：Al2O3＝5：40：1，H2O：SiO26: 1, alkali metal content 368 ppm. And (3) crystallizing the mixture to be crystallized in a high-pressure reaction kettle at 175 ℃ for 48h, filtering and washing after crystallization, drying at 120 ℃ for 14 h, and roasting at 550 ℃ for 6h to obtain the hydrogen-type CHA structure molecular sieve C-9.
The XRD spectrum of the molecular sieve C-9 is similar to that of figure 1, the molecular sieve product does not agglomerate, and the dispersity is similar to that of figure 2. The grain size, relative crystallinity, etc. are shown in Table 1.
Example 10
0.10g of alumina (Changling catalyst works, Al) was weighed out2O398% by weight) was mixed with 39.78g of 5,6,7, 8-tetrahydronaphthalen-2-yl-trimethylammonium hydroxide (25% by weight aqueous solution), placed in a polytetrafluoroethylene-lined reactor at 150 ℃ and sealedAfter reacting for 10 hours under the condition, the mixture was cooled to room temperature, and then mixed with 2.24g of seed crystal (CHA structure silica-alumina molecular sieve, silica-alumina molar ratio of 28) and 11.48g of silica gel (Qingdao ocean chemical Co., Ltd., SiO)2Content 98.4 wt.%) and 10.65g of water, the weight ratio of seed crystal to silicon source, calculated as silica, being 20: 100, obtaining a mixture to be crystallized, wherein the molar composition is R: SiO 22：Al2O3＝50：196：1，H2O：SiO212: 1, the alkali metal content was 238 ppm. And (3) crystallizing the mixture to be crystallized in a high-pressure reaction kettle at 165 ℃ for 96 hours, filtering and washing after crystallization, drying at 120 ℃ for 20 hours, and roasting at 550 ℃ for 6 hours to obtain the hydrogen-type CHA structure molecular sieve C-10.
The XRD spectrum of the molecular sieve C-10 is similar to that of figure 1, the molecular sieve product does not agglomerate, and the dispersity is similar to that of figure 2. The grain size, relative crystallinity, etc. are shown in Table 1.
Example 11
0.36g of pseudoboehmite (Changling catalyst plant, Al) was weighed out2O375% by weight) of the above-mentioned polymer was mixed with 122.74g of 5,6,7, 8-tetrahydronaphthalen-2-yl-trimethylammonium hydroxide (25% by weight aqueous solution), the mixture was placed in a polytetrafluoroethylene-lined reaction vessel and reacted at 185 ℃ for 0.5 hour in a closed environment, and then cooled to room temperature, followed by reaction with 10.93g of seed crystals (silica-alumina molecular sieve of CHA structure, silica-alumina molar ratio of 33) and 64.97g of fumed silica (SiO 2, Shenyang chemical Co., Ltd.)2Content 99 wt.%) and 215.94g of water, the weight ratio of seed crystal to silicon source, calculated as silica, being 17: 100, obtaining a mixture to be crystallized, wherein the molar composition is R: SiO 22：Al2O3＝56：405：1，H2O：SiO216: 1, the alkali metal content is 411 ppm. And (3) crystallizing the mixture to be crystallized in a high-pressure reaction kettle at 180 ℃ for 170h, filtering after crystallization, returning filtrate, namely crystallization mother liquor, to be used for preparing the mixture to be crystallized, washing a filter cake, drying at 120 ℃ for 20 h, and roasting at 550 ℃ for 6h to obtain the hydrogen-type CHA structure molecular sieve C-11.
The XRD spectrum of the molecular sieve C-11 is similar to that of figure 1, the molecular sieve product does not agglomerate, and the dispersity is similar to that of figure 2. The grain size, relative crystallinity, etc. are shown in Table 1.
Example 12
0.15g of pseudoboehmite (Changling catalyst works, Al) was weighed out2O375 wt.%) was mixed with 80g of the crystallization mother liquor of example 4, 70.32g of organic template 5,6,7, 8-tetrahydronaphthalen-2-yl-trimethylammonium hydroxide (25 wt.% aqueous solution), placed in a polytetrafluoroethylene-lined reactor, reacted at 120 ℃ under sealed conditions for 22 hours, cooled to room temperature, and then mixed with 1.43g of seed crystals (CHA structure silica-alumina molecular sieves, silica-alumina molar ratio 38) and 7.42g of fumed silica (Shenyang chemical Co., Ltd., SiO)2Content 99 wt.%) and 76.50g of water, the weight ratio of seed crystal to silicon source, calculated as silica, being 19: 100, obtaining a mixture to be crystallized, wherein the molar composition is R: SiO 22：Al2O3＝77：111：1，H2O：SiO295: 1, the alkali metal content was 352 ppm. And (3) crystallizing the mixture to be crystallized in a high-pressure reaction kettle at 135 ℃ for 90 hours, filtering and washing after crystallization, drying at 120 ℃ for 20 hours, and roasting at 550 ℃ for 6 hours to obtain the hydrogen-type CHA structure molecular sieve C-12.
The XRD spectrum of molecular sieve C-12 is similar to that of figure 1, the molecular sieve product does not agglomerate, and the dispersity is similar to that of figure 2. The grain size, relative crystallinity, etc. are shown in Table 1.
Example 13
0.12g of alumina (Changling catalyst works, Al) was weighed out2O398 wt%), and 23.11g of p-vinylbenzene-N, N, N-trimethylammonium hydroxide (25 wt% aqueous solution), the mixture was placed in a polytetrafluoroethylene-lined reaction kettle, reacted at 145 ℃ under a sealed condition for 24 hours, cooled to room temperature, and then mixed with 5.06g of seed crystal (CHA-structured silica-alumina molecular sieve, silica-alumina molar ratio of 25) and 29.30g of precipitated silica (SiO, Seikagaku chemical Co., Ltd.)2Content 93 wt.%) and 144.11g of water, the weight ratio of seed crystal to silicon source, calculated as silica, being 18: 100, obtaining a mixture to be crystallized, wherein the molar composition is R: SiO 22：Al2O3＝28：394：1，H2O：SiO220: 1, the alkali metal content was 117 ppm. To be crystallizedCrystallizing the mixture in a high-pressure reaction kettle at 160 deg.C for 60 hr, filtering, washing, oven drying at 120 deg.C for 24 hr, and calcining at 550 deg.C for 6 hr to obtain hydrogen-type CHA structure molecular sieve C-13.
The XRD spectrum of molecular sieve C-13 is similar to that of figure 1, the molecular sieve product does not agglomerate, and the dispersity is similar to that of figure 2. The grain size, relative crystallinity, etc. are shown in Table 1.
Example 14
0.19g of alumina (Changling catalyst works, Al) was weighed out2O3Content 98 wt%), was mixed with 84.64g of 5,6,7, 8-tetrahydronaphthalen-2-yl-trimethylammonium hydroxide (25 wt% aqueous solution), placed in a polytetrafluoroethylene-lined reaction vessel, reacted at 180 ℃ under a closed condition for 0.6 hour, cooled to room temperature, and then mixed with 0.74g of seed crystal (CHA structure aluminosilicate molecular sieve, silica-alumina molar ratio 23), 27.94g of ethyl silicate (zhanggang new sub chemical limited, content not less than 98 wt%), and 91.74g of water, the weight ratio of the seed crystal to the silicon source in terms of silica being 2.7: 100, obtaining a mixture to be crystallized, wherein the molar composition is R: SiO 22：Al2O3＝56：72：1，H2O：SiO265: 1, alkali metal content 371 ppm. And (3) crystallizing the mixture to be crystallized in a high-pressure reaction kettle at 170 ℃ for 96 hours, filtering and washing after crystallization, drying at 120 ℃ for 24 hours, and roasting at 550 ℃ for 6 hours to obtain the hydrogen-type CHA structure molecular sieve C-14.
The XRD spectrum of molecular sieve C-14 is similar to that of figure 1, the molecular sieve product does not agglomerate, and the dispersity is similar to that of figure 2. The grain size, relative crystallinity, etc. are shown in Table 1.
