CN114405059B - Extraction solvent organic phase for purifying citric acid and method for extracting and separating citric acid - Google Patents
Extraction solvent organic phase for purifying citric acid and method for extracting and separating citric acid Download PDFInfo
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- CN114405059B CN114405059B CN202210077497.1A CN202210077497A CN114405059B CN 114405059 B CN114405059 B CN 114405059B CN 202210077497 A CN202210077497 A CN 202210077497A CN 114405059 B CN114405059 B CN 114405059B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D11/04—Solvent extraction of solutions which are liquid
- B01D11/0492—Applications, solvents used
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- C—CHEMISTRY; METALLURGY
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- 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
- C07C51/48—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D2011/002—Counter-current extraction
Abstract
The invention discloses an extraction solvent organic phase for purifying citric acid and a method for extracting and separating citric acid, wherein the extraction solvent organic phase comprises the following raw materials: the method for extracting and separating the citric acid comprises the following steps: and (3) extraction: carrying out countercurrent extraction on an extraction solvent organic phase for extracting and separating citric acid and a citric acid fermentation liquor to obtain a citric acid loaded organic phase; back extraction: mixing the loaded citric acid organic phase with a stripping agent to obtain an extraction solvent organic phase and a citric acid stripping solution for extracting and separating citric acid; regeneration: washing the organic phase of the extraction solvent after back extraction to obtain a recycled organic phase of the extraction solvent, and decoloring, concentrating and crystallizing the citric acid back extraction solution to obtain a citric acid solid product. The method overcomes the defects in the prior art, is simple and effective in extraction method, and can realize environment-friendly separation and purification of citric acid.
Description
Technical Field
The invention relates to the technical field of citric acid extraction and separation, in particular to an extraction solvent organic phase for purifying citric acid and a method for extracting and separating citric acid.
Background
Citric acid is the first major acid in organic acids, and is the most important organic acid widely used in food, medicine, daily chemical and other industries due to physical properties, chemical properties and derivative properties. And China is the biggest country for producing citric acid products and export countries all over the world. Although the fermentation method in China makes great progress, the method still has a large gap compared with the foreign advanced level, in particular to the aspect of extraction and refining process. Therefore, the technical level of citric acid production in China is improved, the production targets of low consumption, low cost, high efficiency and low pollution are realized, a competitive and more economic production system is established, and the method has extremely important significance on the survival and development of the citric acid industry. After the upstream citric acid fermentation is completed, the downstream separation and purification of citric acid from the fermentation liquor is an important step of the whole production process. The method for separating and purifying citric acid from fermentation liquor at home and abroad mainly comprises a calcium salt method, an ion exchange adsorption method, a liquid membrane separation method, an electrodialysis method and a solvent extraction method.
The calcium salt method has long development time, mature process conditions, easily obtained raw materials and high stability of citric acid products, and is a traditional method for extracting citric acid. However, serious problems exist, such as complex process flow, low total yield of citric acid, the total yield of domestic manufacturers mostly below 75%, hardly reaching 80%, high raw material consumption, high labor intensity, large amount of waste water and waste residue generated in the extraction process, serious influence on environment and the like, and are gradually not suitable for the requirement of clean production.
Compared with a calcium salt extraction method, the ion exchange method for extracting the citric acid has the advantages of simple process operation, lower production cost, no generation of wastes such as calcium sulfate and the like, labor intensity reduction and total yield of the citric acid reaching more than 85 percent. However, the regeneration of the resin can generate a large amount of waste liquid, and meanwhile, the service life of the resin is limited, and the cost of the resin used for industrial production is high, so that the research on the high-performance long-service-life resin capable of being regenerated and recycled for reducing the cost becomes a key technology for popularizing the ion exchange method for extracting the citric acid for industrial production practice.
The liquid membrane method for extracting the citric acid has the advantages of high mass transfer rate, repeated utilization of the organic membrane phase after regeneration and low production cost. However, the preparation process of the liquid film is complicated, the stability is poor, the leakage problem is easy to occur, and meanwhile, the surfactant and the extracting agent for preparing the liquid film have certain toxicity, so that the liquid film can not be used in food and medical industries, and the liquid film with high stability can be prepared through research and used for industrial production of citric acid.
The solvent extraction method mainly utilizes the difference of the solubility of the separated components and other impurities in an extraction system for separation, extracts citric acid into an organic phase through an extraction process, and transfers the citric acid in the organic phase to a water phase through a back extraction process. The back extraction solution is decolorized, concentrated and crystallized to obtain a citric acid solid product, a citric acid extraction system generally comprises three parts of a main complexing agent, a phase regulator and a diluent, and the complexing agent generally comprises alcohols, phosphorus oxygen compounds, organic amines and the like. The phase regulator in the extraction system is selected from high-carbon alcohol, aromatic hydrocarbon, etc. The research on reaction balance and complex structure in the extraction process has a guiding effect on citric acid extraction. The solvent extraction method has good separation effect and can be continuously operated, and meanwhile, the extractant can be recycled for the extraction process after being regenerated, so that the production operation cost is reduced, no waste acid or waste is generated, and the ecological stability is facilitated.
Disclosure of Invention
The invention aims to provide an organic phase of an extraction solvent for purifying citric acid and a method for extracting and separating citric acid, overcomes the defects in the prior art, is simple and effective in extraction method, and can realize environment-friendly separation and purification of citric acid.
In order to achieve the purpose, the invention provides an extraction solvent organic phase for purifying citric acid, which comprises the following raw materials:
an extractant, a diluent and a phase modifier.
Preferably, the extractant is a neutral extractant or a mixture of an alkaline extractant and a neutral extractant.
Preferably, the neutral extractant is a neutral amine extractant or an amide extractant.
Preferably, the neutral amine extractant is one or more of tri-N-octylamine, dodecyl primary amine, hexadecyl primary amine, octadecyl primary amine, N-dodecyl tetradecylamine, N-hexadecyl octadecylamine, dioctadecyl amine, N-dimethyl dodecylamine and N, N-dimethyl octadecylamine.
Preferably, the amide extractant is N, N-di-N-octylbutanamide, N-didodecyl propionamide, N-dihexadecyl acetamide, N-dioctadecyl formamide, N-dodecyl (tetradecyl) acetamide, N, one or more of N-hexadecyl (octadecyl) formamide, N-dioctadecylpropionamide, N-dimethyloctanamide, N-diethyloctanamide and di-N-octylpropionamide.
Preferably, the diluent is one or more of toluene, n-octanol, sec-octanol, methyl isobutyl ketone, isoamyl ether, n-hexyl ether, cyclohexane, isooctane and dodecane, and the diluent has the function of dissolving an extract compound and can also greatly improve the back extraction efficiency.
Preferably, the phase modifier is one or more of n-octanol, isooctanol, sec-octanol, isomeric nonanol, and n-decanol.
Preferably, the neutral amine extractant: the diluent is less than or equal to 1.
A method for extracting and separating citric acid comprises the following steps:
s1, mixing an extracting agent and a diluent to obtain a mixed solution, wherein the volume ratio of the mixed solution to a phase regulator is 100: (8-10) adding a phase regulator to obtain an extraction solvent of the citric acid;
s2, extraction: carrying out countercurrent extraction on an extraction solvent organic phase for extracting and separating citric acid and a citric acid fermentation broth, mixing, heating, stirring, standing and layering to obtain a citric acid loaded organic phase, wherein the volume ratio of the extraction solvent to the citric acid fermentation broth is (2-4): 1;
s3, back extraction: mixing the loaded citric acid organic phase with a stripping agent in a volume ratio of (3-4) to 1, heating, stirring, standing and layering to obtain an extraction solvent organic phase and a citric acid stripping solution for extracting and separating citric acid;
s4, regeneration: washing the organic phase of the extraction solvent after back extraction to obtain a recycled organic phase of the extraction solvent, and decoloring, concentrating and crystallizing the citric acid back extraction solution to obtain a citric acid solid product.
Preferably, the stripping agent is water, and the extraction solvent is a mixture of an extracting agent, a diluent and a phase regulator.
Therefore, the extraction solvent for purifying citric acid and the method for extracting and separating citric acid have the following beneficial effects:
(1) The separation efficiency is high, and the residual concentration of citric acid in the stock solution after extraction and separation is below 1 percent;
(2) The selectivity is strong, only citric acid and substances with the same polarity are adsorbed, and other substances are not adsorbed;
(3) The production cost is low, and other raw and auxiliary materials are not required to be consumed because the extraction separation is carried out under normal pressure;
(4) The separation selectivity is high, the product quality is stable, and the product quality index reaches and partially exceeds the level of international like products;
(5) The method has the advantages of continuous operation, low cost, high quality, environmental friendliness and huge application prospect and potential, and the regenerated organic phase of the extraction solvent can be recycled for the extraction process, so that the production operation cost is reduced, three wastes such as high-concentration organic wastewater, waste acid and waste alkali are not generated, and the method has good environmental benefit.
The technical solution of the present invention is further described in detail by the following examples.
Detailed Description
The technical solution of the present invention is further illustrated by the following examples.
Example 1
A method for extracting and separating citric acid comprises the following steps:
(1) Preparation of an organic phase of an extraction solvent: mixing N, N-dimethyl octadecylamine and dodecane according to a volume ratio of 3:7 to prepare an extraction solvent, and adding N-octanol into the mixture according to a volume ratio of 100.
(2) And (3) extraction: mixing the prepared organic phase of the extraction solvent with the citric acid feed solution according to the volume ratio of 3:1, stirring for 5min at 40 ℃, and standing for layering; the primary extraction rate of the citric acid is 57 percent, and the concentration of the citric acid in the extraction raffinate is detected to be 0.86g/L and the countercurrent extraction rate is 99.3 percent through countercurrent extraction;
(3) Back extraction: mixing the loaded citric acid organic phase with water according to the volume ratio of 3:1, stirring for 5min at 80 ℃, and standing for layering; the detection shows that the first back extraction rate is 86.50 percent, and the counter-extraction solution concentration is 116g/L and the yield is 99.95 percent through counter-current back extraction.
Example 2
A method for extracting and separating citric acid comprises the following steps:
(1) Preparation of an organic phase of an extraction solvent: mixing N, N-di-N-octylbutanamide with 4:6 in volume ratio with cyclohexane to prepare an extraction solvent, and adding N-decanol according to the volume ratio of 100.
(2) Extraction: mixing the prepared extracting agent with a citric acid material solution according to the volume ratio of 2:1, stirring for 5min at 40 ℃, standing for layering, and detecting to obtain the citric acid primary extraction rate of 67%; through countercurrent extraction, the concentration of the citric acid in the raffinate is detected to be 0.52g/L, and the countercurrent extraction rate is 99.7 percent.
(3) Back extraction: mixing the loaded citric acid organic phase and water according to a volume ratio of 3:1, stirring for 5min at 80 ℃, standing for layering, and detecting the once back extraction rate of 84.63%; through counter-current back extraction, the concentration of the back extraction solution is 120g/L, and the yield is 99.93%.
Example 3
A method for extracting and separating citric acid comprises the following steps:
(1) Preparation of an organic phase of an extraction solvent: mixing N-dodecyl tetradecylamine and methyl isobutyl ketone according to a volume ratio of 4:6 to prepare an extraction solvent, and adding sec-octanol into the mixture according to a volume ratio of 100.
(2) And (3) extraction: mixing the prepared extractant organic phase with citric acid feed liquid according to the volume ratio of 2:1, stirring for 5min at 40 ℃, standing for layering, and detecting to obtain the citric acid primary extraction rate of 49%; through countercurrent extraction, the concentration of the citric acid in the raffinate is detected to be 0.92g/L, and the countercurrent extraction rate is 99.3 percent.
(3) Back extraction: mixing the loaded citric acid organic phase and water according to a volume ratio of 4:1, stirring for 5min at 80 ℃, standing for layering, and detecting the once back extraction rate of 78.63%; through counter-current back extraction, the concentration of the back extraction solution is 120g/L, and the yield is 99.92%.
Therefore, the extraction solvent organic phase for purifying the citric acid and the method for extracting and separating the citric acid are adopted, the defects in the prior art are overcome, the extraction method is simple and effective, and the environment-friendly separation and purification of the citric acid can be realized.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting the same, and although the present invention is described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that: modifications and equivalents may be made to the invention without departing from the spirit and scope of the invention.
Claims (5)
1. An extraction solvent organic phase for purifying citric acid is characterized by comprising the following raw materials:
an extractant, diluent, and phase modifier;
the extraction agent is N, N-dimethyl octadecyl amine, the diluent is dodecane, and the phase regulator is N-octanol;
mixing the N, N-dimethyl octadecylamine and the dodecane according to a volume ratio of 3:7 to prepare an extraction solvent, and mixing the extraction solvent and the N-octanol according to a volume ratio of 100.
2. An extraction solvent organic phase for purifying citric acid is characterized by comprising the following raw materials:
an extractant, diluent, and phase modifier;
the extracting agent is N, N-di-N-octyl butyramide, the diluent is cyclohexane, and the phase regulator is N-decanol;
mixing the N, N-di-N-octylbutanamide with the cyclohexane according to a volume ratio of 4:6 to prepare an extraction solvent, and mixing the extraction solvent with the N-decanol according to a volume ratio of 100.
3. The method for extracting and separating citric acid by the organic phase of the extraction solvent according to claim 1, which comprises the following steps:
s1, preparing an organic phase of an extraction solvent: mixing N, N-dimethyl octadecylamine and dodecane according to a volume ratio of 3:7 to prepare an extraction solvent, and adding N-octanol into the extraction solvent according to a volume ratio of 100;
s2, extraction: mixing the prepared organic phase of the extraction solvent with the citric acid feed solution according to the volume ratio of 3:1, stirring for 5min at 40 ℃, and standing for layering;
s3, back extraction: mixing the loaded citric acid organic phase with water according to the volume ratio of 3:1, stirring for 5min at 80 ℃, and standing for layering.
4. The method for extracting and separating citric acid by the organic phase of the extraction solvent according to claim 2, which comprises the following steps:
s1, preparing an organic phase of an extraction solvent: mixing N, N-di-N-octylbutanamide with 4:6 in volume ratio with cyclohexane to prepare an extraction solvent, and adding N-decanol according to the volume ratio of 100;
s2, extraction: mixing the prepared organic phase of the extraction solvent with the citric acid feed solution according to the volume ratio of 2:1, stirring for 5min at 40 ℃, and standing for layering;
s3, back extraction: mixing the loaded citric acid organic phase with water according to the volume ratio of 3:1, stirring for 5min at 80 ℃, and standing for layering.
5. The method for extracting and separating citric acid according to claim 4, wherein: the water is a stripping agent.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4275234A (en) * | 1972-06-19 | 1981-06-23 | Imi (Tami) Institute For Research And Development | Recovery of acids from aqueous solutions |
| CN1356923A (en) * | 1999-04-29 | 2002-07-03 | Dsm生物技术股份有限公司 | Method for separating organic substances from aqueous mixture |
| WO2005087692A2 (en) * | 2004-02-27 | 2005-09-22 | Dow Global Technologies Inc. | Process for recovering organic compounds from aqueous streams containing same |
| CN106146549A (en) * | 2015-04-02 | 2016-11-23 | 中国科学院宁波材料技术与工程研究所 | Bio-based alkylthio phosphoric acid or derivatives thereof, its preparation method and application |
| CN107050924A (en) * | 2017-05-16 | 2017-08-18 | 郑州天萃取科技有限公司 | The method that citric acid is extracted using centrifugal extractor |
| US9969676B1 (en) * | 2017-06-28 | 2018-05-15 | Vitaworks Ip, Llc | Process for the separation of long chain amino acids and dibasic acids |
-
2022
- 2022-01-24 CN CN202210077497.1A patent/CN114405059B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4275234A (en) * | 1972-06-19 | 1981-06-23 | Imi (Tami) Institute For Research And Development | Recovery of acids from aqueous solutions |
| CN1356923A (en) * | 1999-04-29 | 2002-07-03 | Dsm生物技术股份有限公司 | Method for separating organic substances from aqueous mixture |
| WO2005087692A2 (en) * | 2004-02-27 | 2005-09-22 | Dow Global Technologies Inc. | Process for recovering organic compounds from aqueous streams containing same |
| CN106146549A (en) * | 2015-04-02 | 2016-11-23 | 中国科学院宁波材料技术与工程研究所 | Bio-based alkylthio phosphoric acid or derivatives thereof, its preparation method and application |
| CN107050924A (en) * | 2017-05-16 | 2017-08-18 | 郑州天萃取科技有限公司 | The method that citric acid is extracted using centrifugal extractor |
| US9969676B1 (en) * | 2017-06-28 | 2018-05-15 | Vitaworks Ip, Llc | Process for the separation of long chain amino acids and dibasic acids |
Non-Patent Citations (2)
| Title |
|---|
| 伊敏,彭启秀,陈定芳,彭立娥,张茂良,温瑞媛,牟西茹,王文清.N,N二烷基取代酰胺萃取食用柠檬酸及其机理.北京大学学报(自然科学版).1987,(第04期),全文. * |
| 朱萍,古国榜.溶剂萃取从酸性溶液中回收钯.贵金属.2003,(第04期),全文. * |
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