CN1060522C - Process for separating and purifying citric acid - Google Patents
Process for separating and purifying citric acid Download PDFInfo
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- CN1060522C CN1060522C CN96109807A CN96109807A CN1060522C CN 1060522 C CN1060522 C CN 1060522C CN 96109807 A CN96109807 A CN 96109807A CN 96109807 A CN96109807 A CN 96109807A CN 1060522 C CN1060522 C CN 1060522C
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- citric acid
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Abstract
The present invention provides a process for separating and purifying citric acid, which is characterized in that starch or glucose fermenting liquid can be adopted as raw material; an adsorption and cross-linking process is added, in which weak-alkaline anionic adsorption and cross-linking resin with large capacity and strong fouling resistance is used; by changing pressure in adsorption and cross-linking columns, the adsorption and cross-linking resin is shaken in order to omit a 'regeneration' process; an alkali desorption method is adopted; in order to thoroughly remove impurities and accelerate reaction, diluted alkali is added in desorption liquid to regulate pH value at 7.5 to 14, while pressure and temperature are changed.
Description
The present invention relates to a kind of method of separating and purifying citric acid.
Extracting methods of citric acid at present from thick starchy material fermented liquid or fermented glucose liquid has " calcium salt method " " ion exchange method " to reach " extraction process ".
Calcium salt method:
Because of adopting coarse fodder is raw material, adds CaO on stream, CaCO
3, neutralize, adopt dense H
2SO
4Carry out acidolysis and take off, so there is following shortcoming:
1. citric acid separation purification recovery rate only is 75%.
2. produce a large amount of CaSO
4Waste residue produces 1 ton of citric acid usually and can produce 2 tons of CaSO
4Waste residue still can't be administered at present and causes accumulation, serious environment pollution and reduce final product quality.
3. the intermediate citrate of lime is the sludge thing, makes the production can not serialization, has strengthened labour intensity.
4. carry out its equipment of acidolysis with the vitriol oil and pipeline perishable, and adopt stainless steel, improved cost.
5. neutralization all needs to carry out the CaSO that obtains in addition under 80 ℃ of-90 ℃ of temperature with the acidolysis process
4For solid-state, need to use mechanical transmission, therefore power consumption is big.
6. when adopting thick potato dry powder raw material, because raw material impurity is many, the citric acid impurity of producing is also many, does not reach elaboration citric acid level.
Ion exchange method, its technical process is as follows:
Weak point:
1. the citric acid concentration of the pure citric acid solution in decolouring back only is about 5%, again with its evaporation concentration to state of saturation, just need to consume a large amount of energy.
2. soluble protein, sugar, colloid and other impurity remove unclean in the citric acid solution after freeing, decolouring, remain in the mother liquor in a large number, mother liquor still need adopt " calcium salt method " to reclaim citric acid, has not only increased operation, and a series of shortcomings of bringing " calcium salt method " to exist again.
Extraction process is to adopt special extraction agent that the citric acid extracting and separating is purified, and its shortcoming is: because of adopting coarse fodder is raw material, and wherein impurity is many, thereby reduces extraction coefficient.Obtain citric acid concentration at last and be up to 5%, thus the energy expenditure of increase back operation; The production cost height; Extract the recovery rate instability simultaneously.
The external glucose fermentation liquid that adopts is that raw material is produced citric acid with calcium salt method or extraction process more, and its shortcoming is:
1. raw material is that fine fodder is a fermented glucose liquid, is not suitable for China's national situation.
2. thereby owing to produce the shortcoming that citric acid has brought calcium salt method with calcium salt method.
3. the extraction agent that adopts when producing citric acid as with extraction process is poisonous, so the citric acid of production can not be used for food, only is used in industrial abroad.
The objective of the invention is to provide in order to overcome the shortcoming that exists in the above-mentioned prior art a kind of can with the coarse fodder raw material can with fine fodder produce citric acid and realize efficient, energy-conservation, reduce cost, reduce environmental pollution, separate and remove organic impurity and extract recovery rate and finally improve the citric acid final product quality and try to achieve the novel process that in same technical process, can produce Trisodium Citrate simultaneously to greatest extent to improve citric acid concentration, to improve.
The present invention be achieved in that this method comprise with citric acid fermentation broth filter, negatively charged ion absorption exchanges, free, positive post transition, decolouring, evaporation concentration, crystallization, separation, its raw material of drying step be thick starchiness or fermented glucose liquid, operation obtains directly going up anion column absorption exchange after the clear liquid after filtration, and used weakly-basic anion absorption exchange resin is a 0.8-1.0g/g over dry resin; Free in the operation that to adopt concentration be the NaOH of 4%-20% or the NH of 8%-30%
4OH carries out alkaline hydrolysis and takes off, and changes absorption exchange column internal pressure simultaneously and promptly is forced into 4.9 * 10
4Emptying to pressure is zero behind the Pa, and 2 to 3 times so repeatedly, adding dilute alkali in freeing liquid more afterwards and transferring pH value is 7.5-14, changes the pressure and temperature of freeing liquid simultaneously, and its method is: adopted the normal pressure heated and boiled 10-15 minute; Or employing reduces pressure 8.7 * 10
4The Pa heating under vacuum was boiled 10-15 minute; Or employing is pressurized to 4.9 * 10
4Pa-9.8 * 10
4Pa heats up 100 ℃-120 ℃ and boiled 10-15 minute; Or adopt the normal pressure heated and boiled to be chilled to the method for room temperature after 10-15 minute.Extract recovery rate to quicken the removing impurity process with raising impurity-eliminating effect, raising citric acid.
The invention will be further described below in conjunction with accompanying drawing.
Fig. 1: process flow sheet of the present invention.
The present invention makes citric acid fermentation broth take the starchiness such as potato class or glucose as raw material after fermentation, Be clear liquid after filtering then impurity such as removing mycelium, adopt weakly-basic anion absorption exchanger resin, its Inhale the friendship capacity and can reach greatly 0.8-1.0g/g over dry resin, and have stronger antifouling property, can be straight Connect filtered fluid upper prop absorption exchange (without the decolouring removal of impurities), citric acid is adsorbed on the absorption exchanger resin Upward separate with other impurity. Separate, free the colloidal nature of liquid according to citric acid, the present invention changes former Come acidolysis to take off the shortcoming that reduced sugar is higher, readily carbonizable substances is not up to standard that method exists. Add 4-and adopt 20%NaOH or 8-30%NH4The alkaline hydrolysis of OH takes off method citric acid is separated from the absorption exchanger resin Take off. Be in the scope of 8-10 by the PH that regulates that adds dilute alkali simultaneously. Destroy citric acid and free liquid Colloidal stability, make the impurity coacervations such as a small amount of soluble protein of sneaking into, sugar, colloid, heteroacid from lemon The lemon acidolysis is taken off in the liquid and is separated. Because having adopted, the present invention changes the absorption exchange column when the absorption exchange process Internal pressure (4.9 * 104Pa is to emptying, 2 to 3 times repeatedly) and the absorption exchanger resin is fully mixed Method still need not criticized " regeneration " so do not need to resemble from the friendship method after washing glue process resin, can reach Free in the liquid citric acid concentration 15% or more and to improve total recovery rate be 85% to improving citric acid, same The time reduced the consumption of water, acid, alkali.
The present invention is by changing the pressure and temperature method, accelerate impurity coacervation above-mentioned, promote the reaction of the substance decomposition such as carbohydrate and protein and other material and protein, change pressure and temperature can adopt four kinds of methods as: heating was boiled 10-15 minute under the normal pressure, or decompression (8.7 * 104The pa vacuum) boils also available pressurization (4.9 * 10 in 10-15 minute4Pa-9．8×10
4Pa) be heated to 100-120 ℃ Boiled 10-15 minute, also available heating is boiled after 10-15 minute and is cooled to rapidly room temperature, namely with React under upper any pressure and temperature condition and can make all that citric acid content reaches in the citric acid solution More than 15%, residual sugar content below 0.02%, readily carbonizable substances reaches British Standard, do not detect simultaneously The heteroacid such as oxalic acid, gluconic acid. Free in the liquid at this then and add powder activated carbon and decolour, filter After positive post operation transition, remove metal ion (Na with cationic ion-exchange resin+、NH
4 +) again through two Get the elaboration citric acid after inferior decolouring, evaporation and concentration, crystallization, the separation. If absorption exchanges and alkaline hydrolysis in front Take off operation adopt NaOH should free liquid again through remove organic impurities, decolorization filtering is straight transition without positive post Each operation (seeing Fig. 1) then can get the natrium citricum finished product after tapping into capable secondary decolourization. This shows same Only need save positive post operation transition in one technological process and can obtain another kind of product-natrium citricum. And the citric acid that obtains through separation or (natrium citricum) mother liquor can return and inhale hand over order or evaporation and concentration operation Continue to purify. The present invention to the waste liquid that produces in the separating and purifying citric acid process through evaporation, concentrate, crystallization, Produce (NH after the separation4)
2SO
4、(NH
4)
3PO
4、Na
2SO
4Or Na3PO
4Can be used as of byproduct Worker's raw material and chemical fertilizer have been realized comprehensive utilization, have avoided environmental pollution, have reduced cost.
Advantage of the present invention is: reduces environmental pollution, takes off method because of adopting alkaline hydrolysis, thus a large amount of mud shape CaCO that avoided calcium salt method to produce
3The accumulation of waste residue.The waste liquid that the present invention produces after treatment, the intermediate that can fully utilize, produces is that fluid does not need mechanical transmission only to get final product with pump, so save energy, cost are low, can separate, remove soluble protein, sugar, colloid to greatest extent, and organic impurity such as other heteroacid, the final product quality height can reach elaboration citric acid level; Citric acid concentration can reach more than 15%, extracts recovery rate and reaches 85%.
Embodiment 1:
Get potato dry powder fermented liquid 1000ml (citric acid content 13.0%, residual sugar (reducing sugar) 1.0%), remove residue 10g such as mycelium after filtration, get clear liquid (citric acid 11.8%, residual sugar 0.96%) and adopt M through the absorption exchange
1: 8310# anionite-exchange resin (M-1 adsorbs exchange resin) separates citric acid with other impurity, free to such an extent that free liquid with thin liquid ammonia (10-20%), wherein residual sugar content is) 0.1%, adding alkali again transfers PH=9.0 10 minutes after-filtration of heated and boiled under normal pressure to remove organic impurity 4g to get clear liquid, remove NH through Zeo-karb again
4 +Can get citric acid content and be 18% liquid, getting citric acid content after the decolouring again is that 17% residual sugar content is 0.015% pure citric acid solution, and this pure citric acid solution can be made the Citric Acid, usp, Anhydrous Powder that 115 grams reach British Standard through conventional operations such as evaporation concentration, crystallization, dryings.Its citric acid content of mother liquor that separate to obtain be 15% altogether 10ml return evaporative crystallization or once more the absorption exchange reclaim to purify.Zeo-karb H
2SO
4Regeneration, effusive waste liquid (NH
4)
2SO
4Can get (NH through concentrating
4)
2SO
4Crystallization is used as chemical fertilizer or industrial chemicals.
Embodiment 2:
Get citric acid fermentation filtered liquid 2000ml (citric acid content 8.5% residual sugar content 0.4%) and adopt M through the absorption exchange
2: 8351
#Anionite-exchange resin (M-2 adsorbs exchange resin) with thin liquid ammonia (10%-20%) free residual sugar content 0.09% free liquid, transfer pH value 8.0 pressurizations 9.8 * 10 with thin liquid ammonia again
4Pa boils insulation taking-up in 10 minutes, adding 10g powder activated carbon decolouring after-filtration is removed residue 3g such as organic impurity and partial pigment, obtains clear liquid.Remove NH through Zeo-karb again
4 +Obtain the citric acid solution of citric acid content 18%850ml, get the pure citric acid solution 950ml of citric acid content 16%, residual sugar content 0.008% again through secondary decolourization, with its evaporation, concentrate, after the operations such as crystallization, drying, must reach Citric Acid, usp, Anhydrous Powder 146 grams of British Standard.Separation acquisition mother liquor citric acid content 15% 10ml altogether returns evaporative crystallization or adsorbs exchange, separation purification.Zeo-karb adopts H
3PO
4Regeneration is with the effusive waste liquid (NH of cationic exchange coloum
4)
3PO
4Can get (NH through concentrating
4)
3PO
4Crystallization is used for chemical fertilizer or industrial chemicals.
Embodiment 3:
Getting starchiness is the citric acid fermentation broth 1000ml (citric acid content 18%, residual sugar content 0.2%) of raw material, removes residue 5g after filtration, obtains clear liquid (citric acid content 16.0%, residual sugar content 0.19%), adopts M through the absorption exchange
3: 845
#Anionite-exchange resin (M-3 adsorbs exchange resin) back citric acid separates diluted alkaline NaOH with 4%-6% again frees and must free liquid by 1100ml with other impurity, residual sugar content is 0.1%), add diluted alkaline NaOH and transfer pH value 7.5 heated and boiled after 10 minutes under normal pressure, adding the 5g activated carbon decolours, cross residue 2g such as filtering organic impurity and pigment, get the 1000ml clear liquid.
1. get the 500ml clear liquid and remove Na through Zeo-karb
+Obtaining citric acid content through secondary decolourization again is 20%, and residual sugar content is that 0.01% pure citric acid solution 400ml is again through concentrating, making the Citric Acid, usp, Anhydrous Powder 75 that reaches British Standard after the operations such as crystallization, drying and restrain.The 5ml mother liquor that separates the citric acid content 15% that obtains returns evaporative crystallization or adsorbs exchange once more and reclaims to purify.Zeo-karb H
2SO
4Regeneration, the effusive Na of positive post
2SO
4Liquid becomes crystallization after concentrating, can make industrial chemicals.
2. get remaining 500ml clear liquid in addition, directly carry out secondary decolourization can obtain pure Trisodium Citrate 450ml again through concentrate, crystallization, drying can get 100g Trisodium Citrate finished product.The Trisodium Citrate mother liquor that separates acquisition returns evaporation concentration or adsorbs exchange once more and reclaims to purify.
Claims (4)
1. the method for a separating and purifying citric acid, this method comprise with citric acid fermentation broth filter, negatively charged ion absorption exchanges, free, positive post transition, decolouring, evaporation concentration, crystallization, separation, its raw material of drying step be thick starchiness or fermented glucose liquid, operation obtains directly going up anion column absorption exchange after the clear liquid after filtration, and used weakly-basic anion absorption exchange resin is a 0.8-1.0g/g over dry resin; Free in the operation that to adopt concentration be the NaOH of 4%-20% or the NH of 8%-30%
4OH carries out alkaline hydrolysis and takes off, and changes absorption exchange column internal pressure simultaneously and promptly is forced into 4.9 * 10
4Emptying to pressure is zero behind the Pa, and 2 to 3 times so repeatedly, adding dilute alkali in freeing liquid more afterwards and transferring pH value is 7.5-14, changes the pressure and temperature of freeing liquid simultaneously, and its method is: adopted the normal pressure heated and boiled 10-15 minute; Or employing reduces pressure 8.7 * 10
4The Pa heating under vacuum was boiled 10-15 minute; Or employing is pressurized to 4.9 * 10
4Pa-9.8 * 10
4Pa heats up 100 ℃-120 ℃ and boiled 10-15 minute; Or adopt the normal pressure heated and boiled to be chilled to the method for room temperature after 10-15 minute.
2. according to the method for the described separating and purifying citric acid of claim 1, it is characterized in that: the pH value of the described adjusting that adds dilute alkali is in the scope of 8-10.
3. method of producing Trisodium Citrate is characterized in that: in the described production methods of citric acid according to claim 1, save positive post this step that makes the transition after freeing with NaOH described free in the operation.
4. produce (NH for one kind
4)
2SO
4, (NH
4)
3PO
4, Na
2SO
4Or Na
3PO
4The method of byproduct is characterized in that: in the described production methods of citric acid according to claim 1, the positive column regeneration of positive post step transition wherein adopts H
2SO
4Or H
3PO
4And collect and free liquid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96109807A CN1060522C (en) | 1996-01-30 | 1996-09-17 | Process for separating and purifying citric acid |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96100738.9 | 1996-01-30 | ||
| CN96100738 | 1996-01-30 | ||
| CN96109807A CN1060522C (en) | 1996-01-30 | 1996-09-17 | Process for separating and purifying citric acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1156183A CN1156183A (en) | 1997-08-06 |
| CN1060522C true CN1060522C (en) | 2001-01-10 |
Family
ID=25743935
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96109807A Expired - Fee Related CN1060522C (en) | 1996-01-30 | 1996-09-17 | Process for separating and purifying citric acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1060522C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102850210A (en) * | 2012-09-21 | 2013-01-02 | 中粮生物化学（安徽）股份有限公司 | Method for purifying sodium citrate mother liquor |
| CN103058848B (en) * | 2012-11-01 | 2016-04-13 | 南京工业大学 | A kind of method intending homogeneous phase weak base anion-exchange resin separating organic acid |
| CN104557517B (en) * | 2014-12-19 | 2016-12-07 | 日照金禾博源生化有限公司 | A kind of useless sodium citrate mother liquor comprehensive processing technique |
| CN109053430A (en) * | 2018-08-30 | 2018-12-21 | 河北乐开节能科技股份有限公司 | A method of efficiently separating heteroacid in citric acid |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4851573A (en) * | 1986-12-18 | 1989-07-25 | Uop | Separation of citric acid from fermentation broth with a weakly basic anionic exchange resin adsorbent |
| US4924027A (en) * | 1986-12-18 | 1990-05-08 | Uop | Separation of salts of citric acid from fermentation broth with a weakly basic anionic exchange resin adsorbent |
| CN1090264A (en) * | 1992-10-07 | 1994-08-03 | 塞里斯塔控股有限公司 | The preparation method of alkali metal citrate |
| CN1105980A (en) * | 1994-11-04 | 1995-08-02 | 秦涛 | Method of extracting citric acid from citric acid fermentation liquor |
-
1996
- 1996-09-17 CN CN96109807A patent/CN1060522C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4851573A (en) * | 1986-12-18 | 1989-07-25 | Uop | Separation of citric acid from fermentation broth with a weakly basic anionic exchange resin adsorbent |
| US4924027A (en) * | 1986-12-18 | 1990-05-08 | Uop | Separation of salts of citric acid from fermentation broth with a weakly basic anionic exchange resin adsorbent |
| CN1090264A (en) * | 1992-10-07 | 1994-08-03 | 塞里斯塔控股有限公司 | The preparation method of alkali metal citrate |
| CN1105980A (en) * | 1994-11-04 | 1995-08-02 | 秦涛 | Method of extracting citric acid from citric acid fermentation liquor |
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| Publication number | Publication date |
|---|---|
| CN1156183A (en) | 1997-08-06 |
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