CN103551185A - Preparation method of molecular sieve film-loaded noble metal catalyst - Google Patents
Preparation method of molecular sieve film-loaded noble metal catalyst Download PDFInfo
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- CN103551185A CN103551185A CN201310553229.3A CN201310553229A CN103551185A CN 103551185 A CN103551185 A CN 103551185A CN 201310553229 A CN201310553229 A CN 201310553229A CN 103551185 A CN103551185 A CN 103551185A
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Abstract
The invention discloses a preparation method of a molecular sieve film-loaded noble metal catalyst. The preparation method is characterized in that the molecular sieve film-loaded noble metal catalyst consists of an alpha-Al2O3 ceramic tube, a molecular sieve film carrier layer and a catalyst layer, wherein noble metal is one or more of Pt, Pd, Rh, Ru, Ir, Ag and Au; weight of the noble metal is 0.3%-1.5% of the weight of the metal carrier layer; an assistant exists on the catalyst layer in the form of an oxide, and is at least one of Na, K, Cr and rear-earth metals; the rear-earth metals are La, Ce, Pr and Nd. The preparation method comprises the following steps: (1) roasting the alpha-Al2O3 ceramic tube; (2) coating or soaking a molecular sieve crystal seed layer on the surface; (3) roasting and curing the crystal seed layer; (4) placing the crystal seed layer carrier into molecular sieve synthesis liquor to carry out synthesis twice or multiple times; (5) preparing active liquor with noble metal content of 0.05 g/ml-0.30g/ml; (6) coating or soaking the active liquor to the surface of the carrier layer and roasting; (7) soaking repeatedly and roasting; and (8) reducing by using a hydrogen gas.
Description
Technical field
The invention belongs to catalyst application, relate to a kind of preparation method of molecular sieve film carrier noble metal catalyst.
Background technology
Molecular screen membrane is except having good high temperature resistant, corrosion-resistant of inoranic membrane, resistance to microbial attack, and chemically stable, intensity is high, and swelling, outside the advantages such as easy cleaning and regeneration, does not also have the feature of molecular sieve.Molecular screen membrane aperture homogeneous, adjustable, therefore can realize according to its pore size the screening separation of different molecular.Simultaneously, the silica alumina ratio of molecular sieve is adjustable, cation can be by other ion-exchange, Si or Al atom can be replaced by other hetero atom, molecular screen membrane has broad prospects in field of catalytic reactions, in addition, molecular screen membrane can realization response process and the effective integration of separation process, reaches the object that improves reaction conversion ratio and strengthening course of reaction.
The catalyst that the metal of generally take is carrier, carried noble metal active component.Such catalyst has higher catalytic efficiency, and still, these metal carrier catalysts also exist some shortcomings.Due to metal carrier surface atresia, smoother, be difficult for supported catalyst layer, and catalyst layer do not mate with the coefficient of expansion of metallic carrier, cause the conjugation of catalyst layer and metal carrier layer low, easily come off; Metallic carrier specific area is less, is difficult for adsorption catalyst, and catalyst is bad in metal carrier surface dispersiveness, therefore need repeatedly coated catalysts just can reach the amount of required catalyst, to reach good activity, causes complicated process of preparation, and cost is high.If be carried on Large ratio surface molecular screen membrane carrier and can be obtained good catalyst.The method is easy and simple to handle, high with substrate combinating strength, incrust.
Summary of the invention
The object of the present invention is to provide a kind of molecular sieve film carrier noble metal catalyst and preparation method thereof, in described catalyst, the bond strength of catalyst layer and molecular screen membrane carrier is high, active constituent is uniformly dispersed, have the advantages that start-up temperature is low, activity is high, mithridatism ability strong, adapt to high temperature, high humidity environment, preparation method is simple, and cost is low.
The present invention is a kind of preparation method of molecular sieve film carrier noble metal catalyst, it is characterized in that:
The composition of described molecular sieve film carrier noble metal catalyst:
By α-Al
2o
3earthenware, molecular screen membrane carrier layer and catalyst layer form, α-Al
2o
3the molecular screen membrane of growing on earthenware, catalyst layer applies or impregnated in molecular screen membrane porous material layer surface;
Described molecular screen membrane carrier layer materials is α-Al
2o
3porous material, being selected from zeolite molecular sieve is NaA, ZSM-5, SAPO-5, HY, USY or β; Aperture is 200nm～5um; Be shaped as tubulose or flat board, support layer thickness is 0.3～1mm, and caliber is 5～15mm, and long is 200mm～1.2m; Described molecular screen membrane layer thickness is 1～50 μ m;
Described catalyst layer is comprised of noble metal and the auxiliary agent with catalytic activity; Wherein, noble metal is one or more in Pt, Pd, Rh, Ru, Ir, Ag and Au, and weight is metal carrier layer 0.3～1.5%; Auxiliary agent is present on catalyst layer with the form of oxide, is at least one in Na, K, Cr and rare earth metal; Described rare earth metal is La, Ce, Pr, Nd; Auxiliary agent is 0.1～6.5% of catalyst layer gross weight;
Preparation method's step of described molecular sieve film carrier noble metal catalyst is as follows:
1), in air, under ℃ condition of temperature programming to 850～1100, calcine α-Al
2o
3earthenware 1～20 hour, makes α-Al
2o
3earthenware is removed organic impurities, and then cooling is used hydrochloric acid 1M and NaOH1M to clean each 30min, and washing is to neutral and dry;
2) after processing Al
2o
3surface applies or impregnated zeolite crystal seed layer;
3) by step 2) the crystal seed layer baking and curing that obtains, wherein bake out temperature is 80～120 ℃, the time is 2～6 hours; Sintering temperature is 300～750 ℃, and preferably 400～500 ℃, the time is 2～6 hours;
4) carrier that step 3) must be contained to crystal seed layer is put into Zeolite synthesis liquid, and to carry out secondary synthetic or repeatedly synthetic;
5) with salt or the acids of noble metal, be mixed with the solution that bullion content is 0.05～0.30g/ml, in solution, add auxiliary agent, obtain having the solution of catalytic activity;
6) solution with catalytic activity step 5) being prepared applies or is impregnated into the carrier layer surface with porous character that step (4) obtains, and roasting after drying, and wherein bake out temperature is 80～120 ℃, and the time is 2～6 hours; Sintering temperature is 300～750 ℃, and preferably 400～500 ℃, the time is 2～6 hours;
7) repeating step 6), making bullion content is 0.3～1.5% of metal carrier layer weight;
8) product step 7) being obtained with hydrogen reducing 5～10h, obtains described molecular sieve film carrier noble metal catalyst in 230～650 ℃ of temperature ranges.
Beneficial effect
1. α-the Al making by calcining
2o
3the bond strength of carrier layer and crystal seed layer is higher, makes diauxic growth molecular screen membrane and carrier bond strength higher.
2. good anti-strip, makes α-Al by growth molecular screen membrane
2o
3carrier layer surface has loose structure, can effectively combine with the active catalyst layer of subsequent coated.
3. because molecular sieve rete has higher specific area, than being easier to adsorption activity component, and make noble metal catalyst there is good dispersiveness, make the catalyst layer that applies or flood there is higher activity and heat-resisting quantity, in the time of can guaranteeing to use under hot conditions, activity does not decline, while avoiding high temperature because the transformation of carrier sintering or crystal formation is shone into catalyst activity and is lost.
4. because molecular sieve rete has higher specific area, than being easier to adsorption catalyst layer, make to apply or the minimizing of dipping number of times, reduced labour intensity, optimized preparation method.
5. due to the porous character of molecular sieve rete, make the catalyst good dispersion that applies or flood, there is higher activity, therefore reduced the demand of noble metal amount, and the metal carrier layer cost using is low, makes molecular sieve film carrier noble metal catalyst of the present invention have lower cost.
The specific embodiment
Embodiment 1
Get α-Al of 5 13 * 800mm
2o
3earthenware, every thick is 0.6mm, aperture is 500nm, in 950 ℃ of calcinings 4 hours, cooling rear taking-up, put into the mixed liquor of hydrochloric acid, hydrogen peroxide and deionized water, wherein, in mixed liquor, the mass ratio of each component is hydrochloric acid: hydrogen peroxide: deionized water=1:1:10, then cleans to neutral in deionized water for ultrasonic, then puts into the mixed liquor of ammoniacal liquor, hydrogen peroxide and deionized water, wherein, in mixed liquor, the mass ratio of each component is ammoniacal liquor: hydrogen peroxide: deionized water=1:1:10, then in deionized water for ultrasonic, clean to neutral, after 120 ℃ of oven dry; α-Al after cleaning
2o
3the molecular sieve crystal seed of surface vacuum pumping painting one deck 200nm size, in 120 ℃ of bakings 2 hours, at 450 ℃, roasting was 3 hours, and the thickness that gained is coated with molecular sieve crystal seed layer is 6 μ m, puts into drying box standby.
By sodium aluminate, Ludox, NaOH and deionized water, Na2O:Al2O3:SiO2:H2O=2:1:2:120 is made into synthetic liquid in molar ratio, the carrier that is coated with 200nm size crystal seed layer is put into the rotary oven that synthetic liquid is 15r/min at rotating speed to be synthesized 4～6 hours at 100 ℃, then extremely neutral by washed with de-ionized water, repeatedly be blended into and have high-quality molecular screen membrane (can measure by the infiltration evaporation of divided gas flow or liquid the quality of film), this experiment has higher repeatability.
Measure respectively the H that concentration is 0.1gPd/ml
2pdCl
4the H of solution 5ml, 0.1gPt/ml
2ptCl
6solution 10ml pours infuser into, and wherein, the concentration of noble metal is 0.1g/ml, adds the Ce (NO of 0.12gCe/ml
3)
3after solution 3ml, there is molecular screen membrane carrier to put into infuser growth and flood, and be dried 4 hours at 120 ℃.Then roasting 3 hours at 450 ℃, repeated impregnations, and dry after roasting 3 times, now, noble metal (Pd, Pt) gross weight is molecular sieve layer 0.5%, auxiliary agent Ce content is 0.1% of catalyst layer gross weight.Then 450 ℃, air speed 1000 hours
-1under condition, use hydrogen reducing 5 hours, naturally cool to room temperature, obtain molecular screen membrane of the present invention as the hydrogen-eliminating catalyst of carrier, wherein, in described catalyst, molecular screen membrane is grown directly upon α-Al
2o
3in carrier layer, catalyst layer impregnated in molecular screen membrane porous material layer surface.
In evaluating flow process, catalyst activity packs 5 catalyst samples making into, at normal temperatures and pressures, air speed 20000 hours
-1, density of hydrogen is the hydrogen activity evaluation that disappears under 2% condition, hydrogen, through catalyst sample, generates water with airborne oxygen reaction under catalytic action, obtaining hydrogen conversion was 83%, 80 ℃, relative humidity 100%, normal pressure, air speed 20000 hours
-1, density of hydrogen is the hydrogen activity evaluation that disappears under 2% condition, obtaining hydrogen conversion is 91%.
Embodiment 2
Get α-Al of 5 13 * 800mm
2o
3earthenware, every thick is 0.6mm, aperture is 500nm, in 950 ℃ of calcinings 4 hours, cooling rear taking-up, put into the mixed liquor of hydrochloric acid, hydrogen peroxide and deionized water, wherein, in mixed liquor, the mass ratio of each component is hydrochloric acid: hydrogen peroxide: deionized water=1:1:10, then cleans to neutral in deionized water for ultrasonic, then puts into the mixed liquor of ammoniacal liquor, hydrogen peroxide and deionized water, wherein, in mixed liquor, the mass ratio of each component is ammoniacal liquor: hydrogen peroxide: deionized water=1:1:10, then in deionized water for ultrasonic, clean to neutral, after 120 ℃ of oven dry; α-Al after cleaning
2o
3the molecular sieve crystal seed of surface vacuum pumping painting one deck 400nm size, in 120 ℃ of bakings 2 hours, at 450 ℃, roasting was 3 hours, and the thickness that gained is coated with molecular sieve crystal seed layer is 6 μ m, puts into drying box standby.
By sodium aluminate, Ludox, NaOH and deionized water, Na2O:Al2O3:SiO2:H2O=2:1:2:120 is made into synthetic liquid in molar ratio, the carrier that is coated with 400nm size crystal seed layer is put into the rotary oven that synthetic liquid is 15r/min at rotating speed to be synthesized 4～6 hours at 100 ℃, then extremely neutral by washed with de-ionized water, repeatedly be blended into and have high-quality molecular screen membrane (can measure by the infiltration evaporation of divided gas flow or liquid the quality of film), this experiment has higher repeatability.
Measure respectively the H that concentration is 0.1gPd/ml
2pdCl
4the H of solution 5ml, 0.1gPt/ml
2ptCl
6the AgNO of solution 6ml and 0.15gAg/ml
3solution 4ml pours infuser into, and wherein, the concentration of noble metal is 0.11g/ml, adds the Ce (NO of 0.12gCe/ml
3)
3after solution 3ml, there is molecular screen membrane carrier to put into infuser growth and flood, and be dried 5 hours at 100 ℃.Then roasting 2.5 hours at 500 ℃, repeated impregnations, and dry after roasting 3 times, now, noble metal (Pd, Pt, Ag) gross weight is molecular sieve layer 0.5%, auxiliary agent Ce content is 0.1% of catalyst layer gross weight.Then 500 ℃, air speed 1000 hours
-1under condition, use hydrogen reducing 5 hours, naturally cool to room temperature, obtain molecular screen membrane of the present invention as the hydrogen-eliminating catalyst of carrier, wherein, in described catalyst, molecular screen membrane is grown directly upon α-Al
2o
3in carrier layer, catalyst layer impregnated in molecular screen membrane porous material layer surface.
In evaluating flow process, catalyst activity packs the heel piece catalyst sample of making into, at normal temperatures and pressures, air speed 20000 hours
-1, density of hydrogen is the hydrogen activity evaluation that disappears under 2% condition, hydrogen, through catalyst sample, generates water with airborne oxygen reaction under catalytic action, obtaining hydrogen conversion was 86%, 80 ℃, relative humidity 100%, normal pressure, air speed 20000 hours
-1, density of hydrogen is the hydrogen activity evaluation that disappears under 2% condition, obtaining hydrogen conversion is 92%.
Embodiment 3
Get α-Al of 5 13 * 800mm
2o
3earthenware, every thick is 0.6mm, aperture is 500nm, in 1050 ℃ of calcinings 4 hours, cooling rear taking-up, put into the mixed liquor of hydrochloric acid, hydrogen peroxide and deionized water, wherein, in mixed liquor, the mass ratio of each component is hydrochloric acid: hydrogen peroxide: deionized water=1:1:10, then cleans to neutral in deionized water for ultrasonic, then puts into the mixed liquor of ammoniacal liquor, hydrogen peroxide and deionized water, wherein, in mixed liquor, the mass ratio of each component is ammoniacal liquor: hydrogen peroxide: deionized water=1:1:10, then in deionized water for ultrasonic, clean to neutral, after 120 ℃ of oven dry; α-Al after cleaning
2o
3the molecular sieve crystal seed of surface vacuum pumping painting one deck 800nm size, in 120 ℃ of bakings 2 hours, at 450 ℃, roasting was 3 hours, and the thickness that gained is coated with molecular sieve crystal seed layer is 8 μ m, puts into drying box standby.
By sodium aluminate, Ludox, NaOH and deionized water, Na2O:Al2O3:SiO2:H2O=2:1:2:120 is made into synthetic liquid in molar ratio, the carrier that is coated with 800nm size crystal seed layer is put into the rotary oven that synthetic liquid is 15r/min at rotating speed to be synthesized 4～6 hours at 100 ℃, then extremely neutral by washed with de-ionized water, repeatedly be blended into and have high-quality molecular screen membrane (can measure by the infiltration evaporation of divided gas flow or liquid the quality of film), this experiment has higher repeatability.
Measure respectively the H that concentration is 0.12gPd/ml
2pdCl
4the H of solution 3ml, 0.07gPt/ml
2ptCl
6the AgNO of solution 2ml and 0.19gAg/ml
3solution 1ml pours infuser into, and wherein, the concentration of noble metal is 0.12g/ml, adds 0.2gK
2cO
3, stir and make coating liquid.Coating liquid is brushed to growth to be had on molecular screen membrane carrier, and is dried 2 hours at 80 ℃.Then roasting 4 hours at 400 ℃, repeat to brush, and dry after roasting 3 times, now, noble metal (Pd, Pt, Ag) gross weight is 0.5% of molecular sieve rete, auxiliary agent K content is 0.1% of catalyst layer gross weight.Then 500 ℃, air speed 1000 hours
-1under condition, use hydrogen reducing 5 hours, naturally cool to room temperature, obtain molecular screen membrane of the present invention as the hydrogen-eliminating catalyst of carrier, wherein, in described catalyst, molecular screen membrane is grown directly upon α-Al
2o
3in carrier layer, catalyst layer impregnated in molecular screen membrane porous material layer surface.
In evaluating flow process, catalyst activity packs 5 catalyst samples making into, at normal temperatures and pressures, air speed 20000 hours
-1, density of hydrogen is the hydrogen activity evaluation that disappears under 2% condition, hydrogen, through catalyst sample, generates water with airborne oxygen reaction under catalytic action, obtaining hydrogen conversion was 85%, 80 ℃, relative humidity 100%, normal pressure, air speed 20000 hours
-1, density of hydrogen is the hydrogen activity evaluation that disappears under 2% condition, obtaining hydrogen conversion is 82%.
The present invention includes but be not limited to above embodiment, every any being equal to of carrying out under the principle of spirit of the present invention, replaces or local improvement, all will be considered as within protection scope of the present invention.
Claims (2)
1. a preparation method for molecular sieve film carrier noble metal catalyst, is characterized in that:
The composition of described molecular sieve film carrier noble metal catalyst:
By α-Al
2o
3earthenware, molecular screen membrane carrier layer and catalyst layer form, α-Al
2o
3the molecular screen membrane of growing on earthenware, catalyst layer applies or impregnated in molecular screen membrane porous material layer surface;
Described molecular screen membrane carrier layer materials is α-Al
2o
3porous material, being selected from zeolite molecular sieve is NaA, ZSM-5, SAPO-5, HY, USY or β; Aperture is 200nm～5um; Be shaped as tubulose or flat board, support layer thickness is 0.3～1mm, and caliber is 5～15mm, and long is 200mm～1.2m; Described molecular screen membrane layer thickness is 1～50 μ m;
Described catalyst layer is comprised of noble metal and the auxiliary agent with catalytic activity; Wherein, noble metal is one or more in Pt, Pd, Rh, Ru, Ir, Ag and Au, and weight is metal carrier layer 0.3～1.5%; Auxiliary agent is present on catalyst layer with the form of oxide, is at least one in Na, K, Cr and rare earth metal; Described rare earth metal is La, Ce, Pr, Nd; Auxiliary agent is 0.1～6.5% of catalyst layer gross weight;
Preparation method's step of described molecular sieve film carrier noble metal catalyst is as follows:
1), in air, under ℃ condition of temperature programming to 850～1100, calcine α-Al
2o
3earthenware 1～20 hour, makes α-Al
2o
3earthenware is removed organic impurities, and then cooling is used hydrochloric acid 1M and NaOH1M to clean each 30min, and washing is to neutral and dry;
2) after processing Al
2o
3surface applies or impregnated zeolite crystal seed layer;
3) by step 2) the crystal seed layer baking and curing that obtains, wherein bake out temperature is 80～120 ℃, the time is 2～6 hours; Sintering temperature is 300～750 ℃, and the time is 2～6 hours;
4) carrier that step 3) must be contained to crystal seed layer is put into Zeolite synthesis liquid, and to carry out secondary synthetic or repeatedly synthetic;
5) with salt or the acids of noble metal, be mixed with the solution that bullion content is 0.05～0.30g/ml, in solution, add auxiliary agent, obtain having the solution of catalytic activity;
6) solution with catalytic activity step 5) being prepared applies or is impregnated into the carrier layer surface with porous character that step (4) obtains, and roasting after drying, and wherein bake out temperature is 80～120 ℃, and the time is 2～6 hours; Sintering temperature is 300～750 ℃, and the time is 2～6 hours;
7) repeating step 6), making bullion content is 0.3～1.5% of metal carrier layer weight;
8) product step 7) being obtained with hydrogen reducing 5～10h, obtains described molecular sieve film carrier noble metal catalyst in 230～650 ℃ of temperature ranges.
2. according to preparation method claimed in claim 1, it is characterized in that:
In step 3), crystal seed layer sintering temperature is 400～500 ℃,
Carrier in step 6) after coating or dipping, sintering temperature is 400～500 ℃.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106881147A (en) * | 2015-12-15 | 2017-06-23 | 中国科学院大连化学物理研究所 | The preparation and catalyst film and application of ZSM-5 Type Zeolites agent film in metal passage |
| CN109126863A (en) * | 2018-10-08 | 2019-01-04 | 中海油天津化工研究设计院有限公司 | A kind of condensed-nuclei aromatics adds the preparation method of the porous Pd composite membrane of hydrogen production mononuclear aromatics |
| CN111375314A (en) * | 2020-04-08 | 2020-07-07 | 福州大学 | Molecular sieve membrane and preparation method and application thereof |
| CN112536062A (en) * | 2019-09-23 | 2021-03-23 | 中国海洋石油集团有限公司 | Hydrodewaxing catalyst, preparation method and application thereof |
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| CN101028605A (en) * | 2007-03-27 | 2007-09-05 | 天津大学 | Method for producing zeolite molecular sieve film carrier noble metal catalyst |
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| CN101028605A (en) * | 2007-03-27 | 2007-09-05 | 天津大学 | Method for producing zeolite molecular sieve film carrier noble metal catalyst |
Non-Patent Citations (1)
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106881147A (en) * | 2015-12-15 | 2017-06-23 | 中国科学院大连化学物理研究所 | The preparation and catalyst film and application of ZSM-5 Type Zeolites agent film in metal passage |
| CN109126863A (en) * | 2018-10-08 | 2019-01-04 | 中海油天津化工研究设计院有限公司 | A kind of condensed-nuclei aromatics adds the preparation method of the porous Pd composite membrane of hydrogen production mononuclear aromatics |
| CN112536062A (en) * | 2019-09-23 | 2021-03-23 | 中国海洋石油集团有限公司 | Hydrodewaxing catalyst, preparation method and application thereof |
| CN112536062B (en) * | 2019-09-23 | 2023-05-12 | 中国海洋石油集团有限公司 | Hydrodewaxing catalyst and preparation method and application thereof |
| CN111375314A (en) * | 2020-04-08 | 2020-07-07 | 福州大学 | Molecular sieve membrane and preparation method and application thereof |
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Application publication date: 20140205 |