CN114733538B - Method for synthesizing 3-hydroxy-2-pentanone by selective hydrogenation - Google Patents
Method for synthesizing 3-hydroxy-2-pentanone by selective hydrogenation Download PDFInfo
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- CN114733538B CN114733538B CN202210284505.XA CN202210284505A CN114733538B CN 114733538 B CN114733538 B CN 114733538B CN 202210284505 A CN202210284505 A CN 202210284505A CN 114733538 B CN114733538 B CN 114733538B
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- HDKKRASBPHFULQ-UHFFFAOYSA-N 3-Hydroxy-2-pentanone Chemical compound CCC(O)C(C)=O HDKKRASBPHFULQ-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 238000000034 method Methods 0.000 title claims abstract description 48
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 13
- 238000005984 hydrogenation reaction Methods 0.000 title abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 63
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 62
- TZMFJUDUGYTVRY-UHFFFAOYSA-N pentane-2,3-dione Chemical compound CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 claims abstract description 50
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 33
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 12
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 11
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims abstract description 11
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000006722 reduction reaction Methods 0.000 claims abstract description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 238000000227 grinding Methods 0.000 claims abstract description 9
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 9
- 239000011574 phosphorus Substances 0.000 claims abstract description 9
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 7
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 5
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 5
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- JBANFLSTOJPTFW-UHFFFAOYSA-N azane;boron Chemical compound [B].N JBANFLSTOJPTFW-UHFFFAOYSA-N 0.000 claims description 12
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims description 8
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 229940068041 phytic acid Drugs 0.000 claims description 8
- 235000002949 phytic acid Nutrition 0.000 claims description 8
- 239000000467 phytic acid Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000002135 nanosheet Substances 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 claims description 2
- XFZRQAZGUOTJCS-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OP(O)(O)=O.NC1=NC(N)=NC(N)=N1 XFZRQAZGUOTJCS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims 2
- 239000004408 titanium dioxide Substances 0.000 claims 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims 1
- QMXCHEVUAIPIRM-UHFFFAOYSA-N 2-hydroxy-pentan-3-one Chemical compound CCC(=O)C(C)O QMXCHEVUAIPIRM-UHFFFAOYSA-N 0.000 description 32
- 239000000047 product Substances 0.000 description 22
- 238000001027 hydrothermal synthesis Methods 0.000 description 12
- 230000003197 catalytic effect Effects 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 238000011065 in-situ storage Methods 0.000 description 5
- 238000009826 distribution Methods 0.000 description 4
- 235000013305 food Nutrition 0.000 description 4
- 125000000468 ketone group Chemical group 0.000 description 4
- 238000005834 sharpless asymmetric dihydroxylation reaction Methods 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- 238000006256 asymmetric dihydroxylation reaction Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 150000004678 hydrides Chemical class 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical compound [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 150000002085 enols Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 235000011962 puddings Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
-
- 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
- B01J23/892—Nickel and noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/64—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of functional groups containing oxygen only in singly bound form
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a method for synthesizing 3-hydroxy-2-pentanone by selective hydrogenation, which comprises the following steps: adding tetrabutyl titanate into acetic acid, transferring into a synthesis kettle for hydrothermal treatment, filtering and drying to obtain TiO 2 ；TiO 2 Grinding with phosphorus source, transferring to tube furnace, roasting to obtain P-TiO 2 The method comprises the steps of carrying out a first treatment on the surface of the P-TiO 2 Placing the carrier in nickel source and platinum source, then making reduction reaction in hydrazine hydrate solution, centrifugal drying so as to obtain NiPt/P-TiO 2 A catalyst. The invention adopts the method for synthesizing 3-hydroxy-2-pentanone by selective hydrogenation of the structure, adopts NiPt/P-TiO 2 As a catalyst, the high-selectivity synthesis of the 3-hydroxy-2-pentanone by the 2, 3-pentanedione under mild conditions is realized, and the reaction temperature can be remarkably reduced without high-pressure reaction.
Description
Technical Field
The invention relates to the technical field of fine chemical engineering, in particular to a method for synthesizing 3-hydroxy-2-pentanone by selective hydrogenation.
Background
3-hydroxy-2-pentanone is an important food flavor, is widely applied to food essence such as beverage, milk, pudding and the like, and along with the rapid development of modern industry, the extraction of the substances from the nature can not meet the development requirement of the food industry, and the development of a novel 3-hydroxy-2-pentanone production process is needed.
At present, an asymmetric dihydroxylation reaction method and a high-pressure hydrogenation method are studied, wherein the asymmetric dihydroxylation reaction method takes 2-pentanone as a starting material, and 3-hydroxy-2-pentanone is prepared by using Sharpless asymmetric dihydroxylation through a thermodynamically stable enol silyl ether intermediate, but the yield of the 3-hydroxy-2-pentanone in the process can only reach 71.9% at most. The high-pressure hydrogenation method is generally prepared by catalyzing 2, 3-pentanedione with Pt, the reaction in the process needs to be carried out under high-pressure hydrogen, the selectivity of the reaction is not ideal, and the existing selectivity is only 68.5 percent at most, so that the development of an efficient 3-hydroxy-2-pentanone production process is important for the development of the food industry.
Disclosure of Invention
The invention aims to provide a method for synthesizing 3-hydroxy-2-pentanone by selective hydrogenation, which aims to solve the problems that the method for synthesizing 3-hydroxy-2-pentanone is not ideal in selectivity and requires high pressure.
To achieve the above object, the present invention provides a NiPt/P-TiO for synthesizing 3-hydroxy-2-pentanone from 2, 3-pentanedione 2 A method for preparing a catalyst comprising the steps of:
(1) Adding tetrabutyl titanate into acetic acid, transferring to a synthesis kettle for hydrothermal treatment, filtering and drying to obtain the required TiO 2 ；
(2) The prepared TiO 2 Grinding with phosphorus source, transferring into tube furnace, roasting to obtain P-TiO 2 ；
(3) The prepared P-TiO 2 Placing the carrier in nickel source and platinum source, then making reduction reaction in hydrazine hydrate solution, centrifugal drying so as to obtain NiPt/P-TiO 2 A catalyst.
Preferably, the mass ratio of tetrabutyl titanate to acetic acid is 1: (30-40).
Preferably, the hydrothermal temperature of the hydrothermal treatment in the step (1) is 160-190 ℃, and the hydrothermal time is 18-22 h.
Preferably, tiO 2 The mass ratio of the phosphorus source is 1: (0.1-0.3).
Preferably, the roasting temperature of the roasting treatment in the step (2) is 280-320 ℃ and the roasting time is 2-4 h.
Preferably, P-TiO 2 The mass ratio of the nickel source to the platinum source is 1: (0.4-0.7): (0.1-0.2).
Preferably, the concentration of hydrazine hydrate in the step (3) is 0.05-0.15 mol/L, the reduction temperature of the reduction reaction is 0-4 ℃, and the reduction time is 2.0-4.5 h.
Preferably, the nickel source is one or two of nickel oxalate and nickel chloride, the phosphorus source is one or two of phytic acid and melamine phosphate, and the platinum source is one or two of chloroplatinic acid and potassium chloroplatinate.
Preferably, niPt/P-TiO 2 The catalyst comprises Ni, pt and P-TiO 2 A nano-sheet.
NiPt/P-TiO for synthesizing 3-hydroxy-2-pentanone from 2, 3-pentanedione 2 Application of catalyst, niPt/P-TiO 2 The catalyst is placed in a three-neck flask and is prepared by N 2 Replacing, then injecting 2, 3-pentanedione, ethanol and ammonia borane solution into a three-neck flask, stirring to react at 10-30 ℃, and removing NiPt/P-TiO after the reaction is finished 2 The catalyst is used for obtaining the target product 3-hydroxy-2-pentanone; the mass ratio of the 2, 3-pentanedione, the ethanol and the ammonia borane is 1 (4-7) to 0.3-0.8.
Therefore, the method for synthesizing 3-hydroxy-2-pentanone by selective hydrogenation of the structure has the following beneficial effects:
1. the invention synthesizes P-TiO by using a phosphorus source precursor 2 Then adopting a dipping reduction method to prepare NiPt/P-TiO 2 Catalyst, P-TiO 2 The in-situ doped P source can obviously improve the charge distribution of the catalyst, and the charge distribution of a metal valence band orbit is changed by adjusting the content of the phosphorus source, the proportion of metal components, the concentration of a reducing agent and the reaction condition, so that the selectivity of the catalytic reaction is adjusted. In addition, the strong interaction of the metal and the metal carrier is obviously enhanced, and the catalytic activity is effectively improved.
2. The invention uses NiPt/P-TiO 2 As a catalyst, ammonia borane in-situ hydrogen release is used as a hydrogen source, and the selective hydrogenation of 2, 3-pentanedione under the conditions of liquid phase normal pressure and mild temperature is realized to synthesize 3-hydroxy-2-pentanone. Selective hydrogenation of 2, 3-pentanedione to 3-hydroxy using the catalystThe conversion rate of the base-2-pentanone is more than 94%, the selectivity of the target product 3-hydroxy-2-pentanone can reach more than 80%, and the selectivity of the byproduct 2-hydroxy-3-pentanone is controlled below 20%, which is far superior to the existing high-pressure hydrogenation and Sharpless asymmetric dihydroxylation process.
3. The in-situ hydrogen release of the hydride can obviously reduce the reaction temperature and does not need high-pressure reaction, so that the 3-hydroxy-2-pentanone can be synthesized with high selectivity under mild conditions, and the catalyst can be recycled for 50 times and still maintain good catalytic stability.
The technical scheme of the invention is further described in detail through the drawings and the embodiments.
Drawings
FIG. 1 is a TEM image of an embodiment of a process for the selective hydrogenation of 3-hydroxy-2-pentanone according to the invention.
Detailed Description
The present invention will be further described below, and it should be noted that the present embodiment provides a detailed implementation manner and a specific operation procedure on the premise of the present technical solution, but the present invention is not limited to the present embodiment.
Example 1
Process for preparing a catalyst
Adding 1g of tetrabutyl titanate into 30g of acetic acid, transferring to a hydrothermal synthesis kettle, carrying out hydrothermal reaction at 160 ℃ for 22h, filtering and drying to obtain the required TiO 2 The method comprises the steps of carrying out a first treatment on the surface of the Taking 0.5g of prepared TiO 2 Grinding with 0.05g phytic acid, transferring into a tube furnace, and roasting at 280 deg.C for 4 hr to obtain P-TiO 2 The method comprises the steps of carrying out a first treatment on the surface of the Weighing the prepared P-TiO 2 0.1g of the mixture is placed in a solution containing 0.04g of nickel nitrate and 0.01g of chloroplatinic acid, and reduced for 4.5 hours at 0 ℃ by using a hydrazine hydrate solution with the concentration of 0.05mol/L, thus obtaining NiPt/P-TiO 2 A catalyst.
Hydrogenation reaction process
The NiPt/P-TiO prepared by the method 2 The catalyst is placed in a three-neck flask and is prepared by N 2 Displacing, injecting a solution containing 1g of 2, 3-pentanedione, 4g of ethanol and 0.3g of ammonia borane into a three-neck flask, stirring, heating to 10 ℃ for reaction, removing a catalyst after the reaction is finished, and separating to obtain a target product 3-hydroxy-2-pentanone.
The reaction product is analyzed by adopting a gas chromatography-mass spectrometry, the conversion rate of the reactant 2, 3-pentanedione is 95.4 percent, the selectivity of the 3-hydroxy-2-pentanone in the product is 86.8 percent, the selectivity of the 2-hydroxy-3-pentanone is 12.1 percent, after the catalyst is recycled for 50 times, the conversion rate is 95.2 percent, the selectivity of the 3-hydroxy-2-pentanone in the product is 86.4 percent, and the selectivity of the 2-hydroxy-3-pentanone in the product is 12.2 percent. From the above, it can be seen that the selectivity of 3-hydroxy-2-pentanone after the catalyst is recycled for 50 times is not significantly reduced compared with the selectivity of 3-hydroxy-2-pentanone used for the first time, which indicates that the catalyst can maintain good catalytic stability.
Example 2
Process for preparing a catalyst
Adding 1g of tetrabutyl titanate into 40g of acetic acid, transferring to a hydrothermal synthesis kettle, carrying out hydrothermal reaction at 190 ℃ for 18h, filtering and drying to obtain the required TiO 2 The method comprises the steps of carrying out a first treatment on the surface of the Taking 0.5g of prepared TiO 2 Grinding with 0.15g phytic acid, transferring into a tube furnace, and roasting at 320 deg.C for 2 hr to obtain P-TiO 2 The method comprises the steps of carrying out a first treatment on the surface of the Weighing the prepared P-TiO 2 0.1g of the mixture is placed in a solution containing 0.07g of nickel nitrate and 0.02g of chloroplatinic acid, and reduced for 2.0h at 4 ℃ by using a hydrazine hydrate solution with the concentration of 0.15mol/L, thus obtaining NiPt/P-TiO 2 A catalyst.
Hydrogenation reaction process
The NiPt/P-TiO prepared by the method 2 The catalyst is placed in a three-neck flask and is prepared by N 2 And (3) replacing, then injecting a solution containing 1g of 2, 3-pentanedione, 7g of ethanol and 0.8g of ammonia borane into a three-neck flask, stirring, heating to 30 ℃ for reaction, removing a catalyst after the reaction is finished, and separating to obtain the target product of 3-hydroxy-2-pentanone.
By adopting gas chromatography-mass spectrometry to analyze the reaction product, the conversion rate of the reactant 2, 3-pentanedione is 98.4%, the selectivity of 3-hydroxy-2-pentanone in the product is 92.8%, the selectivity of 2-hydroxy-3-pentanone is 6.1%, after the catalyst is recycled for 50 times, the conversion rate is 98.2%, the selectivity of 3-hydroxy-2-pentanone in the product is 92.4%, and the selectivity of 2-hydroxy-3-pentanone is 5.9%, which indicates that the catalyst can maintain good catalytic stability.
Example 3
Process for preparing a catalyst
Adding 1g of tetrabutyl titanate into 35g of acetic acid, transferring to a hydrothermal synthesis kettle, carrying out hydrothermal reaction at 180 ℃ for 19h, filtering and drying to obtain the required TiO 2 The method comprises the steps of carrying out a first treatment on the surface of the Taking 0.5g of prepared TiO 2 Grinding with 0.10g phytic acid, transferring into a tube furnace, and roasting at 300deg.C for 3 hr to obtain P-TiO 2 The method comprises the steps of carrying out a first treatment on the surface of the Weighing the prepared P-TiO 2 0.1g of the mixture is placed in a solution containing 0.05g of nickel nitrate and 0.012g of chloroplatinic acid, and reduced for 3.0h at 2 ℃ by using a hydrazine hydrate solution with the concentration of 0.012mol/L, thus obtaining NiPt/P-TiO 2 A catalyst.
Hydrogenation reaction process
The NiPt/P-TiO prepared by the method 2 The catalyst is placed in a three-neck flask and is prepared by N 2 And (3) replacing, then injecting a solution containing 1g of 2, 3-pentanedione, 6g of ethanol and 0.7g of ammonia borane into a three-neck flask, stirring, heating to 25 ℃ for reaction, removing a catalyst after the reaction is finished, and separating to obtain the target product of 3-hydroxy-2-pentanone.
By adopting gas chromatography-mass spectrometry to analyze the reaction product, the conversion rate of the reactant 2, 3-pentanedione is 96.3 percent, the selectivity of 3-hydroxy-2-pentanone in the product is 82.8 percent, the selectivity of 2-hydroxy-3-pentanone is 16.1 percent, after the catalyst is recycled for 50 times, the conversion rate is 96.2 percent, the selectivity of 3-hydroxy-2-pentanone in the product is 82.4 percent, and the selectivity of 2-hydroxy-3-pentanone is 15.9 percent, which indicates that the catalyst can maintain good catalytic stability.
Example 4
Process for preparing a catalyst
Adding 1g of tetrabutyl titanate into 32g of acetic acid, transferring to a hydrothermal synthesis kettle, carrying out hydrothermal reaction at 165 ℃ for 21h, filtering and drying to obtain the required TiO 2 The method comprises the steps of carrying out a first treatment on the surface of the Taking 0.5g of prepared TiO 2 Grinding with 0.14g phytic acid, transferring into a tube furnace, and roasting at 315 deg.C for 2.5 hr to obtain P-TiO 2 The method comprises the steps of carrying out a first treatment on the surface of the Weighing the prepared P-TiO 2 0.1g of the mixture is placed in a solution containing 0.05g of nickel nitrate and 0.014g of chloroplatinic acid, and reduced for 3.5h at 3 ℃ by using a hydrazine hydrate solution with the concentration of 0.13mol/L, thus obtaining NiPt/P-TiO 2 A catalyst.
Hydrogenation reaction process
The NiPt/P-TiO prepared by the method 2 The catalyst is placed in a three-neck flask and is prepared by N 2 And (3) replacing, then injecting a solution containing 1g of 2, 3-pentanedione, 4g of ethanol and 0.4g of ammonia borane into a three-neck flask, stirring, heating to 18 ℃ for reaction, removing a catalyst after the reaction is finished, and separating to obtain the target product of 3-hydroxy-2-pentanone.
By adopting gas chromatography-mass spectrometry to analyze the reaction product, the conversion rate of the reactant 2, 3-pentanedione is 95.2%, the selectivity of 3-hydroxy-2-pentanone in the product is 86.7%, the selectivity of 2-hydroxy-3-pentanone is 12.1%, after the catalyst is recycled for 50 times, the conversion rate is 94.8%, the selectivity of 3-hydroxy-2-pentanone in the product is 86.5%, and the selectivity of 2-hydroxy-3-pentanone is 12.1%, which indicates that the catalyst can keep good catalytic stability.
Example 5
Process for preparing a catalyst
Adding 1g of tetrabutyl titanate into 37g of acetic acid, transferring to a hydrothermal synthesis kettle, carrying out hydrothermal reaction at 185 ℃ for 19h, filtering and drying to obtain the required TiO 2 The method comprises the steps of carrying out a first treatment on the surface of the Taking 0.5g of prepared TiO 2 Grinding with 0.08g phytic acid, transferring into a tube furnace, and roasting at 290 ℃ for 3.5h to obtain P-TiO 2 The method comprises the steps of carrying out a first treatment on the surface of the Weighing the prepared P-TiO 2 0.1g of the mixture is placed in a solution containing 0.06g of nickel nitrate and 0.016g of chloroplatinic acid, and reduced for 4.5 hours at 1 ℃ by using a hydrazine hydrate solution with the concentration of 0.07mol/L, thus obtaining NiPt/P-TiO 2 A catalyst.
Hydrogenation reaction process
The NiPt/P-TiO prepared by the method 2 The catalyst is placed in a three-neck flask and is prepared by N 2 And (3) replacing, then injecting a solution containing 1g of 2, 3-pentanedione, 6g of ethanol and 0.6g of ammonia borane into a three-neck flask, stirring, heating to 25 ℃ for reaction, removing a catalyst after the reaction is finished, and separating to obtain the target product of 3-hydroxy-2-pentanone.
By adopting gas chromatography-mass spectrometry to analyze the reaction product, the conversion rate of the reactant 2, 3-pentanedione is 94.7%, the selectivity of 3-hydroxy-2-pentanone in the product is 87.8%, the selectivity of 2-hydroxy-3-pentanone is 11.1%, after the catalyst is recycled for 50 times, the conversion rate is 94.5%, the selectivity of 3-hydroxy-2-pentanone in the product is 87.5%, and the selectivity of 2-hydroxy-3-pentanone is 11.0%, which indicates that the catalyst can maintain good catalytic stability.
Example 6
Process for preparing a catalyst
Adding 1g of tetrabutyl titanate into 38g of acetic acid, transferring to a hydrothermal synthesis kettle, carrying out hydrothermal reaction at 175 ℃ for 22h, filtering and drying to obtain the required TiO 2 The method comprises the steps of carrying out a first treatment on the surface of the Taking 0.5g of prepared TiO 2 Grinding with 0.05g phytic acid, transferring into a tube furnace, and roasting at 320 deg.C for 3.5 hr to obtain P-TiO 2 The method comprises the steps of carrying out a first treatment on the surface of the Weighing the prepared P-TiO 2 0.1g of the mixture is placed in a solution containing 0.06g of nickel nitrate and 0.02g of chloroplatinic acid, and reduced for 4.5 hours at 3 ℃ by using a hydrazine hydrate solution with the concentration of 0.05mol/L, thus obtaining NiPt/P-TiO 2 A catalyst.
Hydrogenation reaction process
The NiPt/P-TiO prepared by the method 2 The catalyst is placed in a three-neck flask and is prepared by N 2 And (3) replacing, then injecting a solution containing 1g of 2, 3-pentanedione, 7g of ethanol and 0.3g of ammonia borane into a three-neck flask, stirring, heating to 30 ℃ for reaction, removing a catalyst after the reaction is finished, and separating to obtain the target product of 3-hydroxy-2-pentanone.
By adopting gas chromatography-mass spectrometry to analyze the reaction product, the conversion rate of the reactant 2, 3-pentanedione is 98.9%, the selectivity of 3-hydroxy-2-pentanone in the product is 94.8%, the selectivity of 2-hydroxy-3-pentanone is 4.7%, after the catalyst is recycled for 50 times, the conversion rate is 98.7%, the selectivity of 3-hydroxy-2-pentanone in the product is 94.5%, and the selectivity of 2-hydroxy-3-pentanone is 4.6%, which indicates that the catalyst can keep good catalytic stability.
For NiPt/P-TiO prepared in example 1 2 The catalyst was tested and it can be seen from the TEM image of FIG. 1 that NiPt metal particles were uniformly distributed in the P-TiO 2 The surface of the carrier, the doping of the P element can obviously improve TiO in the catalyst preparation process 2 The valence band orbitals of the electron structure of (a) are changed, at the same time NiPt metal is loaded on P-TiO 2 The surface can obviously improve the charge distribution of metal particles due to the strong interaction between the metal and the carrier, thereby affecting the catalytic activity of the catalyst; in the hydrogenation reaction process, 2, 3-pentanedione can be selectedThe selective hydrogenation is carried out to synthesize 3-hydroxy-2-pentanone and 2-hydroxy-3-pentanone, and the above charge distribution and valence band orbit are adjusted, so that the adsorption energy of the ketone group at the 3 position in 2, 3-pentanone on the surface of the catalyst is lower (that is, the ketone group at the 3 position is easier to adsorb on the surface of the catalyst relative to the ketone group at the 2 position), the hydrogenation reaction of the ketone group at the 3 position is easier to occur, thereby realizing high selectivity of synthesizing 3-hydroxy-2-pentanone and reducing the yield of 2-hydroxy-3-pentanone.
Therefore, the invention adopts a method for synthesizing 3-hydroxy-2-pentanone by selective hydrogenation of the structure and adopts NiPt/P-TiO 2 As a catalyst, the in-situ hydrogen release of ammonia borane is used as a hydrogen source, the selective hydrogenation of 2, 3-pentanedione can be realized to synthesize 3-hydroxy-2-pentanone, the conversion rate is over 94%, the selectivity of the target product 3-hydroxy-2-pentanone can be over 80%, the selectivity of the byproduct 2-hydroxy-3-pentanone is controlled below 20%, the catalyst is far superior to the existing high-pressure hydrogenation and Sharpless asymmetric dihydroxylation processes, particularly, the in-situ hydrogen release of the hydride can obviously reduce the reaction temperature and does not need high-pressure reaction, the high-selectivity synthesis of 3-hydroxy-2-pentanone is realized under mild conditions, and the catalyst can still maintain good catalytic stability after being recycled for 50 times.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention and not for limiting it, and although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that: the technical scheme of the invention can be modified or replaced by the same, and the modified technical scheme cannot deviate from the spirit and scope of the technical scheme of the invention.
Claims (9)
1. NiPt/P-TiO 2 The application of the catalyst in synthesizing 3-hydroxy-2-pentanone from 2, 3-pentanedione is characterized in that: niPt/P-TiO 2 The catalyst is placed in a three-neck flask and is prepared by N 2 Replacing, then injecting 2, 3-pentanedione, ethanol and ammonia borane solution into a three-neck flask, stirring to react at 10-30 ℃, and removing NiPt/P-TiO after the reaction is finished 2 The catalyst can obtain the target product3-hydroxy-2-pentanone; the mass ratio of the 2, 3-pentanedione, the ethanol and the ammonia borane is 1: (4-7): (0.3 to 0.8);
the NiPt/P-TiO 2 A method for preparing a catalyst comprising the steps of:
(1) Adding tetrabutyl titanate into acetic acid, transferring to a synthesis kettle for hydrothermal treatment, filtering and drying to obtain the required TiO 2 ；
(2) The prepared TiO 2 Grinding with phosphorus source, transferring into tube furnace, roasting to obtain P-TiO 2 ；
(3) The prepared P-TiO 2 Placing the carrier in nickel source and platinum source, then making reduction reaction in hydrazine hydrate solution, centrifugal drying so as to obtain NiPt/P-TiO 2 A catalyst.
2. The use according to claim 1, characterized in that: the mass ratio of tetrabutyl titanate to acetic acid is 1: (30-40).
3. The use according to claim 1, characterized in that: the hydrothermal temperature of the hydrothermal treatment in the step (1) is 160-190 ℃ and the hydrothermal time is 18-22 h.
4. The use according to claim 1, characterized in that: tiO (titanium dioxide) 2 The mass ratio of the phosphorus source is 1: (0.1-0.3).
5. The use according to claim 1, characterized in that: the roasting temperature of the roasting treatment in the step (2) is 280-320 ℃ and the roasting time is 2-4 h.
6. The use according to claim 1, characterized in that: P-TiO 2 The mass ratio of the nickel source to the platinum source is 1: (0.4-0.7): (0.1-0.2).
7. The use according to claim 1, characterized in that: the concentration of hydrazine hydrate in the step (3) is 0.05-0.15 mol/L, the reduction temperature of the reduction reaction is 0-4 ℃, and the reduction time is 2.0-4.5 h.
8. The use according to claim 1, characterized in that: the nickel source is one or two of nickel oxalate and nickel chloride, the phosphorus source is one or two of phytic acid and melamine phosphate, and the platinum source is one or two of chloroplatinic acid and potassium chloroplatinate.
9. The use according to claim 1, characterized in that: niPt/P-TiO 2 The catalyst comprises Ni, pt and P-TiO 2 A nano-sheet.
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| CN101371981A (en) * | 2007-08-21 | 2009-02-25 | 黑龙江大学 | Nano titanic oxide photocatalyst of high activity with phosphoric acid surface modification as well as synthetic method |
| CN107512732A (en) * | 2017-09-14 | 2017-12-26 | 西北师范大学 | A kind of yellow titanium dioxide nanocrystalline and preparation method thereof |
| CN110508312A (en) * | 2019-09-05 | 2019-11-29 | 安徽工业大学 | With the method for Ni-Pt nanometer sheet catalyst visible light catalytic ammonia borine dehydrogenation |
| CN110813281A (en) * | 2019-11-15 | 2020-02-21 | 中国科学院金属研究所 | Application of nano-carbon supported cluster-state palladium-based catalyst in preparation of primary amine by catalytic hydrogenation of nitrile compound |
| CN111777160A (en) * | 2020-07-01 | 2020-10-16 | 贵州大学 | Method for auxiliary treatment of gold dressing and smelting wastewater through photocatalytic oxidation |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101371981A (en) * | 2007-08-21 | 2009-02-25 | 黑龙江大学 | Nano titanic oxide photocatalyst of high activity with phosphoric acid surface modification as well as synthetic method |
| CN107512732A (en) * | 2017-09-14 | 2017-12-26 | 西北师范大学 | A kind of yellow titanium dioxide nanocrystalline and preparation method thereof |
| CN110508312A (en) * | 2019-09-05 | 2019-11-29 | 安徽工业大学 | With the method for Ni-Pt nanometer sheet catalyst visible light catalytic ammonia borine dehydrogenation |
| CN110813281A (en) * | 2019-11-15 | 2020-02-21 | 中国科学院金属研究所 | Application of nano-carbon supported cluster-state palladium-based catalyst in preparation of primary amine by catalytic hydrogenation of nitrile compound |
| CN111777160A (en) * | 2020-07-01 | 2020-10-16 | 贵州大学 | Method for auxiliary treatment of gold dressing and smelting wastewater through photocatalytic oxidation |
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