CN101029036B - Process for producing isovitamine C by membrane-resin method - Google Patents
Process for producing isovitamine C by membrane-resin method Download PDFInfo
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- CN101029036B CN101029036B CN2006100242294A CN200610024229A CN101029036B CN 101029036 B CN101029036 B CN 101029036B CN 2006100242294 A CN2006100242294 A CN 2006100242294A CN 200610024229 A CN200610024229 A CN 200610024229A CN 101029036 B CN101029036 B CN 101029036B
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Abstract
A process for preparing isovitamin C by membrane-resin method includes such steps as membrane filtering of the fermented liquid of sodium diketogluconate, ion exchange and concentrating by ion exchange resin, esterifying, converting and refining.
Description
Technical field
The present invention relates to a kind of chemical technique, relate in particular to a kind of film-resin method that adopts and from fermented liquid, extract the technology that diketo-maltonic acid is produced isoascorbic acid.
Background technology
Sodium isoascorbate is a kind of antioxidant as safe as a house, is widely used in the food-processing.Diketo-maltonic acid is the important as precursors of producing sodium isoascorbate, and diketo-maltonic acid is through methanol esterification, and then transforms with sodium methylate and to obtain sodium isoascorbate.
At present, diketo-maltonic acid adopts fermentative Production.Along with the accumulative total of diketo-maltonic acid, fermented liquid pH descends during the fermentation.For avoiding fermented liquid to reduce because of pH, suppress thalli growth, must add a certain amount of alkaline matter during the fermentation as the reduction of neutralizing agent with inhibition pH.Neutralizing agent is generally CaCO
3, Ca (OH)
2(calcium salt method traditional technology) or NaOH, Na
2CO
3, ammoniacal liquor etc.Therefore, when fermentation ends, the diketo gluconic acid exists with the form of salt.In the production technique,, select for use neutralizing agent to select CaCO usually for use at present for ease of the separation and Extraction of diketo gluconic acid
3, Ca (OH)
2, therefore when fermentation ends, product exists with the form of diketo calglucon in the fermented liquid.
Calcium salt method technology is all adopted in the production of present domestic diketo gluconic acid.
The simple process route of calcium salt method technology as shown in Figure 1.
The problem that calcium salt method technology exists is:
1, the filtration yield is low: because after adding sulfuric acid, produce a large amount of calcium sulfate (calcium sulphate content is about 8%), thalline and calcium sulfate flco are more tiny, can stop up sheet frame filter cloth and flocculating aids layer when adopting Plate Filtration, therefore, filtration difficulty, the top is washed and is difficult in the process product of carrying secretly in thalline and the calcium sulfate is washed out, therefore it is low to filter yield, less than 94%.
2, with sour cost height: because the calcium sulfate solubility product is higher, if will then sulfuric acid must be excessive in a large number with the thorough precipitated calcium ion of sulfuric acid, but during excess sulfuric acid, to cross low follow-up upgrading unit very high to the thickening equipment requirement for acidizing fluid pH on the one hand; Technologies such as a large amount of on the other hand excessive sulfate radical interfere with subsequent esterifications, conversion.Therefore, use, and behind the elimination calcium sulfate, also need to add the further precipitated calcium ion of oxalic acid with the calcium ion equivalent or a little less than the normal sulfuric acid precipitation calcium ion of calcium ion.Thereby the oxalate in the solution is easy to form the removal effect that oxalic acid hydrogen root reduces calcium ion when hanging down with the oxalic acid decalcification because pH crosses, the large usage quantity of oxalic acid, and only calcium ion can be taken off about 400ppm.Because the oxalic acid price is higher, and the oxalic acid price also will constantly rise under present Market Situation, so the decalcification cost is very high.
3, diketo glucose acid solution is of poor quality: diketo calglucon fermented liquid is only with just entering unit such as follow-up concentrated esterification behind sulfuric acid and the oxalic acid precipitation calcium ion, diketo glucose acid solution is not through any purifying, the darker follow-up decolouring burden of color is heavier on the one hand, on the other hand owing to also may have the sheet frame little flco calcium sulfate and the thalline of filtering fully in the filtrate, the crystal moulding in the serious interfere with crystallization.
4, pipeline and evaporation concentrator fouling are serious: because employing sulfuric acid and oxalic acid can't be removed the calcium ion in the diketo glucose acid solution fully, so pipeline and very easily fouling of thickener.Cause on the one hand after the fouling that the thickener heat-transfer effect is relatively poor to cause energy dissipation, thereby cause in the concentration process feed liquid inhomogeneous generation local superheating of being heated on the other hand easily.Therefore the snaking of pipeline and thickener must be very frequent, seriously disturbs the production order, and the replacing of pipeline equipment simultaneously is also relatively more frequent.
5, environmental burden is heavy: owing to adopt traditional calcium salt method technology will produce a large amount of solid waste such as calcium sulfate, can't handle, cause serious environmental to pollute, bring heavy environmental burden to manufacturer.
Summary of the invention
Purpose of the present invention is to overcome the prior art calcium salt method and extracts the problems referred to above that diketo-maltonic acid is produced the technology existence of isoascorbic acid, provides a kind of film-resin method to produce the technology of isoascorbic acid.
The objective of the invention is to be achieved through the following technical solutions: a kind of technology that adopts film-resin method to produce isoascorbic acid is raw material with diketo Sunmorl N 60S maturing fermentation liquid, may further comprise the steps:
A, membrane filtration
With membrane filtration diketo Sunmorl N 60S maturing fermentation liquid, remove wherein the insoluble substance that comprises thalline, high molecular weight protein, colloid, polysaccharide and most soluble proteins, obtain the diketo Sunmorl N 60S filtrate of clear;
B, ion exchange resin make the transition
The resulting filtrate of step a is handled with hydrogen type cation exchange resin, make be the diketo gluconic acid diketo Sunmorl N 60S transition in the filtrate, obtain diketo gluconic acid ion exchange liquid;
C, subsequent disposal
The resulting diketo gluconic acid of step b ion exchange liquid is obtained diketo gluconic acid intermediate through concentrating, again through esterification, conversion, the refining isoascorbic acid product that obtains.
Working pressure during membrane filtration described in the step a is controlled at 0.1～50kg/cm
2, service temperature is controlled at 1～100 ℃.
The service temperature of ion exchange resin described in step b transition is controlled at 1～80 ℃, flow rate of liquid be controlled at 1～100 times of resin volume/hour.
Film described in the step a is polymer material film or inorganic material film, and wherein the molecular weight cut-off of polymeric membrane is greater than 200 dalton, and the aperture of holding back of mineral membrane is 1nm-1000nm.
Described polymer material film comprises polyethersulfone, polysulfones, polyacrylonitrile, polyvinylidene difluoride (PVDF), cellulose acetate etc., and described inorganic material film comprises ceramic membrane and stainless steel membrane.
The present invention makes it have following significant advantage and characteristics owing to adopted above technical scheme:
1, filters the yield height: adopt embrane method to filter diketo Sunmorl N 60S fermented liquid,, only need to wash the bacterium slurry and can reach filtration yield more than 99% with the less water top owing to the thalline cycles of concentration can reach 20-30 doubly.
2, low with sour cost: it is the hydrochloric acid of the required consumption of h type resin that the sour cost of required usefulness is the resin regeneration of sodium type.Owing to be to remove the calcium ion in the fermented liquid more thorough when adopting calcium salt method technology, it is excessive that sulfuric acid that is consumed and oxalic acid need, and the total yield number that acid consumes when adopting film-resin method technology only is 85% of a calcium salt method, only is 70% of calcium salt method technology with sour cost.
3, diketo glucose acid solution quality is good: after adopting film-resin method technology, insoluble substance and most of soluble proteinss such as the thalline in the fermented liquid, solid protein behind membrane filtration, have thoroughly been removed, and diketo Sunmorl N 60S pH after ion-exchange becomes the diketo gluconic acid can be reduced to below 1.5, all albumen, the equal ionization of amino acid go out positive charge and can be compared by resin absorption up hill and dale and remove under this condition, thereby reduced the generation of Maillard reaction in the concentration process significantly, reduced the melanic generation of melanochrome class.Simultaneously, thus the positively charged ion pigment that resin can be removed in the filtrate plays decolorization.Thereby can alleviate the decolouring burden significantly, reduce significantly because the yield losses that decolouring brings.
4, pipeline and thickener do not have scale formation: because employing film-resin method can be with Ca
2+Concentration is controlled at below the 10ppm, scale formation can not take place.
5, environmental burden is light: the generation that film-resin method technology has thoroughly been stopped calcium sulfate from the source, filtering a small amount of bacterium slurry that produces only needs promptly to can be used as feed after a small amount of energy drying and sells.
6, change sour rate height: adopt the commentaries on classics acid rate height of film-resin method technology diketo Sunmorl N 60S, can reach more than 99% to diketo glucose.
Description of drawings
Fig. 1 is the process route chart that the prior art calcium salt method is produced isoascorbic acid;
Fig. 2 is that the present invention adopts film-resin method to produce the process route chart of isoascorbic acid.
Embodiment
The technology that film of the present invention-resin method is produced diketo-maltonic acid can be described as follows in conjunction with Fig. 2:
With diketo Sunmorl N 60S maturing fermentation liquid is raw material, at first filter diketo Sunmorl N 60S maturing fermentation liquid with membrane separation plant, remove insoluble substance and most soluble proteinss such as wherein thalline, high molecular weight protein, colloid, polysaccharide, obtain the filtrate of the clear of diketo Sunmorl N 60S, bacterium is starched (volume only is the 3-5% of fermentating liquid volume) but sells as feed behind the dry solidification.The film that adopts in the membrane filtration is polymer material film or mineral membrane, and polymer material film comprises polyethersulfone, polysulfones, polyacrylonitrile, polyvinylidene difluoride (PVDF), cellulose acetate etc., and inorganic material film comprises ceramic membrane and stainless steel membrane.Wherein the molecular weight cut-off of polymeric membrane is greater than 200 dalton, mineral membrane hold back aperture 1nm-1000nm.The working pressure that adopts is controlled at 0.5-50kg/cm
2, service temperature is controlled at 5-100 ℃.Then filtrate is handled with hydrogen type cation exchange resin, make the diketo Sunmorl N 60S in the filtrate be the diketo gluconic acid transition, obtain containing the ion exchange liquid of diketo gluconic acid.The service temperature of ion-exchange is controlled at 1-80 ℃, flow rate of liquid be controlled at 1-10 times of resin volume/hour.Then ion exchange liquid is obtained diketo-maltonic acid through concentrating, again through esterification, conversion, the refining finished product isoascorbic acid that obtains.
Hydrogen type cation exchange resin in the said process is after using for some time, and making the transition is sodium type Zeo-karb, and the acceptable salts acid regeneration is to come into operation again behind the hydrogen type cation exchange resin.
Adopt film of the present invention-resin method to produce the technology of diketo-maltonic acid, filter yield up to more than 99%, the total yield number that acid consumes only is 85% of a calcium salt method, with sour cost only is 70% of calcium salt method technology, and the diketo Sunmorl N 60S can reach more than 99% the commentaries on classics acid rate of diketo glucose.Has remarkable economic efficiency and use value.
Embodiment 1
With diketo Sunmorl N 60S maturing fermentation liquid is raw material, adopts stainless steel membrane as the Sterile Filtration film, and red-tape operati pressure is 4-5kg/cm
2, the red-tape operati temperature is 35-40 ℃, filters diketo Sunmorl N 60S maturing fermentation liquid, obtains the diketo Sunmorl N 60S filtrate of clear.Then filtrate is handled with hydrogen type cation exchange resin, the red-tape operati temperature is 5-50 ℃, the controlled liq flow velocity be 2-4 times of resin volume/hour, make be the diketo gluconic acid diketo Sunmorl N 60S transition in the filtrate, obtain containing the ion exchange liquid of diketo gluconic acid.Then ion exchange liquid is steamed through being concentrated into no moisture, obtain diketo-maltonic acid of the present invention, again through esterification, conversion, the refining isoascorbic acid product that obtains.
Embodiment 2
With diketo Sunmorl N 60S maturing fermentation liquid is raw material, adopts ceramic membrane as filtering membrane, and red-tape operati pressure is 6-8kg/cm
2, the red-tape operati temperature is 60-80 ℃, filters diketo Sunmorl N 60S maturing fermentation liquid, obtains the diketo Sunmorl N 60S filtrate of clear.Then filtrate is handled with hydrogen type cation exchange resin, the red-tape operati temperature is 5-50 ℃, the controlled liq flow velocity be 4-7 times of resin volume/hour, make be the diketo gluconic acid diketo Sunmorl N 60S transition in the filtrate, obtain containing the ion exchange liquid of diketo gluconic acid.Then ion exchange liquid is steamed through being concentrated into no moisture, obtain diketo-maltonic acid of the present invention, again through esterification, conversion, the refining isoascorbic acid product that obtains.
Embodiment 3
With diketo Sunmorl N 60S maturing fermentation liquid is raw material, and as filtering membrane, red-tape operati pressure is 4-10kg/cm with poly (ether sulfone) film
2, the red-tape operati temperature is 10-50 ℃, filters diketo Sunmorl N 60S maturing fermentation liquid, obtains the diketo Sunmorl N 60S filtrate of clear.Then filtrate is handled with hydrogen type cation exchange resin, the red-tape operati temperature is 5-50 ℃, the controlled liq flow velocity be 6-9 times of resin volume/hour, make be the diketo gluconic acid diketo Sunmorl N 60S transition in the filtrate, obtain containing the ion exchange liquid of diketo gluconic acid.Then ion exchange liquid is steamed through being concentrated into no moisture, obtain diketo-maltonic acid of the present invention, again through esterification, conversion, the refining isoascorbic acid product that obtains.
Claims (1)
1. technology that adopts film-resin method to produce isoascorbic acid, it is characterized in that: with diketo Sunmorl N 60S maturing fermentation liquid is raw material, may further comprise the steps:
A, membrane filtration
With membrane filtration diketo Sunmorl N 60S maturing fermentation liquid, remove wherein the insoluble substance that comprises thalline, high molecular weight protein, colloid, polysaccharide and most soluble proteins, obtain the diketo Sunmorl N 60S filtrate of clear;
B, ion exchange resin make the transition
The resulting filtrate of step a is handled with hydrogen type cation exchange resin, make be the diketo gluconic acid diketo Sunmorl N 60S transition in the filtrate, obtain diketo gluconic acid ion exchange liquid;
C, subsequent disposal
The resulting diketo gluconic acid of step b ion exchange liquid is obtained diketo gluconic acid intermediate through concentrating, again through esterification, conversion, the refining isoascorbic acid product that obtains;
Working pressure during membrane filtration described in the step a is controlled at 0.1～50kg/cm
2, service temperature is controlled at 1～100 ℃;
The service temperature of ion exchange resin described in step b transition is controlled at 1～80 ℃, flow rate of liquid be controlled at 1～100 times of resin volume/hour;
Film described in the step a is polymer material film or inorganic material film, and wherein the molecular weight cut-off of polymeric membrane is greater than 200 dalton, and the aperture of holding back of mineral membrane is 1nm-1000nm;
Described polymer material film comprises polyethersulfone, polysulfones, polyacrylonitrile, polyvinylidene difluoride (PVDF) and cellulose acetate, and described inorganic material film comprises ceramic membrane and stainless steel membrane.
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| CN2006100242294A CN101029036B (en) | 2006-02-28 | 2006-02-28 | Process for producing isovitamine C by membrane-resin method |
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| CN2006100242294A CN101029036B (en) | 2006-02-28 | 2006-02-28 | Process for producing isovitamine C by membrane-resin method |
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| CN101029036B true CN101029036B (en) | 2011-02-09 |
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| CN106620746B (en) * | 2015-11-02 | 2019-06-14 | 中国石油化工股份有限公司 | A method of it reducing Maillard reaction and microorganism growth and fermentation inhibitory is acted on |
| CN109265417A (en) * | 2018-09-19 | 2019-01-25 | 河北乐开节能科技股份有限公司 | A kind of pair of 2- ketone group aqueous gluconic acid is supersonic induced to crystallize the method for preparing different VC |
| CN110294726A (en) * | 2019-07-29 | 2019-10-01 | 新拓洋生物工程股份有限公司 | The preparation method of ISOASCORBIC ACID potassium |
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Non-Patent Citations (4)
| Title |
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| 孙文敬 等.我国D-异抗坏血酸钠的研究和生产现状.微生物学通报 3.1990,(3),170-172. |
| 孙文敬等.我国D-异抗坏血酸钠的研究和生产现状.微生物学通报 3.1990,(3),170-172. * |
| 李春燕 等.维生素生产工艺进展.中国医药工业杂志32 1.2001,32(1),38-41. |
| 李春燕等.维生素生产工艺进展.中国医药工业杂志32 1.2001,32(1),38-41. * |
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