CN111482166B - Nano carbon-based material and preparation method thereof and etherification method of propylene oxide - Google Patents
Nano carbon-based material and preparation method thereof and etherification method of propylene oxide Download PDFInfo
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- CN111482166B CN111482166B CN201910081692.XA CN201910081692A CN111482166B CN 111482166 B CN111482166 B CN 111482166B CN 201910081692 A CN201910081692 A CN 201910081692A CN 111482166 B CN111482166 B CN 111482166B
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/02—Preparation of ethers from oxiranes
- C07C41/03—Preparation of ethers from oxiranes by reaction of oxirane rings with hydroxy groups
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The disclosure relates to a nano carbon-based material and a preparation method thereof, and an etherification method of propylene oxide. The etherification method of the propylene oxide comprises the following steps: the propylene oxide and the etherifying agent are contacted to react in the presence of a catalyst, wherein the catalyst contains a nanocarbon-based material. According to the method, a special nano carbon-based material is used as a catalyst to catalyze the etherification reaction of the propylene oxide, the etherification of the propylene oxide can be realized under a mild condition, the raw material conversion rate is high, and the selectivity of a target product is optimized.
Description
Technical Field
The disclosure relates to a nano carbon-based material, a preparation method thereof and an etherification method of propylene oxide.
Background
Carbon-based materials include carbon nanotubes, activated carbon, graphite, graphene, fullerenes, carbon nanofibers, nanodiamonds, and the like. Scientific research on nanocarbon catalysis began in the 90's of the last century. Researches show that the surface chemical properties of the nano carbon material (mainly carbon nano tubes and graphene) can be flexibly regulated, and saturated and unsaturated functional groups containing oxygen, nitrogen and other heteroatoms can be modified on the surface of the nano carbon material, so that the nano carbon material has certain acid-base properties and redox capability, and can be directly used as a catalyst material. Research and development of new catalytic materials related to fullerene (carbon nano tube) and broadening of the application of the new catalytic materials in the fields of petrochemical industry, fine chemical industry and the like have profound theoretical significance and huge potential application prospects.
Propylene glycol ether has important application in the chemical field, such as propylene glycol monomethyl ether, also called propylene glycol methyl ether, and has an ether group and a hydroxyl group in the molecular structure, so that the propylene glycol ether has very excellent solubility, has the characteristics of proper volatilization rate, reaction activity and the like, and has wide application. The existing production of propylene glycol ether is basically obtained by combining propylene as a raw material with alcohols. However, most of the propylene glycol ether production in the world currently adopts a chlorohydrin method and an oxidation method, wherein the chlorohydrin method is seriously corroded and polluted, and the oxidation method has large investment and co-produces a large amount of byproducts, so that the production of the propylene glycol ether is restricted from raw materials.
Disclosure of Invention
An object of the present disclosure is to provide a nanocarbon-based material having excellent catalytic performance for etherification of propylene oxide, and a method for preparing the same.
It is another object of the present disclosure to provide a process for the etherification of propylene oxide which results in higher propylene oxide conversion and propylene glycol ether selectivity.
To achieve the above object, a first aspect of the present disclosure: the preparation method of the nano carbon-based material comprises the following steps:
a. mixing carbohydrate with silica gel particles with the particle size of less than 20 meshes, and reacting in a closed reactor at 300-1500 ℃ for 1-24 h to obtain a reacted material; wherein the number of carbon atoms of the carbohydrate is 10 or more;
b. and c, mixing the reacted material obtained in the step a with a mineralizer, treating for 1-48 h at 20-80 ℃, and collecting a solid product.
Optionally, theThe weight ratio of the carbohydrate to the silica gel particles to the mineralizer is 100: (1-500): (2 to 1000), preferably 100: (2-250): (5-500), wherein the silica gel particles are made of SiO 2 And (6) counting.
Optionally, the weight average molecular weight of the carbohydrate is 200-2000000, and preferably, the carbohydrate is sucrose, starch, lignin, cellulose, hemicellulose, complex polysaccharide or sugar derivative.
