CN102372624B - Method for extracting sodium gulonate from sodium gulonate fermented liquid - Google Patents
Method for extracting sodium gulonate from sodium gulonate fermented liquid Download PDFInfo
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Abstract
The invention provides a method for extracting sodium gulonate from sodium gulonate fermented liquid, which comprises the following steps that: the sodium gulonate fermented liquid is firstly centrifugally treated at a high speed, then clear liquid after the high-speed centrifugal treatment is processed by a ultra-filtration system, and the slag liquid after the high-speed centrifugal treatment is re-filtered by a ceramic membrane system. The method adopts different membranes to process the clear liquid and the slag liquid of the sodium gulonate fermented liquid after being centrifuged at the high speed, so on the one hand the abrasion of the high-concentration liquid on the ultra-filtration membrane can be greatly reduce, and the weakness of the original production process that the service life is short by only utilizing the ultra-filtration membrane can be solved; on the other hand, a single-batch processing time of the sodium gulonate fermented liquid is reduced, and the production efficiency is improved; and the ceramic membrane is used for substituting an original flocculation-precipitation process to process the slag liquid after the centrifugal separation and to process the slag after the ultra-filtration, no medicine is added, and the separated slag can be used for processing feed or organic fertilizer, so the economic benefit can be increased, and the pollutant emission can be reduced.
Description
Technical field
The invention belongs to Progresses of Vitamin C Productive Technology field, particularly a kind of extracting method of sodium gulonate from sodium gulonate fermented liquid.
Background technology
Vitamins C has another name called xitix, is the acid polyol with six carbon atom.Vitamins C is not only closely related with the growth of animal, and its immunizing power, disease resistance and anti allergic reaction are all had to vital role.Main as livestock and poultry animal fodder additives in Animal nutrition research.
Approximately 90% of world's vitamins C output concentrate on China at present, the technical process of production of vitamin C is mainly divided into fermentation, extraction, conversion, refining four large steps, production of vitamin C raw material sorbyl alcohol produces sodium colombate through fermentation using bacteria, sodium colombate is converted into crude vitamin C after extracting, concentrating again, and crude vitamin C becomes finished product vitamins C after refining.
At present, the topmost mode of production of domestic vitamins C is two-step fermenting.The process that two stage fermentation synthesis method is produced vitamins C experiment can be divided into fermentation, extracts and transform three large steps.Fermentation: the-step of two-step fermenting is, with Pseudomonas, sorbyl alcohol is changed into L-sorbose.In addition, weak oxidized acetic acid bacteria, raw Black Grape saccharic acid bacillus, stench bacillus aceticus, acetic acid bacillus aceticus, intend the bacteriums such as glue bacillus and also have this transformation function.Fermentation second step adopts composting fermentation, uses bacillus megaterium and oxidizing glucose acidfast bacilli mixed culture, and L-sorbose is converted into sodium colombate, and wherein large bacterium is concomitance bacterium, and little bacterium is acid-producing bacteria.In addition, in the production practice of vitamins C experiment two-step fermenting, find, the concomitance bacterium that can combine as the acid-producing bacteria of oxidizing glucose acidfast bacilli also has striped pseudomonas, bacillus cereus and bacillus macerans etc.Extract: the extraction process of fermented liquid is the problem of outbalance in vitamins C experiment production industry.Extraction is by means such as separation, ion-exchanges, to obtain the precursor KGA (hereinafter to be referred as 2-KLG) of vitamins C experiment.Through Secondary Fermentation, in fermented liquid, 2-KLG sodium content is only 6% ~ 9%, and the impurity such as residual mycelium, protein and suspended particulates, and separating-purifying is more difficult, and the ratio that the expense of aftertreatment accounts for total cost is very large.
Transform: by 2-KLG, be converted into vitamins C, have acid to transform and two kinds of methods of alkali conversion.
In production of vitamin C flow process, owing to adopting fermentation using bacteria, in fermented liquid, protein-colloid and opsonigenous substances are difficult problems of extracting workshop section with the separated of sodium colombate feed liquid.In production, the extraction method of application mainly contains thermal precipitation method, chemical coagulation method and ultrafiltration and extracts 3 kinds.Heating can make sodium colombate Partial digestion affect yield; Flocculation need be added two kinds of flocculation agents in fermented liquid, and price is more expensive, has increased production cost, runs into serious microbiological contamination lot number, and flocculating effect is very poor, simultaneously owing to needing to add flocculation agent in flocculation process, thereby separating material slag cannot be recycled, and has increased discharge amount of pollution.Ultrafiltration extract have without phase transformation, energy-conservation, easy and simple to handle, do not cause the new advantages such as environmental pollution, now obtain aborning widespread use, but ultrafiltration extract exist that diaphragm work-ing life is short, replacement charge is high, the problem such as high for film cleaning charge.
At < < application ultra-filtration technique, improve Vc production technique > > (author: Zhang Linmao, Gao Yongtao, Li Jing, membrane science and technology, the 20th the 5th phase of volume) in, a kind of improvement technique has been proposed, sodium colombate fermented liquid → pre-treatment → membrane sepn → resin desalination → condensing crystal → 2-keto-L-gulonic acid, this process using ultra-filtration technique is removed protein and colloid in fermented liquid.Ultra-filtration membrane, be that a kind of aperture specification is consistent, specified pore diameter range is the micropore filtering film of 0.001-0.02 micron, in a side of film, imposes suitable pressure, just can sift out the solute molecule that is less than aperture, with isolated molecule amount, be greater than the particle that 500 dalton, particle diameter are greater than 2～20 nanometers.But while using due to ultra-filtration membrane, diaphragm work-ing life is short, replacement charge is high, film cleaning charge is with high, and the filter residue after ultra-filtration filters also contains a certain amount of sodium colombate.At present slag liquid is generally taked the method for flocculation, poor and unstable but this part slag liquid adopts flocculation to exist treatment effect, the problems such as the serious and production cost height of pollutant emission.Therefore need to provide that a kind of long service life, working cost are low, the extracting method of environmental protection.
Summary of the invention
The extracting method that the object of the invention is a kind of sodium gulonate from sodium gulonate fermented liquid of proposing for the problems referred to above.This extracting method first carries out high speed centrifugation separation to sodium colombate fermented liquid, then to clear liquid and slag liquid, take different films to carry out separated, solved that simple employing ultra-filtration membrane work-ing life is short, replacement charge is high and adopted that flocculation treatment effect is poor and unstable, pollutant emission is serious and the defect such as production cost is high.
To achieve these goals, technical scheme of the present invention is:
A kind of extracting method of sodium gulonate from sodium gulonate fermented liquid, first sodium colombate fermented liquid is carried out to high speed centrifugation processing, then the clear liquid obtaining after high speed centrifugation being processed adopts ultrafiltration system to process, and the slag liquid obtaining after high speed centrifugation is processed adopts ceramic membrane system to carry out filtration treatment again.
The ultra-filtration membrane filter residue that described clear liquid obtains after uf processing adopts ceramic membrane system to carry out filtration treatment again.
The technique of the filtration treatment of described employing ceramic membrane system comprises the following steps:
(1) the slag liquid and the ultra-filtration membrane filter residue that after high speed centrifugation processing, obtain are transported to prefilter, carry out pre-filtering processing, obtain pre-filtering liquid, the described incoming stock tank of pre-filtering liquid;
(2) the pre-filtering liquid in head tank is squeezed in first step ceramic membrane system by charging pump, carry out thickening filtration processing, obtain first step filtrate and first step concentrated solution, first step filtrate enters next step ion exchange treatment, and first step concentrated solution enters in secondary ceramic membrane system;
(3) the first concentrated solution is carried out to dialysis treatment, obtain second stage filtrate, second stage filtrate enters next step ion exchange treatment; Described dialysis treatment adds pure water by feeding line, when effective constituent is less than certain numerical value in concentrated residue, stops adding pure water, shuts down;
(4) raffinate of emptying prefilter, head tank and ceramic membrane system, washes film and processes, repetition above-mentioned steps after washing film and completing.
In described thickening filtration processing, pre-filtering liquid is concentrated into 3-5 doubly.
In thickening filtration processing, pre-filtering liquid is concentrated into 4 times.
The described film processing of washing comprises the cleaning to the cleaning of ceramic membrane systemic circulation side and ceramic membrane system per-meate side, and the described device of washing film processing employing is purge tank and scavenging pump.
Described ceramic membrane is inorganic ceramic film, and described inorganic ceramic film is in wide-aperture supporting body surface, to apply the fine and close microporous film layers of 4 ~ 6 micron thickness.
The aperture of described ultra-filtration membrane is 10 nanometers, and the aperture of described ceramic membrane is 50 nanometers.
The invention has the beneficial effects as follows:
(1) clear liquid and the slag liquid of the sodium colombate fermented liquid of extracting method of the present invention after to high-speed separation adopt different films to process, on the one hand greatly reduce the wearing and tearing of high density feed liquid to ultra-filtration membrane, solved the simple defect that work-ing life is short while using ultra-filtration membrane, replacement charge is high in original production technique; Reduce on the other hand single batch processing time of sodium colombate fermented liquid, improved production efficiency;
(2) the slag liquid after adopting ceramic membrane to centrifugation and the filter residue after ultrafiltration are processed again, and separation accuracy is high, can increase substantially product yield, reduces loss of material;
(3) because sepn process is without adding auxiliary agent, therefore the filter residue after ceramic membrane is processed is pollution-free, can be directly used in processing feed or organic fertilizer, realizes resource circulation utilization, increases income;
(4) adopt extracting method of the present invention, wastewater discharge reduces greatly, and in waste water, COD significantly reduces, and alleviates the pressure of follow-up sewage disposal;
(5) adopt extracting method of the present invention, equipment investment is low, and working cost is low.
Below in conjunction with drawings and Examples, the present invention is described in detail.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of extraction process of the present invention.
Fig. 2 is the material balance figure of the embodiment of the present invention 5.
Embodiment
Referring to Fig. 1, a kind of extracting method of sodium gulonate from sodium gulonate fermented liquid, first sodium colombate fermented liquid is carried out to high speed centrifugation processing, then the clear liquid after high speed centrifugation being processed adopts ultrafiltration system to carry out filtration treatment, and the slag liquid obtaining after high speed centrifugation is processed adopts ceramic membrane system to carry out filtration treatment again.
What the present invention proposed is a kind of extracting method of sodium gulonate from sodium gulonate fermented liquid, first sodium colombate fermented liquid 1 being carried out to high speed centrifugation 2 processes, then the clear liquid after high speed centrifugation being processed adopts ultra-filtration membrane 3 to carry out uf processing, ultra-filtration membrane filtrate after uf processing is sodium colombate solution, be collected into sodium colombate solution storage tank 4 in order to next step ion exchange treatment use, and the residue of uf processing is ultra-filtration membrane filter residue; Slag liquid after high speed centrifugation is processed adopts ceramic membrane to carry out filtration treatment again, ceramic membrane filtrate after filtration treatment is sodium colombate solution, also be collected into sodium colombate solution storage tank, carry out follow-up ion exchange treatment with the sodium colombate solution merging after uf processing, residue after ceramic membrane filter is processed is ceramic membrane filter residue, because ceramic membrane filter residue contains a large amount of protein, and in filtration treatment, nothing is added any chemical substance, can be directly used in processing feed or fertilizer.
Sodium colombate fermented liquid is after high speed centrifugation art breading, and clear liquid is comparatively transparent, and contained solid content is lower, adopts ultra-filtration membrane to process; And the lower floor slag liquid solid content of high speed centrifugation after processing is higher, if adopt ultra-filtration membrane to filter, ultra-filtration membrane is easy to result in blockage, and can increase the wash number of ultra-filtration membrane, therefore causes the production time to increase, and ultra-filtration membrane shortens work-ing life; And ceramic membrane is high temperature resistant, chemical stability is good, the antimicrobial degraded of energy; For organic solvent, etchant gas and microbial attack performance satisfactory stability; Physical strength is high, high pressure resistant, has good wear-resisting, flushing resistance; Pore size distribution is narrow, and separation performance is good, and infiltration capacity is large, repeatedly cleaning and regeneration.But the cost of ceramic membrane is higher, so the present invention adopts ultra-filtration membrane and ceramic membrane-bound extracting method, adopts ultra-filtration membrane to process clear liquid, and adopts ceramic membrane to process slag liquid, can collect to greatest extent the effective constituent in filter residue, improves the yield of product.The sodium colombate solution clear obtaining through extraction process of the present invention, reaches more than 99% the rejection of thalline, and the filter residue after ceramic membrane filter can be directly used in processing feed or organic fertilizer; Simultaneously to the extraction yield of sodium colombate in the molten sodium fermented liquid of 2-KLG liquid up to 99%, higher than the technique that only adopts ultrafiltration membrance filter.
The filter residue of traditional sodium colombate fermented liquid is processed the method for generally taking flocculation, flocculation need be added two kinds of flocculation agents in fermented liquid, price is more expensive, increased production cost, run into serious microbiological contamination lot number, flocculating effect is very poor, simultaneously owing to needing to add flocculation agent in flocculation process, thereby separating material slag cannot be recycled, increased discharge amount of pollution.
Adopt the impurity phase such as albumen, starch, polysaccharide in the sodium colombate fermented liquid that extracting method of the present invention obtains to reduce for traditional technology content, greatly reduce the pollution burden of follow-up ion exchange resin, vaporizer, can reduce the protein emulsifying phenomenon producing when solvent extracts simultaneously, improve quality product, shortened the production time.
The comparing result that table 1 adopts different process to process for sodium colombate fermentation melt cinder liquid:
| Technique | Yield % | Transmittance % |
| Flocculation | 72.2 | 48 |
| Ceramic membrane | 94.56 | 70 |
The technique that adopts ceramic membrane to process slag liquid is compared with former flocculation process, and yield improves 23.64%, and transmittance improves 31.5%.Yield in table 1 is the yield that sodium colombate contained in slag liquid is extracted.Transmittance in table 1 represents the transmittance of the sodium colombate solution reclaiming after high speed centrifugation slag liquid is processed, and transmittance is higher, represents that filter effect is better, and the protein content in solution is lower.
The comparing result that table 2 adopts different process to process for sodium colombate fermented liquid:
| Technique | Yield % | Transmittance % |
| Ultrafiltration+flocculation | 92.34 | 51 |
| Ultra-filtration membrane | 90 | 73 |
| Ceramic membrane | 97.21 | 63 |
| Ultrafiltration+ceramic membrane | 98.42 | 72 |
Table 2 adopts the comparative result of the resulting sodium colombate solution of different technique for sodium colombate fermented liquid.Yield in table 2 is the yield that sodium colombate contained in sodium colombate fermented liquid is extracted.Transmittance in table 2 represents the transmittance of the sodium colombate solution reclaiming after slag liquid is processed, and transmittance is higher, represents that filter effect is better, and the protein content in solution is lower.The yield of analyzing the treatment process can obtain adopting ultrafiltration+ceramic membrane by table 2 is higher than the yield that adopts the recovery process of ultrafiltration+flocculation, and treatment effect is better than adopting merely the treatment process (according to transmittance) of ceramic membrane.
The present embodiment is the improvement of carrying out on the basis of embodiment 1, the part identical with embodiment 1 in the present embodiment, please refer to disclosed content in embodiment 1 and understand, the disclosed content of embodiment 1 should, as the content of the present embodiment, not be repeated in this description herein yet.
Referring to Fig. 1, the extracting method of embodiment 1 also comprises that the ultra-filtration membrane filter residue that clear liquid is obtained after uf processing adopts ceramic membrane system to carry out filtration treatment again.Because the aperture of ultra-filtration membrane is generally 1-20 nanometer, therefore the filter residue after ultrafiltration membrance filter may contain a small amount of sodium colombate, the present invention also adopts this part ultra-filtration membrane filter residue together with the slag liquid of ceramic membrane system and centrifugal treating and carries out filtration treatment again, can reclaim sodium colombate contained in ultra-filtration membrane filter residue, further improve yield, and do not need to increase any equipment.The filter residue that just obtains after uf processing adopts ceramic membrane system to carry out again the yield of sodium colombate after filtration treatment can to reach more than 99.3%, further improve yield, and do not needed to increase any facility investment.
The present embodiment is the improvement of carrying out on the basis of embodiment 1, the part identical with embodiment 1 in the present embodiment, please refer to disclosed content in embodiment 1 and understand, the disclosed content of embodiment 1 should, as the content of the present embodiment, not be repeated in this description herein yet.
Referring to Fig. 1, the technique of the filtration treatment of the employing ceramic membrane system described in embodiment 1 comprises the following steps:
(1) the slag liquid and the ultra-filtration membrane filter residue that after high speed centrifugation processing, obtain are transported to prefilter 5, carry out pre-filtering processing, remove particulate state contained in slag liquid, fibrous impurity etc., obtain pre-filtering liquid, the incoming stock tank 6 of described pre-filtering liquid;
(2) the pre-filtering liquid in head tank is squeezed in first step ceramic membrane system 7 by charging pump, carry out thickening filtration processing, obtain first step filtrate and first step concentrated solution, first step filtrate enters next step ion exchange treatment, be collected into sodium colombate solution storage tank, first step concentrated solution enters in secondary ceramic membrane system 8;
(3) first step concentrated solution is carried out to dialysis treatment, obtain second stage filtrate and ceramic membrane residue, second stage filtrate enters next step ion exchange treatment, is collected into sodium colombate solution storage tank; Ceramic membrane residue can reclaim as feed or organic fertilizer; Described dialysis treatment adds pure water by feeding line, when effective constituent is less than certain numerical value in concentrated residue, stops adding pure water, shuts down; Described filtrate is sodium colombate solution;
(4) raffinate of emptying prefilter, head tank and ceramic membrane system, washes film and processes, repetition above-mentioned steps after washing film and completing.
The design parameter of ceramic membrane such as ceramic membrane areas etc. are determined according to concrete processing condition.
Take 120 cubic metres of every days for the treatment of capacity is example, and 60 liters every square metre of design average filtration flux is per hour, approximately 150 square metres of the required membrane areas of ceramic membrane system.In the present embodiment, ceramic membrane system adopts commercially available ceramic membrane.
Embodiment 4
The present embodiment is the improvement of carrying out on the basis of embodiment 3, the part identical with embodiment 3 in the present embodiment, please refer to disclosed content in embodiment 3 and understand, the disclosed content of embodiment 3 should, as the content of the present embodiment, not be repeated in this description herein yet.
In treatment step described in embodiment 3 (2), in thickening filtration processing, pre-filtering liquid is concentrated into 3-5 doubly.
The present embodiment is the improvement of carrying out on the basis of embodiment 4, the part identical with embodiment 4 in the present embodiment, please refer to disclosed content in embodiment 4 and understand, the disclosed content of embodiment 4 should, as the content of the present embodiment, not be repeated in this description herein yet.
In treatment step described in embodiment 3 (2), in thickening filtration processing, pre-filtering liquid is concentrated into 4 times.
When pre-filtering liquid is concentrated into 3 times, the extraction yield of sodium colombate fermentation melt cinder liquid is low, and while being concentrated into 5 times, the production time is long, and cycles of concentration be the extraction yield of 4 o'clock up to 99%, the economic worth of considering remaining sodium colombate from economic angle is compared with working cost does not have the meaning extracted.
With pre-filtering liquid 120 m
3/ d(cubic meter/sky) be example, the material balance figure of the technique of the filtration treatment of described employing ceramic membrane is referring to Fig. 2.
Pre-filtering liquid in head tank is 120 m
3/ d, squeezes in first step ceramic membrane system by charging pump, carries out thickening filtration processing, concentrated 4 times, obtains first step filtrate 90 m
3/ d and first step concentrated solution 30 m
3/ d, first step filtrate enters next step ion exchange treatment, and first step concentrated solution enters in secondary ceramic membrane system; First step concentrated solution is carried out to dialysis treatment, add pure water 90 m
3/ d, obtains second stage filtrate 90 m
3/ d and ceramic membrane residue 30 m
3/ d, second stage filtrate enters next step ion exchange treatment; The total liquid finally obtaining is 180 m
3/ d.
Therefore the required membrane area of ceramic membrane system approximately: 180 ÷ 20 ÷ 0.06=150.0(square metre).
Embodiment 6
The present embodiment is the improvement of carrying out on the basis of embodiment 3, the part identical with embodiment 3 in the present embodiment, please refer to disclosed content in embodiment 3 and understand, the disclosed content of embodiment 3 should, as the content of the present embodiment, not be repeated in this description herein yet.
The described film processing of washing comprises the cleaning to the cleaning of ceramic membrane systemic circulation side and ceramic membrane system per-meate side, and the described device of washing film processing employing is purge tank and scavenging pump.The clean-out system adopting is conventional ceramic membrane cleaning agent.Film in the present embodiment cleans and adopts automatic control system to control.
Ceramic membrane has excellent chemical stability and high physical strength, so ceramic membrane cleaning can adopt any chemical reagent.In the present embodiment, adopting mass concentration is 1 ~ 2% common acid alkaline cleaner, so can save cleaning charge and use.
Embodiment 6
The present embodiment is the improvement of carrying out on the basis of embodiment 1, the part identical with embodiment 1 in the present embodiment, please refer to disclosed content in embodiment 1 and understand, the disclosed content of embodiment 1 should, as the content of the present embodiment, not be repeated in this description herein yet.
Described ceramic membrane is inorganic ceramic film, and described inorganic ceramic film is in wide-aperture supporting body surface, to apply the fine and close microporous film layers of 4 ~ 6 micron thickness.
Embodiment 7
The present embodiment is the improvement of carrying out on the basis of embodiment 1, the part identical with embodiment 1 in the present embodiment, please refer to disclosed content in embodiment 1 and understand, the disclosed content of embodiment 1 should, as the content of the present embodiment, not be repeated in this description herein yet.
In the present embodiment, the aperture of described ultra-filtration membrane is 10 nanometers, the solute molecule that can molecular weight cut-off be greater than 100,000, and the aperture of described ceramic membrane is 50 nanometers, the solute molecule that can molecular weight cut-off be greater than 500,000.
Claims (6)
1. the extracting method of a sodium gulonate from sodium gulonate fermented liquid, it is characterized in that: first sodium colombate fermented liquid is carried out to high speed centrifugation processing, then the clear liquid obtaining after high speed centrifugation being processed adopts ultrafiltration system to process, and the slag liquid obtaining after high speed centrifugation is processed adopts ceramic membrane system to carry out filtration treatment again;
Further, the ultra-filtration membrane filter residue that described clear liquid obtains after uf processing adopts ceramic membrane system to carry out filtration treatment again;
Further, the technique of the filtration treatment of described employing ceramic membrane system comprises the following steps:
(1) the slag liquid and the ultra-filtration membrane filter residue that after high speed centrifugation processing, obtain are transported to prefilter, carry out pre-filtering processing, obtain pre-filtering liquid, the described incoming stock tank of pre-filtering liquid;
(2) the pre-filtering liquid in head tank is squeezed in first step ceramic membrane system by charging pump, carry out thickening filtration processing, obtain first step filtrate and first step concentrated solution, first step filtrate enters next step ion exchange treatment, and first step concentrated solution enters in secondary ceramic membrane system;
(3) first step concentrated solution is carried out to dialysis treatment, obtain second stage filtrate, second stage filtrate enters next step ion exchange treatment; Described dialysis treatment adds pure water by feeding line, when effective constituent is less than certain numerical value in concentrated residue, stops adding pure water, shuts down;
(4) raffinate of emptying prefilter, head tank and ceramic membrane system, washes film and processes, repetition above-mentioned steps after washing film and completing.
2. extracting method according to claim 1, is characterized in that: in described thickening filtration processing, pre-filtering liquid is concentrated into 3-5 doubly.
3. extracting method according to claim 1, is characterized in that: in thickening filtration processing, pre-filtering liquid is concentrated into 4 times.
4. extracting method according to claim 1, is characterized in that: the described film processing of washing comprises the cleaning to the cleaning of ceramic membrane systemic circulation side and ceramic membrane system per-meate side, and the described device of washing film processing employing is purge tank and scavenging pump.
5. extracting method according to claim 1, is characterized in that described ceramic membrane is inorganic ceramic film, and described inorganic ceramic film is in wide-aperture supporting body surface, to apply the fine and close microporous film layers of 4 ~ 6 micron thickness.
6. extracting method according to claim 1, is characterized in that the aperture of described ultra-filtration membrane is 10 nanometers, and the aperture of described ceramic membrane is 50 nanometers.
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| CN104383813B (en) * | 2014-11-04 | 2017-05-31 | 帝斯曼江山制药（江苏）有限公司 | A kind of integrated conduct method of gulonic acid ferment liquid |
| CN109851491A (en) * | 2019-04-16 | 2019-06-07 | 同舟纵横（厦门）流体技术有限公司 | A kind of method and device of gulonate feed liquid decoloration removal of impurities |
| CN114262267A (en) * | 2021-12-29 | 2022-04-01 | 上海科琅膜科技有限公司 | Method for treating gulonic acid mash |
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| CN101643408A (en) * | 2009-08-31 | 2010-02-10 | 厦门世达膜科技有限公司 | Production method of gulonic acid in production of vitamin C |
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| CN1754869A (en) * | 2004-09-28 | 2006-04-05 | 三达膜科技（厦门）有限公司 | Process for extracting gulonic acid |
| CN101643408A (en) * | 2009-08-31 | 2010-02-10 | 厦门世达膜科技有限公司 | Production method of gulonic acid in production of vitamin C |
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