CN112705197B - Carbon nano tube supported palladium-calcium monolithic catalyst and application thereof in cinnamaldehyde hydrogenation - Google Patents
Carbon nano tube supported palladium-calcium monolithic catalyst and application thereof in cinnamaldehyde hydrogenation Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 68
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 40
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 40
- 239000011575 calcium Substances 0.000 title claims abstract description 33
- 229910052791 calcium Inorganic materials 0.000 title claims abstract description 31
- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 title claims abstract description 23
- 229940117916 cinnamic aldehyde Drugs 0.000 title claims abstract description 21
- KJPRLNWUNMBNBZ-UHFFFAOYSA-N cinnamic aldehyde Natural products O=CC=CC1=CC=CC=C1 KJPRLNWUNMBNBZ-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 18
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 56
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 27
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 22
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 15
- 239000001257 hydrogen Substances 0.000 claims abstract description 15
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 14
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 14
- 239000000661 sodium alginate Substances 0.000 claims abstract description 14
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- 238000001354 calcination Methods 0.000 claims abstract description 10
- 239000012298 atmosphere Substances 0.000 claims abstract description 8
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 27
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- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 230000032683 aging Effects 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- 239000012752 auxiliary agent Substances 0.000 claims description 8
- 238000009777 vacuum freeze-drying Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000011068 loading method Methods 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- YGCZTXZTJXYWCO-UHFFFAOYSA-N 3-phenylpropanal Chemical compound O=CCCC1=CC=CC=C1 YGCZTXZTJXYWCO-UHFFFAOYSA-N 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical group [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000292 calcium oxide Substances 0.000 claims description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-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
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 claims description 2
- 229910000020 calcium bicarbonate Inorganic materials 0.000 claims description 2
- YYRMJZQKEFZXMX-UHFFFAOYSA-L calcium bis(dihydrogenphosphate) Chemical compound [Ca+2].OP(O)([O-])=O.OP(O)([O-])=O YYRMJZQKEFZXMX-UHFFFAOYSA-L 0.000 claims description 2
- YALMXYPQBUJUME-UHFFFAOYSA-L calcium chlorate Chemical compound [Ca+2].[O-]Cl(=O)=O.[O-]Cl(=O)=O YALMXYPQBUJUME-UHFFFAOYSA-L 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- 229940062672 calcium dihydrogen phosphate Drugs 0.000 claims description 2
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 2
- 239000002134 carbon nanofiber Substances 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 235000019691 monocalcium phosphate Nutrition 0.000 claims description 2
- 239000002048 multi walled nanotube Substances 0.000 claims description 2
- 229940078552 o-xylene Drugs 0.000 claims description 2
- 239000003960 organic solvent Substances 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
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- 239000000203 mixture Substances 0.000 abstract description 15
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 238000005530 etching Methods 0.000 abstract 1
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- 150000001299 aldehydes Chemical class 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
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- 239000002778 food additive Substances 0.000 description 2
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
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- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- 230000003993 interaction Effects 0.000 description 1
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- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- JUBNUQXDQDMSKL-UHFFFAOYSA-N palladium(2+);dinitrate;dihydrate Chemical compound O.O.[Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O JUBNUQXDQDMSKL-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
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- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- 238000004627 transmission electron microscopy 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/58—Platinum group metals with alkali- or alkaline earth metals
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- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
- C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention provides a carbon nano tube supported palladium-calcium monolithic catalyst and application thereof in cinnamaldehyde hydrogenation. Adding a proper amount of water into the carbon nano tube for ultrasonic crushing treatment, mixing the carbon nano tube with a palladium-based compound (palladium nitrate) and sodium alginate according to a certain proportion at a certain temperature, and dripping the mixture into a calcium chloride solution with a certain concentration to form a regular and uniform palladium-calcium carbon-based monolithic catalyst. Then air calcination treatment is carried out at a certain temperature (200-450 ℃), and reduction treatment is carried out at a certain temperature (200-450 ℃) in a hydrogen atmosphere. Then the palladium-calcium carbon-based monolithic catalyst loaded by the carbon nano tube with different calcium contents is obtained by etching treatment with hydrochloric acid (0.1 mol/L-2 mol/L) with certain concentration. When the palladium-carbon based catalyst is applied to cinnamaldehyde hydrogenation reaction, the electronic characteristics of the palladium-carbon based catalyst can be regulated and controlled by calcium, so that the catalyst can exert better activity and product selectivity.
Description
Technical Field
The invention belongs to the field of material synthesis and catalytic application, and particularly relates to a preparation method and application of a novel palladium-calcium bimetallic supported carbon nanotube integral multi-carbon spherical composite catalyst.
Background
Hydrogenation of α, β unsaturated aldehydes α, β unsaturated alcohols obtained by hydrogenation of C ═ O and C ═ C bonds, and saturated aldehydes, are important intermediates for food additives and medical compounds. The palladium-based catalyst is suitable for the reaction of preparing hydrocinnamaldehyde by hydrogenation of cinnamaldehyde because the d-band center theory contributes to the hydrogenation reaction of C ═ C double bonds. However, a single palladium-based catalyst, although having significant catalytic activity for the hydrogenation of cinnamaldehyde, is not very selective. Generally, the electronic structure of a palladium-based catalyst is usually controlled by controlling the carrier of the palladium-based catalyst, adding an auxiliary agent, or preparing a double alloy. Alkali metals and alkaline earth metals such as lithium, sodium, potassium, magnesium are often used as promoters in cinnamaldehyde hydrogenation reactions and generally improve catalyst selectivity, but adversely affect the activity of the reaction due to plugging or poisoning of palladium-based active sites by the promoters.
Disclosure of Invention
The invention aims to provide a preparation method of a novel palladium-calcium bimetallic supported carbon nanotube monolithic multi-carbon spherical composite catalyst, and the catalyst is used for cinnamaldehyde hydrogenation reaction with application prospect. The invention regulates and controls the content of calcium in the palladium-calcium bimetallic multi-carbon composite catalyst by using dilute hydrochloric acid, thereby regulating and controlling the electrons of palladium on the surface and also utilizing the strong interaction between palladium and carbon to supply palladium electrons. Thereby improving the catalytic activity of the palladium-calcium bimetallic carbon-based catalyst in the hydrogenation of cinnamaldehyde. The preparation method of the catalyst has the advantages of simplicity, short reaction time, no need of any complex operation and special equipment and the like. The target reaction is simple, the toxicity is low, and the cinnamaldehyde can be used as a food additive.
The technical scheme adopted by the invention is as follows:
the invention provides a carbon nano tube monolithic supported catalyst, which comprises a carrier, an active center and an auxiliary agent; the carrier is a carbon sphere formed by a carbon nano tube; the active center is metal palladium; the auxiliary agent is calcium oxide; the size of the carbon spheres is 0.5-4 mm; the loading amount of the metal palladium is 0.05-3 wt%; the loading amount of the metal calcium (metal calcium in calcium oxide) is 0.01-4 wt%, the metal palladium exists in a metal state, and the metal calcium exists in an oxide state. The carbon spheres are composed of carbon nanotubes and sodium alginate.
The invention also provides a preparation method of the supported catalyst, which comprises the following steps:
(1) dissolving a carbon nano tube in a solvent at 15-30 ℃, and then carrying out ultrasonic crushing treatment to obtain a carbon nano tube suspension, wherein the concentration of the added carbon nano tube is 10-40 mg/mL;
(2) heating the carbon nanotube suspension at a certain temperature (40-80 ℃) for 5-30 min, adding a palladium source, and adding sodium alginate after the carbon nanotube suspension is stabilized in a water bath kettle at a certain temperature (40-80 ℃) for 10-20 min to obtain a mixed solution A;
(3) and mixing the mixed solution A with a calcium source, and standing and aging for 24-72 hours at a certain temperature (15-30 ℃).
(4) Washing, drying, and calcining in air at 200-450 ℃ for 2-4 h; reducing the calcined sample in a hydrogen atmosphere to obtain Pd @ CNT beads;
(5) soaking and cleaning the Pd @ CNT beads by hydrochloric acid to obtain the supported catalyst; the mass ratio of the carbon nano tube to the sodium alginate is 1-4: 1.
Based on the above technical solution, preferably, the carbon nanotube includes one or more of a single-walled carbon nanotube, a multi-walled carbon nanotube and a carbon nanofiber; the palladium source is one or a plurality of compounds of palladium nitrate, palladium chloride, palladium sulfate, palladium acetate and palladium acetylacetonate; the calcium source is calcium chloride, calcium chlorate, calcium dihydrogen phosphate, calcium nitrate or calcium bicarbonate.
Based on the technical scheme, preferably, the crushing treatment is ultrasonic crushing treatment; the power of ultrasonic treatment is 200-800w, the treatment time is 0.5-3h, and the drying is vacuum freeze drying, vacuum drying and common drying. The carbon nanotubes used in the present invention are treated with an acid to remove ash such as metal ions before being dissolved in water.
Based on the technical scheme, the preferable reduction temperature of the hydrogen is 200-450 ℃, and the reduction time is 2-6 h.
Based on the technical scheme, the following steps are preferred: treating the catalyst with hydrochloric acid to obtain catalysts with different calcium contents, wherein the concentration of the hydrochloric acid in the step (5) is 0.5-2 mol/L; the soaking and cleaning time is 1-4 h.
The invention also provides an application of the supported catalyst, and the supported catalyst is applied to the reaction of preparing the hydrogenated cinnamaldehyde by cinnamaldehyde hydrogenation.
Based on the technical scheme, the preferable reaction device for the reaction is a kettle type reactor, the hydrogen pressure in the reaction is 5-20 bar, the reaction temperature is 50-100 ℃, the mass ratio of the catalyst to the reaction substrate cinnamaldehyde is 0.05-0.5: 1, dioxane is used as an organic solvent in the reaction, and o-xylene is used as an internal standard.
The specific steps for preparing the novel palladium-calcium bimetallic supported multi-carbon spherical composite catalyst can be summarized as follows:
(1) at room temperature, a certain amount of carbon nano tubes are put into a proper amount of solvent for ultrasonic crushing treatment. The mass of the added carbon nano tube is 1g and 2g respectively; the added solvent is water, the volume is 50mL, the power of a crushing ultrasonic machine is 400w, and the ultrasonic time is 1 h.
(2) The crushed carbon nanotube mixture is put into a water bath kettle to be heated at 50 ℃ with stirring at 500r/min, and then a proper amount of 2.6mg/mL palladium nitrate dihydrate solution is added into the mixture, wherein the adding volumes are 5mL, 10mL and 15mL respectively.
(3) After the temperature is stabilized for 10 minutes in the water bath kettle, adding a proper amount of sodium alginate, wherein the mass of the added sodium alginate is 500mg and 1000mg respectively;
(4) then preparing about 1000mL of 3 wt% calcium chloride solution;
(5) then the sticky mixture is dripped into the prepared 3 wt% calcium chloride solution at a constant speed. Balling and aging for 24 h.
(6) After aging, the carbon spheres are repeatedly washed, and then subjected to programmed vacuum freeze drying, and then air calcination treatment at a certain temperature. The calcination temperature was 300 deg.C, 350 deg.C, 400 deg.C, respectively.
(7) The calcined sample was reduced with hydrogen at 400 ℃ to give Pd @ CNT beads.
(8) And soaking and cleaning the obtained Pd @ CNT beads catalyst for 2 hours and 4 hours by 1mol/L hydrochloric acid.
Aiming at the problems of the catalyst in the prior art, the invention adopts calcium as an auxiliary agent to be added into the palladium-carbon catalyst to prepare the palladium-calcium bimetallic carbon-based monolithic catalyst, and the catalyst is treated by dilute hydrochloric acid to control the content of the auxiliary agent calcium so as to reduce the poisoning of the auxiliary agent on the palladium-based catalyst.
Advantageous effects
(1) The catalyst obtained by the invention is an integral carbon-based catalyst and is of a spherical integral structure, and compared with a powdery material, the catalyst is easier to recycle and reuse.
(2) The carbon sphere carrier is formed by taking carbon nano tubes and sodium alginate as carbon sources, and the conversion of one-dimensional carbon-based materials into three-dimensional carbon composite materials can help to increase the exposed surface of active sites.
(3) The preparation method adopts hydrochloric acid for soaking and cleaning, reduces the load of calcium while ensuring the load of palladium, and helps to improve the catalytic performance of the palladium-based catalyst by proper calcium content.
Drawings
FIG. 1 is a scanning electron microscope image of Pd @ CNT beads as spherical monolithic catalysts prepared in example 1.
FIG. 2 shows Pd @ CNT as a spherical monolithic catalyst prepared in example 1 HCl-2h Transmission electron microscopy of beads.
FIG. 3 shows Pd @ CNT as a spherical monolithic catalyst prepared in example 1 HCl-2h XRD pattern of beads.
FIG. 4 is a graph comparing the performance of the spherical monolithic catalysts prepared in comparative example 1, example 1 and example 2 for the hydrogenation of cinnamaldehyde to produce hydrogenated cinnamaldehyde.
Detailed Description
The following is a further description with reference to specific examples and comparative examples.
Comparative example 1
Putting 1g of carbon nano tube subjected to acid treatment into 50mL of ultrapure water for ultrasonic crushing treatment, putting the crushed mixture into a 50 ℃ water bath kettle for heating and stirring treatment for 10min, then adding 10mL of 2.6mg/mL palladium nitrate solution, then adding 500mg of sodium alginate, stirring uniformly, dropping the uniform and viscous mixture into the prepared 3 wt% calcium chloride solution at a constant speed for self-assembly into balls, and aging for 24 h. And then putting the catalyst into a vacuum freeze drying box for programmed temperature rise freeze drying after being washed by ultrapure water for multiple times, calcining at 350 ℃ for 2 hours in an air atmosphere after freeze drying, and then reducing at 400 ℃ for 2 hours to obtain Pd @ CNT beads, wherein the content of palladium in the catalyst is 0.92%, and the content of calcium in the catalyst is 4.33%.
Example 1
The Pd @ CNT beads obtained in the comparative example are treated with 1mol/L dilute hydrochloric acid for 2h to obtain the Pd @ CNT HCl-2h The resulting catalyst had a palladium content of 0.97% and a calcium content of 0.28%. As can be seen from FIG. 1, the size of the carbon spheres is 0.5-4 mm, the carbon sphere carrier is a spherical structure assembled by carbon nanotubes, and the small particles loaded on the carrier are metal Pd. As can be seen from the XRD chart of fig. 3, the catalyst prepared by the present invention shows diffraction peaks of carbon nanotubes and metallic Pd.
Example 2
The other steps are the same as example 1 except that the time of dilute hydrochloric acid treatment is changed to 4 hours to obtain the catalyst Pd @ CNT HCl-4h The content of palladium in the obtained catalyst was 0.93%, and the content of calcium was 0.06%.
Table 1 shows Pd @ CNT as spherical monolithic catalysts prepared in comparative example 1 and examples 1 and 2 HCl-xh Palladium and calcium content of beads are shown.
From the combination of table 1 and fig. 4, in the preparation method of the present invention, after hydrochloric acid treatment, the Ca loading is significantly reduced, and the Ca loading can reduce the influence on metal Pd, and regulate and control the performance of the catalyst.
Example 3
1g of the carbon nano tube treated by the acid is put into 50mL of ultrapure water for ultrasonic crushing treatment, and the crushed mixture is put into a water bath kettle at 50 ℃ for heating and stirringTreating for 10min, then adding 5mL of 2.6mg/mL palladium nitrate solution, then adding 500mg of sodium alginate, stirring uniformly, dropping the uniform viscous mixture into the prepared 3 wt% calcium chloride solution at a constant speed, self-assembling into balls, and aging for 24 h. And then, washing with ultrapure water for multiple times, putting into a vacuum freeze drying box for programmed temperature rise freeze drying, after freeze drying, calcining at 350 ℃ for 2 hours in an air atmosphere, and then performing hydrogen reduction treatment under certain conditions to obtain the Pd @ CNT beads. Then respectively treating the solution with 1mol/L diluted hydrochloric acid for 2 hours to obtain Pd @ CNT HCl-2h beads。
Example 4
The catalyst Pd @ CNT was obtained by following the same procedures as in example 3 while changing the treatment time of dilute hydrochloric acid to 4 hours HCl-4h beads。
Example 5
Putting 1g of the carbon nano tube subjected to acid treatment into 50mL of ultrapure water for ultrasonic crushing treatment, putting the crushed mixture into a 50 ℃ water bath kettle for heating and stirring treatment for 10min, then adding 15mL of 2.6mg/mL palladium nitrate solution, then adding 500mg of sodium alginate, stirring uniformly, dropping the uniform and viscous mixture into the prepared 3 wt% calcium chloride solution at a constant speed for self-assembly into balls, and aging for 24 h. And then putting the ball into a vacuum freeze drying box for programmed temperature rise freeze drying after being washed by ultrapure water for multiple times, calcining the ball at 300 ℃ for 2 hours in an air atmosphere after freeze drying, and then performing hydrogen reduction treatment under certain conditions to obtain the Pd @ CNT beads. Then treating the solution for 2 hours by using 0.5mol/L dilute hydrochloric acid to obtain Pd @ CNT HCl-2h beads。
Example 6
The catalyst Pd @ CNT was obtained by following the same procedures as in example 5 while changing the treatment time of dilute hydrochloric acid to 4 hours HCl-4h beads。
Example 7
Placing 2g of the carbon nano tube subjected to acid treatment into 50mL of ultrapure water for ultrasonic crushing treatment, placing the crushed mixture into a 50 ℃ water bath kettle for heating and stirring treatment for 10min, then adding 15mL of 2.6mg/mL palladium nitrate solution, then adding 500mg of sodium alginate, and stirring uniformlyUniformly dropping the uniform viscous mixture into the prepared 3 wt% calcium chloride solution at a constant speed, self-assembling into balls, and aging for 24 h. And then, washing with ultrapure water for multiple times, putting into a vacuum freeze drying box for programmed temperature rise freeze drying, after freeze drying, calcining at 400 ℃ for 2 hours in an air atmosphere, and then performing hydrogen reduction treatment under certain conditions to obtain the Pd @ CNT beads. Then respectively treating the solution with 2mol/L diluted hydrochloric acid for 2 hours to obtain Pd @ CNT HCl-2h beads。
Example 8
The other steps are the same as example 7 except that the time of dilute hydrochloric acid treatment is changed to 4h, and the catalyst Pd @ CNT is obtained HCl-4h beads。
Example 9
Putting 2g of the carbon nano tube subjected to acid treatment into 50mL of ultrapure water for ultrasonic crushing treatment, putting the crushed mixture into a water bath kettle at 50 ℃, heating and stirring for 10min, then adding 15mL of 2.6mg/mL palladium nitrate solution, then adding 500mg of sodium alginate, uniformly stirring, dropping the uniform and viscous mixture into the prepared 3 wt% calcium chloride solution at a constant speed, self-assembling into balls, and aging for 24 h. And then, washing with ultrapure water for multiple times, putting into a vacuum freeze drying box for programmed temperature rise freeze drying, after freeze drying, calcining at 350 ℃ for 2 hours in an air atmosphere, and then performing hydrogen reduction treatment under certain conditions to obtain the Pd @ CNT beads. Then, the mixture is treated for 2 hours by using 2mol/L diluted hydrochloric acid respectively.
Example 10
The catalyst prepared in the comparative example 1 and the examples 1 and 2 is used for reaction research of hydrogenation preparation of hydrocinnamaldehyde by cinnamaldehyde, wherein the pressure of hydrogen in a reaction kettle is 10bar, the reaction temperature is 80 ℃, the mass of the catalyst is 30mg, 5ml of 0.45mol/L cinnamaldehyde reaction liquid is used, and the reaction time is 30min.
Example 11
The catalysts prepared in the above examples 3 and 4 were used in the reaction study of hydrogenation of cinnamaldehyde to prepare hydrocinnamaldehyde, wherein the pressure of hydrogen in the reaction kettle was 10bar, the reaction temperature was 80 ℃, the mass of the catalyst used was 30mg, and 5ml of 0.45mol/L cinnamaldehyde reaction solution was used for 120 min.
Example 12
The catalysts prepared in the above examples 5 and 6 were used in the reaction study of hydrogenation of cinnamaldehyde to prepare hydrocinnamaldehyde, wherein the pressure of hydrogen in the reaction kettle was 5bar, the reaction temperature was 60 ℃, the mass of the catalyst used was 30mg, and 5ml of 0.45mol/L cinnamaldehyde reaction solution was used for 30min.
Claims (6)
1. A load type catalyst integrally formed by carbon nano tubes is characterized by comprising a carrier, an active center and an auxiliary agent; the carrier is a carbon sphere formed by a carbon nano tube; the active center is metal palladium; the auxiliary agent is calcium oxide; the size of the carbon spheres is 0.5-4 mm; the loading amount of the metal palladium is 0.05-3 wt%; the loading amount of the metal calcium is 0.01-4.0 wt%;
the preparation method of the supported catalyst integrally formed by the carbon nano tube comprises the following steps:
(1) dissolving a carbon nanotube in water at 15-30 ℃, and carrying out ultrasonic crushing treatment to obtain a carbon nanotube suspension, wherein the concentration of the carbon nanotube suspension is 10-40 mg/mL;
(2) heating and stirring the carbon nanotube suspension at 40-80 ℃ for 5-30 min, then adding a palladium source, stirring for 10-20 min, and adding sodium alginate to obtain a mixed solution A;
(3) mixing the mixed solution A with a calcium source, and standing and aging for 24-72 h at 15-30 ℃;
(4) washing, drying, and calcining in air at 200-450 ℃ for 2-4 h; reducing the calcined sample in a hydrogen atmosphere to obtain Pd @ CNT beads;
(5) soaking and cleaning the Pd @ CNT beads by hydrochloric acid to obtain the supported catalyst;
the concentration of the hydrochloric acid in the step (5) is 0.1-2 mol/L; the soaking and cleaning time is 1-4 h;
the mass ratio of the carbon nano tube to the sodium alginate is 1-4: 1.
2. The supported catalyst of claim 1, wherein: the carbon nano-tube is at least one of a single-walled carbon nano-tube, a multi-walled carbon nano-tube or a carbon nano-fiber; the palladium source is at least one of palladium nitrate, palladium chloride, palladium sulfate, palladium acetate and palladium acetylacetonate; the calcium source is calcium chloride, calcium chlorate, calcium dihydrogen phosphate, calcium nitrate or calcium bicarbonate.
3. The supported catalyst of claim 1, wherein: the crushing treatment is ultrasonic crushing treatment, the power of the ultrasonic treatment is 200-800w, the treatment time is 0.5-3h, and the drying is vacuum freeze drying, vacuum drying or common drying.
4. The supported catalyst of claim 1, wherein: the reduction temperature of the hydrogen is 200-450 ℃, and the reduction time is 1-6 h.
5. Use of the carbon nanotube monolithic supported catalyst of claim 1 in the preparation of hydrocinnamaldehyde by hydrogenation of cinnamaldehyde.
6. The application of claim 5, wherein the reaction device is a kettle reactor, the pressure of hydrogen in the reaction is 5-20 bar, the reaction temperature is 50-100 ℃, the mass ratio of the catalyst to the reaction substrate cinnamaldehyde is 0.05-0.5: 1, and the reaction uses dioxane as an organic solvent and o-xylene as an internal standard.
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