CN100588641C - Method for synthesizing lactic acid by using glycerol - Google Patents
Method for synthesizing lactic acid by using glycerol Download PDFInfo
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- CN100588641C CN100588641C CN200810057540A CN200810057540A CN100588641C CN 100588641 C CN100588641 C CN 100588641C CN 200810057540 A CN200810057540 A CN 200810057540A CN 200810057540 A CN200810057540 A CN 200810057540A CN 100588641 C CN100588641 C CN 100588641C
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Abstract
The invention discloses a synthesis method of lactic acid by using glycerol, which is characterized in that the glycerol is adopted as the material; the lactic acid is obtained via reaction under thealkaline condition with the reaction pressure of 1 to 15 atm, the reaction temperature of 20 to 140 DEG C, the reaction time of 0.5 to 48 h and the catalyst and the oxidant existing; and when the synthesis method of lactic acid is adopted, the glycerol can be partially converted into the lactic acid with conversion rate of the glycerol being 12% to 70%, selectivity of the lactic acid being 33% to81% and yield of the lactic acid being 9.7% to 32%. The synthesis method of lactic acid by using glycerol has the advantages that high reaction temperature is not needed, and the reaction can be conducted under the condition of normal temperature or close to normal temperature, thus a large amount of energy is saved; the reaction is conducted under the condition of atmospheric pressure or close toatmospheric pressure with the oxygen existing, thus requirement to equipments is low and investment is small; and the reaction system is simple which is beneficial to industrialization, and the catalyst has long service life without loss.
Description
Technical field
The present invention relates to a kind of method of utilizing the glycerine synthesizing lactic acid.
Background technology
Lactic acid is a kind of broad-spectrum organic acid, has purposes widely at aspects such as food, medicine, light industry, tobacco, plastics and paint, the poly(lactic acid) that is obtained by lactic acid is because its biodegradability and excellent physical and chemical performance are the macromolecular materials of future ideality.The main method of present industrial production lactic acid is amylo process and chemical synthesis.Wherein, amylo process exist can not serialization production, problems such as raw material consumption is big, energy consumption is high, unstable product quality; Chemical synthesis mainly contains lactonitrile method and vinyl cyanide method, and this method can continuous production, production cost is low, energy consumption is low, but owing to adopted the materials such as prussic acid of acetaldehyde and severe toxicity in the raw material, has bigger pollution and produce danger.
Glycerine is the by product of association in the production of biodiesel process, and along with improving constantly of yield of biodiesel, the output of glycerine is considerable.Utilize transformation of glycerol to produce product in the middle of a series of chemical and the chemistry, with present be that the technology of raw material is compared with ethene, benzene or other petroleum hydrocarbon, except renewable and CO
2Outside the zero release characteristics such as (photosynthetic results), be rich in active hydroxyl in the glycerine, be easy to be replaced and synthetic many special chemical articles that in the past will just can obtain through very complicated hydrocarbon reaction, thereby demonstrate huge advantage by functional group.Discovering recently, can be the raw material synthesizing lactic acid with glycerine, and this method has not only been developed the new purposes of glycerine, also provides continuable raw material sources for lactic acid.
Mainly contain two kinds of methods with glycerine for the raw material synthesizing lactic acid at present:
1, the reaction of the glycerol dehydrogenase under the alkaline condition obtains lactic acid
This reaction is medium with water, and the mineral alkali of adding is NaOH or CaO, chooses H
2Pressure is 40bar, and temperature of reaction is 200 ℃, is catalyzer with Pt and C or Ru and C, and the reaction times is 5 hours, and can obtain glycerol conversion yield is 20%, and the lactic acid selectivity is 65%.The problem that this method exists is: need to use a large amount of H in (1) reaction
2As reaction raw materials, and H
2Itself be a kind of very important energy material, its source is limited, cost is higher, and is difficult for storing and transportation; (2) higher hydrogen pressure, the alkaline environment under the hot conditions is higher for equipment requirements in the reaction process, causes equipment corrosion inevitably, and increase equipment drops into expense, and operating process is dangerous.
2, directly under the high temperature strong alkaline condition, transform and obtain lactic acid
This method, was reacted 90 minutes under the hydrothermal condition of 300 ℃ of 1.25mol/L (mol ratio of alkali and substrate is 4: 1) NaOH not by any catalyzer, and the productive rate of the lactic acid that obtains reaches 90%.The problem that this method exists is: reaction process is temperature required higher, has proposed harsh requirement for production unit.
Summary of the invention
The purpose of this invention is to provide a kind of method of utilizing the glycerine synthesizing lactic acid.
Method provided by the present invention is to be raw material with glycerine, is that 1-15atm (1atm=101.325kPa), temperature of reaction are that 20-140 ℃, reaction times are 0.5-48h in reaction pressure, and under the alkaline condition that catalyzer and oxygenant exist, reaction obtains lactic acid.
Described reaction pressure specifically can be 1-5atm, and described temperature of reaction specifically can be 30-90 ℃, and the described reaction times specifically can be 1-8h.
Reaction of the present invention needs to carry out under alkaline condition, and used alkali can be NaOH, KOH, CaO, K
2CO
3, Na
2CO
3Deng, be preferably NaOH.
The alkali number of reaction process is a 0.01-16mol/mol glycerine, is preferably 0.25-10mol/mol glycerine.
Described catalyzer can be loading type Au catalyzer.
The addition of described catalyzer specifically can be 0.05-0.2g/g glycerine.
The carrier of described catalyzer can be metal oxide or activated carbon.
Described metal oxide specifically can be Al
2O
3, ZrO
2, TiO
2, Fe
2O
3, MgO or CeO
2
Described oxygenant specifically can be oxygen.
The present invention under alkaline condition, utilizes oxygen as oxygenant by oxidative pathway, and the rearrangement reaction of the intermediate that obtains through peroxidation glycerine obtains lactic acid.The inventive method is an oxygenant with oxygen, has realized that glycerine transforms by the highly selective of mode of oxidizing to lactic acid, and the lactic acid selectivity reaches 33-81%, and glycerol conversion yield reaches 12-70%, and the productive rate of lactic acid reaches 9.9-32%.The inventive method does not need higher temperature of reaction, can take place at normal temperature or under near the condition of normal temperature, has saved a large amount of energy; The inventive method is carried out under normal pressure or the condition that exists near non-pressurized oxygen, for equipment require lowly, invest little; The inventive method reaction system is simple, is easy to industrialization, and catalyst life is long, does not have to run off.
Description of drawings
Figure 1A is the color atlas of lactic acid standard substance
Figure 1B is the color atlas of embodiment 1 reaction product
Fig. 2 A is the color atlas of lactic acid standard substance
Fig. 2 B is the color atlas of embodiment 2 reaction product
Fig. 3 A is the color atlas of lactic acid standard substance
Fig. 3 B is the color atlas of embodiment 3 reaction product
Fig. 4 A is the color atlas of lactic acid standard substance
Fig. 4 B is the color atlas of embodiment 4 reaction product
Fig. 5 A is the color atlas of lactic acid standard substance
Fig. 5 B is the color atlas of embodiment 5 reaction product
Fig. 6 A is the color atlas of lactic acid standard substance
Fig. 6 B is the color atlas of embodiment 6 reaction product
Embodiment
Method described in the following embodiment if no special instructions, is ordinary method.
Embodiment 1, the direct synthesizing lactic acid of glycerine oxidation
Be dissolved in 2g glycerine (Glycerol A.R. Beijing chemical reagents corporation) and 3.46g sodium hydroxide (Sodiumhydroxide A.R. Beijing northization fine chemicals limited liability company) in the 40mL water and be transferred in three mouthfuls of round-bottomed flasks of 100mL.Add 0.13g Au/TiO
2Catalyzer (World Gold Council world gold board of management), feeding the 1atm flow velocity is the O of 70ml/min
2, be heated to 90 ℃, reacted 3 hours.Three repetitions are established in experiment, repeat 10 bottles at every turn.
Reaction finishes the back according to following method, the amount of lactic acid in the assaying reaction liquid:
Adopt high performance liquid chromatography to reaction product carry out qualitative and quantitative analysis (separator column is for Agilent 1100 Series HPLC, Beijing Agilent company limited: Alltech OA-1000 Organic Acids, with rare H
2SO
4The aqueous solution is moving phase, flow 0.3ml/min, and UV-detector detects wavelength 195nm, 50 ℃ of service temperatures.With lactic acid (Tianjin chemical reagent six subsidiary factories of factory, article No. is Q/12HG 3-522-98) as standard substance, the production standard curve.
Detected result as shown in Figure 1, wherein A is the color atlas of lactic acid standard substance, B is the color atlas of reaction product.The lactic acid typical curve is y=277504x-13.315, R
2=0.9999.The result shows that product lactic acid is identical with the retention time at the peak of lactic acid standard substance on color atlas at the peak on the color atlas, is 18.1min, and the online ultraviolet spectrogram of product analysis process (190-800nm scope) is also identical with standard specimen.Calculate glycerol conversion yield, lactic acid selectivity and lactic acid yield with method for normalizing according to the following equation.Wherein, lactic acid optionally is defined as: the growing amount of lactic acid accounts for the ratio with the generation total amount of the product of same unit representation.
In the above-mentioned formula, carbon number is meant contained carbon number in amount of substance * this material molecule.
Following result is 10 multiple mean values.The result shows that glycerine partly is converted into lactic acid, and the transformation efficiency of glycerine is 12%, and the selectivity of lactic acid is 81%, obtains 0.20g lactic acid (concentration in reaction solution is 1336 for the 0.0050g/ml peak area) altogether, and lactic acid yield is 9.7%.
Embodiment 2, the direct synthesizing lactic acid of glycerine oxidation
Be dissolved in 2g glycerine (Glycerol A.R. Beijing chemical reagents corporation) and 1.73g sodium hydroxide (Sodiumhydroxide A.R. Beijing northization fine chemicals limited liability company) in the 40mL water and be transferred in three mouthfuls of round-bottomed flasks of 100mL.Add 0.10g Au/C catalyzer (World Gold Council world gold board of management), feeding the 1atm flow velocity is the O of 70ml/min
2, be heated to 140 ℃, reacted 2 hours.Three repetitions are established in experiment, repeat 10 bottles at every turn.
Reaction finishes the back according to embodiment 1 described method, the amount of lactic acid in the assaying reaction liquid.
The chromatogram detected result of reaction product as shown in Figure 2.The lactic acid typical curve is y=277504x-13.315, R
2=0.9999.The result shows that product lactic acid is identical with the retention time at the peak of lactic acid standard substance on color atlas at the peak on the color atlas, is 18.1min, and the online ultraviolet spectrogram of product analysis process (190-800nm scope) is also identical with standard specimen.Calculate glycerol conversion yield, lactic acid selectivity and lactic acid yield according to embodiment 1 described formula with method for normalizing.
Following result is 10 multiple mean values.The result shows that glycerine partly is converted into lactic acid, and the transformation efficiency of glycerine is 56%, and the selectivity of lactic acid is 54%, obtains 0.60g lactic acid (concentration in reaction solution is 4183 for the 0.015g/ml peak area) altogether, and lactic acid yield is 30.2%.
Embodiment 3, the direct synthesizing lactic acid of glycerine oxidation
Be dissolved in 0.8g glycerine (Glycerol A.R. Beijing chemical reagents corporation) and 3.46g potassium hydroxide (Potassiumhydroxide A.R. Beijing northization fine chemicals limited liability company) in the 40mL water and be transferred in three mouthfuls of round-bottomed flasks of 100mL.Add 0.13g Au/ZrO
2Catalyst agent (World Gold Council world gold board of management), feeding the 1atm flow velocity is the O of 70ml/min
2, be heated to 60 ℃, reacted 4 hours.Three repetitions are established in experiment, repeat 10 bottles at every turn.
Reaction finishes the back according to embodiment 1 described method, the amount of lactic acid in the assaying reaction liquid.
The chromatogram detected result of reaction product as shown in Figure 3.The lactic acid typical curve is y=277504x-13.315R
2=0.9999.The result shows that product lactic acid is identical with the retention time at the peak of lactic acid standard substance on color atlas at the peak on the color atlas, is 18.1min, and the online ultraviolet spectrogram of product analysis process (190-800nm scope) is also identical with standard specimen.Calculate glycerol conversion yield, lactic acid selectivity and lactic acid yield according to embodiment 1 described formula with method for normalizing.
Following result is 10 multiple mean values.The result shows that glycerine partly is converted into lactic acid, and the transformation efficiency of glycerine is 20%, and the selectivity of lactic acid is 78%, obtains 0.312g lactic acid (concentration in reaction solution is 2151 for the 0.0078g/ml peak area) altogether, and lactic acid yield is 16%.
Embodiment 4, the direct synthesizing lactic acid of glycerine oxidation
Be dissolved in 2g glycerine (Glycerol A.R. Beijing chemical reagents corporation) and 0.87g sodium hydroxide (Sodiumhydroxide A.R. Beijing northization fine chemicals limited liability company) in the 40mL water and be transferred in three mouthfuls of round-bottomed flasks of 100mL.Add 0.10g Au/Fe
2O
3Catalyzer (World Gold Council world gold board of management), feeding the 1atm flow velocity is the O of 70ml/min
2, be heated to 60 ℃, reacted 48 hours.Three repetitions are established in experiment, repeat 10 bottles at every turn.
Reaction finishes the back according to embodiment 1 described method, the amount of lactic acid in the assaying reaction liquid.
The chromatogram detected result of reaction product as shown in Figure 4.The lactic acid typical curve is y=277504x-13.315R
2=0.9999.The result shows that product lactic acid is identical with the retention time at the peak of lactic acid standard substance on color atlas at the peak on the color atlas, is 18.1min, and the online ultraviolet spectrogram of product analysis process (190-800nm scope) is also identical with standard specimen.Calculate glycerol conversion yield, lactic acid selectivity and lactic acid yield according to embodiment 1 described formula with method for normalizing.
Following result is 10 multiple mean values.The result shows that glycerine partly is converted into lactic acid, and the transformation efficiency of glycerine is 41%, and the selectivity of lactic acid is 33%, obtains 0.27g lactic acid (concentration in reaction solution is 1864 for the 0.0068g/ml peak area) altogether, and lactic acid yield is 14%.
Embodiment 5, the direct synthesizing lactic acid of glycerine oxidation
Be dissolved in 2g glycerine (Glycerol A.R. Beijing chemical reagents corporation) and 1.73g sodium hydroxide (Sodiumhydroxide A.R. Beijing northization fine chemicals limited liability company) in the 40mL water and be transferred in the 100mL autoclave.Add 0.10g Au/CeO
2Catalyzer (World Gold Council world gold board of management) pours 15atm O
2And keep airtight, and be heated to 20 ℃, reacted 2 hours.10 repetitions are established in experiment.
Reaction finishes the back according to embodiment 1 described method, the amount of lactic acid in the assaying reaction liquid.
The chromatogram detected result of reaction product as shown in Figure 5.The lactic acid typical curve is y=277504x-13.315R
2=0.9999.The result shows that product lactic acid is identical with the retention time at the peak of lactic acid standard substance on color atlas at the peak on the color atlas, is 18.1min, and the online ultraviolet spectrogram of product analysis process (190-800nm scope) is also identical with standard specimen.Calculate glycerol conversion yield, lactic acid selectivity and lactic acid yield according to embodiment 1 described formula with method for normalizing.
Following result is 10 multiple mean values.The result shows that glycerine partly is converted into lactic acid, and the transformation efficiency of glycerine is 70%, and the selectivity of lactic acid is 46%, obtains 0.64g lactic acid (concentration in reaction solution is 4455 for the 0.016g/ml peak area) altogether, and lactic acid yield is 32%.
Embodiment 6, the direct synthesizing lactic acid of glycerine oxidation
Be dissolved in 2g glycerine (Glycerol A.R. Beijing chemical reagents corporation) and 0.87g sodium hydroxide (Sodiumhydroxide A.R. Beijing northization fine chemicals limited liability company) in the 40mL water and be transferred in the 100mL autoclave.Add 0.13g Au/TiO
2Catalyzer (World Gold Council world gold board of management) pours 5atm O
2And keep airtight, and be heated to 90 ℃, reacted 0.5 hour.10 repetitions are established in experiment.
Reaction finishes the back according to embodiment 1 described method, the amount of lactic acid in the assaying reaction liquid.
The chromatogram detected result of reaction product as shown in Figure 6.The lactic acid typical curve is y=277504x-13.315R
2=0.9999.The result shows that product lactic acid is identical with the retention time at the peak of lactic acid standard substance on color atlas at the peak on the color atlas, is 18.1min, and the online ultraviolet spectrogram of product analysis process (190-800nm scope) is also identical with standard specimen.Calculate glycerol conversion yield, lactic acid selectivity and lactic acid yield according to embodiment 1 described formula with method for normalizing.
Following result is 10 multiple mean values.The result shows that glycerine partly is converted into lactic acid, and the transformation efficiency of glycerine is 33%, and the selectivity of lactic acid is 54%, obtains 0.36g lactic acid (concentration in reaction solution is 2460 for the 0.0089g/ml peak area) altogether, and lactic acid yield is 18%.
Claims (9)
1, a kind of method of utilizing glycerine to produce lactic acid is to be raw material with glycerine, is that 1-15atm, temperature of reaction are that 20-140 ℃, reaction times are 0.5-48h in reaction pressure, and under the alkaline condition that catalyzer and oxygenant exist, reaction obtains lactic acid; Described catalyzer is a loading type Au catalyzer.
2, method according to claim 1 is characterized in that: described reaction pressure is 1-5atm, and described temperature of reaction is 30-90 ℃, and the described reaction times is 1-8h.
3, method according to claim 1 and 2 is characterized in that: described alkaline condition is to add NaOH, KOH, CaO, K in reaction system
2CO
3Or Na
2CO
3Obtain.
4, method according to claim 3 is characterized in that: the consumption of described NaOH is a 0.01-16mol/mol glycerine.
5, method according to claim 4 is characterized in that: the consumption of described NaOH is a 0.25-10mol/mol glycerine.
6, method according to claim 1 and 2 is characterized in that: the addition of described catalyzer is a 0.05-0.2g/g glycerine.
7, method according to claim 1 and 2 is characterized in that: the carrier of described catalyzer is metal oxide or activated carbon.
8, method according to claim 7 is characterized in that: described metal oxide is Al
2O
3, ZrO
2, TiO
2, Fe
2O
3, MgO or CeO
2
9, method according to claim 1 and 2 is characterized in that: described oxygenant is an oxygen.
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Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BRPI1004306B1 (en) | 2010-08-18 | 2018-04-17 | Int - Instituto Nacional De Tecnologia | OXIDATIVE CATALYTIC PROCESS FOR LACTIC ACID SYNTHESIS |
| AT511965B1 (en) | 2011-10-11 | 2013-04-15 | Amitava Dipl Ing Dr Kundu | PROCESS FOR THE PREPARATION OF MILKY ACID |
| LV14490B (en) | 2011-12-23 | 2012-05-20 | Rīgas Tehniskā Universitāte | Selective catalysts for producing lactic acid from glycerol |
| BR102012027339B1 (en) | 2012-10-25 | 2019-08-27 | Instituto Nac De Tecnologia Int | process for direct lactic acid synthesis |
| WO2014081951A1 (en) | 2012-11-21 | 2014-05-30 | University Of Tennesee Research Foundation | Methods, systems and devices for simultaneous production of lactic acid and propylene glycol from glycerol |
| FR2999571B1 (en) * | 2012-12-19 | 2015-02-27 | Novance | TRANSFORMATION OF GLYCEROL BY HETEROGENEOUS CATALYSIS |
| FR3011838B1 (en) | 2013-10-15 | 2015-11-13 | Pivert | SUPPORTED BIMETALLIC CATALYST AND USE THEREOF FOR SELECTIVE GLYCEROL OXIDATION |
| CN104045544B (en) * | 2014-06-27 | 2016-03-02 | 江苏大学 | A kind of supported copper catalyst catalyzing glycerol produces the method for 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 |
| CN108654667A (en) * | 2018-04-20 | 2018-10-16 | 东北电力大学 | A kind of technique converting glycerol into lactic acid in a mild condition using NiCu alloys loaded catalyst |
| CN110523426B (en) * | 2019-01-10 | 2022-11-18 | 中国石油大学(华东) | Preparation method of catalyst for glycerol oxidation |
| CN115403460B (en) * | 2022-09-20 | 2023-08-25 | 北方民族大学 | Method for preparing glyceric acid by catalytic oxidation of glycerol at room temperature |
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Non-Patent Citations (2)
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| 乳酸及其衍生物的合成和应用. 陈连喜，李世普.湖北化工，第3卷. 2001 |
| 乳酸及其衍生物的合成和应用. 陈连喜，李世普.湖北化工，第3卷. 2001 * |
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