CN105478114A - Preparation method of palladium catalyst supported on ceramic membrane - Google Patents
Preparation method of palladium catalyst supported on ceramic membrane Download PDFInfo
- Publication number
- CN105478114A CN105478114A CN201510870391.7A CN201510870391A CN105478114A CN 105478114 A CN105478114 A CN 105478114A CN 201510870391 A CN201510870391 A CN 201510870391A CN 105478114 A CN105478114 A CN 105478114A
- Authority
- CN
- China
- Prior art keywords
- film
- catalyst
- ceramic membrane
- preparation
- palladium catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 103
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 239000012528 membrane Substances 0.000 title claims abstract description 50
- 239000000919 ceramic Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 33
- 239000000243 solution Substances 0.000 claims abstract description 26
- 238000007598 dipping method Methods 0.000 claims abstract description 18
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 8
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 9
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 7
- 230000032683 aging Effects 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 5
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 238000011084 recovery Methods 0.000 claims description 5
- 239000004246 zinc acetate Substances 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 239000003381 stabilizer Substances 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 abstract description 11
- 238000000576 coating method Methods 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 7
- 238000000926 separation method Methods 0.000 abstract description 5
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 3
- 239000002245 particle Substances 0.000 abstract description 3
- 150000002940 palladium Chemical class 0.000 abstract 1
- 239000012266 salt solution Substances 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 19
- 230000003197 catalytic effect Effects 0.000 description 18
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000002994 raw material Substances 0.000 description 11
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 239000002103 nanocoating Substances 0.000 description 8
- 230000009467 reduction Effects 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 6
- 238000007599 discharging Methods 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000011943 nanocatalyst Substances 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- DIWNCNINVWYUCD-UHFFFAOYSA-N acetyl acetate;zinc Chemical compound [Zn].CC(=O)OC(C)=O DIWNCNINVWYUCD-UHFFFAOYSA-N 0.000 description 3
- 238000010531 catalytic reduction reaction Methods 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OEHNVKBOQOXOJN-UHFFFAOYSA-N 2-(4-nitrophenyl)phenol Chemical compound OC1=CC=CC=C1C1=CC=C([N+]([O-])=O)C=C1 OEHNVKBOQOXOJN-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000635 Spelter Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- DBJUEJCZPKMDPA-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O DBJUEJCZPKMDPA-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000010458 rotten stone Substances 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/60—Platinum group metals with zinc, cadmium or mercury
-
- B01J35/59—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0228—Coating in several steps
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
Abstract
The invention relates to a preparation method of a palladium catalyst supported on a ceramic membrane, and belongs to the technical field of catalyst. The catalyst adopts the ceramic membrane as a carrier, and the preparation method comprises the following steps: modifying the surface and tunnels of the ceramic membrane with a nano-ZnO coating, dipping the obtained ceramic membrane in an active component palladium salt solution, and reducing the obtained solution by hydrazine hydrate to prepare the catalyst. Nanometer palladium catalyst particles are supported on the nano-ZnO coating modified ceramic membrane, so the combination force between the catalyst particles and the membrane is enhanced, the stability of the catalyst is improved, and the subsequent separation problem of the catalyst and a product is avoided, thereby the catalyst can be widely applied in the hydrogenation reaction process.
Description
Technical field
The present invention relates to a kind of preparation method of loaded catalyst, particularly relate to the preparation method of the ceramic membrane loaded palladium catalyst for hydrogenation process, belong to catalysis technical field.
Background technology
The physical and chemical performance of nano-noble metal catalyst by noble metal uniqueness and the property of nano material---specific area is large, blemish is many, the combination such as short, high adsorption capacity of diffusion admittance in crystal, show excellent catalytic performance, cause the extensive concern of people.But in production application, there is the problem that catalyst activity and catalyst separation are difficult to balance, the catalyst efficiency of suspended state is higher than loaded catalyst, but nanocatalyst is separated with product difficulty, limits its application.
In order to develop the more excellent palladium nanocatalyst of catalytic performance, researchers attempt being loaded to by Pd nano particle on various carrier, such as carbon, ceramic membrane, tripoli, hydroxyapatite, molecular sieve, organic backbone etc.In these carriers, ceramic membrane is with the advantage of its uniqueness, and namely excellent chemical stability, good mechanical strength and longer life-span, as the carrier of prioritizing selection.Film catalyst normally by palladium, platinum, nickel isoreactivity component by the method load such as surface impregnation, ion-exchange and chemical deposition on the surface of the film or immerse in fenestra, film forms catalyst together with catalytic active component, and film plays the effect of separation and catalyst carrier.Film catalyst efficiently solves the problem of nanocatalyst and separation of products difficulty.
The catalytic performance of film catalyst depends on following factor to a great extent: film surface nature, preparation method, film geometry.Patent (ZL201010617062.9) reports a kind of preparation method of film catalyst, namely first carry out amino modified to ceramic membrane carrier, then be immersed in the anion solutions of active component palladium, and then electronation obtains film catalyst, improve the catalytic activity of catalyst.Patent (ZL201110117813.5) reports a kind of device preparing film catalyst, force in this device the solution containing catalytic active component to be flowed through film surface and duct, make catalytic activity component load to film surface with in duct, improve the load capacity of active component and the catalytic efficiency of film catalyst.Although have carried out some research the preparation method of film catalyst, preparation facilities, its catalytic performance also increases, but compared to powder-type catalyst, the catalytic performance of film catalyst is also lower, this mainly due to: in unit volume film catalyst, active component content is still fewer; Adhesion between catalytic active component and film is more weak.Therefore, the preparation of high performance membrane catalyst remains a challenge.
In recent years, adopt nano coating modification technique to carry out surface of solids modification to attract wide attention.By adopting nano coating modification technique, can the surface characteristic of modulation solid, improve its physical and chemical performance.This patent adopts nano coating to modify ceramic-film tube, then supported palladium nano particle, prepares the film catalyst of catalytic performance excellence.
Summary of the invention
The object of the invention is to adopt nano oxidized spelter coating to modify ceramic membrane, strengthen the adhesion between palladium catalyst particle and film, improve the stability of catalyst, improve the catalytic performance of institute's loaded palladium catalyst.
Technical scheme of the present invention is:
A preparation method for the palladium catalyst of ceramic membrane load, comprises the steps:
Step one: take zinc acetate as solute, monoethanolamine is stabilizing agent, EGME that volume ratio is 1:1 and absolute ethyl alcohol mixed solution be solvent, be made into colloidal solution, under uniform temperature, the transparent shape of stirring and dissolving, still aging;
Step 2: film pipe is put into container, vacuumizes, then slowly adds above-mentioned colloidal solution, soaks certain hour;
Step 3: the film pipe after soaking is calcined in air atmosphere;
Step 4: by the dipping solution that to infiltrate with palladium be solute, acetone is solvent of the film pipe after calcining, take out nature after dipping certain hour and dry;
Step 5: use the film pipe of hydrazine hydrate solution to step 4 gained to reduce;
Step 6: use deionized water washing film pipe, natural drying.
Described ceramic membrane preferential oxidation aluminium film, zirconium oxide film, silicon oxide film or oxidation titanium film, the average pore size of ceramic-film tube is 2nm ~ 10 μm.
In the colloidal solution prepared in step one, acetic acid zinc concentration is 0.01 ~ 1mol/L, monoethanolamine and zinc acetate equimolar amounts, and stirring and dissolving temperature is 20 ~ 100 DEG C, and the still aging time is 12 ~ 48h.
Pumpdown time described in step 2 is 10 ~ 60min, and soak time is 30 ~ 120min.
Calcining film pipe described in step 3 is be heated to 300 ~ 800 DEG C with the heating rate of 1 ~ 5 DEG C/min, and calcining 60 ~ 240min, calcines 1 ~ 5 time.
In dipping solution described in step 4, the concentration of palladium is 0.02 ~ 1mol/L, and dip time is 6 ~ 48h, and dipping temperature is 20 ~ 60 DEG C.
The concentration of hydrazine hydrate solution described in step 5 is 0.1 ~ 2mol/L, and temperature is 20 ~ 60 DEG C, and the recovery time is 1 ~ 4h.
The film of washed with de-ionized water described in step 6 pipe 3 ~ 8 times.
It is the catalytic performance that model reaction evaluates prepared catalyst that the present invention adopts p-nitrophenol catalytic hydrogenation to prepare para-aminophenol.
Carry out in the forced convection device that this hydrogenation reaction is reported in patent (ZL201110117813.5).Taking 1.25g p-nitrophenol adds in raw material liquid trough, adds 10ml absolute ethyl alcohol, dissolves, then adds 490ml deionized water, be configured to the p-nitrophenyl phenol solution of 500ml by magnetic stirrer.Take 1.0g sodium borohydride, join in p-nitrophenyl phenol solution, after substantially releasing without gas, open valve, start peristaltic pump, material liquid is by interior pipe charging aperture, flow through film catalyst duct and enter interior pipe hollow part, flow back to raw material liquid trough by upper cover discharging opening.React after 60 minutes, stop reaction, cleaning device and film pipe, then react next time.Adopt content of p-nitrophenol in efficient liquid phase chromatographic analysis reactant liquor, calculate feed stock conversion according to calibration curve, carry out the catalytic activity of evaluated for film catalyst with the conversion ratio of p-nitrophenol.
Beneficial effect of the present invention:
1. the present invention adopts nano-ZnO coating to modify film, and loads on ceramic membrane by Pd nano particle; Preparing film catalyst is applied in catalytic hydrogenation reaction, can avoid the problem of nanocatalyst and separation of products;
2. the present invention is by the preparation of control ZnO colloidal solution, calcination condition and the preparation of consequent activities component palladium salting liquid, effectively prepare the film catalyst of high activity, high stability, the stability of the film catalyst after coating exceeds nearly 10% than the film catalyst not carrying out coating, can be advantageously applied in liquid-phase hydrogenatin reaction.
Accompanying drawing explanation
Fig. 1 is the SEM figure of the palladium catalyst of ceramic membrane load, and wherein (a) is ceramic membrane surface, and (b) is nano-ZnO coating modification caudacoria surface, and (c) is Pd-ZnO-ceramic membrane surface.
Detailed description of the invention
To do the present invention below in conjunction with embodiment and further explain, the following example only for illustration of the present invention, but is not used for limiting practical range of the present invention.
Embodiment 1Pd/Al
2o
3the preparation of film catalyst
(1) nano coating is modified
Weigh 0.367g acetic anhydride zinc, get 0.12mL monoethanolamine and join in 100mL ethanol and 100mL EGME mixed solution, be stirred to transparent at 60 DEG C, ageing 12h, obtained colloidal sol.Al is soaked by deionized water
2o
3film pipe, membrane aperture is 5 μm, dry for standby.Film pipe is put into bottle,suction, vacuumizes 10min, add colloidal sol by pyriform funnel, continue to take out negative pressure and soak 30min, take out.Again film pipe is heated to 600 DEG C with the heating rate of 2 DEG C/min, calcines 60min in air atmosphere, Temperature fall.
(2) preparation of catalyst
Dipping: the palladium/acetone soln 100mL of preparation 0.02mol/L is in raw material liquid trough, ceramic-film tube is put in membrane module fixing in pipe, dipping solution is made to squeeze among the annular space of pipe and ceramic-film tube in membrane module by pump, pipe hollow part in ceramic membrane is flowed into by duct from the outer surface of ceramic membrane, and return raw material liquid trough through upper cover discharging opening, make palladium active component be attached in film surface and duct, dipping 12h, control temperature is 30 DEG C.
Reduction: the hydrazine hydrate solution 150mL of configuration 0.1mol/L, solvent adopts deionized water, and the operation identical according to above-mentioned impregnation steps is reduced, and controls that reduction temperature is 30 DEG C, the recovery time is 1h.Take out the ceramic membrane catalyst prepared, spend deionized water 4 times, naturally dry stand-by.The Pd-ZnO-film catalyst prepared is numbered A.
Not adopting nano-ZnO coating to modify, adopting with preparing the identical raw material of film catalyst A and method, preparation Pd-film catalyst, is numbered B.
The surperficial SEM picture that Fig. 1 is ceramic membrane carrier, ZnO nano coating modifies caudacoria, film catalyst A.Compared to ceramic membrane carrier, nano coating modify after film configuration of surface there is significantly change, successful load nano-ZnO coating is described on ceramic membrane, and film surface roughness is obviously increased, and the average grain diameter of ZnO is about 300nm.Figure (b) and figure (c) surface are not significantly distinguished, and this may be because palladium nano-particles is less.
Film catalyst A, B of preparing are used for catalytic reduction p-nitrophenol to prepare in para-aminophenol reaction, and carry out 6 circular responses, investigate its stability, its result is as shown in table 1.Can find, the stability of film catalyst A is obviously better than film catalyst B: in first set reaction, and the activity of two catalyst is suitable; When second time is reacted, the activity decrease of catalyst A is a little less than B; Along with the increase of reaction times, the activity of catalyst B declines greatly; Until during six secondary responses, the activity decrease 12.01% of catalyst A, the activity decrease 21.82% of catalyst B.Illustrate that Pd-ZnO-film catalyst stability prepared by the present invention is better.
Table 1 film catalyst A, B are used for the catalytic performance of p-nitrophenol para-aminophenol
Embodiment 2Pd/ZrO
2the preparation of film catalyst
(1) nano coating is modified
Weigh 36.7g acetic anhydride zinc, get 12mL monoethanolamine and join in 100mL ethanol and 100mL EGME mixed solution, be stirred to transparent at 100 DEG C, ageing 48h, obtained colloidal sol.ZrO is soaked by deionized water
2film pipe, membrane aperture is 200nm, dry for standby.Film pipe is put into bottle,suction, vacuumizes 60min, add colloidal sol by pyriform funnel, continue to take out negative pressure and soak 120min, take out.Again film pipe is heated to 800 DEG C with the heating rate of 5 DEG C/min, calcines 120min in air atmosphere, Temperature fall.Repeat colloidal sol immersion-calcining step again 2 times.
(2) preparation of catalyst
Dipping: the palladium/acetone soln 100mL of preparation 0.5mol/L is in raw material liquid trough, ceramic-film tube is put in membrane module fixing in pipe, dipping solution is made to squeeze among the annular space of pipe and ceramic-film tube in membrane module by pump, pipe hollow part in ceramic membrane is flowed into by duct from the outer surface of ceramic membrane, and return raw material liquid trough through upper cover discharging opening, make palladium active component be attached in film surface and duct, dipping 6h, control temperature is 60 DEG C.
Reduction: the hydrazine hydrate solution 150mL of configuration 0.5mol/L, solvent adopts deionized water, and the operation identical according to above-mentioned impregnation steps is reduced, and controls that reduction temperature is 20 DEG C, the recovery time is 4h.Take out the ceramic membrane catalyst prepared, spend deionized water 3 times, naturally dry stand-by.The Pd-ZrO prepared
2-film catalyst is numbered C
Not adopting nano-ZnO coating to modify, adopting with preparing the identical raw material of film catalyst C and method, preparation Pd-film catalyst, is numbered D.
Film catalyst C, D of preparing are used for catalytic reduction p-nitrophenol to prepare in para-aminophenol reaction, and carry out 6 circular responses, investigate its stability, its result is as shown in table 2.Can find, the stability of film catalyst C is obviously better than film catalyst D: in first set reaction, and the activity of two catalyst is suitable; When second time is reacted, the activity decrease of two catalyst is very nearly the same; Along with the increase of reaction times, the activity of catalyst D declines greatly; Until during six secondary responses, the activity decrease 9.14% of catalyst C, the activity decrease 17.07% of catalyst D.Pd-ZrO prepared by the present invention is described
2-film catalyst stability is better.
Table 2 film catalyst C, D are used for the catalytic performance of p-nitrophenol para-aminophenol
Embodiment 3Pd/TiO
2the preparation of film catalyst
(1) nano coating is modified
Weigh 11.01g acetic anhydride zinc, get 3.6mL monoethanolamine and join in 100mL ethanol and 100mL EGME mixed solution, be stirred to transparent at 20 DEG C, ageing 24h, obtained colloidal sol.TiO is soaked by deionized water
2film pipe, membrane aperture is 50nm, dry for standby.Film pipe is put into bottle,suction, vacuumizes 60min, add colloidal sol by pyriform funnel, continue to take out negative pressure and soak 60min, take out.Again film pipe is heated to 300 DEG C with the heating rate of 1 DEG C/min, calcines 240min in air atmosphere, Temperature fall.Repeat colloidal sol immersion-calcining part again 4 times.
(2) preparation of catalyst
Dipping: the palladium/acetone soln 100mL of preparation 1mol/L is in raw material liquid trough, ceramic-film tube is put in membrane module fixing in pipe, dipping solution is made to squeeze among the annular space of pipe and ceramic-film tube in membrane module by pump, pipe hollow part in ceramic membrane is flowed into by duct from the outer surface of ceramic membrane, and return raw material liquid trough through upper cover discharging opening, make palladium active component be attached in film surface and duct, dipping 48h, control temperature is 20 DEG C.
Reduction: the hydrazine hydrate solution 150mL of configuration 2mol/L, solvent adopts deionized water, and the operation identical according to above-mentioned impregnation steps is reduced, and controls that reduction temperature is 60 DEG C, the recovery time is 2h.Take out the ceramic membrane catalyst prepared, spend deionized water 8 times, naturally dry stand-by.The Pd-TiO prepared
2-film catalyst is numbered E.
Not adopting nano-ZnO coating to modify, adopting with preparing the identical raw material of film catalyst E and method, preparation Pd-film catalyst, is numbered F.
Film catalyst E, F of preparing are used for catalytic reduction p-nitrophenol to prepare in para-aminophenol reaction, and carry out 6 circular responses, investigate its stability, its result is as shown in table 3.Can find, the stability of film catalyst E is obviously better than film catalyst F: first set reaction, and the activity of two catalyst is suitable; When second time is reacted, the activity decrease of catalyst E is a little less than F; Along with the increase of reaction times, the activity of catalyst F declines greatly; Until during six secondary responses, the activity decrease 11.99% of catalyst E, the activity decrease 22.29% of catalyst B.Pd-TiO prepared by the present invention is described
2-film catalyst stability is better.
Table 3 film catalyst E, F are used for the catalytic performance of p-nitrophenol para-aminophenol
Claims (8)
1. a preparation method for the palladium catalyst of ceramic membrane load, is characterized in that, comprises the steps:
Step one: take zinc acetate as solute, monoethanolamine is stabilizing agent, EGME that volume ratio is 1:1 and absolute ethyl alcohol mixed solution be solvent, be made into colloidal solution, under uniform temperature, the transparent shape of stirring and dissolving, still aging;
Step 2: film pipe is put into container, vacuumizes, then slowly adds above-mentioned colloidal solution, soaks certain hour;
Step 3: the film pipe after soaking is calcined in air atmosphere;
Step 4: by the dipping solution that to infiltrate with palladium be solute, acetone is solvent of the film pipe after calcining, take out nature after dipping certain hour and dry;
Step 5: use the film pipe of hydrazine hydrate solution to step 4 gained to reduce;
Step 6: use deionized water washing film pipe, natural drying.
2. the preparation method of the palladium catalyst of ceramic membrane load according to claim 1, it is characterized in that described ceramic membrane selective oxidation aluminium film, zirconium oxide film, silicon oxide film or oxidation titanium film, the average pore size of ceramic-film tube is 2nm ~ 10 μm.
3. the preparation method of the palladium catalyst of ceramic membrane load according to claim 1, it is characterized in that in the colloidal solution prepared in step one, zinc acetate concentration is 0.01 ~ 1mol/L, monoethanolamine and zinc acetate equimolar amounts, stirring and dissolving temperature is 20 ~ 100 DEG C, and the still aging time is 12 ~ 48h.
4. the preparation method of the palladium catalyst of ceramic membrane load according to claim 1, it is characterized in that the pumpdown time described in step 2 is 10 ~ 60min, soak time is 30 ~ 120min.
5. the preparation method of the palladium catalyst of ceramic membrane load according to claim 1, is characterized in that calcining film pipe described in step 3 is be heated to 300 ~ 800 DEG C with the heating rate of 1 ~ 5 DEG C/min, and calcining 60 ~ 240min, calcines 1 ~ 5 time.
6. the preparation method of the palladium catalyst of ceramic membrane load according to claim 1, it is characterized in that the concentration of palladium in dipping solution described in step 4 is 0.02 ~ 1mol/L, dip time is 6 ~ 48h, and dipping temperature is 20 ~ 60 DEG C.
7. the preparation method of the palladium catalyst of ceramic membrane load according to claim 1, it is characterized in that the concentration of hydrazine hydrate solution described in step 5 is 0.1 ~ 2mol/L, temperature is 20 ~ 60 DEG C, and the recovery time is 1 ~ 4h.
8. the preparation method of the palladium catalyst of ceramic membrane load according to claim 1, is characterized in that the film of washed with de-ionized water described in step 6 pipe 3 ~ 8 times.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510870391.7A CN105478114B (en) | 2015-12-01 | 2015-12-01 | A kind of preparation method of the palladium catalyst of ceramic membrane load |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510870391.7A CN105478114B (en) | 2015-12-01 | 2015-12-01 | A kind of preparation method of the palladium catalyst of ceramic membrane load |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105478114A true CN105478114A (en) | 2016-04-13 |
| CN105478114B CN105478114B (en) | 2018-04-03 |
Family
ID=55665596
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510870391.7A Active CN105478114B (en) | 2015-12-01 | 2015-12-01 | A kind of preparation method of the palladium catalyst of ceramic membrane load |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105478114B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106238102A (en) * | 2016-08-26 | 2016-12-21 | 北京理工大学 | There are the preparation method and applications of chirality Salen catalysis ceramic membrane |
| CN108160024A (en) * | 2018-01-11 | 2018-06-15 | 南京工业大学 | A kind of preparation method of ceramic tube supporter supported ionic sieve |
| CN108355649A (en) * | 2017-01-27 | 2018-08-03 | 通用汽车环球科技运作有限责任公司 | Pass through trapping activity platinum group metal（PGM）The anti-sintering rugged catalyst system of catalyst material |
| CN109772292A (en) * | 2019-03-16 | 2019-05-21 | 殷红平 | A kind of ceramic membrane and preparation method thereof loading nano-scale photocatalyst |
| CN110228880A (en) * | 2019-06-11 | 2019-09-13 | 潍坊科技学院 | A kind of photocatalysis-nanofiltration ceramic membrane advanced water purifying processing unit and preparation method thereof |
| CN110841633A (en) * | 2019-11-27 | 2020-02-28 | 南京工业大学 | Preparation method of catalytic membrane |
| CN111359543A (en) * | 2020-05-11 | 2020-07-03 | 信阳学院 | Metal ceramic membrane reactor for natural gas conversion |
| US11951465B2 (en) | 2017-01-05 | 2024-04-09 | GM Global Technology Operations LLC | Solution-based approach to make porous coatings for sinter-resistant catalysts |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1189483A (en) * | 1997-01-31 | 1998-08-05 | 中国科学院大连化学物理研究所 | Gas phase catalytic dehydrogenating and hydrogenation coupled reaction in palladium/ceramic composite membrane reactor |
| CN1410394A (en) * | 2001-09-24 | 2003-04-16 | 中国科学院理化技术研究所 | Method of forming metal composite titanium dioxide nano particle film on ceramic surface |
| WO2009117114A2 (en) * | 2008-03-20 | 2009-09-24 | University Of Akron | Ceramic nanofibers containing nanosize metal catalyst particles and medium thereof |
| CN104080728A (en) * | 2011-09-28 | 2014-10-01 | 康涅狄格大学 | Metal oxide nanorod arrays on monolithic substrates |
| CN104492491A (en) * | 2014-12-12 | 2015-04-08 | 大连理工大学 | ZIF-8 film coated millimeter-level large-sphere Pd/Al2O3 eggshell type catalyst and preparation method thereof |
| CN104906946A (en) * | 2015-04-29 | 2015-09-16 | 南京工业大学 | Preparation method of catalytic membrane used for gas purifying |
-
2015
- 2015-12-01 CN CN201510870391.7A patent/CN105478114B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1189483A (en) * | 1997-01-31 | 1998-08-05 | 中国科学院大连化学物理研究所 | Gas phase catalytic dehydrogenating and hydrogenation coupled reaction in palladium/ceramic composite membrane reactor |
| CN1410394A (en) * | 2001-09-24 | 2003-04-16 | 中国科学院理化技术研究所 | Method of forming metal composite titanium dioxide nano particle film on ceramic surface |
| WO2009117114A2 (en) * | 2008-03-20 | 2009-09-24 | University Of Akron | Ceramic nanofibers containing nanosize metal catalyst particles and medium thereof |
| CN104080728A (en) * | 2011-09-28 | 2014-10-01 | 康涅狄格大学 | Metal oxide nanorod arrays on monolithic substrates |
| CN104492491A (en) * | 2014-12-12 | 2015-04-08 | 大连理工大学 | ZIF-8 film coated millimeter-level large-sphere Pd/Al2O3 eggshell type catalyst and preparation method thereof |
| CN104906946A (en) * | 2015-04-29 | 2015-09-16 | 南京工业大学 | Preparation method of catalytic membrane used for gas purifying |
Non-Patent Citations (1)
| Title |
|---|
| 姜元国等: "钯/陶瓷膜催化剂上对硝基苯酚加氢宏观动力学", 《化学工程》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106238102A (en) * | 2016-08-26 | 2016-12-21 | 北京理工大学 | There are the preparation method and applications of chirality Salen catalysis ceramic membrane |
| US11951465B2 (en) | 2017-01-05 | 2024-04-09 | GM Global Technology Operations LLC | Solution-based approach to make porous coatings for sinter-resistant catalysts |
| CN108355649A (en) * | 2017-01-27 | 2018-08-03 | 通用汽车环球科技运作有限责任公司 | Pass through trapping activity platinum group metal（PGM）The anti-sintering rugged catalyst system of catalyst material |
| CN108355649B (en) * | 2017-01-27 | 2021-06-15 | 通用汽车环球科技运作有限责任公司 | Anti-sintering stable catalyst system by trapping mobile Platinum Group Metal (PGM) catalyst species |
| CN108160024A (en) * | 2018-01-11 | 2018-06-15 | 南京工业大学 | A kind of preparation method of ceramic tube supporter supported ionic sieve |
| CN109772292A (en) * | 2019-03-16 | 2019-05-21 | 殷红平 | A kind of ceramic membrane and preparation method thereof loading nano-scale photocatalyst |
| CN110228880A (en) * | 2019-06-11 | 2019-09-13 | 潍坊科技学院 | A kind of photocatalysis-nanofiltration ceramic membrane advanced water purifying processing unit and preparation method thereof |
| CN110228880B (en) * | 2019-06-11 | 2024-03-26 | 潍坊科技学院 | Photocatalysis-nanofiltration ceramic membrane deep water purification treatment device and preparation method thereof |
| CN110841633A (en) * | 2019-11-27 | 2020-02-28 | 南京工业大学 | Preparation method of catalytic membrane |
| CN110841633B (en) * | 2019-11-27 | 2022-04-29 | 南京工业大学 | Preparation method of catalytic membrane |
| CN111359543A (en) * | 2020-05-11 | 2020-07-03 | 信阳学院 | Metal ceramic membrane reactor for natural gas conversion |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105478114B (en) | 2018-04-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105478114B (en) | A kind of preparation method of the palladium catalyst of ceramic membrane load | |
| CN104549368B (en) | A kind of supported bi-metallic type Cu Pt/TiO2The preparation method of NBs catalyst and application | |
| CN103736484B (en) | A kind of support type class integral catalyzer for purifying formaldehyde and preparation method thereof | |
| CN103394373B (en) | A kind of preparation method of hydrogenation catalyst | |
| CN102039205B (en) | Monolithic nitrogen oxide selective reduction catalyst and preparation method thereof | |
| CN106000459A (en) | Preparation method of supported palladium nanocatalyst | |
| CN102626619B (en) | Preparation method of palladium carbon catalyst | |
| JP5999548B2 (en) | Photocatalyst and method for producing the same | |
| CN103523891B (en) | Containing the method for organism Catalytic Wet Air Oxidation for Wastewater | |
| CN102366723A (en) | Precious metal monolithic catalyst for organic waste gas treatment and manufacturing method thereof | |
| CN104307514B (en) | A kind of titania/silica compound spherical shell parcel nano catalyst and preparation method thereof | |
| CN103908976A (en) | Method for preparing selectivity-adjustable efficient supported precious-metal core-shell catalyst coated with metal-organic framework ZIF-8 membrane | |
| CN107029705B (en) | Preparation and application of supported metal catalysts | |
| JP4402937B2 (en) | Nanoparticle dispersion material, nanoparticle dispersion sheet, and nanoparticle dispersion laminate sheet | |
| CN108786793A (en) | A kind of preparation method of loaded catalyst for flow type catalysis reaction | |
| CN106955681A (en) | A kind of preparation method of integral catalyzer for purifying formaldehyde | |
| CN103178274B (en) | Anode catalyst of PdMo/TiO2 nanowire direct methanol fuel cell and preparation method | |
| CN111514905A (en) | Noble metal and transition metal composite catalyst and preparation method thereof | |
| CN102626621B (en) | Hydrogenation catalyst using cellular titanium dioxide as carrier and preparation method thereof | |
| CN102247837A (en) | Titanium oxide supported catalyst for eliminating formaldehyde in microenvironment air | |
| CN1435277A (en) | Supported palladium catalyst for producing hydrogen peroxide by anthraquinone process and preparing method thereof | |
| CN104959136B (en) | A kind of preparation method for adding hydrogen into resin egg-shell catalyst | |
| CN106040230B (en) | A kind of preparation method of the integrated catalyst for formaldehyde low-temperature catalytic oxidation | |
| CN105126828A (en) | Porous carbon load noble metal catalyst and preparation method thereof | |
| CN101244386A (en) | Integral catalyst without coating and method of producing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |