CN1188100A - Method for preparing pyruvic acid and its calcium salt from lactic acid - Google Patents
Method for preparing pyruvic acid and its calcium salt from lactic acid Download PDFInfo
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- CN1188100A CN1188100A CN97112512A CN97112512A CN1188100A CN 1188100 A CN1188100 A CN 1188100A CN 97112512 A CN97112512 A CN 97112512A CN 97112512 A CN97112512 A CN 97112512A CN 1188100 A CN1188100 A CN 1188100A
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- acid
- lactic acid
- pyruvic acid
- pyruvic
- phase
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Abstract
The present invention discloses an improved method for preparing pyroracemic acid and its calcium salt by using lactic acid through such processes of oxidation, phase separation, vacuum rectification, neutralization or saponification. As compared with tartaric acid method for preparing pyroracemic acid, it is easy to operate, low in cost, and its waste is easy to be treated, and its product calcium pyruvate is more stable.
Description
The present invention relates to a kind of manufacture method of chemicals, particularly be raw material with lactic acid, become the method for pyruvic acid through selective oxidation.
Existing technology is to be raw material by tartrate, adds potassium pyrosulfate or sal enixum.Be heated to more than 200 ℃ to 245 ℃, make tartrate slough a part CO
2And a part H
2O forms pyruvic acid, and it has some inconvenience:
1. it is a solid state reaction.Become sticky thing during heating, inconvenience is stirred.Make it the temperature inequality, influence yield.
2. heating reaches 240 ℃, and general steam heating does not reach, and needs electric heating or oil heat, and energy expenditure is big, must special-purpose oil-heating installation.
3. two this technologies of water tartrate, theoretical yield only 46.3%.Cost is higher, process exploitation, and the potentiality that reduce cost are little.
4. solids sticks on wall, and discharging is difficult for mechanize.
5. the macromolecule resin thing is arranged in the waste residue.Handle in the environmental protection and be difficult for.
At above 5 points: the inventor has studied the improvement technology of lactic acid system pyruvic acid or CALCIUM PYRUVIC, in the hope of using the universalization construction equipment, reduces cost, and improves environmental protection benefit.Be convenient to produce by batch.Its processing method is as follows:
Article one: be ethyl lactate with lactic acid with the excess ethyl alcohol esterification earlier.This is a prior art.Again with ethyl lactate under temperature＜20 ℃, add catalyzer and phase-splitting agent.Use KMnO
4Oxidation in addition.Become Pyruvic Acid Ethyl ester.This also is we be improved to of prior art (638 pages of organic synthesis topical reference books): 1. temperature is determined a scope, has 2. selected different catalyzer for use, has 3. improved different phase-splitting agent, has 4. tried out H
2O
2Oxygen is to reduce cost and to eliminate solid slag and pollute.So that show processing method practicability more.
After having obtained Pyruvic Acid Ethyl ester, use C again
a(OH)
2Saponification in addition.Can directly obtain the pyruvic acid calcium salt after steaming ethanol.Because of the two solubleness in water differs very big, so water can extract CALCIUM PYRUVIC and purifying.
The second method is to be direct oxidation into pyruvic acid with lactic acid.Rectification under vacuum gets the pure product of pyruvic acid under the condition of＜75 ℃/20m.m.Hg again.1. oxidizing condition on this technology, 2. oxygenant, 3. carbonyl-protection agent, 4. catalysts selective, 5. phase-splitting agent is an essential condition.Its principle of work be at first select a kind of little to lactic acid solubility, the big organic solvent of pyruvic acid solubleness is done the phase-splitting agent, make oxidation one produce pyruvic acid and promptly mixed by organic, continued oxidation at aqueous phase lactic acid.And do not destroy resultant.For make pyruvic acid be stabilized in organism mutually in, must select for use carbonyl to get protective material so that it is stable in organic phase.
About the selection of oxidizing condition and oxygenant, be a mutual relationship condition.At first select suitable oxygenant KMnO for use
4But it generates MnO
2And a small amount of manganous salt.Cover acceleration raw material and finished product are decomposed into the small-molecule substance of non-object.Therefore will control the condition of oxidation and the object that stablizer just can obtain yield well.As use H
2O
2Oxidation, just industry becomes table opinion, is most economical scheme in theory, and the by-product refuse is easy to processing, helps environmental protection.But proof need carefully be chosen stablizer, the result that the condition of controlling well just can obtain in the experiment.Therefore:
An object of the present invention is to provide a kind of method that gets pyruvic acid with the lactic acid direct oxidation.
Another object of the present invention provides a kind ofly makes Pyruvic Acid Ethyl ester with lactic acid through ethyl lactate, and resaponifying becomes the method for CALCIUM PYRUVIC.
Another purpose of the present invention is to have improved technology, uses promotor, stablizer, uses hydrogen peroxide oxidation.Produce pyruvic acid and calcium salt thereof.Production cost is reduced significantly, and simplified sewage disposal.Help environment protection.
The present invention realizes by following processing method.
80% industrial lactic acid with buying is put in the three-necked flask, add a kind of to pyruvic acid solubleness greater than to the little and water-fast organic solvent of lactic acid dissolution degree as the phase-splitting agent.Bringing Selection In property catalyzer again, control reaction temperature: 18 ℃.Drip KMnO
4Saturated aqueous solution carries out oxidation.After finishing, oxidation carries out phase-splitting.Water is used a little extracted with diethyl ether again, and extraction liquid is merged in organic phase.Carry out drying with a small amount of anhydrous sodium sulphate.Afterwards organic phase is put in the distilling flask, vacuumizes and boiled off camera earlier, carry out fractionation in 75 ℃～80 ℃/25mmHg down to 65 ℃/10m.m.Hg again.Collect pure pyruvic acid.Pyruvic acid with the calcium hydroxide neutralization, generates CALCIUM PYRUVIC more afterwards, adds suitable stablizer.Vacuum-drying makes it to meet commercial supply of material standard.
Also having a method is with the new system lactic acid of buying, and adds excess ethyl alcohol and generates ethyl lactate (document Merck Index, 10,3762 earlier with the acid catalyst catalytic esterification; 11,3733).The ethyl lactate that newly makes is put into there-necked flask.Add catalyzer, phase-splitting agent (sherwood oil etc.).Controlled temperature: 15 ℃, slowly drip saturated KMnO
4Do not move back in one minute to purple and to be terminal point.Reaction is finished, and tells sherwood oil.Residuum is used the sherwood oil extracting once again.Merge the saturated CaCl of sherwood oil liquid
2Solution washing.Elder generation's steaming petroleum ether reclaims, and fractionation gets Pyruvic Acid Ethyl ester under 56～57 ℃/20mmHg again.Again with calcium hydroxide with the saponification of gained Pyruvic Acid Ethyl ester.Boil off ethanol and promptly get CALCIUM PYRUVIC, add stablizer again, meet commercial supply of material standard between the moisture content 10_12% in being dried under the vacuum.
Embodiment one:
Get a 250ml there-necked flask, load onto agitator, add industrial 80% lactic acid 50ml (about 0.4Mol).Add ether 50ml, get K again
2Cr
2O
732g is dissolved in the 120ml water, is controlled at room temperature and slowly under agitation drips in above-mentioned solution.Dress condenser backflow ether on a bite, question response finishes, and tells ether layer, and surplus liquid is used the 30ml extracted with diethyl ether again.Merge ether solution, the dress vacuum distilling apparatus steams ether earlier and reclaims, and steams pyruvic acid again under 70.8 ℃/20mmHg.On the IR instrument, beat praseodymium.Confirm with the contrast of standard pyruvic acid collection of illustrative plates.
Embodiment two:
Get a 500ml three-necked flask, agitator is loaded onto in the centre.Add 62.5ml industry 80% lactic acid, (about 0.5mol) adds ether 100ml again, puts into ice bath and is cooled to below 15 ℃, adds special-purpose promotor.Drip the 250mlKmno of 49g (about 0.31Mol)
4Solution, and be chilled to below 15 ℃.Stir down and carefully drip in above-mentioned flask.Temperature control: 15 ℃ finish until reaction.Tell the ether layer.Surplus liquid 30ml extracted with diethyl ether merges ether solution in vacuum distilling apparatus, steams ether earlier and reclaims.Under 70.8 ℃/20mm, Hg, steam pyruvic acid again.Use Ca (OH) afterwards
2Emulsion adds thermo-neutrality.65～70 ℃ of oven dry in electro-heat vacuum drier.Get CALCIUM PYRUVIC.Survey moisture content at 10-12%.In pyruvic acid 65～70% controlling index, get finished product
Embodiment three:
Buy industrial ethyl lactate, first pure product of distillation, get 154 ℃ near fraction.Get the fine purification of lactic acid ethyl ester.Or with lactic acid and excess ethyl alcohol at H
2SO
4Catalysis refluxes down and makes new ethyl lactate by literature method.
Extracting lactic acid ethyl ester 56 grams (about 0.5Mol), 60 ℃ of sherwood oil 150ml put into the 500ml three-necked flask, add KH
2PO
4(or NaH
2PO
4) 10 grams.Dropwise 5 0g is dissolved in the KMnO in the 200ml water under the violent stirring
4, temperature control＜15 ℃.Reaction finishes.Tell sherwood oil, use the Pyruvic Acid Ethyl ester in the surplus liquid of 50ml petroleum ether extraction again.Merge sherwood oil liquid, put CaCl
2Dried bean noodles is dry, and sherwood oil liquid distillation earlier reclaims sherwood oil.The back steams Pyruvic Acid Ethyl ester under 69～71 ℃/40m.m.Hg.The propyl ester acetoacetic ester that obtains, metering ground Ca (OH)
2The concentrated emulsion saponification.Boil off ethanol and get CALCIUM PYRUVIC.Electrothermal vacuum is evaporated to and meets commercial criterion.
Claims (6)
1, a kind of method with lactic acid system pyruvic acid, it is characterized in that using phase-splitting agent, catalyzer, stablizer and oxygenant to lactic acid write the oxidation of selecting property, again rectification under vacuum and pyruvic acid.
2, phase-splitting agent according to claim 1 be a kind of to pyruvic acid dissolving obviously greater than lactic acid and water-fast organic solvent, ethers, ester class etc.
3, stablizer according to claim 1 is to shield to the pyruvic acid that generates in reaction, makes it be difficult for the chemical substance of recurrence chemical transformation.
4, oxygenant according to claim 1 is in potassium permanganate and the certain chromic anhydride of peroxidation oxygen and dichromic acid salt oxygenant are also included within.
5, be in 0-20 ℃ of PH3-13 temperature, to carry out vacuum tightness 1-30 mmhg according to the described oxidizing process condition of claim 1.
6, a kind of with lactic acid earlier the system ethyl lactate, make Pyruvic Acid Ethyl ester, get CALCIUM PYRUVIC with the calcium hydroxide saponification and add stablizer and make it decomposition and slow down again through the phase-splitting catalyzed oxidation again.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97112512A CN1188100A (en) | 1997-07-08 | 1997-07-08 | Method for preparing pyruvic acid and its calcium salt from lactic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97112512A CN1188100A (en) | 1997-07-08 | 1997-07-08 | Method for preparing pyruvic acid and its calcium salt from lactic acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1188100A true CN1188100A (en) | 1998-07-22 |
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ID=5172310
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97112512A Pending CN1188100A (en) | 1997-07-08 | 1997-07-08 | Method for preparing pyruvic acid and its calcium salt from lactic acid |
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|---|---|
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108640829A (en) * | 2018-04-18 | 2018-10-12 | 肖锦 | A kind of method that aqueous catalysis Oxidation of Lactic prepares pyruvic acid |
-
1997
- 1997-07-08 CN CN97112512A patent/CN1188100A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108640829A (en) * | 2018-04-18 | 2018-10-12 | 肖锦 | A kind of method that aqueous catalysis Oxidation of Lactic prepares pyruvic acid |
| CN108640829B (en) * | 2018-04-18 | 2021-08-03 | 上海德浦生物医药科技有限公司 | Method for preparing pyruvic acid by catalyzing and oxidizing lactic acid in water phase |
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| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
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