Example 15
A CHA structure molecular sieve was synthesized as in example 1, except that the pseudoboehmite was not first treated with 5,6,7, 8-tetrahydronaphthalen-2-yl-trimethylammonium hydroxide, but was directly mixed with 5,6,7, 8-tetrahydronaphthalen-2-yl-trimethylammonium hydroxide, silica gel and water for crystallization. This example synthesizes hydrogen-form CHA structure molecular sieve C-15.
The XRD spectrum of the molecular sieve C-15 is similar to that of figure 1, the molecular sieve product does not agglomerate, and the dispersity is similar to that of figure 2. The grain size, relative crystallinity, etc. are shown in Table 1.
Example 16
A CHA structure molecular sieve was synthesized as in example 8, except that the pseudoboehmite, 5,6,7, 8-tetrahydronaphthalen-2-yl-trimethylammonium hydroxide, seed crystal, silica gel and water were directly mixed for crystallization without first being subjected to a mixed reaction with 5,6,7, 8-tetrahydronaphthalen-2-yl-trimethylammonium hydroxide. This example synthesizes hydrogen-form CHA structure molecular sieve C-16.
The XRD spectrum of the molecular sieve C-16 is similar to that of figure 1, the molecular sieve product does not agglomerate, and the dispersity is similar to that of figure 2. The grain size, relative crystallinity, etc. are shown in Table 1.
TABLE 1
Examples Grain size, μm Relative degree of crystallinity,% BET surface area, m2/g SiO2/Al2O3Molar ratio of
Example 1 1 92 652 21
Example 2 1.4 90 640 35
Example 3 0.7 93 665 181
Example 4 2.2 87 611 388
Example 5 1.4 82 580 92
Example 6 0.6 96 682 362
Example 7 2.3 95 671 61
Example 8 0.8 93 663 24
Example 9 1.2 91 643 37
Example 10 0.4 94 665 185
Example 11 1.8 88 627 388
Example 12 1.1 86 607 97
Example 13 0.4 98 704 373
Example 14 1.8 97 693 61
Example 15 3.2 83 612 18
Example 16 1.9 85 642 20
It can be seen from examples 1-16 that the CHA structured molecular sieve prepared by the method of the present application has a high specific surface area of micropores and a relative crystallinity, and the use of an expensive and toxic organic template can be avoided. As can be seen from a comparison of examples 1-7 and examples 8-14, when the mixture to be crystallized also contains seed crystals, it is advantageous to further increase the specific surface area of micropores and the relative crystallinity of the CHA structure molecular sieve. From the comparison between examples 1 to 7, it can be seen that when in the mixture to be crystallized R: SiO 22：Al2O3＝(2-60)：(15-450)：1，H2O：SiO2(6-70): 1, time; or the crystallization treatment temperature is 160-170 ℃, and the time is 2.5-4 days, which is beneficial to further improving the specific surface area and the relative crystallinity of the micropores of the CHA structure molecular sieve. As can be seen from a comparison of examples 1, 8 and 15-16, it is advantageous when the organic templating agent is first mixed with an aluminum source and treated at 45-190 ℃ for 0.5-50 hours in a closed environment before being mixed with a silicon source, optionally waterThe specific surface area and the relative crystallinity of the micropores of the CHA structure molecular sieve are improved.
The preferred embodiments of the present disclosure are described in detail with reference to the accompanying drawings, however, the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present disclosure within the technical idea of the present disclosure, and these simple modifications all belong to the protection scope of the present disclosure.
It should be noted that, in the foregoing embodiments, various features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various combinations that are possible in the present disclosure are not described again.
In addition, any combination of various embodiments of the present disclosure may be made, and the same should be considered as the disclosure of the present disclosure, as long as it does not depart from the spirit of the present disclosure.

