CN104045546A - Method for preparing lactic acid through catalyzing glycerol - Google Patents
Method for preparing lactic acid through catalyzing glycerol Download PDFInfo
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- CN104045546A CN104045546A CN201410296449.7A CN201410296449A CN104045546A CN 104045546 A CN104045546 A CN 104045546A CN 201410296449 A CN201410296449 A CN 201410296449A CN 104045546 A CN104045546 A CN 104045546A
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- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/02—Preparation of carboxylic acids or their salts, halides or anhydrides from salts of carboxylic acids
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- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
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Abstract
The invention relates to the technical field of lactic acid preparation and particularly relates to a method for preparing lactic acid through catalyzing glycerol. According to the method provided by the invention, reaction is carried out on glycerol which serves as a raw material for 0.5-4 hours in a high-pressure reactor at the temperature of 150-230 DEG C under anaerobic alkaline conditions in the presence of nano cuprous oxide, thereby obtaining lactic acid. The method has the advantages that the reaction temperature and reaction pressure are low, the catalyst activity is high, the selectivity is good, the reaction rate is high, and the process flow is safe and environmental-friendly and the like, so that the industrial prospect is good.
Description
Technical field
The present invention relates to lactic acid preparing technical field, refer in particular to a kind of method that catalyzing glycerol is prepared lactic acid.
Background technology
Lactic acid (Lactic Acid), chemical system name 2 hydroxy propanoic acid (2-Hydroxypropanoic Acid); Because alpha site of carboxyl group carbon atom in lactic acid molecules is unsymmetrical carbon, so lactic acid has left-handed (L-type) and dextrorotation (D type) enantiomer of two kinds of opticities; Lactic acid found by Scheele early than 1850 in yogurt milk, and therefore lactic acid gain the name, and lactic acid is one of three large organic acids of generally acknowledging in the world, is extensively present among the metabolism of human body, animal and microorganism, was also present in all respects that people live.
Lactic acid is broad-spectrum organic acid, is mainly used in food and medicine industry; The lactic acid that functional quality mark is 80% in brewery industry can prevent miscellaneous bacteria breeding, promote yeast to grow, prevent the muddy of wine and strengthen the local flavor of wine, the lactic acid that in foodstuffs industry, general functional quality mark is 50%, lactic acid is as anticorrosive mildewproof oxidation inhibitor, also be the conventional acidic flavoring agents such as beverage, cake, jam, candy, its tart flavour is soft tasty and refreshing, and don't covers food fragrance and natural flavour mountaineous; Lactic acid can be directly as compounding medicine patent medicine in medicine industry, also oral administration is for enteron aisle sterilization, due to its strong polarity and wetting ability, energy solubilising protein, cutin and many insoluble medicines, and very responsive to pathological tissues corrosive nature, can be used for treating the diseases such as white monkey, lupus, aditus laryngis tuberculosis, it is again as convergency sterilant simultaneously, can also reduce serum cholesterol, strengthen body immunity; Lactic acid has purposes widely in the industries such as leather industry, cosmetic industry, production of cigarettes, lactic acid can synthesizing polylactic acid, poly(lactic acid) is as biodegradable plastic, can be widely used in manufacturing disposable food packing bag, food product containers, wrapping paper, shopping bag, sanitary paper, agricultural film etc., be conducive to preserve the ecological environment, prevent the pollution of the environment; Poly(lactic acid) can also be used as surgical sewing thread, drug controlled release system field, the immobilization material in orthopaedics field and the propping material of field of tissue engineering technology, and therefore, the demand of lactic acid is by increasing.
Glycerine is the by product in production of biodiesel process, and the biofuel that every production is ten tons just has the glycerine of one ton to produce, and along with the increase year after year of yield of biodiesel, the output of glycerine is very huge also; Utilize transformation of glycerol to produce a series of chemical and the middle product of chemistry, the feature with renewable and carbon dioxide zero discharge, and in glycerine, be rich in active hydroxyl, be easy to through replacing synthetic special chemical article, so the exploitation of glycerine have huge prospect; Recently research is found, utilizes glycerine to prepare the new purposes that lactic acid has not only been developed glycerine, also for lactic acid provides continuable raw material sources; From bibliographical information, glycerine is prepared lactic acid fermentation method and chemical synthesis, chemical synthesis has precious metal aerobic catalysis method and high temperature hydro-thermal anaerobic oxidation method, and the cost of fermentation method and precious metal aerobic catalysis method is very high, glycerine reaction concentration is low and the reaction times waits so long shortcoming, high temperature hydro-thermal anaerobic oxidation method is had relatively high expectations to temperature of reaction and reaction pressure; Debdut Roy etc. adopt industrial Cu/SiO
2, CuO/Al
2o
3and Cu
2o, can reduce temperature of reaction effectively, but temperature of reaction, reaction times and lactic acid selectivity are all to be improved.
Summary of the invention
The object of the present invention is to provide a kind of nano cuprous oxide catalyzing glycerol under alkaline condition to prepare the method for lactic acid, the chemical equation of dehydrogenation oxidation process is as follows:
Method provided by the present invention, is to take glycerine as raw material, and temperature of reaction is 0.5-4 h at 150-230 ℃, reaction times, under the anaerobic alkaline condition existing, reacts and obtain lactic acid in autoclave at nano cuprous oxide.
Alkaline condition of the present invention can be provided by following alkali source: comprise sodium hydroxide, potassium hydroxide, sodium carbonate and salt of wormwood.
It is that glycerine is mixed with to the aqueous solution that the glycerine of described reaction adds form, and the glycerine solution concentration of its preparation is 1.0-10 mol/L.
The alkali number of described reaction process is 0.5-1.5 mol/mol glycerine, is preferably 1.0-1.2 mol/mol glycerine.
The particle median size of described nano cuprous oxide catalyzer is at 40-500 nm.
The addition of described nano cuprous oxide catalyzer specifically can be 0.01-0.1 mol/mol glycerine.
Described oxygen free condition is emptying for carrying out with High Purity Nitrogen before reaction, and the pressure of nitrogen is on almost not impact of reaction.
The preparation method of described nano cuprous oxide can consult Aidong Tang et al, preparation, photo-catalytic acitivity of cuprous oxide nano-crystallites with different sizes. Journal of Alloys and Compounds. 2008, the documents such as 457:447-451., for routine techniques means, no longer describe in detail here.
The technical characterictic that the present invention distinguishes prior art is: adopt nano level Red copper oxide, reduce well glycerine and prepared temperature of reaction and the reaction pressure of lactic acid, the concentration that has simultaneously improved glycerine reaction, has shortened the reaction times effectively, has improved the selectivity of transformation efficiency and the lactic acid of glycerine.
The present invention, by oxidative pathway, under alkaline condition, utilizes nitrogen purge, and the rearrangement reaction of the intermediate product obtaining through peroxidation glycerine in autoclave obtains lactic acid; The inventive method is under oxygen free condition, and the highly selective to lactic acid transforms by mode of oxidizing to have realized glycerine, and the selectivity of lactic acid can reach 66-93%, and glycerol conversion yield can reach 60-100%; The inventive method does not need too high temperature of reaction, gets final product completing of realization response at 150-230 ℃, has saved a large amount of energy; The inventive method is carried out under oxygen free condition, for conversion unit require lowly, invest little; The inventive method system is simple, is easy to industrialization, and catalyst life is long, without running off.
The advantages such as the present invention has temperature of reaction and reaction pressure is low, catalyst activity is high and selectivity is good, speed of reaction fast, technological process safety and environmental protection, have good industrial prospect.
Embodiment
Below in conjunction with specific embodiment, the present invention will be further described: method described in following embodiment, if no special instructions, is ordinary method.
embodiment 1
Take 4.8 g sodium hydroxide (Chemical Reagent Co., Ltd., Sinopharm Group) and 0.72 g nano cuprous oxide (d
on average=50 nm), join together in 400 mL autoclaves, take again 9.20 g glycerine (Chemical Reagent Co., Ltd., Sinopharm Group) and carry out constant volume with 100 mL volumetric flasks, join in reactor, passing into nitrogen carries out emptying, then airtight good, be heated to 230 ℃ after timing, react 2 hours.
When reaction finishes, with hydrochloric acid, being acidified to pH is 2 ~ 3, and volume after measurement acidifying pipettes 2 mL with transfer pipet and uses deionized water constant volume to 25 mL, carries out high performance liquid chromatography detection, measures the output of lactic acid; With transfer pipet, pipette after 5 mL acidifyings in sample to 10 mL volumetric flask, add 1 mL propyl carbinol, by methanol constant volume, carry out gas chromatographic analysis, analysis draws, glycerol conversion yield 99%, lactic acid selectivity 92%.
Reaction conditions: glycerol concentration: 1.0 M; NaOH/ glycerine mol ratio: 1.2:1; Red copper oxide/glycerine mol ratio: 0.05.
embodiment 2
Take 6.72 g potassium hydroxide (Chemical Reagent Co., Ltd., Sinopharm Group) and 0.72 g nano cuprous oxide (d
on average=115 nm), join together in 400 mL autoclaves, take again 9.20 g glycerine (Chemical Reagent Co., Ltd., Sinopharm Group) and carry out constant volume with 100 mL volumetric flasks, join in reactor, passing into nitrogen carries out emptying, then airtight good, be heated to 230 ℃ after timing, react 2 hours.
When reaction finishes, with hydrochloric acid, being acidified to pH is 2 ~ 3, and volume after measurement acidifying pipettes 2 mL with transfer pipet and uses deionized water constant volume to 25 mL, carries out high performance liquid chromatography detection, measures the output of lactic acid; With transfer pipet, pipette after 5 mL acidifyings in sample to 10 mL volumetric flask, add 1 mL propyl carbinol, by methanol constant volume, carry out gas chromatographic analysis, analysis draws, glycerol conversion yield 90%, lactic acid selectivity 90%.
Reaction conditions: glycerol concentration: 1.0 M; KOH/ glycerine mol ratio: 1.2:1; Red copper oxide/glycerine mol ratio: 0.05.
embodiment 3
Take 4.8 g sodium hydroxide (Chemical Reagent Co., Ltd., Sinopharm Group) and 0.72 g nano cuprous oxide (d
on average=115 nm), join together in 400 mL autoclaves, take again 9.20 g glycerine (Chemical Reagent Co., Ltd., Sinopharm Group) and carry out constant volume with 100 mL volumetric flasks, join in reactor, passing into nitrogen carries out emptying, then airtight good, be heated to 220 ℃ after timing, react 2 hours.
When reaction finishes, with hydrochloric acid, being acidified to pH is 2 ~ 3, and volume after measurement acidifying pipettes 2 mL with transfer pipet and uses deionized water constant volume to 25 mL, carries out high performance liquid chromatography detection, measures the output of lactic acid; With transfer pipet, pipette after 5 mL acidifyings in sample to 10 mL volumetric flask, add 1 mL propyl carbinol, by methanol constant volume, carry out gas chromatographic analysis, analysis draws, glycerol conversion yield 88%, lactic acid selectivity 86%.
Reaction conditions: glycerol concentration: 1.0 M; NaOH/ glycerine mol ratio: 1.2:1; Red copper oxide/glycerine mol ratio: 0.05.
embodiment 4
Take 7.2 g sodium hydroxide (Chemical Reagent Co., Ltd., Sinopharm Group) and 0.54 g nano cuprous oxide (d
on average=115 nm), join together in 400 mL autoclaves, take again 13.80 g glycerine (Chemical Reagent Co., Ltd., Sinopharm Group) and carry out constant volume with 100 mL volumetric flasks, join in reactor, passing into nitrogen carries out emptying, then airtight good, be heated to 210 ℃ after timing, react 2 hours.
When reaction finishes, with hydrochloric acid, being acidified to pH is 2 ~ 3, and volume after measurement acidifying pipettes 2 mL with transfer pipet and uses deionized water constant volume to 25 mL, carries out high performance liquid chromatography detection, measures the output of lactic acid; With transfer pipet, pipette after 5 mL acidifyings in sample to 10 mL volumetric flask, add 1 mL propyl carbinol, by methanol constant volume, carry out gas chromatographic analysis, analysis draws, glycerol conversion yield 80%, lactic acid selectivity 88%.
Reaction conditions: glycerol concentration: 1.5 M; NaOH/ glycerine mol ratio: 1.2:1; Red copper oxide/glycerine mol ratio: 0.025.
embodiment 5
Take 2.4 g sodium hydroxide (Chemical Reagent Co., Ltd., Sinopharm Group) and 0.36 g nano cuprous oxide (d
on average=115 nm), join together in 400 mL autoclaves, take again 9.20 g glycerine (Chemical Reagent Co., Ltd., Sinopharm Group) and carry out constant volume with 100 mL volumetric flasks, join in reactor, passing into nitrogen carries out emptying, then airtight good, be heated to 150 ℃ after timing, react 4 hours.
When reaction finishes, with hydrochloric acid, being acidified to pH is 2 ~ 3, and volume after measurement acidifying pipettes 2 mL with transfer pipet and uses deionized water constant volume to 25 mL, carries out high performance liquid chromatography detection, measures the output of lactic acid; With transfer pipet, pipette after 5 mL acidifyings in sample to 10 mL volumetric flask, add 1 mL propyl carbinol, by methanol constant volume, carry out gas chromatographic analysis, analysis draws, glycerol conversion yield 70%, lactic acid selectivity 76%.
Reaction conditions: glycerol concentration: 1.0 M; NaOH/ glycerine mol ratio: 0.6:1; Red copper oxide/glycerine mol ratio: 0.025.
embodiment 6
Take 4.8 g sodium hydroxide (Chemical Reagent Co., Ltd., Sinopharm Group) and 0.72 g nano cuprous oxide (d
on average=160 nm), join together in 400 mL autoclaves, take again 9.20 g glycerine (Chemical Reagent Co., Ltd., Sinopharm Group) and carry out constant volume with 100 mL volumetric flasks, join in reactor, passing into nitrogen carries out emptying, then airtight good, be heated to 230 ℃ after timing, react 0.5 hour.
When reaction finishes, with hydrochloric acid, being acidified to pH is 2 ~ 3, and volume after measurement acidifying pipettes 2 mL with transfer pipet and uses deionized water constant volume to 25 mL, carries out high performance liquid chromatography detection, measures the output of lactic acid; With transfer pipet, pipette after 5 mL acidifyings in sample to 10 mL volumetric flask, add 1 mL propyl carbinol, by methanol constant volume, carry out gas chromatographic analysis, analysis draws, glycerol conversion yield 80%, lactic acid selectivity 83%.
Reaction conditions: glycerol concentration: 1.0 M; NaOH/ glycerine mol ratio: 1.2:1; Red copper oxide/glycerine mol ratio: 0.05.
embodiment 7
Take 4.8 g sodium hydroxide (Chemical Reagent Co., Ltd., Sinopharm Group) and 0.72 g nano cuprous oxide (d
on average=500 nm), join together in 400 mL autoclaves, take again 9.20 g glycerine (Chemical Reagent Co., Ltd., Sinopharm Group) and carry out constant volume with 100 mL volumetric flasks, join in reactor, passing into nitrogen carries out emptying, then airtight good, be heated to 230 ℃ after timing, react 2 hours.
When reaction finishes, with hydrochloric acid, being acidified to pH is 2 ~ 3, and volume after measurement acidifying pipettes 2 mL with transfer pipet and uses deionized water constant volume to 25 mL, carries out high performance liquid chromatography detection, measures the output of lactic acid; With transfer pipet, pipette after 5 mL acidifyings in sample to 10 mL volumetric flask, add 1 mL propyl carbinol, by methanol constant volume, carry out gas chromatographic analysis, analysis draws, glycerol conversion yield 80%, lactic acid selectivity 78%.
Reaction conditions: glycerol concentration: 1.0 M; NaOH/ glycerine mol ratio: 1.2:1; Red copper oxide/glycerine mol ratio: 0.05.
embodiment 8
Take 48.0 g sodium hydroxide (Chemical Reagent Co., Ltd., Sinopharm Group) and 3.6 g nano cuprous oxide (d
on average=115 nm), join together in 400 mL autoclaves, take again 92.0 g glycerine (Chemical Reagent Co., Ltd., Sinopharm Group) and carry out constant volume with 100 mL volumetric flasks, join in reactor, passing into nitrogen carries out emptying, then airtight good, be heated to 230 ℃ after timing, react 2 hours.
When reaction finishes, with hydrochloric acid, being acidified to pH is 2 ~ 3, and volume after measurement acidifying pipettes 2 mL with transfer pipet and uses deionized water constant volume to 25 mL, carries out high performance liquid chromatography detection, measures the output of lactic acid; With transfer pipet, pipette after 5 mL acidifyings in sample to 10 mL volumetric flask, add 1 mL propyl carbinol, by methanol constant volume, carry out gas chromatographic analysis, analysis draws, glycerol conversion yield 84%, lactic acid selectivity 83%.
Reaction conditions: glycerol concentration: 10.0 M; NaOH/ glycerine mol ratio: 1.2:1; Red copper oxide/glycerine mol ratio: 0.025.
embodiment 9
Take 6.4 g sodium carbonate (Chemical Reagent Co., Ltd., Sinopharm Group) and 0.72 g nano cuprous oxide (d
on average=500 nm), join together in 400 mL autoclaves, take again 9.20 g glycerine (Chemical Reagent Co., Ltd., Sinopharm Group) and carry out constant volume with 100 mL volumetric flasks, join in reactor, passing into nitrogen carries out emptying, then airtight good, be heated to 200 ℃ after timing, react 4 hours.
When reaction finishes, with hydrochloric acid, being acidified to pH is 2 ~ 3, and volume after measurement acidifying pipettes 2 mL with transfer pipet and uses deionized water constant volume to 25 mL, carries out high performance liquid chromatography detection, measures the output of lactic acid; With transfer pipet, pipette after 5 mL acidifyings in sample to 10 mL volumetric flask, add 1 mL propyl carbinol, by methanol constant volume, carry out gas chromatographic analysis, analysis draws, glycerol conversion yield 78%, lactic acid selectivity 76%.
Reaction conditions: glycerol concentration: 1.0 M; Na
2cO
3/ glycerine mol ratio: 0.6:1; Red copper oxide/glycerine mol ratio: 0.05.
comparative example
Take 4.8 g sodium hydroxide (Chemical Reagent Co., Ltd., Sinopharm Group) and 0.72 g Red copper oxide (Chemical Reagent Co., Ltd., Sinopharm Group) (d
on average=2.57 μ m), join together in 400 mL autoclaves, take again 9.20 g glycerine (Chemical Reagent Co., Ltd., Sinopharm Group) and carry out constant volume with 100 mL volumetric flasks, join in reactor, passing into nitrogen carries out emptying, then airtight good, be heated to 230 ℃ after timing, react 2 hours.
When reaction finishes, with hydrochloric acid, being acidified to pH is 2 ~ 3, and volume after measurement acidifying pipettes 2 mL with transfer pipet and uses deionized water constant volume to 25 mL, carries out high performance liquid chromatography detection, measures the output of lactic acid; With transfer pipet, pipette after 5 mL acidifyings in sample to 10 mL volumetric flask again, add 1 mL propyl carbinol, by methanol constant volume, carry out gas chromatographic analysis; Analysis draws, glycerol conversion yield 35%, lactic acid selectivity 60%.
Reaction conditions: glycerol concentration: 1.0 M; NaOH/ glycerine mol ratio: 1.2:1; Red copper oxide/glycerine mol ratio: 0.05.
The catalytic effect of the nano cuprous oxide that thus prepared by industrial common Red copper oxide and experiment, by embodiment 1,7 and comparative example, contrast and can obtain, under identical reaction conditions, be that the transformation efficiency of glycerine or the selectivity of lactic acid are all significantly improved when using nano cuprous oxide.
Claims (8)
1. a catalyzing glycerol is prepared the method for lactic acid, the selectivity of lactic acid can reach 66-93%, glycerol conversion yield can reach 60-100%, it is characterized in that: be to take glycerine as raw material, take nano cuprous oxide as catalyzer, under anaerobic, the alkaline condition that provided by alkali source, in autoclave, react and obtain lactic acid.
2. a kind of catalyzing glycerol according to claim 1 is prepared the method for lactic acid, it is characterized in that: described temperature of reaction is 150-230 ℃, and the described reaction times is 0.5-4 h.
3. a kind of catalyzing glycerol according to claim 1 is prepared the method for lactic acid, it is characterized in that: the described alkaline condition being provided by alkali source refers to adopt the alkali source that comprises sodium hydroxide, potassium hydroxide, sodium carbonate and salt of wormwood.
4. a kind of catalyzing glycerol according to claim 1 is prepared the method for lactic acid, it is characterized in that: described anaerobic refers to High Purity Nitrogen, carry out emptying before reaction.
5. a kind of catalyzing glycerol according to claim 1 is prepared the method for lactic acid, it is characterized in that: the form that adds of described glycerine is that glycerine is mixed with to the aqueous solution, and the glycerine solution concentration of its preparation is 1.0-10 mol/L.
6. a kind of catalyzing glycerol according to claim 1 is prepared the method for lactic acid, it is characterized in that: the particle diameter of described nano cuprous oxide catalyzer is 40 ~ 500 nm, and the addition of nano cuprous oxide catalyzer is 0.01-0.1 mol/mol glycerine.
7. a kind of catalyzing glycerol according to claim 1 is prepared the method for lactic acid, it is characterized in that: the add-on of described alkali source is 0.5-1.5 mol/mol glycerine, is preferably 1.0-1.2 mol/mol glycerine.
8. a kind of catalyzing glycerol according to claim 1 is prepared the method for lactic acid, it is characterized in that reaction conditions: glycerol concentration: 1.0 M; NaOH/ glycerine mol ratio: 1.2:1; Red copper oxide/glycerine mol ratio: 0.05, temperature of reaction is 230 ℃, the described reaction times is 2h.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106316839A (en) * | 2016-08-18 | 2017-01-11 | 江苏大学 | One-step method for synthesizing methyl lactate from biomass glycerol |
| CN106810436A (en) * | 2015-11-30 | 2017-06-09 | 中国科学院大连化学物理研究所 | A kind of method that catalysis oxidation glycerine prepares lactic acid |
| CN109529833A (en) * | 2018-10-18 | 2019-03-29 | 江苏大学 | A kind of graphene oxide-loaded copper catalyst and its preparation method and application |
| CN114345337A (en) * | 2021-12-17 | 2022-04-15 | 广东省科学院化工研究所 | Preparation method of lactic acid |
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| US20120253067A1 (en) * | 2011-03-30 | 2012-10-04 | Chaudhari Raghunath V | Catalyst System and Process for Converting Glycerol to Lactic Acid |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106810436A (en) * | 2015-11-30 | 2017-06-09 | 中国科学院大连化学物理研究所 | A kind of method that catalysis oxidation glycerine prepares lactic acid |
| CN106810436B (en) * | 2015-11-30 | 2020-06-30 | 中国科学院大连化学物理研究所 | Method for preparing lactic acid by catalytic oxidation of glycerol |
| CN106316839A (en) * | 2016-08-18 | 2017-01-11 | 江苏大学 | One-step method for synthesizing methyl lactate from biomass glycerol |
| CN106316839B (en) * | 2016-08-18 | 2019-03-05 | 江苏大学 | A method of by biomass glycerol one-step synthesis method methyl lactate |
| CN109529833A (en) * | 2018-10-18 | 2019-03-29 | 江苏大学 | A kind of graphene oxide-loaded copper catalyst and its preparation method and application |
| CN114345337A (en) * | 2021-12-17 | 2022-04-15 | 广东省科学院化工研究所 | Preparation method of lactic acid |
| CN114345337B (en) * | 2021-12-17 | 2024-03-22 | 广东省科学院化工研究所 | Lactic acid preparation method |
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