CN104262139A - Preparation method of sodium citrate crystal through solvent-out crystallization - Google Patents
Preparation method of sodium citrate crystal through solvent-out crystallization Download PDFInfo
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- CN104262139A CN104262139A CN201410429852.2A CN201410429852A CN104262139A CN 104262139 A CN104262139 A CN 104262139A CN 201410429852 A CN201410429852 A CN 201410429852A CN 104262139 A CN104262139 A CN 104262139A
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- sodium citrate
- citric acid
- mixed solution
- sodium
- trisodium citrate
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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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- 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
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
Abstract
The invention relates to a preparation method of sodium citrate crystal through solvent-out crystallization. The preparation method comprises the following steps: (A) carrying out salt-forming reactions: preparing critic acid and a salt forming agent according to a certain mole ratio, dissolving the salt forming agent into water at first, then slowly adding critic acid into the water, controlling the reaction temperature at a range of 20 to 30 DEG C, wherein the pH value of the solution is in a range of 7.5 to 9.0 when the reactions finish, and filtering the solution after the reactions so as to obtain a mixed solution, wherein the mixed solution concentration calculated by waterless sodium citrate is 285 g/L to 570 g/L; (B) carrying out solvent-out crystallization: adding a solvent-out agent into the mixed solution obtained in the step (A) according to a certain volume ratio to crystallize the sodium citrate crystals, and controlling the crystallization temperature at 20 to 75 DEG C; (C) filtering and drying so as to obtain the sodium citrate product; wherein the sodium citrate product comprises waterless sodium citrate, dihydrate sodium citrate, and pentahydrate sodium citrate. The provided preparation method is simple and convenient, the yield is high, the crystal is large, the purity is high, and the sodium citrate quality is largely improved.
Description
Technical field
The present invention relates to a kind of industrial production process of Trisodium Citrate, especially a kind of solventing-out process prepares the method for Trisodium Citrate.
Background technology
Trisodium Citrate is that a kind of outward appearance is in white or colourless organic compound crystal, be widely used in food, beverage, chemical industry and medicine and other fields, can be used as the seasonings in food, buffer reagent, emulsifying agent and stablizer etc., also can be used as the acidity buffer reagent etc. of the blood anticoagulant in medicine, body fluid and urine, the production of current Trisodium Citrate is employing calcium citrate salts neutralisation, ion-exchange is sent and prepared Trisodium Citrate, obtains Trisodium Citrate finished product after then being purified by gained Trisodium Citrate.
Existing industry is prepared Trisodium Citrate and is generally adopted evaporation concentration mother liquor crystallization method, namely the concentrated sodium citrate mother liquor of heating makes its crystallize out, this method need evaporate large water gaging, there is energy consumption high, inefficient problem, and the material containing the easy carbonization of metal ion, a small amount of protein colloid and the organic impuritys etc. such as higher iron in sodium citrate mother liquor, these impurity are along with being heated and water loss, easily remain in the product, make the darkening of sodium citrate mother liquor, viscosity becomes large, and then affect the quality of gained Trisodium Citrate product.How effectively to remove the impurity in Trisodium Citrate, the crystalline quality improving product becomes the current technical issues that need to address.
Summary of the invention
The technical issues that need to address of the present invention are to provide a kind of method that solventing-out process prepares Trisodium Citrate crystal, to substitute existing evaporation concentration mother liquor crystallization method, have that product purity is high, production efficiency is high, production energy consumption is low, the feature of environment-friendly and green.
For solving the problems of the technologies described above, the technical solution used in the present invention is:
Dilution crystallization prepares a method for Trisodium Citrate crystal, comprises the following steps,
A) salt-forming reaction, get citric acid and salt forming agent in molar ratio, first salt forming agent is dissolved in the water, slowly add citric acid again, the mol ratio of citric acid and salt forming agent is 1:3 ~ 1:3.5, control temperature of reaction at 20 DEG C ~ 30 DEG C, reaction end pH is between 7.5 ~ 9.0, carries out filtering to obtain mixed solution after reaction; The concentration range of described mixed solution counts 285g/L ~ 570g/L with Citric Acid, usp, Anhydrous Powder sodium; Described salt forming agent is one or more in sodium hydroxide, sodium carbonate, sodium bicarbonate;
B) dilution crystallization, toward steps A) mixed solution in add dissolved agent by volume and make Trisodium Citrate crystallization, the volume ratio of mixed solution and dissolved agent is 1:3 ~ 1:5, crystallization control temperature is 20 DEG C ~ 75 DEG C, and described dissolved agent is one or more in acetone, methyl alcohol, ethanol, propyl alcohol, Virahol, ethylene glycol, Diethylene Glycol, propylene glycol, glycerol;
C) filtration drying, obtains Trisodium Citrate product, and described Trisodium Citrate is one or more in Citric Acid, usp, Anhydrous Powder sodium, Sodium Citrate, usp, Dihydrate Powder and five water citric acid sodium.
Further improvement of the present invention is: described steps A) in, the mol ratio of citric acid and salt forming agent is 1:3 ~ 1:3.15.
Further improvement of the present invention is: described step B) in, the volume ratio of mixed solution and dissolved agent is 1:3 ~ 1:3.5.
Owing to have employed technique scheme, the technical progress acquired by the present invention is:
The present invention adopts organic solvent solventing-out process to prepare Trisodium Citrate, the Trisodium Citrate crystal prepared is comparatively pure, whole preparation process has the following advantages: one is that this preparation method is comparatively gentle, the heat utilizing citric acid and alkali reaction to generate makes the autologous intensification of reaction solution, simultaneously can crystallize out at a lower temperature, reduce the energy waste of preparation process; Two is that this preparation method more can remove impurity, impurity also can be avoided to be heated and side reaction occurs, ensure that the purity of product; Three is that organic solvent used is three kind solvents, and boiling point is low, is easy to recycling, environmental protection.Therefore, the Trisodium Citrate crystal yield that the method for the invention obtains is high, crystal grain is homogeneous, and crystal purity is high, substantially increases the quality of Trisodium Citrate, simultaneously, preparation method's energy consumption of the present invention is low, pollutes little, compared with evaporating crystallization method with tradition, be more suitable for industrial applications, there is higher economic benefit and social benefit.
The pH value of reaction end mixed solution is preferably between 7.5 ~ 9.0, mixed solution is made to be alkalescence, the positively charged ions such as the iron ion under alkaline condition in mixed solution can change salt into hydroxide radical, carbonate etc. and precipitate, be beneficial to remove metal ion, metal ion is avoided to be wrapped in crystal, the alkali simultaneously added or salt, also can make the protein colloidal impurity sex change sedimentation in mixed solution.
The concentration range of mixed solution is preferably 285g/L-570g/L in Citric Acid, usp, Anhydrous Powder sodium, which ensure that Trisodium Citrate mixed solution subsequent processes can be carried out smoothly, if concentration is too low, then can use a large amount of dissolved agent in follow-up dilution crystallization process, both add production cost, too increase the risk of environmental pollution; If concentration is too high, then can be too sticky due to Trisodium Citrate mixed solution, being unfavorable for formation and the growth of crystal in follow-up dilution crystallization process, making to produce a large amount of nucleus when adding dissolved agent in mixed solution, cause the crystal grain preparing crystal too small, be unfavorable for subsequent disposal.
Control dilution crystallization temperature, the Trisodium Citrate containing different crystal water can be obtained.Utilize Trisodium Citrate at different temperatures crystallize out time the crystal water number that combines be different, when dropping dissolved agent temperature is lower than obtaining five water citric acid sodium when 50 DEG C, when temperature is higher than 50 DEG C, obtain Sodium Citrate, usp, Dihydrate Powder; Five water citric acid sodium lose three crystal water and become Sodium Citrate, usp, Dihydrate Powder 100 DEG C time, and Sodium Citrate, usp, Dihydrate Powder loses crystal water and obtains Citric Acid, usp, Anhydrous Powder sodium 150 DEG C time.
Simultaneously in dilution crystallization process, the organic impurity etc. in Trisodium Citrate mixed solution can be dissolved in dissolved agent, and then is removed from Trisodium Citrate by these impurity, makes the Trisodium Citrate crystal prepared comparatively pure; The dissolved agent such as alcohols are also beneficial to the sedimentation of protein colloidal impurity.
Embodiment
Embodiment is for further describing the present invention below, but does not limit the present invention in any form.
Embodiment 1
Get sodium hydroxide 9mol(0.36kg) add in reactor, then add 1.5L water, stir and sodium hydroxide is dissolved; Citric Acid, usp, Anhydrous Powder 3mol(0.576kg is slowly added at 20 DEG C), stirring reaction is stablized constant to pH8.7.Drip 4.5L ethanol at 20 DEG C, drip rear filtration, naturally dry.Obtain five water citric acid sodium 1.14kg.Yield 98.96%, content 99.74%.
Embodiment 2
Get sodium hydroxide 11.5mol(0.46kg) and sodium carbonate 20mol(2.12kg) add in reactor, then add 5L water, be stirred to dissolve.Citric Acid, usp, Anhydrous Powder 10mol(1.92kg is slowly added at 25 DEG C), stirring reaction is stablized constant to pH8.5.Drip 20L methyl alcohol at 55 DEG C, drip rear filtration, naturally dry.Obtain Sodium Citrate, usp, Dihydrate Powder 3.23kg.Yield 97.93%, content 99.66%.
Embodiment 3
Get sodium carbonate 35mol(3.71kg) add in reactor, then add 10L water, be stirred to dissolve.Citric Acid, usp, Anhydrous Powder 10mol(1.92kg is slowly added at 25 DEG C), stirring reaction is stablized constant to pH9.0.Drip 35L Virahol at 55 DEG C, drip rear filtration, 150 DEG C of dryings.Obtain Citric Acid, usp, Anhydrous Powder sodium 2.87kg.Yield 97.48%, content 99.65%.
Embodiment 4
Get sodium hydroxide 200mol(8kg) and sodium carbonate 100mol(10.6kg) mixture, add water 50L, is stirred to dissolve.Citric Acid, usp, Anhydrous Powder 100mol(19.2kg is slowly added under room temperature), stirring reaction is stablized constant to pH9.0.Drip 250L acetone at 75 DEG C, drip rear filtration, 150 DEG C of dryings.Obtain Citric Acid, usp, Anhydrous Powder sodium 28.78kg.Yield 97.85%, content 99.59%.
Although the present invention only lists the concrete material of above-mentioned 4 embodiments and proportioning mole number and volume, but preparation method of the present invention can on the basis of above-described embodiment, the ratio between raw material involved in the present invention and raw material is utilized to expand further and revise, particularly feed ratio is done and expand further and the suitability for industrialized production of carrying out, all can reach object of the present invention.
Claims (3)
1. dilution crystallization prepares a method for Trisodium Citrate crystal, it is characterized in that: comprise the following steps,
A) salt-forming reaction, get citric acid and salt forming agent in molar ratio, first salt forming agent is dissolved in the water, slowly add citric acid again, the mol ratio of citric acid and salt forming agent is 1:3 ~ 1:3.5, control temperature of reaction at 20 DEG C ~ 30 DEG C, reaction end pH is between 7.5 ~ 9.0, carries out filtering to obtain mixed solution after reaction; The concentration range of described mixed solution counts 285g/L ~ 570g/L with Citric Acid, usp, Anhydrous Powder sodium; Described salt forming agent is one or more in sodium hydroxide, sodium carbonate, sodium bicarbonate;
B) dilution crystallization, toward steps A) mixed solution in add dissolved agent by volume and make Trisodium Citrate crystallization, the volume ratio of mixed solution and dissolved agent is 1:3 ~ 1:5, crystallization control temperature is 20 DEG C ~ 75 DEG C, and described dissolved agent is one or more in acetone, methyl alcohol, ethanol, propyl alcohol, Virahol, ethylene glycol, Diethylene Glycol, propylene glycol, glycerol;
C) filtration step B) in the crystal of separating out, drying obtains Trisodium Citrate product, and described Trisodium Citrate product is one or more in Citric Acid, usp, Anhydrous Powder sodium, Sodium Citrate, usp, Dihydrate Powder, five water citric acid sodium.
2. a kind of dilution crystallization according to claim 1 prepares the method for Trisodium Citrate crystal, it is characterized in that, described steps A) in, the mol ratio of citric acid and salt forming agent is 1:3 ~ 1:3.15.
3. a kind of dilution crystallization according to claim 1 prepares the method for Trisodium Citrate crystal, it is characterized in that, described step B) in, the volume ratio of mixed solution and dissolved agent is 1:3 ~ 1:3.5.
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| CN201410429852.2A CN104262139B (en) | 2014-08-28 | 2014-08-28 | A kind of dilution crystallization is prepared the method for natrium citricum crystal |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106831402A (en) * | 2016-12-24 | 2017-06-13 | 句容亿格纳米材料厂 | A kind of process for purification of sodium citrate |
| CN106904637A (en) * | 2017-03-14 | 2017-06-30 | 苏州博洋化学股份有限公司 | A kind of high activity potassium hydroxide purifying technique |
| CN107963614A (en) * | 2016-10-20 | 2018-04-27 | 王亚玲 | A kind of quick method for preparing high-purity thiosulfuric acid sodium crystal |
| CN108794323A (en) * | 2018-05-23 | 2018-11-13 | 连云港树人科创食品添加剂有限公司 | A kind of preparation method of sodium citrate |
| CN109438225A (en) * | 2018-11-21 | 2019-03-08 | 大自然生物集团有限公司 | A kind of preparation method of bulky grain anhydrous citric acid sodium |
| CN114773182A (en) * | 2022-03-29 | 2022-07-22 | 南京化学试剂股份有限公司 | Synthetic method of medicinal sodium citrate |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1072169A (en) * | 1992-08-08 | 1993-05-19 | 湖南省宁乡石油化工总厂 | New technology for preparing sodium citrate |
| EP0747340A1 (en) * | 1995-06-06 | 1996-12-11 | Jungbunzlauer Ges.m.b.H. | Anhydrous trisodiumcitrate, process for its preparation and its use as carriers |
| CN101407454A (en) * | 2007-10-13 | 2009-04-15 | 黄石兴华生化有限公司 | Process for preparing citrate salt from mother liquor for citric acid production |
| JP4796494B2 (en) * | 2004-06-25 | 2011-10-19 | 協和発酵バイオ株式会社 | L-ornithine citrate crystals |
| CN103787870A (en) * | 2014-01-09 | 2014-05-14 | 日照鲁信金禾生化有限公司 | Method for removing readily carbonizable substances out of sodium citrate |
-
2014
- 2014-08-28 CN CN201410429852.2A patent/CN104262139B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1072169A (en) * | 1992-08-08 | 1993-05-19 | 湖南省宁乡石油化工总厂 | New technology for preparing sodium citrate |
| EP0747340A1 (en) * | 1995-06-06 | 1996-12-11 | Jungbunzlauer Ges.m.b.H. | Anhydrous trisodiumcitrate, process for its preparation and its use as carriers |
| JP4796494B2 (en) * | 2004-06-25 | 2011-10-19 | 協和発酵バイオ株式会社 | L-ornithine citrate crystals |
| CN101407454A (en) * | 2007-10-13 | 2009-04-15 | 黄石兴华生化有限公司 | Process for preparing citrate salt from mother liquor for citric acid production |
| CN103787870A (en) * | 2014-01-09 | 2014-05-14 | 日照鲁信金禾生化有限公司 | Method for removing readily carbonizable substances out of sodium citrate |
Non-Patent Citations (3)
| Title |
|---|
| 周勇: "柠檬酸(钠)清洁生产工艺的研究", 《国优秀硕士学位论文全文数据库电子期刊工程Ⅰ辑》, 27 November 2009 (2009-11-27), pages 25 - 26 * |
| 赵君民等: "柠檬酸钠生产新工艺研究", 《西北大学学报自然科学版》, vol. 28, no. 1, 25 February 1998 (1998-02-25) * |
| 赵君民等: "柠檬酸钠生产新工艺研究", 《西北大学学报自然科学版》, vol. 28, no. 1, 25 February 1998 (1998-02-25), pages 48 - 50 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107963614A (en) * | 2016-10-20 | 2018-04-27 | 王亚玲 | A kind of quick method for preparing high-purity thiosulfuric acid sodium crystal |
| CN106831402A (en) * | 2016-12-24 | 2017-06-13 | 句容亿格纳米材料厂 | A kind of process for purification of sodium citrate |
| CN106904637A (en) * | 2017-03-14 | 2017-06-30 | 苏州博洋化学股份有限公司 | A kind of high activity potassium hydroxide purifying technique |
| CN108794323A (en) * | 2018-05-23 | 2018-11-13 | 连云港树人科创食品添加剂有限公司 | A kind of preparation method of sodium citrate |
| CN109438225A (en) * | 2018-11-21 | 2019-03-08 | 大自然生物集团有限公司 | A kind of preparation method of bulky grain anhydrous citric acid sodium |
| CN114773182A (en) * | 2022-03-29 | 2022-07-22 | 南京化学试剂股份有限公司 | Synthetic method of medicinal sodium citrate |
| CN114773182B (en) * | 2022-03-29 | 2023-02-03 | 南京化学试剂股份有限公司 | Synthetic method of medicinal-grade sodium citrate |
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