CN102040509A - Method for preparing citric acid - Google Patents
Method for preparing citric acid Download PDFInfo
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- CN102040509A CN102040509A CN2009102365254A CN200910236525A CN102040509A CN 102040509 A CN102040509 A CN 102040509A CN 2009102365254 A CN2009102365254 A CN 2009102365254A CN 200910236525 A CN200910236525 A CN 200910236525A CN 102040509 A CN102040509 A CN 102040509A
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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
- C07C51/02—Preparation of carboxylic acids or their salts, halides or anhydrides from salts of carboxylic acids
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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
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
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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
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
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Abstract
The invention discloses a method for preparing citric acid. The preparation method comprises the following steps of: (1) performing contact reaction on citric acid fermentation clear liquid and calcium carbonate and/or calcium hydroxide, converting the citric acid in the fermentation clear liquid into calcium hydrogen citrate under the condition of the contact reaction, and performing solid-liquid separation on the obtained slurry so as to obtain solid phase calcium hydrogen citrate and a first liquid phase; (2) performing acidolysis on the solid phase calcium hydrogen citrate obtained in the step (1) to obtain the citric acid; and (3) performing the contact reaction on the first liquid phase obtained in the step (1) and the calcium carbonate and/or the calcium hydroxide, converting the calcium hydrogen citrate dissolved in the first liquid phase into calcium citrate under the condition of the contact reaction, performing solid-liquid separation on the obtained slurry so as to obtain solid phase calcium citrate and a second liquid phase, returning the calcium citrate to the step (1) and repeating the operation in the step (1). The technical scheme for obtaining the calcium hydrogen citrate by a one-step reaction is beneficial to the improvement on the yield of the citric acid and operation steps are greatly simplified at the same time.
Description
Technical field
The present invention relates to a kind of preparation method of citric acid.
Background technology
Citric acid is a kind of organic acid that is widely used in industries such as beverage, food and medicine, and the preparation of citric acid generally comprises: raw material is carried out pre-treatment and fermentation obtains fermentation clear liquid, and further purifying citric acid from fermentation clear liquid, and carry out aftertreatment.The method of purifying citric acid from fermentation clear liquid of prior art comprises calcium salt method, hydrogen calcium method and chromatography, because chromatography is carried out pre-treatment to material step more complicated, and the off-set facility investment is higher, and calcium salt method that general common employing is more traditional or hydrogen calcium method are purified to the citric acid that fermentation obtains.
For example, CN101117315A discloses a kind of production method of citric acid, and this method comprises the steps:
1) earlier adding lime carbonate and/or calcium hydroxide in the citric acid sterilization filament clear liquid are reacted, reaction end pH value is 3-9, separates waste water and obtains citrate of lime;
2) with citrate of lime and the reaction of citric acid sterilization filament clear liquid, regulating the pH value is 1.5-6, generates hydrogen citrate calcium and/or dihydrogen citrate calcium;
3) carry out solid-liquid separation and wash solid phase then, liquid phase is returned in the step 1), and solid phase is carried out acidolysis reaction, generates citric acid and calcium salt;
4) carry out solid-liquid separation and handle, the washing solid phase, liquid phase obtains the citric acid product through aftertreatment again.
But, adopt the yield of the citric acid that existing hydrogen calcium method prepares lower.
Goal of the invention
Goal of the invention of the present invention is the lower defective of yield that overcomes the citric acid that the preparation methods of citric acid of prior art obtains, and a kind of preparation method with citric acid of higher yields is provided.
The present inventor finds, the CN101117315A disclosed method is earlier the citric acid neutralization to be citrate of lime, again citrate of lime and the reaction of citric acid sterilization filament clear liquid are generated hydrogen citrate calcium and/or dihydrogen citrate calcium, carry out solid-liquid separation then and wash solid phase, solid phase is carried out acidolysis obtain citric acid, liquid phase is returned in the step 1).Owing to contain a large amount of water and small part dissolved hydrogen citrate calcium in the described liquid phase, this liquid phase is being returned when handling once more in the step 1), on the one hand, can increase the processing pressure of step 1), on the other hand, after in citric acid fermentation that a large amount of liquid phases is returned step 1) cleans, the one, meeting reduces the concentration of citric acid fermentation clear liquid, thereby reduction speed of response, the 2nd, because the amount of liquid phase of returning in this step 1) is bigger, after this step reaction generates citrate of lime, the solution loss of the citrate of lime in the isolating waste water also can correspondingly increase considerably, thereby has influenced the yield of citric acid.
The invention provides a kind of preparation method of citric acid, wherein, this method comprises the steps:
(1) with citric acid fermentation clear liquid and lime carbonate and/or calcium hydroxide contact reacts, catalytic condition makes the citric acid in the fermentation clear liquid be converted into hydrogen citrate calcium, and the slurries that obtain are carried out solid-liquid separation, obtains the solid phase hydrogen citrate calcium and first liquid phase;
(2) the solid phase hydrogen citrate calcium acidolysis that step (1) is obtained obtains citric acid;
(3) first liquid phase that step (1) is obtained and lime carbonate and/or calcium hydroxide contact reacts, catalytic condition makes that dissolved hydrogen citrate calcium is converted into citrate of lime in the liquid phase of winning, the slurries that obtain are carried out solid-liquid separation, obtain the solid phase citrate of lime and second liquid phase, and citrate of lime is returned the operation of repeating step (1) in the step (1).
In the preparation method of citric acid of the present invention, exactly because the citric acid yield lower reason place of contriver by having found after analyzing to adopt existing calcium salt method to prepare, and pass through the liquid phase continuation behind the solid-liquid separation hydrogen citrate calcium and lime carbonate and/or calcium hydroxide reaction, obtain citrate of lime, and citrate of lime returned the operation of repeating step (1) in the step (1), and realized the purpose of effective raising citric acid yield.In addition, the step that the present invention adopts single step reaction can obtain hydrogen citrate calcium also is to be beneficial to the prerequisite that improves the citric acid yield, and has simplified operation steps simultaneously greatly.
Embodiment
According to the present invention, the preparation method of described citric acid comprises the steps:
(1) with citric acid fermentation clear liquid and lime carbonate and/or calcium hydroxide contact reacts, catalytic condition makes the citric acid in the fermentation clear liquid be converted into hydrogen citrate calcium, and the slurries that obtain are carried out solid-liquid separation, obtains the solid phase hydrogen citrate calcium and first liquid phase;
(2) the solid phase hydrogen citrate calcium acidolysis that step (1) is obtained obtains citric acid;
(3) first liquid phase that step (1) is obtained and lime carbonate and/or calcium hydroxide contact reacts, catalytic condition makes that dissolved hydrogen citrate calcium is converted into citrate of lime in the liquid phase of winning, the slurries that obtain are carried out solid-liquid separation, obtain the solid phase citrate of lime and second liquid phase, and citrate of lime is returned the operation of repeating step (1) in the step (1).
According to the present invention, in step (1), citric acid fermentation clear liquid and lime carbonate and/or the catalytic condition of calcium hydroxide are comprised the pH value of reaction end is 2.5-3.5, be preferably 2.9-3.1; Temperature of reaction is 75-85 ℃; Reaction times is 4-7 hour.In addition, above-mentioned first liquid phase that step (1) is obtained and lime carbonate and/or the catalytic condition of calcium hydroxide can also satisfy very a spot of unreacted citric acid that will be present in first liquid phase and also be converted into citrate of lime in the lump.
According to the present invention, this method also is included in the solid phase hydrogen citrate calcium that step (1) is obtained and carries out before the acidolysis, washing hydrogen citrate calcium is to remove the step of residual citric acid fermentation clear liquid, and mixture and the lime carbonate and/or the calcium hydroxide contact reacts of first liquid phase that the hydrogen citrate calcium water lotion that obtains and step (1) are obtained, catalytic condition makes that dissolved hydrogen citrate calcium is converted into citrate of lime in dissolved hydrogen citrate calcium in this hydrogen citrate calcium water lotion, residual citric acid fermentation clear liquid and first liquid phase.In addition, the mixture of first liquid phase that this hydrogen citrate calcium water lotion and step (1) are obtained and lime carbonate and/or the catalytic condition of calcium hydroxide can also satisfy the unreacted citric acid of seldom amount that will be present in first liquid phase and also be converted into citrate of lime in the lump.The method of described washing can well known to a person skilled in the art method and condition for employing.For example, wash hydrogen citrate calcium with the method for water wash or dipping.As long as the condition of washing and method are with residual citric acid fermentation clear liquid flush away.
Because the solubleness of hydrogen citrate calcium in water is much larger than the solubleness of citrate of lime, therefore, in order to obtain higher citric acid yield, the consumption of washing water and the time of washing remove with the citric acid fermentation clear liquid that will remain in hydrogen citrate calcium surface as far as possible and are as the criterion.The present inventor finds, in order to obtain balance preferably aspect citric acid quality (removing the partial impurities of plane of crystal) and the citric acid yield, that is, both can well guarantee remained on surface is removed, and can reduce solution loss again.The consumption of described washing water is preferably the 10-35% of fermentation clear liquid volume.The temperature of washing can be 70-95 ℃ usually, is preferably 80-90 ℃
According to the present invention, with the method and the condition of the acidolysis of hydrogen citrate calcium is conventionally known to one of skill in the art, for example, in step (2), the solid phase hydrogen citrate calcium acidolysis that step (1) is obtained obtains methods of citric acid and comprises hydrogen citrate calcium is contacted with aqueous acid; The condition of acidolysis comprises that the pH value can be 1.5-1.8; The temperature of acidolysis can be 70-95 ℃, is preferably 80-90 ℃; The time of acidolysis can be 40-60 minute.The kind of the acid that acidolysis is used can be for well known to a person skilled in the art various acid, and generally, functional quality per-cent is 98% the vitriol oil.
According to the present invention, in step (3), first liquid phase that step (1) is obtained comprises that with lime carbonate and/or the catalytic condition of calcium hydroxide the pH value of reaction end can be 4.5-5.5, is preferably 4.5-5.0; Temperature of reaction can be 60-80 ℃, is preferably 70-75 ℃; Reaction times is 30-60 minute, is preferably 40-60 minute.
According to the present invention, this method also comprises the step that second liquid phase that step (3) is obtained is carried out wastewater treatment, and the concrete grammar of described wastewater treatment and condition can be with reference to the CN101293716A disclosed methods.
According to the present invention, the preparation method of described citric acid fermentation clear liquid can adopt and well known to a person skilled in the art that prepared in various methods obtains, for example, described preparation method comprises maize raw material is pulverized, the crushed products that obtains is liquefied, fermentation obtains the citric acid product, and the content of citric acid is generally the 100-120 gram in every liter of lemon fermented clear liquid.
According to the present invention, this method comprises also that the citric acid that step (2) is obtained carries out ion-exchange, concentrates, crystallization and drying and other steps, described ion-exchange, concentrate, crystallization and dry concrete grammar and condition be conventionally known to one of skill in the art.
Except that containing pigment, also has a small amount of Ca in the described citric acid acidolysis liquid
2+, Mg
2+, Fe
3+, Cl
-, SO
4 2-Deng foreign ion, ion-exchange can be adopted the method for absorption exchange, removes pigment and deleterious Ca in the thick citric acid solution by gac and Zeo-karb, anionite-exchange resin
2+, Mg
2+, Fe
3+, Cl
-Plasma obtains the process of exquisite citric acid solution, and the skill parameter index can be destainer transmittance＞96%, ion exchange liquid transmittance＞96.5%, ion exchange liquid ion content Fe from handing over
3+＜4ppm, Cl
-＜4ppm, ion-exchange liquid acidity are about 35%.
Concentrate, crystallization, drying is to discharge after with a part of water vapor in the citric acid solution of low concentration with the method for heating, citric acid liquid (solution) is transformed into the solid-liquid liquid suspension under certain conditions, the citric acid crystal grain is separated with mother liquor, drying obtains higher citric acid of concentration (a water acid) or citric acid crystal grain (anhydrous acid), spissated one, two, the triple effect temperature can be respectively 105 ℃, 90 ℃, 70 ℃, one, two, triple effect vacuum tightness can be respectively-10kpa,-40kpa,-90kpa, obtain citric acid crystal grain and anhydrous mother liquor about Citric Acid, usp, Anhydrous Powder production line blanking flow 5.5M3/H, (one section: 45 ℃ in citric acid crystal grain drying machine, two sections: 40 ℃, three sections: 20 ℃, about 7 ℃ of frozen water temperature) utilize convection of air that citric acid surface moisture content is vaporized and drying; Citric acid monohydrate Food grade crystal grain drying machine (one section: 55 ℃, two sections: 45 ℃, three sections: 10 ℃, about 7 ℃ of frozen water temperature) utilize convection of air that citric acid surface moisture content is vaporized and drying.
To further describe in detail the present invention by specific embodiment below.
Used citric acid fermentation clear liquid makes by the following method among the following embodiment: 0.872 kg corn is pulverized with SFSP series beater disintegrating machine, and obtaining average particulate diameter is 0.871 kilogram of crushed products of 2 millimeters (adopting the Accu Sizer TM 780 optics particle diameter detectors of U.S. PPS company to measure); 83 ± 1 ℃ of liquefaction temperatures, 93 ± 1 ℃ of secondary liquefaction controlled temperature mix crushed products and to carry out steam ejection liquefaction with amylase, and holding time is 40-60 minute, and the pH value of described enzymolysis maintains 5.7-6.2; The α-Dian Fenmei 0.7g/kg Semen Maydis powder (Novozymes Company buys) of adding vigor 〉=2000u/ml; Temperature is reduced to 38 ℃, the inoculation biomass is the aspergillus niger of 18g/l (fermented liquid), the gained mixture under 37 ℃ in fermentor tank stir culture 65 hours, obtain the mix products that ferments, and filter and obtain 5 liters of citric acid fermentation clear liquids (content of citric acid is 110 grams in every liter of citric acid fermentation clear liquid).
Embodiment 1
Present embodiment is used to illustrate the preparation method of citric acid provided by the invention.
(1) under 75 ℃, lime carbonate is joined in 5 liters of citric acid fermentation clear liquids, the control endpoint pH is 2.95 o'clock, stops to add lime carbonate, and the reaction times is 5 hours, carries out solid-liquid separation then, and filtering separation obtains solid phase hydrogen citrate calcium and 4.54 liter of first liquid phase; Hydrogen citrate calcium is washed to remove residual citric acid fermentation clear liquid, and the temperature of washing water is 80 ℃, and the consumption of washing water is 1 liter; Obtain 613.36 gram hydrogen citrate calcium, obtain totally 5.54 liters of the mixed solutions of first liquid phase and water lotion;
(2) under 85 ℃, the hydrogen citrate calcium after the washing that step (1) is obtained and the 261.34 gram vitriol oils (sulfuric acid concentration is 98 weight %) mix, control pH value is 1.7, reacts 50 minutes, and acidolysis obtains 1.35 liters of citric acid solutions (citric acid content is 380 grams per liters);
(3) lime carbonate is joined in the mixed solution of first liquid phase that 5.54 liters of steps (1) obtain and water lotion, the control endpoint pH is 5 o'clock, stop to add lime carbonate, reaction times is 45 minutes, carry out solid-liquid separation then, filtering separation obtains solid phase citrate of lime 29.3 gram and second liquid phases, and described citrate of lime is returned the operation of repeating step (1) in the step (1); And second liquid phase carried out wastewater treatment; After operation cycle was stable, each operation can obtain citric acid 534.61 grams altogether; And the yield that calculates citric acid according to the following equation is 97.2%.
The content of citric acid during the amount * 100%/citric acid fermentation of citric acid yield (%)=citric acid that acidolysis obtains is clear.
Comparative Examples 1
This Comparative Examples is used to illustrate the reference preparation method of citric acid.
(1) under 75 ℃, lime carbonate is slowly joined in 5 liters of citric acid fermentation clear liquids (content of citric acid is 110 grams in every liter of citric acid fermentation clear liquid), control pH value is 4.8 o'clock, stop to add lime carbonate, reacted 60 minutes, after the layering of question response liquid, filtering separation waste water obtains the pulpous state citrate of lime;
(2) under 85 ℃, above-mentioned citric acid fermentation clear liquid is slowly joined in 2.59 liters of gram pulpous state citrate of lime that step (1) obtains, control pH value is 3.1 o'clock, stop to add the citric acid fermentation clear liquid, to react the gained mixture and carry out solid-liquid separation, 6.43 liters of liquid phases be returned the operation of repeating step (1) in the step (1); Isolated solid phase is standby after with 50 ℃ water washing; Described solid phase is hydrogen citrate calcium and/or dihydrogen citrate calcium;
(3) under 70 ℃, step (2) is separated the washing obtain after 621.28 gram solid phases mix with the 264.72 gram vitriol oils (sulfuric acid concentration is 98 weight %), controlling the pH value is 1.8, reacts 50 minutes, acidolysis obtains citric acid and calcium sulfate;
(4) filter, isolate citric acid, after 50 ℃ of washings, obtain 1.365 liters of citric acids (518.6 gram);
And be 94.3% according to the yield that the formula of embodiment 1 calculates citric acid.
Contrast by the foregoing description 1 and Comparative Examples 1 is as can be seen:
With respect to the inlet amount of same citric acid fermentation clear liquid, according to the method for embodiment 1, first liquid phase that step (1) obtains and the mixed solution of water lotion are 5.54 liters, and the amount of returning the citrate of lime in the step (1) only is 29.3 grams; And adopt the method for Comparative Examples 1 to turn back to the amount of the liquid phase in the step (1) up to 6.43 liters.Therefore, illustrate, return a large amount of liquid phases on the one hand at every turn, can increase the processing pressure of step (1), reduce speed of reaction; On the other hand, after the liquid phase that is dissolved with hydrogen citrate calcium and/or dihydrogen citrate calcium in a large number returned step (1), the amount of the citrate of lime of molten damage and small part hydrogen citrate calcium and dihydrogen citrate calcium can roll up in the isolated waste water, thereby has increased the loss amount of citric acid and influenced its yield.
Embodiment 2
Present embodiment is used to illustrate the preparation method of citric acid provided by the invention.
(1) under 85 ℃, lime carbonate is joined in 5 liters of citric acid fermentation clear liquids, the control endpoint pH is 2.5 o'clock, stop to add lime carbonate, reaction times is 4 hours, carries out solid-liquid separation then, and filtering separation obtains 606.37 gram solid phase hydrogen citrate calcium and 4.45 liter of first liquid phase;
(2) under 75 ℃, the hydrogen citrate calcium that step (1) is obtained mixes with the 258.37 gram vitriol oils (sulfuric acid concentration is 98 weight %), and control pH value is 1.5, reacts 40 minutes, and acidolysis obtains 1.33 liters of citric acid solutions;
(3) lime carbonate is joined in first liquid phase that 4.45 liters of steps (1) obtain, the control endpoint pH is 4.5 o'clock, stop to add lime carbonate, reaction times is 40 minutes, carry out solid-liquid separation then, filtering separation obtains solid phase citrate of lime 39.68 gram and second liquid phases, and described citrate of lime is returned the operation of repeating step (1) in the step (1); And second liquid phase carried out wastewater treatment; After operation cycle was stable, each operation can obtain citric acid 536.8 grams altogether, and was 97.6% according to the yield that the formula among the embodiment 1 calculates citric acid.
At last the citric acid that obtains carried out ion-exchange, concentrate, crystallization and drying obtain the citric acid product.
Embodiment 3
Present embodiment is used to illustrate the preparation method of citric acid provided by the invention.
(1) under 80 ℃, lime carbonate is joined in 5 liters of citric acid fermentation clear liquids, the control endpoint pH is 3.5 o'clock, stop to add lime carbonate, reaction times is 7 hours, carries out solid-liquid separation then, and filtering separation obtains 621.67 gram solid phase hydrogen citrate calcium and 4.53 liter of first liquid phase;
(2) under 90 ℃, the hydrogen citrate calcium that step (1) is obtained mixes with the 264.89 gram vitriol oils (sulfuric acid concentration is 98 weight %), and control pH value is 1.6, reacts 45 minutes, and acidolysis obtains 1.37 liters of citric acid solutions;
(3) lime carbonate is joined in first liquid phase that 4.53 liters of steps (1) obtain, the control endpoint pH is 5.3 o'clock, stop to add lime carbonate, reaction times is 50 minutes, carry out solid-liquid separation then, filtering separation obtains solid phase citrate of lime 21.98 gram and second liquid phases, and described citrate of lime is returned the operation of repeating step (1) in the step (1); And second liquid phase carried out wastewater treatment; After operation cycle was stable, each operation can obtain citric acid 535.91 grams altogether, and was 97.4% according to the yield that the formula among the embodiment 1 calculates citric acid.
At last the citric acid that obtains carried out ion-exchange, concentrate, crystallization and drying obtain the citric acid product.
Embodiment 4
Present embodiment is used to illustrate the preparation method of citric acid provided by the invention.
Method according to embodiment 1 prepares citric acid, and different is that in step (1), the consumption of washing water is 0.75 liter; Obtain 613.36 gram hydrogen citrate calcium, obtain totally 5.29 liters of the mixed solutions of first liquid phase and water lotion; Other step and condition are with embodiment 1, and after operation cycle was stable, each operation can obtain citric acid 533.52 grams altogether, and yield is 97.0%.
Embodiment 5
Present embodiment is used to illustrate the preparation method of citric acid provided by the invention.
Method according to embodiment 1 prepares citric acid, and different is that in step (1), the consumption of washing water is 1.5 liters; Obtain 613.36 gram hydrogen citrate calcium, obtain totally 6.04 liters of the mixed solutions of first liquid phase and water lotion; Other step and condition are with embodiment 1, and after operation cycle was stable, each operation can obtain citric acid 532.42 grams altogether, and yield is 96.8%.
Embodiment 6
Present embodiment is used to illustrate the preparation method of citric acid provided by the invention.
Method according to embodiment 1 prepares citric acid, and different is that in step (1), the consumption of washing water is 2 liters; Obtain 613.36 gram hydrogen citrate calcium, obtain totally 6.54 liters of the mixed solutions of first liquid phase and water lotion; Other step and condition are with embodiment 1, and after operation cycle was stable, each operation can obtain citric acid 528 grams altogether, and yield is 96.0%.
Embodiment 7
Present embodiment is used to illustrate the preparation method of citric acid provided by the invention.
Method according to embodiment 1 prepares citric acid, and different is that in step (1), the consumption of washing water is 0.35 liter; Obtain 613.36 gram hydrogen citrate calcium, obtain totally 4.89 liters of the mixed solutions of first liquid phase and water lotion; Other step and condition are with embodiment 1, and after operation cycle was stable, each operation can obtain citric acid 529.65 grams altogether, and yield is 96.3%.
Claims (9)
1. the preparation method of a citric acid is characterized in that, this method comprises the steps:
(1) with citric acid fermentation clear liquid and lime carbonate and/or calcium hydroxide contact reacts, catalytic condition makes the citric acid in the fermentation clear liquid be converted into hydrogen citrate calcium, and the slurries that obtain are carried out solid-liquid separation, obtains the solid phase hydrogen citrate calcium and first liquid phase;
(2) the solid phase hydrogen citrate calcium acidolysis that step (1) is obtained obtains citric acid;
(3) first liquid phase that step (1) is obtained and lime carbonate and/or calcium hydroxide contact reacts, catalytic condition makes that dissolved hydrogen citrate calcium is converted into citrate of lime in the liquid phase of winning, the slurries that obtain are carried out solid-liquid separation, obtain the solid phase citrate of lime and second liquid phase, and citrate of lime is returned the operation of repeating step (1) in the step (1).
2. method according to claim 1, wherein, in step (1), citric acid fermentation clear liquid and lime carbonate and/or the catalytic condition of calcium hydroxide are comprised the pH value of reaction end is 2.5-3.5, temperature of reaction is 75-85 ℃, and the reaction times is 4-7 hour.
3. method according to claim 1 and 2, wherein, the content of citric acid is the 100-120 gram in every liter of citric acid fermentation clear liquid.
4. method according to claim 1, wherein, this method also is included in the solid phase hydrogen citrate calcium that step (1) is obtained and carries out before the acidolysis, washing hydrogen citrate calcium is to remove the step of residual citric acid fermentation clear liquid, and mixture and the lime carbonate and/or the calcium hydroxide contact reacts of first liquid phase that the hydrogen citrate calcium water lotion that obtains and step (1) are obtained, catalytic condition makes that dissolved hydrogen citrate calcium is converted into citrate of lime in dissolved hydrogen citrate calcium in this hydrogen citrate calcium water lotion, residual citric acid fermentation clear liquid and first liquid phase.
5. method according to claim 4, wherein, the consumption of described washing water is the 10-35% of citric acid fermentation clear liquid volume, the temperature of washing is 70-95 ℃.
6. according to claim 1 or 4 described methods, wherein, in step (2), the solid phase hydrogen citrate calcium acidolysis that step (1) is obtained obtains methods of citric acid and comprises hydrogen citrate calcium is contacted with aqueous acid; The condition of acidolysis comprises that the pH value is 1.5-1.8, and the temperature of acidolysis is 70-95 ℃, and the time of acidolysis is 40-60 minute.
7. according to claim 1 or 4 described methods, wherein, in step (3), the mixture of first liquid phase that step (1) is obtained and lime carbonate and/or the catalytic condition of calcium hydroxide and first liquid phase that hydrogen citrate calcium water lotion and step (1) are obtained comprises that with lime carbonate and/or the catalytic condition of calcium hydroxide the pH value of reaction end is 4.5-5.5, temperature of reaction is 60-80 ℃, and the reaction times is 30-60 minute.
8. method according to claim 1, wherein, this method also comprises the step that second liquid phase that step (3) is obtained is carried out wastewater treatment.
9. method according to claim 1, wherein, this method comprises also that the citric acid that step (2) is obtained carries out ion-exchange, concentrates, crystallization and exsiccant step.
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| PCT/CN2010/077992 WO2011047634A1 (en) | 2009-10-23 | 2010-10-22 | Method for preparing citric acid |
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| CN102351687A (en) * | 2011-08-04 | 2012-02-15 | 中粮生物化学（安徽）股份有限公司 | Preparation method of calcium carbonate slurry and preparation method of citric acid |
| CN102390877A (en) * | 2011-08-04 | 2012-03-28 | 中粮生物化学（安徽）股份有限公司 | Treatment method of calcium hydrogen citrate washes and preparation method of citric acid |
| CN102816059A (en) * | 2012-08-28 | 2012-12-12 | 中粮生物化学（安徽）股份有限公司 | Production method and application of calcium hydrogen citrate |
| CN103528975A (en) * | 2013-09-30 | 2014-01-22 | 中粮生物化学（安徽）股份有限公司 | Determination method for readily carbonizable substances in calcium salt of citric acid and applications |
| CN108360249A (en) * | 2018-02-07 | 2018-08-03 | 枣庄市书源笔业有限公司 | A kind of multi-process writing brush sofening treatment technique |
| CN114307389A (en) * | 2021-12-16 | 2022-04-12 | 潍坊英轩实业有限公司 | Filtering method for improving citric acid extraction yield and feed liquid quality |
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| JPH0648979A (en) * | 1992-07-29 | 1994-02-22 | Idemitsu Petrochem Co Ltd | Method for purifying citric acid |
| CN101117315A (en) * | 2007-07-10 | 2008-02-06 | 安徽丰原生物化学股份有限公司 | Production method of lemon acid |
| CN101643411A (en) * | 2009-06-26 | 2010-02-10 | 安徽丰原发酵技术工程研究有限公司 | Neutralization method of citric acid |
| 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 |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102351687A (en) * | 2011-08-04 | 2012-02-15 | 中粮生物化学（安徽）股份有限公司 | Preparation method of calcium carbonate slurry and preparation method of citric acid |
| CN102390877A (en) * | 2011-08-04 | 2012-03-28 | 中粮生物化学（安徽）股份有限公司 | Treatment method of calcium hydrogen citrate washes and preparation method of citric acid |
| CN102390877B (en) * | 2011-08-04 | 2013-04-03 | 中粮生物化学（安徽）股份有限公司 | Treatment method of calcium hydrogen citrate washes and preparation method of citric acid |
| CN102351687B (en) * | 2011-08-04 | 2013-10-30 | 中粮生物化学（安徽）股份有限公司 | Preparation method of calcium carbonate slurry and preparation method of citric acid |
| CN102816059A (en) * | 2012-08-28 | 2012-12-12 | 中粮生物化学（安徽）股份有限公司 | Production method and application of calcium hydrogen citrate |
| CN103528975A (en) * | 2013-09-30 | 2014-01-22 | 中粮生物化学（安徽）股份有限公司 | Determination method for readily carbonizable substances in calcium salt of citric acid and applications |
| CN103528975B (en) * | 2013-09-30 | 2016-01-13 | 中粮生物化学（安徽）股份有限公司 | The assay method of readily carbonizable substance and application thereof in a kind of calcium citrate salts |
| CN108360249A (en) * | 2018-02-07 | 2018-08-03 | 枣庄市书源笔业有限公司 | A kind of multi-process writing brush sofening treatment technique |
| CN114307389A (en) * | 2021-12-16 | 2022-04-12 | 潍坊英轩实业有限公司 | Filtering method for improving citric acid extraction yield and feed liquid quality |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2011047634A1 (en) | 2011-04-28 |
| CN102040509B (en) | 2013-06-19 |
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