CN103204517A - Method for synthesizing microporous molecular sieve with methylene doped in skeleton without template - Google Patents
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Abstract
The invention discloses a method for synthesizing a microporous molecular sieve with methylene doped in a skeleton without a template. In the method, a dry gel crystallization method is adopted, an organic-inorganic hybrid microporous molecular sieve with methylene doped in the skeleton and with MOR, FAU and MFI structure with no addition of an organic template. An aluminium source, sodium hydroxide, a silicon source and deionized water are used as reaction raw materials; a reaction mixture with a certain composition is made in to dry gel powder; the dry gel powder is crystallized for 24-360 hours at a temperature of 95-220 DEG C; and a product is washed for a plurality of times with the deionized water, is subjected to centrifugal separation and dried. By adopting the method to synthesize the organic-inorganic hybrid microporous molecular sieve, Si-CH2-Si structures can be efficiently prevented from breaking in a strong alkaline solution medium; and doping content of organic groups in the sieve is greatly increased. The method is simple in reaction process, easy to operate and low in synthetic cost; and the whole process is friendly to the environment. The synthesized organic-inorganic hybrid microporous molecular sieve presents excellent catalytic activity in organic catalytic reaction after ion exchange.
Description
Technical field
The invention belongs to the synthetic method of the micro porous molecular sieve of skeleton doping methylene radical, particularly adopt dried glue crystallization method, the synthetic microporous molecular sieve catalyst with skeleton doping methylene radical of MOR, FAU and MFI structure of no template.
Background technology
The hybrid inorganic-organic micro porous molecular sieve is the character that a class not only combines organic group and inorganic molecule sieve, and has the new function material of self peculiar property and composition, causes chemist's very big interest in recent years.
Hybrid inorganic-organic micro porous molecular sieve synthetic mainly is divided into two kinds of the silanizations of traditional hydrothermal synthesis method and layer molecule sieve.As Davis research group, adopt hydrothermal synthesis method the styroyl group to be hung in the duct of Beta molecular sieve, obtain the Beta molecular sieve of styroyl functionalization, this molecular sieve shows good catalytic activity and shape selective (C.W.Jones in the reaction of cyclic ketone and vinyl ethylene glycol after sulfonation is handled, K.Tsuji, M.Davis, Nature, 1998,52-54); People such as Yamamoto are incorporated into methylene radical in the skeleton structure of molecular sieve by hydrothermal synthesis method, replace part bridging Sauerstoffatom, form to have Si-CH
2The LTA of-Si structure (Linde Type A), MFI (ZSM-5) type molecular sieve, this molecular sieve shows excellent (K.Yamamoto aspect the interaction of regulatory molecule sieve skeleton frame and object organic or inorganic molecule, Y.Sakata, Y.Nohara, Y.Takahashi, T.Tatsumi, Science, 2003,470-472).But, adopt the synthetic hybrid inorganic-organic micro porous molecular sieve of hydrothermal synthesis method to have the low problem of organic group doping, this is because the result that fracture causes takes place under the strong alkali solution ambient condition Si-C key in the organosilicon source easily, the more important thing is, adopt the organic formwork agent in the synthetic hybrid inorganic-organic micro porous molecular sieve of this method to be removed effectively, when removing organic formwork agent by the method for chemical extraction, quite a few can not be removed by the organic formwork agent of envelope in micropore canals, and the method for employing high-temperature vacuum roasting or air atmosphere calcination process, when organic formwork agent was removed, the organic group that is introduced into also can be damaged.2007, people such as Tatsumi have been developed a kind of by layer molecule sieve presoma being carried out the method synthesizing organic-inorganic hydridization micro porous molecular sieve of silanization, this molecular sieve has the ability (S.Inagaki of absorption benzene molecular, T.Yokoi, Y.Kubota, T.Tatsumi, Chem.Commun., 2007,5188-5190).But, adopt this method synthesizing organic-inorganic hydridization micro porous molecular sieve, at first to synthesize layer molecule sieve presoma by hydrothermal synthesis method, again by its alkylated reaction under hot conditions, make layer molecule sieve presoma connect into the molecular sieve with three-dimensional framework structure, so the reaction process more complicated, experiment condition is not easy control, synthetic cost is higher, and the content of the organic group of introducing is not high yet.
