CN112441597A - Preparation method of Y-type molecular sieve - Google Patents
Preparation method of Y-type molecular sieve Download PDFInfo
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- CN112441597A CN112441597A CN201910813251.4A CN201910813251A CN112441597A CN 112441597 A CN112441597 A CN 112441597A CN 201910813251 A CN201910813251 A CN 201910813251A CN 112441597 A CN112441597 A CN 112441597A
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- molecular sieve
- type molecular
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- activated clay
- drying
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000004927 clay Substances 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 230000004913 activation Effects 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 12
- 235000019353 potassium silicate Nutrition 0.000 claims abstract description 11
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000006229 carbon black Substances 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 239000003513 alkali Substances 0.000 claims abstract description 8
- 238000000227 grinding Methods 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- 239000012670 alkaline solution Substances 0.000 claims abstract description 3
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 10
- 235000012211 aluminium silicate Nutrition 0.000 claims description 10
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 10
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 claims description 4
- 229960000892 attapulgite Drugs 0.000 claims description 4
- 229910052621 halloysite Inorganic materials 0.000 claims description 4
- 229910052625 palygorskite Inorganic materials 0.000 claims description 4
- 239000004113 Sepiolite Substances 0.000 claims description 3
- 229910052624 sepiolite Inorganic materials 0.000 claims description 3
- 235000019355 sepiolite Nutrition 0.000 claims description 3
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 8
- 238000003786 synthesis reaction Methods 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 4
- 239000012452 mother liquor Substances 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 229910021536 Zeolite Inorganic materials 0.000 description 7
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 7
- 238000011065 in-situ storage Methods 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- 239000010457 zeolite Substances 0.000 description 7
- 239000002131 composite material Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- 238000002791 soaking Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/20—Faujasite type, e.g. type X or Y
- C01B39/24—Type Y
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention relates to a preparation method of a Y-type molecular sieve, which is characterized by comprising the following steps: 1) adding clay into alkaline solution to be soaked until saturation, drying and then carrying out activation treatment to obtain activated clay; 2) mixing and grinding the activated clay obtained in the step 1), white carbon black, water glass, alkali liquor and guiding agent according to a certain proportion; 3) and (3) placing the mixture obtained in the step 2) into a sealed reaction kettle, heating to 90-120 ℃, crystallizing for 8-30 hours, and after the reaction is finished, cooling, washing, filtering and drying to obtain the Y-type molecular sieve. The method has the advantages of low-cost and easily-obtained raw materials and simple process, solves the problems of pollution and the like caused by a large amount of mother liquor generated by the traditional hydrothermal synthesis method, and can realize green, economic and efficient synthesis of the Y-type molecular sieve.
Description
Technical Field
The invention relates to a preparation method of a Y-type molecular sieve, in particular to a Y-type molecular sieve prepared by using activated clay through an in-situ synthesis method. Belonging to the field of inorganic material synthesis.
Background
Molecular sieves refer to a class of materials having uniform micropores with pore sizes comparable to the typical molecular size. The inner diameter of the supercage cavity in the Y-type molecular sieve structure is about 1.3nm, and the diameter of the orifice of the twelve-membered ring is 0.74 nm. Just because the Y-type molecular sieve has a larger cavity and a three-dimensional twelve-membered ring channel system, a plurality of organic molecules can enter the supercage and perform catalytic reaction.
At present, the most common Y-type molecular sieve synthesis methods are hydrothermal synthesis methods and hydrothermal conversion methods. USP 3119659 published 1964 that studies on synthesizing zeolite from natural clay minerals have been continuously conducted since in-situ synthesis of zeolite molecular sieves using hydrothermal conversion method using kaolin as raw material, such as USP 3367886, USP 3391994, USP 4493902, CN 106673031B, CN 104477938A, CN 108439427 a, etc. The zeolite molecular sieve synthesized by the in-situ technology has higher stability, stronger diffusion capacity, more surface active centers, more ideal pore structure distribution and longer service life, and fully shows the unique advantages of the natural clay in the aspect of preparing the porous molecular sieve by crystal transformation. The traditional synthetic method has the defects of low solid content, low single kettle yield, resource waste, high wastewater proportion, serious environmental pollution and the like. Therefore, the synthesis method of the molecular sieve with economy, environmental protection, high efficiency and safety is always a hotspot of research in the field of materials.
The invention relates to a preparation method of a Y-type molecular sieve, which adopts an in-situ synthesis technology, a clay activation modification technology and the like to synthesize the Y-type molecular sieve, and the material has higher Y-type molecular sieve content, high stability and rich medium-large pore structures. The method solves a series of problems of pollution and the like caused by a large amount of mother liquor generated in the process of hydro-thermal synthesis of the Y-type molecular sieve by utilizing cheap and easily available raw materials and a simple process, and can realize the aim of green synthesis.
Disclosure of Invention
The invention aims to provide a method for synthesizing a Y-type zeolite molecular sieve, which is simple and easy to control and has low cost, or a method for synthesizing the molecular sieve in a green way by using a solid-like system. The invention synthesizes a composite material containing a Y-type molecular sieve by an in-situ conversion method. The preparation method comprises the following steps:
1) adding clay into alkaline solution to be soaked until saturation, drying and then carrying out activation treatment to obtain activated clay;
2) mixing and grinding the activated clay obtained in the step 1), white carbon black, water glass, alkali liquor and guiding agent according to a certain proportion;
3) and (3) placing the mixture obtained in the step 2) into a sealed reaction kettle, heating to 90-120 ℃, crystallizing for 8-30 hours, and after the reaction is finished, cooling, washing, filtering and drying to obtain the Y-type molecular sieve.
2. The method according to claim 1, wherein the activation treatment in step 1) is carried out at an activation temperature of 300 to 500 ℃ for 1 to 5 hours.
3. The method according to claim 1, wherein in the step 1), the clay is one or more of kaolin, halloysite, sepiolite, diatomite, attapulgite and montmorillonite; the addition amount of the kaolin is more than 60 percent.
4. The method according to claim 1, wherein the alkaline substance is added in an amount of 15 to 35% by weight based on the weight of the clay in step 1).
5. The method according to claim 1, wherein in the step 2), the addition amount of the white carbon black is 10-30% of that of the activated clay.
6. The method according to claim 1, wherein in the step 2), the activated clay, the water glass, the white carbon black, the alkali liquor and the guiding agent are uniformly mixed and then ground, and the grinding time is 30-120 min.
Compared with the prior art, the invention also has the following advantages:
(1) the clay activation temperature of the invention is greatly reduced, the problem of high cost of a hydrothermal conversion method is effectively solved, and the invention has higher social benefit and economic benefit.
(2) The main raw material of the invention is clay with wide distribution and low price. The characteristics of higher thermal stability, abundant large and medium pore structures, heavy metal resistance, wear resistance and the like of the Y-type molecular sieve synthesized by the in-situ crystallization method are reserved.
(3) The preparation method of the invention only needs to effectively grind all the raw materials, then put the raw materials into a reaction kettle for reaction, and then wash and dry the raw materials to obtain the molecular sieve, namely the in-situ conversion method for synthesizing the molecular sieve under a solid-like system. The method overcomes the defects of a large amount of waste water, easy corrosion of equipment, large pressure of a synthesis system and the like in the synthesis process of the conventional hydrothermal method; meanwhile, the synthesis process is simple, and the volume utilization rate of the reaction kettle is improved.
Detailed Description
The following describes in detail specific embodiments of the present invention. The specific embodiments described herein are merely illustrative and explanatory of the invention and are not restrictive thereof.
Preparation of a guiding agent: the material feeding proportion is according to Na2O:SiO2:Al2O3:H2Calculation of O ═ 16:15:1:320 (molar ratio)The amount of sodium metaaluminate and water glass is used. Adding sodium metaaluminate into water glass at room temperature, stirring for 30 minutes, standing and aging for 10-30 hours at 25-30 ℃ to obtain the guiding agent.
Example 1
(1) Adding 650g of kaolin, 150g of sepiolite and 200g of diatomite into 697ml of sodium hydroxide solution, soaking until saturation, drying, and then carrying out activation treatment, wherein the activation condition is roasting at 500 ℃ for 2 hours to obtain activated clay;
(2) uniformly mixing 500g of the activated clay obtained in the step (1), 50g of white carbon black, 393ml of water glass, 120ml of alkali liquor and 155ml of guiding agent, and grinding for 60 min;
(3) and (3) placing the mixture obtained in the step (2) into a sealed reaction kettle, heating to 97 ℃, crystallizing for 24 hours, and after the reaction is finished, cooling, washing and drying to obtain the Y-type molecular sieve.
The composite material was found to contain 49.6 wt% of Y-type zeolite molecular sieve and had a specific surface area of 536m2Per g, pore volume 0.33cm3/g。
Example 2
(1) Adding 500g of kaolin, 50g of halloysite and 200g of attapulgite into 450ml of sodium hydroxide and 200ml of water glass solution, soaking until saturation, drying, and then performing activation treatment, wherein the activation condition is that the kaolin, the halloysite and the attapulgite are roasted for 5 hours at 300 ℃ to obtain activated clay;
(2) uniformly mixing 300g of the activated clay obtained in the step (1), 90g of white carbon black, 415ml of water glass, 90ml of alkali liquor and 160ml of guiding agent, and grinding for 30 min;
(3) and (3) placing the mixture obtained in the step (2) into a sealed reaction kettle, heating to 120 ℃, crystallizing for 10 hours, and after the reaction is finished, cooling, washing and drying to obtain the Y-type molecular sieve.
The composite material was found to contain 54.5 wt% of Y-type zeolite molecular sieve and had a specific surface area of 581m2Per g, pore volume 0.32cm3/g。
Example 3
(1) Adding 100g of kaolin into 63ml of sodium hydroxide solution, soaking until saturation, drying, and then performing activation treatment, wherein the activation condition is that the kaolin is roasted for 3 hours at 400 ℃ to obtain activated clay;
(2) uniformly mixing 50g of the activated clay obtained in the step (1), 10g of white carbon black, 67ml of water glass, 14ml of alkali liquor and 13ml of guiding agent, and grinding for 120 min;
(3) and (3) placing the mixture obtained in the step (2) into a sealed reaction kettle, heating to 110 ℃, crystallizing for 18 hours, and after the reaction is finished, cooling, washing and drying to obtain the Y-type molecular sieve.
The composite material was found to contain 63.7 wt% of Y-type zeolite molecular sieve and had a specific surface area of 622m2Per g, pore volume 0.32cm3/g。
Claims (6)
1. A preparation method of a Y-type molecular sieve specifically comprises the following steps:
1) adding clay into alkaline solution to be soaked until saturation, drying and then carrying out activation treatment to obtain activated clay;
2) mixing and grinding the activated clay obtained in the step 1), white carbon black, water glass, alkali liquor and guiding agent according to a certain proportion;
3) and (3) placing the mixture obtained in the step 2) into a sealed reaction kettle, heating to 90-120 ℃, crystallizing for 8-30 hours, and after the reaction is finished, cooling, washing, filtering and drying to obtain the Y-type molecular sieve.
2. The method according to claim 1, wherein the activation treatment in step 1) is carried out at an activation temperature of 300 to 500 ℃ for 1 to 5 hours.
3. The method according to claim 1, wherein in the step 1), the clay is one or more of kaolin, halloysite, sepiolite, diatomite, attapulgite and montmorillonite; the addition amount of the kaolin is more than 60 percent.
4. The method according to claim 1, wherein the alkaline substance is added in an amount of 15 to 35% by weight based on the weight of the clay in step 1).
5. The method according to claim 1, wherein in the step 2), the addition amount of the white carbon black is 10-30% of that of the activated clay.
6. The method according to claim 1, wherein in the step 2), the activated clay, the water glass, the white carbon black, the alkali liquor and the guiding agent are uniformly mixed and then ground, and the grinding time is 30-120 min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910813251.4A CN112441597A (en) | 2019-08-30 | 2019-08-30 | Preparation method of Y-type molecular sieve |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910813251.4A CN112441597A (en) | 2019-08-30 | 2019-08-30 | Preparation method of Y-type molecular sieve |
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| CN201910813251.4A Pending CN112441597A (en) | 2019-08-30 | 2019-08-30 | Preparation method of Y-type molecular sieve |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3130007A (en) * | 1961-05-12 | 1964-04-21 | Union Carbide Corp | Crystalline zeolite y |
| CN1709794A (en) * | 2004-06-16 | 2005-12-21 | 中国石油化工股份有限公司 | A kind of synthetic method of Y-type zeolite composite material |
| CN1789127A (en) * | 2004-12-15 | 2006-06-21 | 中国石油化工股份有限公司 | Preparation method of Y type molecular sieve enriched with mesopore |
| CN101746778A (en) * | 2008-11-28 | 2010-06-23 | 中国石油化工股份有限公司 | Composite material containing double-pore structure Y-type zeolite, and preparation method thereof |
| CN105645433A (en) * | 2016-03-29 | 2016-06-08 | 东北大学 | Method for synthesizing Y-shaped molecular sieve dynamically by kaoline |
| CN108439427A (en) * | 2018-01-31 | 2018-08-24 | 中海油天津化工研究设计院有限公司 | A kind of method that fabricated in situ is rich in mesoporous NaY molecular sieve |
| CN109534357A (en) * | 2018-12-27 | 2019-03-29 | 中国神华能源股份有限公司 | A kind of Y type molecular sieve prepared using white clay as raw material and its method |
-
2019
- 2019-08-30 CN CN201910813251.4A patent/CN112441597A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3130007A (en) * | 1961-05-12 | 1964-04-21 | Union Carbide Corp | Crystalline zeolite y |
| CN1709794A (en) * | 2004-06-16 | 2005-12-21 | 中国石油化工股份有限公司 | A kind of synthetic method of Y-type zeolite composite material |
| CN1789127A (en) * | 2004-12-15 | 2006-06-21 | 中国石油化工股份有限公司 | Preparation method of Y type molecular sieve enriched with mesopore |
| CN101746778A (en) * | 2008-11-28 | 2010-06-23 | 中国石油化工股份有限公司 | Composite material containing double-pore structure Y-type zeolite, and preparation method thereof |
| CN105645433A (en) * | 2016-03-29 | 2016-06-08 | 东北大学 | Method for synthesizing Y-shaped molecular sieve dynamically by kaoline |
| CN108439427A (en) * | 2018-01-31 | 2018-08-24 | 中海油天津化工研究设计院有限公司 | A kind of method that fabricated in situ is rich in mesoporous NaY molecular sieve |
| CN109534357A (en) * | 2018-12-27 | 2019-03-29 | 中国神华能源股份有限公司 | A kind of Y type molecular sieve prepared using white clay as raw material and its method |
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Application publication date: 20210305 |