CN101353337B - Vitamin c clean production method - Google Patents
Vitamin c clean production method Download PDFInfo
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- CN101353337B CN101353337B CN2008100793597A CN200810079359A CN101353337B CN 101353337 B CN101353337 B CN 101353337B CN 2008100793597 A CN2008100793597 A CN 2008100793597A CN 200810079359 A CN200810079359 A CN 200810079359A CN 101353337 B CN101353337 B CN 101353337B
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Abstract
The invention discloses a cleaner production method of Vitamin C. In the method, the steps of converting sodium gulonic acid into gulonic acid are as follows: a. strong acid is added into sodium gulonic acid solution and then the pH of the solution is regulated to be 3.0 to 4.5; b. the solution film with the regulated pH is ultrafiltered; c. the strong acid is added into the ultrafiltered solution so as to regulate the pH to be 1.6 to 1.7; d. the solution with regulated pH in step c is subjected to concentration, crystallization and centrifugation so as to prepare mixed dry products; e. the mixed dry products are dissolved in methanol and then filtered so as to prepare the methanol solution of the gulonic acid. The production method of the invention has the advantages that a large amount of water, caustic soda liquid and hydrochloric acids are saved, and basically no sewage is discharged in the process of conversion, thereby solving the problem of environmental contamination, and meeting the discharge standard prescribed by the state. The production method has basically no loss on yield in the process of conversion, thereby greatly reducing investment and production costs.
Description
Technical field
The present invention relates to a kind of medical production field, especially a kind of vitamin C clean production method.
Background technology
Vitamins C (Vc) manufacturing enterprise generally adopts ion exchange method that sodium colombate liquid is made the transition into ancient imperial acid solution at present, again through concentrated, crystallization, the centrifugal imperial sour dry product of Gu of producing, then the imperial sour dry product of Gu is put into and carried out the esterification conversion in a certain amount of methyl alcohol, finally make Vc-Na or Vc.This, method was to make ancient imperial acid crystal by sodium colombate solution through cation-exchange step transition.In carrying out this step, after Zeo-karb is saturated, need with a large amount of tap water backwashes, add 4% liquid caustic soda regeneration 2 hours then, again with tap water soda to PH be 8, add the regeneration of hydrochloric acid 2 hours of 7-8%, with washing acid from the beginning to PH be 4, add pure water again and soak standby.This, there was a unsurmountable shortcoming in method transition, not only will consume a large amount of water exactly in transformation process, and will produce a large amount of saliferous and organic sewage, and Here it is causes the major cause of Vc production industry high pollution.Want to handle these sewage, need huge fund to build large-scale sewage treatment facility, nonetheless, some enterprise also is difficult to reach the emission standard of national increasingly stringent, has a strong impact on the survival and development of enterprise.
In on December 6th, 2000 disclosed Chinese invention patent CN1275569A, mention a kind of novel process for production of vitamin C and solved above-mentioned with serious pollution problem.Its processing step is: without directly sodium colombate liquid condensing crystal being produced the sodium colombate dry product transition; Then the sodium colombate dry product is put in a certain amount of methyl alcohol, added vitriol oil reacting by heating again, generate and contain Na
2SO
4The methanol solution of ancient dragon acid; Filter out the Na that reaction generates
2SO
4After, the methanol solution of ancient dragon acid transforms through esterification and produces Vc-Na and Vc.In this Vc production technique,, in preparation process, can part decompose, thereby cause yield losses, so this method was not approved by Vc manufacturing enterprise over past ten years always because sodium colombate is unstable in the aqueous solution.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of vitamin C clean production method that large amount of sewage can not cause yield losses again that neither can produce.
For solving the problems of the technologies described above, processing step of the present invention is: (1), sodium colombate liquid made the methanol solution of ancient dragon acid; (2), ancient dragon acid esterification in methyl alcohol transforms, and makes finished product Vc-Na or Vc.Wherein, step (1) adopts following processing step: a, adds strong acid in sodium colombate liquid, regulator solution PH to 3.0-4.5; B, with the solution film ultrafiltration behind the above-mentioned adjusting PH; Add strong acid in c, the solution after ultrafiltration, regulate PH to 1.6-1.7; D, with regulate among the step c behind the PH solution through concentrate, crystallization, the centrifugal mixing dry product that makes; E, with in the above-mentioned mixing dry product dissolving methyl alcohol, filter, make the methanol solution of ancient dragon acid.
The feed ratio that mixes dry product and methyl alcohol among the step e is: every 1000kg mixing dry product is dissolved into 3-7m
3Methyl alcohol in.
Strong acid described in step b and the c is the vitriol oil.
Among the step a, regulator solution PH to 3.5-4.0.
Among the step c, regulator solution PH to 1.65.
The design concept of the inventive method is: utilize strong acid to regulate the pH value of sodium colombate liquid, sodium colombate liquid is changed into ancient imperial acid and Na
2SO
4Solution is made ancient imperial acid and Na then
2SO
4The mixing dry product, utilize Na
2SO
4Be insoluble to the character of methyl alcohol, will mix dry product and put in the methyl alcohol, filter, make the methanol solution of ancient dragon acid.
Adopt the beneficial effect that technique scheme produced to be: the inventive method does not need ion-exchange, and transition, the back feed liquid did not need dilution, a large amount of waters, liquid caustic soda and hydrochloric acid have been saved, and basic without sewage discharge in transformation process, solve problem of environmental pollution, reached national specified discharge standard.Technological process of the present invention is carried out at normal temperatures, can not decompose because of heat causes sodium colombate, and yield is lossless substantially in transformation process.The present invention has saved ion-exchange unit, nanofiltration equipment and sewage disposal device, greatly reduces cost of investment, thereby production cost is reduced.
Embodiment
The processing step of this vitamin C clean production method is: (1), sodium colombate liquid made the methanol solution of ancient dragon acid; (2), ancient dragon acid esterification in methyl alcohol transforms, and makes finished product Vc-Na or Vc.Wherein sodium colombate liquid can adopt prior art for preparing, by sorbyl alcohol, corn steep liquor, light calcium carbonate, urea, sal epsom, yellow soda ash, potassium primary phosphate, Glacial acetic acid, bubble enemy, glucose by fermentation after, make through behind the flocculating settling again.Ancient dragon acid esterification conversion process in methyl alcohol can adopt prior art, adds sulfuric acid and carry out esterification in the methanol solution of ancient imperial acid, drops into then quantitatively to transform, and obtains the Vc-Na crystal after cooling, the separation.The Vc-Na crystal adds methyl alcohol, sulfuric acid carries out acidifying, obtains Vc solution, obtains the Vc crude product through concentrated, crystallization, can obtain finished product Vc through refining again.
Embodiment 1: with the sodium colombate liquid that existing processing method is made, the adding massfraction is 70% the vitriol oil in sodium colombate liquid, regulator solution PH to 3.5; With the solution film ultrafiltration behind the above-mentioned adjusting PH, remove albumen then; The adding massfraction is 98.3% the vitriol oil in the solution after ultrafiltration, regulates PH to 1.65; With the solution of above-mentioned PH to 1.65 concentrate after with activated carbon decolorizing, crystallization, centrifugal ancient imperial acid and the Na of making
2SO
4The mixing dry product; In above-mentioned mixing dry product dissolving methyl alcohol, the feed ratio that wherein mixes dry product and methyl alcohol is: every 1000kg mixing dry product is dissolved into 3m
3Methyl alcohol in, filter, make the methanol solution of ancient dragon acid; Adopt existing processing step to prepare Vc-Na and Vc at last by the methanol solution of ancient dragon acid.
Embodiment 2: with the sodium colombate liquid that existing processing method is made, the adding massfraction is 98% the vitriol oil in sodium colombate liquid, regulator solution PH to 4; Then with the solution film ultrafiltration behind the above-mentioned adjusting PH; The adding massfraction is 98% the vitriol oil in the solution after ultrafiltration, regulates PH to 1.65; With the solution of above-mentioned PH to 1.65 concentrate after with activated carbon decolorizing, crystallization, centrifugal ancient imperial acid and the Na of making
2SO
4The mixing dry product; In above-mentioned mixing dry product dissolving methyl alcohol, the feed ratio that wherein mixes dry product and methyl alcohol is: every 1000kg mixing dry product is dissolved into 7m
3Methyl alcohol in, filter, make the methanol solution of ancient dragon acid; Adopt existing processing step to prepare Vc-Na and Vc at last by the methanol solution of ancient dragon acid.
Embodiment 3: with the sodium colombate liquid that existing processing method is made, the adding massfraction is 36% concentrated hydrochloric acid in sodium colombate liquid, regulator solution PH to 3.0; Then with the solution film ultrafiltration behind the above-mentioned adjusting PH; The adding massfraction is 36% concentrated hydrochloric acid in the solution after ultrafiltration, regulates PH to 1.6; With the solution of above-mentioned PH to 1.6 concentrate after with activated carbon decolorizing, crystallization, the centrifugal mixing dry product that makes ancient imperial acid and NaCl; In above-mentioned mixing dry product dissolving methyl alcohol, the feed ratio that wherein mixes dry product and methyl alcohol is: every 1000kg mixing dry product is dissolved into 6m
3Methyl alcohol in, filter, make the methanol solution of ancient dragon acid; Adopt existing processing step to prepare Vc-Na and Vc at last by the methanol solution of ancient dragon acid.
Embodiment 4: with the sodium colombate liquid that existing processing method is made, the adding massfraction is 98.3% the vitriol oil in sodium colombate liquid, regulator solution PH to 4.5; Then with the solution film ultrafiltration behind the above-mentioned adjusting PH; The adding massfraction is 98.3% the vitriol oil in the solution after ultrafiltration, regulates PH to 1.7; With the solution of above-mentioned PH to 1.7 concentrate after with activated carbon decolorizing, crystallization, centrifugal ancient imperial acid and the Na of making
2SO
4The mixing dry product; In above-mentioned mixing dry product dissolving methyl alcohol, the feed ratio that wherein mixes dry product and methyl alcohol is: every 1000kg mixing dry product is dissolved into 4m
3Methyl alcohol in, filter, make the methanol solution of ancient dragon acid; Adopt existing processing step to prepare Vc-Na and Vc at last by the methanol solution of ancient dragon acid.
Embodiment 5: with the sodium colombate liquid that existing processing method is made, the adding massfraction is 98.3% the vitriol oil in sodium colombate liquid, regulator solution PH to 3.7; Then with the solution film ultrafiltration behind the above-mentioned adjusting PH; The adding massfraction is 98.3% the vitriol oil in the solution after ultrafiltration, regulates PH to 1.65; With the solution of above-mentioned PH to 1.65 concentrate after with activated carbon decolorizing, crystallization, centrifugal ancient imperial acid and the Na of making
2SO
4The mixing dry product; In above-mentioned mixing dry product dissolving methyl alcohol, the feed ratio that wherein mixes dry product and methyl alcohol is: every 1000kg mixing dry product is dissolved into 5m
3Methyl alcohol in, filter, make the methanol solution of ancient dragon acid; Adopt existing processing step to prepare Vc-Na and Vc at last by the methanol solution of ancient dragon acid.
Calculate through the contrast experiment, embodiment 1-5 compares with adopting existing technology, and the yield of ancient dragon acid can improve more than 2%.
In this vitamin C clean production method, the feed ratio that mixes dry product and methyl alcohol is can be according to the demand of practical production adjustment, and the methyl alcohol ratio of adding is many more, and the transformation efficiency of ancient dragon acid is high more, but the recycling amount of methyl alcohol is big more, is preferably in every 1000kg mixing dry product and drops into 3-7m
3Methyl alcohol.
Claims (5)
1. vitamin C clean production method, the processing step of this method is: (1), sodium colombate liquid made the methanol solution of ancient dragon acid; (2), ancient dragon acid esterification in methyl alcohol transforms, and makes finished product Vc-Na or Vc, it is characterized in that step (1) adopts following processing step: a, adds strong acid in sodium colombate liquid, regulator solution PH to 3.0-4.5; B, with the solution film ultrafiltration behind the above-mentioned adjusting PH; Add strong acid in c, the solution after ultrafiltration, regulate PH to 1.6-1.7; D, with regulate among the step c behind the PH solution through concentrate, crystallization, the centrifugal mixing dry product that makes; E, with in the above-mentioned mixing dry product dissolving methyl alcohol, filter, make the methanol solution of ancient dragon acid.
2. vitamin C clean production method according to claim 1, it is characterized in that the feed ratio that mixes dry product and methyl alcohol among the step e is: every 1000kg mixing dry product is dissolved into 3-7m
3Methyl alcohol in.
3. vitamin C clean production method according to claim 1 is characterized in that the strong acid described in step b and the c is the vitriol oil.
4. according to claim 1,2 or 3 described vitamin C clean production methods, it is characterized in that among the step a regulator solution PH to 3.5-4.0.
5. according to claim 1,2 or 3 described vitamin C clean production methods, it is characterized in that among the step c regulator solution PH to 1.65.
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| CN2008100793597A CN101353337B (en) | 2008-09-08 | 2008-09-08 | Vitamin c clean production method |
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|---|---|---|---|
| CN2008100793597A CN101353337B (en) | 2008-09-08 | 2008-09-08 | Vitamin c clean production method |
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| CN101353337A CN101353337A (en) | 2009-01-28 |
| CN101353337B true CN101353337B (en) | 2011-04-06 |
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| CN2008100793597A Expired - Fee Related CN101353337B (en) | 2008-09-08 | 2008-09-08 | Vitamin c clean production method |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101508496B (en) * | 2009-03-12 | 2010-10-20 | 南京大学 | Method for purification of macromolecule chromophoric matter in water from Vc fermentation wastewater by biochemical treatment |
| CN104152507B (en) * | 2014-07-10 | 2018-10-02 | 东北制药集团股份有限公司 | A method of preparing 2-KLG methanol solution |
| CN104211594B (en) * | 2014-08-15 | 2016-04-27 | 东北制药集团股份有限公司 | A kind of method improving L-sodium colombate sulfuric acid acidation extraction efficiency |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1122802A (en) * | 1994-12-28 | 1996-05-22 | 华东理工大学 | Method for preparing ascorbic acid by quantitative conversion of sodium colombate |
| CN1130627A (en) * | 1995-11-24 | 1996-09-11 | 中原制药厂 | Process for preparing sodium (or potassium) L-ascorbate |
| CN1275569A (en) * | 1999-06-01 | 2000-12-06 | 淄博华航药业有限公司 | Novel process for production of vitamin C |
| CN1754869A (en) * | 2004-09-28 | 2006-04-05 | 三达膜科技（厦门）有限公司 | Process for extracting gulonic acid |
-
2008
- 2008-09-08 CN CN2008100793597A patent/CN101353337B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1122802A (en) * | 1994-12-28 | 1996-05-22 | 华东理工大学 | Method for preparing ascorbic acid by quantitative conversion of sodium colombate |
| CN1130627A (en) * | 1995-11-24 | 1996-09-11 | 中原制药厂 | Process for preparing sodium (or potassium) L-ascorbate |
| CN1275569A (en) * | 1999-06-01 | 2000-12-06 | 淄博华航药业有限公司 | Novel process for production of vitamin C |
| CN1754869A (en) * | 2004-09-28 | 2006-04-05 | 三达膜科技（厦门）有限公司 | Process for extracting gulonic acid |
Non-Patent Citations (3)
| Title |
|---|
| 徐静.以古龙酸钠代替古龙酸合成维生素C中间体VC_Na的工艺改进.佳木斯医学院学报.1997,20(5),47页，特别是实验部分. * |
| 谢占武.维生素C的生产工艺发展.实用药物与临床.2005,81-2. * |
| 陈建荣.维生素C生产技术进展.河北化工.2001,(2),7-8，13. * |
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