CN110407782A - One kind extracting ascorbic chromatographic process by raw material conversion of 2-KLG - Google Patents
One kind extracting ascorbic chromatographic process by raw material conversion of 2-KLG Download PDFInfo
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- CN110407782A CN110407782A CN201910728733.XA CN201910728733A CN110407782A CN 110407782 A CN110407782 A CN 110407782A CN 201910728733 A CN201910728733 A CN 201910728733A CN 110407782 A CN110407782 A CN 110407782A
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- klg
- acid
- vitamin
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- acidic
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/62—Three oxygen atoms, e.g. ascorbic acid
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The present invention relates to one kind to extract ascorbic chromatographic process by raw material conversion of 2-KLG, includes the following steps: that (1) mixes 2-KLG, acidic catalyst, sufficiently reacts, obtain 2-KLG and ascorbic mixed solution；(2) chromatographic isolation at least once is carried out to the mixed solution, using chromatography filler resin as stationary phase, using 2-KLG and vitamin C mixed liquor as mobile phase, respectively obtains Cologne acid solution and vitamin c solution；(3) the Cologne acid solution is recycled, the vitamin c solution is refined.Compared with prior art, method provided by the invention is easy to operate, avoids corrosion of the acidic materials to production equipment of high concentration, reduce equipment requirement, the consumption for reducing the energy and chemicals decreases the processing of waste water since reaction condition mildly reduces the generation of waste.
Description
Technical field
The present invention relates to chemical fields, and in particular to a kind of to extract ascorbic chromatography side by raw material conversion of 2-KLG
Method.
Background technique
Vitamin C (Vitamin C, vitamin C) is a kind of polyol, and structure is similar to glucose, molecule
In the 2nd and the 3rd upper two adjacent enolic hydroxyls easily dissociate and release H+, therefore there is the property of acid, it is also known as anti-bad
Hematic acid.Vitamin C has very strong reproducibility, plays regulatory role in redox metabolism reaction, is arranged by the World Health Organization
It is nutritional ingredient needed by human for one of essential drugs in 26.Vitamin C is mainly sent out using glucose as raw material through microorganism
Ferment is produced using chemical synthesis, is widely used in many important industry fields such as medicine, food and drink, chemical industry, feed.With
The increase of the industries to vitamin C and its derivative demand such as food, medicine, chemical industry, the market competitiveness is increasing, to dimension
Higher requirements are also raised for the conversion extraction process of raw element C.
Vitamin C preparation method is mainly acid system and alkaline process in traditional handicraft.Wherein, acid system is with 2-KLG or 2-KLG
Sodium is raw material, using acid as catalyst, is converted into vitamin C under certain reaction condition.For example, Chinese patent
It is ascorbic method through acid catalyzed conversion that CN104693160A, which is mentioned using gulonate as raw material, and this method is due to making
Add HCl gas with the hydrochloric acid of high concentration, therefore the requirement to equipment is extremely harsh.In addition, BASF group, Germany utilizes 2-KLG
Esterification occurs under the catalysis of sulfuric acid for sodium, then generates vitamin C through hydrochloric acid catalysis, and this method is due to having used sulfuric acid and salt
Acid, technique corrosivity is stronger, and the requirement to equipment is high, and reaction time is long.
Summary of the invention
Traditional acid system is strong to equipment corrosion in order to solve, the problem of production operation difference, the invention proposes one kind with
2-KLG is that ascorbic chromatographic process is extracted in raw material conversion.
Specifically, method provided by the invention includes the following steps:
(1) 2-KLG, acidic catalyst are mixed, sufficiently reacts, obtains 2-KLG and ascorbic mixed solution；
(2) chromatographic isolation at least once is carried out to the mixed solution, using chromatography filler resin as stationary phase, with Gu
Imperial acid and vitamin C mixed liquor are mobile phase, respectively obtain Cologne acid solution and vitamin c solution；
(3) the Cologne acid solution is recycled, the vitamin c solution is refined.
Part 2-KLG is first converted to vitamin C first with the catalytic action of acidic catalyst by method provided by the invention
2-KLG and vitamin C mixed liquor are formed, 2-KLG is separated with vitamin C mixed liquor using chromatography, to obtain
Vitamin c solution, vitamin c solution are vitamin C product further according to further purification is needed.
Inorganic acid, acidic metal oxide, acid nonmetal oxide, acid can be selected in the acidic catalyst that the present invention uses
One of property resin is a variety of.The inorganic acid can be hydrochloric acid, sulfuric acid, phosphoric acid etc., and present invention preferably employs hydrochloric acid and sulphur
Acid.The acidic metal oxide can be titanium oxide or zirconium oxide.It is described acidity nonmetal oxide can be molecular sieve or
Zeolite.The acidic catalyst that the present invention uses it is preferable to use acidic resins or inorganic acid, or mixtures thereof.As of the invention one
Kind preferred embodiment, the acidic catalyst are made of acidic resins and hydrochloric acid or sulfuric acid.
For method provided by the invention when step (1) reacts and generates vitamin C, the solvent of use is preferably water.It is with water
Solvent, raw material are easy to get, environmental-friendly, are conducive to industrialized production.
Method provided by the invention is preferably being performed under heating conditions reaction, and heating temperature can be 30~100 DEG C, preferably
It is 40~100 DEG C, more preferably 50~90 DEG C.
Contain 2-KLG and ascorbic mixed solution for what step (1) obtained, the present invention is divided using chromatography
From.Specifically, carrying out color using 2-KLG and vitamin c solution as mobile phase using the filler resin in chromatographic column as stationary phase
Spectrum separation, respectively obtains Cologne acid solution and vitamin c solution.In the mobile phase, suitable inorganic acid conduct can be added
Elutriant, to improve separating effect.
Chromatographic isolation temperature can be different according to the difference of chromatography filler, and reaction temperature is more mild, without obvious
By-product generates, smaller to the processing load of chromatography.
Before the present invention carries out chromatographic isolation to the mixed solution, it can first be filtered separation to it, collect acid respectively
Property catalyst and 2-KLG and vitamin C mixed liquor.Carrying out recycling circulation to the acidic catalyst collected after being separated by filtration makes
With.
In production process provided by the invention, restored acid catalyst and 2-KLG can be used as feedstock circulation and make
With.
The present invention relates to operation be unless otherwise specified this field routine operation, related separation equipment can be
Known conventional separation equipment in industry.
On the basis of common knowledge of the art, above-mentioned each optimum condition, can be combined with each other, obtain specific embodiment party
Formula.
Compared with prior art, method provided by the invention is easy to operate, and the concentration of added inorganic acid is low, avoids highly concentrated
Corrosion of the acidic materials of degree to production equipment reduces equipment requirement, and institute's Plus acidic resin is recyclable to be recycled, and reduces
The consumption of the energy and chemicals, reaction condition is more mild, and by-product is few, therefore reduces the generation of waste.
Specific embodiment
The preferred embodiment of the present invention is described in detail below in conjunction with embodiment.
Cologne acid content described in following embodiment determines that the concentration of vitamin C in the solution is logical through liquid chromatography
Oxidization-reduction titration determines.
Embodiment 1
A kind of ascorbic preparation method is present embodiments provided, specifically:
(1) successively weigh 240g 2-KLG (98.6%) solid, 160g acidic resins (content 40~60%), 140g water with
And 60g hydrochloric acid (36-38%, w/w) is placed in 1000ml conical flask, places stirrer, conical flask rubber stopper plug in bottle in advance
On prevent from evaporating；Above-mentioned apparatus is placed in 75 DEG C of water-bath, starts to react, reaction carries out to 3h stopping, and turns
Changing vitamin C concentration of the reaction after 3h is 20.87%, and Cologne acid concentration is 20.25%, and the color after reaction is that yellowish-brown is saturating
Bright, by MaterialBalance Computation, its selectivity is 98%；
(2) resin is filtered out, by filtered vitamin C and 2-KLG mixed liquor into chromatographic column, with chromatograph packing material tree
Rouge is stationary phase, and 2-KLG forms mobile phase with vitamin C mixed liquor and hydrochloric acid (0.1%, W/W) elutriant with volume ratio 1:4,
It is separated according to flow velocity 1BV/h；
(3) the Cologne acid solution after separation is recycled, the vitamin c solution is refined.
Through detecting, the present embodiment obtains vitamin c solution and Cologne acid solution through 6 grades of chromatographic isolations.It is collected into vitamin C
Solution quality is 347g, and gained vitamin c solution content vitamin C is 5.45%, and Cologne acid content is 0.29%；It is collected into Gu
Imperial acid solution quality is 174g, and solution Cologne acid content is 10.44%, Vitamin C content 1.23%.To sum up data dimension is raw
Plain C chromatographic isolation yield is 90.4%.
Embodiment 2
A kind of ascorbic preparation method is present embodiments provided, specifically:
(1) successively weigh 30g 2-KLG (98.6%) solid, 40g acidic resins (content be 40~60%), 56g water with
And 13.5g hydrochloric acid (36-38%, w/w) is placed in 250ml conical flask, places stirrer, conical flask rubber stopper plug in bottle in advance
On prevent from evaporating；Above-mentioned apparatus is placed in 75 DEG C of water-bath, starts to react, reaction carries out to 3h stopping, and ties up
Raw element C concentration is 10.5%, and Cologne acid concentration is 13.7%, and the color after reaction is that light yellowish brown is transparent, by material balance meter
Calculating its selectivity is 96.2%；
(2) resin is filtered out, by filtered vitamin C and 2-KLG mixed liquor into chromatographic column, with chromatograph packing material tree
Rouge is stationary phase, and 2-KLG forms mobile phase with vitamin C mixed liquor and hydrochloric acid (0.1%, W/W) elutriant with volume ratio 1:5,
It is separated according to flow velocity 0.5BV/h；
(3) the Cologne acid solution after separation is recycled, the vitamin c solution is refined.
Through detecting, the present embodiment obtains vitamin c solution and Cologne acid solution through 6 grades of chromatographic isolations.It is collected into vitamin C
Solution quality is 397g, and gained vitamin c solution content vitamin C is 2.20%, and Cologne acid content is 0.52%；It is collected into Gu
Imperial acid solution quality is 234g, and solution Cologne acid content is 5.09%, Vitamin C content 0.67%.To sum up data dimension is raw
It is 83% that plain color, which composes separation yield,.
Embodiment 3
A kind of ascorbic preparation method is present embodiments provided, specifically:
(1) successively weigh 240g 2-KLG (98.6%) solid, 160g acidic resins (content be 40~60%), 140g with
And 60g hydrochloric acid (36-38%, w/w) is placed in 1000ml conical flask, places stirrer, conical flask rubber stopper plug in bottle in advance
On prevent from evaporating；Above-mentioned apparatus being placed in 80 DEG C of water-bath, starts to react, reaction carries out to 3.5h stopping,
Vitamin C concentration is 18.96%, and Cologne acid concentration is 23.72%, and the color after reaction is that light yellowish brown is transparent, is put down by material
It is 94.3% that weighing apparatus, which calculates its selectivity,；
(2) resin is filtered out, by filtered vitamin C and 2-KLG mixed liquor into chromatographic column, with chromatograph packing material tree
Rouge is stationary phase, and 2-KLG forms mobile phase with vitamin C mixed liquor and hydrochloric acid elutriant (0.1%, W/W) with volume ratio 1:7,
It is separated according to flow velocity 0.5BV/h；
Through detecting, the present embodiment obtains vitamin c solution and Cologne acid solution through 6 grades of chromatographic isolations.It is collected into vitamin C
Solution quality is 556g, and gained vitamin c solution content vitamin C is 2.90%, and Cologne acid content is 0.34%；It is collected into Gu
Imperial acid solution quality is 304g, and solution Cologne acid content is 7.02%, Vitamin C content 0.75%.To sum up data dimension is raw
It is 86% that plain color, which composes separation yield,.
(3) the Cologne acid solution is recycled, the vitamin c solution is refined.
To sum up example has a small amount of 2-KLG not separate completely in the vitamin c solution being collected into, accounts for the ratio of total solution
It is less, it can be removed in subsequent purification；Contain a small amount of vitamin C in the Cologne acid solution being collected into, it can be with Cologne acid solution
Return step (1) is recycled.
Although above having used general explanation, specific embodiment and test, the present invention is made to retouch in detail
It states, but on the basis of the present invention, it can be made some modifications or improvements, this is apparent to those skilled in the art
's.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, belong to claimed
Range.
Claims (10)
1. a kind of extract ascorbic chromatographic process by raw material conversion of 2-KLG, which comprises the steps of:
(1) 2-KLG, acidic catalyst are mixed, sufficiently reacts, obtains 2-KLG and ascorbic mixed solution；
(2) chromatographic isolation at least once is carried out to the mixed solution, using chromatography filler resin as stationary phase, with 2-KLG
It is mobile phase with vitamin C mixed liquor, respectively obtains Cologne acid solution and vitamin c solution；
(3) the Cologne acid solution is recycled, the vitamin c solution is refined.
2. the method according to claim 1, wherein the acidic catalyst is inorganic acid, acid metal oxidation
One of object, acid nonmetal oxide, acidic resins or a variety of mixing.
3. according to the method described in claim 2, it is characterized in that, the acidic catalyst is inorganic acid, acidic resins or nothing
The combination of machine acid and acidic resins.
4. according to the method in claim 2 or 3, which is characterized in that the inorganic acid be sulfuric acid, hydrochloric acid or phosphoric acid, preferably
For sulfuric acid or hydrochloric acid.
5. according to the method described in claim 2, it is characterized in that, the acidic metal oxide is titanium oxide or zirconium oxide.
6. according to the method described in claim 2, it is characterized in that, the acidity nonmetal oxide is acidic molecular sieve or boiling
Stone.
7. method described in any one according to claim 1~6, which is characterized in that the solvent of step (1) described reaction is
Water.
8. method described in any one according to claim 1~7, which is characterized in that the reaction temperature is 30~110 DEG C,
Preferably 40~100 DEG C, more preferably 50~90 DEG C.
9. the method according to claim 1, wherein to the mixed solution carry out chromatographic isolation before, to its into
Row is separated by filtration, and collects acidic catalyst and 2-KLG and vitamin C mixed liquor respectively；Preferably, to being received after being separated by filtration
The acidic catalyst of collection recycles.
10. the method according to claim 1, wherein the temperature of the chromatographic isolation is filled out according to the chromatography
The activity of material resin is set.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910728733.XA CN110407782A (en) | 2019-08-08 | 2019-08-08 | One kind extracting ascorbic chromatographic process by raw material conversion of 2-KLG |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910728733.XA CN110407782A (en) | 2019-08-08 | 2019-08-08 | One kind extracting ascorbic chromatographic process by raw material conversion of 2-KLG |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3843389A1 (en) * | 1988-12-23 | 1990-06-28 | Basf Ag | Process for the preparation of ascorbic acid |
| CN1507440A (en) * | 2000-12-22 | 2004-06-23 | �Ϻ���ͨ��ѧ | Continuous process for producing L-ascorbic acid |
| CN101041649A (en) * | 2007-04-10 | 2007-09-26 | 三达膜科技（厦门）有限公司 | Production method of reclaiming vitamin C and gulonic acid from vitamin C mother liquid |
| CN101284824A (en) * | 2008-06-06 | 2008-10-15 | 郑州拓洋实业有限公司 | Preparation method of cenolate |
-
2019
- 2019-08-08 CN CN201910728733.XA patent/CN110407782A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3843389A1 (en) * | 1988-12-23 | 1990-06-28 | Basf Ag | Process for the preparation of ascorbic acid |
| CN1507440A (en) * | 2000-12-22 | 2004-06-23 | �Ϻ���ͨ��ѧ | Continuous process for producing L-ascorbic acid |
| CN101041649A (en) * | 2007-04-10 | 2007-09-26 | 三达膜科技（厦门）有限公司 | Production method of reclaiming vitamin C and gulonic acid from vitamin C mother liquid |
| CN101284824A (en) * | 2008-06-06 | 2008-10-15 | 郑州拓洋实业有限公司 | Preparation method of cenolate |
Non-Patent Citations (2)
| Title |
|---|
| CARSTEN SCHINSCHEL等: "Proteus mirabilis Dehydrogenates Aldonates and Aldarates with an (R)-Configured α-Carbon Atom to the Corresponding 2-Oxocarboxylates", 《BIOORGANIC & MEDICINAL CHEMISTRY》 * |
| 徐静等: "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》 * |
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