At the problems referred to above, the present invention adopts dried glue crystallization method, under the condition of not using organic formwork agent, synthesizes the hybrid inorganic-organic micropore Si-Al molecular sieve that a series of novel methylene radical mix.Dried glue crystallization method (Dry gel conversion) is the synthetic method of a kind of molecular sieve, dry glue powder end converted in-situ under the promotion of steam in the crystallization process, need not directly to be soaked in the strong alkali solution medium, have that consumption of template agent is few, an advantage such as molecular sieve yield height, technology are simple.The present invention makes dry glue powder after aluminium source, sodium hydroxide and silicon source are mixed, 95～220 ℃ of crystallization 24～360 hours, product repeatedly washs, dries after the centrifugation through deionized water, obtain the hybrid inorganic-organic micro porous molecular sieve that methylene radical mixes, thereby realize the modification (hydrophilic/hydrophobic in aperture size, pore volume, duct, shape selective etc.) to molecular sieve pore passage, the hybrid inorganic-organic micro porous molecular sieve that synthetic methylene radical mixes can directly carry out ion-exchange and show excellent catalytic activity in organic catalytic reaction.This method has organic group doping height, simple, synthetic low, the advantages of environment protection of cost of operating process.
Summary of the invention
The object of the present invention is to provide a kind of synthetic method of hybrid inorganic-organic microporous molecular sieve catalyst of skeleton doping methylene radical.The present invention adopts dried glue crystallization method, synthesizes the hybrid inorganic-organic micro porous molecular sieve of the skeleton doping methylene radical of have MOR (mordenite), FAU (faujasite) and MFI (ZSM-5) structure under the condition that does not add organic formwork agent.
Detailed description of the present invention:
(1) under the room temperature, with aluminium source and dissolution of sodium hydroxide in a certain amount of deionized water;
(2) in said mixture, add the silicon source, after stirring for some time, place 60～80 ℃ of water-baths to continue to stir reaction mixture, become dried glue until it;
(3) dried glue is finely ground to dry glue powder, Φ 20 * 500mm polytetrafluoroethyllining lining of packing into (little lining), little lining places the stainless steel cauldron that Φ 30 * 1000mm polytetrafluoroethyllining lining (big lining) is housed, big substrate portion adds a certain amount of deionized water, and the stainless steel cauldron sealing was placed on 95～220 ℃ of baking ovens 24～360 hours;
(4) product through deionized water repeatedly wash, after the centrifugation, 110 ℃ of oven dry.
In aforesaid method, the mol ratio in the described dried glue between each reaction raw materials is: Al
2O
3: Na
2O: SiO
2: H
2O=1.0: (1.0～10.0): (5.0～100): (5.0～100).
In aforesaid method, the amount that described big substrate portion adds deionized water is 0.05～40ml.
In aforesaid method, it is 0.5～48 hour that described silicon source adds the back churning time.
In aforesaid method, described aluminium source is aluminum nitrate or Tai-Ace S 150 or sodium aluminate.
In aforesaid method, described silicon source is the mixture of organosilicon or organosilicon and inorganic silicon.
In aforesaid method, described organosilicon is two (triethoxy is silica-based) methane.
In aforesaid method, described inorganic silicon is white carbon black or silicon sol or water glass.
In aforesaid method, when described silicon source was the mixture of organosilicon and inorganic silicon, the mol ratio of organosilicon and inorganic silicon was 0.05～∞.
The present invention has following advantage:
(1) adopt the hybrid inorganic-organic micro porous molecular sieve of the synthetic skeleton doping methylene radical of this method can effectively avoid organic Si-CH
2The fracture of-Si structure under the strong alkali solution ambient condition improved the doping of organic group in molecular sieve greatly;
(2) this method is not used organic formwork agent, has reduced synthetic cost, and whole process is environmentally friendly;
(3) this method reaction process is simple, easy handling, reaction process good reproducibility;
(4) the hybrid inorganic-organic micro porous molecular sieve of He Cheng skeleton doping methylene radical can directly carry out ion-exchange and show excellent catalytic activity in organic catalytic reaction.
Embodiment
Below by specific embodiment technical scheme of the present invention is further described.Following examples do not constitute limitation of the invention.
