CN107185525A - Octahedra Pt nanometer particle loads γ Al2O3The preparation method of type catalyst - Google Patents
Octahedra Pt nanometer particle loads γ Al2O3The preparation method of type catalyst Download PDFInfo
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- CN107185525A CN107185525A CN201710368014.2A CN201710368014A CN107185525A CN 107185525 A CN107185525 A CN 107185525A CN 201710368014 A CN201710368014 A CN 201710368014A CN 107185525 A CN107185525 A CN 107185525A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 239000002245 particle Substances 0.000 title claims abstract description 23
- 238000001354 calcination Methods 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 10
- 239000013206 MIL-53 Substances 0.000 claims description 107
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 48
- 229910003158 γ-Al2O3 Inorganic materials 0.000 claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 239000000843 powder Substances 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 23
- 239000002243 precursor Substances 0.000 claims description 21
- 239000007787 solid Substances 0.000 claims description 21
- 239000000725 suspension Substances 0.000 claims description 19
- 229910001868 water Inorganic materials 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 238000012545 processing Methods 0.000 claims description 13
- 239000008246 gaseous mixture Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 10
- 239000012298 atmosphere Substances 0.000 claims description 8
- 238000002604 ultrasonography Methods 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229910002621 H2PtCl6 Inorganic materials 0.000 claims description 5
- 229910020427 K2PtCl4 Inorganic materials 0.000 claims description 5
- 229910020437 K2PtCl6 Inorganic materials 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 238000011084 recovery Methods 0.000 claims description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 abstract description 26
- 239000000463 material Substances 0.000 abstract description 16
- 239000012621 metal-organic framework Substances 0.000 abstract description 14
- 239000002105 nanoparticle Substances 0.000 abstract description 13
- 230000003647 oxidation Effects 0.000 abstract description 11
- 238000007254 oxidation reaction Methods 0.000 abstract description 11
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract description 10
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 4
- 150000004706 metal oxides Chemical class 0.000 abstract description 4
- 231100000252 nontoxic Toxicity 0.000 abstract description 4
- 230000003000 nontoxic effect Effects 0.000 abstract description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052593 corundum Inorganic materials 0.000 abstract description 3
- 239000002638 heterogeneous catalyst Substances 0.000 abstract description 3
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 abstract description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract description 3
- 238000006722 reduction reaction Methods 0.000 description 23
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 12
- 230000000694 effects Effects 0.000 description 10
- 238000006555 catalytic reaction Methods 0.000 description 8
- 238000003825 pressing Methods 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 150000001335 aliphatic alkanes Chemical class 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- PDLRAWUYNOBPIS-UHFFFAOYSA-N aniline;nitrobenzene Chemical compound NC1=CC=CC=C1.[O-][N+](=O)C1=CC=CC=C1 PDLRAWUYNOBPIS-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- -1 agriculturals Substances 0.000 description 2
- 238000005485 electric heating Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000008649 adaptation response Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect 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
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/72—Organic compounds not provided for in groups B01D53/48 - B01D53/70, e.g. hydrocarbons
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
-
- B01J35/615—
-
- 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
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
- B01J37/035—Precipitation on carriers
-
- 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
- B01J37/08—Heat treatment
-
- 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
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/01—Engine exhaust gases
- B01D2258/012—Diesel engines and lean burn gasoline engines
Abstract
A kind of octahedra Pt nanometer particle loads γ Al that the present invention is provided2O3Pt presomas, are carried on after MIL 53 (Al) by the preparation method of type catalyst using Double solvent method, by reduction, calcining, you can catalyst Pt/γ Al are made2O3；By MOFs materials both can as metal oxide presoma, γ Al can be can be used as in preparation process as the two features of the carrier of heterogeneous catalyst, MIL 53A (Al) again2O3Presoma, Pt nano-particles are can induce again and regenerate a length of octahedral structure.Pt/ γ Al prepared by the present invention2O3Pt load capacity is the shape of octahedron that 1.7%~10.1%, Pt particle performances are rule in type catalyst, and average-size is about 13nm, and can be uniformly dispersed in carrier γ Al2O3Surface, catalyst surface area is higher, can reach 208.5m2/g.Propylene complete catalysts oxidation can be nontoxic CO within 270 DEG C by the catalyst2And H2O, the catalytic selectivity of p-nitrophenyl reduction aniline reaction processed can reach more than 60% at 100 DEG C.
Description
Technical field
The present invention relates to inorganic nano catalysis material field, and in particular to one kind can be used for the catalysis of hydrocarbon (HC)
Oxidation is eliminated and nitrobenzene is catalyzed the octahedra Pt nanometer particle loads γ-Al of reduction aniline processed2O3The preparation side of type catalyst
Method.
Background technology
Pt nanometer particle load γ-Al2O3Type catalyst (Pt/ γ-Al2O3) at vehicle maintenance service, exhaust gas from diesel vehicle
There is important application in the multiple fields such as reason, hydrocarbon selective hydrogenation.For example in vapour, exhaust gas from diesel vehicle processing, Pt/ γ-Al2O3
It can play a part of eliminating HC catalysis oxidations；In industries such as fuel, medicine, agriculturals, Pt/ γ-Al can be used2O3It is catalyzed nitro
Benzene reduction hydrogenation produces aniline.
The patterns of Pt nano-particles, size and in carrier γ-Al2O3On decentralization be influence catalytic activity and selection
The key factor of property, such as octahedral bodily form Pt nano-particles are considered as having in alkane hydrogenation reaction and VOC complete oxidations
Higher activity.Therefore, in catalyst synthesis processes, pattern, the size of Pt nano-particles how are controlled, and how to be improved
Pt is in carrier γ-Al2O3On decentralization be still current key issue.It is main at present to use microemulsion method and electrochemical deposition
Method etc. synthesizes carried noble metal nanocatalyst, controls the shape of nano-particle using surfactant etc. as template
Looks, size and the decentralization on carrier, but the Pt/ γ-Al prepared using these methods2O3Pt decentralization is not in catalyst
Height, the performance of catalyst is also general, and further relates to the processing of sequent surface activating agent, and cost is higher.
Metal organic framework (MOFs) material is received significant attention because of the particularity of its structure；MOFs materials are matched somebody with somebody by organic
Body and metal " node " composition, are a kind of porous materials of long-range order, are used as carrier and prepare catalyst, but with
MOFs materials are poor as the heat endurance and water stability of the catalyst of carrier, are limited when using more.But MOFs materials
The metal oxide with specific structure can be used to prepare as presoma, is also used as synthesizing monodisperse nanoparticle
" template ", this gives Pt/ γ-Al2O3The preparation of catalyst provides a new approaches.
Therefore, the present invention devises a kind of Pt/ γ-Al2O3The preparation method of catalyst, make use of metal organic framework
(MOFs) material, has prepared the high Pt/ γ-Al of Pt decentralization2O3Catalyst.
The content of the invention
In view of this, the present invention provides a kind of octahedra Pt nanometer particle loads γ-Al2O3The preparation method of type catalyst,
It is medium from the Al base MOFs materials MIL-53 (Al) with " flexibility " one-dimensional pore structure, passes through " solvent pairs " normal direction MIL-53
(Al) introduce to calcine after Pt nano-particles in and Pt/ γ-Al are made2O3Pt has very high scattered in catalyst, obtained catalyst
Degree, catalyst performance is excellent, and hydrocarbon oxidation catalyst can be converted into nontoxic CO2And H2O, for nitrobenzene reduction
During aniline processed, the selectivity of obtained aniline is reached to more than 60%.
The octahedra Pt nanometer particle loads γ-Al that the present invention is provided2O3The preparation method of type catalyst, it is characterised in that：
Pt presomas are carried on after MIL-53 (Al) using Double solvent method, by reduction, calcining, you can obtained catalyst Pt/γ-
Al2O3；
Further, following steps are specifically included：
A, utilize Double solvent method carry out Pt presoma loads：Take after n-hexane and MIL-53 (Al) mixing, through ultrasound, stirring
MIL-53 (Al) suspension is made, Pt precursor water solutions are slowly dropped to MIL-53 (Al) suspension under stirring
In, mixed solution is made, gained mixed solution is persistently stirred after certain time, separation of solid and liquid processing is carried out, by gained solid
It is placed under room temperature condition and is dried in vacuo certain time, produces MIL-53 (Al) powder for having loaded Pt presomas；
It is prepared by b, Pt/MIL-53 (Al)：Gained powder in step a is used into H under the high temperature conditions2/ Ar gaseous mixtures are reduced, i.e.,
Obtain Pt/MIL-53 (Al) mixture；
c、Pt/γ-Al2O3Catalyst preparation：Pt/MIL-53 (Al) mixture of gained in step b is carried out in atmosphere
High-temperature calcination, produces final catalyst Pt/ γ-Al2O3；
Further, in the step c, calcining heat is 600~700 DEG C, and calcination time is 3~6h；
Further, in the step a, the concentration of Pt precursor water solutions is 0.004~0.104mol/L, and in mass ratio
Pt precursor water solutions are added drop-wise in MIL-53 (Al) suspension for 0.5%~2.0%；
Further, it is in mass ratio 66 in the step a:1~176:1 takes n-hexane and MIL-53 (Al)；
Further, in the step a, Pt presoma includes K2PtCl4、K2PtCl6、H2PtCl6In one kind；
Further, in the step b, reduction temperature is 200 DEG C~500 DEG C, and the recovery time is 4~8h, during reduction, H2/
The flow of Ar gaseous mixtures is 50~300mL/min；
Further, in the step b, by H2Volume ratio with Ar is 1/9~1/1 preparation H2/ Ar gaseous mixtures；
Further, the preparation process of the MIL-53 (Al) includes：Take terephthalic acid (TPA), Al (NO3)3·9H2O and go from
After sub- water is mixed, 72~96h of isothermal reaction at a temperature of being placed in 215~225 DEG C, then by after the mixed liquor cooling obtained by reaction
Separation of solid and liquid processing is carried out, 280~300 DEG C of 42~50h of temperature lower calcination is placed in after gained solid is washed, produces MIL-53
(Al) powder；
Further, by weight 0.96~1.15:4.6~5.2:20 take terephthalic acid (TPA), Al (NO3)3·9H2O and go from
Sub- water.
Beneficial effects of the present invention：The present invention by MOFs materials both can as metal oxide presoma, again may be used
Using the two features of the carrier as heterogeneous catalyst, from the Al base MOFs materials MIL-53 with " flexibility " one-dimensional pore structure
(Al) it is medium, Pt/ γ-Al is made by introducing to calcine after Pt nano-particles in " solvent pairs " normal direction MIL-53 (Al)2O3Catalysis
Agent, MIL-53A (Al) can be used as γ-Al in preparation process2O3Presoma, the regeneration of Pt nano-particles is can induce again a length of
Octahedral structure.
Pt/ γ-Al prepared by the present invention2O3Pt load capacity is 1.7%~10.1%, Pt particle performances in type catalyst
For the shape of octahedron of rule, average-size is about 13nm, and can be uniformly dispersed in carrier γ-Al2O3Surface, catalyst
Surface area is higher, can reach 208.5m2/g.Propylene complete catalysts oxidation can be nontoxic within 270 DEG C by the catalyst
CO2And H2O, the catalytic selectivity of p-nitrophenyl reduction aniline reaction processed can reach more than 60% at 100 DEG C.Therefore, this is urged
Agent has good application prospect during catalytic removal hydrocarbon (HC) and catalysis reduction nitrobenzene aniline etc..
Brief description of the drawings
The invention will be further described with reference to the accompanying drawings and examples：
Fig. 1 is obtained catalyst Pt/γ-Al2O3X-ray diffraction (XRD) spectrogram, wherein curve A, B, C, D difference
Correspondence comparative example, embodiment 1, embodiment 2, the sample of embodiment 3；
Fig. 2 is obtained catalyst Pt/γ-Al2O3It is catalyzed the activity curve of propylene complete oxidation, wherein curve A, B, C, D
Embodiment 1, embodiment 2, embodiment 3, the sample of comparative example are corresponded to respectively；
Fig. 3 is obtained catalyst Pt/γ-Al2O3The activity curve of catalysis nitrobenzene reduction aniline, wherein curve A,
B, C, D correspond to embodiment 1, embodiment 2, embodiment 3, the sample of comparative example respectively；
Fig. 4 is the transmission electron microscope photo of comparative example；
Fig. 5 is the transmission electron microscope photo of the sample of embodiment 1.
Embodiment
The octahedra Pt nanometer particle loads γ-Al of the present embodiment2O3The preparation method of type catalyst, it is characterised in that：Profit
Pt presomas are carried on after MIL-53 (Al) with Double solvent method, by reduction, calcining, you can obtained catalyst Pt/γ-
Al2O3；By MOFs materials both can as metal oxide presoma, again can as heterogeneous catalyst carrier this two
Individual feature, is medium from the Al base MOFs materials MIL-53 (Al) with " flexibility " one-dimensional pore structure, passes through " solvent pairs " method
Introduce to calcine after Pt nano-particles into MIL-53 (Al) and Pt/ γ-Al are made2O3Catalyst；MIL-53 (Al) is in catalyst preparation
During can not only be used for γ-Al2O3Presoma, Pt nano-particles are can induce again and regenerate a length of octahedral structure, the Pt/ of preparation
γ-Al2O3Pt load capacity is the shape of octahedron that 1.7%~10.1%, Pt particle performances are rule in type catalyst, average
Size is about 13nm, and can be uniformly dispersed in carrier γ-Al2O3Surface, catalyst surface area is higher, can reach
208.5m2/g.Propylene complete catalysts oxidation can be nontoxic CO within 270 DEG C by the catalyst2And H2O, at 100 DEG C
The catalytic selectivity that lower p-nitrophenyl reduces aniline reaction processed can reach more than 60%.Therefore, the catalyst is in catalytic removal carbon
There is good application prospect during hydrogen compound (HC) and catalysis reduction nitrobenzene aniline etc..
In the present embodiment, following steps are specifically included：
A, utilize Double solvent method carry out Pt presoma loads：Take after n-hexane and MIL-53 (Al) mixing, through ultrasound, stirring
MIL-53 (Al) suspension is made, mixing time is 2~4h, and Pt precursor water solutions are slowly dropped under stirring
In MIL-53 (Al) suspension, mixed solution is made, gained mixed solution is persistently stirred after certain time, preferably last for stirring
2~4h, carries out separation of solid and liquid processing, gained solid is placed under room temperature condition and is dried in vacuo certain time, is preferably dried in vacuo
12~24h, produces MIL-53 (Al) powder for having loaded Pt presomas；
It is prepared by b, Pt/MIL-53 (Al)：Gained powder in step a is used into H under the high temperature conditions2/ Ar gaseous mixtures are reduced, i.e.,
Obtain Pt/MIL-53 (Al) mixture；
c、Pt/γ-Al2O3Catalyst preparation：Pt/MIL-53 (Al) mixture of gained in step b is carried out in atmosphere
High-temperature calcination, produces final catalyst Pt/ γ-Al2O3；This method this method condition is easily controlled, and catalyst preparation has good
Reappearance.
In the present embodiment, in the step c, calcining heat is 600~700 DEG C, preferably 650 DEG C；Calcination time be 3~
6h, preferably 4h；This calcination condition is selected to be conducive to obtaining function admirable, the catalyst Pt that Pt can be dispersed/γ-Al2O3,
Temperature is too high or overlong time can influence the performance of catalyst, and temperature is too low or time too short then possible calcining is incomplete, shadow
Ring the yield of catalyst and the performance of catalyst.
In the present embodiment, in the step a, the concentration of Pt precursor water solutions is 0.004~0.104mol/L, preferably dense
Spend for 0.008~0.052mol/L, and Pt precursor water solutions are added drop-wise to MIL-53 for 0.5%~2.0% in mass ratio
(Al) in suspension, preferred mass compares 1.0%；Here the preparation of Pt precursor water solutions is specifically to take Pt's by setting concentration
Presoma is dissolved in deionized water, is made after stirring；The Pt precursor water solutions of this concentration, it is possible to achieve Pt nanometers
Particle it is dispersed, it is too high to easily cause scattered inequality, it is too low, influence catalyst activity, finally influence properties of product.
It is in mass ratio 66 in the step a in the present embodiment:1~176:1 takes n-hexane and MIL-53 (Al)；This
Proportioning can prepare the Al base MOFs materials MIL-53 (Al) of " flexibility " one-dimensional pore structure of excellent performance.
In the present embodiment, in the step a, Pt presoma includes K2PtCl4、K2PtCl6、H2PtCl6In one kind, this
A little Pt presomas are easily loaded in MIL-53 (Al) material, and are subsequently easily reduced into Pt/MIL-53 (Al) mixture.
In the present embodiment, in the step b, reduction temperature is 200 DEG C~500 DEG C, preferably 250~300 DEG C, recovery time
For 4~8h, preferably 5~6h；During reduction, H2The flow of/Ar gaseous mixtures is 50~300mL/min；Reduction reaction is set to occur more
Plus fully.
In the present embodiment, in the step b, by H2Volume ratio with Ar is 1/9~1/1 preparation H2/ Ar gaseous mixtures；Ensure
There is enough hydrogen to be used for occurring reduction reaction.
In the present embodiment, the preparation process of the MIL-53 (Al) includes：Take terephthalic acid (TPA), Al (NO3)3·9H2O and
After deionized water is mixed, 72~96h of isothermal reaction at a temperature of being placed in 215~225 DEG C is permanent at a temperature of being preferably disposed in 220 DEG C
Temperature reaction 72h, then separation of solid and liquid processing will be carried out after the mixed liquor cooling obtained by reaction, gained solid is washed with deionized
After be placed in 280~300 DEG C of 42~50h of temperature lower calcination, be preferably disposed in 300 DEG C of temperature lower calcination 48h, produce MIL-53 (Al) powder
End；Preparation method is simple, and obtained MIL-53 (Al) material structure function admirable, same excellent available for processability
Pt/γ-Al2O3Catalyst.
In the present embodiment, by weight 0.96~1.15:4.6~5.2:20 take terephthalic acid (TPA), Al (NO3)3·9H2O and
Deionized water；It is preferred that by weight 1.15:5.2:20, MIL-53 (Al) material structure performance is excellent made from this conditions of mixture ratios
It is good.
In the present embodiment, selection tube furnace, which is used to reduce, prepares Pt/MIL-53 (Al), and selection Muffle furnace is used for Pt/MIL-
53 (Al) calcinings prepare Pt/ γ-Al2O3Catalyst, the heating rate of Muffle furnace is 2 DEG C~10 DEG C/min.
In the present embodiment, Pt load capacity (mass fraction) control is 0.3%~2% in the Pt/MIL-53 mixtures,
It is preferred that 0.5%~1.5%；The final catalyst Pt/ γ-Al2O3Middle Pt load capacity (mass fraction) be 1.7%~
10.1%；Pt decentralization is improved, makes it scattered evenly.
In the present embodiment, device therefor is laboratory common equipment.
Pt/ γ-Al manufactured in the present embodiment2O3Catalyst is primarily useful for the complete catalysts oxidation of hydrocarbon and urged
Change reduction nitrobenzene aniline；
(1) application in the reaction of propylene complete catalysts oxidation：When density of propylene is 1%, air speed is 30000h-1When, can
Propylene is fully converted to CO at 270 DEG C2And H2O。
(2) application in nitrobenzene reduction aniline reaction：By nitrobenzene/He gaseous mixtures that concentration is 0.3%, use
3% hydrogen reduces 10min at 100 DEG C, and the selectivity of aniline is reached to more than 60%.
It is specific embodiment below：
Embodiment 1
(1) prepared by MIL-53 (Al)：Take terephthalic acid (TPA) (1.15g, 6.94mmol), Al (NO3)3·9H2O(5.2g,
13.86mmol) it is mixed into 100mL with deionized water (20mL, 1.11mol) and presses certainly in kettle in cup, ultrasonic vibration is put after 10 minutes
Enter stainless steel from pressing in kettle and screwing, reacted 72 hours in 220 DEG C of electrocaloric effects, the white powder of acquisition is the MIL-53 of moistening
(Al) sample；Calcined 48 hours in 300 DEG C of Muffle furnaces after moistening sample is washed with deionized, obtain dry MIL-53
(Al) powder；
(2) Pt presoma loads are carried out using Double solvent method：Take 0.3g dry MIL-53 (Al) be added to 60mL just oneself
In alkane, quick stirring 2 hours, is made MIL-53 (Al) suspension after several minutes of ultrasound；By K2PtCl4It is dissolved in deionized water and makes
The Pt precursor solutions that standby concentration is 0.013mol/L；0.6mLPt precursor solutions are slowly dropped under stirring
In MIL-53 (Al) suspension, continue after stirring 2 hours, carry out separation of solid and liquid processing, gained solid is placed under room temperature condition
24h is dried in vacuo, MIL-53 (Al) powder for having loaded Pt presomas is produced；
(3) prepared by Pt/MIL-53 (Al)：By obtained MIL-53 (Al) powder for having loaded Pt presomas in step (2),
The H in 200 DEG C of tube furnaces2Reduction obtains Pt/MIL-53 in 5 hours under/Ar (volume ratio is 1/9, and flow is 200mL/min) atmosphere
(Al) mixture；
(4)Pt/γ-Al2O3Catalyst preparation：Obtained Muffle furnaces of the Pt/MIL-53 (Al) at 600 DEG C in step (3)
In, calcine 3 hours, obtain target Pt/ γ-Al2O3Catalyst；Muffle furnace heating rate is 2 DEG C/min.
Embodiment 2
(1) prepared by MIL-53 (Al)：Take terephthalic acid (TPA) (1.15g, 6.94mmol), Al (NO3)3·9H2O(5.2g,
13.86mmol) it is mixed into 100mL with deionized water (20mL, 1.11mol) and presses certainly in kettle in cup, ultrasonic vibration is put after 10 minutes
Enter stainless steel from pressing in kettle and screwing, reacted 72 hours in 220 DEG C of electrocaloric effects, obtain MIL-53 of the white powder for moistening
(Al) sample；After moistening sample is washed with deionized, is calcined 48 hours in 300 DEG C of Muffle furnaces, obtain dry MIL-
53 (Al) powder；
(2) Pt presoma loads are carried out using Double solvent method：Take 0.3g dry MIL-53 (Al) be added to 60mL just oneself
In alkane, quick stirring 2 hours, is made MIL-53 (Al) suspension after several minutes of ultrasound；By K2PtCl4It is dissolved in deionized water and makes
The Pt precursor solutions that standby concentration is 0.026mol/L；0.6mLPt precursor solutions are slowly dropped under stirring
In MIL-53 (Al) suspension, continue after stirring 2 hours, carry out separation of solid and liquid processing, gained solid is placed under room temperature condition
12h is dried in vacuo, MIL-53 (Al) powder for having loaded Pt presomas is produced；
(3) prepared by Pt/MIL-53 (Al)：By obtained MIL-53 (Al) powder for having loaded Pt presomas in step (2),
The H in 200 DEG C of tube furnaces2Reduction obtains Pt/MIL- in 6 hours under/Ar (volume ratio is 1/9, flow is 300mL/min) atmosphere
53 (Al) mixtures；
(4)Pt/γ-Al2O3Catalyst preparation：Obtained Pt/MIL-53 (Al) is in 650 DEG C of Muffle furnace in step (3)
Calcining 4 hours, obtains target Pt/ γ-Al2O3Catalyst；Muffle furnace heating rate is 5 DEG C/min.
Embodiment 3
(1) prepared by MIL-53 (Al)：Take terephthalic acid (TPA) (1.15g, 6.94mmol), Al (NO3)3·9H2O(5.2g,
13.86mmol) it is mixed into 100mL with deionized water (20mL, 1.11mol) and presses certainly in kettle in cup, ultrasonic vibration is put after 10 minutes
Enter stainless steel from pressing in kettle and screwing, reacted 72 hours in 220 DEG C of electrocaloric effects, obtain MIL-53 of the white powder for moistening
(Al) sample；Calcined 48 hours in 300 DEG C of Muffle furnaces after moistening sample is washed with deionized, obtain dry MIL-53
(Al) powder；
(2) Pt presoma loads are carried out using Double solvent method：Take 0.3g dry MIL-53 (Al) be added to 80mL just oneself
In alkane, quick stirring 2 hours, is made MIL-53 (Al) suspension after several minutes of ultrasound；By H2PtCl6It is dissolved in deionized water and makes
The Pt precursor solutions that standby concentration is 0.026mol/L；1.2mLPt precursor solutions are slowly dropped under stirring
In MIL-53 (Al) suspension, continue after stirring 2 hours, carry out separation of solid and liquid processing, gained solid is placed under room temperature condition
24h is dried in vacuo, MIL-53 (Al) powder for having loaded Pt presomas is produced；
(3) prepared by Pt/MIL-53 (Al)：By obtained MIL-53 (Al) powder for having loaded Pt presomas in step (2),
The H in 300 DEG C of tube furnaces2Reduction obtains Pt/MIL-53 in 4 hours under/Ar (volume ratio is 1/9, and flow is 50mL/min) atmosphere
(Al) mixture；
(4)Pt/γ-Al2O3Catalyst preparation：Obtained Pt/MIL-53 (Al) is in 600 DEG C of Muffle furnace in step (3)
Calcining 4 hours, obtains target Pt/ γ-Al2O3Catalyst；Muffle furnace heating rate is 5 DEG C/min.
Embodiment 4
(1) prepared by MIL-53 (Al)：Take terephthalic acid (TPA) 0.96g, Al (NO3)3·9H2O 4.6g and deionized water 20mL
100mL is mixed into from pressing in kettle in cup, ultrasonic vibration inserts stainless steel from pressing in kettle and screwing, in 215 DEG C of electric heating after 10 minutes
Reacted 96 hours in case, obtain MIL-53 (Al) sample of white powder for moistening；After moistening sample is washed with deionized
Calcined 50 hours in 280 DEG C of Muffle furnaces, obtain dry MIL-53 (Al) powder；
(2) Pt presoma loads are carried out using Double solvent method：Take 0.45g dry MIL-53 (Al) be added to 80mL just oneself
In alkane, quick stirring 4 hours, is made MIL-53 (Al) suspension after several minutes of ultrasound；By K2PtCl6It is dissolved in deionized water and makes
The Pt precursor solutions that standby concentration is 0.104mol/L；0.4mLPt precursor solutions are slowly dropped under stirring
In MIL-53 (Al) suspension, continue after stirring 4 hours, carry out separation of solid and liquid processing, gained solid is placed under room temperature condition
24h is dried in vacuo, MIL-53 (Al) powder for having loaded Pt presomas is produced；
(3) prepared by Pt/MIL-53 (Al)：By obtained MIL-53 (Al) powder for having loaded Pt presomas in step (2),
The H in 500 DEG C of tube furnaces2Reduction obtains Pt/MIL-53 in 8 hours under/Ar (volume ratio is 1/1, and flow is 100mL/min) atmosphere
(Al) mixture；
(4)Pt/γ-Al2O3Catalyst preparation：Obtained Pt/MIL-53 (Al) is in 700 DEG C of Muffle furnace in step (3)
Calcining 6 hours, obtains target Pt/ γ-Al2O3Catalyst；Muffle furnace heating rate is 5 DEG C/min.
Embodiment 5
(1) prepared by MIL-53 (Al)：Take terephthalic acid (TPA) 0.96g, Al (NO3)3·9H2O 4.6g and deionized water 20mL
100mL is mixed into from pressing in kettle in cup, ultrasonic vibration inserts stainless steel from pressing in kettle and screwing, in 225 DEG C of electric heating after 10 minutes
Reacted 84 hours in case, obtain MIL-53 (Al) sample of white powder for moistening；After moistening sample is washed with deionized
Calcined 42 hours in 300 DEG C of Muffle furnaces, obtain dry MIL-53 (Al) powder；
(2) Pt presoma loads are carried out using Double solvent method：Take 0.55g dry MIL-53 (Al) be added to 60mL just oneself
In alkane, quick stirring 4 hours, is made MIL-53 (Al) suspension after several minutes of ultrasound；By H2PtCl6It is dissolved in deionized water and makes
The Pt precursor solutions that standby concentration is 0.004mol/L；1.2mLPt precursor solutions are slowly dropped under stirring
In MIL-53 (Al) suspension, continue after stirring 4 hours, carry out separation of solid and liquid processing, gained solid is placed under room temperature condition
24h is dried in vacuo, MIL-53 (Al) powder for having loaded Pt presomas is produced；
(3) prepared by Pt/MIL-53 (Al)：By obtained MIL-53 (Al) powder for having loaded Pt presomas in step (2),
The H in 200 DEG C of tube furnaces2Reduction obtains Pt/MIL-53 in 8 hours under/Ar (volume ratio is 1/5, and flow is 50mL/min) atmosphere
(Al) mixture；
(4)Pt/γ-Al2O3Catalyst preparation：Obtained Pt/MIL-53 (Al) is in 600 DEG C of Muffle furnace in step (3)
Calcining 4 hours, obtains target Pt/ γ-Al2O3Catalyst；Muffle furnace heating rate is 5 DEG C/min.
Comparative example：
(1) prepared by MIL-53 (Al)：Take terephthalic acid (TPA) (1.15g, 6.94mmol), Al (NO3)3·9H2O(5.2g,
13.86mmol) it is mixed into 100mL with deionized water (20mL, 1.11mol) and presses certainly in kettle in cup, ultrasonic vibration is put after 10 minutes
Enter stainless steel from pressing in kettle and screwing, reacted 72 hours in 220 DEG C of electrocaloric effects, obtain MIL-53 of the white powder for moistening
(Al) sample；Calcined 48 hours in 300 DEG C of Muffle furnaces after moistening sample is washed with deionized, obtain dry MIL-53
(Al) powder；
(2) prepared by comparative sample：The MIL-53 (Al) that 0.3g is dried is calcined 4 hours in 600 DEG C of Muffle furnaces, is obtained not
γ-the Al of supporting Pt nano-particle2O3It is as a comparison sample.
Test preparing gained sample, test case is as follows：
1st, respectively to example 1 sample, the sample of example 2, the sample of example 3 and comparative example carries out X-ray diffraction
Experiment, as a result as shown in Figure 1.
As seen from the figure, comparative example shows γ-Al2O3Phase diffraction maximum；Sample, the sample of example 2, the example of example 1
3 sample shows Pt diffraction maximum.
2nd, respectively to embodiment 1 sample, the sample of example 2, the sample of example 3, the sample of comparative example has carried out propylene
The activity rating of catalysis oxidation.
Catalyst amount is 30mg, and tabletting sieving (40~60 mesh) mixes the loading quartz reactions of φ 6 with 270mg quartz sands afterwards
Pipe.Unstripped gas composition is propylene (1%), O2 (10%), N2 (3%), He balance, and reaction velocity is 30000h-1.With 20 DEG C/h's
Reactor is risen to 400 DEG C by speed from room temperature, is passed through using gas-chromatography (Shimadzu GC 2014) on-line checking gaseous mixture
The CO produced after beds2Concentration.
Test result is as shown in Fig. 2 curve A, B, C correspond to sample, the sample of example 2, the example of embodiment 1 respectively in figure
The catalytic activity of 3 sample.From result, propylene can be fully converted to CO by gained catalyst within 270 DEG C2And H2O。
3rd, in gas phase fixed bed reactors respectively to embodiment 1 sample, the sample of embodiment 2, the sample of embodiment 3
Product, the sample of comparative example be catalyzed the activity rating of nitrobenzene reduction aniline.
Catalyst amount is 5mg, and powder catalyst loads the adaptive response that internal diameter is 1cm after being mixed with 1g quartz sands
Pipe.Gas phase nitrobenzene is provided using He at 70 DEG C by the method for liquid nitrobenzene.Unstripped gas composition is nitrobenzene
(0.3%), H2 (3%), He (96.7%), unstripped gas total flow are 100mL/min.With 20 DEG C/h speed by reactor from room
Temperature rise is to 200 DEG C, using gas-chromatography (Shimadzu GC 2014) on-line checking gaseous mixture by being produced after beds
Concentration of aniline.
Test result is as shown in figure 3, curve A, B, C, D correspond to sample, the sample of embodiment 2 of embodiment 1 respectively in figure
With the catalytic activity of the sample of embodiment 3.From result, better catalytic activity of the gained catalyst at 100 DEG C, aniline
Highest selectively about 61%.
4th, to embodiment 1 sample and comparative example carries out transmission electron microscope (TEM) test, gained TEM photos
As shown in Figure 4, Figure 5, wherein Fig. 4 is the TEM pictures that TEM pictures, Fig. 5 of comparative example are the sample of embodiment 1.From Fig. 4
In can be seen that gained Pt nano-particles are in octahedral body structure, particle size is about 13nm.
Finally illustrate, the above embodiments are merely illustrative of the technical solutions of the present invention and it is unrestricted, although with reference to compared with
The present invention is described in detail good embodiment, it will be understood by those within the art that, can be to skill of the invention
Art scheme is modified or equivalent substitution, and without departing from the objective and scope of technical solution of the present invention, it all should cover at this
Among the right of invention.
Claims (10)
1. a kind of octahedra Pt nanometer particle loads γ-Al2O3The preparation method of type catalyst, it is characterised in that：Utilize solvent pairs
Pt presomas are carried on after MIL-53 (Al) by method, by reduction, calcining, you can catalyst Pt/γ-Al are made2O3。
2. octahedra Pt nanometer particle loads γ-Al according to claim 12O3The preparation method of type catalyst, its feature
It is：Specifically include following steps：
A, utilize Double solvent method carry out Pt presoma loads：Take after n-hexane and MIL-53 (Al) mixing, be made through ultrasound, stirring
MIL-53 (Al) suspension, Pt precursor water solutions are slowly dropped under stirring in MIL-53 (Al) suspension, system
Mixed solution is obtained, gained mixed solution is persistently stirred after certain time, separation of solid and liquid processing is carried out, gained solid is placed in room
Certain time is dried in vacuo under the conditions of temperature, MIL-53 (Al) powder for having loaded Pt presomas is produced；
It is prepared by b, Pt/MIL-53 (Al)：Gained powder in step a is used into H under the high temperature conditions2/ Ar gaseous mixtures are reduced, and produce Pt/
MIL-53 (Al) mixture；
c、Pt/γ-Al2O3Catalyst preparation：Pt/MIL-53 (Al) mixture of gained in step b is subjected to high temperature in atmosphere
Calcining, produces final catalyst Pt/ γ-Al2O3。
3. octahedra Pt nanometer particle loads γ-Al according to claim 22O3The preparation method of type catalyst, its feature
It is：In the step c, calcining heat is 600~700 DEG C, and calcination time is 3~6h.
4. octahedra Pt nanometer particle loads γ-Al according to claim 22O3The preparation method of type catalyst, its feature
It is：In the step a, the concentration of Pt precursor water solutions is 0.004~0.104mol/L, and in mass ratio for 0.5%~
2.0% is added drop-wise to Pt precursor water solutions in MIL-53 (Al) suspension.
5. octahedra Pt nanometer particle loads γ-Al according to claim 22O3The preparation method of type catalyst, its feature
It is：It is in mass ratio 66 in the step a:1~176:1 takes n-hexane and MIL-53 (Al).
6. octahedra Pt nanometer particle loads γ-Al according to claim 22O3The preparation method of type catalyst, its feature
It is：In the step a, Pt presoma includes K2PtCl4、K2PtCl6、H2PtCl6In one kind.
7. octahedra Pt nanometer particle loads γ-Al according to claim 22O3The preparation method of type catalyst, its feature
It is：In the step b, reduction temperature is 200 DEG C~500 DEG C, and the recovery time is 4~8h, during reduction, H2/ Ar gaseous mixtures
Flow is 50~300mL/min.
8. octahedra Pt nanometer particle loads γ-Al according to claim 22O3The preparation method of type catalyst, its feature
It is：In the step b, by H2Volume ratio with Ar is 1/9~1/1 preparation H2/ Ar gaseous mixtures.
9. octahedra Pt nanometer particle loads γ-Al according to claim 12O3The preparation method of type catalyst, its feature
It is：The preparation process of the MIL-53 (Al) includes：Take terephthalic acid (TPA), Al (NO3)3·9H2O and deionized water mixing are stirred
After mixing, 72~96h of isothermal reaction at a temperature of being placed in 215~225 DEG C, then solid-liquid point will be carried out after the mixed liquor cooling obtained by reaction
From processing, 280~300 DEG C of 42~50h of temperature lower calcination are placed in after gained solid is washed, MIL-53 (Al) powder is produced.
10. octahedra Pt nanometer particle loads γ-Al according to claim 72O3The preparation method of type catalyst, it is special
Levy and be：By weight 0.96~1.15:4.6~5.2:20 take terephthalic acid (TPA), Al (NO3)3·9H2O and deionized water.
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