CN106480113A - A kind of preparation method of organic acid - Google Patents
A kind of preparation method of organic acid Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method of organic acid, the step of prepare L-TARTARIC ACID or its salt, and/or glycolic or its salt with following operation A～C, by glucose：(A) pass through the microorganism by glucose production 5- ketone-maltonic acid, in the presence of 5- ketone-maltonic acid can be made to form the alkali of water soluble salt, with the nutrient solution culture containing glucose, operation A of the nutrient solution of the water soluble salt containing 5- ketone-maltonic acid is obtained；(B) by the pH of the nutrient solution of the water soluble salt containing 5- ketone-maltonic acid obtained in operation A is adjusted and is maintained in the range of 7～12, obtain 5- ketone-maltonic acid water soluble salt be converted to L-TARTARIC ACID or its salt, and/or glycolic or its salt reactant liquor process B；(C) operation C of L-TARTARIC ACID or its salt, and/or glycolic or its salt, by the reactant liquor obtained in process B, is extracted.The present invention is highly effective and inexpensive, can be used in industrial preparation, and practicality is high.
Description
Technical field
The present invention relates to organic acid field, specially a kind of preparation method of organic acid.
Background technology
L-TARTARIC ACID or its salt, are used as acid, pH regulator in field of food, are used as cosmetics, dyeing, lotion, coating in industrial circle, be used as pharmaceutical raw material etc. in medicine field, be the useful material extensively utilized in industrial circle at present.Additionally, when preparing L- tartaric acid by glucose, with L- tartaric acid while the glycolic for producing is the useful material as metal detergent, coating additive, cosmetics additive, the raw material of hard class Biodegradable polymer etc..Preparation method as L-TARTARIC ACID, it is known that various methods, but now the residue by wine production and the intermediate maleic anhydride from oil are preparing.Additionally, glycolic is prepared by the method on petrochemistry.On the other hand, use glucose as initiation material, through 5- ketone gluconic acid, the method for preparing tartaric acid and glycolic is still conceptual phase, has carried out various researchs in the past.Method as 5- ketone-D- gluconic acid is converted to by glucose, it was recently reported that using the acetic acid bacteria for belonging to Gluconobacter or acetobacter, the method for generating 5- ketone-maltonic acid through gluconic acid fermentation by glucose.In the fermentation of the reality of 5- ketone-maltonic acid is generated, known pH control is carried out by the use of calcium carbonate as nertralizer or using calcium hydroxide, 5- ketone-maltonic acid is separated out in the way of the calcium salt of the 5- ketone-maltonic acid of slightly water-soluble, the method that the calcium salt of the 5- ketone-maltonic acid is reclaimed by zymotic fluid.
It is furthermore well known that belong to a lot of acetic acid bacterias of Gluconobacter or acetobacter, by glucose while gluconic acid generates 5- ketone-D- gluconic acid, also by above-mentioned gluconic acid while generating 2- ketone-D- gluconic acid.2- ketone-D- the gluconic acid can not form L- tartaric acid, glycolic, therefore cause the harvest yield of 5- ketone-D- gluconic acid to reduce.Therefore, by inducing the nonproductive bacterial strain of 2- ketone-D- gluconic acid, the rising of the yield of 5- ketone-D- gluconic acid is realized.But, a lot of acetic acid bacterias, not only there is the enzyme for being generated 5- ketone gluconic acid by glucose through gluconic acid, and with the 5- ketone-D- gluconic acid reductase for being converted to gluconic acid by 5- ketone-D- gluconic acid in cytoplasm.Known reduced gluconic acid is consumed due to the metabolic pathway such as pentose phosphate pathway and En Tena Du Duoluofu approach, and the growing amount for becoming the 5- ketone-D- gluconic acid of the raw material of L- tartaric acid and glycolic reduces.
On the other hand, exist with regard to preparing tartaric report by 5- ketone-D- gluconic acid.Prior art is reported and uses the 5- ketone-D- gluconic acid calcium salt of slightly water-soluble as initiation material, so which is contacted with sodium carbonate first and be converted to water miscible 5- ketone-D- gluconic acid sodium salt, then reacted in 1 molar sodium hydroxide solution, tartaric acid is obtained with about 10% harvest yield.In the preparation method, due to producing the calcium carbonate of water byproduct slightly solubility, before 5- ketone-D- gluconic acid is converted to tartaric acid, it is necessary to remove calcium carbonate from reactant liquor in advance.Additionally, the calcium carbonate for being removed is necessary to be processed as discarded object, therefore cause the high cost of this preparation method.Additionally, according to this preparation method, it is low to there is tartaric harvest yield, about 10%, and the unwanted organic acid of a large amount of accessory substances is produced in addition to tartaric acid, it is therefore necessary to the problems such as they are separated, it is impossible to in industrial tartaric preparation.
Method as tartaric harvest yield is improved further, reporting makes 5- ketone-maltonic acid under alkaline conditions, in the buffer solution containing carbonate ions or phosphate ion with noble metal catalyst oxidisability contact, thus tartaric preparation method is produced with high harvest yield.Report further under these conditions, tartaric acid is produced with harvest yield high further if vanadic acid being used as catalyst.But, exist in these preparation methods the buffer that uses carbonic acid etc. expensive as prepare material and due to uses for people show toxicity vanadic acid must be high as catalyst purifying cost the shortcomings of.
Subsequently report further, under alkaline conditions, so that 5- ketone-D- gluconic acid is contacted in the aqueous solution, carbonic acid, phosphoric acid, pyrophosphoric acid or phosphate buffer with rare metal C catalysts such as platinum, thus tartaric preparation method is produced with 61% harvest yield.But, in the preparation method, due to using carbonic acid buffer as solution, cause the high cost in tartaric acid production.
As previously discussed, based on conventional knowledge, it is considered to when preparing tartaric method by glucose, the preparation method is made up of following operation：The calcium salt of 5- ketone-D- gluconic acid is generated by glucose by fermentable, separate the operation of 5- ketone-D- gluconic acid calcium salt, 5- ketone-D- gluconic acid the calcium salt of obtained slightly water-soluble is converted to the operation of water miscible salt, and then water miscible 5- ketone-D- gluconate is chemically converted to tartaric operation.But, have the shortcomings that in the preparation method that operation is many, operate cost time in addition, therefore required high preparation cost.So thinking the tartaric preparation method that can not industrially realize being made up of above-mentioned operation so far.
Method as disadvantages mentioned above is made up, report the tartaric preparation method for adding vanadic acid catalyst necessary to ensuing reaction process (5- ketone-D- gluconate is converted to tartaric operation) in the culture medium that 5- ketone-D- gluconic acid is converted to using acetic acid bacteria by glucose of initial operation.In the preparation method, a small amount of tartaric acid of 43g (obtain yield 5.2 weight %) is only obtained by the glucose of 1000g.In this way, the harvest yield of the preparation method, due to very low, the preparation method is cannot be used in industrial tartaric preparation.
On the other hand, for by chemical reaction, the method that glycolic is prepared by 5- ketone-D- gluconic acid, so far an only known report, the low molecular organic acid of a large amount of accessory substances is also produced in reactant liquor in addition to glycolic, and a small amount of glycolic of 11.6g/L is only produced by the 5- ketone-D- gluconic acid of 796g/L.In this way, as the harvest yield of the preparation method is very low, the preparation method is cannot be used in the preparation of industrial glycolic.
Content of the invention
For the shortcoming of above-mentioned prior art, the present invention provide can by glucose effectively and prepare L- tartaric acid or its salt, and/or glycolic or its salt at low cost, method that the practicality that can be used in industrial preparation is high.
The present invention solves above-mentioned technical problem and employs the following technical solutions：A kind of preparation method of organic acid, prepares L- tartaric acid or the step of its salt, and/or glycolic or its salt with following operation A～C, by glucose,
(A) pass through the microorganism by glucose production 5- ketone-D- gluconic acid, in the presence of 5- ketone-D- gluconic acid can be made to form the alkali of water soluble salt, with the nutrient solution culture containing glucose, operation A of the nutrient solution of the water soluble salt containing 5- ketone-D- gluconic acid is obtained；
(B) by the pH of the nutrient solution of the water soluble salt containing 5- ketone-D- gluconic acid obtained in operation A is adjusted and is maintained in the range of 7～12, obtain 5- ketone-D- gluconic acid water soluble salt be converted to L- tartaric acid or its salt, and/or glycolic or its salt reactant liquor process B；
(C) operation C of L- tartaric acid or its salt, and/or glycolic or its salt, by the reactant liquor obtained in process B, is extracted.
Preferably, using the nutrient solution containing transition-metal catalyst further in nutrient solution in the process B.
Preferably, transition-metal catalyst is the transition-metal catalyst selected from a kind or more than 2 kinds in the group of palladium, rhodium, ruthenium, platinum, manganese, copper, cobalt, nickel, zinc, vanadium and iron composition.
Preferably, the concentration of transition-metal catalyst is 0.00002～2%.
Preferably, the concentration of transition-metal catalyst is 0.0001～1%.
Preferably, being the microorganism for belonging to Gluconobacter or acetobacter by the microorganism of glucose production 5- ketone-D- gluconic acid.
Preferably, the pH of the nutrient solution in the process B being adjusted and being maintained in the range of 8～11.
Preferably, the nutrient solution pH in the process B is adjusted and is maintained in the range of 9～10.
Preferably, in the process B, adjust and maintain nutrient solution pH when, further the temperature of nutrient solution is adjusted and maintains in the range of 0 DEG C～70 DEG C.
Preferably, in the process B, adjust and maintain nutrient solution pH when, further the temperature of nutrient solution is adjusted and maintains in the range of 20 DEG C～60 DEG C.
The present invention is had the advantage that compared with prior art：According to the present invention it is possible to highly effective by glucose and prepare L- tartaric acid or its salt, and/or glycolic or its salt at low cost.Therefore, the preparation method of the present invention, can be used in industrial preparation, and practicality is high.
Specific embodiment
In order that technological means, creation characteristic, reached purpose and effect that the present invention is realized are easy to understand, with reference to specific embodiment, the present invention is expanded on further.It should be appreciated that specific embodiment described herein is not intended to limit the present invention only in order to explain the present invention.
" method that L- tartaric acid or its salt, and/or glycolic or its salt are prepared by glucose " as the present invention, as long as with passing through the microorganism by glucose production 5- ketone-D- gluconic acid, in the presence of 5- ketone-D- gluconic acid can be made to form the alkali of water soluble salt, with the nutrient solution culture containing glucose, operation A of the nutrient solution of the water soluble salt containing 5- ketone-D- gluconic acid is obtained；By the pH of the nutrient solution of the water soluble salt containing 5- ketone-D- gluconic acid obtained in operation A is adjusted and is maintained in the range of 7～12, obtain 5- ketone-D- gluconic acid water soluble salt be converted to L- tartaric acid or its salt, and/or glycolic or its salt reactant liquor process B；And by the reactant liquor obtained in process B, extract operation C of L- tartaric acid or its salt, and/or glycolic or its salt, be then not particularly limited.By having this series of processes A～C, can be highly effective by glucose and L- tartaric acid or its salt, and/or glycolic be prepared at low cost or " L- tartaric acid or its salt, and/or glycolic or its salt " (is only meant as " L- tartaric acid etc. " by its salt below.).Although particularly obtain the nutrient solution (above-mentioned operation A) of the water soluble salt containing 5- ketone-D- gluconic acid, but 5- ketone-D- gluconic acid is not isolated and purified by the nutrient solution, and directly as described in above-mentioned B, by being converted to L- tartaric acid etc., the preparation efficiency of L- tartaric acid etc. is significantly improved, additionally, the cost for being prepared needed for L- tartaric acid etc. therewith is significantly reduced.
Embodiment 1：（2- ketone-nonproductive bacterium of maltonic acid and the acquirement of 5- ketone-maltonic acid on-consumable dissociant）
In order to the nonproductive bacterial strain of 2- ketone-D- gluconic acid from 3172 bacterial strain of gluconobacter oxydans NBRC is prepared, NTG variation process is carried out for 3172 bacterial strain of NBRC, attempts carrying out the screening of the nonproductive bacterium of 2- ketone-D- gluconic acid.Specifically, carried out with following method.
3172 bacterial strain of gluconobacter oxydans NBRC by growth in MA agar medium [2.5% mannitol, 0.5% yeast extract, 0.2% peptone, 1.5% agar (adjusting nothing pH)], after in the 300mL capacity conical flask of the MA culture medium for being inoculated into the 30mL at addition has at 121 DEG C with autoclave sterilization in 20 minutes with 1 platinum circle, per 1 minute 220 turns of shaken cultivation 19 hours, to obtain cell by the nutrient solution by centrifugation aseptic at 30 DEG C.Obtained cell is washed after 1 time with 0.85% sterile saline, is suspended in sterile saline.To in the developmental tube of sterilizing successively after dispensing Tris hydrochloride buffer (pH=8.0, final concentration=50mM) and washed cell suspension, the NTG solution of 2000 μ g/mL concentration is added to form 5mL so that final concentration respectively 0,50,100,200,300 μ g/mL.These developmental tubes are transferred to complex oscillation 30 minutes with 30 DEG C, per minute 250, thus enters row variation process.Reactant liquor in developmental tube is washed with sterile saline after 2 times, settling flux.The suspension is periodically diluted to 107 times, each dilution is coated on MA agar medium, with 30 DEG C of constant temperature machine culture 3～5 days.Randomly 2600 bacterium colonies are selected in identical agar medium by the bacterium colony for growing, screened using the thalline that cultivates 1～2 day at 30 DEG C.Suspend in 96 orifice plates of the 50mM kaliumphosphate buffer (pH=6.0) of 2% sodium gluconate containing 100 μ L the thalline of 1 platinum circle in dispensing, and vibration under room temperature carries out resting thalli reaction in 1 day.By the 1 μ L point sample of reaction supernatant on Silica gel TLC, launched with n-butanol-acetic acid-water (3: 2: 1), then after air-drying after the alkaline tetrazolium blue reagent of spraying, at 100 DEG C, heating colour developing, visually confirms the generation ratio of 2- ketone-D- gluconic acid and 5- ketone-D- gluconic acid.
As a result, 3172 bacterial strain of gluconobacter oxydans NBRC of parent strain generates 2- ketone-D- gluconic acid and 5- ketone-D- gluconic acid with substantially 1: 1 ratio, on the other hand, 7 plants of main only generation 5- ketone-D- gluconic acids are obtained, hardly generates the bacterial strain (the unproductive bacterial strain of 2- ketone-D- gluconic acid) of 2- ketone-D- gluconic acid.Further, gluconobacter oxydans TABT-200 bacterial strain for 1 plant in the nonproductive bacterial strain of obtained 7 plants of 2- ketone-D- gluconic acids, NTG variation process is carried out by method same as described above, attempts the screening of 5- ketone-D- gluconic acid on-consumable dissociant.1600 bacterium colonies obtained after NTG is processed are selected in agar medium, using the thalline grown at 30 DEG C.In dispensing containing 75 μ L 0.3% 5- ketone-D- gluconic acid 100mM kaliumphosphate buffer (pH=6.0) 96 orifice plates in suspend the thalline of 1 platinum circle, similarly carry out thalline reaction.After reaction, 15 μ L of supernatant is got in 96 flat orifice plates, add and 5- ketone-D- gluconic acid is specifically developed the color for peach 1- methyl isophthalic acid-phenyl hydrazine solution, heating at 95 DEG C carries out chromogenic reaction in 60 minutes, visually the consumption of investigation 5- ketone-D- gluconic acid.As a result 3 plants are obtained except not consuming in addition to unproductive and the dissociant of 5- ketone-D- gluconic acid with 2- ketone-D- gluconic acid completely.These dissociants due to for 2- ketone-D- gluconic acid unproductive and for 5- ketone-D- gluconic acid non-expendable, it is taken as that by glucose 5- ketone-D- gluconic acid productivity improve.The gluconobacter oxydans TADK-267 bacterial strain of 1 plant in obtained 3 plants is used in later experiment.
Embodiment 2：(tartaric acid and glycolic (interpolation transition-metal catalyst) are prepared by glucose)
At the gluconobacter oxydans TADK-267 inoculation obtained in above-described embodiment 1 is had at 121 DEG C to addition in the developmental tube 3 of the MB culture medium [2.5% mannitol, 0.5 yeast extract, 0.3% peptone] of the sterilized 20 minutes 5mL of heating, at 28 DEG C, complex oscillation culture is transferred to 17 hours with 250.Nutrient solution in this 3 developmental tubes is incorporated as kind of a nutrient solution.This culture is carried out as follows, in the fermentation tank of 1L, add containing 6% glucose, 0.09% ammonium chloride, 0.06% potassium dihydrogen phosphate, 0.18% Dried Corn Steep Liquor Powder, 0.1% yeast extract, 0.015% magnesium sulfate, 7 water salt, 0.0029% manganese sulfate, 5 water salt, 0.12% calcium chloride culture medium 500mL, after similarly heating sterilization, above-mentioned kind of nutrient solution 10mL of inoculation starts this culture.While pH being adjusted to more than 5.5 with 6M potassium hydroxide solution, row air agitation culture is rotated into 30 DEG C, 1vvm, 800, after nutrient solution is diluted 51 times with 1M hydrochloric acid solution, carry out being centrifuged the HPLC analysis time dependent ground quantitative amount of product of supernatant.The 50th hour after culture starts, the glucose in nutrient solution is consumed completely, remains the gluconic acid of 2.2g/L, but generate the 5- ketone-D- gluconic acid of 70.5g/L in nutrient solution.After in the nutrient solution, the pH of nutrient solution is increased to 9.6 by interpolation 6M potassium hydroxide solution, while directly adding the potassium hydroxide solution pH of nutrient solution maintained more than 9.6, continue air agitation until after the 144th hour, generating the tartaric acid of 12.1g/L and the gluconic acid of 6.0g/L.If in view of due to evaporating and adding the liquid measure change caused by potassium hydroxide solution, and as caused liquid measure is sampled in midway reduce part being calculated, then by glucose tartaric molar yield be 23.0%, by glucose glycolic molar yield be 22.5%.
Embodiment 3：（Tartaric acid and glycolic (interpolation palladium carbon) are prepared by glucose）
After gluconobacter oxydans TADK-267 being used fermentation tank culture 50 hours in the same manner as above-described embodiment 2, glucose is consumed completely, is remained the gluconic acid of 2.8g/L, but is generated the 5- ketone-D- gluconic acid of 67.4g/L in the solution.After in the nutrient solution, the pH of nutrient solution is increased to 9.6 by interpolation 6M potassium hydroxide solution, add the palladium activated carbon (10%) of 10g, while pH is maintained more than 9.6 by interpolation potassium hydroxide solution afterwards, continue air agitation until after the 144th hour, obtaining the reactant liquor of the glycolic of the tartaric acid containing 31.9g/L and 15.9g/L.If in view of due to evaporating and adding the liquid measure change caused by potassium hydroxide solution, and as caused liquid measure is sampled in midway reduce part being calculated, then by glucose tartaric molar yield be 61%, by glucose glycolic molar yield be 60%.
Embodiment 4：（Tartaric acid and the extraction of glycolic）
The reactant liquor total amount obtained in above-described embodiment 3 is rotated into row centrifugal treating with 5000 together with the washing lotion of fermentation tank, after the insoluble cut such as separating thallus residue, palladium carbon, with the water washing of about 100mL once, merge centrifugation supernatant, purified by the solution of 635mL.It is analyzed to identify by HPLC, the glycolic of the tartaric acid containing 13.1g and 5.9g in obtained solution.Be slowly added to in above-mentioned obtained solution after pH is reduced to 3.7 by concentrated hydrochloric acid, precipitation is generated, carry out centrifugal treating, be separated into precipitation and supernatant after therefore an evening being placed at 5 DEG C.Contain tartaric acid in precipitation, in supernatant, contain glycolic.Precipitation contains fine palladium carbon, somewhat grey, but is analyzed to identify by HPLC, and tartaric peak area value accounts for the 94% of gross area value.The precipitation is suspended in water, is slowly added into after potassium hydroxide solution dissolved, lentamente pH is reduced to 3.7 with 1M hydrochloric acid and is recrystallized, one potassium 14.1g of tartaric acid is obtained in the form of white powder.Then for the tartaric acid for being extracted, detected by the method in the zymetology of described below.As standard substance, L- tartaric acid, D- tartaric acid and mesotartaric acid, preparation 0,2.5,5,7.5mM solution is respectively properly weighed.20mM manganese chloride is added in the microcuvette of sample side, 2mM dithiothreitol (DTT), 15mM NAD, the D-malic acid dehydrogenase of 5 units, 60mM glycylglycine buffers (pH being adjusted to 9.0 with potassium hydroxide) and the L- tartaric acid containing each concentration of above-mentioned preparation, the mixed liquor (150 μ L of total amount) of D- tartaric acid or mesotartaric acid, this extroversion adds the water of 150 μ L in the microcuvette of control sides, the increase of the absorbance of 50 minutes is determined using UV2200 spectrophotometer under the wavelength of 340mm.As a result, for L- tartaric acid, the increase of 3.75 absorbance is shown under the concentration of 7.5mM, using 0,2.5,5, the increase of each absorbance of 7.5mM solution is used as the longitudinal axis, understand after tartaric for L- concentration is drawn as transverse axis, for all of L- tartaric acid standard liquid, it is plotted on the straight line by initial point.On the other hand, for D- tartaric acid, the increase of absorbance under all concentration, is not found completely, further for the mesotartaric acid of high concentration, it was found that absorbance somewhat increases, but the increase of the degree for ignoring if compared with the increasing of the tartaric absorbance of L-.Therefore, the tartaric acid for being extracted thought for one potassium of tartaric acid, correctly weighs the solution for preparing 5mM, by the increase of method mensuration absorbance same as described above.As a result, the increase of absorbance shows as 2.45, is distinguished by the tartaric calibration curve of L-, and obtained tartaric acid is the L- tartaric acid of purity 99.7%.
After pH is adjusted to 7.0 with 5M NaOH by the upper honest and upright and thrifty 630mL containing glycolic being centrifugally separating to obtain, by the chromatographic column of the CG400 anion exchange resin of 1000mL.After the chromatographic column is washed with the 20mM sodium formate solution of 1000mL, circulate 200mM sodium formate solution, and the eluent is fractionated per 10mL.Cut to being fractionated carries out HPLC analysis, collects and has the eluting fraction shown with the cut sequence number 54～205 at the peak of ethanol standard acid solution identical retention time.In order to remove the cations such as sodium ion by the eluent, after the chromatographic column of 50W × 8 cationic ion-exchange resin (OH- type) of 2000mL, washed with the deionized water of 500mL further.The non-adsorbed cut and washing lotion are collected together, after pH being adjusted to 7.0 with 2mM ammonia solution, by the neutralization solution, at 35 DEG C, reduced pressure concentration removes ammonium formate.Drying over night under vacuum decompression further, obtain the white powder of the alcohol acid phosphate of 4.7g.A part for the powder is dissolved in water, LCMS-2010A liquid chromatographic mass analyzer is made to be connected with chromatographic column, in the solvent system of acetonitrile/0.1% aqueous formic acid containing 0.1% formic acid, acetonitrile containing 0.1% formic acid is linearly increased to 50% from 0%, with the flow rate 28 minutes per 1 minute 0.3mL, carry out the liquid chromatogram under the wavelength of 210nm, the ultraviolet absorption spectrum at peak for being detected and ion mass spectrum, mass chromatography and determine.As a result, in the material for extracting, peak is detected with liquid chromatogram at 10.2 minutes, the retention time of the glycolic of the peak and standard items, ultraviolet absorption spectrum, with the ion mass spectrum that m/z=75.05,121.05 are characterized, and the mass chromatography of their anion is consistent.As a result identify extracted material for glycolic.
Embodiment 5：（The recycling of palladium carbon）
Add the palladium carbon of 40mg in the 0.45M sodium carbonate buffer (pH9.55) of the 5mL of the 5- ketone-D- gluconic acid sylvite containing 1%, vibrate 9 days.As a result the L- tartaric acid of 4g/L and the glycolic of 1g/L is generated, remains the 5- ketone-D- gluconic acid of 0.7g/L.Palladium carbon is reclaimed in the reactant liquor centrifugation of the 3.5mL, add the identical sodium carbonate buffer 3.15mL of 0.5M and 0.10% 5- ketone-D- K-IAO 35mL, after vibration 7 days, the L- tartaric acid of 5g/L and the glycolic of 1.2g/L is generated, remains the 5- ketone-D- gluconic acid of 2.1g/L.
General principle and principal character and the advantages of the present invention of the present invention has been shown and described above; it should be understood by those skilled in the art that; the present invention is not restricted to the described embodiments; merely illustrating the principles of the invention described in above-described embodiment and specification; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications; these changes and improvements are both fallen within scope of the claimed invention, and the claimed scope of the invention is by appending claims and its equivalent thereof.
Claims (10)
1. a kind of preparation method of organic acid, it is characterised in that：L- tartaric acid is prepared with following operation A～C, by glucose or the step of its salt, and/or glycolic or its salt,
(A) pass through the microorganism by glucose production 5- ketone-D- gluconic acid, in the presence of 5- ketone-D- gluconic acid can be made to form the alkali of water soluble salt, with the nutrient solution culture containing glucose, operation A of the nutrient solution of the water soluble salt containing 5- ketone-D- gluconic acid is obtained；
(B) by the pH of the nutrient solution of the water soluble salt containing 5- ketone-D- gluconic acid obtained in operation A is adjusted and is maintained in the range of 7～12, obtain 5- ketone-D- gluconic acid water soluble salt be converted to L- tartaric acid or its salt, and/or glycolic or its salt reactant liquor process B；
(C) operation C of L- tartaric acid or its salt, and/or glycolic or its salt, by the reactant liquor obtained in process B, is extracted.
2. the method as described in claim 1, it is characterised in that using the nutrient solution containing transition-metal catalyst further in the nutrient solution in the process B.
3. the method as described in claim 2, it is characterised in that transition-metal catalyst is the transition-metal catalyst selected from a kind or more than 2 kinds in the group of palladium, rhodium, ruthenium, platinum, manganese, copper, cobalt, nickel, zinc, vanadium and iron composition.
4. the method as described in claim 2 or 3, it is characterised in that the concentration of transition-metal catalyst is 0.00002～2%.
5. the method as described in any one in claim 2～4, it is characterised in that the concentration of transition-metal catalyst is 0.0001～1%.
6. the method as described in any one in claim 1～5, it is characterised in that the microorganism by glucose production 5- ketone-D- gluconic acid is the microorganism for belonging to Gluconobacter or acetobacter.
7. the method as described in any one in claim 1～6, it is characterised in that the pH of the nutrient solution in the process B is adjusted and is maintained in the range of 8～11.
8. the method as described in any one in claim 1～7, it is characterised in that the nutrient solution pH in the process B is adjusted and maintained in the range of 9～10.
9. the method as described in any one in claim 1～8, it is characterised in that in the process B, adjust and maintain nutrient solution pH when, further the temperature of nutrient solution is adjusted and maintains in the range of 0 DEG C～70 DEG C.
10. the method as described in any one in claim 1～9, it is characterised in that in the process B, adjust and maintain nutrient solution pH when, further the temperature of nutrient solution is adjusted and maintains in the range of 20 DEG C～60 DEG C.
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| CN110408802A (en) * | 2019-09-04 | 2019-11-05 | 贵州理工学院 | A method of the leaching recovering rare earth of ardealite containing rare earth |
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| CN105026548A (en) * | 2012-06-04 | 2015-11-04 | 盐水港精糖株式会社 | D-glucaric acid-producing bacterium, and method for manufacturing d-glucaric acid |
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| CN101184717A (en) * | 2005-05-27 | 2008-05-21 | 旭化成化学株式会社 | Method for producing glycolic acid |
| CN102471786A (en) * | 2009-07-03 | 2012-05-23 | 株式会社海法杰尼西斯 | Process for production of organic acids |
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| CN110408802A (en) * | 2019-09-04 | 2019-11-05 | 贵州理工学院 | A method of the leaching recovering rare earth of ardealite containing rare earth |
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