Claims (13)

1. A method of synthesizing a CHA structured molecular sieve, the method comprising the steps of:
a. mixing an organic template agent, an aluminum source, a silicon source and optional water to obtain a mixture to be crystallized, wherein the ratio of R: SiO 22：Al2O3＝(1-100)：(10-500)：1，H2O：SiO2(5-100): 1, wherein R represents the mole number of the organic template in the mixture to be crystallized;
b. b, crystallizing the mixture to be crystallized obtained in the step a, and recovering a solid product;
wherein the organic template agent is 5,6,7, 8-tetrahydronaphthalene-2-yl-trimethyl ammonium hydroxide and/or p-vinyl phenyl-N, N, N-trimethyl ammonium hydroxide.
2. The method of claim 1, wherein the method further comprises: in the step a, the organic template agent and an aluminum source are mixed, and are processed for 0.5 to 50 hours at the temperature of between 45 and 190 ℃ under a closed condition to obtain an aluminum-containing colloid, and then the aluminum-containing colloid is mixed with a silicon source and optional water to obtain a mixture to be crystallized.
3. The method of claim 1, wherein the method further comprises: in the step a, the mixture to be crystallized also contains a seed crystal, the seed crystal is a CHA structure silicon-aluminum molecular sieve, and the weight ratio of the seed crystal to the silicon source calculated by silicon oxide is (1-20): 100.
4. the method of claim 3, wherein the seed crystal has a silica to alumina molar ratio of 10 to 40 on an oxide basis.
5. The method of claim 3, wherein the method further comprises: in the step a, firstly, mixing an organic template agent and an aluminum source, and processing for 0.5-50 hours at 45-190 ℃ under a closed condition to obtain an aluminum-containing colloid, and then mixing the aluminum-containing colloid with seed crystals, a silicon source and optional water to obtain a mixture to be crystallized.
6. The process of claim 1 or 3, wherein in step a, the aluminum source is at least one selected from the group consisting of aluminum, boehmite, pseudoboehmite, gibbsite, aluminum hydroxide, alumina and aluminum alcoholate.
7. The method according to claim 1 or 3, wherein in step a, the silicon source is at least one selected from the group consisting of silicate, silica, silicic acid, silica gel, clay, and ethyl silicate.
8. The process as claimed in claim 1 or 3, wherein in step a, the content of alkali metal in the mixture to be crystallized is not higher than 1000ppm, based on the total weight of the mixture to be crystallized.
9. The method of claim 1 or 3, wherein the method further comprises: and collecting crystallization mother liquor obtained by the crystallization treatment, and returning the crystallization mother liquor to be used for preparing the mixture to be crystallized.
10. The method as claimed in claim 1 or 3, wherein in step b, the crystallization treatment conditions are as follows: the temperature is 120 ℃ and 190 ℃, and the time is 1-10 days.
11. The method of claim 1 or 3, wherein the method further comprises: and recovering the solid product, and then drying and roasting.
12. The method of claim 11, wherein the drying conditions are: the temperature is 50-120 ℃, and the time is 4-24 hours;
the roasting conditions are as follows: the temperature is 300 ℃ and 700 ℃ and the time is 1-10 hours.
13. A CHA structured molecular sieve synthesized by the method of any one of claims 1 to 12.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103601211A (en) * 2013-12-04 2014-02-26 北京化工大学 Synthesis method of molecular sieve SSZ-13
CN105236440A (en) * 2015-09-14 2016-01-13 天津大学 Method for synthesizing CHA molecular sieve by using tetraethyl ammonium hydroxide as templating agent
CN106927474A (en) * 2015-12-30 2017-07-07 中触媒新材料股份有限公司 A kind of SSZ-13 molecular sieves and preparation method and application

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103601211A (en) * 2013-12-04 2014-02-26 北京化工大学 Synthesis method of molecular sieve SSZ-13
CN105236440A (en) * 2015-09-14 2016-01-13 天津大学 Method for synthesizing CHA molecular sieve by using tetraethyl ammonium hydroxide as templating agent
CN106927474A (en) * 2015-12-30 2017-07-07 中触媒新材料股份有限公司 A kind of SSZ-13 molecular sieves and preparation method and application

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