CN104492491A - ZIF-8 film coated millimeter-level large-sphere Pd/Al2O3 eggshell type catalyst and preparation method thereof - Google Patents
ZIF-8 film coated millimeter-level large-sphere Pd/Al2O3 eggshell type catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention provides a ZIF-8 film coated millimeter-level large-sphere Pd/Al2O3 eggshell type catalyst and belongs to the field of novel materials. According to the ZIF-8 film coated millimeter-level large-sphere Pd/Al2O3 eggshell type catalyst, a Pd/Al2O3 core takes millimeter-level spherical Al2O3 as a carrier, and the particle size of the spherical Al2O3 carrier is 1-3mm. The preparation method comprises the following steps: preparing a supported Pd/Al2O3 catalyst by virtue of an impregnation method; introducing a zinc oxide nanoparticle layer onto the supported Pd/Al2O3 catalyst in advance, thereby obtaining a Pd/Al2O3 carrier with the zinc oxide nanoparticle layer; taking the zinc oxide nanoparticle layer as a growth binding point of the ZIF-8 film eggshell layer and the Pd/Al2O3 carrier, and growing to obtain the continuous ZIF-8 film eggshell layer. According to the ZIF-8 film eggshell layer with the molecular sieving function, the supported noble metal catalyst is endowed with high selectivity for reactants and products.
Description
Technical field
The invention belongs to field of novel, be specifically related to the large ball Pd/Al of the coated grade of a kind of ZIF-8 film
2o
3egg-shell catalyst and preparation method thereof.
Background technology
Noble metal catalyst, due to its catalytic activity that can not be substituted and selective, occupies extremely important status in oil refining, petrochemical industry and organic synthesis.Pd/Al
2o
3catalyst, as a kind of finished industrial product catalyst, has good hydrogenation activity, is widely used in the essential industry catalytic reaction of hydrogenation, oxidation reaction.But the subject matter of existence is that catalyst loss, reunion, sintering, poisoning, the selective problem such as not high appear in loaded noble metal catalyst.In recent years, appearance and the extensively research of nucleocapsid structure type metallic catalyst is formed as shell clad nano metal ion using organic polymer or inorganic oxide, for the metal loss and anti-poisoning problem that solve loaded catalyst specify direction, there is good investigation and application prospect.
Metallic organic framework (Metal organic frameworks, MOFs) is by metal ion or metal cluster and the organic ligand a kind of porous crystalline material by covalency or ionic-covalent effect self assembly.The outstanding advantages such as it has high-specific surface area, porous, skeleton structure is adjustable, atmosphere storage be separated, there is great application potential in heterogeneous catalysis, molecular recognition and sensing etc.Zeolitic imidazolate framework material (Zeoliticimidazolate frameworks, ZIFs), as a kind of MOFs of extensively research, compared with the metallic organic framework of other types, has high thermal stability and chemical resistance.The topological structure of ZIF-8 is similar to Si-Al zeolite molecular sieve: the oxygen atom of sial tetrahedron and bridging is replaced by metal ion and imidazoles respectively, and its hole dimension only allows kinetic diameter to be less than
molecule freely come in and go out, thus have molecule screening feature.Adopt ZIF-8 to carry out coated loaded noble metal catalyst as membrane material, can obtain a kind of there is protection core central active particle resistant to aggregation, Multifunction nucleocapsid catalyst that anti-poisoning and shell has shape selectivity.
At present, be that the core-shell material preparation method of shell mainly contains four kinds with ZIF-8: 1) modification, is applicable to the nuclear material with inactive surfaces, as existing in people such as Fu by SiO
2put into 3-aminopropyl triethoxysilane (3-aminopropyltriethoxysilane, APTES) in solution, in advance carboxyl is modified to its surface, thus the growth of induction ZIF-8 film, and using the core-shell particles that obtains as the Stationary liquid of high performance liquid chromatography, obtain higher separating effect [Fu Y Y, et al.Chem-Eur J, 2013,19 (40): 13484-13491.]; 2) layer assemble method, be applicable to have the nuclear material enriching surface charge, as people such as Ren, polyacrylic acid (Polyacrilic acid, PAA) nano particle is successively impregnated in the methanol solution of zinc nitrate hexahydrate and glyoxal ethyline, obtain ZIF-8 film, this material has the drug loading capacity of superelevation, can be used for Co ntrolled release [Ren H, the et al.Chem Common to medicine, 2014,50 (8): 1000-1002.]; 3) secondary seed crystal method, if the people such as Sorribas are at mesoporous SiO
2surface first grows the crystal seed of ZIF-8, then is put in film forming liquid and obtain ZIF-8 SiO
2core-shell material [Sorribas S, et al.Chem Common, 2012,48 (75): 9388-9390]; 4) in-situ synthesis, be applicable to have the nuclear material enriching surface-active functional group, as people such as Lee, directly carboxylic for rich surface polystyrene microsphere is put in the synthesis liquid of ZIF-8, in-situ preparation ZIF-8 film, and the thickness and integrality [Lee H J, the et al.ChemCommon that regulate ZIF-8 film by changing membrane formation times, 2012,48 (2): 221-223].Although adopt above-mentioned each method successfully can synthesize ZIF-8 base core-shell material, but can find, they or higher to the Property requirements of carrier surface, or the operating procedure needed is more loaded down with trivial details, not only complexity consuming time, and the function singleness of prepared core-shell material, all do not relate to the application of catalytic field.
Summary of the invention
The technical problem to be solved in the present invention proposes carried noble metal nucleocapsid catalyst of the coated grade size of a kind of novel ZIF-8 film and preparation method thereof for current loaded noble metal catalyst and the preparing Problems existing of ZIF-8 base core-shell material.Be mainly reflected in and use simple and effective unique preparation method, its feature is first with the Al of grade size
2o
3microballoon, as carrier, by Pd nanometer particle load on this is microsphere supported, forms Pd/Al
2o
3.Then with Pd/Al
2o
3for egg core introduces layer of ZnO nanoparticle layers as ZIF-8 growth inducing layer on its surface, thus the ZIF-8 film eggshell layer forming continuous uniform on its surface can be easy to, obtain the Pd/Al of the grade size with high selectivity
2o
3@ZIF-8 egg-shell catalyst, also contributes to solving catalyst active center simultaneously and the problem such as easily to run off, and be verified in hydrogenation reaction.
Technical scheme of the present invention is as follows:
The coated Pd/Al of a kind of ZIF-8 film
2o
3microballoon egg-shell catalyst, its feature is that choosing particle diameter is the spherical Al of 1-3mm
2o
3as carrier, use NaBH by ion-exchange load P d ion
4carried out reduction Pd
0; Then at Pd/Al
2o
3the inducing layer that layer of ZnO nanoparticle layers is formed as the growth of ZIF-8 film eggshell is introduced on surface for egg core, finally synthesizes growth in liquid at ZIF-8 and obtains the coated Pd/Al of ZIF-8 film
2o
3eggshell type structure microspheres.Coated Pd/Al
2o
3the ZIF-8 egg shell membrane thickness of egg core is 1-20um.
The large ball Pd/Al of a kind of coated grade of ZIF-8 film
2o
3the preparation method of egg-shell catalyst, previously prepared acquisition loading type Pd/Al
2o
3catalyst, then at loading type Pd/Al
2o
3one deck zinc oxide nano-particle layer introduced in advance by catalyst, obtains the carrier with zinc oxide nano-particle layer; Zinc oxide nano-particle layer, as the binding site of ZIF-8 film and carrier, obtains continuous print ZIF-8 film, thus obtains Pd/Al
2o
3@ZIF-8 egg-shell catalyst.
The large ball Pd/Al of a kind of coated grade of ZIF-8 film
2o
3the preparation method of egg-shell catalyst, concrete steps are as follows:
(1) Pd/Al
2o
3the preparation of catalyst
Take 0.079 gram of PdCl
2be dissolved in 50 grams of deionized waters, the HCl solution 0.96ml then getting 1mol/L joins in solution, is configured to the H of 8mmol/L
2pdCl
4solution, then takes 8.6 grams through pretreated γ-Al
2o
3carrier beads puts into solution, fully floods, and rotates evaporate to dryness under constant temperature 333K, and sample is under the condition of 5K/min with heating rate in muffle furnace afterwards, and 823K calcination process 6h, can obtain Pd/Al
2o
3catalyst.
(2) Al
2o
3microballoon is introduced the preparation of ZnO nanoparticle inducing layer
Adopt conventional sol-gel process making ZnO inducing layer, namely first preparation, containing zinc sol solutions, utilizes infusion process at Pd/Al
2o
3bead surface is introduced containing zinc glue-line; At 80 ~ 120 DEG C, dry 0.5 ~ 3h, then roasting 3h at 400 DEG C, obtain the Pd/Al that ZnO nanoparticle inducing layer is coated
2o
3carrier;
(3) pretreatment of ZnO nanoparticle inducing layer
The Pd/Al that ZnO nanoparticle inducing layer step (2) obtained is coated
2o
3carrier is placed in the glyoxal ethyline alcoholic solution of 0.5mol/L, 50 DEG C of process 1-2h, then dry under 50-70 DEG C of condition, obtains pretreated ZnO/Pd/Al
2o
3carrier;
(4) ZnO/Pd/Al after process step (3) obtained
2o
3carrier is placed in the ZIF-8 film forming liquid prepared, then inject in the stainless steel still containing polytetrafluoro liner, be fixed on after sealing in rotary oven and rotate with the speed of 3-8r/min, reaction temperature is 60 ~ 120 DEG C, and solvent-thermal process 4 ~ 12h obtains the ZIF-8 film of different-thickness; Consisting of of synthesis liquid: zinc chloride, glyoxal ethyline, sodium formate, methyl alcohol are as film forming liquid raw material; Wherein,
The mol ratio of synthesis liquid is:
Zn：2meIM：HCOONa：CH
3OH＝1:1.5:0.15:400。(methyl alcohol is as solvent formula)
Zn:2meIM:HCOONa:CH
3cH
2oH=1:2:0.15:300 (ethanol is as solvent formula)
The invention solves the problem that functional material outer cladding ZIF-8 film step is more, synthesis temperature is higher and generated time is long, give catalyst with adjustable optionally simultaneously, contribute to solving the activated centre that conventional multiphase catalyst faces easily run off, poisoning, high temperature easily assembles the problem of sintering, is with a wide range of applications.
Accompanying drawing explanation
Fig. 1 is Pd/Al
2o
3the surperficial SEM figure of@ZIF-8 eggshell catalyst.
Fig. 2 is Pd/Al
2o
3surperficial SEM figure (partial enlarged drawing of Fig. 1) of@ZIF-8 eggshell catalyst.
Fig. 3 is Pd/Al
2o
3the section S EM figure of@ZIF-8 eggshell catalyst.
Fig. 4 is Pd/Al
2o
3the XRD figure of@ZIF-8 eggshell catalyst sample.
Detailed description of the invention
The specific embodiment of the present invention is described in detail below in conjunction with technical scheme and accompanying drawing.
Embodiment 1
(1) Pd/Al
2o
3the preparation of catalyst
Take 0.079 gram of PdCl
2be dissolved in 50 grams of deionized waters, the HCl solution 0.96ml then getting 1mol/L joins in solution, is configured to the H of 8mmol/L
2pdCl
4solution, then takes 8.6 grams through pretreated Al
2o
3carrier beads puts into solution, fully floods, and rotates evaporate to dryness under constant temperature 333K, and sample is under the condition of 5K/min with heating rate in muffle furnace afterwards, and 823K calcination process 6h, can obtain Pd/Al
2o
3catalyst.
(2) Al
2o
3microballoon is introduced the preparation of ZnO nanoparticle inducing layer
Adopt conventional sol-gel technique making ZnO nano particle inducing layer, namely first prepare 0.5 ~ 2mol/L containing zinc sol solutions, then utilize infusion process at Pd/Al
2o
3bead surface is introduced containing zinc glue-line; Dry 0.5 ~ 3h at 80 ~ 120 DEG C, then at 400 DEG C, roasting 3h obtains ZnO nanoparticle inducing layer;
(3) pretreatment of ZnO nanoparticle inducing layer
The glyoxal ethyline methanol solution of preparation 0.5mol/L, by the ZnO/Pd/Al that step (2) obtains
2o
3carrier is pretreatment 1-2h under 40-60 DEG C of condition, then dry under 50-70 DEG C of condition, obtains pretreated ZnO/Pd/Al
2o
3carrier;
(4) by pretreated ZnO/Pd/Al that step (3) obtains
2o
3carrier is placed in the ZIF-8 film forming liquid prepared, then inject in the stainless steel still containing polytetrafluoro liner, be fixed on after sealing in rotary oven and rotate with the speed of 3 ~ 8r/min, reaction temperature is 60 ~ 120 DEG C, and solvent-thermal process 4 ~ 12h obtains the ZIF-8 film of different-thickness; Consisting of of synthesis liquid: zinc chloride, glyoxal ethyline (2meIM), sodium formate, methyl alcohol are as film forming liquid raw material; Wherein,
The mol ratio of synthesis liquid is: Zn:2meIM:HCOONa:CH
3oH=1:1.5:0.15:400;
(5) dry under the catalyst that step (4) obtains being placed in 50-70 DEG C of condition, obtain Pd/Al
2o
3@ZIF-8 eggshell catalyst.
(6) get 0.3g catalyst respectively and be placed in reaction unit, then add 19ml ethyl acetate, then respectively to adding 1ml n-hexylene in device, 0.8ml cyclohexene, 0.5ml cyclo-octene, adopts hydrogen purge reaction unit 3 times, 35 DEG C of reaction 24h.After reaction terminates, adopt gas-chromatography (chromatographic column: HP-5; FID) different sample catalyst catalytic performance result (table 1) is detected.Again get 0.3g catalyst respectively and be placed in reaction unit, then add 19ml ethyl acetate, 1ml n-hexylene, add the benzothiazole of different amount, be configured to concentration be 50ppm, 100ppm, 200ppm as poisonous substance molecule, adopt hydrogen purge reaction unit 3 times, 35 DEG C of reaction 24h.After reaction terminates, adopt gas-chromatography (chromatographic column: HP-5; FID) detect catalyst and resist poisoning result (table 2).
Embodiment 2
(1) Pd/Al
2o
3the preparation of catalyst
Take 0.079 gram of PdCl
2be dissolved in 50 grams of deionized waters, the HCl solution 0.96ml then getting 1mol/L joins in solution, is configured to the H of 8mmol/L
2pdCl
4solution, then takes 8.6 grams through pretreated Al
2o
3carrier beads puts into solution, fully floods, and rotates evaporate to dryness under constant temperature 333K, and sample is under the condition of 5K/min with heating rate in muffle furnace afterwards, and 823K calcination process 6h, can obtain Pd/Al
2o
3catalyst.
(2) get 0.3g catalyst respectively and be placed in reaction unit, then add 19ml ethyl acetate, then respectively to adding 1ml n-hexylene in device, 0.8ml cyclohexene, 0.5ml cyclo-octene, adopts hydrogen purge reaction unit 3 times, 35 DEG C of reaction 24h.After reaction terminates, adopt gas-chromatography (chromatographic column: HP-5; FID) different sample catalyst catalytic performance result (table 1) is detected.Again get 0.3g catalyst respectively and be placed in reaction unit, then add 19ml ethyl acetate, 1ml n-hexylene, add the benzothiazole of different amount, be configured to concentration be 50ppm, 100ppm, 200ppm as poisonous substance molecule, adopt hydrogen purge reaction unit 3 times, 35 DEG C of reaction 24h.After reaction terminates, adopt gas-chromatography (chromatographic column: HP-5; FID) detect catalyst and resist poisoning result (table 2).
Embodiment 3
(1) Pd/Al
2o
3the preparation of catalyst
Take 0.079 gram of PdCl
2be dissolved in 50 grams of deionized waters, the HCl solution 0.96ml then getting 1mol/L joins in solution, is configured to the H of 8mmol/L
2pdCl
4solution, then takes 8.6 grams through pretreated γ-Al
2o
3carrier beads puts into solution, fully floods, and rotates evaporate to dryness under constant temperature 333K, and sample is under the condition of 5K/min with heating rate in muffle furnace afterwards, and 823K calcination process 6h, can obtain Pd/Al
2o
3catalyst.
(2) Al
2o
3microballoon is introduced the preparation of ZnO nanoparticle inducing layer
Adopt conventional sol-gel technique making ZnO nano particle inducing layer, namely first prepare 0.5 ~ 2mol/L containing zinc sol solutions, then utilize infusion process at Pd/Al
2o
3bead surface is introduced containing zinc glue-line; Dry 0.5 ~ 3h at 80 ~ 120 DEG C, then at 400 DEG C, roasting 3h obtains ZnO nanoparticle inducing layer;
(3) pretreatment of ZnO nanoparticle inducing layer
The glyoxal ethyline ethanolic solution of preparation 0.5mol/L, by the ZnO/Pd/Al that step (2) obtains
2o
3carrier is pretreatment 1-2h under 40-60 DEG C of condition, then dry under 50-70 DEG C of condition, obtains pretreated ZnO/Pd/Al
2o
3carrier;
(4) by pretreated ZnO/Pd/Al that step (3) obtains
2o
3carrier is placed in the ZIF-8 film forming liquid prepared, then inject in the stainless steel still containing polytetrafluoro liner, be fixed on after sealing in rotary oven and rotate with the speed of 3 ~ 8r/min, reaction temperature is 60 ~ 120 DEG C, and solvent-thermal process 4 ~ 12h obtains the ZIF-8 film of different-thickness; Consisting of of synthesis liquid: zinc chloride, glyoxal ethyline (2meIM), sodium formate, ethanol are as film forming liquid raw material; Wherein,
The mol ratio of synthesis liquid is: Zn:2meIM:HCOONa:CH
3cH
2oH=1:2:0.15:300;
(5) dry under the catalyst that step (4) obtains being placed in 50-70 DEG C of condition, obtain Pd/Al
2o
3@ZIF-8 eggshell catalyst.
(6) get 0.3g catalyst respectively and be placed in reaction unit, then add 19ml ethyl acetate, then respectively to adding 1ml n-hexylene in device, 0.8ml cyclohexene, 0.5ml cyclo-octene, adopts hydrogen purge reaction unit 3 times, 35 DEG C of reaction 24h.After reaction terminates, adopt gas-chromatography (chromatographic column: HP-5; FID) different sample catalyst catalytic performance result (table 1) is detected.Again get 0.3g catalyst respectively and be placed in reaction unit, then add 19ml ethyl acetate, 1ml n-hexylene, add the benzothiazole of different amount, be configured to concentration be 50ppm, 100ppm, 200ppm as poisonous substance molecule, adopt hydrogen purge reaction unit 3 times, 35 DEG C of reaction 24h.After reaction terminates, adopt gas-chromatography (chromatographic column: HP-5; FID) detect catalyst and resist poisoning result (table 2).
Table 1. is different sample catalytic performance results.
Table 1
Table 2. is the anti-poisoning performance result of different sample.
Table 2
Claims (4)
1. the large ball Pd/Al of the coated grade of ZIF-8 film
2o
3egg-shell catalyst, is characterized in that, the large ball Pd/Al of the coated grade of this ZIF-8 film
2o
3pd/Al in egg-shell catalyst
2o
3core is with spherical Al
2o
3for carrier, spherical Al
2o
3the particle diameter of carrier is 1-3mm, with load at spherical Al
2o
3pd nano particle on carrier is catalyst active center; At Pd/Al
2o
3the inducing layer that layer of ZnO layer synthesizes as ZIF-8 film is introduced on core surface; Be coated with the Pd/Al of ZnO layer
2o
3core external sheath one deck has the ZIF-8 film of regular pore canal, is the coated Pd/Al of ZIF-8 film
2o
3egg-shell catalyst; Coated Pd/Al
2o
3the ZIF-8 film thickness of core is 1-20um.
2. the coated megalosphericus Pd/Al of ZIF-8 film according to claim 1
2o
3the preparation method of egg-shell catalyst, is characterized in that, step is as follows:
(1) introducing of ZnO nanoparticle inducing layer
Adopt sol-gel process making ZnO nano particle inducing layer, namely first preparation, containing zinc sol solutions, utilizes infusion process at Pd/Al
2o
3bead surface is introduced containing zinc glue-line; At 80 ~ 120 DEG C, dry 0.5 ~ 3h, then roasting 3h at 400 DEG C, obtain the Pd/Al that ZnO nanoparticle inducing layer is coated
2o
3carrier;
(2) Pd/Al that ZnO nanoparticle inducing layer is coated
2o
3vehicle element
The Pd/Al that ZnO nanoparticle inducing layer step (1) obtained is coated
2o
3carrier is placed in the glyoxal ethyline alcoholic solution of 0.5mol/L, 50 DEG C of pretreatment 1-2h, dry under 50-70 DEG C of condition, obtains pretreated ZnO/Pd/Al
2o
3carrier;
(3) by pretreated ZnO/Pd/Al that step (2) obtains
2o
3carrier is placed in ZIF-8 film forming liquid, is placed in the stainless steel still containing polytetrafluoro liner by ZIF-8 film forming liquid, is fixed in rotary oven after sealing, is under the condition of 60 ~ 120 DEG C in temperature, and solvent-thermal process 4 ~ 12h obtains the ZIF-8 film of different-thickness;
Consisting of of described ZIF-8 film forming liquid: zinc chloride, glyoxal ethyline, sodium formate and methyl alcohol;
Or zinc chloride, glyoxal ethyline, sodium formate and ethanol;
In ZIF-8 film forming liquid, the mol ratio of each composition is:
Zinc chloride: glyoxal ethyline: sodium formate: methyl alcohol=1:1.5:0.15:400;
Zinc chloride: glyoxal ethyline: sodium formate: ethanol=1:2:0.15:300.
3. preparation method according to claim 2, is characterized in that, by the method for the preparation of grade loaded noble metal catalyst Pd/SiO
2or Pt/SiO
2.
4. the preparation method according to Claims 2 or 3, is characterized in that, by the method for the preparation of zinc-containing metal organic framework film ZIF-7, ZIF-11 or ZIF-69.
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| CN105478114A (en) * | 2015-12-01 | 2016-04-13 | 南京工业大学 | Preparation method of palladium catalyst supported on ceramic membrane |
| CN107020387A (en) * | 2016-02-01 | 2017-08-08 | 北京化工大学 | A kind of method that normal temperature and pressure quickly prepares copper nano-wire-metal organic framework ZIF-8 composites |
| CN108067306A (en) * | 2018-01-10 | 2018-05-25 | 南开大学 | A kind of Pt/ZIF-8@Al2O3The preparation method of catalyst and its application in catalytic hydrogenation reaction |
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| CN105478114A (en) * | 2015-12-01 | 2016-04-13 | 南京工业大学 | Preparation method of palladium catalyst supported on ceramic membrane |
| CN107020387A (en) * | 2016-02-01 | 2017-08-08 | 北京化工大学 | A kind of method that normal temperature and pressure quickly prepares copper nano-wire-metal organic framework ZIF-8 composites |
| CN109772321A (en) * | 2017-11-13 | 2019-05-21 | 中国科学院福建物质结构研究所 | A kind of copper Si catalyst and its preparation and application based on metal organic frame |
| CN109772321B (en) * | 2017-11-13 | 2021-07-16 | 中国科学院福建物质结构研究所 | Copper-silicon catalyst based on metal organic framework and preparation and application thereof |
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| CN108067306B (en) * | 2018-01-10 | 2020-10-02 | 南开大学 | Pt/ZIF-8@ Al2O3Preparation method of catalyst and application of catalyst in catalytic hydrogenation reaction |
| CN108855219A (en) * | 2018-06-27 | 2018-11-23 | 福州大学 | A kind of hollow covalent organic frame cage composite material of yolk-eggshell structural metal@and its preparation and application |
| CN108855219B (en) * | 2018-06-27 | 2021-04-27 | 福州大学 | Yolk-eggshell structure metal @ hollow covalent organic framework cage composite material and preparation and application thereof |
| CN110075804A (en) * | 2019-04-03 | 2019-08-02 | 天津大学 | Metal-organic framework material UiO-66 coats γ-Al2O3Particle and preparation method thereof |
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