Optionally, the silica gel particles have a particle size of 20 to 10000 mesh, preferably 30 to 8000 mesh.
Optionally, the mineralizer is hydrofluoric acid or sodium hydroxide, and the concentration of the mineralizer is more than 5 wt%, preferably 10 to 40 wt%.
Optionally, in step a, the initial oxygen content in the closed reactor is less than 20 vol%, preferably less than 10 vol%, more preferably less than 1 vol%.
In a second aspect of the present disclosure: there is provided a nanocarbon-based material prepared by the method according to the first aspect of the present disclosure.
A third aspect of the disclosure: provided is a method for etherifying propylene oxide, the method comprising: and (b) contacting propylene oxide and an etherifying agent to react in the presence of a catalyst, wherein the catalyst contains the nanocarbon-based material according to the second aspect of the present disclosure.
Optionally, the reaction is carried out in a slurry bed reactor, and the amount of the catalyst is 10 to 1000mg, preferably 20 to 200mg, based on 100mL of the propylene oxide.
Optionally, the reaction is carried out in a fixed bed reactor, and the weight hourly space velocity of the propylene oxide is 0.01-500 h -1 Preferably 0.05 to 2 hours -1 。
Optionally, the etherifying agent is methanol, ethanol, ethylene glycol or glycerol, or a combination of two or three thereof; and/or the presence of a gas in the atmosphere,
the amount of the etherifying agent used is 10 to 500mL, preferably 20 to 200mL, based on 100mL of the propylene oxide.
Optionally, the reaction conditions are: the temperature is 50-200 ℃, preferably 60-180 ℃; the pressure is 0 to 20MPa, preferably 0 to 1MPa; the time is 1 to 72 hours, preferably 2 to 24 hours.
According to the technical scheme, the etherification reaction of the propylene oxide is catalyzed by adopting the special nano carbon-based material as the catalyst, the etherification of the propylene oxide can be realized under mild conditions, the raw material conversion rate is high, and the selectivity of a target product is optimized.
Additional features and advantages of the disclosure will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present disclosure. 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: the preparation method of the nano carbon-based material comprises the following steps:
a. mixing carbohydrate with silica gel particles with the particle size of less than 20 meshes, and reacting in a closed reactor at 300-1500 ℃ for 1-24 h to obtain a reacted material; wherein the number of carbon atoms of the carbohydrate is 10 or more;
b. and c, mixing the reacted material obtained in the step a with a mineralizer, treating for 1-48 h at 20-80 ℃, and collecting a solid product.
According to the present disclosure, the weight ratio of the carbohydrate, silica gel particles, and mineralizer is 100: (1-500): (2 to 1000), preferably 100: (2-250): (5-500), wherein the silica gel particles are made of SiO 2 And (6) counting.
According to the disclosure, in step a, the number of carbon atoms of the carbohydrate may further be 10 to 60000, and the weight average molecular weight thereof may be 200 to 2000000, and specific species may be, for example, sucrose, starch, lignin, cellulose, hemicellulose, a complex polysaccharide (such as lentinan, flammulina velutipes polysaccharide, hericium erinaceus polysaccharide, tremella polysaccharide, and ganoderma lucidum polysaccharide), or a sugar derivative (such as fructose 1, 6-diphosphate, chitin), and the like. The silica gel particles may further have a particle size of 20 to 10000 mesh, preferably 30 to 8000 mesh. The initial oxygen content in the closed reactor may be less than 20 vol%, preferably less than 10 vol%, more preferably less than 1 vol%, wherein the initial oxygen content refers to the oxygen content in the closed reactor at the start of the reaction.
According to the present disclosure, in step b, the mineralizer may be hydrofluoric acid or sodium hydroxide. The mineralizer may be in the form of an aqueous mineralizer solution having a concentration, for example, an aqueous mineralizer solution having a concentration of greater than 5 wt%, preferably 10 to 40 wt%.
