CN105439831B - A kind of method of load type gold catalyst catalysis oxidation glycerol production C3H6O3 - Google Patents
A kind of method of load type gold catalyst catalysis oxidation glycerol production C3H6O3 Download PDFInfo
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- CN105439831B CN105439831B CN201510817848.8A CN201510817848A CN105439831B CN 105439831 B CN105439831 B CN 105439831B CN 201510817848 A CN201510817848 A CN 201510817848A CN 105439831 B CN105439831 B CN 105439831B
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- glycerine
- dihydroxyacetone
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- 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
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
- C07C45/39—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups being a secondary hydroxyl group
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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
- B01J23/005—Spinels
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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
- B01J23/007—Mixed salts
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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
- B01J23/66—Silver or gold
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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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8926—Copper and noble metals
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Abstract
The invention discloses a kind of load type gold catalyst catalysis oxidation glycerol productions 1, the method of 3- dihydroxyacetone (DHA)s, this method is using glycerine water solution and oxygen as raw material, using ZnO, copper aluminum hydrotalcite or spinelle gold-supported as catalyst, under conditions of alkali-free, realize highly selective conversion of the glycerine by mode of oxidizing to 1,3-Dihydroxyacetone.The method of the present invention carries out under the conditions of alkali-free, and the requirement to consersion unit is low, and investment is small；Catalyst preparation process is simple, and reaction raw materials are easy to get, and reaction process is mild, environmentally friendly, pollution-free, and catalyst has the advantages that convenient recycling, long lifespan, has good industrial prospect.
Description
Technical field
The invention belongs to the preparing technical fields of 1,3-Dihydroxyacetone, and in particular to a kind of load type gold catalyst catalysis
The method for aoxidizing glycerol production C3H6O3.
Background technology
Increasingly reduce in fossil class non-renewable resources reserves, rise in price, the deterioration of the ecological environment caused by greenhouse effects
Today of getting worse is the research of Material synthesis fuels and chemicals by more and more using renewable resources such as biomass
Concern.Glycerine mostlys come from the by-product generated in the production process of biodiesel as a kind of important platform chemicals
Object, since biodiesel production capacity constantly expands, glycerine is in the presence of that supply exceed demand, how to be translated under high added value
Chemicals (such as glyceric acid, glyceraldehyde, dihydroxyacetone (DHA), lactic acid) is swum, research hotspot is become.
1,3-Dihydroxyacetone (abbreviation DHA) is simplest three carbon ketose, food additives, cosmetics sun-screening agent,
There is extensive use in pharmaceutical intermediate and Chemical Manufacture.Currently, the production of DHA has bioanalysis and chemical method, the former is mainly
By fermentation, but there are the low yield of fermenting and producing strain, fermentation period is long, product separating-purifying is of high cost etc. lacks
Point.And chemical method is because it is mild with reaction condition, low and simple to production equipment requirement, product yield is high and purity is high, anti-
The advantages that answering process environmentally safe receives people's concern.
The acquisition most direct mode of C3H6O3 is by glycerine under catalyst and oxygen existence condition by one
Step reaction.For example, Hiroshi Kimura etc. are sweet using the oxidation of Pt/C, Pt-Bi/C and Pt-Bi-Ce/C catalyst
Oil prepares 1,3-Dihydroxyacetone, achieve certain catalytic effect (Appl.Catal., A, 1993,96:217-228.)；
For Wenbin Hu etc. by the composition and consersion unit of improvement Pt-Bi/C catalyst, it is 48% to obtain yield in acid condition
C3H6O3 and 80% glycerol conversion yield (Ind.Eng.Chem.Res., 2010,49 (21):10876-
10882.)；Ling Dan etc. under neutrallty condition, are realized high by changing the composition and reaction system of Pt-Bi/C catalyst
Glycerol conversion yield (91.5%) and 49% C3H6O3 selectivity (Chin.J.Catal., 2011,32:1831-
1837.)；Renfeng Nie etc. load to Pt-Sb on multi-walled carbon nanotube, and glycerine is aoxidized under the conditions of alkali-free, at 90% turn
Under rate C3H6O3 selectively for 51.4% (Appl.Catal.B, 2012,127:212-220.).Nearest Shu-
Sen Liu et al. is found using Au/CuO as catalyst, under neutrallty condition, when glycerine and golden molar ratio 1000, is obtained more highly selective
1,3-Dihydroxyacetone (82.3%), but glycerol conversion yield is relatively low (20%), when improving the ratio of glycerine and gold (100),
Glycerine is totally converted, but 1,3-Dihydroxyacetone the selective range of decrease larger (54.6%) (ACS Catal., 2014,4:2226-
2230.).Therefore, the yield for how improving 1,3-Dihydroxyacetone becomes the common purpose of researchers.
Invention content
A kind of easy to operate technical problem to be solved by the present invention lies in providing, under the conditions of alkali-free, load type gold is urged
The method of agent catalysis oxidation glycerine high conversion, highly selective production C3H6O3.
Technical solution is used by solving above-mentioned technical problem：Glycerine and oxygen are catalyzed in load type gold catalyst and made
Under, reacted in autoclave, obtain 1,3-Dihydroxyacetone, the carrier of the load type gold catalyst be ZnO,
Copper aluminum hydrotalcite, copper aluminium ratio are 5:1 or 1:Any one in 3 spinelle.
Golden load capacity is preferably 1%~3% in above-mentioned load type gold catalyst, and the preferred copper aluminium ratio of carrier is 5:1 point
Spar.
The molar ratio of glycerine and gold is 100~1000 in above-mentioned preparation method, and the molar ratio of preferably glycerine and gold is 100,
The reaction temperature is 60~80 DEG C, the reaction time is 2~5 hours, oxygen pressure is 1~2MPa, preferable reaction temperature 80
DEG C, the reaction time be 2~3 hours, oxygen pressure is 1~2MPa.
Load type gold catalyst of the present invention is prepared using deposition-precipitation method, and specific preparation method is：By HAuCl4Add
Enter in distilled water, be uniformly mixed, urea and corresponding carrier is then added, be heated with stirring to 70~80 DEG C, is kept for 6~8 hours,
It is down to room temperature, is kept for 16~20 hours, is filtered, is washed to no Cl-In the presence of then 100~110 DEG C of dryings 4~6 hours are being flowed
200 DEG C are warming up to 1~2 DEG C/min in dynamic air, constant temperature calcining 4~5 hours after natural cooling, obtains load type gold catalysis
Agent.
The present invention is with ZnO, copper aluminum hydrotalcite or copper aluminate gold-supported using glycerine water solution and oxygen as raw material
Catalyst realizes highly selective conversion of the glycerine by mode of oxidizing to 1,3-Dihydroxyacetone under conditions of alkali-free.This
Inventive method carries out under the conditions of alkali-free, and the requirement to consersion unit is low, and investment is small；Catalyst preparation process is simple, and reaction is former
Material is easy to get, and reaction process is mild, environmentally friendly, pollution-free, and catalyst has the advantages that convenient recycling, long lifespan, tool
There is good industrial prospect.
Specific implementation mode
With reference to embodiment, the present invention is described in more detail, but protection scope of the present invention is not limited only to these realities
Apply example.
Embodiment 1
According to the molar ratio 100 of glycerine and gold:1, by 24mL 0.1mol/L glycerine water solutions, 0.1576g 3%Au/ points
(copper al mole ratio is 5 to spar in spinelle:1) be added in 50mL autoclaves, it is closed completely after, at room temperature with high pure oxygen
Gas is emptied three times, and 1.0MPa high purity oxygen gas is then charged with, and is heated with stirring to 80 DEG C, isothermal reaction 2 hours, reaction terminates
Afterwards, it being cooled with an ice bath to room temperature, centrifugation, filtering, reaction solution carries out high performance liquid chromatography detection, measures the conversion ratio and 1 of glycerine,
The yield of 3- dihydroxyacetone (DHA)s.Analysis show that glycerol conversion yield 76.7%, 1,3-Dihydroxyacetone is selectively 97.3%.
Embodiment 2
According to the molar ratio 100 of glycerine and gold:1, by 24mL 0.1mol/L glycerine water solutions, 0.1576g 3%Au/ZnO
Be added in 50mL autoclaves, it is closed completely after, emptied three times with high purity oxygen gas at room temperature, be then charged with 1.0MPa
High purity oxygen gas is heated with stirring to 80 DEG C, and isothermal reaction 2 hours is cooled with an ice bath to room temperature, centrifugation, filtering after reaction,
Reaction solution carries out high performance liquid chromatography detection, measures the conversion ratio of glycerine and the yield of 1,3-Dihydroxyacetone.Analysis obtains, sweet
Oily conversion ratio is 87.1%, and 1,3-Dihydroxyacetone is selectively 74.8%.
Embodiment 3
According to the molar ratio 100 of glycerine and gold:1, by 24mL 0.1mol/L glycerine water solutions, 0.1576g 3%Au/ copper
Aluminum hydrotalcite is added in 50mL autoclaves, it is closed completely after, emptied three times with high purity oxygen gas, then filled at room temperature
Entering 1.0MPa high purity oxygen gas, is heated with stirring to 80 DEG C, isothermal reaction 2 hours is cooled with an ice bath to room temperature after reaction, from
The heart, filtering, reaction solution carry out high performance liquid chromatography detection, measure the conversion ratio of glycerine and the yield of 1,3-Dihydroxyacetone.Point
Analysis show that glycerol conversion yield 61.5%, 1,3-Dihydroxyacetone is selectively 98.0%.
Embodiment 4
According to the molar ratio 100 of glycerine and gold:1, by 24mL 0.1mol/L glycerine water solutions, 0.1576g 3%Au/ points
(copper al mole ratio is 1 to spar in spinelle:3) be added in 50mL autoclaves, it is closed completely after, at room temperature with high pure oxygen
Gas is emptied three times, and 1.0MPa high purity oxygen gas is then charged with, and is heated with stirring to 80 DEG C, isothermal reaction 2 hours, reaction terminates
Afterwards, it being cooled with an ice bath to room temperature, centrifugation, filtering, reaction solution carries out high performance liquid chromatography detection, measures the conversion ratio and 1 of glycerine,
The selectivity of 3- dihydroxyacetone (DHA)s.Analysis obtains, glycerol conversion yield 68.4%, and 1,3-Dihydroxyacetone is selectively
94.7%.
Embodiment 5
According to the molar ratio 100 of glycerine and gold:1, by 24mL 0.1mol/L glycerine water solutions, 0.1576g 3%Au/ points
(copper al mole ratio is 5 to spar in spinelle:1) be added in 50mL autoclaves, it is closed completely after, at room temperature with high pure oxygen
Gas is emptied three times, and 2.0MPa high purity oxygen gas is then charged with, and is heated with stirring to 60 DEG C, isothermal reaction 4.5 hours, reaction terminates
Afterwards, it being cooled with an ice bath to room temperature, centrifugation, filtering, reaction solution carries out high performance liquid chromatography detection, measures the conversion ratio and 1 of glycerine,
The selectivity of 3- dihydroxyacetone (DHA)s.Analysis obtains, glycerol conversion yield 66.6%, and 1,3-Dihydroxyacetone is selectively
97.3%.
Embodiment 6
According to the molar ratio 500 of glycerine and gold:1, by 24mL 0.1mol/L glycerine water solutions, 0.0315g 3%Au/ points
(copper al mole ratio is 5 to spar in spinelle:1) be added in 50mL autoclaves, it is closed completely after, at room temperature with high pure oxygen
Gas is emptied three times, and 1.0MPa high purity oxygen gas is then charged with, and is heated with stirring to 80 DEG C, isothermal reaction 2 hours, reaction terminates
Afterwards, it being cooled with an ice bath to room temperature, centrifugation, filtering, reaction solution carries out high performance liquid chromatography detection, measures the conversion ratio and 1 of glycerine,
The selectivity of 3- dihydroxyacetone (DHA)s.Analysis obtains, glycerol conversion yield 42.4%, and 1,3-Dihydroxyacetone is selectively
96.6%.
Embodiment 7
According to the molar ratio 1000 of glycerine and gold:1, by 24mL 0.1mol/L glycerine water solutions, 0.0158g 3%Au/ points
(copper al mole ratio is 5 to spar in spinelle:1) be added in 50mL autoclaves, it is closed completely after, at room temperature with high pure oxygen
Gas is emptied three times, and 1.0MPa high purity oxygen gas is then charged with, and is heated with stirring to 80 DEG C, isothermal reaction 2 hours, reaction terminates
Afterwards, it being cooled with an ice bath to room temperature, centrifugation, filtering, reaction solution carries out high performance liquid chromatography detection, measures the conversion ratio and 1 of glycerine,
The selectivity of 3- dihydroxyacetone (DHA)s.Analysis obtains, glycerol conversion yield 21.6%, and 1,3-Dihydroxyacetone is selectively
94.8%.
Claims (1)
1. a kind of method of load type gold catalyst catalysis oxidation glycerol production 1,3-Dihydroxyacetone, it is characterised in that：It will be sweet
Oil and oxygen are reacted in autoclave under load type gold catalyst catalytic action, obtain 1,3-Dihydroxyacetone,
The carrier of the load type gold catalyst is that copper aluminium ratio is 5:1 spinelle, golden load capacity is 3% in load type gold catalyst,
The molar ratio of the glycerine and gold is 100, and the temperature of reaction is 80 DEG C, the time is 2 hours, oxygen pressure 1.0MPa.
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| CN201510817848.8A CN105439831B (en) | 2015-11-23 | 2015-11-23 | A kind of method of load type gold catalyst catalysis oxidation glycerol production C3H6O3 |
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| CN201510817848.8A CN105439831B (en) | 2015-11-23 | 2015-11-23 | A kind of method of load type gold catalyst catalysis oxidation glycerol production C3H6O3 |
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108273502A (en) * | 2018-03-28 | 2018-07-13 | 北京化工大学 | One kind preparing C3H6O3 catalyst and preparation method thereof by glycerine |
| CN108686682B (en) * | 2018-05-16 | 2020-08-25 | 扬州工业职业技术学院 | Green oxidation synthesis method of glyceraldehyde |
| CN109400461A (en) * | 2018-09-17 | 2019-03-01 | 南京工程学院 | The method and its application of hydrogen peroxide catalyzed glycerol |
| CN109503340A (en) * | 2018-12-22 | 2019-03-22 | 江西师范大学 | A kind of preparation process of C3H6O3 |
| CN110102293A (en) * | 2019-06-14 | 2019-08-09 | 北方民族大学 | Gold/oxide catalyst and the application in DHA is prepared in catalysis oxidation glycerol |
| CN110252298B (en) * | 2019-06-26 | 2021-06-25 | 北京化工大学 | Catalyst for preparing DHA (docosahexaenoic acid) by efficiently catalyzing glycerol through metal oxide supported gold and preparation method thereof |
| CN110227450A (en) * | 2019-06-26 | 2019-09-13 | 北京化工大学 | A kind of metal cooperates with efficient catalytic glycerol to prepare the catalyst and preparation method thereof of DHA with carrier alkalinity |
| CN110872215A (en) * | 2019-11-25 | 2020-03-10 | 北方民族大学 | Mesoporous CuO-CeO2Application of composite oxide supported Au catalyst in catalytic oxidation of glycerol |
| CN114689704B (en) * | 2020-12-26 | 2023-05-09 | 四川汇宇制药股份有限公司 | Method for detecting 1,3-dihydroxyacetone and related impurities |
| CN114029058A (en) * | 2021-11-30 | 2022-02-11 | 中国石油大学(华东) | Catalyst for preparing 1,3-dihydroxyacetone by glycerol oxidation and method thereof |
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