Embodiment 1
0.21g aluminum nitrate and 0.023g sodium hydroxide are dissolved in the appropriate amount of deionized water, treat that its dissolving slowly adds 0.24g two (triethoxy is silica-based) methane in the back fully, stir after 0.5 hour under the room temperature, place 60 ℃ of water-baths to continue to stir the homogeneous gel that obtains, become dried glue until it, the water content of dried glue is about 0.025g, dried glue is finely ground to the dry glue powder polytetrafluoroethyllining lining (little lining) of packing into, little lining places the stainless steel cauldron that polytetrafluoroethyllining lining (big lining) is housed, big substrate portion adds the 0.05ml deionized water, 180 ℃ of crystallization 120 hours, the molecular screen primary powder that obtains is through deionized water wash repeatedly, centrifugation, 110 ℃ of oven dry, obtain having the micro porous molecular sieve of the skeleton doping methylene radical of MOR structure, the micro porous molecular sieve of synthetic skeleton doping methylene radical is carried out Co
2+Ion-exchange, it shows 90% transformation efficiency and 85% epoxy selectivity in selective epoxidation reaction of styrene catalyzed and air.
Embodiment 2
0.1g Tai-Ace S 150 and 0.22g sodium hydroxide are dissolved in the appropriate amount of deionized water, treat that its dissolving slowly adds 0.68g two (triethoxy is silica-based) methane in the back fully, stirs 48 hours under the room temperature; Other gets 0.08g Tai-Ace S 150 and 0.2g sodium hydroxide is dissolved in the appropriate amount of deionized water, add the 2.3g white carbon black, then that hydrolysis is good two (triethoxy is silica-based) methane adds wherein, stir, place 80 ℃ of water-baths to continue to stir the homogeneous gel that obtains, become dried glue until it, the water content of dried glue is about 0.95g, dried glue is finely ground to the dry glue powder polytetrafluoroethyllining lining (little lining) of packing into, little lining places the stainless steel cauldron that polytetrafluoroethyllining lining (big lining) is housed, big substrate portion adds the 40ml deionized water, 220 ℃ of crystallization 360 hours, the molecular screen primary powder that obtains is through deionized water wash repeatedly, centrifugation is 110 ℃ of oven dry, obtain having the micro porous molecular sieve of the skeleton doping methylene radical of MOR structure, the micro porous molecular sieve of synthetic skeleton doping methylene radical is carried out H
+Ion-exchange, it is in the reaction of catalysis acetic acid and ethanol synthesizing ethyl acetate, and the productive rate of ethyl acetate can reach 92%.
Embodiment 3
0.14g sodium aluminate and 0.34g sodium hydroxide are dissolved in the appropriate amount of deionized water, treat that its dissolving slowly adds 7.24g two (triethoxy is silica-based) methane in the back fully, stir after 24 hours under the room temperature, place 60 ℃ of water-baths to continue to stir the homogeneous gel that obtains, become dried glue until it, the water content of dried glue is about 0.75g, dried glue is finely ground to the dry glue powder polytetrafluoroethyllining lining (little lining) of packing into, little lining places the stainless steel cauldron that polytetrafluoroethyllining lining (big lining) is housed, big substrate portion adds the 20ml deionized water, 200 ℃ of crystallization 240 hours, the molecular screen primary powder that obtains is through deionized water wash repeatedly, centrifugation, 110 ℃ of oven dry, obtain having the micro porous molecular sieve of the skeleton doping methylene radical of MOR structure, the micro porous molecular sieve of synthetic skeleton doping methylene radical is carried out H
+Ion-exchange, it is in the reaction of catalysis acetic acid and ethanol synthesizing ethyl acetate, and the productive rate of ethyl acetate can reach 92%.
Embodiment 4
0.05g Tai-Ace S 150 and 0.05g sodium hydroxide are dissolved in the appropriate amount of deionized water, treat that its dissolving slowly adds 0.24g two (triethoxy is silica-based) methane, stirring at room 10 hours in the back fully; Other gets 0.03g Tai-Ace S 150 and 0.11g sodium hydroxide is dissolved in the appropriate amount of deionized water, add 0.76g water glass, then that hydrolysis is good two (triethoxy is silica-based) methane adds wherein, stir, to obtain the homogeneous gel places 80 ℃ of water-baths to continue to stir, become dried glue until it, the water content of dried glue is about 0.34g, dried glue is finely ground to the dry glue powder polytetrafluoroethyllining lining (little lining) of packing into, little lining places the stainless steel cauldron that polytetrafluoroethyllining lining (big lining) is housed, big substrate portion adds the 30ml deionized water, 170 ℃ of crystallization 60 hours, the molecular screen primary powder that obtains is through deionized water wash repeatedly, centrifugation is 110 ℃ of oven dry, obtain having the micro porous molecular sieve of the skeleton doping methylene radical of MOR structure, the micro porous molecular sieve of synthetic skeleton doping methylene radical is carried out Co
2+Ion-exchange, it shows 93% transformation efficiency and 91% epoxy selectivity in selective epoxidation reaction of styrene catalyzed and air.
