CN103086395B - Preparation method of SAPO series molecular sieve membrane with metal oxide as carrier - Google Patents
Preparation method of SAPO series molecular sieve membrane with metal oxide as carrier Download PDFInfo
- Publication number
- CN103086395B CN103086395B CN201310020539.9A CN201310020539A CN103086395B CN 103086395 B CN103086395 B CN 103086395B CN 201310020539 A CN201310020539 A CN 201310020539A CN 103086395 B CN103086395 B CN 103086395B
- Authority
- CN
- China
- Prior art keywords
- metal oxide
- crystal seed
- preparation
- carrier
- molecular sieve
- 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.)
- Active
Links
Landscapes
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a preparation method of an SAPO series molecular sieve membrane with a metal oxide as a carrier. The preparation method disclosed by the invention is a diauxic growth preparation method for preparing an SAPO series molecular sieve on the surface of the metal oxide by adopting a method of pre-spraying crystal seeds. The preparation method comprises the following steps: firstly pre-coating a gel layer on the surface of the metal oxide, wherein the gel layer can effectively inhibit dissolution or melting of the metal oxide during the crystallization process; further dispersing the crystal seeds in ethanol to form a suspension, coating the suspension on the surface of the metal oxide after pretreatment, and drying to get a crystal seed layer; and placing the metal oxide coated with the crystal seed layer into synthetic fluid and crystallizing at the temperature of 170-230 DEG C to get the continuous and compact SAPO series molecular sieve membrane. According to the preparation method disclosed by the invention, the SAPO series molecular sieve with a special pore canal structure and catalytic performance and the metal oxide with the better catalytic performance can be combined to form a catalytic membrane reactor, and the preparation method further has good application potential in the fields of catalysis and separation.
Description
Technical field
The invention belongs to inorganic material film preparing technical field, particularly relating to a kind of take metal oxide as the SAPO Series Molecules sieve membrane preparation method of carrier.
Technical background
The homogeneous pore size distribution of SAPO Series Molecules sieve membrane and good catalytic performance make it have concurrently to be separated and catalysis dual-use function.Colorado university Nobel teach problem group is done a lot of work in the research of SAPO-34 molecular screen membrane, and the SAPO-34 molecular screen membrane prepared by it is to CO
2/ CH
4separation selectivity oneself reach about 200.Zhang etc. (Stud.Surf.Sci.Catl., 1997,105, p2211) by hydrothermal synthesis method at porous α-A1
2o
3disk synthesizes SAPO-34 film, and used it for H
2/ N
2and CO
2/ N
2be separated.In the report in past, SAPO Series Molecules sieve membrane great majority are with porous α-A1
2o
3, stainless steel and porous ceramics piece or pipe be carrier, application is also more is confined to gas delivery for it.
Secondary growth method is also known as crystal seed method, and the fundamental principle of crystal seed method first forms one deck molecular sieve crystal seed or film on the surface of supporter, then supporter is placed in molecular sieve synthesis mother liquid, crystallization film forming under certain hydrothermal synthesizing condition.Crystal seed method can save nucleus formation stages in sieve synthesis procedure, saves crystallization time, is also conducive to the preferred orientation growth of zeolite crystal simultaneously.Metal oxide surface direct hydrothermal synthesis SAPO Series Molecules sieve membrane, in crystallization process, dissolving or melting phenomenon easily appears in metal oxide, is not easy to film forming.What metal oxide was more is applied to catalyzed reaction, and as copper and zinc oxide are used for methanol-fueled CLC, manganese and ferriferous oxide are used for catalytic denitration process etc.Multiple reaction coupling effectively can be realized at metal oxide surface coated SAPO Series Molecules sieve membrane, not only can improve reaction yield by equilibrium-limited and selectivity by a certain component removed selectively in product, also allow to carry out two or more reaction in same reactor simultaneously, make first product reacted participate in second or other reactions through film selectively, the separation and the katalysis that make full use of film improve reaction efficiency.
Summary of the invention
The object of the invention is for the dissolving of existing metal oxide in synthesis SAPO Series Molecules sieve membrane process or melting phenomenon, providing a kind of take metal oxide as the SAPO Series Molecules sieve membrane preparation method of carrier.
The technical solution adopted for the present invention to solve the technical problems comprises the steps:
(1) SAPO Series Molecules sieve JZPD capsule: by Al
2o
3: P
2o
5: SiO
2: TEAOH:H
2o is (0.3 ~ 3) with mol ratio: (0.5 ~ 2): (0.01 ~ 2.5): (0.1 ~ 5): night is synthesized in (1 ~ 500) preparation, and the synthesis liquid of preparation is put into autoclave, at 150 ~ 230 DEG C of hydro-thermal reaction 2 ~ 120h, and obtained SAPO Series Molecules sieve crystal seed.
(2) Vehicle element: metal oxide carrier is first clean with deionized water wash in ultrasonic cleaner, then through 80 ~ 150 DEG C of dryings, then at metal oxide surface coating layer of gel layer, 40 ~ 100 DEG C of drying for standby.
(3) molecular sieve crystal seed coating: by ultrasonic for the suspension of obtained molecular sieve crystal seed and ethanol, by on the suspension of molecular sieve crystal seed metal oxide carrier after the pre-treatment, be coated with the metal oxide carrier of molecular sieve crystal seed in 40 ~ 120 DEG C of dryings.
(4) molecular screen membrane synthesis: by Al
2o
3: P
2o
5: SiO
2: TEAOH:H
2o is (0.3 ~ 3) with mol ratio: (0.1 ~ 3): (0.01 ~ 2.5): (0.1 ~ 5): (1 ~ 500) preparation secondary synthesis liquid, the metal oxide carrier of coating molecular sieve crystal seed and secondary synthesis liquid are put into autoclave simultaneously, hydro-thermal reaction 2 ~ 120h in 170 ~ 230 DEG C, obtained SAPO Series Molecules sieve membrane.
(5) washing is dry: use deionized water wash molecular screen membrane, then dry under 50 ~ 120 DEG C of conditions.
Described metal oxide is the mixture of one or more in cupric oxide, zinc oxide, zirconium white, nickel oxide, cobalt oxide, cerium oxide, ferric oxide, manganese oxide, aluminum oxide, and metal oxide is particulate state, bulk, spherical or strip.
The gel coat of described metal oxide surface coating is aluminum oxide or silica gel.And control thickness and uniformity coefficient by the mode repeatedly applied.
The molecular screen membrane of the present invention's synthesis is observed through SEM and is shown do not have stray crystal to generate, and carrier surface generates the fine and close continuous thin film of one deck.
Beneficial effect of the present invention is as follows:
In the inventive method process, the mode of metal oxide surface precoating gel coat suppresses the dissolving of metal oxide in crystallization process or melting phenomenon, and adopt seeded method to prepare SAPO Series Molecules sieve membrane at metal oxide surface, be expected to there is good application potential at absorption, separation, catalytic field; The present invention is using metal oxide as carrier, support shapes also expands to particulate state, bulk, spherical or strip, preferably metal oxide and SAPO Series Molecules sieve membrane can be combined into membrane catalytic reactor, make SAPO Series Molecules sieve membrane better be applied to catalytic field.
Accompanying drawing explanation
Fig. 1 is the SEM figure of the embodiment of the present invention 1 metal oxide carrier.
Fig. 2 is the SEM figure of the embodiment of the present invention 1 metal oxide carrier surface-coated crystal seed.
Fig. 3 is the SEM figure of the SAPO Series Molecules sieve membrane that the embodiment of the present invention 1 is synthesized.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is further elaborated.
embodiment 1
(1) JZPD capsule: Al
2o
3: P
2o
5: SiO
2: TEAOH:H
2the mol ratio of O is 0.3:0.5:1.2:2.5:100, and the synthesis liquid of configuration is put into autoclave, at 150 DEG C of hydro-thermal reaction 120h, and obtained SAPO Series Molecules sieve crystal seed.
(2) Vehicle element: metal oxide carrier is first clean with deionized water wash in ultrasonic cleaner, then through 80 DEG C of dryings, metal oxide SEM figure is shown in Fig. 1.At oxide surface coating layer of gel layer, 40 DEG C of drying for standby.
(3) crystal seed coating: by ultrasonic for the suspension of crystal seed and ethanol, be coated with the carrier of crystal seed in 120 DEG C of dryings, the metal oxide SEM figure after coating crystal seed is shown in Fig. 2.
(4) film synthesis: secondary synthesis liquid Al
2o
3: P
2o
5: SiO
2: TEAOH:H
2the mol ratio of O is 0.3:0.1:1.2:2:250, is put in autoclave by the carrier of coating crystal seed, at 170 DEG C of hydro-thermal reaction 120h, and obtained SAPO Series Molecules sieve membrane.
(5) washing is dry: use deionized water wash molecular screen membrane, dry under 120 DEG C of conditions, the molecular screen membrane of the continuous densification of one deck that metal oxide surface is coated as shown in Figure 3.
embodiment 2
(1) JZPD capsule: Al
2o
3: P
2o
5: SiO
2: TEAOH:H
2the mol ratio of O is 3:2:0.01:0.1:1, and the synthesis liquid of configuration is put into autoclave, at 230 DEG C of hydro-thermal reaction 2h, and obtained SAPO Series Molecules sieve crystal seed.
(2) Vehicle element: metal oxide carrier is first clean with deionized water wash in ultrasonic cleaner, then through 150 DEG C of dryings, at oxide surface coating layer of gel layer, 100 DEG C of drying for standby.
(3) crystal seed coating: by ultrasonic for the suspension of crystal seed and ethanol, be coated with the carrier of crystal seed in 40 DEG C of dryings.
(4) film synthesis: secondary synthesis liquid Al
2o
3: P
2o
5: SiO
2: TEAOH:H
2the mol ratio of O is 3:3:0.01:0.1:1, is put in autoclave by the carrier of coating crystal seed, at 230 DEG C of hydro-thermal reaction 2h, and obtained SAPO Series Molecules sieve membrane.
(5) washing is dry: use deionized water wash molecular screen membrane, dry under 50 DEG C of conditions.
embodiment 3
(1) JZPD capsule: Al
2o
3: P
2o
5: SiO
2: TEAOH:H
2the mol ratio of O is 1.65:1.25:2.5:5:500, and the synthesis liquid of configuration is put into autoclave, at 200 DEG C of hydro-thermal reaction 60h, and obtained SAPO Series Molecules sieve crystal seed.
(2) Vehicle element: metal oxide carrier is first clean with deionized water wash in ultrasonic cleaner, then through 100 DEG C of dryings, at oxide surface coating layer of gel layer, 80 DEG C of drying for standby.
(3) crystal seed coating: by ultrasonic for the suspension of crystal seed and ethanol, be coated with the carrier of crystal seed in 100 DEG C of dryings.
(4) film synthesis: secondary synthesis liquid Al
2o
3: P
2o
5: SiO
2: TEAOH:H
2the mol ratio of O is 1.65:1.65:2.5:5:100, is put in autoclave by the carrier of coating crystal seed, at 200 DEG C of hydro-thermal reaction 60h, and obtained SAPO Series Molecules sieve membrane.
(5) washing is dry: use deionized water wash molecular screen membrane, dry under 80 DEG C of conditions.
embodiment 4
(1) JZPD capsule: Al
2o
3: P
2o
5: SiO
2: TEAOH:H
2the mol ratio of O is 3:2:1.5:0.1:500, and the synthesis liquid of configuration is put into autoclave, at 230 DEG C of hydro-thermal reaction 60h, and obtained SAPO Series Molecules sieve crystal seed.
(2) Vehicle element: metal oxide carrier is first clean with deionized water wash in ultrasonic cleaner, then through 100 DEG C of dryings, at oxide surface coating layer of gel layer, 80 DEG C of drying for standby.
(3) crystal seed coating: by ultrasonic for the suspension of crystal seed and ethanol, be coated with the carrier of crystal seed in 50 DEG C of dryings.
(4) film synthesis: secondary synthesis liquid Al
2o
3: P
2o
5: SiO
2: TEAOH:H
2the mol ratio of O is 3:2:0.5:0.1:500, is put in autoclave by the carrier of coating crystal seed, at 170 DEG C of hydro-thermal reaction 120h, and obtained SAPO Series Molecules sieve membrane.
(5) washing is dry: use deionized water wash molecular screen membrane, dry under 110 DEG C of conditions.
embodiment 5
(1) JZPD capsule: Al
2o
3: P
2o
5: SiO
2: TEAOH:H
2the mol ratio of O is 1.2:0.8:2.5:1.5:70, and the synthesis liquid of configuration is put into autoclave, at 210 DEG C of hydro-thermal reaction 70h, and obtained SAPO Series Molecules sieve crystal seed.
(2) Vehicle element: metal oxide carrier is first clean with deionized water wash in ultrasonic cleaner, then through 90 DEG C of dryings, at oxide surface coating layer of gel layer, 70 DEG C of drying for standby.
(3) crystal seed coating: by ultrasonic for the suspension of crystal seed and ethanol, be coated with the carrier of crystal seed in 60 DEG C of dryings.
(4) film synthesis: secondary synthesis liquid Al
2o
3: P
2o
5: SiO
2: TEAOH:H
2the mol ratio of O is 1.2:0.8:2.5:1:70, is put in autoclave by the carrier of coating crystal seed, at 190 DEG C of hydro-thermal reaction 100h, and obtained SAPO Series Molecules sieve membrane.
(5) washing is dry: use deionized water wash molecular screen membrane, dry under 90 DEG C of conditions.
embodiment 6
(1) JZPD capsule: Al
2o
3: P
2o
5: SiO
2: TEAOH:H
2the mol ratio of O is 2.3:1.9:1:3.2:420, and the synthesis liquid of configuration is put into autoclave, at 180 DEG C of hydro-thermal reaction 80h, and obtained SAPO Series Molecules sieve crystal seed.
(2) Vehicle element: metal oxide carrier is first clean with deionized water wash in ultrasonic cleaner, then through 130 DEG C of dryings, at oxide surface coating layer of gel layer, 60 DEG C of drying for standby.
(3) crystal seed coating: by ultrasonic for the suspension of crystal seed and ethanol, be coated with the carrier of crystal seed in 70 DEG C of dryings.
(4) film synthesis: secondary synthesis liquid Al
2o
3: P
2o
5: SiO
2: TEAOH:H
2the mol ratio of O is 2.3:1.9:1:3.2:300, is put in autoclave by the carrier of coating crystal seed, at 195 DEG C of hydro-thermal reaction 60h, and obtained SAPO Series Molecules sieve membrane.
(5) washing is dry: use deionized water wash molecular screen membrane, dry under 80 DEG C of conditions.
embodiment 7
(1) JZPD capsule: Al
2o
3: P
2o
5: SiO
2: TEAOH:H
2the mol ratio of O is 0.8:1.7:2.2:0.7:100, and the synthesis liquid of configuration is put into autoclave, at 220 DEG C of hydro-thermal reaction 20h, and obtained SAPO Series Molecules sieve crystal seed.
(2) Vehicle element: metal oxide carrier is first clean with deionized water wash in ultrasonic cleaner, then through 140 DEG C of dryings, at oxide surface coating layer of gel layer, 80 DEG C of drying for standby.
(3) crystal seed coating: by ultrasonic for the suspension of crystal seed and ethanol, be coated with the carrier of crystal seed in 70 DEG C of dryings.
(4) film synthesis: secondary synthesis liquid Al
2o
3: P
2o
5: SiO
2: TEAOH:H
2the mol ratio of O is 0.8:1.7:2.2:1:100, is put in autoclave by the carrier of coating crystal seed, at 190 DEG C of hydro-thermal reaction 40h, and obtained SAPO Series Molecules sieve membrane.
(5) washing is dry: use deionized water wash molecular screen membrane, dry under 90 DEG C of conditions.
embodiment 8
(1) JZPD capsule: Al
2o
3: P
2o
5: SiO
2: TEAOH:H
2the mol ratio of O is 2:0.6:1.8:4.1:30, and the synthesis liquid of configuration is put into autoclave, at 210 DEG C of hydro-thermal reaction 80h, and obtained SAPO Series Molecules sieve crystal seed.
(2) Vehicle element: metal oxide carrier is first clean with deionized water wash in ultrasonic cleaner, then through 130 DEG C of dryings, at oxide surface coating layer of gel layer, 60 DEG C of drying for standby.
(3) crystal seed coating: by ultrasonic for the suspension of crystal seed and ethanol, be coated with the carrier of crystal seed in 100 DEG C of dryings.
(4) film synthesis: secondary synthesis liquid Al
2o
3: P
2o
5: SiO
2: TEAOH:H
2the mol ratio of O is 2:0.6:1.8:3:30, is put in autoclave by the carrier of coating crystal seed, at 180 DEG C of hydro-thermal reaction 36h, and obtained SAPO Series Molecules sieve membrane.
(5) washing is dry: use deionized water wash molecular screen membrane, dry under 60 DEG C of conditions.
Claims (1)
1. be the SAPO Series Molecules sieve membrane preparation method of carrier with metal oxide, it is characterized in that comprising the steps:
(1) SAPO Series Molecules sieve JZPD capsule: by Al
2o
3: P
2o
5: SiO
2: TEAOH:H
2o is (0.3 ~ 3) with mol ratio: (0.5 ~ 2): (0.01 ~ 2.5): (0.1 ~ 5): night is synthesized in (1 ~ 500) preparation, the synthesis liquid of preparation is put into autoclave, at 150 ~ 230 DEG C of hydro-thermal reaction 2 ~ 120h, obtained SAPO Series Molecules sieve crystal seed;
(2) Vehicle element: metal oxide carrier is first clean with deionized water wash in ultrasonic cleaner, then through 80 ~ 150 DEG C of dryings, then at metal oxide surface coating layer of gel layer, 40 ~ 100 DEG C of drying for standby; Metal oxide used is particulate state, bulk, spherical or strip; Metal oxide is the mixture of one or more in cupric oxide, zinc oxide, zirconium white, nickel oxide, cobalt oxide, cerium oxide, ferric oxide, manganese oxide, aluminum oxide; Coated gel coat is alumina gel;
(3) molecular sieve crystal seed coating: by ultrasonic for the suspension of obtained molecular sieve crystal seed and ethanol, by on the suspension of molecular sieve crystal seed metal oxide carrier after the pre-treatment, be coated with the metal oxide carrier of molecular sieve crystal seed in 40 ~ 120 DEG C of dryings;
(4) molecular screen membrane synthesis: by Al
2o
3: P
2o
5: SiO
2: TEAOH:H
2o is (0.3 ~ 3) with mol ratio: (0.1 ~ 3): (0.01 ~ 2.5): (0.1 ~ 5): (1 ~ 500) preparation secondary synthesis liquid, the metal oxide carrier of coating molecular sieve crystal seed and secondary synthesis liquid are put into autoclave simultaneously, hydro-thermal reaction 2 ~ 120h in 170 ~ 230 DEG C, obtained SAPO Series Molecules sieve membrane;
(5) washing is dry: use deionized water wash molecular screen membrane, then dry under 50 ~ 120 DEG C of conditions.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310020539.9A CN103086395B (en) | 2013-01-18 | 2013-01-18 | Preparation method of SAPO series molecular sieve membrane with metal oxide as carrier |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310020539.9A CN103086395B (en) | 2013-01-18 | 2013-01-18 | Preparation method of SAPO series molecular sieve membrane with metal oxide as carrier |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103086395A CN103086395A (en) | 2013-05-08 |
| CN103086395B true CN103086395B (en) | 2015-01-28 |
Family
ID=48199600
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310020539.9A Active CN103086395B (en) | 2013-01-18 | 2013-01-18 | Preparation method of SAPO series molecular sieve membrane with metal oxide as carrier |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103086395B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103372379B (en) * | 2013-07-14 | 2015-01-28 | 浙江大学 | Preparation method of molecular sieve composite membrane by taking metallic oxide as carrier |
| CN104340993A (en) * | 2013-08-06 | 2015-02-11 | 中国科学院上海高等研究院 | Preparation method of SAPO-34 molecular sieve membrane |
| CN104418340B (en) * | 2013-09-11 | 2017-01-25 | 青岛科技大学 | Preparation method of molecular sieve membrane |
| CN107840352B (en) * | 2016-09-19 | 2020-08-07 | 中国石油化工股份有限公司 | Preparation method of SAPO molecular sieve membrane |
