CN104003865A - Method for catalytic oxidation of 1,2-propylene glycol at normal pressure - Google Patents
Method for catalytic oxidation of 1,2-propylene glycol at normal pressure Download PDFInfo
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- CN104003865A CN104003865A CN201410206173.9A CN201410206173A CN104003865A CN 104003865 A CN104003865 A CN 104003865A CN 201410206173 A CN201410206173 A CN 201410206173A CN 104003865 A CN104003865 A CN 104003865A
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- catalytic oxidation
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- lactic acid
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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
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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
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1856—Phosphorus; Compounds thereof with iron group metals or platinum group metals with platinum group 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
Abstract
The invention relates to a method for preparing lactic acid, and particularly relates to a method for preparing lactic acid by catalytic oxidation of 1,2-propylene glycol at a normal pressure condition with oxygen or air as an oxygen source and nano-hydroxyapatite (HAP)-loaded precious metal as a catalyst. The method comprises the following steps: adding a hydroxyapatite-loaded precious metal catalyst and sodium hydroxide into a 1,2-propylene glycol aqueous solution; starting stirring to enable the materials to contact fully; heating to 50-100 DEG C; injecting reaction gas with the flow rate being controlled at 40-100 mL/min; controlling the reaction time to be 0.5-10 h, and after the reaction, performing acidification to obtain lactic acid. The catalyst of nanometer magnesium hydroxide-loaded gold, palladium or alloy of gold and palladium prepared in the invention needs no activation treatment during the reaction, is low in using amount, can realize high 1,2-propylene glycol conversion rate and high lactic acid selectivity at a normal pressure condition, and has good catalytic stability.
Description
Technical field
The present invention relates to prepare the method for lactic acid, refer in particular to taking oxygen or air as oxygen source, under condition of normal pressure, taking nanometer hydroxyapatite (HAP) carried noble metal as catalyzer, the method for lactic acid is prepared in the oxidation of catalysis 1,2-PD.
Background technology
Lactic acid is a kind of important chemical, is the starting raw material of poly(lactic acid) (PLA), and taking 1,2-PD as catalytic material, to prepare lactic acid be a kind of new raw material route and synthetic method with important application prospect, high-efficiency environment friendly in oxidation.
At present, disclosed 1, the technology of 2-propylene glycol preparing lactic acid by catalytic oxidation all needs to carry out under pressurized conditions alcohol reaction, for example, patent CN 102249892 discloses the catalyst 1 of the multiple precious metal of a kind of magnesium-containing carrier load, 2-propylene glycol is prepared lactic acid, the about 1.4wt% of precious metal total loading amount, 0.3MPa O
2, 60 DEG C of reaction 7h, can obtain 90% transformation efficiency, and lactic acid selectivity reaches more than 90%, and the reaction times is longer; The use 0.5%Au/ graphite oxygen catalytic oxidation 1,2-PDs such as Hutchings are prepared lactic acid, and 60 DEG C, 1.0MPa reacts 3h, and transformation efficiency reaches 53%, and lactic acid selectivity reaches 71%; In the time improving gold loading, although selectivity can improve, transformation efficiency is 32% (Chemical Communications, 2002,7,696-697) only.
The invention provides a kind of atmosphere-pressure catalytic oxidation 1,2-PD and prepare the method for lactic acid.The method has overcome compressive reaction condition, and has high lactic acid yield, is a kind of safer, green, method of preparing efficiently lactic acid.
Summary of the invention
Prepare a kind of nanometer hydroxyapatite supported precious metal catalyst, prepared lactic acid for the oxidation of catalysis 1,2-PD; This catalyst levels is few, can high reactivity under normal pressure, highly selective prepares lactic acid, and have good catalytic life.
Technical scheme of the present invention is as follows:
Hydroxyapatite-Supported noble metal catalyst catalyzed oxidation 1,2-PD is prepared a method for lactic acid, carries out according to following step:
Be 0.1～0.9mol/L1 to concentration, in 2-aqueous solution of propylene glycol, add Hydroxyapatite-Supported noble metal catalyst, sodium hydroxide; Catalyst levels is 1%～10% of 1,2-PD quality, and sodium hydroxide concentration is 100%～400% of 1,2-PD quality; Open and stir, make fully contact between each material; Rising temperature of reaction to 50～100 DEG C; Pass into reactant gases, coutroi velocity 40～100mL/min; The control reaction times is 0.5～10h, after reaction, obtains lactic acid through acidification, adopts efficient liquid phase chromatographic analysis calculation result.
Described acidification refers to that reaction product, through dripping hydrochloric acid, regulates pH to 2～3.
Hydroxyapatite-Supported noble metal catalyst described in technique scheme, its preparation method is specific as follows: take respectively a certain amount of noble metal precursor body, ensure that noble metal support amount is 0.1～5% of hydroxyapatite quality, putting into concentration is in the 1wt%PVA aqueous solution, and normal temperature lower magnetic force stirs until all dissolve; Adding molar weight is the NaBH of 5 times of noble metal precursor body integral molar quantities
4reduce; Then add carrier nanometer hydroxyapatite, stir 2.5h, filter, washing is dried at 150 DEG C.
The described molar weight that adds is the NaBH of 5 times of noble metal precursor body integral molar quantities
4reduce and refer to normal temperature reduction 0.5h.
The particle diameter of described nanometer hydroxyapatite is 20～50nm.
Described precious metal in above-mentioned Hydroxyapatite-Supported noble metal catalyst is one or both in gold and palladium.
Noble metal precursor body described in above-mentioned method for preparing catalyst is one or both of hydrochloro-auric acid and Palladous chloride.
Gas described in technique scheme is the one of oxygen or air.
Nano-sized magnesium hydroxide gold-supported, palladium or the gold that the present invention is prepared and the catalyzer of palldium alloy, in reaction process, without activation treatment, consumption is few, can obtain high by 1 under condition of normal pressure, 2-propylene glycol transformation efficiency and high lactic acid selectivity have good catalytic stability simultaneously.
Embodiment
Below in conjunction with concrete embodiment, the present invention will be further described.
Embodiment 1
The preparation of catalyzer:
Divide the another name hydrochloro-auric acid of 0.2g and the Palladous chloride of 0.06g to be dissolved in the 14mL 1wt%PVA aqueous solution, magnetic agitation is until all dissolve; Add 0.1gNaBH
4reduce.Then adding 5g particle diameter is the hydroxyapatite of 50nm, and violent stirring 2.5h filters, and washing is dried at 150 DEG C, has prepared 1.5%Au-0.5%Pd/ hydroxyapatite catalyzer.
Propylene glycol oxidizing reaction:
Be the there-necked flask that the 0.26mol/L 1,2-PD aqueous solution is placed in 100mL by 60mL concentration; Add 0.1g1.5%Au-0.5%Pd/ nanometer hydroxyapatite catalyzer; Add again 2.4gNaOH; Open magnetic agitation, each material is fully contacted; Rising temperature of reaction to 80 DEG C; Pass into oxygen, O
2flow is 80mL/min; The control reaction times is 6h; Reaction product, through dripping concentrated hydrochloric acid, regulates pH to 2～3, obtains product lactic acid; Adopt efficient liquid phase chromatographic analysis calculation result.The results are shown in Table 1.
Embodiment 2
With embodiment 1, the temperature that only changes reactor is respectively 50 DEG C, 100 DEG C, carries out the reaction of 1,2-PD hydro-oxidation, the transformation efficiency of gained lactic acid selectivity and 1,2-PD is in table 1, when improving temperature of reaction, 1,2-PD transformation efficiency obviously improves, and the selectivity of lactic acid declines to some extent.
Lactic acid selectivity and 1,2-PD transformation efficiency at table 1 differential responses temperature
Embodiment 3
With embodiment 1, be respectively 0.5h but change the reaction times, 3h, 6h, 10h acquired results is respectively in table 2, and along with the prolongation in reaction times, 1,2-PD transformation efficiency raises, but the elective reduction of lactic acid.
Lactic acid selectivity and 1,2-PD transformation efficiency under the table 2 differential responses time
Embodiment 4
With embodiment 1, be respectively 40ml/min but change oxygen gas flow rate, 100mL/min, acquired results is in table 3, and result shows, improves oxygen gas flow rate and is conducive to improve 1,2-PD transformation efficiency, but the elective reduction of lactic acid.
Lactic acid selectivity and 1,2-PD transformation efficiency under the different oxygen gas flow rates of table 3
Embodiment 5
With embodiment 1, be 100% and 300% of 1,2-PD quality but change sodium hydroxide concentration, i.e. 1.2g and 3.6g, acquired results is in table 4, and result shows, and lower sodium hydroxide concentration is unfavorable for that 1,2-PD transforms generation lactic acid.
The different sodium hydroxide concentrations of table 4 optionally affect 1,2-PD transformation efficiency and lactic acid
Embodiment 6
With embodiment 1, be respectively 0.42% and 1.66% of 1,2-PD quality but change catalyst levels, consumption is 0.05,0.2g, acquired results is in table 5, and result shows, increase catalyst levels and be conducive to improve the conversion of 1,2-PD, but be unfavorable for the generation of lactic acid.
Table 5 different catalysts consumption optionally affects 1,2-PD transformation efficiency and lactic acid
Embodiment 7
With embodiment 1, but the consumption of change hydrochloro-auric acid and Palladous chloride is respectively 0.26g and 0g; 0g and 0.216g, the catalyst loadings that simultaneously oxygen is changed into air gained with and catalytic result in table 6, result shows, in the time that content of metal is consistent, bimetallic catalytic effect will be higher than the catalyzer of monometallic load, in addition, in the time being oxygenant with air, compared with oxygen, can obtain high lactic acid selectivity, but transformation efficiency is lower.
Table 6 in the time that air is oxygenant, 1,2-PD transformation efficiency and lactic acid selectivity under different catalysts effect
Claims (10)
1. a method for atmosphere-pressure catalytic oxidation 1,2-PD, is characterized in that: using nanometer hydroxyapatite carried noble metal as catalyzer, lactic acid is prepared in the oxidation of catalysis 1,2-PD.
2. the method for a kind of atmosphere-pressure catalytic oxidation 1,2-PD as claimed in claim 1, is characterized in that: be 0.1 ~ 0.9 mol/L1 to concentration, add nanometer hydroxyapatite supported precious metal catalyst, sodium hydroxide in 2-aqueous solution of propylene glycol; Catalyst levels is 1% ~ 10% of 1,2-PD quality, and sodium hydroxide concentration is 100% ~ 400% of 1,2-PD quality; Open and stir, make fully contact between each material; Rising temperature of reaction to 50 ~ 100 DEG C; Pass into reactant gases, coutroi velocity 40 ~ 100 mL/min; Controlling the reaction times is 0.5 ~ 10 h, after reaction, obtains lactic acid through acidification.
3. the method for a kind of atmosphere-pressure catalytic oxidation 1,2-PD as claimed in claim 2, is characterized in that: described acidification refers to that reaction product, through dripping hydrochloric acid, regulates pH to 2 ~ 3.
4. a kind of atmosphere-pressure catalytic oxidation 1 as claimed in claim 2, the method of 2-propylene glycol, it is characterized in that: the preparation method of described nanometer hydroxyapatite carried noble metal is specific as follows: take respectively a certain amount of noble metal precursor body, ensure that noble metal support amount is 0.1 ~ 5% of hydroxyapatite quality, putting into concentration is in the 1wt%PVA aqueous solution, and normal temperature lower magnetic force stirs until all dissolve; Adding molar weight is the NaBH of 5 times of noble metal precursor body integral molar quantities
4reduce; Then add carrier nanometer hydroxyapatite, stir, filter, washing, dries.
5. the method for a kind of atmosphere-pressure catalytic oxidation 1,2-PD as claimed in claim 4, is characterized in that: described in to add molar weight be the NaBH of 5 times of noble metal precursor body integral molar quantities
4reduce and refer to normal temperature reduction 0.5h.
6. the method for a kind of atmosphere-pressure catalytic oxidation 1,2-PD as claimed in claim 1, is characterized in that: the particle diameter of described nanometer hydroxyapatite is 20 ~ 50 nm.
7. the method for a kind of atmosphere-pressure catalytic oxidation 1,2-PD as claimed in claim 1, is characterized in that: described precious metal is one or both in gold and palladium.
8. the method for a kind of atmosphere-pressure catalytic oxidation 1,2-PD as claimed in claim 4, is characterized in that: described noble metal precursor body is one or both of hydrochloro-auric acid and Palladous chloride.
9. the method for a kind of atmosphere-pressure catalytic oxidation 1,2-PD as claimed in claim 4, is characterized in that: described gas is the one of oxygen or air.
10. the method for a kind of atmosphere-pressure catalytic oxidation 1,2-PD as claimed in claim 1, is characterized in that: described temperature of reaction is 80 DEG C; Reaction times is 6 h; Reactant gases flow velocity 80 mL/min; Sodium hydroxide concentration is 200% of 1,2-PD quality; Catalyst levels is 0.84% of 1,2-PD quality; Nanometer hydroxyapatite supported precious metal catalyst is .5%Au-0.5%Pd/ nanometer hydroxyapatite.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105413722A (en) * | 2015-11-27 | 2016-03-23 | 河南金丹乳酸科技股份有限公司 | Compound catalyst used for chemically catalyzing and oxidizing lactic acid to be derived and converted to produce pyroracemic acid |
| CN105601494A (en) * | 2016-03-04 | 2016-05-25 | 江苏大学 | Method for carrying out catalytic oxidation on 1,2-propylene glycol with nano-copper |
| CN107162897A (en) * | 2017-06-08 | 2017-09-15 | 南京工业大学 | A kind of method that mandelic acid is prepared by styrene oxide |
| CN110560103A (en) * | 2019-08-06 | 2019-12-13 | 江苏大学 | Preparation method and application of porous nano hydroxyapatite-loaded nano gold catalyst |
| CN110860297A (en) * | 2019-10-24 | 2020-03-06 | 江苏大学 | Preparation method of Cu-Ag/La @ HAP catalyst and application of Cu-Ag/La @ HAP catalyst in preparation of lactic acid by catalytic oxidation of 1, 2-propylene glycol |
| CN112191256A (en) * | 2020-08-31 | 2021-01-08 | 浙江工业大学 | Application of metal mesh loaded metal particle catalyst in reaction of preparing lactic acid by catalytic oxidation of 1, 2-propylene glycol |
| CN113861020A (en) * | 2020-06-30 | 2021-12-31 | 江苏索普工程科技有限公司 | Preparation method of lactic acid |
| CN114029077A (en) * | 2021-11-30 | 2022-02-11 | 中国石油大学(华东) | Catalyst for preparing hydroxy acid by catalytic oxidation of polyol and method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102249892A (en) * | 2010-05-19 | 2011-11-23 | 中国科学院大连化学物理研究所 | Method for preparing lactic acid by catalytic oxidation of 1,2-propylene glycol |
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Patent Citations (1)
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| CN102249892A (en) * | 2010-05-19 | 2011-11-23 | 中国科学院大连化学物理研究所 | Method for preparing lactic acid by catalytic oxidation of 1,2-propylene glycol |
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| 丁世红等: "用于催化剂载体的羟基磷灰石的合成研究", 《天津化工》, vol. 20, no. 1, 31 January 2006 (2006-01-31), pages 47 - 48 * |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105413722A (en) * | 2015-11-27 | 2016-03-23 | 河南金丹乳酸科技股份有限公司 | Compound catalyst used for chemically catalyzing and oxidizing lactic acid to be derived and converted to produce pyroracemic acid |
| CN105601494A (en) * | 2016-03-04 | 2016-05-25 | 江苏大学 | Method for carrying out catalytic oxidation on 1,2-propylene glycol with nano-copper |
| CN105601494B (en) * | 2016-03-04 | 2018-01-16 | 江苏大学 | A kind of method of nanometer of propane diols of copper catalysis 1,2 oxidation |
| CN107162897A (en) * | 2017-06-08 | 2017-09-15 | 南京工业大学 | A kind of method that mandelic acid is prepared by styrene oxide |
| CN110560103A (en) * | 2019-08-06 | 2019-12-13 | 江苏大学 | Preparation method and application of porous nano hydroxyapatite-loaded nano gold catalyst |
| CN110560103B (en) * | 2019-08-06 | 2021-11-23 | 江苏大学 | Preparation method and application of porous nano hydroxyapatite-loaded nano gold catalyst |
| CN110860297B (en) * | 2019-10-24 | 2022-05-20 | 江苏大学 | Preparation method of Cu-Ag/La @ HAP catalyst and application of catalyst in preparation of lactic acid by catalytic oxidation of 1, 2-propanediol |
| CN110860297A (en) * | 2019-10-24 | 2020-03-06 | 江苏大学 | Preparation method of Cu-Ag/La @ HAP catalyst and application of Cu-Ag/La @ HAP catalyst in preparation of lactic acid by catalytic oxidation of 1, 2-propylene glycol |
| CN113861020A (en) * | 2020-06-30 | 2021-12-31 | 江苏索普工程科技有限公司 | Preparation method of lactic acid |
| CN112191256A (en) * | 2020-08-31 | 2021-01-08 | 浙江工业大学 | Application of metal mesh loaded metal particle catalyst in reaction of preparing lactic acid by catalytic oxidation of 1, 2-propylene glycol |
| CN112191256B (en) * | 2020-08-31 | 2023-05-23 | 浙江工业大学 | Application of metal mesh supported metal particle catalyst in reaction for preparing lactic acid by catalytic oxidation of 1, 2-propylene glycol |
| CN114029077A (en) * | 2021-11-30 | 2022-02-11 | 中国石油大学(华东) | Catalyst for preparing hydroxy acid by catalytic oxidation of polyol and method thereof |
| CN114029077B (en) * | 2021-11-30 | 2024-01-19 | 中国石油大学(华东) | Catalyst for preparing hydroxy acid by catalytic oxidation of polyol and method thereof |
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