CN108786793A - Preparation method of supported catalyst for flow-through catalytic reaction - Google Patents
Preparation method of supported catalyst for flow-through catalytic reaction Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 98
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 20
- 239000012528 membrane Substances 0.000 claims abstract description 78
- 239000000919 ceramic Substances 0.000 claims abstract description 73
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 51
- VEXZGXHMUGYJMC-UHFFFAOYSA-N hydrochloric acid Substances Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 44
- 230000003197 catalytic effect Effects 0.000 claims abstract description 17
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 15
- 230000004048 modification Effects 0.000 claims abstract description 13
- 238000012986 modification Methods 0.000 claims abstract description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 12
- 239000002105 nanoparticle Substances 0.000 claims abstract description 11
- 239000002071 nanotube Substances 0.000 claims abstract description 10
- 239000011148 porous material Substances 0.000 claims abstract 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 49
- 239000000243 solution Substances 0.000 claims description 44
- 238000006243 chemical reaction Methods 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 11
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 8
- 229910052763 palladium Inorganic materials 0.000 claims description 8
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 8
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000003860 storage Methods 0.000 claims description 8
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 claims description 7
- 239000011780 sodium chloride Substances 0.000 claims description 7
- 230000002572 peristaltic effect Effects 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 3
- 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
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 239000011259 mixed solution Substances 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
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 11
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 238000005530 etching Methods 0.000 abstract 2
- 239000002073 nanorod Substances 0.000 abstract 2
- 239000006087 Silane Coupling Agent Substances 0.000 abstract 1
- 125000000524 functional group Chemical group 0.000 abstract 1
- 238000005470 impregnation Methods 0.000 abstract 1
- 239000003643 water by type Substances 0.000 description 10
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 9
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 8
- 238000006722 reduction reaction Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 7
- 230000009467 reduction Effects 0.000 description 7
- 239000003755 preservative agent Substances 0.000 description 6
- 230000002335 preservative effect Effects 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 208000012839 conversion disease Diseases 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011943 nanocatalyst Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- 235000013339 cereals Nutrition 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 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 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000005909 ethyl alcohol group Chemical group 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 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
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
- B01J35/59—Membranes
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a preparation method of a supported catalyst for flow-through catalytic reaction. The catalyst takes a ceramic membrane as a carrier, and firstly adopts a two-step hydrothermal method to grow TiO on the surface of the ceramic membrane and in a pore channel2Nanorod, and hydrothermal etching TiO with hydrochloric acid2Etching the nano-rod into TiO2And (3) introducing an amino functional group into the nanotube through silane coupling agent modification, and finally loading Pd nanoparticles by a sol-gel impregnation method to prepare the supported catalyst. The invention has the advantages that TiO is adopted2The nanotube modifies the surface and the pore channel of the ceramic membrane, so that the surface area of the membrane catalyst can be improved, more Pd nanoparticles are loaded on the surface and the pore channel of the ceramic membrane, and the catalytic performance of the catalyst is improved; meanwhile, due to the porous characteristic of the ceramic membrane, the prepared membrane catalyst can construct a flow-through catalytic membrane reactor, so that the problem that the catalyst and a product are difficult to separate subsequently is avoided, and the membrane catalyst can be widely applied to the flow-through catalytic reaction process.
Description
Technical field
The present invention relates to a kind of preparation methods of loaded catalyst, the more particularly, to catalyst preparation of hydrogenation process
Method belongs to catalysis technical field.
Background technology
Nanocatalyst has excellent catalytic since its grain diameter is small, large specific surface area, surface defect
Energy.But in production application, nanocatalyst is difficult to detach with product, limits its extensive use.By nanocatalyst
It is a kind of effective solution approach to load in the surface and duct of film and prepare support type film catalyst.
Film catalyst can improve the conversion ratio and selectivity of reaction, reduce reaction temperature, energy consumption be saved, in catalysis industry
Field has very high application value.Since film has porosity characteristic, catalyst, Neng Gouqi are constituted together with catalytic active component
To the effect of separation and catalyst carrier.The application of film catalyst nevertheless suffers from active component content in unit volume film catalyst
The limitation for the problems such as binding force of less, film and catalyst is weaker.
Researcher has carried out some research work, improves the performance of film catalyst.Patent（CN105478114A）Report
A kind of preparation method of the palladium catalyst of ceramic membrane load, modifies film surface and duct using nano-ZnO coating, so
Catalyst is made through hydrazine hydrate reduction using active component salt solution dipping, again afterwards, improves the catalytic activity of catalyst.Patent
（CN102091626A）A kind of p-nitrophenol catalytic hydrogenation catalyst and preparation method thereof is reported, first to ceramic membrane carrier
It carries out amino modified, is then immersed in the anion solutions of active component palladium, and then film catalyst is made in electronation,
Improve the load capacity of active component and the catalytic efficiency of film catalyst.
Although obtaining remarkable break-throughs in terms of the research of film catalyst, film catalyst from practical application also have very greatly away from
From preparing high performance film catalyst or a major challenge.
Invention content
The purpose of the present invention is use TiO2Then the surface and duct of nanometer tube modified ceramic membrane load Pd nanometers
Grain, prepares high performance film catalyst.
The technical scheme is that：A kind of preparation method of loaded catalyst for flow type catalysis reaction, packet
Include following steps：
Step 1：Butyl titanate is dissolved in aqueous hydrochloric acid solution and configures hydrothermal solution, ceramic membrane is then put into water heating kettle
Middle progress first step hydro-thermal reaction introduces one layer of TiO in ceramic membrane surface2Crystal seed；
Step 2：Butyl titanate is dissolved in hydrochloric acid, water, NaCl mixed solutions and configures hydrothermal solution, then by ceramic membrane
It is put into progress second step hydro-thermal reaction in water heating kettle, prepares TiO2The ceramic membrane of nanometer rods modification；
Step 3：By TiO2The ceramic membrane of nanometer rods modification is put into progress acid etch hydro-thermal reaction, TiO in aqueous hydrochloric acid solution2It receives
Rice stick is converted into TiO2Nanotube, to prepare TiO2Nanometer tube modified ceramic membrane；
Step 4：Ceramic membrane after modification is impregnated into the dichloromethane of N- (β-aminoethyl)-γ-aminopropyltrimethoxysilane
In solution, amino-functional group is introduced in ceramic membrane surface；
Step 5：Palladium and polyvinylpyrrolidone are added in absolute ethyl alcohol, heating stirring prepares Pd nano particle colloidal sols；
Step 6：Ceramic membrane after step 4 is modified is immersed in Pd nano particle colloidal sols, load active component Pd, final to make
It is standby go out support type film catalyst.
It is applied to flow type catalytic film reactor, flow type catalysis using the film catalyst that preparation method of the present invention is prepared
Membrane reactor includes storage tank, membrane module and peristaltic pump；Reaction solution stirs evenly in storage tank, then enters film by peristaltic pump
Component, reaction solution flow through film catalyst surface and duct in membrane module, contact and react with active component, be then return to storing
Tank is reacted with circulating pattern.
Ceramic membrane selective oxidation aluminium film, zirconium oxide film, silicon oxide film or oxidation titanium film of the present invention, ceramic membrane are averaged
Aperture is 2 nm ~ 10 μm, and ceramic membrane is configured as chip film.
The molar concentration of butyl titanate described in step 1 is 0.03~0.09 mol/L, the volume ratio of water and hydrochloric acid
It is 1:2~1:0.5, hydrothermal temperature is 90 ~ 180 DEG C, and the hydro-thermal time is 1 ~ 5 h.
The molar concentration of butyl titanate described in step 2 is 0.03~0.09 mol/L, the volume ratio of water and hydrochloric acid
It is 1:2~1:0.5, NaCl a concentration of 2 ~ 6.16 mol/L, hydrothermal temperature are 90 ~ 180 DEG C, and the hydro-thermal time is 10 ~ 25 h.
The volume ratio of water and hydrochloric acid is 1 in step 3:2~1:0.5, hydrothermal temperature be 90 ~ 180 DEG C, the hydro-thermal time be 8 ~
20 h。
A concentration of 0.2~1.5 g/L of N- (β-aminoethyl)-γ-aminopropyltrimethoxysilane described in step 4,
Dip time is 4 ~ 10 h.
The collosol concentrations of Pd nano particles described in step 5 are 0.02~0.07 mol/L, polyvinylpyrrolidone and Pd's
Molar ratio is 1~40, and the preparation temperature of colloidal sol is 40 ~ 70 DEG C.
Dipping temperature described in step 6 is 30 ~ 60 DEG C, and the time is 6~24 h.
The present invention is that model reaction is commented to restore para-aminophenol processed as reducing agent, catalysis p-nitrophenol with sodium borohydride
The catalytic performance of valence prepared catalyst.
P-nitrophenol reduction reaction carries out in flow type catalytic film reactor as shown in Figure 1.Reactor is by film group
The water bath device composition of part, storage tank, peristaltic pump and temperature control.The reaction solution of 60 mL is configured first（0.45 g p-nitrophenyls
Phenol is dissolved in 10 mL absolute ethyl alcohols, adds 50 mL deionized waters constant volumes to 60 mL, and 0.65 g sodium borohydrides are then added and stir
It mixes uniformly）It is added in storage tank；Later on peristaltic pump, reaction solution are flowed through film catalyst surface and duct and are born by peristaltic pump
The active component of load is reacted；It is returned in storage tank from the bottom end of membrane module by the reaction solution of film catalyst and recycle instead
It answers.Reaction time is 10 min, using content of p-nitrophenol in efficient liquid phase chromatographic analysis reaction solution, calculates p-nitrophenol
Conversion ratio, the catalytic activity of film catalyst is evaluated with the conversion ratio of p-nitrophenol.
Advantageous effect：
1. the present invention uses TiO2Nanotube modifies ceramic membrane surface and duct, improves the surface area of ceramic membrane, can
More active component attachment sites are provided, more Pd nano particles are loaded, to prepare the catalyst haveing excellent performance.
2. the film catalyst that the present invention prepares can build flow type catalytic film reactor, catalyst and product are avoided
The problem of follow-up difficult separation, it can be widely applied to flow type catalytic reaction process.
Description of the drawings
Fig. 1 is the schematic diagram of flow type catalytic film reactor in the present invention.
Fig. 2 is that film catalyst surface SEM schemes in embodiment 1：(a) Pd/ ceramics film catalyst, (b) Pd/TiO2Nanotube
The ceramic film catalyst of modification.
Specific implementation mode
The method of the present invention and the using effect of catalyst are illustrated below by embodiment.The following example is only used for
The bright present invention, but be not used to limit the practical range of the present invention.
1 Pd/TiO of embodiment2Nanometer tube modified Al2O3The preparation of ceramic membrane
（1）TiO2Nanometer tube modified Al2O3The preparation of ceramic membrane
First step hydro-thermal：It measures 20 mL deionized waters and stirs 5 min with 20 mL mixed in hydrochloric acid, 0.955 mL metatitanic acids, four fourth is added
Ester（0.07 mol/L）10 min are stirred, hydrothermal solution is configured；Ceramic membrane (diameter：3.2 cm, material：Al2O3, membrane aperture：3 μ
M) it is disposed vertically in 50 mL water heating kettles, pours into hydrothermal solution, 5 h of hydro-thermal reaction is carried out at a temperature of 150 DEG C, in ceramic membrane table
Look unfamiliar long one layer of TiO2Crystal seed.
Second step hydro-thermal：By 20 mL hydrochloric acid, the NaCl solution of 20 mL deionized waters, a concentration of 6.16 mol/L of 3 mL
5 min are mixed, 0.955 mL butyl titanates are added（0.07 mol/L）10 min configuration hydrothermal solutions are stirred, will be coated
TiO2The ceramic membrane of crystal seed is disposed vertically in 50 mL water heating kettles, pours into above-mentioned hydrothermal solution, hydro-thermal is carried out at a temperature of 150 DEG C
20 h are reacted, grow TiO in ceramic membrane surface2Nanometer rods.
10 min are mixed in 20 mL hydrochloric acid and 20 mL deionized waters, acid etch solution are configured, by TiO2Nanometer rods
The ceramic membrane of modification is disposed vertically in 50 mL water heating kettles, pours into above-mentioned acid etch solution, and it is anti-to carry out hydro-thermal at a temperature of 150 DEG C
16 h are answered, by TiO2Nanometer rods are converted to TiO2Nanotube prepares TiO2Nanometer tube modified ceramic membrane.
（2）The preparation of film catalyst
It is silane coupler modified：By 0.05 g N- (β-aminoethyl)-γ-aminopropyltrimethoxysilane（1 g/L）It is dissolved in 50
In mL dichloromethane, it is ultrasonically treated 10 min.By TiO2Nanometer tube modified ceramic membrane is placed in 50 mL beakers, is poured into above-mentioned
Solution is sealed with preservative film, and 8 h are impregnated at 25 DEG C, are then rinsed with deionized water.
Load active component Pd：By 0.56 g（0.05 mol/L）Palladium, 50 mL ethyl alcohol（As solvent and reduction
Agent）, 5.55 g polyvinylpyrrolidones（PVP）It is added in conical flask, 2 h of magnetic agitation, prepares Pd at a temperature of 60 DEG C
Grain colloidal sol.By TiO2Nanometer tube modified ceramic diaphragm is vertically disposed in 50 mL beakers, is then poured into Pd particle colloidal sols, is used
Preservative film wraps, after 12 h are impregnated at a temperature of 40 DEG C taking-up cleaned with ethyl alcohol, finally prepare Pd/TiO2It is nanometer tube modified
Ceramic film catalyst, prepare film catalyst number be B.
Do not use TiO2Film catalyst that is nanometer tube modified, being prepared using the identical raw materials of same film catalyst B and method,
Number is A.
Fig. 2 (b) is Pd/TiO2Nanometer tube modified ceramic membrane catalyst surface SEM figures.Compared to Fig. 2 (a) Pd/ ceramics
Film catalyst, Pd/TiO2Apparent variation occurs for the configuration of surface of nanometer tube modified ceramic film catalyst, illustrates TiO2Nanometer
Pipe is successfully grown on ceramic membrane, TiO2The width of nanotube, wall thickness, length are respectively 500-800nm, 50 nm, 4 μm of left sides
It is right.Pd nano particles are not observed in figure, this is because palladium nano-particles are smaller (4nm or so).
The film catalyst prepared is prepared for being catalyzed reduction p-nitrophenol in para-aminophenol reaction, it is investigated and urges
Change performance, the results are shown in table below.It can be found that the catalytic performance of film catalyst B is substantially better than film catalyst A：For the first time
Reaction, uses the reaction conversion ratio of film catalyst B 28 % higher than film catalyst A；After circular response 5 times, the activity of film catalyst A
Occur being decreased obviously, drops to 37.6% from 45.1%；And the activity of film catalyst B is held essentially constant.Illustrate the present invention's
Method can prepare the film catalyst haveing excellent performance.
2 Pd/TiO of embodiment2Nanometer tube modified ZrO2The preparation of ceramic membrane
（1）TiO2Nanometer tube modified ZrO2The preparation of ceramic membrane
First step hydro-thermal：It measures 27 mL deionized waters and stirs 5 min with 13 mL mixed in hydrochloric acid, 1.228 mL metatitanic acids, four fourth is added
Ester（0.09 mol/L）10 min are stirred, hydrothermal solution is configured；Ceramic membrane (diameter：3.2 cm, material：ZrO2, membrane aperture：50
Nm it) is disposed vertically in 50 mL water heating kettles, pours into hydrothermal solution, 5 h of hydro-thermal reaction is carried out at a temperature of 180 DEG C, in ceramic membrane
Surface grows one layer of TiO2Crystal seed.
Second step hydro-thermal：The NaCl solution of 27 mL deionized waters, 13 mL hydrochloric acid, a concentration of 4 mol/L of 3 mL are mixed
5 min are stirred, 1.228 mL butyl titanates are added（0.09 mol/L）10 min configuration hydrothermal solutions are stirred, TiO will be coated2
The ceramic membrane of crystal seed is disposed vertically in 50 mL water heating kettles, pours into above-mentioned hydrothermal solution, hydro-thermal reaction is carried out at a temperature of 180 DEG C
25 h grow TiO in ceramic membrane surface2Nanometer rods.
27 mL deionized waters and 13 mL mixed in hydrochloric acid are stirred into 10 min, acid etch solution are configured, by TiO2Nanometer rods
The ceramic membrane of modification is disposed vertically in 50 mL water heating kettles, pours into above-mentioned acid etch solution, and it is anti-to carry out hydro-thermal at a temperature of 180 DEG C
20 h are answered, by TiO2Nanometer rods are converted to TiO2Nanotube prepares TiO2Nanometer tube modified ceramic membrane.
（2）The preparation of film catalyst
It is silane coupler modified：By 0.075 g N- (β-aminoethyl)-γ-aminopropyltrimethoxysilane（1.5 g/L）Dissolving
In 50 mL dichloromethane, it is ultrasonically treated 10 min.By TiO2Nanometer tube modified ceramic membrane is placed in 50 mL beakers, is poured into
Above-mentioned solution, is sealed with preservative film, and 10 h are impregnated at 25 DEG C, are then rinsed with deionized water.
Load active component Pd：By 0.784 g（0.07 mol/L）Palladium, 50 mL ethyl alcohol（As solvent and reduction
Agent）, 11.1 g PVP be added in conical flasks, 2 h of magnetic agitation at a temperature of 70 DEG C prepares Pd particle colloidal sols.By TiO2Nanometer
The ceramic diaphragm of pipe modification is vertically disposed in 50 mL beakers, is then poured into Pd particle colloidal sols, is wrapped with preservative film, 60 DEG C
At a temperature of impregnate 24 h after taking-up cleaned with ethyl alcohol, finally prepare Pd/TiO2It is prepared by nanometer tube modified ceramic film catalyst
Good film catalyst number is D.
Do not use TiO2Film catalyst that is nanometer tube modified, being prepared using the identical raw materials of same film catalyst D and method
Number is C.
The film catalyst prepared is prepared for being catalyzed reduction p-nitrophenol in para-aminophenol reaction, it is investigated and urges
Change performance, the results are shown in table below.It can be found that the catalytic performance of film catalyst D is substantially better than film catalyst C：For the first time
Reaction, uses the reaction conversion ratio of film catalyst D 27.9 % higher than film catalyst C；After circular response 5 times, the work of film catalyst C
Being decreased obviously occurs in property, and drops to 22.4% from 31.2%；And the activity of film catalyst D is held essentially constant.Illustrate the present invention
Method can prepare the film catalyst haveing excellent performance.
3 Pd/TiO of embodiment2Nanometer tube modified TiO2The preparation of ceramic membrane
（1）TiO2Nanometer tube modified TiO2The preparation of ceramic membrane
First step hydro-thermal：It measures 13 mL deionized waters and stirs 5 min with 27 mL mixed in hydrochloric acid, 0.409 mL metatitanic acids, four fourth is added
Ester（0.03 mol/L）10 min are stirred, hydrothermal solution is configured；Ceramic membrane (diameter：3.2 cm, material：TiO2, membrane aperture：800
Nm it) is disposed vertically in 50 mL water heating kettles, pours into hydrothermal solution, 1 h of hydro-thermal reaction is carried out at a temperature of 90 DEG C, in ceramic membrane table
Look unfamiliar long one layer of TiO2Crystal seed.
Second step hydro-thermal：The NaCl solution of 13 mL deionized waters, 27 mL hydrochloric acid, a concentration of 2 mol/L of 3 mL are mixed
5 min are stirred, 0.409 mL butyl titanates are added（0.03 mol/L）10 min configuration hydrothermal solutions are stirred, TiO will be coated2
The ceramic membrane of crystal seed is disposed vertically in 50 mL water heating kettles, pours into above-mentioned hydrothermal solution, hydro-thermal reaction is carried out at a temperature of 90 DEG C
10 h grow TiO in ceramic membrane surface2Nanometer rods.
13 mL deionized waters and 27 mL mixed in hydrochloric acid are stirred into 10 min, acid etch solution are configured, by TiO2Nanometer rods
The ceramic membrane of modification is disposed vertically in 50 mL water heating kettles, pours into above-mentioned acid etch solution, and it is anti-to carry out hydro-thermal at a temperature of 90 DEG C
8 h are answered, by TiO2Nanometer rods are converted to TiO2Nanotube prepares TiO2Nanometer tube modified ceramic membrane.
（2）The preparation of film catalyst
It is silane coupler modified：By 0.01 g N- (β-aminoethyl)-γ-aminopropyltrimethoxysilane（0.2 g/L）It is dissolved in
In 50 mL dichloromethane, it is ultrasonically treated 10 min.By TiO2Nanometer tube modified ceramic membrane is placed in 50 mL beakers, is poured into
Solution is stated, is sealed with preservative film, 4 h are impregnated at 25 DEG C, are then rinsed with deionized water.
Load active component Pd：By 0.224 g（0.02 mol/L）Palladium, 50 mL ethyl alcohol（As solvent and reduction
Agent）, 0.555 g PVP be added in conical flask, 2 h of magnetic agitation at a temperature of 40 DEG C prepares Pd particle colloidal sols.By TiO2It receives
The ceramic diaphragm of mitron modification is vertically disposed in 50 mL beakers, is then poured into Pd particle colloidal sols, is wrapped with preservative film, and 30
Taking-up is cleaned with ethyl alcohol after impregnating 6 h at a temperature of DEG C, finally prepares Pd/TiO2Nanometer tube modified ceramic film catalyst, system
The film catalyst number got ready is F.
Do not use TiO2Film catalyst that is nanometer tube modified, being prepared using the identical raw materials of same film catalyst F and method
Number is E.
The film catalyst prepared is prepared for being catalyzed reduction p-nitrophenol in para-aminophenol reaction, it is investigated and urges
Change performance, the results are shown in table below.It can be found that the catalytic performance of film catalyst F is substantially better than film catalyst E：For the first time
Reaction, uses the reaction conversion ratio of film catalyst F 8.9 % higher than film catalyst E；After circular response 5 times, the work of film catalyst E
Being decreased obviously occurs in property, and drops to 25.8% from 32.3%；And the activity of film catalyst F is held essentially constant.Illustrate the present invention
Method can prepare the film catalyst haveing excellent performance.
Claims (9)
1. a kind of preparation method of loaded catalyst for flow type catalysis reaction, which is characterized in that include the following steps：
Step 1：Butyl titanate is dissolved in aqueous hydrochloric acid solution and configures hydrothermal solution, ceramic membrane is then put into water heating kettle
Middle progress first step hydro-thermal reaction introduces one layer of TiO in ceramic membrane surface2Crystal seed；
Step 2：Butyl titanate is dissolved in hydrochloric acid, water, NaCl mixed solutions and configures hydrothermal solution, then by ceramic membrane
It is put into progress second step hydro-thermal reaction in water heating kettle, prepares TiO2The ceramic membrane of nanometer rods modification；
Step 3：By TiO2The ceramic membrane of nanometer rods modification is put into progress acid etch hydro-thermal reaction, TiO in aqueous hydrochloric acid solution2Nanometer
Stick is converted into TiO2Nanotube, to prepare TiO2Nanometer tube modified ceramic membrane；
Step 4：Ceramic membrane after modification is impregnated into the dichloromethane of N- (β-aminoethyl)-γ-aminopropyltrimethoxysilane
In solution, amino-functional group is introduced in ceramic membrane surface；
Step 5：Palladium and polyvinylpyrrolidone are added in absolute ethyl alcohol, heating stirring prepares Pd nano particle colloidal sols；
Step 6：Ceramic membrane after step 4 is modified is immersed in Pd nano particle colloidal sols, load active component Pd, final to make
It is standby go out support type film catalyst.
2. being prepared using a kind of preparation method of loaded catalyst for flow type catalysis reaction described in claim 1
Film catalyst be applied to flow type catalytic film reactor, flow type catalytic film reactor includes storage tank, membrane module and wriggling
Pump；Reaction solution stirs evenly in storage tank, then enters membrane module by peristaltic pump, and reaction solution flows through the Membrane catalysis in membrane module
Agent surface and duct, contact and are reacted with active component, are then return to storage tank, are reacted with circulating pattern.
3. a kind of preparation method of loaded catalyst for flow type catalysis reaction according to claim 1, special
Sign is that the average pore size of the ceramic membrane selective oxidation aluminium film, zirconium oxide film, silicon oxide film or oxidation titanium film, ceramic membrane is 2
Nm ~ 10 μm, ceramic membrane are configured as chip film.
4. a kind of preparation method of loaded catalyst for flow type catalysis reaction according to claim 1, special
Sign is that the molar concentration of the butyl titanate described in step 1 is 0.03~0.09 mol/L, the volume ratio of water and hydrochloric acid
It is 1:2~1:0.5, hydrothermal temperature is 90 ~ 180 DEG C, and the hydro-thermal time is 1 ~ 5 h.
5. a kind of preparation method of loaded catalyst for flow type catalysis reaction according to claim 1, special
Sign is that the molar concentration of the butyl titanate described in step 2 is 0.03~0.09 mol/L, the volume ratio of water and hydrochloric acid
It is 1:2~1:0.5, NaCl a concentration of 2 ~ 6.16 mol/L, hydrothermal temperature are 90 ~ 180 DEG C, and the hydro-thermal time is 10 ~ 25 h.
6. a kind of preparation method of loaded catalyst for flow type catalysis reaction according to claim 1, special
Sign is that the volume ratio of water and hydrochloric acid is 1 in step 3:2~1:0.5, hydrothermal temperature is 90 ~ 180 DEG C, and the hydro-thermal time is 8 ~ 20
h。
7. a kind of preparation method of loaded catalyst for flow type catalysis reaction according to claim 1, special
Sign is, a concentration of 0.2~1.5 g/L of N- (β-aminoethyl)-γ-aminopropyltrimethoxysilane described in step 4,
Dip time is 4 ~ 10 h.
8. a kind of preparation method of loaded catalyst for flow type catalysis reaction according to claim 1, special
Sign is, the collosol concentrations of Pd nano particles described in step 5 are 0.02~0.07 mol/L, polyvinylpyrrolidone and Pd's
Molar ratio is 1~40, and the preparation temperature of colloidal sol is 40 ~ 70 DEG C.
9. a kind of preparation method of loaded catalyst for flow type catalysis reaction according to claim 1, special
Sign is that dipping temperature described in step 6 is 30 ~ 60 DEG C, and the time is 6~24 h.
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| CN109694128A (en) * | 2019-01-14 | 2019-04-30 | 南京工业大学 | Method for treating high-concentration p-nitrophenol |
| CN110841633A (en) * | 2019-11-27 | 2020-02-28 | 南京工业大学 | Preparation method of catalytic membrane |
| CN113926441A (en) * | 2021-10-12 | 2022-01-14 | 北京林业大学 | Si-doped TiO2Nanorod-grafted photocatalytic coupling self-cleaning modified ceramic membrane and preparation method thereof |
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| CN109694128A (en) * | 2019-01-14 | 2019-04-30 | 南京工业大学 | Method for treating high-concentration p-nitrophenol |
| CN109694128B (en) * | 2019-01-14 | 2021-12-28 | 南京工业大学 | Method for treating high-concentration p-nitrophenol |
| 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 |
| CN114713222A (en) * | 2020-12-22 | 2022-07-08 | 中国石油化工股份有限公司 | Embedded zirconia nanotube catalyst and preparation method and application thereof |
| CN114713222B (en) * | 2020-12-22 | 2023-07-28 | 中国石油化工股份有限公司 | Embedded zirconia nanotube catalyst and preparation method and application thereof |
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| CN114011372A (en) * | 2021-11-30 | 2022-02-08 | 齐鲁工业大学 | Bifunctional microstructure palladium-based membrane reactor and preparation method thereof |
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| CN116493050B (en) * | 2023-04-27 | 2024-07-05 | 南京工业大学 | Palladium-based catalytic membrane, preparation method thereof and method for performing suzuki reaction by using palladium-based catalytic membrane |
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Application publication date: 20181113 |