Embodiment 5
0.18g aluminum nitrate and 0.19g sodium hydroxide are dissolved in the appropriate amount of deionized water, treat that its dissolving slowly adds 16.0g two (triethoxy is silica-based) methane in the back fully, stir after 1.5 hours under the room temperature, place 60 ℃ of water-baths to continue to stir the homogeneous gel that obtains, become dried glue until it, the water content of dried glue is about 0.043g, dried glue is finely ground to the dry glue powder polytetrafluoroethyllining lining (little lining) of packing into, little lining places the stainless steel cauldron that polytetrafluoroethyllining lining (big lining) is housed, big substrate portion adds the 0.5ml deionized water, 95 ℃ of crystallization 24 hours.The molecular screen primary powder that obtains is through repeatedly deionized water wash, centrifugation, 110 ℃ of oven dry, obtains having the micro porous molecular sieve of the skeleton doping methylene radical of FAU structure, and the micro porous molecular sieve of synthetic skeleton doping methylene radical is carried out Co
2+Ion-exchange, it shows 91% transformation efficiency and 87 epoxy selectivity in selective epoxidation reaction of styrene catalyzed and air.
Embodiment 6
0.11g Tai-Ace S 150 and 0.05g sodium hydroxide are dissolved in the appropriate amount of deionized water, treat that its dissolving slowly adds 7.81g two (triethoxy is silica-based) methane in the back fully, after the stirring at room 36 hours, place 80 ℃ of water-baths to continue to stir the homogeneous gel that obtains, become dried glue until it, the water content of dried glue is about 0.23g, dried glue is finely ground to the dry glue powder polytetrafluoroethyllining lining (little lining) of packing into, little lining places the stainless steel cauldron that polytetrafluoroethyllining lining (big lining) is housed, big substrate portion adds the 1.5ml deionized water, 100 ℃ of crystallization 60 hours, the molecular screen primary powder that obtains is through deionized water wash repeatedly, centrifugation, 110 ℃ of oven dry, obtain having the micro porous molecular sieve of the skeleton doping methylene radical of FAU structure, the micro porous molecular sieve of synthetic skeleton doping methylene radical is carried out H
+Ion-exchange, it is in the reaction of catalysis acetic acid and ethanol synthesizing ethyl acetate, and the productive rate of ethyl acetate can reach 88%.
Embodiment 7
0.07g sodium aluminate and 0.033g sodium hydroxide are dissolved in the appropriate amount of deionized water, treat that its dissolving slowly adds 0.068g two (triethoxy is silica-based) methane, stirring at room 30 hours in the back fully; Other gets the 0.06g sodium aluminate and 0.03g sodium hydroxide is dissolved in the appropriate amount of deionized water, add the 0.22g white carbon black, then that hydrolysis is good two (triethoxy is silica-based) methane adds wherein, stir, to obtain the homogeneous gel places 80 ℃ of water-baths to continue to stir, become dried glue until it, the water content of dried glue is about 1.04g, dried glue is finely ground to the dry glue powder polytetrafluoroethyllining lining (little lining) of packing into, little lining places the stainless steel cauldron that polytetrafluoroethyllining lining (big lining) is housed, big substrate portion adds the 10ml deionized water, 95 ℃ of crystallization 48 hours, the molecular screen primary powder that obtains is through deionized water wash repeatedly, centrifugation is 110 ℃ of oven dry, obtain having the micro porous molecular sieve of the skeleton doping methylene radical of FAU structure, the micro porous molecular sieve of synthetic skeleton doping methylene radical is carried out H
+Ion-exchange, it is in the reaction of catalysis acetic acid and ethanol synthesizing ethyl acetate, and the productive rate of ethyl acetate can reach 92%.
Embodiment 8
0.08g sodium aluminate and 0.223g sodium hydroxide are dissolved in the appropriate amount of deionized water, treat that its dissolving slowly adds 10.74g two (triethoxy is silica-based) methane, stirring at room 28 hours in the back fully; Other gets the 0.05g sodium aluminate and 0.4g sodium hydroxide is dissolved in the appropriate amount of deionized water, add the 1.18g silicon sol, then that hydrolysis is good two (triethoxy is silica-based) methane adds wherein, stir, to obtain the homogeneous gel places 80 ℃ of water-baths to continue to stir, become dried glue until it, the water content of dried glue is about 0.5g, dried glue is finely ground to the dry glue powder polytetrafluoroethyllining lining (little lining) of packing into, little lining places the stainless steel cauldron that polytetrafluoroethyllining lining (big lining) is housed, big substrate portion adds the 3.0ml deionized water, 100 ℃ of crystallization 96 hours, the molecular screen primary powder that obtains is through deionized water wash repeatedly, centrifugation is 110 ℃ of oven dry, obtain having the micro porous molecular sieve of the skeleton doping methylene radical of FAU structure, the micro porous molecular sieve of synthetic skeleton doping methylene radical is carried out Co
2+Ion-exchange, it shows 90% transformation efficiency and 85% epoxy selectivity in selective epoxidation reaction of styrene catalyzed and air.
Embodiment 9
0.11g aluminum nitrate and 0.011g sodium hydroxide are dissolved in the appropriate amount of deionized water, treat that its dissolving slowly adds 4.9g two (triethoxy is silica-based) methane in the back fully, after the hydrolysis 3 hours, place 80 ℃ of water-baths to continue to stir the homogeneous gel that obtains, become dried glue until it, the water content of dried glue is about 0.26g, dried glue is finely ground to the dry glue powder polytetrafluoroethyllining lining (little lining) of packing into, little lining places the stainless steel cauldron that polytetrafluoroethyllining lining (big lining) is housed, big substrate portion adds the 2mL deionized water, 170 ℃ of crystallization 96 hours, the molecular screen primary powder that obtains is through deionized water wash repeatedly, centrifugation, 110 ℃ of oven dry, obtain having the micro porous molecular sieve of the skeleton doping methylene radical of MFI structure, the micro porous molecular sieve of synthetic skeleton doping methylene radical is carried out Co
2+Ion-exchange, it shows 92% transformation efficiency and 90% epoxy selectivity in selective epoxidation reaction of styrene catalyzed and air.
Embodiment 10
0.07g Tai-Ace S 150 and 0.09g sodium hydroxide are dissolved in the appropriate amount of deionized water, treat that its dissolving slowly adds 1.39g two (triethoxy is silica-based) methane, hydrolysis 4 hours in the back fully; Other gets 0.05g Tai-Ace S 150 and 0.05g sodium hydroxide is dissolved in the appropriate amount of deionized water, add the 0.49g white carbon black, then that hydrolysis is good two (triethoxy is silica-based) methane adds wherein, stir, to obtain the homogeneous gel places 80 ℃ of water-baths to continue to stir, become dried glue until it, the water content of dried glue is about 0.56g, dried glue is finely ground to the dry glue powder polytetrafluoroethyllining lining (little lining) of packing into, little lining places the stainless steel cauldron that polytetrafluoroethyllining lining (big lining) is housed, big substrate portion adds the 5mL deionized water, 170 ℃ of crystallization 120 hours, the molecular screen primary powder that obtains is through deionized water wash repeatedly, centrifugation is 110 ℃ of oven dry, obtain having the micro porous molecular sieve of the skeleton doping methylene radical of MFI structure, the micro porous molecular sieve of synthetic skeleton doping methylene radical is carried out Co
2+Ion-exchange, it shows 96% transformation efficiency and 94% epoxy selectivity in selective epoxidation reaction of styrene catalyzed and air.
Embodiment 11
0.03g sodium aluminate and 0.16g sodium hydroxide are dissolved in the appropriate amount of deionized water, treat that its dissolving slowly adds 1.19g two (triethoxy is silica-based) methane, hydrolysis 4 hours in the back fully; Other gets the 0.05g sodium aluminate and 0.07g sodium hydroxide is dissolved in the appropriate amount of deionized water, add the 0.69g silicon sol, then that hydrolysis is good two (triethoxy is silica-based) methane adds wherein, stir, to obtain the homogeneous gel places 80 ℃ of water-baths to continue to stir, become dried glue until it, the water content of dried glue is about 0.6g, dried glue is finely ground to the dry glue powder polytetrafluoroethyllining lining (little lining) of packing into, little lining places the stainless steel cauldron that polytetrafluoroethyllining lining (big lining) is housed, big substrate portion adds the 15mL deionized water, 180 ℃ of crystallization 360 hours, the molecular screen primary powder that obtains is through deionized water wash repeatedly, centrifugation is 110 ℃ of oven dry, obtain having the micro porous molecular sieve of the skeleton doping methylene radical of MFI structure, the micro porous molecular sieve of synthetic skeleton doping methylene radical is carried out H
+Ion-exchange, it is in the reaction of catalysis acetic acid and ethanol synthesizing ethyl acetate, and the productive rate of ethyl acetate can reach 93%.
Embodiment 12
0.08g aluminum nitrate and 0.035g sodium hydroxide are dissolved in the appropriate amount of deionized water, treat that its dissolving slowly adds 0.12g two (triethoxy is silica-based) methane, hydrolysis 4 hours in the back fully; Other gets the 0.03g aluminum nitrate and 0.02g sodium hydroxide is dissolved in the appropriate amount of deionized water, add 0.1g water glass, then that hydrolysis is good two (triethoxy is silica-based) methane adds wherein, stir, to obtain the homogeneous gel places 80 ℃ of water-baths to continue to stir, become dried glue until it, the water content of dried glue is about 0.16g, dried glue is finely ground to the dry glue powder polytetrafluoroethyllining lining (little lining) of packing into, little lining places the stainless steel cauldron that polytetrafluoroethyllining lining (big lining) is housed, big substrate portion adds the 20mL deionized water, 185 ℃ of crystallization 120 hours, the molecular screen primary powder that obtains is through deionized water wash repeatedly, centrifugation is 110 ℃ of oven dry, obtain having the micro porous molecular sieve of the skeleton doping methylene radical of MFI structure, the micro porous molecular sieve of synthetic skeleton doping methylene radical is carried out H
+Ion-exchange, it is in the reaction of catalysis acetic acid and ethanol synthesizing ethyl acetate, and the productive rate of ethyl acetate can reach 89%.
Claims (9)
1. one kind is not had the method that template is synthesized the micro porous molecular sieve of skeleton doping methylene radical, it is characterized in that adopting dried glue crystallization method, under the condition that does not add organic formwork agent, synthesize and have MOR, the hybrid inorganic-organic micro porous molecular sieve of the skeleton doping methylene radical of FAU and MFI structure, synthetic method comprises: under the room temperature, with aluminium source and dissolution of sodium hydroxide in a certain amount of deionized water, again to wherein adding the silicon source, after stirring for some time, place 60～80 ℃ of water-baths to continue to stir reaction mixture, until becoming dried glue, dried glue is finely ground to dry glue powder, the polytetrafluoroethyllining lining of packing into (little lining), little lining places the stainless steel cauldron that polytetrafluoroethyllining lining (big lining) is housed, big substrate portion adds a certain amount of deionized water, the stainless steel cauldron sealing was placed on 95～220 ℃ of baking ovens 24～360 hours, product repeatedly washs through deionized water, after the centrifugation, 110 ℃ of oven dry, the micro porous molecular sieve of synthetic methylene radical doping skeleton can directly carry out ion-exchange and be applied to organic catalytic reaction.
2. method according to claim 1 is characterized in that the mol ratio between each reaction raw materials is in the dried glue: Al
2O
3: Na
2O: SiO
2: H
2O=1.0: (1.0～10.0): (5.0～100): (5.0～100).
3. method according to claim 1 is characterized in that the amount that big substrate portion adds deionized water is 0.05～40ml.
4. method according to claim 1 is characterized in that adding that churning time is 0.5～48 hour behind the silicon source.
5. method according to claim 1 is characterized in that described aluminium source is aluminum nitrate or Tai-Ace S 150 or sodium aluminate.
6. method according to claim 1 is characterized in that described silicon source is organosilicon, or the mixture of organosilicon and inorganic silicon.
7. method according to claim 6 is characterized in that described organosilicon is two (triethoxy is silica-based) methane.
8. method according to claim 6 is characterized in that described inorganic silicon is white carbon black or silicon sol or water glass.
9. method according to claim 6, when it is characterized in that described silicon source is the mixture of organosilicon and inorganic silicon, the mol ratio of organosilicon and inorganic silicon is 0.05～∞.
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| CN115304078A (en) * | 2022-08-18 | 2022-11-08 | 中国科学院福建物质结构研究所 | Preparation method and application of molecular sieve |
| CN115304078B (en) * | 2022-08-18 | 2023-10-03 | 中国科学院福建物质结构研究所 | Preparation method and application of molecular sieve |
| CN115814839A (en) * | 2022-12-27 | 2023-03-21 | 中触媒新材料股份有限公司 | Boron or phosphorus doped Silicalite-1 molecular sieve encapsulated metal catalyst and preparation method and application thereof |
| CN115814839B (en) * | 2022-12-27 | 2024-03-22 | 中触媒新材料股份有限公司 | Boron or phosphorus doped Silicalite-1 molecular sieve encapsulated metal catalyst and preparation method and application thereof |
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