CN110743567A - α -iridium carbon catalyst for selective hydrogenation of unsaturated aldehyde and preparation method and application thereof - Google Patents
α -iridium carbon catalyst for selective hydrogenation of unsaturated aldehyde and preparation method and application thereof Download PDFInfo
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- CN110743567A CN110743567A CN201911080000.6A CN201911080000A CN110743567A CN 110743567 A CN110743567 A CN 110743567A CN 201911080000 A CN201911080000 A CN 201911080000A CN 110743567 A CN110743567 A CN 110743567A
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- China
- Prior art keywords
- iridium
- carrier
- unsaturated aldehyde
- catalyst
- selective hydrogenation
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- 239000003054 catalyst Substances 0.000 title claims abstract description 74
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 31
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 title claims abstract 14
- 238000002360 preparation method Methods 0.000 title claims description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 43
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 36
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052788 barium Inorganic materials 0.000 claims abstract description 24
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 22
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 19
- 239000002184 metal Substances 0.000 claims abstract description 19
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 13
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 11
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 10
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 8
- 239000010948 rhodium Substances 0.000 claims abstract description 8
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 51
- 239000002002 slurry Substances 0.000 claims description 45
- 238000005406 washing Methods 0.000 claims description 35
- 239000000243 solution Substances 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 239000012065 filter cake Substances 0.000 claims description 28
- 239000002243 precursor Substances 0.000 claims description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 238000001914 filtration Methods 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 16
- 239000000047 product Substances 0.000 claims description 15
- 150000003839 salts Chemical class 0.000 claims description 15
- 230000007935 neutral effect Effects 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000003638 chemical reducing agent Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 238000000889 atomisation Methods 0.000 claims description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 238000009835 boiling Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 238000007598 dipping method Methods 0.000 claims description 7
- 238000004537 pulping Methods 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 229910021638 Iridium(III) chloride Inorganic materials 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 claims description 6
- GSNZLGXNWYUHMI-UHFFFAOYSA-N iridium(3+);trinitrate Chemical compound [Ir+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GSNZLGXNWYUHMI-UHFFFAOYSA-N 0.000 claims description 5
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 4
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical group FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 235000019253 formic acid Nutrition 0.000 claims description 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 4
- 150000002504 iridium compounds Chemical class 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 239000012279 sodium borohydride Substances 0.000 claims description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 4
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 4
- 239000004280 Sodium formate Substances 0.000 claims description 2
- 150000001805 chlorine compounds Chemical class 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 150000002823 nitrates Chemical class 0.000 claims description 2
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 2
- 235000019254 sodium formate Nutrition 0.000 claims description 2
- 239000003610 charcoal Substances 0.000 claims 5
- 150000001299 aldehydes Chemical class 0.000 description 43
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 8
- DZQBLSOLVRLASG-UHFFFAOYSA-N iridium;methane Chemical compound C.[Ir] DZQBLSOLVRLASG-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 5
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 5
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 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 description 3
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 3
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical group C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical group OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- WCASXYBKJHWFMY-NSCUHMNNSA-N 2-Buten-1-ol Chemical group C\C=C\CO WCASXYBKJHWFMY-NSCUHMNNSA-N 0.000 description 1
- IDEYZABHVQLHAF-XQRVVYSFSA-N 2-Methyl-2-pentenal Chemical group CC\C=C(\C)C=O IDEYZABHVQLHAF-XQRVVYSFSA-N 0.000 description 1
- IDEYZABHVQLHAF-UHFFFAOYSA-N 2-Methyl-2-pentenal Natural products CCC=C(C)C=O IDEYZABHVQLHAF-UHFFFAOYSA-N 0.000 description 1
- OVRDLJJMKGWDHY-UHFFFAOYSA-N 2-methylpent-1-en-1-ol Chemical group CCCC(C)=CO OVRDLJJMKGWDHY-UHFFFAOYSA-N 0.000 description 1
- QVDTXNVYSHVCGW-UHFFFAOYSA-N 3-methylbut-1-en-1-ol Chemical group CC(C)C=CO QVDTXNVYSHVCGW-UHFFFAOYSA-N 0.000 description 1
- SEPQTYODOKLVSB-UHFFFAOYSA-N 3-methylbut-2-enal Chemical group CC(C)=CC=O SEPQTYODOKLVSB-UHFFFAOYSA-N 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical group C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 1
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- WCASXYBKJHWFMY-UHFFFAOYSA-N gamma-methylallyl alcohol Natural products CC=CCO WCASXYBKJHWFMY-UHFFFAOYSA-N 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 125000005245 nitryl group Chemical group [N+](=O)([O-])* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—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
- B01J23/8933—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 also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8946—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 also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali or alkaline earth 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
- B01J35/399—Distribution of the active metal ingredient homogeneously throughout the support particle
-
- 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
-
- 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
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses an α -iridium carbon catalyst for selective hydrogenation of unsaturated aldehyde, which consists of a carrier and a metal component loaded on the carrier, wherein the metal component comprises iridium, barium, nickel and an auxiliary agent, the auxiliary agent is at least one of platinum, palladium, ruthenium or rhodium, the carrier is an activated carbon carrier, and the contents of the components are as follows, according to 100% by weight, iridium is 1-5%, barium is 0.1-0.5%, nickel is 0.1-0.5%, the auxiliary agent is 0.1-1%, and the balance is the carrier.
Description
Technical Field
The invention belongs to the technical field of noble metal catalysts, and particularly relates to an iridium carbon catalyst for selective hydrogenation of α -unsaturated aldehyde, and a preparation method and application thereof.
Background
Compared with compounds containing single groups such as carbon-carbon double bond, nitryl, carbonyl and the like, α -unsaturated aldehyde is more difficult to perform selective hydrogenation reaction, and the selectivity requirement on the catalyst is higher.
At present, supported iridium catalysts for α -unsaturated aldehyde hydrogenation are mainly activated carbon supported nano palladium, platinum and iridium metal catalysts, and the ubiquitous problem of the catalysts is how to further improve the activity and selectivity of the catalysts on the basis of the existing level.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides an iridium carbon catalyst for selective hydrogenation of α -unsaturated aldehyde, and also provides a preparation method and application of the catalyst, which are suitable for catalytic hydrogenation of α -unsaturated aldehyde, and have the advantages of high product yield, high selectivity, stable catalyst performance and reusability.
An α -iridium carbon catalyst for selective hydrogenation of unsaturated aldehyde is composed of a carrier and metal components loaded on the carrier, wherein the metal components comprise iridium, barium, nickel and an auxiliary agent, the auxiliary agent is at least one of platinum, palladium, ruthenium or rhodium, the carrier is an activated carbon carrier, and the iridium comprises 1-5 wt%, barium comprises 0.1-0.5 wt%, nickel comprises 0.1-0.5 wt%, the auxiliary agent comprises 0.1-1 wt%, and the balance is the carrier, wherein the auxiliary agent comprises at least one of platinum, palladium, ruthenium and rhodium.
Preferably, the particle size of the carrier is 200-800 meshes, and the specific surface area is 800-1500 m2/g。
Preferably, the iridium has an average particle size of 10 to 30 mesh.
Preferably, the content of the auxiliary agent is 0.4-0.6%.
More preferably, the content of iridium is 5% and the content of auxiliary agent is 0.5%.
The preparation method of the iridium carbon catalyst for selective hydrogenation of α -unsaturated aldehyde comprises the following steps:
(1) adding the carrier into a 10-15mol/L sodium hydroxide aqueous solution, boiling for 1-2 h, naturally cooling, washing with deionized water until the pH value of a washing solution is neutral, and filtering to obtain a pretreated carrier;
(2) dissolving a soluble iridium compound, soluble salt of barium, soluble salt of nickel and soluble salt of an auxiliary agent in a solvent, and uniformly stirring to obtain a precursor solution; the solvent is water or alcohol;
(3) carrying out ultrasonic atomization treatment on the precursor solution to obtain atomized liquid drops, introducing the atomized liquid drops into a reactor containing the pretreated carrier, uniformly stirring, dipping to obtain slurry, then adjusting the pH value of the slurry to 8-10, continuously stirring for 3-5h, filtering to obtain a filter cake, and washing the filter cake with deionized water until the pH value of a washing liquid is neutral; in the slurry, 20mL of precursor solution is correspondingly added into each gram of pretreated carrier;
(4) and (4) pulping the filter cake washed in the step (3) by using pure water to obtain slurry, adjusting the pH of the slurry to 6-9, adding a reducing agent into the slurry, carrying out reduction treatment for 0.5-6h at the temperature of 30-80 ℃, and then sequentially carrying out filtration, washing and drying treatment.
Preferably, the soluble iridium compound is iridium trichloride or/and iridium nitrate.
Preferably, the soluble salt of barium, the soluble salt of nickel and the soluble salt of the auxiliary agent are all chlorides or nitrates thereof.
Preferably, the reducing agent is sodium hypophosphite, sodium borohydride, potassium borohydride, formaldehyde, sodium formate, formic acid or hydrazine hydrate; the molar weight of the reducing agent is 3-6 times of that of the iridium.
Preferably, the temperature of the drying treatment is 60-100 ℃ and the time is 5-12 h.
A method for catalytically hydrogenating α -unsaturated aldehyde by using the catalyst comprises the steps of adding α -unsaturated aldehyde, the catalyst and a solvent into a high-pressure reaction kettle, introducing hydrogen into the high-pressure reaction kettle, and carrying out catalytic hydrogenation reaction for 1-5 hours at the temperature of 60-100 ℃ under the pressure of 1-3MPa to obtain a hydrogenated product, wherein the solvent is deionized water or methanol, and the mass ratio of the catalyst to the α -unsaturated aldehyde is (0.5-5): 100.
Preferably, when the catalyst is used for carrying out catalytic hydrogenation on α -unsaturated aldehyde, the catalytic hydrogenation is carried out for 3h at the temperature of 70 ℃ under the pressure of 1MPa to obtain a hydrogenated product, and more preferably, the mass ratio of the catalyst to α -unsaturated aldehyde is 1: 100.
The invention has the advantages that:
1. the catalyst prepared by the invention contains barium and nickel, so that the catalytic activity, selectivity and stability of the catalyst are improved;
2. the carrier is pretreated, and the precursor solution of the metal component is subjected to ultrasonic atomization to highly disperse the metal component on the activated carbon carrier, so that the dispersion uniformity of the activated carbon carrier is improved, and the activity of the catalyst is improved;
3. the preparation method of the invention is easy to operate, the raw materials are easy to obtain, and the large-scale industrial production is easy to realize. The prepared catalyst is convenient to recover after use, can realize the production-recovery-reproduction of noble metals, has less loss in the recovery process, and greatly reduces the production cost of the catalyst;
4. the catalyst prepared by the invention is used for selective catalytic hydrogenation of α -unsaturated aldehyde, the product yield is more than 94%, the product yield is improved, the production cost is reduced, the catalyst belongs to a high-efficiency green environment-friendly technology, the catalytic reaction steps are simple, the conditions are mild, and favorable conditions are provided for large-scale application of the catalyst;
5. the catalyst prepared by the method has stable service life, can be reused for many times, reduces the cost problem of using the catalyst for one time, and is easy to realize industrialization.
Detailed Description
Example 1
1. An α -iridium carbon catalyst for selective hydrogenation of unsaturated aldehyde comprises a carrier and metal components loaded on the carrier, wherein the metal components comprise iridium, barium, nickel and an auxiliary agent, the auxiliary agent comprises platinum, palladium, ruthenium and rhodium, the carrier is an activated carbon carrier, the contents of the components are, by weight percentage of 100%, iridium 5%, barium 0.1%, nickel 0.1% and the auxiliary agent 0.5%, the contents of the platinum, the palladium, the ruthenium and the rhodium are equal, and the balance is the carrier;
preferably, the particle size of the carrier is 200-800 meshes, and the specific surface area is 1200 m2/g；
Preferably, the iridium has an average particle size of 10 to 30 mesh.
2. The preparation method of the iridium carbon catalyst for selective hydrogenation of α -unsaturated aldehyde comprises the following steps:
(1) adding 10g of carrier into 15mol/L sodium hydroxide aqueous solution, boiling for 1.5h, naturally cooling, washing with deionized water until the pH value of washing liquor is neutral, and filtering to obtain the pretreated carrier;
(2) dissolving iridium nitrate, barium nitrate, nickel nitrate, platinum chloride, palladium nitrate, ruthenium trichloride and rhodium nitrate in ethanol, and uniformly stirring to obtain a precursor solution;
(3) placing the precursor solution in an ultrasonic atomizer for ultrasonic atomization treatment to obtain atomized liquid drops, introducing the atomized liquid drops into a reactor containing the pretreated carrier, uniformly stirring, dipping for 2 hours to obtain slurry, adjusting the pH of the slurry to 10 by using a sodium hydroxide solution with the mass concentration of 1%, continuously stirring for 3 hours, filtering to obtain a filter cake, and washing the filter cake by using deionized water until the pH value of a washing liquid is neutral; in the slurry, 20mL of precursor solution is correspondingly added into each gram of pretreated carrier;
(4) pulping the filter cake washed in the step (3) by using pure water of which the mass is 20 times that of the filter cake to obtain slurry, adjusting the pH of the slurry to 9 by using a sodium hydroxide solution of which the mass concentration is 1%, then adding a reducing agent sodium borohydride into the slurry, carrying out reduction treatment for 3 hours at 80 ℃, then sequentially filtering and washing, and then carrying out drying treatment for 5 hours at 100 ℃ to obtain the filter cake; wherein the molar weight of the sodium borohydride is 3 times of that of the iridium.
Example 2
1. An α -iridium carbon catalyst for selective hydrogenation of unsaturated aldehyde comprises a carrier and metal components loaded on the carrier, wherein the metal components comprise iridium, barium, nickel and an auxiliary agent, the auxiliary agent is ruthenium, the carrier is an activated carbon carrier, and the iridium, the barium, the nickel and the auxiliary agent comprise, by weight percentage of 100%, 5% of iridium, 0.2% of barium, 0.3% of nickel, 0.4% of auxiliary agent and the balance of carrier;
preferably, the particle size of the carrier is 200-800 meshes, and the specific surface area is 1500 m2/g；
Preferably, the iridium has an average particle size of 10 to 30 mesh.
2. The preparation method of the iridium carbon catalyst for selective hydrogenation of α -unsaturated aldehyde comprises the following steps:
(1) adding 10g of carrier into 15mol/L sodium hydroxide aqueous solution, boiling for 1h, naturally cooling, washing with deionized water until the pH value of washing liquor is neutral, and filtering to obtain the pretreated carrier;
(2) dissolving iridium trichloride, iridium nitrate, barium chloride, nickel nitrate and ruthenium trichloride in water, and uniformly stirring to obtain a precursor solution;
(3) placing the precursor solution in an ultrasonic atomizer for ultrasonic atomization treatment to obtain atomized liquid drops, introducing the atomized liquid drops into a reactor containing the pretreated carrier, uniformly stirring, dipping for 6 hours to obtain slurry, adjusting the pH of the slurry to 9 by using a sodium hydroxide solution with the mass concentration of 1%, continuously stirring for 5 hours, filtering to obtain a filter cake, and washing the filter cake with deionized water until the pH value of a washing liquid is neutral; in the slurry, 20mL of precursor solution is correspondingly added into each gram of pretreated carrier;
(4) pulping the filter cake washed in the step (3) by using pure water of which the mass is 20 times that of the filter cake to obtain slurry, adjusting the pH of the slurry to 7 by using a sodium hydroxide solution of which the mass concentration is 1%, then adding a reducing agent potassium borohydride into the slurry to perform reduction treatment for 1 hour at 70 ℃, then sequentially filtering and washing, and then drying the slurry for 5 hours at 100 ℃; wherein the molar weight of the potassium borohydride is 3 times of that of the iridium.
Example 3
1. An α -iridium carbon catalyst for selective hydrogenation of unsaturated aldehyde comprises a carrier and metal components loaded on the carrier, wherein the metal components comprise iridium, barium, nickel and an auxiliary agent, the auxiliary agent is platinum, the carrier is an activated carbon carrier, and the iridium, the barium, the nickel and the auxiliary agent comprise, by weight percentage of 100%, 5% of iridium, 0.1% of barium, 0.1% of nickel, 1% of auxiliary agent and the balance of carrier;
preferably, the particle size of the carrier is 200-800 meshes, and the specific surface area is 800 m2/g；
Preferably, the iridium has an average particle size of 10 to 30 mesh.
2. The preparation method of the iridium carbon catalyst for selective hydrogenation of α -unsaturated aldehyde comprises the following steps:
(1) adding 10g of carrier into 10mol/L sodium hydroxide aqueous solution, boiling for 2h, naturally cooling, washing with deionized water until the pH value of washing liquor is neutral, and filtering to obtain the pretreated carrier;
(2) dissolving iridium trichloride, iridium nitrate, barium nitrate, nickel nitrate and platinum chloride in water, and uniformly stirring to obtain a precursor solution;
(3) placing the precursor solution in an ultrasonic atomizer for ultrasonic atomization treatment to obtain atomized liquid drops, introducing the atomized liquid drops into a reactor containing the pretreated carrier, uniformly stirring, dipping for 3 hours to obtain slurry, adjusting the pH of the slurry to 10 by using a sodium hydroxide solution with the mass concentration of 1%, continuously stirring for 3 hours, filtering to obtain a filter cake, and washing the filter cake by using deionized water until the pH value of a washing liquid is neutral; in the slurry, 20mL of precursor solution is correspondingly added into each gram of pretreated carrier;
(4) pulping the filter cake washed in the step (3) by using pure water of which the mass is 20 times that of the filter cake to obtain slurry, adjusting the pH of the slurry to 9 by using a sodium hydroxide solution with the mass concentration of 1%, then adding a reducing agent sodium hypophosphite into the slurry, carrying out reduction treatment for 6 hours at 30 ℃, then sequentially filtering and washing, and then carrying out drying treatment for 12 hours at 60 ℃ to obtain the filter cake; wherein the molar weight of the sodium hypophosphite is 4 times of the molar weight of the iridium.
Example 4
1. An α -iridium carbon catalyst for selective hydrogenation of unsaturated aldehyde comprises a carrier and metal components loaded on the carrier, wherein the metal components comprise iridium, barium, nickel and an auxiliary agent, the auxiliary agent comprises platinum and palladium, the carrier is an activated carbon carrier, the contents of the components are, by weight percentage of 100%, iridium 5%, barium 0.5%, nickel 0.5% and auxiliary agent 0.1%, the contents of the platinum and the palladium are equal, and the balance is the carrier;
preferably, the particle size of the carrier is 200-800 meshes, and the specific surface area is 1200 m2/g；
Preferably, the iridium has an average particle size of 10 to 30 mesh.
2. The preparation method of the iridium carbon catalyst for selective hydrogenation of α -unsaturated aldehyde comprises the following steps:
(1) adding 10g of carrier into 15mol/L sodium hydroxide aqueous solution, boiling for 1.5h, naturally cooling, washing with deionized water until the pH value of washing liquor is neutral, and filtering to obtain the pretreated carrier;
(2) dissolving iridium trichloride, barium nitrate, nickel nitrate, platinum chloride and palladium nitrate in water, and uniformly stirring to obtain a precursor solution;
(3) putting the precursor solution into an ultrasonic atomizer for ultrasonic atomization treatment to obtain atomized liquid drops, introducing the atomized liquid drops into a reactor containing the pretreated carrier, uniformly stirring, dipping for 4 hours to obtain slurry, adjusting the pH of the slurry to 8 by using a sodium hydroxide solution with the mass concentration of 1%, continuously stirring for 3 hours, filtering to obtain a filter cake, and washing the filter cake by using deionized water until the pH value of a washing liquid is neutral; in the slurry, 20mL of precursor solution is correspondingly added into each gram of pretreated carrier;
(4) pulping the filter cake washed in the step (3) by using pure water of which the mass is 20 times that of the filter cake to obtain slurry, adjusting the pH of the slurry to 6 by using a sodium hydroxide solution of which the mass concentration is 1%, then adding a reducing agent formic acid into the slurry to perform reduction treatment for 0.5h at 80 ℃, then sequentially filtering and washing, and then drying the slurry for 10h at 90 ℃; wherein the molar weight of the formic acid is 4 times of that of the iridium.
Example 5
1. An α -iridium carbon catalyst for selective hydrogenation of unsaturated aldehyde comprises a carrier and metal components loaded on the carrier, wherein the metal components comprise iridium, barium, nickel and an auxiliary agent, the auxiliary agent comprises platinum, palladium and ruthenium, the carrier is an activated carbon carrier, the contents of the components are, by weight percentage of 100%, iridium 5%, barium 0.2%, nickel 0.1% and the auxiliary agent 0.7%, the contents of the platinum, the palladium and the ruthenium are equal, and the balance is the carrier;
preferably, the particle size of the carrier is 200-800 meshes, and the specific surface area is 1200 m2/g；
Preferably, the iridium has an average particle size of 10 to 30 mesh.
2. The preparation method of the iridium carbon catalyst for selective hydrogenation of α -unsaturated aldehyde comprises the following steps:
(1) adding 10g of carrier into 15mol/L sodium hydroxide aqueous solution, boiling for 2h, naturally cooling, washing with deionized water until the pH value of washing liquor is neutral, and filtering to obtain the pretreated carrier;
(2) dissolving iridium trichloride, barium nitrate, nickel nitrate, platinum chloride, palladium nitrate and ruthenium trichloride in water, and uniformly stirring to obtain a precursor solution;
(3) placing the precursor solution in an ultrasonic atomizer for ultrasonic atomization treatment to obtain atomized liquid drops, introducing the atomized liquid drops into a reactor containing the pretreated carrier, uniformly stirring, dipping for 4 hours to obtain slurry, adjusting the pH of the slurry to 9 by using a sodium hydroxide solution with the mass concentration of 1%, continuously stirring for 4 hours, filtering to obtain a filter cake, and washing the filter cake with deionized water until the pH value of a washing liquid is neutral; in the slurry, 20mL of precursor solution is correspondingly added into each gram of pretreated carrier;
(4) pulping the filter cake washed in the step (3) by using pure water of which the mass is 20 times that of the filter cake to obtain slurry, adjusting the pH of the slurry to 8 by using a sodium hydroxide solution of which the mass concentration is 1%, then adding a reducing agent hydrazine hydrate into the slurry to perform reduction treatment for 3 hours at 60 ℃, then sequentially filtering and washing, and then drying the slurry for 10 hours at 90 ℃; wherein the molar weight of hydrazine hydrate is 5 times of the molar weight of iridium.
Example 6
The auxiliary agent is rhodium, the iridium content is 3%, the corresponding soluble salt in the preparation method is rhodium nitrate, and the rest is the same as the example 2.
Example 7
The auxiliary agent is rhodium, the iridium content is 1%, the corresponding soluble salt in the preparation method is rhodium nitrate, and the rest is the same as the example 2.
Example 8
The auxiliaries are platinum and ruthenium, the iridium content is 5%, the corresponding soluble salts in the preparation method are platinum chloride and ruthenium trichloride, and the rest is the same as in example 4.
Comparative examples 1 to 5
Barium and nickel were not included, and the examples 1 to 5 were the same.
Example 9
The catalysts of examples 1-5 and comparative examples were used to implement the examples as follows:
a method for catalytically hydrogenating α -unsaturated aldehyde by using the catalyst comprises the steps of adding α -unsaturated aldehyde, the catalyst and a solvent into a high-pressure reaction kettle, introducing hydrogen into the high-pressure reaction kettle, and carrying out catalytic hydrogenation reaction for 3 hours at the temperature of 70 ℃ under the pressure of 1MPa to obtain a hydrogenated product, wherein the solvent is methanol, the α -unsaturated aldehyde is 2-butenal, the mass ratio of the catalyst to the α -unsaturated aldehyde is 1: 100, and the hydrogenated product is 2-butenol.
Example 10
The catalysts of examples 1-5 and comparative examples were used to implement the examples as follows:
a method for catalytically hydrogenating α -unsaturated aldehyde by using the catalyst comprises the steps of adding α -unsaturated aldehyde, the catalyst and a solvent into a high-pressure reaction kettle, introducing hydrogen into the high-pressure reaction kettle, and carrying out catalytic hydrogenation reaction for 5 hours at the temperature of 80 ℃ under the pressure of 2MPa to obtain a hydrogenated product, wherein the solvent is methanol, the α -unsaturated aldehyde is acrolein, and the hydrogenated product is allyl alcohol, wherein the mass ratio of the catalyst to the α -unsaturated aldehyde is 5: 100.
Example 11
The catalysts of examples 1-5 and comparative examples were used to implement the examples as follows:
a method for catalytically hydrogenating α -unsaturated aldehyde by using the catalyst comprises the steps of adding α -unsaturated aldehyde, the catalyst and a solvent into a high-pressure reaction kettle, introducing hydrogen into the high-pressure reaction kettle, and carrying out catalytic hydrogenation reaction for 1 hour at the temperature of 100 ℃ under the pressure of 2MPa to obtain a hydrogenated product, wherein the solvent is methanol, the α -unsaturated aldehyde is 3-methyl-butenal, the mass ratio of the catalyst to the α -unsaturated aldehyde is 1: 100, and the hydrogenated product is 3-methyl-butenol.
Example 12
The catalysts of examples 1-5 and comparative examples were used to implement the examples as follows:
a method for catalytically hydrogenating α -unsaturated aldehyde by using the catalyst comprises the steps of adding α -unsaturated aldehyde, the catalyst and a solvent into a high-pressure reaction kettle, introducing hydrogen into the high-pressure reaction kettle, and carrying out catalytic hydrogenation reaction for 5 hours at the temperature of 60 ℃ under the pressure of 3MPa to obtain a hydrogenated product, wherein the solvent is methanol, the α -unsaturated aldehyde is 2-methyl-pentenal, the mass ratio of the catalyst to the α -unsaturated aldehyde is 0.5: 100, and the hydrogenated product is 2-methyl-pentenol.
First, 5mL of the samples of examples 9-12 were collected, filtered, diluted to 50mL with methanol, and analyzed by Shimadzu gas chromatography GC-2014, the results of which are shown in Table 1.
TABLE 1 test yield results for the selective hydrogenation of α -unsaturated aldehydes over different catalysts
As is apparent from Table 1, when the catalyst prepared by the method is used for hydrogenation of α -unsaturated aldehyde, the yield of the product of the catalytic hydrogenation reaction is greatly improved, and the yield exceeds 94%.
Secondly, detecting the stability of the catalyst
The stability of the catalyst was tested by conducting catalytic hydrogenation repeatability tests as described in examples 9-12, the results of which are shown in Table 2.
TABLE 2 test yield results (%) -for repeated catalytic selective hydrogenation of α -unsaturated aldehydes on different catalysts
As is apparent from Table 2, the catalyst provided by the present invention has stable performance and good reproducibility.
Claims (10)
1. An α -iridium carbon catalyst for selective hydrogenation of unsaturated aldehyde is characterized by comprising a carrier and metal components loaded on the carrier, wherein the metal components comprise iridium, barium, nickel and an auxiliary agent, the auxiliary agent is at least one of platinum, palladium, ruthenium or rhodium, the carrier is an activated carbon carrier, and the iridium, the barium, the nickel and the auxiliary agent comprise 1-5 wt%, 0.1-0.5 wt%, 0.1-1 wt% and the balance of the carrier, wherein the auxiliary agent comprises 100 wt%.
2. The α -iridium carbon catalyst for selective hydrogenation of unsaturated aldehyde as claimed in claim 1, wherein the carrier has a particle size of 200-800 meshes and a specific surface area of 800-1500 m2/g。
3. The α -Iridium charcoal catalyst for selective hydrogenation of unsaturated aldehydes as claimed in claim 1, wherein the iridium has an average particle size of 10-30 mesh.
4. The α -Iridium charcoal catalyst for selective hydrogenation of unsaturated aldehyde according to any of claims 1-3, wherein the content of the auxiliary agent is 0.4-0.6%.
5. The method for preparing the iridium charcoal catalyst for selective hydrogenation of α -unsaturated aldehyde according to any one of claims 1-3, comprising the steps of:
(1) adding the carrier into a 10-15mol/L sodium hydroxide aqueous solution, boiling for 1-2 h, naturally cooling, washing with deionized water until the pH value of a washing solution is neutral, and filtering to obtain a pretreated carrier;
(2) dissolving a soluble iridium compound, soluble salt of barium, soluble salt of nickel and soluble salt of an auxiliary agent in a solvent, and uniformly stirring to obtain a precursor solution; the solvent is water or alcohol;
(3) carrying out ultrasonic atomization treatment on the precursor solution to obtain atomized liquid drops, introducing the atomized liquid drops into a reactor containing the pretreated carrier, uniformly stirring, dipping to obtain slurry, then adjusting the pH value of the slurry to 8-10, continuously stirring for 3-5h, filtering to obtain a filter cake, and washing the filter cake with deionized water until the pH value of a washing liquid is neutral; in the slurry, 20mL of precursor solution is correspondingly added into each gram of pretreated carrier;
(4) and (4) pulping the filter cake washed in the step (3) by using pure water to obtain slurry, adjusting the pH of the slurry to 6-9, adding a reducing agent into the slurry, carrying out reduction treatment for 0.5-6h at the temperature of 30-80 ℃, and then sequentially carrying out filtration, washing and drying treatment.
6. The α -method for preparing iridium charcoal catalyst for selective hydrogenation of unsaturated aldehyde according to claim 5, wherein the soluble iridium compound is iridium trichloride or/and iridium nitrate.
7. The method for preparing α -iridium carbon catalyst for selective hydrogenation of unsaturated aldehyde according to claim 5, wherein the soluble salt of barium, the soluble salt of nickel and the soluble salt of auxiliary are all chlorides or nitrates thereof.
8. The preparation method of α -iridium carbon catalyst for selective hydrogenation of unsaturated aldehyde according to claim 5, wherein the reducing agent is sodium hypophosphite, sodium borohydride, potassium borohydride, formaldehyde, sodium formate, formic acid or hydrazine hydrate, and the molar weight of the reducing agent is 3-6 times of the molar weight of iridium.
9. The method for preparing α -iridium charcoal catalyst for selective hydrogenation of unsaturated aldehyde according to claim 5, wherein the drying treatment temperature is 60-100 ℃ and the drying treatment time is 5-12 h.
10. A method for catalytically hydrogenating α -unsaturated aldehyde by using the catalyst as claimed in any one of claims 1 to 3, wherein the method comprises the steps of adding α -unsaturated aldehyde, the catalyst and a solvent into a high-pressure reaction kettle, introducing hydrogen into the high-pressure reaction kettle, and carrying out catalytic hydrogenation reaction for 1 to 5 hours at the temperature of between 60 and 100 ℃ under the pressure of between 1 and 3MPa to obtain a hydrogenated product, wherein the solvent is deionized water or methanol, and the mass ratio of the catalyst to the α -unsaturated aldehyde is (0.5 to 5): 100.
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Inventor after: Li Xiaohu Inventor after: Li Lin Inventor after: Jin Xiaodong Inventor after: Zeng Lihui Inventor after: Li Yuefeng Inventor after: Zeng Yongkang Inventor after: Zhang Zhixiang Inventor before: Li Xiaohu Inventor before: Li Lin Inventor before: Jin Xiaodong Inventor before: Zeng Lihui Inventor before: Li Yuefeng Inventor before: Zeng Yongkang Inventor before: Zhang Zhixiang |