CN111013603A - Supported PdCu bimetallic catalyst for acetylene selective hydrogenation reaction and preparation method thereof - Google Patents
Supported PdCu bimetallic catalyst for acetylene selective hydrogenation reaction and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 57
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 title claims abstract description 30
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229910021392 nanocarbon Inorganic materials 0.000 claims abstract description 35
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 25
- 239000002904 solvent Substances 0.000 claims abstract description 25
- 150000001879 copper Chemical class 0.000 claims abstract description 22
- 150000002940 palladium Chemical class 0.000 claims abstract description 22
- 239000000956 alloy Substances 0.000 claims abstract description 17
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000000725 suspension Substances 0.000 claims abstract description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- 239000002105 nanoparticle Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 230000001105 regulatory effect Effects 0.000 claims abstract description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 32
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 32
- 239000000843 powder Substances 0.000 claims description 24
- 239000010949 copper Substances 0.000 claims description 22
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 20
- 229910017604 nitric acid Inorganic materials 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 17
- 239000012018 catalyst precursor Substances 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 238000000227 grinding Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 238000010992 reflux Methods 0.000 claims description 10
- 229910052763 palladium Inorganic materials 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000002048 multi walled nanotube Substances 0.000 claims description 4
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- 230000009467 reduction Effects 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 230000001276 controlling effect Effects 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229940116318 copper carbonate Drugs 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- ZKXWKVVCCTZOLD-UHFFFAOYSA-N copper;4-hydroxypent-3-en-2-one Chemical compound [Cu].CC(O)=CC(C)=O.CC(O)=CC(C)=O ZKXWKVVCCTZOLD-UHFFFAOYSA-N 0.000 claims description 2
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 239000002113 nanodiamond Substances 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- LWHYKTAISUZRAD-UHFFFAOYSA-L palladium(2+);carbonate Chemical compound [Pd+2].[O-]C([O-])=O LWHYKTAISUZRAD-UHFFFAOYSA-L 0.000 claims description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 2
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 claims description 2
- 239000002109 single walled nanotube Substances 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- 239000002086 nanomaterial Substances 0.000 abstract description 4
- 238000012827 research and development Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract 3
- 239000006185 dispersion Substances 0.000 abstract 1
- 239000002041 carbon nanotube Substances 0.000 description 15
- 229910021393 carbon nanotube Inorganic materials 0.000 description 15
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 12
- 239000005977 Ethylene Substances 0.000 description 12
- 150000003839 salts Chemical class 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 6
- 238000009210 therapy by ultrasound Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 238000013507 mapping Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/08—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds
- C07C5/09—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds to carbon-to-carbon double bonds
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- 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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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Abstract
The invention discloses a supported PdCu bimetallic catalyst for acetylene selective hydrogenation reaction and a preparation method thereof, belonging to the technical field of industrial catalyst research and development. Mixing palladium salt and copper salt in a fixed ratio, adding the mixture into a solvent, adding the mixture into a nano carbon material suspension prepared in advance after ultrasonic full dispersion, removing the solvent through a rotary evaporator, and then reducing the mixture in a hydrogen atmosphere to form a bimetallic alloy structure. The method is simple and convenient to operate, different proportions of the PdCu alloy can be accurately and effectively regulated, and the obtained PdCu alloy nanoparticles are uniformly dispersed on the carbon nano-material. In addition, more importantly, the catalyst obtained by the method has very excellent performance in the selective hydrogenation reaction of acetylene.
Description
Technical Field
The invention relates to the technical field of research and development of industrial catalysts, in particular to a supported PdCu bimetallic catalyst for acetylene selective hydrogenation reaction and a preparation method thereof.
Background
The removal of trace acetylene from a large amount of ethylene is one of the very important processes in petrochemical production, and the ideal way is to convert acetylene into ethylene by selective hydrogenation. The noble metal Pd-based catalyst is widely applied to the reaction because of high acetylene hydrogenation activity, but the ethylene selectivity is low, and simultaneously, the ethylene in the raw material gas is hydrogenated to generate ethane, so that the reaction is out of control and the raw material is wasted. The Pd-based catalyst is regulated and controlled by introducing the second metal component, so that the selectivity of ethylene can be improved to a certain extent. As a cheap non-noble metal, the introduction of Cu not only can effectively improve the selectivity of ethylene, but also can further reduce the economic cost of the catalyst. However, how to accurately control the ratio of two metal components in the PdCu alloy and to uniformly disperse the two metal components in the PdCu alloy at a nanoscale to prepare a catalyst having both high activity and high selectivity, which is economical and practical, is still an important problem to be solved in the art.
Disclosure of Invention
The invention aims to provide supported Pd for acetylene selective hydrogenation reactionxCuyThe preparation method of the catalyst is simple and convenient to operate, different proportions of two metal components in the PdCu alloy can be accurately and effectively regulated, and the obtained PdCu alloy nanoparticles are uniformly dispersed on the carbon nanomaterial. In addition, more importantly, the catalyst obtained by the method has very excellent performance in the selective hydrogenation reaction of acetylene.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a supported PdCu bimetallic catalyst for acetylene selective hydrogenation reaction is disclosed, which comprises the steps of firstly dissolving palladium salt and copper salt with a fixed proportion in a solvent to obtain a mixed solution of the palladium salt and the copper salt; then, fully mixing the mixed solution of palladium salt and copper salt with the oxidized nano carbon material suspension to obtain a mixed material; and removing the solvent in the mixed material through a rotary evaporator, drying, grinding, and then placing in a mixed atmosphere containing hydrogen for reduction to obtain the supported PdCu bimetallic catalyst.
The method specifically comprises the following steps:
(1) preparing a nano carbon material oxidation suspension:
placing the nano carbon material in concentrated nitric acid, refluxing for 2-10 hours at 100-140 ℃, naturally cooling to room temperature, filtering, washing with deionized water to be neutral, drying to obtain an oxidized nano carbon material, and grinding into powder; putting a powdery nano carbon oxide material into a round-bottom flask, adding a solvent, and fully dispersing the nano carbon oxide material under an ultrasonic condition to obtain a nano carbon oxide material suspension;
(2) preparing a metal salt solution:
respectively weighing palladium salt and copper salt, and completely dissolving the palladium salt and the copper salt in a solvent to obtain a mixed solution of the palladium salt and the copper salt;
(3) preparation of a catalyst precursor:
adding a mixed solution of palladium salt and copper salt into the oxidized nano carbon material suspension, fully dispersing by ultrasonic to obtain a mixed material, and removing a solvent in the mixed material by a rotary evaporator to obtain a catalyst precursor;
(4) reduction of catalyst precursor:
and (3) drying the catalyst precursor prepared in the step (3) in an oven at 60-80 ℃ for 1-12 hours, fully grinding the catalyst precursor into powder, placing the powder sample in a tube furnace, and reducing the powder sample in a mixed atmosphere of hydrogen and inert gas to obtain the supported PdCu bimetallic catalyst.
In the step (1), the nano carbon material is a single-walled carbon nanotube, a multi-walled carbon nanotube, a nano carbon fiber, a nano diamond, an activated carbon, graphite or graphene; the solvent is water, dilute hydrochloric acid, dilute nitric acid, ethanol or methanol.
In the step (1), before refluxing in concentrated nitric acid, the nano carbon material is firstly stirred and soaked in concentrated hydrochloric acid for 24 hours, then is washed to be neutral by deionized water, is dried and is ground into powder; then, putting the nano carbon material powder treated by concentrated hydrochloric acid into a round-bottom flask, and adding concentrated nitric acid for reflux treatment; wherein: the volume ratio of the mass of the nano carbon material to the concentrated hydrochloric acid is 1g:100 ml; in the reflux treatment process, the mass ratio of the nanocarbon material treated by the concentrated hydrochloric acid to the concentrated nitric acid is 1g to 100 ml.
In the step (1), the ultrasonic condition is that a desktop ultrasonic instrument is adopted for processing for 1-2 hours, or an ultrasonic cell crusher is adopted for processing for 20-30 min.
In the step (2), the mixed solution of the palladium salt and the copper salt needs to be prepared as it is and kept fresh; the palladium salt is selected from one or more of palladium acetate, palladium chloride, palladium nitrate, palladium carbonate, palladium sulfate and palladium acetylacetonate; the copper salt is one or more of copper acetate, copper chloride, copper nitrate, copper carbonate, copper sulfate and copper acetylacetonate; the solvent is water, dilute hydrochloric acid, dilute nitric acid, ethanol or methanol.
In the step (3), the operating temperature of the rotary evaporator is 40-80 ℃ under a vacuum condition, and the operating time is 0.5-2 hours.
In the step (4), after the powder sample is placed in the tube furnace, the tube furnace is heated to 300-700 ℃ at the heating rate of 1-10 ℃/min, and is naturally cooled to the room temperature after the temperature is kept for 1-4 hours; in the mixed atmosphere, the hydrogen flow rate is 10ml to 100ml/min, and the argon flow rate is 10ml to 100 ml/min.
The invention adopts the method to prepare the supported PdCu bimetallic catalyst, and the catalyst is prepared from PdxCuyThe alloy nano particles are uniformly loaded on the nano carbon material to form the alloy nano particles; when a mixed solution of palladium salt and copper salt is prepared, Pd in the prepared catalyst can be accurately regulated and controlled by controlling the molar ratio of palladium to copper in the mixed solutionxCuyThe ratio of Pd to Cu in the alloy nanoparticles; pdxCuyThe diameter of the alloy nano particles is 3-15 nm.
The invention has the following advantages and beneficial effects:
1. according to the invention, palladium salt and copper salt in a fixed ratio are completely dissolved and fully dispersed in a solvent, and then fully mixed with an oxidized nano carbon material suspension, so that two metal salts are uniformly dispersed on the surface of a nano carbon material by utilizing rich oxygen functional groups of the oxidized nano carbon material, and the two metal salts are simultaneously reduced in a high-temperature hydrogen atmosphere to form the PdCu alloy in a fixed ratio.
2. The PdCu alloy nanoparticles prepared by the method are very uniformly distributed on the oxidized nano carbon material, and the particle size is about 3-15 nm.
3. The supported Pd prepared by the method of the inventionxCuyCompared with the single metal Pd/oCNT catalyst, the ethylene selectivity of the bimetallic acetylene selective hydrogenation catalyst is obviously improved.
Drawings
FIG. 1 is 5 wt.% Pd3Electron microscopy images and EDX mapping images of Cu/otnt catalyst; wherein: (a) taking an electron microscope picture; (b) EDX mapping diagram.
FIG. 2 is 5 wt.% PdCu3Electron microscopy images and EDX mapping images of/otnt catalysts; wherein: (a) taking an electron microscope picture; (b) EDX mapping diagram.
FIG. 3 is 5 wt.% Pd/oCNT catalyst, 5 wt.% Pd3Cu/oCNT catalyst and 5 wt.% PdCu3Comparison of acetylene selective hydrogenation performance of/oCNT catalyst.
Detailed Description
The present invention will be described in detail with reference to examples.
The invention provides a supported PdCu bimetallic acetylene selective hydrogenation catalyst and a preparation method thereof, wherein the method comprises the steps of fully dissolving two metal salts with fixed proportion in a solvent; then fully mixing the carbon nano-material with the carbon nano-material oxide suspension prepared in advance; and removing the solvent by a rotary evaporator, drying, grinding, and reducing in a mixed atmosphere containing hydrogen to obtain the supported PdCu bimetallic acetylene selective hydrogenation catalyst.
Example 1
5 wt.% Pd3The Cu/oCNT bimetal acetylene selective hydrogenation catalyst and the preparation method thereof specifically comprise the following steps:
(1) 3g of multi-walled Carbon Nanotubes (CNT) are stirred and soaked for 24 hours in 300ml of concentrated hydrochloric acid (HCl 37 wt.%), then are washed to be neutral by deionized water, and are dried and ground into powder; concentrated hydrochloric acid (HCl 37 wt.%) treatedCarbon Nanotube (CNT) powder was charged into a round bottom flask, 300ml of concentrated nitric acid (HNO) was added368 wt.%), refluxing nitric acid at 120 deg.c for 4 hr, naturally cooling to room temperature, washing with deionized water to neutrality, drying, and grinding into powder;
(2) weighing 190mg of the oxidized carbon nanotube (oCNT) prepared in the step (1), putting the oxidized carbon nanotube (oCNT) into a 100ml round-bottom flask with the capacity, adding 30ml of 0.1mol/L dilute nitric acid solvent, and carrying out ultrasonic treatment for 30min under the condition of an ultrasonic cell crusher to fully disperse the oxidized carbon nanotube (oCNT) so as to obtain an oxidized carbon nanotube (oCNT) suspension;
(3) 21.3mg of palladium nitrate (Pd (NO)3)2) Salt and 6.3mg copper nitrate (Cu (NO)3)2·3H2O) dissolving the salt in 20ml of 0.1mol/L dilute nitric acid solvent, and performing ultrasonic treatment for 5-10 min under the condition of a desktop ultrasonic instrument to fully dissolve the two metal salts to obtain a light golden transparent solution;
(4) fully mixing the oxidized carbon nanotube (oCNT) suspension prepared in the step (2) with the metal salt solution prepared in the step (3), and carrying out ultrasonic treatment for 10-20 min under the condition of a desktop ultrasonic instrument;
(5) carrying out rotary evaporation on the mixed solution obtained in the step (4) for 1-2 hours at the temperature of 65 ℃ in vacuum by using a rotary evaporator, and fully evaporating the solvent to obtain a catalyst precursor;
(6) drying the catalyst precursor obtained in the step (5) in an oven at 60 ℃ for 2 hours, and then fully grinding the catalyst precursor into powder; powder samples were charged to a tube furnace at 50 vol.% H2Reducing the solution for 2 hours at 500 ℃ under Ar atmosphere, and naturally cooling the solution to room temperature to obtain the 5 wt.% Pd3Cu/oCNT bimetallic acetylene selective hydrogenation catalyst (shown in figure 1). Wherein the heating rate of the tubular furnace is 10 ℃/min; the gas flow rates were 50ml/min for hydrogen and 50ml/min for argon.
Example 2
5 wt.% PdCu3The catalyst for the selective hydrogenation reaction of the/oCNT bimetal acetylene and the preparation method thereof specifically comprise the following steps:
(1) 3g of multiwall Carbon Nanotubes (CNT) were soaked in 300ml of concentrated hydrochloric acid (HCl 37 wt.%) with stirring for 24 hours, then deionizedWashing with water to neutrality, oven drying, and grinding into powder; concentrated hydrochloric acid (HCl 37 wt.%) treated Carbon Nanotube (CNT) powder was charged to a round bottom flask, and 300ml concentrated nitric acid (HNO) was added368 wt.%), refluxing nitric acid at 120 deg.c for 4 hr, naturally cooling to room temperature, washing with deionized water to neutrality, drying, and grinding into powder;
(2) weighing 190mg of the oxidized carbon nanotube (oCNT) prepared in the step (1), putting the oxidized carbon nanotube (oCNT) into a 100ml round-bottom flask with the capacity, adding 30ml of 0.1mol/L dilute nitric acid solvent, and carrying out ultrasonic treatment for 30min under the condition of an ultrasonic cell crusher to fully disperse the oxidized carbon nanotube (oCNT) so as to obtain an oxidized carbon nanotube (oCNT) suspension;
(3) 9.2mg of palladium nitrate (Pd (NO) were weighed3)2) Salt and 24.4mg copper nitrate (Cu (NO)3)2·3H2O) dissolving the salt in 20ml of 0.1mol/L dilute nitric acid solvent, and performing ultrasonic treatment for 5-10 min under the condition of a desktop ultrasonic instrument to fully dissolve the two metal salts to obtain a light golden transparent solution;
(4) fully mixing the oxidized carbon nanotube (oCNT) suspension prepared in the step (2) with the metal salt solution prepared in the step (3), and carrying out ultrasonic treatment for 10-20 min under the condition of a desktop ultrasonic instrument;
(5) carrying out rotary evaporation on the mixed solution obtained in the step (4) for 1-2 hours at the temperature of 65 ℃ in vacuum by using a rotary evaporator, and fully evaporating the solvent to obtain a catalyst precursor;
(6) drying the catalyst precursor obtained in the step (5) in an oven at 60 ℃ for 2 hours, and then fully grinding the catalyst precursor into powder; powder samples were charged to a tube furnace at 50 vol.% H2Reducing the solution for 2 hours at 500 ℃ in an Ar atmosphere, and naturally cooling the solution to room temperature to obtain the 5 wt.% PdCu3The catalyst for the selective hydrogenation reaction of/oCNT bimetallic acetylene (shown in figure 2). Wherein the heating rate of the tubular furnace is 10 ℃/min; the gas flow rates were 50ml/min for hydrogen and 50ml/min for argon.
Example 3
The supported PdCu bimetallic catalysts prepared in examples 1 and 2 (5 wt.% Pd) were mixed3Cu/oCNT catalyst and 5 wt.% PdCu3/otnt catalyst) and conventional 5 wt.% Pd/otnt catalysisThe agent is applied to acetylene selective hydrogenation reaction, and the application process is as follows:
1. the reaction conditions are as follows: acetylene hydrogenation reaction gas component: 5.0 vol.% H2、20vol.％C2H4、0.5vol.％C2H2Helium is used as balance gas, the total flow rate of the gas is 40ml/min, and the reaction temperature is 200 ℃.
2. The catalyst dosage is as follows: 0.1-0.5mg, reaction space velocity: 4800--1·g-1。
3. The effect of the application is shown in figure 3. On the premise of completely converting and removing trace acetylene in the ethylene-rich material flow, the PdCu bimetallic catalyst prepared by the method can still be nearly completely converted: catalyst conversion of 96.8% 5 wt.% Pd/oCNT, 5 wt.% Pd3Cu/oCNT catalyst conversion 98.5%, 5 wt.% PdCu3the/oCNT catalyst conversion was 98.6%.
The selectivity of the catalyst of the invention to the target product ethylene is greatly improved: 5 wt.% Pd/oCNT catalyst ethylene selectivity 39.1%, 5 wt.% Pd3Cu/oCNT catalyst ethylene selectivity of 55.4%, 5 wt.% PdCu3the/oCNT catalyst had an ethylene selectivity of 70.8%.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (9)
1. A preparation method of a supported PdCu bimetallic catalyst for acetylene selective hydrogenation reaction is characterized by comprising the following steps: firstly, dissolving palladium salt and copper salt with a fixed ratio in a solvent to obtain a mixed solution of the palladium salt and the copper salt; then, fully mixing the mixed solution of palladium salt and copper salt with the oxidized nano carbon material suspension to obtain a mixed material; and removing the solvent in the mixed material through a rotary evaporator, drying, grinding, and then placing in a mixed atmosphere containing hydrogen for reduction to obtain the supported PdCu bimetallic catalyst.
2. The preparation method of the supported PdCu bimetallic catalyst for selective hydrogenation of acetylene according to claim 1, characterized in that: the method specifically comprises the following steps:
(1) preparing a nano carbon material oxidation suspension:
placing the nano carbon material in concentrated nitric acid, refluxing for 2-10 hours at 100-140 ℃, naturally cooling to room temperature, filtering, washing with deionized water to be neutral, drying to obtain an oxidized nano carbon material, and grinding into powder; putting a powdery nano carbon oxide material into a round-bottom flask, adding a solvent, and fully dispersing the nano carbon oxide material under an ultrasonic condition to obtain a nano carbon oxide material suspension;
(2) preparing a metal salt solution:
respectively weighing palladium salt and copper salt, and completely dissolving the palladium salt and the copper salt in a solvent to obtain a mixed solution of the palladium salt and the copper salt;
(3) preparation of a catalyst precursor:
adding a mixed solution of palladium salt and copper salt into the oxidized nano carbon material suspension, fully dispersing by ultrasonic to obtain a mixed material, and removing a solvent in the mixed material by a rotary evaporator to obtain a catalyst precursor;
(4) reduction of catalyst precursor:
and (3) drying the catalyst precursor prepared in the step (3) in an oven at 60-80 ℃ for 1-12 hours, fully grinding the catalyst precursor into powder, placing the powder sample in a tube furnace, and reducing the powder sample in a mixed atmosphere of hydrogen and inert gas to obtain the supported PdCu bimetallic catalyst.
3. The preparation method of the supported PdCu bimetallic acetylene selective hydrogenation catalyst as claimed in claim 2, characterized in that: in the step (1), the nano carbon material is a single-walled carbon nanotube, a multi-walled carbon nanotube, a nano carbon fiber, a nano diamond, an activated carbon, graphite or graphene; the solvent is water, dilute hydrochloric acid, dilute nitric acid, ethanol or methanol.
4. The preparation method of the supported PdCu bimetallic acetylene selective hydrogenation catalyst as claimed in claim 2, characterized in that: in the step (1), before refluxing in concentrated nitric acid, the nano carbon material is firstly stirred and soaked in concentrated hydrochloric acid for 24 hours, then is washed to be neutral by deionized water, is dried and is ground into powder; then, putting the nano carbon material powder treated by concentrated hydrochloric acid into a round-bottom flask, and adding concentrated nitric acid for reflux treatment; wherein: the volume ratio of the mass of the nano carbon material to the concentrated hydrochloric acid is 1g:100 ml; in the reflux treatment process, the mass ratio of the nanocarbon material treated by the concentrated hydrochloric acid to the concentrated nitric acid is 1g to 100 ml.
5. The preparation method of the supported PdCu bimetallic acetylene selective hydrogenation catalyst as claimed in claim 2, characterized in that: in the step (1), the ultrasonic condition is that a desktop ultrasonic instrument is adopted for processing for 1-2 hours, or an ultrasonic cell crusher is adopted for processing for 20-30 min.
6. The preparation method of the supported PdCu bimetallic acetylene selective hydrogenation catalyst as claimed in claim 2, characterized in that: in the step (2), the mixed solution of the palladium salt and the copper salt is prepared as required and kept fresh; the palladium salt is selected from one or more of palladium acetate, palladium chloride, palladium nitrate, palladium carbonate, palladium sulfate and palladium acetylacetonate; the copper salt is one or more of copper acetate, copper chloride, copper nitrate, copper carbonate, copper sulfate and copper acetylacetonate; the solvent is water, dilute hydrochloric acid, dilute nitric acid, ethanol or methanol.
7. The preparation method of the supported PdCu bimetallic acetylene selective hydrogenation catalyst as claimed in claim 2, characterized in that: in the step (3), the operating temperature of the rotary evaporator is 40-80 ℃ under a vacuum condition, and the operating time is 0.5-2 hours.
8. The preparation method of the supported PdCu bimetallic acetylene selective hydrogenation catalyst as claimed in claim 2, characterized in that: in the step (4), after the powder sample is placed in a tube furnace, the tube furnace is heated to 300-700 ℃ at the heating rate of 1-10 ℃/min, and is naturally cooled to room temperature after the temperature is kept constant for 1-4 hours; in the mixed atmosphere, the flow rate of hydrogen is 10-100 ml/min, and the flow rate of argon is 10-100 ml/min.
9. A supported PdCu bimetallic catalyst prepared by the process of any one of claims 1 to 8, characterized in that: the catalyst is prepared from PdxCuyThe alloy nano particles are uniformly loaded on the nano carbon material to form the alloy nano particles; when a mixed solution of palladium salt and copper salt is prepared, Pd in the prepared catalyst can be accurately regulated and controlled by controlling the molar ratio of palladium to copper in the mixed solutionxCuyThe ratio of Pd to Cu in the alloy nanoparticles; pdxCuyThe diameter of the alloy nano particles is 3-15 nm.
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