CN108097262A - Catalyst and preparation method and application - Google Patents
Catalyst and preparation method and application Download PDFInfo
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- CN108097262A CN108097262A CN201711353957.4A CN201711353957A CN108097262A CN 108097262 A CN108097262 A CN 108097262A CN 201711353957 A CN201711353957 A CN 201711353957A CN 108097262 A CN108097262 A CN 108097262A
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- btc
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- palladium
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- 239000003054 catalyst Substances 0.000 title claims abstract description 84
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 32
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 27
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 150000002940 palladium Chemical class 0.000 claims abstract description 16
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 14
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 14
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 13
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 239000000908 ammonium hydroxide Substances 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- NOSIKKRVQUQXEJ-UHFFFAOYSA-H tricopper;benzene-1,3,5-tricarboxylate Chemical compound [Cu+2].[Cu+2].[Cu+2].[O-]C(=O)C1=CC(C([O-])=O)=CC(C([O-])=O)=C1.[O-]C(=O)C1=CC(C([O-])=O)=CC(C([O-])=O)=C1 NOSIKKRVQUQXEJ-UHFFFAOYSA-H 0.000 claims description 53
- 239000013148 Cu-BTC MOF Substances 0.000 claims description 52
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 45
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 26
- 150000001879 copper Chemical class 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 12
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 12
- 238000005984 hydrogenation reaction Methods 0.000 claims description 11
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 3
- -1 polyethylene pyrrole Polymers 0.000 claims description 2
- AMXBISSOONGENB-UHFFFAOYSA-N acetylene;ethene Chemical group C=C.C#C AMXBISSOONGENB-UHFFFAOYSA-N 0.000 claims 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 27
- 239000005977 Ethylene Substances 0.000 abstract description 27
- 150000001345 alkine derivatives Chemical class 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 42
- 229910002668 Pd-Cu Inorganic materials 0.000 description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 238000001000 micrograph Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910002666 PdCl2 Inorganic materials 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000004227 thermal cracking Methods 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- UGWKCNDTYUOTQZ-UHFFFAOYSA-N copper;sulfuric acid Chemical compound [Cu].OS(O)(=O)=O UGWKCNDTYUOTQZ-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000003639 trimesic acids Chemical class 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 230000004580 weight loss 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8926—Copper and noble metals
-
- 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
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
- C07C7/163—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation
- C07C7/167—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation for removal of compounds containing a triple carbon-to-carbon bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with noble metals
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to chemical material technical fields, provide a kind of catalyst and preparation method and application.A kind of preparation method of catalyst, including providing soluble palladium salt and Cu BTC, the soluble palladium salt and the amount ratio of Cu BTC are (0.01 0.1) mmol：1g；The soluble palladium salt is completely dissolved in the ammonia solution that palladium is obtained in ammonium hydroxide, addition water, which adjusts pH to 78, into the ammonia solution of palladium obtains reaction solution；The reaction solution is sufficiently mixed with obtaining mixture after Cu BTC；The mixture is dried, roasts and can obtain required catalyst.Using the catalyst obtained by the preparation method of the catalyst especially suitable for removing acetylene in ethylene, while there is higher conversion of alkyne and ethylene selectivity.The present invention also provides a kind of catalyst, are prepared using the preparation method of above-mentioned catalyst.The present invention also provides a kind of applications of catalyst, and above-mentioned catalyst is applied to remove acetylene in ethylene.
Description
Technical field
The present invention relates to chemical material technical fields more particularly to a kind of catalyst and preparation method and application.
Background technology
Ethylene is the important industrial chemicals in organic synthesis industry, can be produced by different polymerisations thousands of
Middle and lower reaches product, yield is even more the mark for being used to weigh a country basic petrochemical industry development level.Now, it is industrial
The main source of ethylene is the thermal cracking of oil.Often contain a small amount of acetylene in the ethylene generated in oil thermal cracking processes, sternly
The catalytic performance of follow-up ethylene rolymerization catalyst is affected again.Selective hydrogenation of acetylene conversion ethylene process has economical, simple
Characteristic, thus as the method for most common removing acetylene industrial at present.The quality of acetylene removal effect is evaluation selective catalysis
The key of the catalyst of hydrogenation, therefore high efficiency selected hydrogenation catalyst how is obtained, it is subject to the extensive concern of scientific research personnel.
At present, Pt-supported catalyst application is wider, it is believed that Pt-supported catalyst shows higher generation ethylene selection
Two reasons of property：First, the absorption bond strength of Thermodynamics, metal Pd and acetylene is far longer than the combination of itself and ethylene
Intensity, and the absorption of acetylene is almost Irreversible Adsorption on metal Pd, i.e., in Pd surfaces Preferential adsorption acetylene；Second is that power
Factor that is, after acetylene hydrogenation generates ethylene, weakens original species and the combination power of Pd, so that the ethylene of generation is in depth
The acetylene for being hydrogenated to that desorption occurs on Pd surfaces and is adsorbed before ethane substitutes.With other metallic catalysts (Cu, Ni)
It compares, Pt-supported catalyst has preferable acetylene hydrogenation catalytic performance, but in higher conversion of alkyne or higher hydrogen
Under gas partial pressure conditions, the selectivity for generating ethylene is not still high.
The content of the invention
It is an object of the invention to provide a kind of catalyst and preparation method and application, and the catalyst is especially suitable for second
Acetylene is removed in alkene, while there is higher conversion of alkyne and ethylene selectivity.
In order to solve the above technical problems, invention uses technical solution as described below.A kind of preparation method of catalyst, bag
It includes and soluble palladium salt and Cu-BTC is provided, the amount ratio of the solubility palladium salt and Cu-BTC are (0.01-0.1) mmol：1g；It will
The solubility palladium salt is completely dissolved in the ammonia solution that palladium is obtained in ammonium hydroxide, and water is added in into the ammonia solution of palladium and adjusts pH to 7-
8 obtain reaction solution；The reaction solution is sufficiently mixed with obtaining mixture after Cu-BTC；The mixture is dried,
Roasting can obtain required catalyst.
Preferably, described be roasted to carries out in a nitrogen environment, gas flow 80-100mL/min；The temperature of the roasting
It spends for 400-600 DEG C, and 20-40min is kept at 400-600 DEG C.
Preferably, the drying is to be placed in the environment that temperature is 60-100 DEG C dry 6-18h.
Preferably, before the reaction solution and Cu-BTC is sufficiently mixed, Cu-BTC is placed in temperature as 60-100 DEG C
Environment in 6-18h.
Preferably, the preparation method of the catalyst further comprises the preparation of Cu-BTC, the preparation bag of the Cu-BTC
It includes：Soluble copper salt, polyvinylpyrrolidone, methanol and trimesic acid, the soluble copper salt, polyvinyl pyrrole are provided
The amount ratio of alkanone and trimesic acid is (0.005-0.02) mol：1g：(0.8-1.5)g；By soluble copper salt, polyethylene pyrrole
Pyrrolidone, which is dissolved in methanol, obtains solution A；Trimesic acid is dissolved in methanol and obtains B solution；B solution is added dropwise
In solution A, solution C is obtained after being sufficiently mixed；Solution C is obtained into solution D at 20-30 DEG C after aging 12-36h, from described
It can isolated required Cu-BTC in solution D.
A kind of catalyst is prepared using the preparation method of above-mentioned catalyst.
Preferably, the BET specific surface area of the catalyst is 100-150m2/g。
Preferably, the average pore size of the catalyst is 10-25nm.
Above-mentioned catalyst is applied to remove acetylene in ethylene, by being catalyzed the acetylene by a kind of application of catalyst
Hydrogenation reaction is carried out so as to be removed.
Preferably, the reaction temperature of the hydrogenation reaction is 100-150 DEG C.
The beneficial effects of the present invention are：
The present invention provides a kind of preparation methods of catalyst, and obtained catalyst in ethylene especially suitable for removing second
Alkynes, while there is higher conversion of alkyne and ethylene selectivity.
The present invention also provides a kind of catalyst, especially suitable for removing acetylene in ethylene, while have higher acetylene
Conversion ratio and ethylene selectivity.
The present invention also provides a kind of applications of catalyst, and above-mentioned catalyst is applied to remove acetylene in ethylene, is led to
It crosses and is catalyzed the acetylene progress hydrogenation reaction so as to be removed.
Description of the drawings
Fig. 1 is the flow diagram of the preparation method of catalyst provided by the present invention.
Fig. 2 is the flow diagram that Cu-BTC is prepared in the preparation method of catalyst provided by the present invention.
Fig. 3 is the XRD spectra of preparation-obtained Cu-BTC in the present invention.
Fig. 4 is the scanning electron microscope image of preparation-obtained Cu-BTC in the present invention.
Fig. 5 is the thermogravimetric analysis figure of preparation-obtained Cu-BTC in the present invention.
Fig. 6 is the scanning electron microscope image of preparation-obtained Pd-Cu/C catalyst in the present invention.
Fig. 7 is the transmission electron microscope image of preparation-obtained Pd-Cu/C catalyst in the present invention.
Fig. 8 is the Nitrogen adsorption isotherm in 77K of preparation-obtained Pd-Cu/C catalyst in the present invention.
Specific embodiment
To make those of ordinary skill in the art that the purpose, technical scheme and advantage of invention be more clearly understood, below
Invention is further elaborated in conjunction with the accompanying drawings and embodiments.
Embodiment one
As shown in Figure 1, a kind of preparation method of catalyst, including：
Step S1：The amount ratio of the soluble palladium salt of offer and Cu-BTC, the solubility palladium salt and Cu-BTC are (0.01-
0.1)mmol：1g；
Step S2：The soluble palladium salt is completely dissolved in the ammonia solution that palladium is obtained in ammonium hydroxide, into the ammonia solution of palladium
Addition water, which adjusts pH to 7-8, obtains reaction solution；
Step S3：The reaction solution is sufficiently mixed with obtaining mixture after Cu-BTC；
Step S4：The mixture is dried, roasts and can obtain required catalyst.The catalyst can be denoted as Pd-
Cu/C catalyst.
In the preparation method of the catalyst, signified soluble palladium salt can be palladium bichloride, palladium nitrate in step S1
Deng.Cu-BTC can be directly commercially available or voluntarily prepare.Preferably, the preparation method of the catalyst into
One step includes the preparation of Cu-BTC, as shown in Fig. 2, the preparation of the Cu-BTC includes：
Step T1：Soluble copper salt, polyvinylpyrrolidone, methanol and trimesic acid, the soluble copper are provided
The amount ratio of salt, polyvinylpyrrolidone and trimesic acid is (0.005-0.02) mol：1g：(0.8-1.5)g；
Step T2：Soluble copper salt, polyvinylpyrrolidone are dissolved in methanol and obtain solution A；
Step T3：Trimesic acid is dissolved in methanol and obtains B solution；
Step T4：B solution is added dropwise in solution A, solution C is obtained after being sufficiently mixed；
Step T5：Solution C is obtained into solution D at 20-30 DEG C after aging 12-36h, it is i.e. separable from the solution D
Obtain required Cu-BTC.
In the preparation of the Cu-BTC, the soluble copper salt described in step T1 can be copper chloride, copper nitrate, sulfuric acid
Copper etc., methanol usage, which is subject to, can dissolve soluble copper salt, polyvinylpyrrolidone, trimesic acid.It is preferred real at some
The amount ratio for applying soluble copper salt described in example, polyvinylpyrrolidone and trimesic acid is (0.006-0.012) mol：1g：
(0.9-1.2)g；It is preferred that the amount ratio of the soluble copper salt, polyvinylpyrrolidone and trimesic acid is
(0.008-0.01)mol：1g：(0.95-1.1)g；It is optimal to be, the soluble copper salt, polyvinylpyrrolidone and equal benzene front three
The amount ratio of acid is 0.009mol：1g：1.08g.
Step T2-T4, using dissolving soluble copper salt, polyvinylpyrrolidone, trimesic acid in batches, and by B solution
The mode in solution A is added dropwise, guarantee obtains homodisperse solution C, and solution C is blue colloidal solution.It is appreciated that
Step T2 and T3 are successively carried out, and can also be carried out at the same time, not sequential requirement.In some preferred embodiments, by B
It during solution A is added dropwise in solution, is persistently stirred, is further ensured that uniformly mixed.
In step T5, a length of 22-26h during preferred aging, specially for 24 hours.Described is isolated from the solution D
Required Cu-BTC can be using modes such as centrifugal filtration or suction filtrations, can be specifically to centrifuge to collect the heavy of blueness
It forms sediment, and is washed three times with methanol.In some preferred embodiments, the precipitation of isolated blueness is placed at 60-100 DEG C
Dry 12-36h obtains required Cu-BTC powder.
The result characterized for obtained Cu-BTC is as shown in Figure 3-Figure 5.
Fig. 3 be Cu-BTC XRD spectra, can be clearly seen that from figure 7 °, 9 °, 12 °, 13.5 °, 15 °, 16.5 °,
17.5 °, 19 °, the positions such as 20 ° there is a series of characteristic diffraction peak, it was demonstrated that is be prepared is exactly Cu-BTC materials, and is not had
There is stray crystal generation.
Fig. 4 is the scanning electron microscope image of Cu-BTC, wherein the amplification factor of (1) is smaller；(2), (3), (4) are put
Big multiple is identical, and is the image at different position.Figure 4, it is seen that obtained Cu-BTC is in class octahedral shape,
And no adhesion that is evenly distributed on conducting resinl, size are regular, size is about 450nm.
Fig. 5 is the thermogravimetric analysis figure of Cu-BTC.Gradually occur with the rise of temperature, Cu-BTC it can be seen from thermal multigraph
It decomposes, specifically there is weightless process three times.It is for the first time before 200 DEG C, this is because being stripped of water, carbon dioxide, methanol etc.
Material molecule；It is in 200-300 DEG C of rapid weight loss, this is because being stripped of remaining ligand (equal benzene front three in duct for the second time
Acid)；Third time is after 300 DEG C, this is because decomposition takes place in the skeleton organic matter of Cu-BTC.
Please continue to refer to Fig. 1, in the preparation method of the catalyst, it is preferably in step S1, the soluble palladium
The amount ratio of salt and Cu-BTC are (0.01-0.05) mmol：1g；It is preferred that the solubility palladium salt and the dosage of Cu-BTC
Than for (0.01-0.03) mmol.In some specific embodiments, the amount ratio of the solubility palladium salt and Cu-BTC are
0.02mmol：1g, the load capacity of Pd is 0.5wt% at this time, which tests to obtain by elemental analysis.
In the preparation method of the catalyst, step S2 first dissolves soluble palladium salt using ammonium hydroxide, ensure wherein palladium from
Son can disperse well, and ensure the quality of final obtained catalyst.Make the abundant solvent of soluble palladium salt can in step S2
To be using in a manner of stirring, ultrasonic vibration etc..It can use to stir that the reaction solution and Cu-BTC are sufficiently mixed in step S3
It mixes, the modes such as ultrasonic vibration.
Preferably, before the reaction solution and Cu-BTC is sufficiently mixed, Cu-BTC is placed in temperature as 60-100 DEG C
Environment in 6-18h.It may further be preferable that Cu-BTC is placed in 12-18h in the environment that temperature is 80 DEG C.
In step s 4, it is preferable that the drying is to be placed in the environment that temperature is 60-100 DEG C dry 6-18h.Into one
Step is preferably, and the drying is to be placed in the environment that temperature is 80 DEG C dry 10-16h.Preferably, it is described to be roasted in nitrogen
It is carried out under environment, gas flow 80-100mL/min；The temperature of the roasting is 400-600 DEG C, and is protected at 400-600 DEG C
Hold 20-40min.
The result characterized for obtained Pd-Cu/C catalyst is as shown in Figure 6, Figure 7.
Fig. 6 is the scanning electron microscope image of Pd-Cu/C catalyst, wherein (1), (2) are the image at different position.
As seen from the figure, after fired processing sample still keep class octahedral structure and be evenly distributed, size uniformity it is regular.In addition catalyst
Surface is covered with duct and small rounded grain, and analysis may be since high-temperature roasting resolves into the organic moiety in Cu-BTC skeletons
Carbon and gas molecule cause hole to increase；Ni metal is reunited at high temperature, is gathered in the surface of Cu-BTC.
Fig. 7 is the transmission electron microscope image of Pd-Cu/C catalyst, wherein (1), (2) is under different amplifications
Image.Black aggregate is the Cu that reunites under high temperature in figure, and the clad of Cu peripheries light color is carbon, the fine particle of carrier inside
For Pd.Metal Pd is understood in carrier inside high degree of dispersion by map analysis, and grain size is minimum.
Fig. 8 is Nitrogen adsorption isotherm of the Pd-Cu/C catalyst in 77K.Since capillary condensation phenomenon curve is there are hysteresis loop,
It is mesoporous material to show Pd-Cu/C catalyst.BET specific surface area is calculated as 100-150m2/ g, in the sample, BET specific surfaces
Product is 134m2/g；Average pore size is calculated by BJH formula to be distributed between 10-25nm.
In addition, carry out EDS analyses for obtained Pd-Cu/C catalyst, it is known that metal Pd is height in Cu-BTC
Homodisperse.
The specific embodiment of the preparation method of a catalyst is provided below
1st, Cu-BTC is prepared
(1) solution A is configured：Weigh 0.9g Cu (NO3) 23H2O and 0.4g PVP are dissolved completely in 50mL methanol solutions
In, obtain clear blue solution；
(2) B solution is configured：0.43g trimesic acids are weighed to be dissolved completely in 50mL methanol solutions.
(3) solution A is added dropwise in B solution with constant pressure funnel, during entire be added dropwise, solution A is persistently stirred.
It treats that two kinds of solution are thoroughly mixed stopping stirring after 10min, obtains mixed solution.
(4) aging is for 24 hours at room temperature for mixed solution.It centrifuges and collects blue precipitate, and washed three times with methanol.Finally
For 24 hours, obtained blue powder is Cu-BTC for drying in 80 DEG C of baking ovens.
2nd, Pd-Cu/C catalyst is prepared
(1) weigh 0.5g Cu-BTC in 80 DEG C of baking ovens it is dry 12 it is small when.
(2) 1.774mg PdCl are weighed2(load capacity 0.5wt%) is poured into the sample cell that capacity is 4mL, is dripped into pipe
Add 1-2 drop ammonium hydroxide, ultrasonic vibration several minutes so that PdCl2It is substantially dissolved in solvent.
(3) by PdCl2Ammonia solution pour into 50mL beakers and add in appropriate amount of deionized water, adjust pH value of solution to close in
Property.The Cu-BTC weighed up is put into thereto, is continuously stirred at room temperature for 24 hours, and sample P d is made in dry 12h in 80 DEG C of baking ovens2+/
Cu-BTC。
(4) calcination process is carried out to it using the OTF-1200X types tube furnace of Hefei Ke Jing Materials Technology Ltd..It is first
First sample is poured into porcelain boat and is paved, pushes it into the middle part of quartz ampoule and shuts tube furnace；Then mounting flange is passed through nitrogen and examines
Instrument air-tightness is looked into, gas flow is maintained at 80-100mL/min.Setting program heating roasted, heating rate for 5 DEG C/
Min is raised to 500 DEG C and 30min is kept at 500 DEG C, is taken out after being then naturally cooling to less than 100 DEG C and collects sample and obtains
Pd-Cu/C catalyst.
Embodiment two
A kind of catalyst is prepared using the preparation method of catalyst in embodiment one.As described in the text and scheme
6-8 understand, the catalyst be in class octahedral structure, and be evenly distributed, size uniformity it is regular.In addition catalyst surface is covered with duct
And small rounded grain.The BET specific surface area of the catalyst is 100-150m2/g.The average pore size of the catalyst is 10-
25nm。
Embodiment three
Catalyst in embodiment two is applied to remove acetylene in ethylene, by being catalyzed by a kind of application of catalyst
It states acetylene and carries out hydrogenation reaction so as to be removed.It is appreciated that acetylene content is less, the purpose of the catalyst is, first,
Acetylene is removed as far as possible, that is, intentionally gets higher conversion of alkyne；Second, more ethylene can be obtained, that is, as far as possible will
Unwanted acetylene is converted to ethylene, that is, intentionally gets higher ethylene selectivity.
It carries out removing acetylene in ethylene using the catalyst, the results are shown in table below：
| Temperature (DEG C) | Conversion of alkyne (%) | Ethylene selectivity (%) |
| 75 | 45 | 96 |
| 100 | 70 | 92 |
| 125 | 86 | 84 |
| 150 | 90 | 80 |
Reaction condition is 2.91vol%H2, 0.97vol%C2H2And 96.11vol%C2H4
As seen from the above table, there is preferable acetylene conversion performance and higher ethylene selectivity using the catalyst.It is and excellent
Choosing, reaction temperature are 100-150 DEG C.
Claims (10)
1. a kind of preparation method of catalyst, it is characterised in that：Including providing soluble palladium salt and Cu-BTC, the soluble palladium
The amount ratio of salt and Cu-BTC are (0.01-0.1) mmol：1g；
The soluble palladium salt is completely dissolved in the ammonia solution that palladium is obtained in ammonium hydroxide, water is added in into the ammonia solution of palladium by pH tune
It saves to 7-8 and obtains reaction solution；
The reaction solution is sufficiently mixed with obtaining mixture after Cu-BTC；
The mixture is dried, roasts and can obtain required catalyst.
2. the preparation method of catalyst as described in claim 1, it is characterised in that：It is described be roasted in a nitrogen environment into
Row, gas flow 80-100mL/min；The temperature of the roasting is 400-600 DEG C, and keeps 20- at 400-600 DEG C
40min。
3. the preparation method of catalyst as described in claim 1, it is characterised in that：The drying is 60-100 to be placed in temperature
DEG C environment in dry 6-18h.
4. the preparation method of catalyst as described in claim 1, it is characterised in that：Be sufficiently mixed the reaction solution with
Before Cu-BTC, Cu-BTC is placed in 6-18h in the environment that temperature is 60-100 DEG C.
5. the preparation method of the catalyst as described in claim any one of 1-4, it is characterised in that：Further comprise Cu-BTC
Preparation, the preparation of the Cu-BTC includes：
Soluble copper salt, polyvinylpyrrolidone, methanol and trimesic acid, the soluble copper salt, polyethylene pyrrole are provided
The amount ratio of pyrrolidone and trimesic acid is (0.005-0.02) mol：1g：(0.8-1.5)g；
Soluble copper salt, polyvinylpyrrolidone are dissolved in methanol and obtain solution A；
Trimesic acid is dissolved in methanol and obtains B solution；
B solution is added dropwise in solution A, solution C is obtained after being sufficiently mixed；
Solution C is obtained into solution D at 20-30 DEG C after aging 12-36h, it can be isolated required from the solution D
Cu-BTC。
6. a kind of catalyst, it is characterised in that：It is prepared using the preparation method of the catalyst described in claim 1.
7. catalyst as claimed in claim 6, it is characterised in that：The BET specific surface area of the catalyst is 100-150m2/g。
8. catalyst as claimed in claim 6, it is characterised in that：The average pore size of the catalyst is 10-25nm.
9. a kind of application of catalyst, it is characterised in that：Catalyst as described in claim 6 is applied to remove in ethylene
Acetylene carries out hydrogenation reaction so as to be removed by being catalyzed the acetylene.
10. the application of the catalyst as described in claim 9 kind, it is characterised in that：The reaction temperature of the hydrogenation reaction is
100-150℃。
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