CN102040509B - Method for preparing citric acid - Google Patents
Method for preparing citric acid Download PDFInfo
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- CN102040509B CN102040509B CN 200910236525 CN200910236525A CN102040509B CN 102040509 B CN102040509 B CN 102040509B CN 200910236525 CN200910236525 CN 200910236525 CN 200910236525 A CN200910236525 A CN 200910236525A CN 102040509 B CN102040509 B CN 102040509B
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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 the 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, due to chromatography, material is carried out the step more complicated of pre-treatment, and the off-set facility investment is higher, and the 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 the method comprises the steps:
1) first will add calcium carbonate and/or calcium hydroxide to react in citric acid sterilization filament clear liquid, reaction end pH value be 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 calcium hydrogen citrate and/or dihydrogen citrate calcium;
3) then carry out solid-liquid separation and wash solid phase, liquid phase is returned to step 1) in, solid phase is carried out acidolysis reaction, generates citric acid and calcium salt;
4) carry out solid-liquid separation and process, the washing solid phase, liquid phase obtains the citric acid product through aftertreatment again.
But, adopt the yield of the standby citric acid that obtains of existing hydrogen calcium legal system 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 method for preparing 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 disclosed method of CN101117315A is for first being citrate of lime with the citric acid neutralization, again citrate of lime and the reaction of citric acid sterilization filament clear liquid are generated calcium hydrogen citrate and/or dihydrogen citrate calcium, then carry out solid-liquid separation and wash solid phase, solid phase is carried out acidolysis obtains citric acid, liquid phase is returned to step 1) in.due to the calcium hydrogen citrate that contains the dissolving of a large amount of water and small part in described liquid phase, this liquid phase is being returned to step 1) in when again processing, on the one hand, meeting increase step 1) processing pressure, on the other hand, when a large amount of liquid phases is returned to step 1) citric acid fermentation clean in after, the one, meeting reduces the concentration of citric acid fermentation aqueous solution, thereby reduction speed of response, the 2nd, owing to returning to this step 1) in amount of liquid phase larger, after this step reaction generates citrate of lime, the solution loss of the citrate of lime in the waste water that separates also can correspondingly increase considerably, thereby affected the yield of citric acid.
The invention provides a kind of preparation method of citric acid, wherein, the method comprises the steps:
(1) with citric acid fermentation aqueous solution and calcium carbonate and/or calcium hydroxide contact reacts, catalytic condition makes the citric acid in fermentation clear liquid be converted into calcium hydrogen citrate, and the slurries that obtain are carried out solid-liquid separation, obtains solid phase calcium hydrogen citrate and the first liquid phase;
(2) the solid phase calcium hydrogen citrate acidolysis that step (1) is obtained obtains citric acid;
(3) the first liquid phase that step (1) is obtained and calcium carbonate and/or calcium hydroxide contact reacts, catalytic condition makes the calcium hydrogen citrate that dissolves in the first liquid phase be converted into citrate of lime, the slurries that obtain are carried out solid-liquid separation, obtain solid phase citrate of lime and second liquid phase, and citrate of lime is returned to the operation of repeating step (1) in 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 after the solid-liquid separation calcium hydrogen citrate and calcium carbonate and/or calcium hydroxide reaction, obtain citrate of lime, and citrate of lime is returned to the operation of repeating step (1) in 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 calcium hydrogen citrate is also to be beneficial to the prerequisite that improves the citric acid yield, and has greatly simplified operation steps simultaneously.
Embodiment
According to the present invention, the preparation method of described citric acid comprises the steps:
(1) with citric acid fermentation aqueous solution and calcium carbonate and/or calcium hydroxide contact reacts, catalytic condition makes the citric acid in fermentation clear liquid be converted into calcium hydrogen citrate, and the slurries that obtain are carried out solid-liquid separation, obtains solid phase calcium hydrogen citrate and the first liquid phase;
(2) the solid phase calcium hydrogen citrate acidolysis that step (1) is obtained obtains citric acid;
(3) the first liquid phase that step (1) is obtained and calcium carbonate and/or calcium hydroxide contact reacts, catalytic condition makes the calcium hydrogen citrate that dissolves in the first liquid phase be converted into citrate of lime, the slurries that obtain are carried out solid-liquid separation, obtain solid phase citrate of lime and second liquid phase, and citrate of lime is returned to the operation of repeating step (1) in step (1).
According to the present invention, in step (1), citric acid fermentation aqueous solution and calcium 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 the first liquid phase that step (1) is obtained and calcium carbonate and/or the catalytic condition of calcium hydroxide can also satisfy the seldom unreacted citric acid of amount that will be present in the first liquid phase and also be converted in the lump citrate of lime.
According to the present invention, the method also is included in before the solid phase calcium hydrogen citrate that step (1) is obtained carries out acidolysis, the washing calcium hydrogen citrate is to remove the step of residual citric acid fermentation aqueous solution, and mixture and calcium carbonate and/or the calcium hydroxide contact reacts of the first liquid phase that the calcium hydrogen citrate water lotion that obtains and step (1) are obtained, catalytic condition makes the calcium hydrogen citrate that dissolves in the calcium hydrogen citrate that dissolves in this calcium hydrogen citrate water lotion, residual citric acid fermentation aqueous solution and the first liquid phase be converted into citrate of lime.The mixture of the first liquid phase that in addition, this calcium hydrogen citrate water lotion and step (1) is obtained and calcium carbonate and/or the catalytic condition of calcium hydroxide can also satisfy the unreacted citric acid of seldom amount that will be present in the first liquid phase and also be converted in the lump citrate of lime.The method of described washing can well known to a person skilled in the art method and condition for employing.For example, wash calcium hydrogen citrate with the method for water wash or dipping.The condition of washing and method are as long as wash away residual citric acid fermentation aqueous solution.
Solubleness due to calcium hydrogen citrate in water is much larger than the solubleness of citrate of lime, and 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 aqueous solution that will remain in the calcium hydrogen citrate surface as far as possible and is 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 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, be conventionally known to one of skill in the art with method and the condition of calcium hydrogen citrate acidolysis, for example, in step (2), the method that the solid phase calcium hydrogen citrate acidolysis that step (1) is obtained obtains citric acid comprises calcium hydrogen citrate 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 various acid that the kind of the acid that acidolysis is used can be known to the skilled person, generally, functional quality per-cent is 98% the vitriol oil.
According to the present invention, in step (3), the first liquid phase that step (1) is obtained comprises that with calcium 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, the method also comprises the step that second liquid phase that step (3) is obtained carries out wastewater treatment, and the concrete grammar of described wastewater treatment and condition can be with reference to the disclosed methods of CN101293716A.
According to the present invention, the preparation method of described citric acid fermentation aqueous solution can adopt and well known to a person skilled in the art that the whole bag of tricks prepares, 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 in every liter of lemon fermented clear liquid, the content of citric acid is generally the 100-120 gram.
According to the present invention, the method comprises that also the citric acid that step (2) is obtained carries out ion-exchange, concentrated, crystallization and drying and other steps, and described ion-exchange, concentrated, crystallization and dry concrete grammar and condition are conventionally known to one of skill in the art.
Except containing pigment, also has a small amount of Ca in described Aoidolysed lemon liguor
2+, Mg
2+, Fe
3+, Cl
-, SO
4 2-Deng foreign ion, ion-exchange can be adopted the method for absorption exchange, removes pigment in thick citric acid solution and harmful Ca 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 35% left and right.
concentrated, 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 solid-liquid suspension under certain conditions, the citric acid crystal grain is separated with mother liquor, drying obtains the higher citric acid of concentration (a water acid) or citric acid crystal grain (anhydrous acid), concentrated one, two, the triple effect temperature can be respectively 105 ℃, 90 ℃, 70 ℃, one, two, triple effect vacuum tightness can be respectively-10kpa,-40kpa,-90kpa, Citric Acid, usp, Anhydrous Powder production line blanking flow 5.5M3/H left and right obtains citric acid crystal grain and anhydrous mother liquor, (one section: 45 ℃, citric acid crystal grain drying machine, two sections: 40 ℃, three sections: 20 ℃, 7 ℃ of left and right of frozen water temperature) utilize convection of air citric acid surface moisture content vaporization and drying, citric acid monohydrate crystal particle drying machine (one section: 55 ℃, two sections: 45 ℃, three sections: 10 ℃, frozen water temperature 7 ℃ of left and right) utilizes convection of air citric acid surface moisture content vaporization and dry.
The below will be further described in detail the present invention by specific embodiment.
In following embodiment, citric acid fermentation aqueous solution used makes by the following method: 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 temperature are controlled in secondary liquefaction, crushed products is mixed with amylase carry out steam ejection liquefaction, and holding time is 40-60 minute, and the pH value of described enzymolysis maintains 5.7-6.2; The α-amylase 0.7g/kg Semen Maydis powder (Novozymes Company buys) that adds vigor 〉=2000u/ml; Temperature is down 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 to obtain 5 liters of citric acid fermentation aqueous solutions (in every liter of citric acid fermentation aqueous solution, the content of citric acid is 110 grams).
Embodiment 1
The present embodiment is used for illustrating the preparation method of citric acid provided by the invention.
(1) under 75 ℃, calcium carbonate is joined in 5 liters of citric acid fermentation aqueous solutions, controlling endpoint pH is 2.95 o'clock, stop adding calcium carbonate, reaction times is 5 hours, then carries out solid-liquid separation, and filtering separation obtains solid phase calcium hydrogen citrate and 4.54 liter of first liquid phase; Calcium hydrogen citrate is washed to remove residual citric acid fermentation aqueous solution, and the temperature of washing water is 80 ℃, and the consumption of washing water is 1 liter; Obtain 613.36 gram calcium hydrogen citrates, obtain totally 5.54 liters of the mixed solutions of the first liquid phase and water lotion;
(2) under 85 ℃, calcium hydrogen citrate after the washing that step (1) is obtained mixes with the 261.34 gram vitriol oils (sulfuric acid concentration is 98 % by weight), controlling the 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) calcium carbonate is joined in the mixed solution of the first liquid phase that 5.54 liters of steps (1) obtain and water lotion, controlling endpoint pH is 5 o'clock, stop adding calcium carbonate, reaction times is 45 minutes, then carry out solid-liquid separation, filtering separation obtains solid phase citrate of lime 29.3 grams and second liquid phase, and described citrate of lime is returned to the operation of repeating step (1) in step (1); And second liquid phase is carried out wastewater treatment; After operation cycle was stable, each operation can obtain altogether citric acid 534.61 grams; And the yield that calculates according to the following equation citric acid is 97.2%.
The content of citric acid during the amount of citric acid yield (%)=citric acid that acidolysis obtains * 100%/citric acid fermentation is clear.
Comparative Examples 1
This Comparative Examples is used for the reference preparation method of explanation citric acid.
(1) under 75 ℃, calcium carbonate is slowly joined in 5 liters of citric acid fermentation aqueous solutions (in every liter of citric acid fermentation aqueous solution, the content of citric acid is 110 grams), controlling the pH value is 4.8 o'clock, stop adding calcium 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 aqueous solution is slowly joined in 2.59 liters of gram pulpous state citrate of lime that step (1) obtains, controlling the pH value is 3.1 o'clock, stop adding citric acid fermentation aqueous solution, to react the gained mixture and carry out solid-liquid separation, 6.43 liters of liquid phases be returned to the operation of repeating step (1) in step (1); Isolated solid phase is standby after with the water washing of 50 ℃; Described solid phase is calcium hydrogen citrate 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 % by weight), control pH value is 1.8, reacts 50 minutes, acidolysis obtains citric acid and calcium sulfate;
(4) filter, isolate citric acid, obtain 1.365 liters of citric acids (518.6 gram) after 50 ℃ of washings;
And be 94.3% according to the yield that the formula of embodiment 1 calculates citric acid.
Contrast by above-described embodiment 1 and Comparative Examples 1 can be found out:
With respect to the inlet amount of same citric acid fermentation aqueous solution, according to the method for embodiment 1, the first liquid phase that step (1) obtains and the mixed solution of water lotion are 5.54 liters, and the amount of returning to the citrate of lime in step (1) is only 29.3 grams; And adopt the method for Comparative Examples 1 to turn back to the amount of the liquid phase in step (1) up to 6.43 liters.Therefore, illustrate, return to 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 in a large number calcium hydrogen citrate and/or dihydrogen citrate calcium is returned to step (1), in isolated waste water, the amount of the citrate of lime of molten damage and small part calcium hydrogen citrate and dihydrogen citrate calcium can roll up, thereby has increased the loss amount of citric acid and affected its yield.
Embodiment 2
The present embodiment is used for illustrating the preparation method of citric acid provided by the invention.
(1) under 85 ℃, calcium carbonate is joined in 5 liters of citric acid fermentation aqueous solutions, controlling endpoint pH is 2.5 o'clock, stop adding calcium carbonate, reaction times is 4 hours, then carries out solid-liquid separation, and filtering separation obtains 606.37 gram solid phase calcium hydrogen citrates and 4.45 liter of first liquid phase;
(2) under 75 ℃, the calcium hydrogen citrate that step (1) is obtained mixes with the 258.37 gram vitriol oils (sulfuric acid concentration is 98 % by weight), and controlling the pH value is 1.5, reacts 40 minutes, and acidolysis obtains 1.33 liters of citric acid solutions;
(3) calcium carbonate is joined in the first liquid phase that 4.45 liters of steps (1) obtain, controlling endpoint pH is 4.5 o'clock, stop adding calcium carbonate, reaction times is 40 minutes, then carry out solid-liquid separation, filtering separation obtains solid phase citrate of lime 39.68 grams and second liquid phase, and described citrate of lime is returned to the operation of repeating step (1) in step (1); And second liquid phase is carried out wastewater treatment; After operation cycle was stable, each operation can obtain altogether citric acid 536.8 grams, and was 97.6% according to the yield of the calculating of the formula in embodiment 1 citric acid.
At last the citric acid that obtains is carried out ion-exchange, concentrated, crystallization and drying and obtain the citric acid product.
Embodiment 3
The present embodiment is used for illustrating the preparation method of citric acid provided by the invention.
(1) under 80 ℃, calcium carbonate is joined in 5 liters of citric acid fermentation aqueous solutions, controlling endpoint pH is 3.5 o'clock, stop adding calcium carbonate, reaction times is 7 hours, then carries out solid-liquid separation, and filtering separation obtains 621.67 gram solid phase calcium hydrogen citrates and 4.53 liter of first liquid phase;
(2) under 90 ℃, the calcium hydrogen citrate that step (1) is obtained mixes with the 264.89 gram vitriol oils (sulfuric acid concentration is 98 % by weight), and controlling the pH value is 1.6, reacts 45 minutes, and acidolysis obtains 1.37 liters of citric acid solutions;
(3) calcium carbonate is joined in the first liquid phase that 4.53 liters of steps (1) obtain, controlling endpoint pH is 5.3 o'clock, stop adding calcium carbonate, reaction times is 50 minutes, then carry out solid-liquid separation, filtering separation obtains solid phase citrate of lime 21.98 grams and second liquid phase, and described citrate of lime is returned to the operation of repeating step (1) in step (1); And second liquid phase is carried out wastewater treatment; After operation cycle was stable, each operation can obtain altogether citric acid 535.91 grams, and was 97.4% according to the yield of the calculating of the formula in embodiment 1 citric acid.
At last the citric acid that obtains is carried out ion-exchange, concentrated, crystallization and drying and obtain the citric acid product.
Embodiment 4
The present embodiment is used for illustrating 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 calcium hydrogen citrates, obtain totally 5.29 liters of the mixed solutions of the first liquid phase and water lotion; Other step and condition are with embodiment 1, and after operation cycle was stable, each operation can obtain altogether citric acid 533.52 grams, and yield is 97.0%.
Embodiment 5
The present embodiment is used for illustrating 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 calcium hydrogen citrates, obtain totally 6.04 liters of the mixed solutions of the first liquid phase and water lotion; Other step and condition are with embodiment 1, and after operation cycle was stable, each operation can obtain altogether citric acid 532.42 grams, and yield is 96.8%.
Embodiment 6
The present embodiment is used for illustrating 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 calcium hydrogen citrates, obtain totally 6.54 liters of the mixed solutions of the first liquid phase and water lotion; Other step and condition are with embodiment 1, and after operation cycle was stable, each operation can obtain altogether citric acid 528 grams, and yield is 96.0%.
Embodiment 7
The present embodiment is used for illustrating 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 calcium hydrogen citrates, obtain totally 4.89 liters of the mixed solutions of the first liquid phase and water lotion; Other step and condition are with embodiment 1, and after operation cycle was stable, each operation can obtain altogether citric acid 529.65 grams, and yield is 96.3%.
Claims (9)
1. the preparation method of a citric acid, is characterized in that, the method comprises the steps:
(1) with citric acid fermentation aqueous solution and calcium carbonate and/or calcium hydroxide contact reacts, catalytic condition makes the citric acid in fermentation clear liquid be converted into calcium hydrogen citrate, the slurries that obtain are carried out solid-liquid separation, obtain solid phase calcium hydrogen citrate and the first liquid phase, the pH value that citric acid fermentation aqueous solution and calcium carbonate and/or the catalytic condition of calcium hydroxide is comprised reaction end is 2.5-3.5, and temperature of reaction is 75-85 ℃;
(2) the solid phase calcium hydrogen citrate acidolysis that step (1) is obtained obtains citric acid;
(3) the first liquid phase that step (1) is obtained and calcium carbonate and/or calcium hydroxide contact reacts, catalytic condition makes the calcium hydrogen citrate that dissolves in the first liquid phase be converted into citrate of lime, the slurries that obtain are carried out solid-liquid separation, obtain solid phase citrate of lime and second liquid phase, and citrate of lime is returned to the operation of repeating step (1) in step (1).
2. method according to claim 1, wherein, in step (1), comprise also that with citric acid fermentation aqueous solution and calcium carbonate and/or the catalytic condition of calcium hydroxide the reaction times is 4-7 hour.
3. method according to claim 1 and 2, wherein, in every liter of citric acid fermentation aqueous solution, the content of citric acid is the 100-120 gram.
4. method according to claim 1, wherein, the method also is included in before the solid phase calcium hydrogen citrate that step (1) is obtained carries out acidolysis, the washing calcium hydrogen citrate is to remove the step of residual citric acid fermentation aqueous solution, and mixture and calcium carbonate and/or the calcium hydroxide contact reacts of the first liquid phase that the calcium hydrogen citrate water lotion that obtains and step (1) are obtained, catalytic condition makes the calcium hydrogen citrate that dissolves in this calcium hydrogen citrate water lotion, the calcium hydrogen citrate that dissolves in residual citric acid fermentation aqueous solution and the first liquid phase is converted into citrate of lime.
5. method according to claim 4, wherein, the consumption of described washing water is the 10-35% of citric acid fermentation aqueous solution volume, the temperature of washing is 70-95 ℃.
6. according to claim 1 or 4 described methods, wherein, in step (2), the method that the solid phase calcium hydrogen citrate acidolysis that step (1) is obtained obtains citric acid comprises calcium hydrogen citrate 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 the first liquid phase that step (1) is obtained and calcium carbonate and/or the catalytic condition of calcium hydroxide and the first liquid phase that calcium hydrogen citrate water lotion and step (1) are obtained comprises that with calcium 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, the method also comprises the step that second liquid phase that step (3) is obtained carries out wastewater treatment.
9. method according to claim 1, wherein, the method comprises that also the citric acid that step (2) is obtained carries out ion-exchange, concentrated, crystallization and dry step.
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| CN 200910236525 CN102040509B (en) | 2009-10-23 | 2009-10-23 | Method for preparing citric acid |
| PCT/CN2010/077992 WO2011047634A1 (en) | 2009-10-23 | 2010-10-22 | Method for preparing citric acid |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| 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 |
| CN102816059B (en) * | 2012-08-28 | 2014-06-04 | 中粮生物化学（安徽）股份有限公司 | Production method and application of calcium hydrogen citrate |
| 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 |
| CN105503572A (en) * | 2015-12-29 | 2016-04-20 | 日照金禾博源生化有限公司 | Production method of calcium citrate salt |
| 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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|---|---|---|---|---|
| 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 |
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| 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 |
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