CN104262139B - A kind of dilution crystallization is prepared the method for natrium citricum crystal - Google Patents
A kind of dilution crystallization is prepared the method for natrium citricum crystal Download PDFInfo
- Publication number
- CN104262139B CN104262139B CN201410429852.2A CN201410429852A CN104262139B CN 104262139 B CN104262139 B CN 104262139B CN 201410429852 A CN201410429852 A CN 201410429852A CN 104262139 B CN104262139 B CN 104262139B
- Authority
- CN
- China
- Prior art keywords
- natrium citricum
- citric acid
- crystallization
- mixed liquor
- sodium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of dilution crystallization preparation method of natrium citricum, comprise the following steps, A) salt-forming reaction, get in molar ratio citric acid and salt forming agent, first salt forming agent is dissolved in the water, more slowly adds citric acid, control reaction temperature at 20 DEG C ~ 30 DEG C, reaction end pH is between 7.5 ~ 9.0, filters to obtain mixed liquor after reaction; The concentration range of described mixed liquor is counted 285g/L-570g/L with anhydrous citric acid sodium; B) dilution crystallization, toward steps A) mixed liquor in add by volume dissolved agent to make natrium citricum crystallization, crystallization control temperature is 20 DEG C ~ 75 DEG C; C) filtration drying, obtains natrium citricum product, and described natrium citricum comprises anhydrous citric acid sodium, Sodium Citrate, usp, Dihydrate Powder and five water citric acid sodium. Preparation method of the present invention is simple and convenient, and the natrium citricum crystal yield making is high, and crystal grain is large, and crystal purity is high, has greatly improved the quality of natrium citricum.
Description
Technical field
The present invention relates to a kind of industrial production process of natrium citricum, especially a kind of dilution crystallization legal system is for the method for natrium citricum.
Background technology
Natrium citricum is that a kind of outward appearance is white in color or colourless organic compound crystal, be widely used in food, beverage, chemical industry and medicine and other fields, can be used as flavor enhancement, buffer, emulsifying agent and stabilizing agent etc. in food, also can be used as the acidity buffer of blood anticoagulant, body fluid and urine in medicine etc., the production of natrium citricum is at present to adopt calcium citrate salts neutralisation, ion-exchange to send and prepare natrium citricum, after then gained natrium citricum being purified, obtains natrium citricum finished product.
Existing industry is prepared natrium citricum and is generally adopted evaporation and concentration mother liquor crystallization method, the concentrated natrium citricum mother liquor of i.e. heating makes its crystallize out, this method need be evaporated large water gaging, exist energy consumption high, inefficient problem, and in natrium citricum mother liquor, contain the easily material of carbonization such as the metal ions such as higher iron, a small amount of protide colloid and organic impurities etc., these impurity are along with being heated and water loss, easily remain in product, make the darkening of natrium citricum mother liquor, viscosity become large, and then affect the quality of gained natrium citricum product. How effectively to remove the impurity in natrium citricum, the crystalline quality that improves 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 the method for a kind of dilution crystallization legal system for natrium citricum crystal, to substitute existing evaporation and concentration mother liquor crystallization method, have that product purity is high, production efficiency is high, 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 is prepared a method for natrium citricum crystal, comprises the following steps,
A) salt-forming reaction, get in molar ratio citric acid and salt forming agent, first salt forming agent is dissolved in the water, slowly add again citric acid, the mol ratio of citric acid and salt forming agent is 1:3 ~ 1:3.5, control reaction temperature at 20 DEG C ~ 30 DEG C, reaction end pH is between 7.5 ~ 9.0, filters to obtain mixed liquor after reaction; The concentration range of described mixed liquor is counted 285g/L ~ 570g/L with anhydrous citric acid sodium; Described salt forming agent is one or more in NaOH, sodium carbonate, sodium acid carbonate;
B) dilution crystallization, toward steps A) mixed liquor in add by volume dissolved agent to make natrium citricum crystallization, the volume ratio of mixed liquor 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, isopropyl alcohol, ethylene glycol, diethylene glycol, propane diols, glycerine;
C) filtration drying, obtains natrium citricum product, and described natrium citricum is one or more in anhydrous citric acid 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 liquor and dissolved agent is 1:3 ~ 1:3.5.
Owing to having adopted technique scheme, the obtained technological progress of the present invention is:
The present invention adopts organic solvent dilution crystallization legal system for natrium citricum, the natrium citricum crystal of preparing is comparatively pure, whole preparation process has the following advantages: the one, and this preparation method is comparatively gentle, the heat that utilizes citric acid and alkali reaction to generate makes the autologous intensification of reactant liquor, while crystallize out at a lower temperature, the energy loss of reduction preparation process; The 2nd, this preparation method can more remove impurity, also can avoid impurity be heated and side reaction occurs, and has ensured the purity of product; The 3rd, organic solvent used is three kind solvents, and boiling point is low, is easy to recycling, environmental protection. Therefore, the natrium citricum crystal yield that the method for the invention makes is high, crystal grain homogeneous, crystal purity is high, has greatly improved the quality of natrium citricum, simultaneously, preparation method's energy consumption of the present invention is low, pollute little, compared with tradition evaporation crystallization method, be more suitable for industrial applications, there is higher economic benefit and social benefit.
The pH value of reaction end mixed liquor is preferably between 7.5 ~ 9.0, make mixed liquor be alkalescence, the cations such as the iron ion under alkali condition in mixed liquor can change salt precipitation into hydroxyl, carbonate etc., be beneficial to remove metal ion, avoid metal ion to be wrapped in crystal, the alkali simultaneously adding or salt, also can make the protide colloidal impurity sex change sedimentation in mixed liquor.
The concentration range of mixed liquor is preferably 285g/L-570g/L in anhydrous citric acid sodium, this has ensured that natrium citricum mixed liquor subsequent processes can carry out smoothly, if concentration is too low, can in follow-up dilution crystallization process, use a large amount of dissolved agent, both increase production cost, also increased the risk of environmental pollution; If concentration is too high, can, because natrium citricum mixed liquor is too sticky, be unfavorable for formation and the growth of crystal in follow-up dilution crystallization process, can make to produce a large amount of nucleus add dissolved agent in mixed liquor time, the crystal grain that causes preparing crystal is too small, is unfavorable for subsequent treatment.
Control dilution crystallization temperature, can obtain the natrium citricum that contains the different crystallizations water. Utilize natrium citricum under different temperatures when crystallize out the crystallization water number of combination be different, in the time dripping dissolved agent temperature lower than 50 DEG C, obtain five water citric acid sodium, when temperature is during higher than 50 DEG C, obtain Sodium Citrate, usp, Dihydrate Powder; Five water citric acid sodium lose three crystallizations water and become Sodium Citrate, usp, Dihydrate Powder in the time of 100 DEG C, and Sodium Citrate, usp, Dihydrate Powder loses the crystallization water and obtains anhydrous citric acid sodium in the time of 150 DEG C.
Simultaneously, in dilution crystallization process, the organic impurities in natrium citricum mixed liquor etc. can be dissolved in dissolved agent, and then these impurity are removed from natrium citricum, makes the natrium citricum crystal prepared comparatively pure; The dissolved agent such as alcohols are also beneficial to the sedimentation of protide colloidal impurity.
Detailed description of the invention
Embodiment is used for further describing the present invention below, but does not limit in any form the present invention.
Embodiment 1
Get NaOH 9mol(0.36kg) add in reactor, then add 1.5L water, stir and make dissolution of sodium hydroxide; At 20 DEG C, slowly add anhydrous citric acid 3mol(0.576kg), stirring reaction is stablized constant to pH8.7. At 20 DEG C, drip 4.5L ethanol, drip rear filtration, naturally dry. Obtain five water citric acid sodium 1.14kg. Yield 98.96%, content 99.74%.
Embodiment 2
Get NaOH 11.5mol(0.46kg) and sodium carbonate 20mol(2.12kg) add in reactor, then add 5L water, be stirred to dissolve. At 25 DEG C, slowly add anhydrous citric acid 10mol(1.92kg), stirring reaction is stablized constant to pH8.5. At 55 DEG C, drip 20L methyl alcohol, 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. At 25 DEG C, slowly add anhydrous citric acid 10mol(1.92kg), stirring reaction is stablized constant to pH9.0. At 55 DEG C, drip 35L isopropyl alcohol, drip rear filtration, 150 DEG C dry. Obtain anhydrous citric acid sodium 2.87kg. Yield 97.48%, content 99.65%.
Embodiment 4
Get NaOH 200mol(8kg) and sodium carbonate 100mol(10.6kg) mixture, the 50L that adds water, is stirred to dissolve. Under room temperature, slowly add anhydrous citric acid 100mol(19.2kg), stirring reaction is stablized constant to pH9.0. At 75 DEG C, drip 250L acetone, drip rear filtration, 150 DEG C dry. Obtain anhydrous citric acid sodium 28.78kg. Yield 97.85%, content 99.59%.
Although the present invention has only enumerated concrete material and proportioning molal quantity and the volume of above-mentioned 4 embodiment, but preparation method of the present invention can be on the basis of above-described embodiment, utilize the ratio of raw material involved in the present invention and stock yard further expand and revise, the suitability for industrialized production of particularly rate of charge being done to further expansion and carry out, all can reach object of the present invention.
Claims (1)
1. dilution crystallization is prepared a method for natrium citricum crystal, it is characterized in that: comprise the following steps,
A) salt-forming reaction, get in molar ratio citric acid and salt forming agent, first salt forming agent is dissolved in the water, slowly add again citric acid, the mol ratio of citric acid and salt forming agent is 1:3 ~ 1:3.15, control reaction temperature at 20 DEG C ~ 30 DEG C, reaction end pH is between 8.5 ~ 9.0, filters to obtain mixed liquor after reaction; The concentration range of described mixed liquor is counted 285g/L ~ 570g/L with anhydrous citric acid sodium; Described salt forming agent is one or more in NaOH, sodium carbonate, sodium acid carbonate;
B) dilution crystallization, toward steps A) mixed liquor in add by volume dissolved agent to make natrium citricum crystallization, the volume ratio of mixed liquor and dissolved agent is 1:3 ~ 1:3.5, 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, isopropyl alcohol, ethylene glycol, diethylene glycol, propane diols, glycerine;
C) filtration step B) in the crystal of separating out, dryly obtain natrium citricum product, described natrium citricum product is one or more in anhydrous citric acid sodium, Sodium Citrate, usp, Dihydrate Powder, five water citric acid sodium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410429852.2A CN104262139B (en) | 2014-08-28 | 2014-08-28 | A kind of dilution crystallization is prepared the method for natrium citricum crystal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410429852.2A CN104262139B (en) | 2014-08-28 | 2014-08-28 | A kind of dilution crystallization is prepared the method for natrium citricum crystal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104262139A CN104262139A (en) | 2015-01-07 |
| CN104262139B true CN104262139B (en) | 2016-05-04 |
Family
ID=52153759
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410429852.2A Active CN104262139B (en) | 2014-08-28 | 2014-08-28 | A kind of dilution crystallization is prepared the method for natrium citricum crystal |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104262139B (en) |
Families Citing this family (6)
| 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 |
| 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 |
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 (2)
| Title |
|---|
| 柠檬酸(钠)清洁生产工艺的研究;周勇;《国优秀硕士学位论文全文数据库电子期刊工程Ⅰ辑》;20091127;25-26 * |
| 柠檬酸钠生产新工艺研究;赵君民等;《西北大学学报自然科学版》;19980225;第28卷(第1期);第48-50页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104262139A (en) | 2015-01-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104262139B (en) | A kind of dilution crystallization is prepared the method for natrium citricum crystal | |
| CN104327100A (en) | Preparation technology of high-purity flomoxef sodium | |
| CN106045879B (en) | Method for preparing cyanoacetic acid | |
| CN100424066C (en) | Process of preparing malonic ester | |
| CN105348310A (en) | Preparation method for nucleating agent | |
| CN104230800A (en) | Preparation method of copper 8-hydroxyquinoline | |
| CN104355990B (en) | Method for recycling and mechanically using L- (+) -tartaric acid in D-ethyl ester production | |
| CN104447290B (en) | A kind of method preparing 2,4 dichlorophenoxyacetic acid | |
| CN103804210B (en) | Purification method for betaine hydrochloride | |
| CN106854166B (en) | Method for preparing octanoyl hydroxamic acid from hydroxylamine sulfate and calcium oxide | |
| CN104610210B (en) | A kind of sodium dehydroacetate anhydride preparation method | |
| CN109796377B (en) | Preparation method of sodium sulfoacetate | |
| CN104829443A (en) | Method of producing calcium formate with calcium chloride and sodium formate | |
| CN111100113A (en) | Preparation method of D-lipoic acid sodium salt | |
| CN105294483A (en) | Preparation method for 4-chlorophenylhydrazine sulfate | |
| CN107814719A (en) | The iodobenzene diacetate preparation method and Recycling Mother Solution using method of high-efficiency environment friendly | |
| CN110697734B (en) | Preparation method for continuously synthesizing phosphorus-free cyanamide | |
| CN109897002B (en) | Preparation of 1-phenyl-2, 3-dimethyl-4-methylaminopyrazolin-5-one-N-methyl magnesium sulfonate hexahydrate | |
| CN105272877A (en) | Preparation method of 3-chlorophenylhydrazine phosphate | |
| CN205295186U (en) | Sodium lactate production system | |
| CN105692672A (en) | Preparation method of mendozite | |
| CN104151383A (en) | Method for producing disodium uridylate | |
| CN105776295A (en) | Method for purifying industrial coarse aluminum sulfate taken as raw material to prepare refined aluminum sulfate | |
| RU2537607C1 (en) | Method of barium nitrate purification | |
| CN105272875A (en) | 4-chlorophenylhydrazine phosphate preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |