CN104556100A - Method for removing organic amine template in borosilicate beta molecular sieve - Google Patents
Method for removing organic amine template in borosilicate beta molecular sieve Download PDFInfo
- Publication number
- CN104556100A CN104556100A CN201310507290.4A CN201310507290A CN104556100A CN 104556100 A CN104556100 A CN 104556100A CN 201310507290 A CN201310507290 A CN 201310507290A CN 104556100 A CN104556100 A CN 104556100A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- temperature
- maturing temperature
- accordance
- borosilicate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention provides a method for removing an organic amine template in a borosilicate beta molecular sieve. The method comprises the following steps: drying the borosilicate beta molecular sieve, roasting the borosilicate beta molecular sieve in air or nitrogen at 150-420 DEG C at segments, reacting the borosilicate beta molecular sieve in an aqueous solution of an oxidant, and washing and drying the obtained solid after the reaction, wherein the oxidant is selected from one or more of perchloric acid, hypochlorous acid, perchlorate and hypochlorite, and the mass ratio of the oxidant to the borosilicate beta molecular sieve is 0.5-2.0. The method is simple to operate and can be used for effectively removing the template in the borosilicate beta molecular sieve.
Description
Technical field
The present invention is the removal methods of organic amine template in a kind of molecular sieve, specifically, is the removal methods of organic amine template in a kind of beta-molecular sieve.
Background technology
Borosilicate zeolite is a kind of class sial hetero-atom molecular-sieve, the aluminium namely on Si-Al molecular sieve skeleton completely a kind of molecular sieve of replacing by boron atom.Borosilicate beta-molecular sieve is Hydrothermal Synthesis in containing the system of organic formwork agent usually, and conventional template has tetraethyl ammonium hydroxide, tetraethylammonium bromide or their mixture, and other organic amine compound.Organic formwork agent is separated with molecular sieve inorganic skeleton, be molecular sieve as before sorbent material or catalyzer, obtain the unobstructed and increasing specific surface area requisite step in duct.The method of the removed template method commonly used for sial beta-molecular sieve is high-temperature roasting method, namely at 500 ~ 550 DEG C of roasting 2 ~ 6h, makes organic formwork agent be decomposed into micro-molecular gas effusion molecular sieve pore passage.But because beta-molecular sieve structural stability is poor, in the process, structure deteriorate is serious, and average crystallinity declines 30 ~ 40%, even more.Therefore, people's exploratory development removes the different methods of organic amine template.
The method of CN1199858C employing segmentation constant temperature calcining removes the organic amine template in beta-molecular sieve, can obtain higher crystallization reservation degree.
CN1041617C and CN1041618C is respectively by adding the step such as strong oxidizer or reductive agent, then roasting removes organic amine in atmosphere, effectively can improve the degree of crystallinity of beta-molecular sieve after beta-molecular sieve organic amine removal efficiency and de-amine.
Need in borosilicate beta-molecular sieve building-up process to add more organic formwork agent, guarantee generates the pure beta-molecular sieve crystalline phase of high-crystallinity.Therefore, compared with sial beta-molecular sieve, containing more template in the former powder of borosilicate beta-molecular sieve, and the structural stability of borosilicate beta-molecular sieve is poorer.Adopt aforesaid method or can not effectively by template removal in borosilicate beta-molecular sieve, or crystallinity loss is large.
Summary of the invention
The object of this invention is to provide the removal methods of organic amine template in a kind of borosilicate beta-molecular sieve, the method is simple to operate, can template in effective elimination borosilicate beta-molecular sieve.
The removal methods of organic amine template in the borosilicate beta-molecular sieve that the inventive method provides, comprise after the drying of borosilicate beta-molecular sieve, in 150 ~ 420 DEG C of baking inphases in air or nitrogen, then react in the aqueous solution of oxygenant, by gained solids wash, drying after reaction, described oxygenant is selected from one or more in perchloric acid, hypochlorous acid, perchlorate and hypochlorite, and the mass ratio of oxygenant and borosilicate beta-molecular sieve is 0.5 ~ 2.0.
The inventive method, can the organic amine template of effective elimination borosilicate beta-molecular sieve by the roasting of low temperature multistage with by oxidizer treatment, improves molecular sieve specific surface area, and retains the degree of crystallinity taking off borosilicate beta-molecular sieve after amine to greatest extent.
Embodiment
The method that the inventive method adopts baking inphases and oxide treatment to combine removes the organic amine template of borosilicate beta-molecular sieve, first baking inphases molecular sieve at a lower temperature, make organic amine that Hofmann DeR fully occur, then use oxidizing agent solution process, make remaining organic amine oxidized further and remove.After the inventive method takes off amine, molecular sieve specific surface area improves, and crystallization reservation degree is high, and carbon residue is low, and the organic amine illustrating in borosilicate beta-molecular sieve obtains and removes comparatively up hill and dale.
Borosilicate beta-molecular sieve, before baking inphases, is first carried out drying by the inventive method, and dry temperature preferably 80 ~ 130 DEG C, more preferably 100 ~ 120 DEG C, time of drying is 2 ~ 20h, more preferably 8 ~ 12h preferably.
Carry out the baking inphases of molecular sieve after drying, baking inphases can be two sections, and also can be three sections or more, roasting can be carried out in atmosphere, also can carry out in rare gas element.Described rare gas element preferred nitrogen.
In the inventive method, dried molecular sieve is in air or nitrogen during point two-stage roasting, and first paragraph maturing temperature is 240 ~ 280 DEG C, and second segment maturing temperature is 380 ~ 420 DEG C.
During two-stage roasting, be warming up to temperature rise rate preferably 0.5 ~ 7 DEG C/min of first paragraph maturing temperature from drying temperature, be warming up to temperature rise rate preferably 0.5 ~ 7 DEG C/min of second segment maturing temperature from first paragraph maturing temperature.
In the inventive method, dried molecular sieve is in air or nitrogen during point three sections of roastings, and first paragraph maturing temperature is 150 ~ 180 DEG C, and second segment maturing temperature is 240 ~ 280 DEG C, and the 3rd section of maturing temperature is 380 ~ 420 DEG C.
During three sections of roastings, temperature rise rate preferably 0.5 ~ 7 DEG C/min of first paragraph maturing temperature is warming up to from drying temperature, be warming up to temperature rise rate preferably 0.5 ~ 7 DEG C/min of second segment maturing temperature from first paragraph maturing temperature, be warming up to temperature rise rate preferably 9 ~ 12 DEG C/min of the 3rd section of maturing temperature from second segment maturing temperature.
In aforesaid method, in baking inphases process, preferably 1 ~ 8 hour time of every section of roasting, more preferably 1 ~ 6 hour.
Molecular sieve after baking inphases carries out oxide treatment, namely reacts in the aqueous solution of oxygenant, temperature of reaction preferably 100 ~ 170 DEG C, more preferably 120 ~ 150 DEG C, preferably 2 ~ 50 hours time, more preferably 10 ~ 48 hours.Gu the aqueous solution of oxygenant used and the liquid of molecular sieve/than being 2 ~ 20ml/g, preferably 2 ~ 15ml/g.The preferred perchloric acid of oxygenant used, hypochlorous acid, perchlorate or hypochlorite, described perchlorate or hypochlorite are preferably its ammonium salt, sodium salt or sylvite.
When oxide treatment is carried out to molecular sieve, the concentration of aqueous solution of oxygenant used is not limited, as long as make the mass ratio of oxygenant and molecular sieve be 0.5 ~ 2.0, preferably 0.5 ~ 1.5.
After oxide treatment, organism residual in molecular sieve changes into the small molecules such as formic acid, acetic acid or carbonic acid gas, removes, finally reach the object removing organic formwork agent completely easily via washing and drying and volatilizing.Described washing can be washing, the drying temperature after washing preferably 90 ~ 120 DEG C, preferably 2 ~ 30 hours time.
In the inventive method, in described borosilicate beta-molecular sieve, organic amine template is tetraethyl ammonium hydroxide and/or tetraethylammonium bromide.
The inventive method is specially adapted to removing of borosilicate beta-molecular sieve organic amine template, and to produce the borosilicate beta-molecular sieve with higher crystallinity, described borosilicate beta-molecular sieve is preferably without sodium form or the Hydrogen beta-molecular sieve of high-temperature roasting.
Further illustrate the present invention below by example, but the present invention is not limited to this.
Example 1
Prepare borosilicate beta-molecular sieve.
Be that the tetraethyl-oxyammonia solution of 25 quality % mixes by 1.0g borax, 1.1g sodium hydroxide and 104.7g concentration, (Cabot company produces to add 20g superfine SiO 2 again, trade mark CAB-O-SILM-5), reactor is moved into after stirring, 140 DEG C of crystallization 15 days, crystallization terminates to be cooled to rapidly 40 DEG C afterwards, and product is after centrifugation washing, gained solid, in 90 DEG C of dryings 10 hours, obtains the former powder S of borosilicate beta-molecular sieve
0, its anhydrous chemical composition (in oxide mol ratio) is: 0.5Na
2oB
2o
322SiO
2.With this former powder for standard specimen, its relative crystallinity is decided to be 100%, its characterization data is in table 1.
Example 2
(1) three section of roasting
By S obtained for 10g example 1
0molecular sieve, in 120 DEG C of dry 12h, in air atmosphere, is warming up to 180 DEG C with the temperature rise rate of 5 DEG C/min, roasting 2h, then is warming up to 260 DEG C of roasting 2h with the temperature rise rate of 5 DEG C/min, is then warming up to 420 DEG C of roasting 4h with the temperature rise rate of 10 DEG C/min.
(2) oxide treatment
Get 5g(1) powder after one-step baking, 5g perchloric acid, 20ml deionized water add in hydrothermal reaction kettle, 140 DEG C of standing and reacting 12h, be cooled to 25 DEG C, product is through centrifugation, gained solid deionized water wash 3 ~ 5 times, 120 DEG C of dry 12h, obtain the borosilicate zeolite S removing organic amine template
1, its characterization data is in table 1.
Example 3
Borosilicate beta-molecular sieve S is removed by the method for example 2
0in organic amine template, unlike (1) step Middle molecule sieve S
0through 120 DEG C of dry 12h, in nitrogen atmosphere, carry out three sections of roastings, and then carry out oxide treatment, the borosilicate zeolite S removing organic amine template obtained by (2) step
2characterization data in table 1.
Example 4
Borosilicate beta-molecular sieve S is removed by the method for example 2
0in organic amine template, unlike (1) step Middle molecule sieve S
0through 120 DEG C of dry 12h, three sections of roastings are carried out in nitrogen atmosphere, (2) in step by 5g(1) one-step baking powder, 10g ammoniumper chlorate, 40ml deionized water join together in hydrothermal reaction kettle and carry out oxide treatment, the borosilicate zeolite S removing organic amine template obtained
3characterization data in table 1.
Example 5
(1) two-stage roasting
By S obtained for 10g example 1
0molecular sieve, in 120 DEG C of dry 12h, in nitrogen atmosphere, is warming up to 240 DEG C of roasting 6h with the temperature rise rate of 5 DEG C/min, then is warming up to 420 DEG C of roasting 4h with the temperature rise rate of 5 DEG C/min.
(2) oxide treatment
Get 5g(1) powder after one-step baking, 5g perchloric acid, 30ml deionized water add in hydrothermal reaction kettle together, 120 DEG C of standing and reacting 24h, be cooled to 25 DEG C, product is through centrifugation, gained solid deionized water wash 3 ~ 5 times, 120 DEG C of dry 12h, obtain the borosilicate zeolite S removing organic amine template
4, its characterization data is in table 1.
Comparative example 1 ~ 2
Adopt the two-stage roasting method of energy effective elimination sial beta-molecular sieve organic amine template, get the molecular sieve S that example 1 is obtained
0in 290 DEG C of roasting 2h, then be warming up to 550 DEG C with the temperature rise rate of 5 DEG C/min, respectively roasting 20min and 4h, the obtained borosilicate beta-molecular sieve DB removing organic amine
1and DB
2, its characterization data is in table 1.
Comparative example 3
Adopt the method for CN1199858C embodiment 4, get the molecular sieve S that example 1 is obtained
0respectively at 170 DEG C of roasting 2h, 260 DEG C of roasting 2h, 420 DEG C of roasting 4h, 550 DEG C of roasting 6h, the obtained borosilicate beta-molecular sieve DB removing organic amine
3, its product characterization data is in table 1.
Comparative example 4
Adopt the method for CN1041618C example 6, get the molecular sieve S that example 1 is obtained
0point to mix with ammonium perchlorate soln for 2 times, roasting, the total amount of ammoniumper chlorate used is molecular sieve S
010% of quality, the obtained borosilicate zeolite DB removing organic amine
4, its characterization data is in table 1.
Comparative example 5
Get the molecular sieve S that 10g example 1 is obtained
0, 10g perchloric acid, 40ml deionized water add in hydrothermal reaction kettle, 140 DEG C of standing and reacting 24h, are cooled to 25 DEG C, and product is through centrifugation, and solid deionized water wash 3 ~ 5 times, 120 DEG C of dry 12h, obtain the borosilicate zeolite DB removing organic amine template
5, its characterization data is in table 1.
As known from Table 1, adopt method provided by the invention, remove the borosilicate beta-molecular sieve after organic amine and there is high-crystallinity, the low carbon left of high-ratio surface sum.Adopt the high-temperature roasting method of comparative example 1 and 2, the crystallinity loss removing the borosilicate beta-molecular sieve after organic amine is large; Adopt the baking inphases of comparative example 3, the molecular sieve crystallinity reservation degree removing organic amine slightly improves, but still undesirable; After the de-amine of comparative example 4 gradation oxidation, gained molecular sieve has higher degree of crystallinity, but carbon residue is higher, and pattern of descriptive parts agent removes not exclusively, and step is comparatively complicated; The aqueous solution of comparative example 5 direct employing oxygenant carries out hydro-thermal reaction and takes off amine, and the de-amine molecule sieve carbon residue obtained is higher, and template removal is incomplete.
Table 1
| Instance number | Molecular sieve is numbered | Relative crystallinity, % | Specific surface area, m 2/g | Carbon residue, quality % |
| 1 | S 0 | 100 | 320 | - |
| 2 | S 1 | 89.9 | 531 | 0.28 |
| 3 | S 2 | 95.2 | 564 | 0.09 |
| 4 | S 3 | 93.4 | 545 | 0.23 |
| 5 | S 4 | 92.6 | 537 | 0.27 |
| Comparative example 1 | DB 1 | 62.6 | 428 | 1.89 |
| Comparative example 2 | DB 2 | 51.8 | 360 | 0.42 |
| Comparative example 3 | DB 3 | 73.7 | 476 | 0.15 |
| Comparative example 4 | DB 4 | 80.2 | 502 | 1.31 |
| Comparative example 5 | DB 5 | 85.9 | 404 | 2.35 |
Claims (11)
1. the removal methods of organic amine template in a borosilicate beta-molecular sieve, comprise after the drying of borosilicate beta-molecular sieve, in 150 ~ 420 DEG C of baking inphases in air or nitrogen, then react in the aqueous solution of oxygenant, by gained solids wash, drying after reaction, described oxygenant is selected from one or more in perchloric acid, hypochlorous acid, perchlorate and hypochlorite, and the mass ratio of oxygenant and borosilicate beta-molecular sieve is 0.5 ~ 2.0.
2. in accordance with the method for claim 1, it is characterized in that the drying temperature of borosilicate beta-molecular sieve is 80 ~ 130 DEG C.
3. in accordance with the method for claim 1, it is characterized in that dried molecular sieve point two-stage roasting in air or nitrogen, first paragraph maturing temperature is 240 ~ 280 DEG C, and second segment maturing temperature is 380 ~ 420 DEG C.
4. in accordance with the method for claim 3, it is characterized in that the temperature rise rate being warming up to first paragraph maturing temperature from drying temperature is 0.5 ~ 7 DEG C/min, the temperature rise rate being warming up to second segment maturing temperature from first paragraph maturing temperature is 0.5 ~ 7 DEG C/min.
5. in accordance with the method for claim 1, it is characterized in that point three sections of roastings in air or nitrogen of dried molecular sieve, first paragraph maturing temperature is 150 ~ 180 DEG C, and second segment maturing temperature is 240 ~ 280 DEG C, and the 3rd section of maturing temperature is 380 ~ 420 DEG C.
6. in accordance with the method for claim 5, it is characterized in that the temperature rise rate being warming up to first paragraph maturing temperature from drying temperature is 0.5 ~ 7 DEG C/min, the temperature rise rate being warming up to second segment maturing temperature from first paragraph maturing temperature is 0.5 ~ 7 DEG C/min, and the temperature rise rate being warming up to the 3rd section of maturing temperature from second segment maturing temperature is 9 ~ 12 DEG C/min.
7., according to the method described in claim 3 or 5, it is characterized in that the time of every section of roasting is 1 ~ 8 hour.
8. in accordance with the method for claim 1, it is characterized in that the temperature that the molecular sieve after baking inphases carries out reacting in the aqueous solution of oxygenant is 100 ~ 170 DEG C, the time is 2 ~ 50 hours.
9. in accordance with the method for claim 1, Gu it is characterized in that the liquid of the aqueous solution with molecular sieve of oxygenant/than being 2 ~ 15ml/g.
10. in accordance with the method for claim 1, it is characterized in that described organic amine template is tetraethyl ammonium hydroxide and/or tetraethylammonium bromide.
11. in accordance with the method for claim 1, it is characterized in that described perchlorate or hypochlorite are its ammonium salt, sodium salt or sylvite.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310507290.4A CN104556100B (en) | 2013-10-24 | 2013-10-24 | The removal methods of organic amine template in a kind of borosilicate beta-molecular sieve |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310507290.4A CN104556100B (en) | 2013-10-24 | 2013-10-24 | The removal methods of organic amine template in a kind of borosilicate beta-molecular sieve |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104556100A true CN104556100A (en) | 2015-04-29 |
| CN104556100B CN104556100B (en) | 2018-04-13 |
Family
ID=53073307
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310507290.4A Active CN104556100B (en) | 2013-10-24 | 2013-10-24 | The removal methods of organic amine template in a kind of borosilicate beta-molecular sieve |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104556100B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110624524A (en) * | 2018-06-25 | 2019-12-31 | 中国石油化工股份有限公司 | Preparation method and application of amino-functionalized MCM molecular sieve |
| CN110803706A (en) * | 2019-12-04 | 2020-02-18 | 宝鸡文理学院 | Method for quickly and efficiently removing mesoporous silicon oxide material template agent |
| CN115430460A (en) * | 2022-09-22 | 2022-12-06 | 浙江大学 | Boron-silicon molecular sieve catalyst for oxidative dehydrogenation of low-carbon alkane and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4683214A (en) * | 1984-09-06 | 1987-07-28 | Mobil Oil Corporation | Noble metal-containing catalysts |
| CN1117472A (en) * | 1994-08-22 | 1996-02-28 | 中国石油化工总公司石油化工科学研究院 | Method No.1 for removing organic amine from silica-alumina zeolite or its compound |
| CN1305952A (en) * | 1999-11-19 | 2001-08-01 | 恩尼彻姆公司 | Method for removing templat agent from synthetic zeolite |
| CN1443710A (en) * | 2002-03-13 | 2003-09-24 | 中国石油化工股份有限公司 | Method for removing organic amine from beta-zoolite |
| CN1515490A (en) * | 2003-08-26 | 2004-07-28 | 复旦大学 | Method for removing organic-inorganic composite porous material organic template agent |
| CN102616800A (en) * | 2011-01-27 | 2012-08-01 | 中国石油化工股份有限公司 | Method for removing organic amine template in molecular sieve |
-
2013
- 2013-10-24 CN CN201310507290.4A patent/CN104556100B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4683214A (en) * | 1984-09-06 | 1987-07-28 | Mobil Oil Corporation | Noble metal-containing catalysts |
| CN1117472A (en) * | 1994-08-22 | 1996-02-28 | 中国石油化工总公司石油化工科学研究院 | Method No.1 for removing organic amine from silica-alumina zeolite or its compound |
| CN1305952A (en) * | 1999-11-19 | 2001-08-01 | 恩尼彻姆公司 | Method for removing templat agent from synthetic zeolite |
| CN1443710A (en) * | 2002-03-13 | 2003-09-24 | 中国石油化工股份有限公司 | Method for removing organic amine from beta-zoolite |
| CN1515490A (en) * | 2003-08-26 | 2004-07-28 | 复旦大学 | Method for removing organic-inorganic composite porous material organic template agent |
| CN102616800A (en) * | 2011-01-27 | 2012-08-01 | 中国石油化工股份有限公司 | Method for removing organic amine template in molecular sieve |
Non-Patent Citations (1)
| Title |
|---|
| 孔德金等: "抑制β沸石骨架脱铝的焙烧研究", 《化学物理学报》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110624524A (en) * | 2018-06-25 | 2019-12-31 | 中国石油化工股份有限公司 | Preparation method and application of amino-functionalized MCM molecular sieve |
| CN110803706A (en) * | 2019-12-04 | 2020-02-18 | 宝鸡文理学院 | Method for quickly and efficiently removing mesoporous silicon oxide material template agent |
| CN110803706B (en) * | 2019-12-04 | 2023-03-28 | 宝鸡文理学院 | Method for quickly and efficiently removing mesoporous silicon oxide material template agent |
| CN115430460A (en) * | 2022-09-22 | 2022-12-06 | 浙江大学 | Boron-silicon molecular sieve catalyst for oxidative dehydrogenation of low-carbon alkane and preparation method thereof |
| CN115430460B (en) * | 2022-09-22 | 2024-01-02 | 浙江大学 | Boron-silicon molecular sieve catalyst for oxidative dehydrogenation of low-carbon alkane and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104556100B (en) | 2018-04-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103100427B (en) | Hydrocracking catalyst carrier containing beta molecular sieve and preparation method thereof | |
| EP3939937A1 (en) | Molecular sieve and its preparation method | |
| CN109894087B (en) | Covalent organic framework and ionic liquid composite material and preparation method and application thereof | |
| CN105967205A (en) | Zeolite production method | |
| CN111099630A (en) | Method for synthesizing SSZ-13 molecular sieve in sodium-free system at low cost | |
| CN104084197B (en) | A kind of be carrier ruthenium system ammonia synthesis catalyst and the preparation thereof of graphitization active carbon | |
| CN108276582B (en) | Metal organic framework material, preparation method and application of metal organic framework material in formaldehyde adsorption | |
| CN104556100A (en) | Method for removing organic amine template in borosilicate beta molecular sieve | |
| CN110104659B (en) | Method for removing template agent in molecular sieve membrane at low temperature | |
| CN106672995A (en) | Modified Y-type molecular sieve and preparation method thereof | |
| CN103922308A (en) | Preparation method of novel nitrogen-doped honeycomb ordered porous carbon material | |
| CN103496777A (en) | Pretreatment method of ammonia-nitrogen wastewater | |
| CN106582807B (en) | Modifying titanium-silicon molecular sieve and method of modifying and the application in propylene ring oxidation reaction | |
| CN108097304A (en) | The preparation method of Cu-SAPO-34 molecular sieve catalysts | |
| CN109081362B (en) | Method for recovering residual template agent in molecular sieve preparation process | |
| CN105536805B (en) | Nano copper-cerium composite oxide catalyst and preparation method and application thereof | |
| CN102336658A (en) | Production method of 3,5-dimethylbenzoic acid | |
| CN104475147B (en) | Nano ZSM-5/gamma-Al2O3 composite catalyst for preparing acraldehyde by glycerol dehydration, and preparation method and application thereof | |
| Taborda et al. | Synthesis of Al–Si-beta and Ti–Si-beta by the aging–drying method | |
| CN103910363B (en) | A kind of method of HTS modification and application thereof | |
| JP2013237045A (en) | Catalyst converting ammonia to nitrogen and hydrogen, method for manufacturing the catalyst, and method for converting ammonia using the catalyst | |
| JP2017128499A5 (en) | ||
| CN103769186A (en) | Catalyst for anthraquinone hydrogenation and preparation method thereof | |
| CN106984152B (en) | It is a kind of for trapping the two-phase mixture of carbon dioxide | |
| CN104193724A (en) | P-tert-butyl sulfone bridge thiacalixarene [4] and method for separating and purifying caesium of p-tert-butyl sulfone bridge thiacalixarene [4] |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |