CN103086395A - 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
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- CN103086395A CN103086395A CN2013100205399A CN201310020539A CN103086395A CN 103086395 A CN103086395 A CN 103086395A CN 2013100205399 A CN2013100205399 A CN 2013100205399A CN 201310020539 A CN201310020539 A CN 201310020539A CN 103086395 A CN103086395 A CN 103086395A
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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 the inorganic material film preparing technical field, relate in particular to a kind of SAPO Series Molecules sieve membrane preparation method take metal oxide as carrier.
Technical background
The pore size distribution of SAPO Series Molecules sieve membrane homogeneous and good catalytic performance have it concurrently to separate and the catalysis dual-use function.The Nobel of Colorado university teach problem group is done a lot of work in the research of SAPO-34 molecular screen membrane, and its prepared SAPO-34 molecular screen membrane is to CO
2/ CH
4Separation selectivity oneself reach 200 left and right.Zhang etc. (Stud.Surf.Sci.Catl., 1997,105, p2211) by hydrothermal synthesis method at porous α-A1
2O
3Synthesize the SAPO-34 film on disk, and used it for H
2/ N
2And CO
2/ N
2Separate.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, it uses the also more gas delivery that is confined to.
The diauxic growth method claims again crystal seed method, and the fundamental principle of crystal seed method is first to form 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, also is conducive to the preferred orientation growth of zeolite crystal simultaneously.The metal oxide surface Direct Hydrothermal synthesizes SAPO Series Molecules sieve membrane, and in crystallization process, metal oxide is prone to dissolving or melting phenomenon, is not easy to film forming.Metal oxide is more is applied to catalyzed reaction, is used for methyl alcohol as copper and zinc oxide synthetic, and manganese and ferriferous oxide are used for catalytic denitration process etc.Coat SAPO Series Molecules sieve membrane at metal oxide surface and can effectively realize a plurality of reaction couplings, not only can improve reaction yield and the selectivity that is subjected to equilibrium-limited by a certain component of removing selectively in product, also allow to carry out simultaneously two or more reactions in same reactor, make the product of first reaction see through selectively second of film participation or other reactions, the separation and the katalysis that take full advantage of film improve reaction efficiency.
Summary of the invention
The objective of the invention is provides a kind of SAPO Series Molecules sieve membrane preparation method take metal oxide as carrier for dissolving or the melting phenomenon of existing metal oxide in synthetic SAPO Series Molecules sieve membrane process.
The technical solution adopted for the present invention to solve the technical problems comprises the steps:
(1) SAPO Series Molecules sieve crystal seed preparation: with Al
2O
3: P
2O
5: SiO
2: TEAOH:H
2O is take mol ratio as (0.3～3): (0.5～2): (0.01～2.5): (0.1～5): night is synthesized in (1～500) preparation, and the synthetic liquid of preparation is put into autoclave, at 150～230 ℃ of hydro-thermal reaction 2～120h, makes SAPO Series Molecules sieve crystal seed.
(2) carrier pre-treatment: metal oxide carrier is first used the deionized water washes clean in ultrasonic cleaner, then through 80～150 ℃ of dryings, then apply layer of gel layer, 40～100 ℃ of drying for standby at metal oxide surface.
(3) the molecular sieve crystal seed applies: the suspension of the molecular sieve crystal seed that makes and ethanol is ultrasonic, the suspension of molecular sieve crystal seed is coated on pretreated metal oxide carrier, is coated with the metal oxide carrier of molecular sieve crystal seed in 40～120 ℃ of dryings.
(4) molecular screen membrane is synthetic: with Al
2O
3: P
2O
5: SiO
2: TEAOH:H
2O is take mol ratio as (0.3～3): (0.1～3): (0.01～2.5): (0.1～5): the synthetic liquid of (1～500) preparation secondary, the metal oxide carrier and the synthetic liquid of secondary that apply the molecular sieve crystal seed are put into autoclave simultaneously, hydro-thermal reaction 2～120h in 170～230 ℃ makes SAPO Series Molecules sieve membrane.
(5) washing is dry: use the deionized water wash molecular screen membrane, and then dry under 50～120 ℃ of conditions.
Described metal oxide is one or more the mixture 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 that described metal oxide surface applies is aluminum oxide or silica gel.And control thickness and uniformity coefficient by the mode that repeatedly applies.
The molecular screen membrane that the present invention synthesizes 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 dissolving or the melting phenomenon of metal oxide in crystallization process, and adopt the seeded method to prepare SAPO Series Molecules sieve membrane at metal oxide surface, being expected to has application potential preferably at absorption, separation, catalytic field; The present invention with metal oxide as carrier, support shapes also expands to particulate state, bulk, spherical or strip, can preferably metal oxide and SAPO Series Molecules sieve membrane be combined into membrane catalytic reactor, make SAPO Series Molecules sieve membrane better be applied to catalytic field.
Description of drawings
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 synthetic SAPO Series Molecules sieve membrane of the embodiment of the present invention 1.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is further elaborated.
(1) crystal seed preparation: 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 synthetic liquid of configuration is put into autoclave, at 150 ℃ of hydro-thermal reaction 120h, makes SAPO Series Molecules sieve crystal seed.
(2) carrier pre-treatment: metal oxide carrier is first used the deionized water washes clean in ultrasonic cleaner, then through 80 ℃ of dryings, metal oxide SEM figure sees Fig. 1.Apply layer of gel layer, 40 ℃ of drying for standby at oxide surface.
(3) crystal seed applies: the suspension of crystal seed and ethanol is ultrasonic, be coated with the carrier of crystal seed in 120 ℃ of dryings, and the metal oxide SEM figure after the coating crystal seed sees Fig. 2.
(4) film is synthetic: secondary synthesizes 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, and the carrier that applies crystal seed is put in autoclave, at 170 ℃ of hydro-thermal reaction 120h, makes SAPO Series Molecules sieve membrane.
(5) washing is dry: use the deionized water wash molecular screen membrane, dry under 120 ℃ of conditions, metal oxide surface has coated one deck molecular screen membrane of densification continuously as shown in Figure 3.
(1) crystal seed preparation: 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 synthetic liquid of configuration is put into autoclave, at 230 ℃ of hydro-thermal reaction 2h, makes SAPO Series Molecules sieve crystal seed.
(2) carrier pre-treatment: metal oxide carrier is first used the deionized water washes clean in ultrasonic cleaner, then through 150 ℃ of dryings, applies layer of gel layer, 100 ℃ of drying for standby at oxide surface.
(3) crystal seed applies: the suspension of crystal seed and ethanol is ultrasonic, be coated with the carrier of crystal seed in 40 ℃ of dryings.
(4) film is synthetic: secondary synthesizes liquid Al
2O
3: P
2O
5: SiO
2: TEAOH:H
2The mol ratio of O is 3:3:0.01:0.1:1, and the carrier that applies crystal seed is put in autoclave, at 230 ℃ of hydro-thermal reaction 2h, makes SAPO Series Molecules sieve membrane.
(5) washing is dry: use the deionized water wash molecular screen membrane, and dry under 50 ℃ of conditions.
Embodiment 3
(1) crystal seed preparation: 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 synthetic liquid of configuration is put into autoclave, at 200 ℃ of hydro-thermal reaction 60h, makes SAPO Series Molecules sieve crystal seed.
(2) carrier pre-treatment: metal oxide carrier is first used the deionized water washes clean in ultrasonic cleaner, then through 100 ℃ of dryings, applies layer of gel layer, 80 ℃ of drying for standby at oxide surface.
(3) crystal seed applies: the suspension of crystal seed and ethanol is ultrasonic, be coated with the carrier of crystal seed in 100 ℃ of dryings.
(4) film is synthetic: secondary synthesizes 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, and the carrier that applies crystal seed is put in autoclave, at 200 ℃ of hydro-thermal reaction 60h, makes SAPO Series Molecules sieve membrane.
(5) washing is dry: use the deionized water wash molecular screen membrane, and dry under 80 ℃ of conditions.
Embodiment 4
(1) crystal seed preparation: 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 synthetic liquid of configuration is put into autoclave, at 230 ℃ of hydro-thermal reaction 60h, makes SAPO Series Molecules sieve crystal seed.
(2) carrier pre-treatment: metal oxide carrier is first used the deionized water washes clean in ultrasonic cleaner, then through 100 ℃ of dryings, applies layer of gel layer, 80 ℃ of drying for standby at oxide surface.
(3) crystal seed applies: the suspension of crystal seed and ethanol is ultrasonic, be coated with the carrier of crystal seed in 50 ℃ of dryings.
(4) film is synthetic: secondary synthesizes liquid Al
2O
3: P
2O
5: SiO
2: TEAOH:H
2The mol ratio of O is 3:2:0.5:0.1:500, and the carrier that applies crystal seed is put in autoclave, at 170 ℃ of hydro-thermal reaction 120h, makes SAPO Series Molecules sieve membrane.
(5) washing is dry: use the deionized water wash molecular screen membrane, and dry under 110 ℃ of conditions.
Embodiment 5
(1) crystal seed preparation: 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 synthetic liquid of configuration is put into autoclave, at 210 ℃ of hydro-thermal reaction 70h, makes SAPO Series Molecules sieve crystal seed.
(2) carrier pre-treatment: metal oxide carrier is first used the deionized water washes clean in ultrasonic cleaner, then through 90 ℃ of dryings, applies layer of gel layer, 70 ℃ of drying for standby at oxide surface.
(3) crystal seed applies: the suspension of crystal seed and ethanol is ultrasonic, be coated with the carrier of crystal seed in 60 ℃ of dryings.
(4) film is synthetic: secondary synthesizes 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, and the carrier that applies crystal seed is put in autoclave, at 190 ℃ of hydro-thermal reaction 100h, makes SAPO Series Molecules sieve membrane.
(5) washing is dry: use the deionized water wash molecular screen membrane, and dry under 90 ℃ of conditions.
Embodiment 6
(1) crystal seed preparation: 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 synthetic liquid of configuration is put into autoclave, at 180 ℃ of hydro-thermal reaction 80h, makes SAPO Series Molecules sieve crystal seed.
(2) carrier pre-treatment: metal oxide carrier is first used the deionized water washes clean in ultrasonic cleaner, then through 130 ℃ of dryings, applies layer of gel layer, 60 ℃ of drying for standby at oxide surface.
(3) crystal seed applies: the suspension of crystal seed and ethanol is ultrasonic, be coated with the carrier of crystal seed in 70 ℃ of dryings.
(4) film is synthetic: secondary synthesizes 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, and the carrier that applies crystal seed is put in autoclave, at 195 ℃ of hydro-thermal reaction 60h, makes SAPO Series Molecules sieve membrane.
(5) washing is dry: use the deionized water wash molecular screen membrane, and dry under 80 ℃ of conditions.
Embodiment 7
(1) crystal seed preparation: 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 synthetic liquid of configuration is put into autoclave, at 220 ℃ of hydro-thermal reaction 20h, makes SAPO Series Molecules sieve crystal seed.
(2) carrier pre-treatment: metal oxide carrier is first used the deionized water washes clean in ultrasonic cleaner, then through 140 ℃ of dryings, applies layer of gel layer, 80 ℃ of drying for standby at oxide surface.
(3) crystal seed applies: the suspension of crystal seed and ethanol is ultrasonic, be coated with the carrier of crystal seed in 70 ℃ of dryings.
(4) film is synthetic: secondary synthesizes 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, and the carrier that applies crystal seed is put in autoclave, at 190 ℃ of hydro-thermal reaction 40h, makes SAPO Series Molecules sieve membrane.
(5) washing is dry: use the deionized water wash molecular screen membrane, and dry under 90 ℃ of conditions.
Embodiment 8
(1) crystal seed preparation: 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 synthetic liquid of configuration is put into autoclave, at 210 ℃ of hydro-thermal reaction 80h, makes SAPO Series Molecules sieve crystal seed.
(2) carrier pre-treatment: metal oxide carrier is first used the deionized water washes clean in ultrasonic cleaner, then through 130 ℃ of dryings, applies layer of gel layer, 60 ℃ of drying for standby at oxide surface.
(3) crystal seed applies: the suspension of crystal seed and ethanol is ultrasonic, be coated with the carrier of crystal seed in 100 ℃ of dryings.
(4) film is synthetic: secondary synthesizes liquid Al
2O
3: P
2O
5: SiO
2: TEAOH:H
2The mol ratio of O is 2:0.6:1.8:3:30, and the carrier that applies crystal seed is put in autoclave, at 180 ℃ of hydro-thermal reaction 36h, makes SAPO Series Molecules sieve membrane.
(5) washing is dry: use the deionized water wash molecular screen membrane, and dry under 60 ℃ of conditions.
Claims (4)
1. the SAPO Series Molecules sieve membrane preparation method take metal oxide as carrier, is characterized in that comprising the steps:
(1) SAPO Series Molecules sieve crystal seed preparation: with Al
2O
3: P
2O
5: SiO
2: TEAOH:H
2O is take mol ratio as (0.3～3): (0.5～2): (0.01～2.5): (0.1～5): night is synthesized in (1～500) preparation, and the synthetic liquid of preparation is put into autoclave, at 150～230 ℃ of hydro-thermal reaction 2～120h, makes SAPO Series Molecules sieve crystal seed;
(2) carrier pre-treatment: metal oxide carrier is first used the deionized water washes clean in ultrasonic cleaner, then through 80～150 ℃ of dryings, then apply layer of gel layer, 40～100 ℃ of drying for standby at metal oxide surface;
(3) the molecular sieve crystal seed applies: the suspension of the molecular sieve crystal seed that makes and ethanol is ultrasonic, the suspension of molecular sieve crystal seed is coated on pretreated metal oxide carrier, is coated with the metal oxide carrier of molecular sieve crystal seed in 40～120 ℃ of dryings;
(4) molecular screen membrane is synthetic: with Al
2O
3: P
2O
5: SiO
2: TEAOH:H
2O is take mol ratio as (0.3～3): (0.1～3): (0.01～2.5): (0.1～5): the synthetic liquid of (1～500) preparation secondary, the metal oxide carrier and the synthetic liquid of secondary that apply the molecular sieve crystal seed are put into autoclave simultaneously, hydro-thermal reaction 2～120h in 170～230 ℃ makes SAPO Series Molecules sieve membrane;
(5) washing is dry: use the deionized water wash molecular screen membrane, and then dry under 50～120 ℃ of conditions.
2. the SAPO Series Molecules sieve membrane preparation method take metal oxide as carrier according to claim 1 is characterized in that metal oxide is one or more the mixture in cupric oxide, zinc oxide, zirconium white, nickel oxide, cobalt oxide, cerium oxide, ferric oxide, manganese oxide, aluminum oxide.
3. the SAPO Series Molecules sieve membrane preparation method take metal oxide as carrier according to claim 2, is characterized in that metal oxide is particulate state, bulk, spherical or strip.
4. the SAPO Series Molecules sieve membrane preparation method take metal oxide as carrier according to claim 1, is characterized in that the gel coat that metal oxide surface applies is aluminum oxide or silica gel.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103372379A (en) * | 2013-07-14 | 2013-10-30 | 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 |
| CN104418340A (en) * | 2013-09-11 | 2015-03-18 | 青岛科技大学 | Preparation method of molecular sieve membrane |
| CN107840352A (en) * | 2016-09-19 | 2018-03-27 | 中国石油化工股份有限公司 | The preparation method of SAPO molecular sieve film |
| CN110697730A (en) * | 2019-11-15 | 2020-01-17 | 林卿 | Double-template agent synthesized Fe3O4Method for preparing @ SAPO-35 composite material |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103372379A (en) * | 2013-07-14 | 2013-10-30 | 浙江大学 | Preparation method of molecular sieve composite membrane by taking metallic oxide as carrier |
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| CN107840352A (en) * | 2016-09-19 | 2018-03-27 | 中国石油化工股份有限公司 | The preparation method of SAPO molecular sieve film |
| CN110697730A (en) * | 2019-11-15 | 2020-01-17 | 林卿 | Double-template agent synthesized Fe3O4Method for preparing @ SAPO-35 composite material |
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