CN114773180B - Synthetic method and catalyst for preparing 3-hydroxybutyric acid by selective oxidation of 1, 3-butanediol - Google Patents
Synthetic method and catalyst for preparing 3-hydroxybutyric acid by selective oxidation of 1, 3-butanediol Download PDFInfo
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- WHBMMWSBFZVSSR-UHFFFAOYSA-N 3-hydroxybutyric acid Chemical compound CC(O)CC(O)=O WHBMMWSBFZVSSR-UHFFFAOYSA-N 0.000 title claims abstract description 162
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 title claims abstract description 154
- 235000019437 butane-1,3-diol Nutrition 0.000 title claims abstract description 77
- 239000003054 catalyst Substances 0.000 title claims abstract description 66
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 43
- 230000003647 oxidation Effects 0.000 title claims abstract description 31
- 238000010189 synthetic method Methods 0.000 title description 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 84
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 41
- 230000035484 reaction time Effects 0.000 claims abstract description 24
- 230000008569 process Effects 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000001301 oxygen Substances 0.000 claims abstract description 14
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 14
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 13
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000007800 oxidant agent Substances 0.000 claims abstract description 11
- 239000003570 air Substances 0.000 claims abstract description 7
- 229910001245 Sb alloy Inorganic materials 0.000 claims abstract description 6
- 230000009467 reduction Effects 0.000 claims abstract description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000001257 hydrogen Substances 0.000 claims abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 38
- 229910052787 antimony Inorganic materials 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- 239000007791 liquid phase Substances 0.000 claims description 12
- 238000011068 loading method Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000001704 evaporation Methods 0.000 claims description 10
- 229910052697 platinum Inorganic materials 0.000 claims description 10
- 238000003786 synthesis reaction Methods 0.000 claims description 10
- 239000012298 atmosphere Substances 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 230000009471 action Effects 0.000 claims description 6
- FAWGZAFXDJGWBB-UHFFFAOYSA-N antimony(3+) Chemical class [Sb+3] FAWGZAFXDJGWBB-UHFFFAOYSA-N 0.000 claims description 5
- 239000002243 precursor Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 239000007810 chemical reaction solvent Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 230000001590 oxidative effect Effects 0.000 abstract description 6
- 238000005470 impregnation Methods 0.000 abstract description 5
- 239000000178 monomer Substances 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000000855 fermentation Methods 0.000 abstract description 3
- 230000004151 fermentation Effects 0.000 abstract description 3
- 230000000813 microbial effect Effects 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract description 2
- HSJKGGMUJITCBW-UHFFFAOYSA-N 3-hydroxybutanal Chemical compound CC(O)CC=O HSJKGGMUJITCBW-UHFFFAOYSA-N 0.000 description 20
- 229920000070 poly-3-hydroxybutyrate Polymers 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 238000009210 therapy by ultrasound Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- -1 polypropylene Polymers 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229940011182 cobalt acetate Drugs 0.000 description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 208000017667 Chronic Disease Diseases 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 208000001132 Osteoporosis Diseases 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 229920000704 biodegradable plastic Polymers 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 206010012601 diabetes mellitus Diseases 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 230000004770 neurodegeneration Effects 0.000 description 1
- 208000015122 neurodegenerative disease Diseases 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
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- 239000002831 pharmacologic agent Substances 0.000 description 1
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- 229920003023 plastic Polymers 0.000 description 1
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- 230000008929 regeneration Effects 0.000 description 1
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- 235000009566 rice Nutrition 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
- C07C51/235—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of —CHO groups or primary alcohol groups
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
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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
- 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
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/644—Arsenic, antimony or bismuth
- B01J23/6445—Antimony
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- 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 Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
The application discloses a synthesis method and a catalyst for preparing 3-hydroxybutyric acid by selective oxidation of 1, 3-butanediol. 3-hydroxybutyric acid is a monomer of a biodegradable material PHB, and the traditional technology is prepared by adopting microbial fermentation. The new process of the application is to prepare the catalyst by taking 1, 3-butanediol as a raw material and adopting a selective catalytic oxidation process. The catalyst of the application is Pt loaded by active carbon or Pt-Sb alloy loaded by active carbon; the catalyst is prepared by adopting an impregnation method and a hydrogen reduction step. The oxidant related by the application is oxygen, air or hydrogen peroxide. The process has the advantages of low-cost and easily-obtained raw materials, simple reaction process, high product selectivity, good catalyst stability and the like. Under the conditions that the initial concentration of the 1, 3-butanediol is 10g/L, the temperature is 70 ℃, the oxygen pressure is 2.0MPa, and the reaction time is 14 hours, the highest yield of the 3-hydroxybutyric acid can reach 78.3 percent.
Description
Technical Field
The application relates to the technical field of catalytic oxidation, in particular to a synthesis method and a catalyst for preparing 3-hydroxybutyric acid by selective oxidation of 1, 3-butanediol.
Background
3-hydroxybutyric acid is a monomer of biodegradable plastic poly 3-hydroxybutyrate (PHB) and is also an important pharmaceutical raw material and pharmacological agent. Has good biocompatibility, is widely applied to the medical field, and has certain treatment effect on chronic diseases such as diabetes, osteoporosis, neurodegenerative diseases and the like.
PHB has high melting point, high crystallinity, biodegradability and biocompatibility, and the tensile strength is equivalent to polypropylene. Therefore, PHB is considered as a substitute for traditional petroleum-based plastics, and has important significance for solving the problem of white pollution.
Currently, the synthetic methods of PHB mainly include biosynthesis and chemistry. The technology for synthesizing PHB by biology has long time consumption, low efficiency and high preparation cost, and limits large-scale industrialized production. The chemical method can take 3-hydroxybutyric acid as a monomer, and PHB is obtained through a polymerization method, so that the production cost of PHB can be obviously reduced, and the large-scale production and application of PHB can be promoted. Therefore, the chemical synthesis of 3-hydroxybutyric acid has important application prospect.
At present, the main way of preparing 3-hydroxybutyric acid by a chemical method is liquid-phase oxidation of 3-hydroxybutyric acid, but related reports at home and abroad are few, and the research progress is slow.
The recent report is that in 2008 Wang Yanfei et al, 3-hydroxybutyraldehyde is used as a raw material, ethyl acetate is used as a solvent, and cobalt acetate is used as a catalyst, and 3-hydroxybutyraldehyde is oxidized into 3-hydroxybutyric acid in an airlift loop reactor to obtain an average yield of 88.10% of 3-hydroxybutyric acid (3-hydroxybutyric acid synthesis process amplification study [ C ]///. Chinese chemical society of 2008 years of petrochemical society and 50 annual society of reporting theory of Beijing chemical society of construction, 2008:233-235.). Yang Wenling et al use cobalt acetate as a catalyst and organic acid ester as a solvent, and the average yield of 3-hydroxybutyric acid obtained after reaction for 30 hours in a pressure reaction kettle at 60 ℃ under oxygen pressure of 0.8MPa reaches 81.75% (chemical synthesis process research of 3-hydroxybutyric acid [ J ]. Chemical engineering, 2002 (05): 74-78+6.).
Although the product yield prepared by the 3-hydroxybutyraldehyde liquid phase oxidation method is higher, the problems of difficult recovery of homogeneous catalyst, large solvent consumption, long reaction time and the like exist, and the method does not accord with the concept of green environmental protection.
In addition, the raw material 3-hydroxybutyraldehyde has active property, and pure products of 3-hydroxybutyraldehyde on the market are rare, high in price and low in purity, and industrial production is not realized yet, so that the cost for preparing 3-hydroxybutyric acid by liquid phase oxidation of 3-hydroxybutyraldehyde is extremely high.
Therefore, developing a catalyst which is high in activity, high in stability and easy to recycle and searching for a relatively low-cost reaction raw material are of great importance for the chemical synthesis of 3-hydroxybutyric acid.
Disclosure of Invention
As described in the background section of the application, the 3-hydroxybutyric acid which is sold at present is mainly prepared by a microbial fermentation method, and the raw material 3-hydroxybutyraldehyde used by a chemical synthesis method is high in price and low in purity; in addition, the liquid-phase oxidation process for preparing 3-hydroxybutyric acid by taking 3-hydroxybutyraldehyde as a raw material has the problems of high cost, unrecoverable catalyst, incapability of recycling and the like.
Aiming at the problems, the application provides a novel process for preparing 3-hydroxybutyric acid by directly oxidizing 1, 3-butanediol selectively, which has the advantages of mild reaction conditions, short reaction time, safe, low-cost, nontoxic and easy storage and transportation of raw material 1, 3-butanediol. The Pt/C and Pt-Sb/C catalyst adopted by the application has the advantages of simple preparation process, high activity, high selectivity, repeated use, recycling and regeneration, and can efficiently oxidize the 1, 3-butanediol into 3-hydroxybutyric acid under mild reaction conditions. The oxidant used in the application is low in cost.
The specific technical scheme is as follows:
in a first aspect, the application provides a synthesis process for preparing 3-hydroxybutyric acid by selective oxidation of 1, 3-butanediol, wherein 1, 3-butanediol is used as a raw material, and liquid-phase oxidation reaction is directly carried out under the action of a catalyst to prepare 3-hydroxybutyric acid; the catalyst is Pt loaded by active carbon or Pt-Sb alloy loaded by active carbon.
In a second aspect, the present application provides a catalyst for preparing 3-hydroxybutyric acid by selective oxidation of 1, 3-butanediol and a preparation method thereof, comprising the steps of:
(1) Uniformly dispersing active carbon in a platinum precursor solution, fully soaking, evaporating the solvent, uniformly dispersing the obtained solid in an ethanol solution of trivalent antimony salt, fully soaking, evaporating the solvent, and obtaining a dried sample; or,
uniformly dispersing active carbon in an ethanol solution of trivalent antimony salt, fully soaking, evaporating the solvent, uniformly dispersing the obtained solid in a platinum precursor solution, fully soaking, evaporating the solvent, and obtaining a dried sample;
(2) And (3) reducing the sample obtained in the step (1) in a hydrogen atmosphere at 300-600 ℃, and then performing heat treatment for 2-5 hours in a nitrogen atmosphere at 700-900 ℃ to obtain the catalyst.
The catalyst of the application takes active carbon as a carrier, takes supported Pt or Pt-Sb alloy as an active component, adopts an impregnation method and passes through H 2 The preparation method comprises a reduction step. Such a preparation method is beneficial to Pt or Pt-Sb alloy nanoThe rice particles are highly dispersed on the surface of the active carbon with high specific area, and are not easy to agglomerate in the reaction process. Therefore, the catalyst has excellent activity, selectivity and stability in catalyzing the reaction of preparing 3-hydroxybutyric acid by selective oxidation of 1, 3-butanediol.
In the catalyst, the loading of platinum is preferably 1-5% of the mass of the activated carbon, more preferably 2-3.5% of the mass of the activated carbon, and the loading of antimony is preferably not more than 15% of the mass of the activated carbon, more preferably 7.5-12.5% of the mass of the activated carbon.
In a preferred embodiment, in the step (1), the activated carbon is vacuum dried before use.
In a preferred embodiment, in the step (1), the platinum precursor solution is an aqueous solution of chloroplatinic acid.
In a preferred embodiment, in step (1), the trivalent antimony salt is SbCl 3 。
In a preferred embodiment, in the step (2), the time for the reduction is 1 to 3 hours.
In a preferred embodiment, in the step (2), the temperature of the reduction in the hydrogen atmosphere is 450 ℃, and the temperature of the heat treatment in the nitrogen atmosphere is 750 ℃.
In the novel process for preparing 3-hydroxybutyric acid, the used oxidant is low in price. In a preferred embodiment, the oxidizing agent used in the liquid phase oxidation reaction includes at least one of oxygen, air, and hydrogen peroxide.
In a preferred example, the reaction solvent used in the liquid phase oxidation reaction is water, the initial concentration of 1, 3-butanediol in the reaction solution is 10-100g/L, and the catalyst is used in an amount of 0.1g/10mL of the reaction solution.
The reaction pressure of the liquid phase oxidation reaction is preferably 0.5 to 3.0MPa, more preferably 1.0 to 1.5MPa, the reaction temperature is preferably 50 to 100 ℃, more preferably 70 to 100 ℃, and the reaction time is preferably 2 to 14 hours.
By adopting the process, the reaction solvent is water, the initial concentration of the 1, 3-butanediol in the reaction solution is 10-100g/L, the reaction pressure is 0.5-3.0MPa, the reaction temperature is 50-100 ℃, and the reaction time is 2-14h; under the action of catalyst, the yield of 3-hydroxybutyric acid can be up to 78.3%.
3-hydroxybutyric acid is a monomer of a biodegradable material PHB, and the traditional technology is prepared by adopting microbial fermentation. The new process of the application is to prepare the catalyst by taking 1, 3-butanediol as a raw material and adopting a selective catalytic oxidation process. The catalyst of the application is Pt loaded by active carbon or Pt-Sb alloy loaded by active carbon; the catalyst is prepared by adopting an impregnation method and a hydrogen reduction step. The oxidant related by the application is oxygen, air or hydrogen peroxide. The process has the advantages of low-cost and easily-obtained raw materials, simple reaction process, high product selectivity, good catalyst stability and the like.
Compared with the prior art, the application has the main advantages that:
1) The synthesis process of 3-hydroxybutyric acid can directly prepare 3-hydroxybutyric acid by selective oxidation of 1, 3-butanediol, and has the advantages of low-cost and easily obtained raw materials, simple reaction process, convenient catalyst recovery and repeated use.
2) The catalyst disclosed by the application is simple in preparation steps, the active phase of the catalyst is highly dispersed on the surface of a carrier and has a definite structure, and the catalyst has high activity, high selectivity and high stability and long service life.
3) The catalyst is applied to the reaction for preparing 3-hydroxybutyric acid by catalyzing the selective oxidation of 1, 3-butanediol, the reaction temperature is controlled to be 50-100 ℃, the oxygen pressure is controlled to be 0.5-3MPa, the reaction time is controlled to be 2-14h, the conversion rate of 1, 3-butanediol can reach 40.9-97.8%, and the yield of 3-hydroxybutyric acid can reach 78.3%.
Detailed Description
The application will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present application and are not intended to limit the scope of the present application. The methods of operation, under which specific conditions are not noted in the examples below, are generally in accordance with conventional conditions, or in accordance with the conditions recommended by the manufacturer.
Example 1
The activated carbon was dried overnight in a vacuum oven at 60℃and 1g of the pretreated activated carbon was weighed and dispersed in 7.5mL of 0.019g/mL SbCl 3 Ultrasonic treatment was performed for 0.5h, and stirring was performed at room temperature for 24h, followed by evaporation to remove the solvent. The black powder obtained was dispersed in 2mL of an aqueous solution of chloroplatinic acid (Pt content: 0.01 g/mL), sonicated for 0.5h, stirred at room temperature for 24h, then allowed to stand for 2h, followed by sonicated for 0.5h, further allowed to stand for 3h, and dried at 120℃for 12h. The dried sample is put into a reducing furnace and then is put into H 2 Reducing for 1h at 450 ℃ under the atmosphere, and then adding N 2 And (3) treating for 2 hours at 750 ℃ in the atmosphere to obtain the 2% Pt-7.5% Sb/C catalyst.
Dispersing 0.1g of the catalyst prepared by the method into 10mL of 1, 3-butanediol aqueous solution with the initial concentration of 10g/L, sealing the reaction kettle, replacing air in the reaction kettle with oxygen, and filling oxygen with the pressure of 2.0 MPa; and placing the reaction kettle in an oil bath pot, and starting stirring to start reaction after the temperature in the kettle reaches 70 ℃ for 2-14h. After the reaction, the reaction vessel was cooled to room temperature, and the reaction solution was centrifuged and quantitatively analyzed. The conversion of 1, 3-butanediol at different reaction times with 2% Pt-7.5% Sb/C and the yield of 3-hydroxybutyric acid are shown in Table 1.
TABLE 1 conversion of 1, 3-butanediol and yield of 3-hydroxybutyric acid at various reaction times
| Reaction time/h | 2 | 4 | 6 | 8 | 10 | 12 | 14 |
| 1, 3-butanediol conversion% | 55.4 | 65.1 | 76.2 | 83.5 | 89.1 | 93.6 | 95.5 |
| 3-hydroxybutyric acid yield% | 22.9 | 37.2 | 51.3 | 60.9 | 67.4 | 75.3 | 78.3 |
The results in Table 1 show that the process described in example 1 can be used to prepare a 2% Pt-7.5% Sb/C catalyst for preparing 3-hydroxybutyric acid by selective oxidation of 1, 3-butanediol with high activity, high selectivity and high stability, the conversion rate of 1, 3-butanediol can be up to 95.5% and the yield of 3-hydroxybutyric acid is 78.3% under the conditions of 70 ℃ and 14h of reaction. And the target product 3-hydroxybutyric acid is relatively stable on the catalyst, and the yield of the 3-hydroxybutyric acid keeps increasing trend along with the extension of the reaction time.
Example 2
Drying activated carbon in vacuum oven at 60deg.C overnight, then weighing 1g of pretreated activated carbon, dispersing in 2mL of chloroplatinic acid aqueous solution (Pt content is 0.01 g/mL), ultrasonic treating for 0.5h, stirring at room temperature for 24h, standing for 2hh, then ultrasonic treatment for 0.5h, standing for 3h, finally drying at 120 ℃ for 12h, evaporating the solvent, dispersing the obtained solid in 1.2-12.5mL of 0.019g/mL SbCl 3 Ultrasonic treatment was performed for 0.5h, and the mixture was stirred at room temperature for 24h and dried at 120℃for 12h. The dried sample is put into a reducing furnace and then is put into H 2 Reducing for 1h at 450 ℃ under the atmosphere, and then adding N 2 The catalyst obtained, labeled ySb-2% Pt/C, was treated at 750℃for 2h under an atmosphere.
The same reaction procedure as in example 1 was followed except that the reaction time was 14 hours, and the conversion of 1, 3-butanediol to ySb-2% Pt/C and the yield of 3-hydroxybutyric acid were as shown in Table 2.
TABLE 2 conversion of ySb-2% Pt/C1, 3-butanediol and yield of 3-hydroxybutyric acid
The results in Table 2 show that the ySb-2% Pt/C catalyst for preparing 3-hydroxybutyric acid by selective oxidation of 1, 3-butanediol prepared using the procedure described in example 2 has an optimum Sb loading of 7.5% of the mass of activated carbon at a Pt loading of 2%. When the loading of Sb is too small or too large, the conversion rate of 1, 3-butanediol and the yield of the target product are obviously reduced.
Example 3
Reference was made to the same preparation and reaction steps as in example 2, except that 7.5mL of 0.019g/mL SbCl was added 3 The conversion of 1, 3-butanediol and the yield of 3-hydroxybutyric acid at different reaction times were obtained with 7.5% Sb-2% Pt/C by maintaining the Sb loading at 7.5% and the reaction time at 2-14 hours as shown in Table 3.
TABLE 3 conversion of 1, 3-butanediol and yield of 3-hydroxybutyric acid from different reaction times
| Reaction time/h | 2 | 4 | 6 | 8 | 10 | 12 | 14 |
| 1, 3-butanediol conversion% | 51.7 | 73.5 | 81.2 | 86.3 | 91.3 | 93.6 | 95.3 |
| 3-hydroxybutyric acid yield% | 19.9 | 37.9 | 45.8 | 56.8 | 62.7 | 66.9 | 70.0 |
The results in Table 3 show that a highly active, highly selective 7.5% Sb-2% Pt/C catalyst for the selective oxidation of 1, 3-butanediol to 3-hydroxybutyric acid can be prepared using the procedure described in example 3, but preferably, the 2% Pt-7.5% Sb/C catalyst prepared in example 1 has a higher selectivity for 3-hydroxybutyric acid due to the altered impregnation sequence, indicating that the impregnation sequence has an important effect on the selective oxidation of 1, 3-butanediol to 3-hydroxybutyric acid.
Example 4
Reference was made to the same preparation and reaction steps as in example 1, except that 15mL0.019g/mL SbCl was added 3 The ethanol solution of (2) ensures that the Sb load is 15%, 1-5mL of chloroplatinic acid aqueous solution (Pt content is 0.01 g/mL) is added, the reaction time is 14h, and the conversion rate of 1, 3-butanediol and the yield of 3-hydroxybutyric acid of xPt-15% Sb/C are shown in Table 4.
TABLE 4 conversion of 1, 3-butanediol to 15% Sb/C and yield of 3-hydroxybutyric acid
The results in Table 4 show that the xPt-15% Sb/C catalyst for preparing 3-hydroxybutyric acid by selective oxidation of 1, 3-butanediol prepared using the procedure described in example 4 had an optimum Pt loading of 3.5% by mass of activated carbon at a Sb loading of 15%. It can be found that although increasing the Pt loading is beneficial to the conversion of 1, 3-butanediol, when the Pt loading is too low or too high, the conversion of 1, 3-butanediol and the yield of the target product are both obviously reduced.
Example 5
The same catalyst preparation and reaction procedure as in example 1 were followed except that the temperature of the 1, 3-butanediol oxidation reaction was controlled to 50-100℃and the reaction time was 6 hours, to obtain the conversion of 1, 3-butanediol and the yield of 3-hydroxybutyric acid at various temperatures as shown in Table 5.
TABLE 5 conversion of 1, 3-butanediol obtained at different temperatures and yield of 3-hydroxybutyric acid
| Reaction temperature/. Degree.C | 50 | 60 | 70 | 80 | 90 | 100 |
| 1, 3-butanediol conversion% | 49.1 | 65.5 | 76.2 | 90.8 | 97.8 | 97.5 |
| 3-hydroxybutyric acid yield% | 26.4 | 40.5 | 51.3 | 67.6 | 75.5 | 76.9 |
The results in Table 5 show that a highly active, highly selective and highly stable 2% Pt-7.5% Sb/C catalyst for the selective oxidation of 1, 3-butanediol to 3-hydroxybutyric acid can be prepared using the procedure described in example 1. The catalyst can selectively oxidize 1, 3-butanediol into 3-hydroxybutyric acid in a wide temperature range (50-100 ℃). When the temperature is higher than 80 ℃, the conversion rate of the 1, 3-butanediol can reach more than 90.8%, and even if the reaction temperature is further increased to 100 ℃, the yield of the 3-hydroxybutyric acid can still reach 76.9%.
Example 6
The same catalyst preparation and reaction procedure as in example 1 were followed except that the 1, 3-butanediol oxidation reaction was conducted at an oxygen pressure of 0.5 to 3MPa, a reaction temperature of 80℃and a reaction time of 6 hours, and the conversion of 1, 3-butanediol and the yield of 3-hydroxybutyraldehyde at different oxygen pressures were obtained as shown in Table 6.
TABLE 6 conversion of 1, 3-butanediol and yield of 3-hydroxybutyric acid obtained under different oxygen pressures
| Oxygen pressure/MPa | 0.5 | 1.0 | 1.5 | 2.0 | 3.0 |
| 1, 3-butanediol conversion% | 92.6 | 94.7 | 92.4 | 90.8 | 89.2 |
| 3-hydroxybutyric acid yield% | 60.5 | 72.4 | 68.4 | 67.6 | 61.0 |
The results in Table 6 show that a highly active, highly selective and highly stable 2% Pt-7.5% Sb/C catalyst for the selective oxidation of 1, 3-butanediol to 3-hydroxybutyric acid can be prepared using the procedure described in example 1. The catalyst can selectively oxidize 1, 3-butanediol into 3-hydroxybutyric acid in a wide pressure range (0.5-3 MPa). The conversion rate of the 1, 3-butanediol is still kept at about 90% no matter under lower reaction pressure (0.5 MPa) or the reaction pressure is increased to 3MPa, and the highest yield of the 3-hydroxybutyric acid can reach 72.4%.
Example 7
The same catalyst preparation and reaction procedure as in example 1 were followed except that the initial concentration of 1, 3-butanediol oxidation reaction was 10-100g/L, the reaction temperature was 80℃and the reaction time was 6 hours, and the conversion of 1, 3-butanediol and the yield of 3-hydroxybutyraldehyde at the different initial concentrations of the raw materials were as shown in Table 7.
TABLE 7 conversion of 1, 3-butanediol at various starting concentrations of starting materials and yield of 3-hydroxybutyric acid
| Initial concentration of raw materials/g.L -1 | 10 | 20 | 40 | 60 | 80 | 100 |
| 1, 3-butanediol conversion% | 90.8 | 84.6 | 78.6 | 72.7 | 63.7 | 53.3 |
| 3-hydroxybutyric acid yield% | 67.6 | 50.8 | 41.3 | 27.2 | 21.2 | 9.1 |
The results in Table 7 show that a highly active, highly selective and highly stable 2% Pt-7.5% Sb/C catalyst for the selective oxidation of 1, 3-butanediol to 3-hydroxybutyric acid can be prepared using the procedure described in example 1. The catalyst can selectively oxidize 1, 3-butanediol to 3-hydroxybutyric acid in a wide initial concentration range (10-100 g/L) of a substrate. The conversion rate of the 1, 3-butanediol is 90.8% under the condition of low initial concentration (10 g/L), and the selectivity of the target product 3-hydroxybutyric acid is as high as 74.5%; when the initial concentration of 1, 3-butanediol is enlarged by 10 times to 100g/L, the conversion rate of 1, 3-butanediol can reach 53.3%, which shows that the catalyst has stronger catalytic oxidation capability.
Comparative example 1
Activated carbon is preparedDrying overnight in a vacuum oven at 60 ℃, then weighing 1g of pretreated activated carbon, dispersing the activated carbon in 2mL of chloroplatinic acid aqueous solution (the Pt content is 0.01 g/mL), carrying out ultrasonic treatment for 0.5h, stirring for 24h at room temperature, standing for 2h, carrying out ultrasonic treatment for 0.5h, standing for 3h, and finally drying for 12h at 120 ℃; the dried sample is put into a reducing furnace and then is put into H 2 Reducing for 1h at 450 ℃ in the atmosphere to obtain the 2 percent Pt/C catalyst.
The conversion of 1, 3-butanediol and the yield of 3-hydroxybutyric acid at various reaction times with 2% Pt/C were obtained with reference to the same reaction procedure in example 1 as shown in Table 8.
TABLE 8 conversion of 1, 3-butanediol and 3-hydroxybutyric acid yield on Pt/C2%
| Reaction time/h | 2 | 4 | 6 | 8 | 10 | 12 | 14 |
| 1, 3-butanediol conversion% | 40.9 | 50.2 | 58.3 | 60.5 | 65.1 | 68.1 | 71.4 |
| 3-hydroxybutyric acid yield% | 5.4 | 9.6 | 13.2 | 16.8 | 21.2 | 25.2 | 30.5 |
The results in Table 8 show that the 2% Pt/C catalyst prepared by selective oxidation of 1, 3-butanediol prepared by the procedure described in comparative example 1 is less reactive and less stable. As the reaction time increases, the catalytic oxidation ability of the catalyst becomes weaker. When the reaction is carried out for 14 hours, the conversion rate of the 1, 3-butanediol is 71.4%, and the yield of the target product 3-hydroxybutyric acid is only 30.5%, which indicates that the catalyst has no excellent reactivity and stability. By adopting the processes described in the examples 1 and 2, the catalyst of 2% Pt-7.5% Sb/C and 7.5% Sb-2% Pt/C for preparing 3-hydroxybutyric acid by selective oxidation of 1, 3-butanediol with high activity, high selectivity and high stability can be prepared, which shows that the addition of Sb is helpful for improving the reactivity and stability of the catalyst.
Example 8
Referring to the same catalyst preparation and reaction steps in example 1, except that the oxidant for the oxidation reaction of 1, 3-butanediol was oxygen, air or hydrogen peroxide, the molar ratio of hydrogen peroxide to 1, 3-butanediol was controlled to be 5:1 (the air in the reaction vessel was replaced by charging nitrogen and the pressure was maintained at 2.0 MPa), the reaction temperature was 80 ℃ and the reaction time was 6 hours, and the conversion rate of 1, 3-butanediol and the yield of 3-hydroxybutyric acid under the action of different oxidants were as shown in table 9.
TABLE 9 conversion of 1, 3-butanediol and yield of 3-hydroxybutyric acid by the action of different oxidants
| Oxidizing agent | Oxygen gas | Air-conditioner | Hydrogen peroxide |
| 1, 3-butanediol conversion% | 90.8 | 90.2 | 92.9 |
| 3-hydroxybutyric acid yield% | 67.6 | 66.8 | 59.0 |
The results in Table 9 show that a highly active, highly selective and highly stable 2% Pt-7.5% Sb/C catalyst for the selective oxidation of 1, 3-butanediol to 3-hydroxybutyric acid can be prepared using the procedure described in example 1. The catalyst can oxidize the 1, 3-butanediol into 3-hydroxybutyric acid under the action of different oxidants, the conversion rate of the 1, 3-butanediol is over 90%, and the highest yield of the 3-hydroxybutyric acid can reach 67.6%. The catalyst has excellent reactivity and catalytic oxidation capability.
Further, it is to be understood that various changes and modifications of the present application may be made by those skilled in the art after reading the above description of the application, and that such equivalents are intended to fall within the scope of the application as defined in the appended claims.
Claims (6)
1. A synthesis process for preparing 3-hydroxybutyric acid by selective oxidation of 1, 3-butanediol is characterized in that 1, 3-butanediol is used as a raw material, and liquid-phase oxidation reaction is directly carried out under the action of a catalyst to prepare 3-hydroxybutyric acid; the catalyst is Pt-Sb alloy loaded by active carbon;
the preparation method of the catalyst comprises the following steps:
(1) Uniformly dispersing active carbon in a platinum precursor solution, fully soaking, evaporating the solvent, uniformly dispersing the obtained solid in an ethanol solution of trivalent antimony salt, fully soaking, evaporating the solvent, and obtaining a dried sample; or,
uniformly dispersing active carbon in an ethanol solution of trivalent antimony salt, fully soaking, evaporating the solvent, uniformly dispersing the obtained solid in a platinum precursor solution, fully soaking, evaporating the solvent, and obtaining a dried sample;
(2) Reducing the sample obtained in the step (1) in a hydrogen atmosphere at 300-600 ℃, and then performing heat treatment for 2-5 hours in a nitrogen atmosphere at 700-900 ℃ to obtain the catalyst;
in the catalyst, the loading of platinum is 1% -5% of the mass of the activated carbon, and the loading of antimony is not more than 15% of the mass of the activated carbon.
2. The synthetic process of claim 1 wherein in step (1), the activated carbon is vacuum dried prior to use.
3. The synthetic process according to claim 1, wherein in step (2), the time of the reduction is 1 to 3 hours.
4. The synthetic process of claim 1 wherein the oxidizing agent used in the liquid phase oxidation reaction comprises at least one of oxygen, air, hydrogen peroxide.
5. The synthesis process according to claim 1, wherein the reaction solvent used in the liquid phase oxidation reaction is water, the initial concentration of 1, 3-butanediol in the reaction solution is 10-100g/L, and the catalyst is used in an amount of 0.1g/10mL reaction solution.
6. The synthesis process according to claim 1, wherein the reaction pressure of the liquid phase oxidation reaction is 0.5-3.0MPa, the reaction temperature is 50-100 ℃, and the reaction time is 2-14h.
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