The method of collecting the solid product according to the present disclosure may be performed using conventional methods, such as filtration, centrifugation, and the like. The process may further comprise a step of drying after collecting the solid product, and the drying conditions may be conventional in the art, for example, the drying conditions may include: the temperature is 100-200 ℃, and the time is 1-24 h.
In a second aspect of the present disclosure: there is provided a nanocarbon-based material prepared by the method according to the first aspect of the present disclosure. The nano carbon-based material disclosed by the invention has excellent catalytic performance and is particularly suitable for catalyzing etherification reaction of propylene oxide.
A third aspect of the disclosure: provided is a method for etherifying propylene oxide, the method comprising: and (b) contacting propylene oxide and an etherifying agent to react in the presence of a catalyst, wherein the catalyst contains the nanocarbon-based material according to the second aspect of the present disclosure.
The process of the present disclosure may be carried out in a variety of conventional catalytic reactors, for example, may be carried out in a batch tank reactor or three-neck flask, or in suitable other reactors such as fixed bed, moving bed, suspended bed, and the like.
In an alternative embodiment of the present disclosure, the reaction is carried out in a slurry bed reactor. In this case, the amount of the catalyst to be used may be 10 to 1000mg, preferably 20 to 200mg, based on 100mL of the propylene oxide.
In another alternative embodiment of the present disclosure, the reaction may be immobilizedIn a bed reactor. In this embodiment, the weight hourly space velocity of the propylene oxide may be from 0.01 to 500h -1 Preferably 0.05 to 2 hours -1 。
According to the present disclosure, the etherifying agent may be methanol, ethanol, ethylene glycol or glycerol, or a combination of two or three thereof. The amount of the etherifying agent used may be 10 to 500mL, preferably 20 to 200mL, based on 100mL of the propylene oxide.
According to the present disclosure, the conditions of the reaction may be: the temperature is 50-200 ℃, preferably 60-180 ℃; the pressure is 0 to 20MPa, preferably 0 to 1MPa; the time is 1 to 72 hours, preferably 2 to 24 hours. In order to make the reaction more sufficient, it is preferable that the reaction is carried out under stirring.
The method takes the nano carbon-based material as the catalyst to catalyze the etherification reaction of the propylene oxide, can realize the etherification of the propylene oxide under mild conditions, and has higher propylene oxide conversion rate and propylene glycol ether selectivity.
The present disclosure is described in detail below with reference to examples, but the scope of the present disclosure is not limited thereby.
Preparation examples 1 to 7 are for explaining the nanocarbon-based material and the preparation method thereof according to the present disclosure.
Preparation of example 1
10g of sucrose (weight average molecular weight 342) and 10g of silica gel particles (SiO) having a particle size of 500 mesh 2 98 percent by weight) and then reacting for 24 hours in a closed reaction kettle (with the initial oxygen content of 0.5 volume percent) at 500 ℃ to obtain a reacted material; and mixing the reacted material with 15g of 10 wt% hydrofluoric acid solution, treating at 50 ℃ for 12h, filtering, washing, collecting a solid product, and drying at 120 ℃ for 2h to obtain the carbon-based nano-material C1.
Preparation of example 2
10g of starch (weight-average molecular weight of about 11000) and 15g of silica gel granules (SiO) having a particle size of 5000 mesh were mixed 2 98 percent by weight) and then reacting for 18 hours in a closed reaction kettle (the initial oxygen content is 0.8 volume percent) at the temperature of 600 ℃ to obtain a reacted material; subjecting the resultant to reactionMixing the material with 25g of 12 wt% sodium hydroxide solution, treating at 40 deg.C for 16h, filtering, washing, collecting solid product, and drying at 120 deg.C for 2h to obtain nanocarbon-based material C2.
Preparation of example 3
10g of sucrose (weight average molecular weight 342) and 30g of silica gel particles (SiO) having a particle size of 500 mesh 2 98 percent by weight) and then reacting for 24 hours in a closed reaction kettle (with the initial oxygen content of 0.5 volume percent) at 500 ℃ to obtain a reacted material; and mixing the reacted material with 60g of hydrofluoric acid with the concentration of 8 wt%, treating at 50 ℃ for 12h, filtering, washing, collecting a solid product, and drying at 120 ℃ for 2h to obtain the carbon-based nano-material C3.
Preparation of example 4
10g of starch (weight-average molecular weight of about 7500) and 10g of silica gel granules (SiO) having a particle size of 25 mesh 2 98 percent by weight) and then reacting for 24 hours in a closed reaction kettle (with the initial oxygen content of 0.5 volume percent) at 500 ℃ to obtain a reacted material; and mixing the reacted material with 15g of hydrofluoric acid with the concentration of 10 wt%, treating at 50 ℃ for 12 hours, filtering, washing, collecting a solid product, and drying at 120 ℃ for 2 hours to obtain the carbon-based nano-material C4.
Preparation of example 5
10g of sucrose (weight average molecular weight 342) and 10g of silica gel particles (SiO) having a particle size of 10000 mesh 2 98 percent by weight) and then reacting for 24 hours in a closed reaction kettle (with the initial oxygen content of 0.5 volume percent) at 500 ℃ to obtain a reacted material; and mixing the reacted material with 15g of hydrofluoric acid with the concentration of 10 wt%, treating at 50 ℃ for 12 hours, filtering, washing, collecting a solid product, and drying at 120 ℃ for 2 hours to obtain the carbon-based nano-material C5.
Preparation of example 6
10g of sucrose (weight average molecular weight 342) and 10g of silica gel particles (SiO) having a particle size of 500 mesh 2 98 percent by weight) and reacting for 24 hours at 500 ℃ in a closed reaction kettle (the initial oxygen content is 5 percent by volume) to obtain a reacted material; the reacted material was mixed with 15g of a 10% strength by weight hydrofluoric acid solutionAnd treating at 50 ℃ for 12h after combination, filtering and washing, collecting a solid product, and drying at 120 ℃ for 2h to obtain the nano carbon-based material C6.
Preparation of example 7
10g of cellulose (weight-average molecular weight of approximately 1600000) and 10g of silica gel granules (SiO) having a particle size of 500 mesh were mixed 2 98 percent by weight) and then reacting for 24 hours in a closed reaction kettle (the initial oxygen content is 15 percent by volume) at 500 ℃ to obtain a reacted material; and mixing the reacted material with 15g of 10 wt% hydrofluoric acid solution, treating at 50 ℃ for 12h, filtering, washing, collecting a solid product, and drying at 120 ℃ for 2h to obtain the carbon-based nano-material C7.
Preparation of comparative example 1
The nanocarbon-based material was prepared according to the method of preparation example 1, except that the silica gel particles having a particle size of 10 mesh were used, and the nanocarbon-based material D1 was prepared.
Preparation of comparative example 2
The nanocarbon-based material was prepared according to the method of preparation example 1, except that the same amount of glucose was used instead of sucrose in example 1, to prepare nanocarbon-based material D2.
Examples 1-12 are presented to illustrate the process of using nanocarbon-based materials of the present disclosure to catalyze the etherification of propylene oxide.
In the following examples and comparative examples, the oxidation products were analyzed by gas chromatography (GC: agilent, 7890A) and gas chromatography-mass spectrometer (GC-MS: thermo Fisher Trace ISQ). Conditions of gas chromatography: nitrogen carrier gas, temperature programmed at 140K: 60 ℃,1 minute, 15 ℃/minute, 180 ℃,15 minutes; split ratio, 10:1; the injection port temperature is 300 ℃; detector temperature, 300 ℃. On the basis, the following formulas are respectively adopted to calculate the conversion rate of the raw materials and the selectivity of the target product:
propylene oxide conversion% = (molar amount of propylene oxide added before reaction-molar amount of propylene oxide remaining after reaction)/molar amount of propylene oxide added before reaction × 100%;
propylene glycol ether selectivity% = (molar amount of propylene glycol ether formed after reaction)/molar amount of propylene oxide added before reaction × 100%.
Example 1
40mg of nanocarbon-based material C1 as a catalyst, 200mL of methanol and 100mL of propylene oxide were charged into a slurry bed reactor, sealed, stirred at 60 ℃ and 1.0MPa for 8 hours, and then the catalyst was separated by centrifugation and filtration, and the product was analyzed by gas chromatography, and the results are shown in Table 1.
Examples 2 to 7
Propylene oxide was catalytically etherified according to the method of example 1, except that C1 was replaced with the same amount of nanocarbon-based materials C2 to C7, respectively. The results of the analysis of the products are shown in Table 1.
Example 8
100mg of nanocarbon-based material C1 as a catalyst, 100mL of ethylene glycol and 100mL of propylene oxide were charged into a slurry bed reactor, sealed, stirred at 70 ℃ and 0.8MPa for 6 hours, and after separating the catalyst by centrifugation and filtration, the product was analyzed by gas chromatography, and the results are shown in Table 1.
Example 9
10mg of nanocarbon material C1 as a catalyst, 10mL of methanol and 100mL of propylene oxide were charged into a slurry bed reactor, sealed, stirred and reacted at 60 ℃ under 1.0MPa for 8 hours, and after separating the catalyst by centrifugation and filtration, the product was analyzed by gas chromatography, and the results are shown in Table 1.
Example 10
600mg of nanocarbon-based material C1 as a catalyst, 500mL of methanol and 100mL of propylene oxide were charged into a slurry bed reactor, sealed, stirred at 60 ℃ and 1.0MPa for reaction for 8 hours, and then the catalyst was separated by centrifugation and filtration, and the product was analyzed by gas chromatography, and the results are shown in Table 1.
Example 11
40mg of nanocarbon-based material C1 as a catalyst, 200mL of methanol and 100mL of propylene oxide were charged into a slurry bed reactor, sealed, stirred at 50 ℃ and 2.0MPa for 30 hours, and then the catalyst was separated by centrifugation and filtration, and the product was analyzed by gas chromatography, and the results are shown in Table 1.
Example 12
Filling a fixed bed reactor with a nano carbon-based material C1 as a catalyst, feeding methanol and propylene oxide into the reactor, wherein the weight hourly space velocity of the propylene oxide is 2h -1 The results of analyzing the oxidized product by gas chromatography after reacting 100mL of propylene oxide with 200mL of methanol at 60 ℃ and 1.0MPa for 8 hours are shown in Table 1.
Comparative example 1
Propylene oxide was catalytically etherified according to the method of example 1, except that the nanocarbon-based material D1 was used as a catalyst. The results of the analysis of the product are shown in Table 1.
Comparative example 2
Propylene oxide was catalytically etherified according to the method of example 1, except that the nanocarbon based material D2 was used as the catalyst. The results of the analysis of the products are shown in Table 1.
Comparative example 3
Propylene oxide was catalytically etherified according to the method of example 1, except that the nanocarbon-based material C1 was not used as a catalyst. The results of the analysis of the products are shown in Table 1.
TABLE 1
| Examples | Percent conversion of propylene oxide% | Propylene glycol ether selectivity% |
| Example 1 | 95 | 94 |
| Example 2 | 93 | 92 |
| Example 3 | 90 | 91 |
| Example 4 | 88 | 87 |
| Example 5 | 85 | 84 |
| Example 6 | 84 | 83 |
| Example 7 | 82 | 81 |
| Example 8 | 92 | 93 |
| Example 9 | 86 | 85 |
| Example 10 | 82 | 81 |
| Example 11 | 80 | 80 |
| Example 12 | 92 | 93 |
| Comparative example 1 | 40 | 76 |
| Comparative example 2 | 36 | 78 |
| Comparative example 3 | 22 | 73 |
As can be seen from table 1, the nanocarbon-based material disclosed by the invention is used as a catalyst to catalyze the etherification reaction of propylene oxide, which is beneficial to improving the conversion rate of propylene oxide and the selectivity of propylene glycol ether.
The preferred embodiments of the present disclosure have been described in detail above, 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 fall within 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 (19)
1. A preparation method of a nano carbon-based material is characterized by comprising the following steps:
a. mixing carbohydrate with silica gel particles with the particle size of less than 20 meshes, and reacting in a closed reactor at 300 to 1500 ℃ for 1 to 24h to obtain a reacted material; wherein the number of carbon atoms of the carbohydrate is 10 or more; the carbohydrate is sucrose, starch or cellulose;
b. b, mixing the reacted material obtained in the step a with a mineralizer, processing at 20 to 80 ℃ for 1 to 48h, and collecting a solid product; the mineralizer is hydrofluoric acid or sodium hydroxide.
2. The method of claim 1, wherein the weight ratio of carbohydrate, silica gel particles, and mineralizer is 100: (1 to 500): (2 to 1000), wherein the silica gel particles are made of SiO 2 And (6) counting.
3. The method of claim 2, wherein the weight ratio of carbohydrate, silica gel particles, and mineralizer is 100: (2 to 250): (5 to 500).
4. The method according to claim 1 or 2, wherein the weight average molecular weight of the carbohydrate is from 200 to 2000000;
the particle size of the silica gel particles is 20 to 10000 meshes;
the concentration of the mineralizer is greater than 5 wt%.
5. The method according to claim 4, wherein the silica gel particles have a particle size of 30 to 8000 mesh.
6. The method of claim 4, wherein the concentration of the mineralizer is 10 to 40 wt%.
7. A process according to claim 1 or 2, wherein in step a the initial oxygen content in the closed reactor is less than 20% by volume.
8. A process as claimed in claim 7, wherein in step a, the initial oxygen content within the closed reactor is less than 10% by volume.
9. The method of claim 8, wherein in step a, the initial oxygen content within the closed reactor is less than 1% by volume.
10. The nanocarbon-based material prepared by the method according to any one of claims 1 to 9.
11. A method for etherifying propylene oxide, the method comprising: reacting propylene oxide with an etherifying agent in contact in the presence of a catalyst, wherein the catalyst comprises the nanocarbon-based material according to claim 10.
12. The process as claimed in claim 11, wherein the reaction is carried out in a slurry bed reactor, the catalyst being used in an amount of from 10 to 1000mg, based on 100mL of the propylene oxide.
13. The method of claim 12, wherein the catalyst is used in an amount of 20 to 200mg.
14. The method as claimed in claim 11, wherein the reaction is carried out in a fixed bed reactor, and the weight hourly space velocity of the propylene oxide is 0.01 to 500h -1 。
15. The method of claim 14, wherein the weight hourly space velocity of the propylene oxide is 0.05 to 2h -1 。
16. The method according to any one of claims 11 to 15, wherein the etherifying agent is methanol, ethanol, ethylene glycol or glycerol, or a combination of two or three thereof;
the dosage of the etherifying agent is 10 to 500mL based on 100mL of the propylene oxide.
17. The method according to claim 16, wherein the amount of the etherifying agent is 20 to 200mL.
18. The method according to any one of claims 11 to 15, wherein the reaction conditions are as follows: the temperature is 50 to 200 ℃; the pressure is 0 to 20MPa; the time is 1 to 72h.
19. The process of claim 18, wherein the reaction conditions are: the temperature is 60 to 180 ℃; the pressure is 0 to 1MPa; the time is 2 to 24h.
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| CN108126740A (en) * | 2017-12-29 | 2018-06-08 | 中触媒新材料股份有限公司 | Have magnetic Ti-MWW microsphere zeolite catalysts preparation method and application |
| CN108479707A (en) * | 2018-05-25 | 2018-09-04 | 黄智慧 | A kind of preparation method of material for air purification |
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