CN103641708A - Method for eliminating oxalic acid during citric acid fermentation process - Google Patents
Method for eliminating oxalic acid during citric acid fermentation process Download PDFInfo
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- CN103641708A CN103641708A CN201310600231.1A CN201310600231A CN103641708A CN 103641708 A CN103641708 A CN 103641708A CN 201310600231 A CN201310600231 A CN 201310600231A CN 103641708 A CN103641708 A CN 103641708A
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- citric acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/487—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to chemical modification
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Abstract
The invention discloses a method for eliminating oxalic acid during the critic acid fermentation process. The method comprises the following steps: taking corn as the raw material, carrying out fermentation by utilizing excellent strains of aspergillus niger so as to obtain fermenting mash, adding calcium carbonate slurry into the fermenting mash, then subjecting the mixture to carry out reactions with oxalic acid, utilizing the difference between the pH of the solution in the endpoint of the reaction between oxalic acid and calcium carbonate and the pH of the solution in the endpoint of the reaction between critic acid and calcium carbonate, automatically on-line controlling the pH so as to determine the endpoint of reaction between oxalic acid and calcium carbonate, and eliminating the oxalic acid through a method of controlling the total time of operation. The method has the advantage of easy and simple operation in the industrial production, reduces the energy consumption and cost, has a high elimination rate of oxalic acid, and improves the quality of critic acid product.
Description
Technical field
A kind of removal method that the present invention relates to oxalic acid, relates in particular to a kind of remove oxalic acid in citric acid production method.
Background technology
Citric acid, formal name used at school 2-hydroxy propane-1,2,3-tricarboxylic acid, molecular formula C
6h
8o
7(anhydride), is a kind of food that is widely used in, the organic acid of medicine and chemical field.Along with expanding economy, all trades and professions will grow steadily to the demand of citric acid, and the challenge that each enterprise faces certainly and opportunity are also more and more.Be mainly used in foodstuffs industry, pharmaceutical sector, chemical industry, and also have very wide application in the industrial circles such as electronics, weaving, oil, leather, building, photography, plastics, casting and pottery.
Industrial production citric acid mainly be take microorganism fermentation as main, the method for comparative maturity be utilize aspergillus niger by saccharine material corn fermentation to produce citric acid, in fermenting process, under aspergillus niger effect, can produce by product oxalic acid, it affects the quality of citric acid and salt thereof.The removal of oxalic acid at present mainly adopts the plant and instrument such as ion exchange resin, chromatography, its weak point is: apparatus expensive, the utilization ratio of use are low, energy consumption is high, maintenance cost is high, work-ing life and bearing capacity limited etc., and the quality of citric acid product is had to certain impact.
Summary of the invention
For the problems referred to above, the present invention proposes a kind of removal method of Citric Acid Fermentation mesoxalic acid, in fermentation liquid, add calcium carbonate serosity, make it to react with oxalic acid, while utilizing oxalic acid, citric acid from calcium carbonate reaction terminal, pH's is different, on-line automatic control pH determines the reaction end of oxalic acid and calcium carbonate, and removes oxalic acid by the method for red-tape operati total time.The present invention is simple and easy handling control in industrial production, has reduced energy consumption and cost, and oxalic acid clearance is high, has improved the quality of citric acid product.
A kind of removal method of Citric Acid Fermentation mesoxalic acid, in undergoing microbial fermentation the fermentation liquid obtaining, corn adds calcium carbonate serosity, make it to react with oxalic acid, while utilizing oxalic acid, citric acid from calcium carbonate reaction terminal, pH's is different, on-line automatic control pH determines the reaction end of oxalic acid and calcium carbonate, and removes oxalic acid by the method for red-tape operati total time.
The removal method of described Citric Acid Fermentation mesoxalic acid, concrete operation steps is as follows:
(1) corn the is undergone microbial fermentation fermentation liquid obtaining is heated to 60-70 ℃, filters, and obtains filtrate;
(2) calcium carbonate and water be take to the ratio furnishing slurries that weight ratio is 30-50:100;
(3) step (2) gained slurries are joined in step (1) gained filtrate, stir, when pH value is reaction end during for 3.5-4.5, stop adding of slurries, obtain reaction solution;
(4) perlite and water be take to the ratio furnishing perlite slurries that weight ratio is 1-4:100;
(5) the described perlite slurries of step (4) are uniformly coated on the filter cloth of plate-and-frame filter press, then step (3) gained reaction solution are squeezed into plate-and-frame filter press and filtered, obtain filtrate, be removal oxalic acid.
The described fermentation liquid of step of the present invention (1) obtains while being the conventional microorganism fermentation production of citric acid of corn process, for guaranteeing the transformation efficiency of saccharic acid, in g/100mL, when fermentor tank normally produces, acid is per hour is no more than 0.1%, reducing sugar is no more than 1.0%, at this moment the fermentation liquid obtaining is the described fermentation liquid of step (1), contains citric acid, oxalic acid, residual sugar, protein, black-koji mould filament and a small amount of insoluble suspended substance; Further, wherein in g/100mL, in the described fermentation liquid of step (1), the content of citric acid is 15-19%, and the content of oxalic acid is 0.3-0.5%, and the content of residual sugar is 0.5-1.0%, and the content of protein is 0.3-0.5%, with this, judges that fermenting process finishes.
Step (1) is heated to 60-70 ℃ by fermentation liquid.Why fermentation liquid is heat-treated, its role is to: (1) kills black-koji mould filament, prevent the further metabolism of citric acid, stop fermentation; (2) make protein denaturation and flocculate, reducing the viscosity of feed liquid, being beneficial to filtration; (3) part citric acid in black-koji mould filament is discharged.But the Heating temperature in this process is not more high better, excess Temperature can make black-koji mould filament break and self-dissolving, discharges the protein of thalline self, makes on the contrary feed liquid viscosity increase, and color browning, brings very large difficulty to follow-up removal oxalic acid.Therefore, fermentation liquid thermal treatment temp is determined between 60-70 ℃.
Described in step (1), filtering employing is plate-and-frame filter press, is commercially available prod with step (5) plate-and-frame filter press used, and model is J200/1250, purchases in Jing County, Hebei plate-and-frame filter press factory, and its filter cloth is 0.5 order, and 5mm is thick.
The time of filtering described in step (1) is 25min, and pressure is 0.5 MPa.
The described filtration of step (1) is by black-koji mould filament, foreign protein and a small amount of insoluble suspended substance in gained fermentation liquid after removal thermal treatment; In the described filtrate of step (1), contain citric acid, oxalic acid and residual sugar.
One of inventive point of the present invention is to adopt calcium carbonate to remove oxalic acid, and its key is the concentration of calcium carbonate serosity, and the described calcium carbonate of step (2) is food grade light calcium carbonate, and calcium carbonate and water be take to the ratio furnishing slurries that weight ratio is 30-50:100.If this concentration of slurry is too high, poor fluidity, comparatively strict to equipment and requirements for pipes, and concentration of slurry is too high, more easily cause oxalic acid comparatively violent with reacting of calcium carbonate, not only affect the formation of caoxalate, but also can cause part citric acid generation citrate of lime that reacts with it, thereby reduce the yield of citric acid; But if concentration is too low, can increase the processing cost of water consumption and postorder operation.Therefore the ratio furnishing slurries that the weight ratio of calcium carbonate and water being take is 30-50:100, preferred weight ratio is 35::100.
Because citric acid and oxalic acid all can react with calcium carbonate, but when at citric acid and oxalic acid, the two exists simultaneously, oxalic acid elder generation and calcium carbonate reaction, after oxalic acid thoroughly reacts completely, citric acid just can react with calcium carbonate.Therefore,, for fear of citric acid and calcium carbonate reaction, must strictly control the pH of reaction end and total filtration time.
Step (3) adopts calcium carbonate to react oxalic calcium with oxalic acid, caoxalate is water insoluble, then adopts step (5) to filter to remove oxalic acid, thereby improves the purity of citric acid product, improve product competitiveness, so determining of reaction end pH value plays conclusive effect to the purifying of product.The control of the described reaction end of step (3) is determined by pH value, when pH value is reaction end during for 3.5-4.5, now stop adding of calcium carbonate serosity, its pH value is to show by pH on-line monitoring equipment, thereby control reaction end by controlling pH value, to remove oxalic acid, thereby improve the purity of citric acid product, improve product competitiveness.When the present invention utilizes oxalic acid, citric acid just from calcium carbonate reaction, pH's is different, that is to say that citric acid does not react with calcium carbonate when pH value is 3.5-4.5.If pH value is too high, oxalic acid clearance is higher, but in reaction process, citric acid also can more participate in this reaction, produces indissoluble thing citrate of lime, reduces the yield of citric acid; If pH is too low, calcium carbonate add-on is few, can not guarantee that oxalic acid effectively removes, therefore based on these 2 considerations, the pH value of reaction end is controlled as 3.5-4.5, oxalic acid clearance and citric acid yield all can obtain effective balance, so key point of the present invention is also the control of oxalic acid and calcium carbonate reaction endpoint pH.
The described perlite of step (4) is commercially available prod, tap density is 90g/cm3, hardness 800, because its proterties is light specific gravity and irregular bar shaped solid powdery, so need to add after water is sized mixing, could use, the present invention take by perlite and water the ratio furnishing perlite slurries that weight ratio is 1-4:100, and preferred weight ratio is 1-2:100.Described perlite can play bridging action in filtration procedure, keeps compared with high voidage, increases effective filtration area, improves the filtration efficiency of sheet frame.If perlite concentration of slurry is higher, the thickness being coated on filter cloth will be thicker, and filtrate is more clear, and filter effect is better, but can improve the ability to bear of filter pressure and equipment like this, extends filtration time, reduces the utilization ratio of equipment; If perlite concentration of slurry is lower, the perlite coating on filter cloth is thinner, can reduce filtrate quality, affects filter effect.
In order to reduce citric acid, participate in this reaction, described reaction times of step (3) and the described filtration time summation of step (5) are 15-30min.The length that contriver finds described reaction times of step (3), the described filtration time of step (5) substantially without impact, therefore, only needs to control total time to the yield of citric acid.
The pressure of the described filtration of step (5) is 0.5MPa.
Filtration procedure described in step (5) has filtered the macromolecular substance such as calcium oxalate precipitation that oxalic acid and calcium carbonate reaction generate, protein, and oxalic acid clearance is up to more than 99%, and in step (5), gained filtrate is removal oxalic acid.
The fermentation liquid that the present invention undergoes microbial fermentation corn to obtain, add calcium carbonate serosity, while utilizing oxalic acid, citric acid from calcium carbonate reaction terminal, pH's is different, the reaction end of the definite oxalic acid of on-line automatic control pH value and calcium carbonate, and by control react and filter total time remove oxalic acid.The present invention is simple and easy handling control in industrial production, has reduced energy consumption and cost, and oxalic acid clearance is high, has improved the quality of citric acid product.
Embodiment
Embodiment 1
A removal method for Citric Acid Fermentation mesoxalic acid, concrete operation steps is as follows:
(1) corn the is undergone microbial fermentation fermentation liquid obtaining is heated to 60 ℃, adopts plate-and-frame filter press to filter 25min at pressure under the condition that is 0.5MPa, obtains filtrate;
(2) food grade light calcium carbonate and water be take to the ratio furnishing slurries that weight ratio is 30:100;
(3) step (2) gained slurries are joined in step (1) gained filtrate, stir, be reaction end when pH value is 3.5, stops adding of slurries, obtains reaction solution;
(4) perlite and water be take to the ratio furnishing perlite slurries that weight ratio is 1:100;
(5) the described perlite slurries of step (4) are uniformly coated on the filter cloth of plate-and-frame filter press, then step (3) gained reaction solution are squeezed under the condition that plate-and-frame filter press is 0.5MPa at pressure and filtered, obtain filtrate, be removal oxalic acid;
In the described fermentation liquid of step (1), in g/100mL, the content of citric acid is 15%, and the content of oxalic acid is 0.5%, and the content of residual sugar is 1.0%;
The described perlitic tap density 90g/cm of step (4)
3, hardness is 800;
The temporal summation of the described reaction of step (3) and the described filtration of step (5) is 30min;
The order number of step (1) and the described filter cloth for plate-frame type filter presses of step (5) is 0.5 order, and thickness is 5mm.
Embodiment 2
A removal method for Citric Acid Fermentation mesoxalic acid, concrete operation steps is as follows:
(1) corn the is undergone microbial fermentation fermentation liquid obtaining is heated to 67 ℃, adopts plate-and-frame filter press to filter 25min at pressure under the condition that is 0.5MPa, obtains filtrate;
(2) food grade light calcium carbonate and water be take to the ratio furnishing slurries that weight ratio is 50:100;
(3) step (2) gained slurries are joined in step (1) gained filtrate, stir, be reaction end when pH value is 4.0, stops adding of slurries, obtains reaction solution;
(4) perlite and water be take to the ratio furnishing perlite slurries that weight ratio is 3:100;
(5) the described perlite slurries of step (4) are uniformly coated on the filter cloth of plate-and-frame filter press, then step (3) gained reaction solution are squeezed under the condition that plate-and-frame filter press is 0.5MPa at pressure and filtered, obtain filtrate, be removal oxalic acid;
In the described fermentation liquid of step (1), in g/100mL, the content of citric acid is 19%, and the content of oxalic acid is 0.4%, and the content of residual sugar is 0.5%;
The described perlitic tap density 90g/cm of step (4)
3, hardness is 800;
The temporal summation of the described reaction of step (3) and the described filtration of step (5) is 20min;
The order number of step (1) and the described filter cloth for plate-frame type filter presses of step (5) is 0.5 order, and thickness is 5mm.
Embodiment 3
A removal method for Citric Acid Fermentation mesoxalic acid, concrete operation steps is as follows:
(1) corn the is undergone microbial fermentation fermentation liquid obtaining is heated to 70 ℃, adopts plate-and-frame filter press to filter 25min at pressure under the condition that is 0.5MPa, obtains filtrate;
(2) food grade light calcium carbonate and water be take to the ratio furnishing slurries that weight ratio is 40:100;
(3) step (2) gained slurries are joined in step (1) gained filtrate, stir, be reaction end when pH value is 4.5, stops adding of slurries, obtains reaction solution;
(4) perlite and water be take to the ratio furnishing perlite slurries that weight ratio is 4:100;
(5) the described perlite slurries of step (4) are uniformly coated on the filter cloth of plate-and-frame filter press, then step (3) gained reaction solution are squeezed under the condition that plate-and-frame filter press is 0.5MPa at pressure and filtered, obtain filtrate, be removal oxalic acid;
In the described fermentation liquid of step (1), in g/100mL, the content of citric acid is 17%, and the content of oxalic acid is 0.3%, and the content of residual sugar is 1.5%;
The described perlitic tap density 90g/cm of step (4)
3, hardness is 800;
The temporal summation of the described reaction of step (3) and the described filtration of step (5) is 15min.
The order number of step (1) and the described filter cloth for plate-frame type filter presses of step (5) is 0.5 order, and thickness is 5mm.
Embodiment 4
A removal method for Citric Acid Fermentation mesoxalic acid, concrete operation steps is as follows:
(1) corn the is undergone microbial fermentation fermentation liquid obtaining is heated to 65 ℃, adopts plate-and-frame filter press to filter 25min at pressure under the condition that is 0.5MPa, obtains filtrate;
(2) food grade light calcium carbonate and water be take to the ratio furnishing slurries that weight ratio is 35:100;
(3) step (2) gained slurries are joined in step (1) gained filtrate, stir, be reaction end when pH value is 4.1, stops adding of slurries, obtains reaction solution;
(4) perlite and water be take to the ratio furnishing perlite slurries that weight ratio is 2:100;
(5) the described perlite slurries of step (4) are uniformly coated on the filter cloth of plate-and-frame filter press, then step (3) gained reaction solution are squeezed under the condition that plate-and-frame filter press is 0.5MPa at pressure and filtered, obtain filtrate, be removal oxalic acid;
In the described fermentation liquid of step (1), in g/100mL, the content of citric acid is 18%, and the content of oxalic acid is 0.4%, and the content of residual sugar is 0.8%;
The described perlitic tap density 90g/cm of step (4)
3, hardness is 800;
The temporal summation of the described reaction of step (3) and the described filtration of step (5) is 25min.
The order number of step (1) and the described filter cloth for plate-frame type filter presses of step (5) is 0.5 order, and thickness is 5mm.
Embodiment 5
A removal method for Citric Acid Fermentation mesoxalic acid, concrete operation steps is as follows:
(1) corn the is undergone microbial fermentation fermentation liquid obtaining is heated to 62 ℃, adopts plate-and-frame filter press to filter 25min at pressure under the condition that is 0.5MPa, obtains filtrate;
(2) food grade light calcium carbonate and water be take to the ratio furnishing slurries that weight ratio is 45:100;
(3) step (2) gained slurries are joined in step (1) gained filtrate, stir, be reaction end when pH value is 3.8, stops adding of slurries, obtains reaction solution;
(4) perlite and water be take to the ratio furnishing perlite slurries that weight ratio is 1.5:100;
(5) the described perlite slurries of step (4) are uniformly coated on the filter cloth of plate-and-frame filter press, then step (3) gained reaction solution are squeezed under the condition that plate-and-frame filter press is 0.5MPa at pressure and filtered, obtain filtrate, be removal oxalic acid;
In the described fermentation liquid of step (1), in g/100mL, the content of citric acid is 16%, and the content of oxalic acid is %, and the content of residual sugar is 1.2%;
The described perlitic tap density 90g/cm of step (4)
3, hardness is 800;
The temporal summation of the described reaction of step (3) and the described filtration of step (5) is 30min.
The order number of step (1) and the described filter cloth for plate-frame type filter presses of step (5) is order, and thickness is 5mm.
The indices of embodiment 1-5 and prior art intermediate ion exchange resin are removed to Oxalic Acid Method and contrast, result is as following table:
As can be seen from the above table, the yield of citric acid and the clearance of oxalic acid are considered in overall equilbrium, the effect of embodiment 4 is optimum, and this absolutely proves that the method for the invention can reach and the equally even better effect of ion exchange resin removal Oxalic Acid Method on basis simple to operate, equipment is cheap.
Claims (10)
1. a removal method for Citric Acid Fermentation mesoxalic acid, is characterized in that: concrete operation steps is as follows:
(1) corn the is undergone microbial fermentation fermentation liquid obtaining is heated to 60-70 ℃, filters, and obtains filtrate;
(2) calcium carbonate and water be take to the ratio furnishing slurries that weight ratio is 30-50:100;
(3) step (2) gained slurries are joined in step (1) gained filtrate, stir, when pH value is reaction end during for 3.5-4.5, stop adding of slurries, obtain reaction solution;
(4) perlite and water be take to the ratio furnishing perlite slurries that weight ratio is 1-4:100;
(5) the described perlite slurries of step (4) are uniformly coated on the filter cloth of plate-and-frame filter press, then step (3) gained reaction solution are squeezed into plate-and-frame filter press and filtered, obtain filtrate, be removal oxalic acid.
2. the removal method of Citric Acid Fermentation mesoxalic acid according to claim 1, it is characterized in that: in the described fermentation liquid of step (1) in g/100mL, the content of citric acid is 10-12%, and the content of oxalic acid is 0.3-0.5%, and the content of residual sugar is 0.5-1.5%.
3. the removal method of Citric Acid Fermentation mesoxalic acid according to claim 1, is characterized in that: the time of filtering described in step (1) is 25min, and pressure is 0.5MPa.
4. the removal method of Citric Acid Fermentation mesoxalic acid according to claim 1, is characterized in that: the described calcium carbonate of step (2) is food grade light calcium carbonate.
5. the removal method of Citric Acid Fermentation mesoxalic acid according to claim 1, is characterized in that: the weight ratio of the described calcium carbonate of step (2) and water is 35:100.
6. the removal method of Citric Acid Fermentation mesoxalic acid according to claim 1, is characterized in that: the described perlitic tap density 90g/cm of step (4)
3, hardness is 800.
7. the removal method of Citric Acid Fermentation mesoxalic acid according to claim 1, is characterized in that: in step (4), perlite and water be take the ratio furnishing perlite slurries that weight ratio is 1-2:100.
8. the removal method of Citric Acid Fermentation mesoxalic acid according to claim 1, is characterized in that: the temporal summation of the described reaction of step (3) and the described filtration of step (5) is 15-30min.
9. the removal method of Citric Acid Fermentation mesoxalic acid according to claim 1, is characterized in that: the pressure of the described filtration of step (5) is 0. 5MPa.
10. the removal method of Citric Acid Fermentation mesoxalic acid according to claim 1, is characterized in that: the order number of the described filter cloth for plate-frame type filter presses of step (5) is 0.5 order, and thickness is 5mm.
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| CN201310600231.1A CN103641708B (en) | 2013-11-25 | 2013-11-25 | A kind of minimizing technology of Citric Acid Fermentation mesoxalic acid |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101029317A (en) * | 2006-02-27 | 2007-09-05 | 吴玉华 | Technology for rapidly dissolving calcium citrin by potato slag |
| CN101648864A (en) * | 2009-07-31 | 2010-02-17 | 安徽丰原生物化学股份有限公司 | Purification method of citric acid fermentation broth |
| CN103058853A (en) * | 2012-12-17 | 2013-04-24 | 日照金禾博源生化有限公司 | Method for producing calcium hydrogen citrate |
-
2013
- 2013-11-25 CN CN201310600231.1A patent/CN103641708B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101029317A (en) * | 2006-02-27 | 2007-09-05 | 吴玉华 | Technology for rapidly dissolving calcium citrin by potato slag |
| CN101648864A (en) * | 2009-07-31 | 2010-02-17 | 安徽丰原生物化学股份有限公司 | Purification method of citric acid fermentation broth |
| CN103058853A (en) * | 2012-12-17 | 2013-04-24 | 日照金禾博源生化有限公司 | Method for producing calcium hydrogen citrate |
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Effective date of registration: 20161031 Address after: 276500 Laiyang Road, Juxian Economic Development Zone, Shandong, No. 209, No. Patentee after: Rizhao Rijin Boyuan Biochemistry Co., Ltd. Address before: 276800 west section of Xing Hai Road, Shandong, Rizhao City Patentee before: Rizhao Luxin RZBC Co., Ltd. |