| CN110697730B (en) * | 2019-11-15 | 2021-06-01 | 海南医学院 | Double-template agent synthesized Fe3O4Method for preparing @ SAPO-35 composite material |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1786540A4 (en) * | 2004-08-03 | 2008-05-07 | Univ Colorado | Membranes for highly selective separations |
| CN101279207A (en) * | 2008-05-20 | 2008-10-08 | 吉林大学 | Preparation of SAPO-34 molecular sieve film for selectively separating methane gas |
| CN101544379B (en) * | 2009-04-30 | 2012-06-06 | 浙江大学 | Method for synthesizing molecular sieve membrane by dip coating-rubbing crystal-coating method |
| CN102336414B (en) * | 2011-06-29 | 2012-12-05 | 同济大学 | Method for preparing high quality SAPO-34 zeolite membrane by clear sol method |
-
2013
- 2013-01-18 CN CN201310020539.9A patent/CN103086395B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN103086395A (en) | 2013-05-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103086395B (en) | Preparation method of SAPO series molecular sieve membrane with metal oxide as carrier | |
| CN105233702A (en) | Preparation method for forming metal organic framework ZIF-67 film by utilizing cobalt nano array layer conversion | |
| CN103394373B (en) | A kind of preparation method of hydrogenation catalyst | |
| CN101279207A (en) | Preparation of SAPO-34 molecular sieve film for selectively separating methane gas | |
| Chai et al. | Free-standing NiO-MgO-Al2O3 nanosheets derived from layered double hydroxides grown onto FeCrAl-fiber as structured catalysts for dry reforming of methane | |
| CN106268933B (en) | Application in hud typed ZSM-5/SAPO-5 composite molecular sieve film and preparation method thereof and biomass gas purifying | |
| CN101555022A (en) | Preparation method of metal-modified SAPO-34 molecular sieve and catalyst containing the molecular sieve | |
| CN106669432A (en) | Method for preparing metal organic framework membrane by utilizing stainless steel mesh modified by electro-deposition method | |
| CN102989511A (en) | Fischer-Tropsch synthesis catalyst, and preparation and application thereof | |
| CN101992126B (en) | Porous zeolite molecular sieve coating material on surface of silicon carbide ceramics and preparation method thereof | |
| CN110064372A (en) | A kind of metal organic framework magnetic composite and its preparation method and application | |
| CN108465385A (en) | A kind of MAF-4 metallic organic frame films and its application | |
| Wang et al. | Ultrasonic-assisted fabrication of high flux T-type zeolite membranes on alumina hollow fibers | |
| CN108295672A (en) | A kind of preparation method of metal organic framework ZIF-8 films | |
| CN110016145A (en) | Porous organo-metallic skeleton material, preparation method and its adsorbing separation application | |
| CN103962140A (en) | Micro spherical hollow structure nickel-based hydrogenation catalyst as well as preparation method thereof | |
| CN102512978A (en) | Paper sintering metal fiber load molecular sieve membrane and preparation method thereof | |
| CN102303906B (en) | Ascorbic-acid-aided colloidal crystal template method used for preparing three-dimensionally ordered macroporous BiVO4 | |
| CN103372379B (en) | Preparation method of molecular sieve composite membrane by taking metallic oxide as carrier | |
| CN103212450B (en) | Method for preparing alumina catalyst carrier on stainless steel base body | |
| CN104418340B (en) | Preparation method of molecular sieve membrane | |
| CN104437557B (en) | A kind of sulfonated graphene-Pd/ sieve and silica-sesquioxide catalyst, its preparation method and application | |
| CN105013463A (en) | Preparation method for Cu-Zn-Zr supported aluminium-doped mesoporous catalyst | |
| Lin et al. | SUZ-4 zeolite membrane fabricated by dynamic hydrothermal crystallization for pervaporation separation of MeOH/MMA mixture | |
| Korelskiy et al. | Reprint of: An experimental study of micropore defects in MFI membranes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |