CN106040302A - Hydrogenation catalyst - Google Patents
Hydrogenation catalyst Download PDFInfo
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- CN106040302A CN106040302A CN201610465897.4A CN201610465897A CN106040302A CN 106040302 A CN106040302 A CN 106040302A CN 201610465897 A CN201610465897 A CN 201610465897A CN 106040302 A CN106040302 A CN 106040302A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 37
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 19
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 86
- 239000002105 nanoparticle Substances 0.000 claims abstract description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 30
- 239000000243 solution Substances 0.000 claims abstract description 25
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 15
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 15
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 15
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 11
- 239000011591 potassium Substances 0.000 claims abstract description 11
- 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 10
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 30
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000007864 aqueous solution Substances 0.000 claims description 16
- 238000006722 reduction reaction Methods 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 229910052763 palladium Inorganic materials 0.000 claims description 12
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 10
- -1 polyethylene pyrrole Pyrrolidone Polymers 0.000 claims description 9
- 238000011084 recovery Methods 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000013153 zeolitic imidazolate framework Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 4
- 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 claims description 2
- 238000000643 oven drying Methods 0.000 claims description 2
- 230000004044 response Effects 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 239000011259 mixed solution Substances 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 239000002245 particle Substances 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 239000013078 crystal Substances 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 229910021536 Zeolite Inorganic materials 0.000 abstract 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 abstract 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 abstract 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 abstract 1
- 239000010457 zeolite Substances 0.000 abstract 1
- 230000009467 reduction Effects 0.000 description 13
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 8
- AOGKEHFITGSWOS-UHFFFAOYSA-N dichloromethane pyrrolidin-2-one Chemical compound ClCCl.O=C1CCCN1 AOGKEHFITGSWOS-UHFFFAOYSA-N 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000002082 metal nanoparticle Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 3
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000002242 deionisation method Methods 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 241000226585 Antennaria plantaginifolia Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 240000000136 Scabiosa atropurpurea Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001629 suppression 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
-
- B01J35/393—
-
- B01J35/396—
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
- B01J2531/0216—Bi- or polynuclear complexes, i.e. comprising two or more metal coordination centres, without metal-metal bonds, e.g. Cp(Lx)Zr-imidazole-Zr(Lx)Cp
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/26—Zinc
Abstract
The invention relates to a hydrogenation catalyst with Pd nano particles dispersed in a frame of a zeolite imidazate framework material ZIF-L and belongs to the technical field of catalysis. The catalyst Pd@ZIF-L is a supported metal catalyst. The hydrogenation catalyst is prepared through the following steps of reducing a mixed solution of palladium acetate and polyvinylpyrrolidone by use of a mixed reducing solution of hydrazine hydrate, potassium borohydride and sodium hydroxide, thereby obtaining Pd nano particles wrapped with polyvinylpyrrolidone; adding the Pd nano particles during a ZIF-L crystal formation process, thereby obtaining a cross-shaped Pd@ZIF-L catalyst with size grade level tens of microns. The hydrogenation catalyst has the advantages that the Pd nano particles can be uniformly and stably packed in the ZIF-L frame, so that the catalytic activity and stability of the catalyst are enhanced; the Pd@ZIF-L catalyst is relatively large in particle diameter and can be easily separated from a product; the catalyst is simple and easily controllable in preparation process and excellent in performance and can be widely applied to catalytic hydrogenation reaction.
Description
Technical field
The present invention relates to a kind of loaded catalyst, particularly for the catalyst of hydrogenation reaction, belong to catalysis technique
Field.
Background technology
Metal nanoparticle has higher surface activity and big specific surface area, is widely used as catalyst.But metal
Nano-particle belongs to metastable material, especially sensitive to surrounding, although using stabilizer, still there will be clustering phenomena, making
Catalysis activity substantially reduces.Therefore, in order to ensure the stability of nano-particle and obtain higher metal dispersity, often by nanometer
Particulate load, on the carrier with high-specific surface area, utilizes the interaction between metal and carrier or space to limit, makes grain
It is spaced from each other to stop their migration and gathering between son.
Zeolitic imidazolate framework material (ZIF) is class particulate metal organic backbone with imidazoles or derivatives thereof as part
Structural material, has bigger specific surface area, homogeneous adjustable duct and the stability of excellence, can as the carrier of catalyst,
Its pore structure can be with provider's environment, in order to wrap up or to load metal nanoparticle, suppression metal nanoparticle reunion or
Run off, improve its catalytic performance.
Selecting suitable ZIF material is a very important link as carrier package metals nano-particle.Because choosing
Select the catalytic performance of the ZIF material meeting appreciable impact prepared catalyst of different physical-chemical performances (such as pore structure)
(CN103394373A).ZIF-L is a kind of novel zeolitic imidazolate framework material, for foliaceous layer structure, has uniqueness
Pincushion cavity, its two adjacent unit by hydrogen bond be connected, parallel units spacing is 3.97, and pincushion cavity is 6.64
Å.The pore structure of this uniqueness makes the ZIF-L can be as the carrier of catalyst.
The present invention prepares Pd@ZIF-L catalyst with ZIF-L for carrier, and detailed process is in process crystal formation for ZIF-L
The Pd nano-particle of middle addition polyvinylpyrrolidone parcel, Pd nano-particle adsorbs the ZIF-L plane of crystal in constantly growth,
Thus prepare Pd@ZIF-L catalyst.In Pd@ZIF-L catalyst, Pd nano-particle is encapsulated in ZIF-L framework completely, makes
Pd@ZIF-L shows the catalytic performance of excellence；The particle diameter of Pd@ZIF-L catalyst is bigger, it is easy to separate from product.
Summary of the invention
It is an object of the invention to ZIF-L as carrier, Pd nano-particle is uniformly encapsulated in ZIF-L framework, preparation height
The hydrogenation catalyst of performance.
The technical scheme is that
A kind of hydrogenation catalyst, Pd@ZIF-L, its concrete preparation process is:
Step one: a certain amount of polyvinylpyrrolidone dichloromethane solution is added in palladium dichloromethane solution, then by
Be added dropwise to hydrazine hydrate, potassium borohydride, sodium hydroxide mixed aqueous solution carry out reduction reaction, control palladium concentration, polyethylene pyrrole
Pyrrolidone concentration, reducing solution concentration, recovery time, prepare the Pd nano-particle of polyvinylpyrrolidone parcel；
Step 2: the Pd nano-particle described in a certain amount of step one, 2-methylimidazole aqueous solution, zinc nitrate aqueous solution are mixed
Close, react a period of time at a certain temperature；
Step 3: the sample obtained in step 2, by deionized water rinse, is finally placed in baking oven drying.
In step one, palladium concentration is 0.02 mol/L, and Pd is 1:10～1 with the mol ratio of polyvinylpyrrolidone:
60, hydrazine hydrate, potassium borohydride, the mol ratio of sodium hydroxide are 3:20:1, and reducing solution concentration is 5～20 mmol/L, during reduction
Between be 2～6 h.
In step 2, Pd concentrations of nanoparticles is 5 mmol/L, and zinc nitrate aqueous solution concentration is 2.5 mmol/L, zinc nitrate
Being 1:8～1:25 with the mol ratio of 2-methylimidazole, reaction temperature is 0～30 DEG C, and the response time is 6～48 h.
In step 3, deionized water rinse number of times is 2～5 times, and drying temperature is 80～150 DEG C, and drying time is 8 ~ 24
h。
The present invention uses paranitrophenol Hydrogenation to be that model reaction studies urging of made Pd ZIF-L for para-aminophenol
Changing performance, detailed process is as follows.
Reaction is carried out in the centrifuge tube of 50 ml.By 0.10 g paranitrophenol, 10 ml deionized waters, 10 ml second
Alcohol, 0.03 g Pd@ZIF-L catalyst, 2.648 g sodium borohydrides are sequentially added in centrifuge tube.Reaction is maintained with water bath with thermostatic control
Temperature is 30 DEG C, and reaction carries out stopped reaction after 90 min.Negate and use efficient liquid phase chromatographic analysis after answering product dilution, according to
Standard curve calculates feed stock conversion and selectivity of product.
Beneficial effects of the present invention:
(1) Pd nano-particle is encapsulated in ZIF-L framework equably, adds catalysis activity and the stability of catalyst；
(2) particle diameter of Pd@ZIF-L catalyst is bigger, it is easy to separate from product.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of the Pd@ZIF-L of embodiment 1 preparation.
Fig. 2 is the transmission electron microscope picture of the Pd@ZIF-L of embodiment 1 preparation.
Detailed description of the invention
Illustrate preparation and the using effect of Pd@ZIF-L below by embodiment, the following example is merely to illustrate this
Invention, but it is not used to limit the practical range of the present invention.
Embodiment 1
First prepare the palladium dichloromethane solution of 25 ml 0.02 mol/L, and add the 15 ml 6.67 poly-second of mol/L
Alkene pyrrolidone dichloromethane solution (mol ratio of Pd/ polyvinylpyrrolidone is 1:20).Use 11 mL 10 mmol/L
Hydrazine hydrate, potassium borohydride, sodium hydroxide mixed solution (three's mol ratio is 3:20:1) Dichlorodiphenyl Acetate palladium reduce, reduction
Temperature is room temperature, and the recovery time is 4 h.Reduction takes the Pd nano-particle colloidal sol on upper strata after terminating, and be scattered in 100 ml go from
In sub-water.
By 10 ml 5 mmol/L Pd nano-particle colloidal sols, 100 ml 50 mmol/L 2-methylimidazole aqueous solutions, 100
The mixing of ml 2.5 mmol/L zinc nitrate aqueous solution is placed at 30 DEG C reacts 48 h.Product is obtained by centrifugal, uses deionized water
Rinse 3 times, is placed in 80 DEG C of baking ovens and dries 12 h.
Fig. 1 is the scanning electron microscope (SEM) photograph of [email protected] can be seen that made Pd@ZIF-L is unique crossed body pattern, grain
Footpath is about 20 μm, hence it is evident that the particle diameter (0.3 μm) of the Pd@ZIF-8 that reports for work higher than patent CN103394373A.Fig. 2 is Pd@ZIF-L
Transmission electron microscope picture, Pd nano-particle can be clearly seen and be evenly dispersed in ZIF-L, its size is about 3 nm.
Being applied in paranitrophenol Hydrogenation Experiment by catalyst Pd@ZIF-L, after reacting 90 min, conversion ratio is 100%,
Selectivity is 100%.
Embodiment 2
First prepare the palladium dichloromethane solution of 25 ml 0.02 mol/L, and add the 15 ml 3.33 poly-second of mol/L
Alkene pyrrolidone dichloromethane solution (mol ratio of Pd/ polyvinylpyrrolidone is 1:10).Use 11 mL 5 mmol/L's
Hydrazine hydrate, potassium borohydride, sodium hydroxide mixed solution (three's mol ratio is 3:20:1) Dichlorodiphenyl Acetate palladium reduce, reduction temperature
Degree is room temperature, and the recovery time is 6 h.Reduction takes the Pd nano-particle colloidal sol on upper strata after terminating, and is scattered in 100 ml deionizations
In water.
By 10 ml 5 mmol/L Pd nano-particle colloidal sols, 100 ml 50 mmol/L 2-methylimidazole solution, 100
The mixing of ml 2.5 mmol/L zinc nitrate solution is placed at 0 DEG C reacts 48 h.Product is obtained by centrifugal, moistens with deionized water
Wash 2 times, be placed in 150 DEG C of baking ovens and dry 8 h.
Applying in paranitrophenol Hydrogenation Experiment by catalyst Pd@ZIF-L, after reacting 90 min, conversion ratio is 76.6%,
Selectivity is 100%.
Embodiment 3
First prepare the palladium dichloromethane solution of 25 ml 0.02 mol/L, and add 15 ml 20 mol/L polyethylene pyrroles
Pyrrolidone dichloromethane solution (mol ratio of Pd/ polyvinylpyrrolidone is 1:60).Use the water of 11 mL 20 mmol/L
Conjunction hydrazine, potassium borohydride, sodium hydroxide mixed solution (three's mol ratio is 3:20:1) Dichlorodiphenyl Acetate palladium reduce, reduction temperature
For room temperature, the recovery time is 2 h.Reduction takes the Pd nano-particle colloidal sol on upper strata after terminating, and is scattered in 100 ml deionized waters
In.
By 10 ml 5 mmol/L Pd nano-particle colloidal sols, 100 ml 50 mmol/L 2-methylimidazole solution, 100
The mixing of ml 2.5 mmol/L zinc nitrate solution is placed at 30 DEG C reacts 6 h.Product is obtained by centrifugal, moistens with deionized water
Wash 5 times, be placed in 120 DEG C of baking ovens and dry 12 h.
Applying in paranitrophenol Hydrogenation Experiment by catalyst Pd@ZIF-L, after reacting 90 min, conversion ratio is 90.5%,
Selectivity is 100%.
Embodiment 4
First prepare the palladium dichloromethane solution of 25 ml 0.02 mol/L, and add the 15 ml 6.67 poly-second of mol/L
Alkene pyrrolidone dichloromethane solution (mol ratio of Pd/ polyvinylpyrrolidone is 1:20).Use 11 mL 10 mmol/L
Hydrazine hydrate, potassium borohydride, sodium hydroxide mixed solution (three's mol ratio is 3:20:1) Dichlorodiphenyl Acetate palladium reduce, reduction
Temperature is room temperature, and the recovery time is 4 h.Reduction takes the Pd nano-particle colloidal sol on upper strata after terminating, and be scattered in 100 ml go from
In sub-water.
By 10 ml 5 mmol/L Pd nano-particle colloidal sols, 100 ml 20 mmol/L 2-methylimidazole aqueous solutions, 100
The mixing of ml 2.5 mmol/L zinc nitrate aqueous solution is placed at 30 DEG C reacts 48 h.Product is obtained by centrifugal, uses deionization
Water rinse 3 times, is placed in 80 DEG C of baking ovens and dries 12 h.
Being applied in paranitrophenol Hydrogenation Experiment by catalyst Pd@ZIF-L, after reacting 90 min, conversion ratio is 100%,
Selectivity is 100%.
Embodiment 5
First prepare the palladium dichloromethane solution of 25 ml 0.02 mol/L, and add the 15 ml 6.67 poly-second of mol/L
Alkene pyrrolidone dichloromethane solution (mol ratio of Pd/ polyvinylpyrrolidone is 1:20).Use 11 mL 10 mmol/L
Hydrazine hydrate, potassium borohydride, sodium hydroxide mixed solution (three's mol ratio is 3:20:1) Dichlorodiphenyl Acetate palladium reduce, reduction
Temperature is room temperature, and the recovery time is 4 h.Reduction takes the Pd nano-particle colloidal sol on upper strata after terminating, and be scattered in 100 ml go from
In sub-water.
By 10 ml 5 mmol/L Pd nano-particle colloidal sols, 100 ml 62.5 mmol/L 2-methylimidazole aqueous solutions,
100 ml 2.5 mmol/L zinc nitrate aqueous solution mixing are placed at 30 DEG C reacts 6 h.Product is obtained by centrifugal, spend from
Sub-water rinse 3 times, is placed in 80 DEG C of baking ovens and dries 12 h.
Being applied in paranitrophenol Hydrogenation Experiment by catalyst Pd@ZIF-L, after reacting 90 min, conversion ratio is 67.3%,
Selectivity is 100%.
Embodiment 6
First prepare the palladium dichloromethane solution of 25 ml 0.02 mol/L, and add the 15 ml 6.67 poly-second of mol/L
Alkene pyrrolidone dichloromethane solution (mol ratio of Pd/ polyvinylpyrrolidone is 1:20).Use 11 mL 20 mmol/L
Hydrazine hydrate, potassium borohydride, sodium hydroxide mixed solution (three's mol ratio is 3:20:1) Dichlorodiphenyl Acetate palladium reduce, reduction
Temperature is room temperature, and the recovery time is 4 h.Reduction takes the Pd nano-particle colloidal sol on upper strata after terminating, and be scattered in 100 ml go from
In sub-water.
By 10 ml 5 mmol/L Pd nano-particle colloidal sols, 100 ml 62.5 mmol/L 2-methylimidazole aqueous solutions,
100 ml 2.5 mmol/L zinc nitrate aqueous solution mixing are placed at 0 DEG C reacts 48 h.Product is obtained by centrifugal, spend from
Sub-water rinse 3 times, is placed in 80 DEG C of baking ovens and dries 24 h.
Being applied in paranitrophenol Hydrogenation Experiment by catalyst Pd@ZIF-L, after reacting 90 min, conversion ratio is 54.1%,
Selectivity is 100%.
Claims (4)
1. a hydrogenation catalyst, it is characterised in that: Pd nano-particle is dispersed in the framework of zeolitic imidazolate framework material ZIF-L
In, forming load type metal catalyst, its preparation process is as follows:
Step one: a certain amount of polyvinylpyrrolidone dichloromethane solution is added in palladium dichloromethane solution, then by
Be added dropwise to hydrazine hydrate, potassium borohydride, sodium hydroxide mixed aqueous solution carry out reduction reaction, control palladium concentration, polyethylene pyrrole
Pyrrolidone concentration, reducing solution concentration, recovery time, prepare the Pd nano-particle of polyvinylpyrrolidone parcel；
Step 2: the Pd nano-particle described in a certain amount of step one, 2-methylimidazole aqueous solution, zinc nitrate aqueous solution are mixed
Close, react a period of time at a certain temperature；
Step 3: the sample obtained in step 2, by deionized water rinse, is finally placed in baking oven drying.
A kind of hydrogenation catalyst the most according to claim 1, it is characterised in that palladium concentration described in preparation process one
Being 0.02 mol/L, Pd is 1:10～1:60 with the mol ratio of polyvinylpyrrolidone, hydrazine hydrate, potassium borohydride, hydroxide
The mol ratio of sodium is 3:20:1, and reducing solution concentration is 5～20 mmol/L, and the recovery time is 2～6 h.
A kind of hydrogenation catalyst the most according to claim 1, it is characterised in that Pd nano-particle described in preparation process two
Concentration is 5 mmol/L, and zinc nitrate aqueous solution concentration is 2.5 mmol/L, and zinc nitrate is 1:8 with the mol ratio of 2-methylimidazole
～1:25, reaction temperature is 0～30 DEG C, and the response time is 6～48 h.
A kind of hydrogenation catalyst the most according to claim 1, it is characterised in that deionized water described in preparation process three moistens
Washing number of times is 2～5 times, and drying temperature is 80～150 DEG C, and drying time is 8 ~ 24 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610465897.4A CN106040302A (en) | 2016-06-23 | 2016-06-23 | Hydrogenation catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610465897.4A CN106040302A (en) | 2016-06-23 | 2016-06-23 | Hydrogenation catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106040302A true CN106040302A (en) | 2016-10-26 |
Family
ID=57165554
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610465897.4A Pending CN106040302A (en) | 2016-06-23 | 2016-06-23 | Hydrogenation catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106040302A (en) |
Cited By (8)
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| CN106916110A (en) * | 2017-03-10 | 2017-07-04 | 国家纳米科学中心 | A kind of carried noble metal nano composition and preparation method thereof |
| CN107349964A (en) * | 2017-07-15 | 2017-11-17 | 北京化工大学 | A kind of preparation method of nano particle@small sized metallic organic framework materials |
| CN108097316A (en) * | 2017-12-05 | 2018-06-01 | 中国科学院兰州化学物理研究所苏州研究院 | A kind of preparation method of the MOFs nano materials of supported nano-gold metal particles |
| CN109174086A (en) * | 2018-10-07 | 2019-01-11 | 吴亚良 | A kind of preparation method of high-performance noble metal catalyst |
| CN111440329A (en) * | 2020-05-06 | 2020-07-24 | 江南大学 | Preparation method for MOF crystal form transformation |
| CN111744550A (en) * | 2019-03-27 | 2020-10-09 | 南京工业大学 | Preparation method of two-dimensional nanosheet layer hydrogenation catalyst |
| CN113304785A (en) * | 2021-06-04 | 2021-08-27 | 南京工业大学 | Preparation method of p-nitrophenol hydrogenation catalyst |
| CN114425450A (en) * | 2020-10-13 | 2022-05-03 | 中国石油化工股份有限公司 | Catalyst for preparing unsaturated carbonate, preparation method and application thereof |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106916110A (en) * | 2017-03-10 | 2017-07-04 | 国家纳米科学中心 | A kind of carried noble metal nano composition and preparation method thereof |
| CN106916110B (en) * | 2017-03-10 | 2020-03-24 | 国家纳米科学中心 | Supported noble metal nanoparticle composite material and preparation method thereof |
| CN107349964A (en) * | 2017-07-15 | 2017-11-17 | 北京化工大学 | A kind of preparation method of nano particle@small sized metallic organic framework materials |
| CN108097316A (en) * | 2017-12-05 | 2018-06-01 | 中国科学院兰州化学物理研究所苏州研究院 | A kind of preparation method of the MOFs nano materials of supported nano-gold metal particles |
| CN108097316B (en) * | 2017-12-05 | 2020-09-15 | 中国科学院兰州化学物理研究所苏州研究院 | Preparation method of MOFs nano material loaded with nano metal particles |
| CN109174086A (en) * | 2018-10-07 | 2019-01-11 | 吴亚良 | A kind of preparation method of high-performance noble metal catalyst |
| CN111744550A (en) * | 2019-03-27 | 2020-10-09 | 南京工业大学 | Preparation method of two-dimensional nanosheet layer hydrogenation catalyst |
| CN111440329A (en) * | 2020-05-06 | 2020-07-24 | 江南大学 | Preparation method for MOF crystal form transformation |
| CN114425450A (en) * | 2020-10-13 | 2022-05-03 | 中国石油化工股份有限公司 | Catalyst for preparing unsaturated carbonate, preparation method and application thereof |
| CN114425450B (en) * | 2020-10-13 | 2023-08-29 | 中国石油化工股份有限公司 | Catalyst for preparing unsaturated carbonate, preparation method and application thereof |
| CN113304785A (en) * | 2021-06-04 | 2021-08-27 | 南京工业大学 | Preparation method of p-nitrophenol hydrogenation catalyst |
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Application publication date: 20161026 |