CN110386908A - It is a kind of to prepare ascorbic method by the alkali conversion method of raw material of Cologne hydrochlorate - Google Patents
It is a kind of to prepare ascorbic method by the alkali conversion method of raw material of Cologne hydrochlorate Download PDFInfo
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- CN110386908A CN110386908A CN201910728734.4A CN201910728734A CN110386908A CN 110386908 A CN110386908 A CN 110386908A CN 201910728734 A CN201910728734 A CN 201910728734A CN 110386908 A CN110386908 A CN 110386908A
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- Prior art keywords
- cologne
- gulonate
- acid
- hydrochlorate
- raw material
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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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Furan Compounds (AREA)
Abstract
Ascorbic method is prepared by the alkali conversion method of raw material of Cologne hydrochlorate the present invention relates to a kind of, include the following steps: (1) using Cologne hydrochlorate as raw material, esterification is carried out with alcohols material under the action of acidic catalyst, obtains the solution containing Gulonate；The acidic catalyst is the combination of the inorganic acid or itself and acidic resins not including sulfuric acid；(2) alkaline non-nitrogen containing catalyst is added in the solution containing Gulonate, carries out lactonization reaction, obtains vitamin C；The alkalinity non-nitrogen containing catalyst is solid-state alkaline matter, basic resin or combinations thereof.Method provided by the invention can avoid the generation of sodium sulfate byproduct in production process, while the recyclable recycling of non-expendable solid peracid, alkaline matter and resin, has reached circular economy effect, has reduced the generation of waste water, saved production cost.
Description
Technical field
The present invention relates to chemical products production technical fields, and in particular to a kind of using Cologne hydrochlorate as the alkali conversion method of raw material
Prepare ascorbic method.
Background technique
Vitamin C (Vitamin C, Vc) is a kind of polyol, and structure is similar to glucose, the 2nd in molecule
And the 3rd upper two adjacent enolic hydroxyls easily dissociate and release H+, therefore there is the property of acid, also known as ascorbic acid.
Vc has very strong reproducibility, plays regulatory role in redox metabolism reaction, is classified as in 26 substantially by the World Health Organization
One of drug is nutritional ingredient needed by human.Vc is mainly closed using glucose as raw material through microbial fermentation or using chemistry
It is produced at method, is widely used in many important industry fields such as medicine, food and drink, chemical industry, feed.With food, medicine, change
Increase of the industries such as work to Vc and its derivative demand, the market competitiveness is increasing, also mentions to the conversion extraction process of Vc
Higher requirement is gone out.
Production of vitamin C has one-step fermentation and two-step fermenting, and existing Vc production technology is mostly two-step fermenting.According to
Agents useful for same is different, and two-step fermenting production vitamin C can be divided into sour conversion method and alkali conversion method.For example, Chinese patent
CN101914079A provides a kind of ascorbic method of use alkali conversion method production, and this method is existed using gulonate crystal
Under sulphuric acid catalysis, esterification is carried out with n-butanol and produces 2-KLG N-butyl solution；Add Na2CO3Lactonize anti-
Vitamine C sodium should be generated, last vitamine C sodium carries out acidification and active carbon decoloring obtains vitamin C.However, this method is with dense
Sulfuric acid is catalyst, before carrying out alkali conversion, need to be increased with sodium bicarbonate sulfate radical (SO4 2-) reaction step and filtering step
Suddenly, the production cycle is not only extended, but also causes the waste of man power and material, and sulfuric acid has strong oxidizing property, if in esterifying liquid
Sulfate radical processing is not clean, also will affect the quality and yield of crude vitamin C.
Summary of the invention
It is an object of the invention to overcome the deficiencies of existing technologies, providing one kind using Cologne hydrochlorate is raw material using alkali conversion
Method prepares ascorbic new method.
Specifically, method provided by the invention the following steps are included:
(1) using Cologne hydrochlorate as raw material, esterification is carried out with alcohols material under acidic catalyst effect, is obtained containing Gu
The solution of imperial acid esters；
(2) alkaline non-nitrogen containing catalyst is added in the solution containing Gulonate, carries out lactonization reaction, must tie up
Raw element C.
In method provided by the invention, the Cologne hydrochlorate as raw material can pass through fermentation, chemical synthesis or other this fields
Known approach obtains.The Cologne hydrochlorate is preferably gulonate.
The acidic catalyst that the present invention uses for not including sulfuric acid inorganic acid or its combined with acidic resins, wherein
Acidic resins are recyclable to be recycled.Specifically, the inorganic acid includes hydrochloric acid, phosphoric acid and boric acid etc..
In method provided by the invention, the alcohols material is the cell alcohol or polyalcohol for including 1~24 carbon atom,
It preferably include the cell alcohol of 1~4 carbon atom, such as methanol, ethyl alcohol and n-butanol.
The basic catalyst that the present invention uses is solid-state alkaline matter, basic resin or combinations thereof.The solid-state basic species
It is recyclable after matter use, such as magnesia, calcium oxide, barium monoxide, strontium oxide strontia, calcium carbonate or magnesium carbonate, preferably oxygen
Change calcium or magnesia.The basic resin can be recycled after usage with reclaiming.
As a preferred solution of the present invention, described method includes following steps:
(1) using gulonate as raw material, not including sulfuric acid inorganic acid or its catalysis combined with acidic resins
Effect is lower to carry out esterification with the cell alcohol containing 1~4 carbon atom, obtains the solution containing Gulonate；
(2) magnesia, calcium oxide, magnesium carbonate, calcium carbonate or alkalinity tree are added in the solution containing Gulonate
One of rouge or a variety of combinations carry out lactonization reaction, obtain vitamin C.
Vitamin C crude product can be obtained in method provided by the invention, mentions if it is desired, can separate by method well known in industry
The pure vitamin C product for high-purity.
The present invention relates to operation be unless otherwise specified this field routine operation.Pressure, temperature in reaction etc.
Actual conditions can be adjusted according to factors such as catalyst properties, to meet production needs.
Compared with prior art, method provided by the invention can reduce the consumption of sulfuric acid in production process, reduce by-product
The generation of sodium sulphate, while non-expendable solid-state alkaline matter and the recyclable recycling of acid, basic resin, have reached circulation warp
Ji effect, reduces the generation of waste water, reduces production cost.
Specific embodiment
The preferred embodiment of the present invention is described in detail below in conjunction with embodiment.
Embodiment 1
A kind of ascorbic preparation method is present embodiments provided, specifically:
(1) 49.5 grams of gulonate are weighed in 500 milliliters of there-necked flasks, the acid tree with the transposed moisture of n-butanol is added
After 50 grams of rouge (amount containing butanol 20%), then plus 312.5 grams and 25 grams concentrated hydrochloric acids (37%w/w) of n-butanol, setting be condensed back
Device opens stirring under 99 DEG C of oil bath heatings, after reacting 4.5 hours, obtains 2-KLG N-butyl solution；
(2) in the 2-KLG N-butyl solution, convert into 2-KLG molal weight 100% is added 15 grams of calcium oxide,
It is filtered after reacting for 3 hours under 70 DEG C of water-baths, collects the filtrate containing Vc, filter cake is eluted with equal proportion pure water, and collection is washed
De- liquid.
Through detecting, original Vc content is 0.28% in the 2-KLG N-butyl solution, under the catalytic action of calcium oxide,
Vc% increases to 3.25% in reaction solution after 3 hours, illustrates that calcium oxide has certain catalytic effect.The present embodiment overall reaction Vc is received
Rate is 56%.
Embodiment 2
A kind of ascorbic preparation method is present embodiments provided, specifically:
(1) 55 grams of gulonate are weighed in 1 liter of there-necked flask, addition crosses the acidic resins of moisture with methanol replacement (containing first
Alcohol amount 25%) after 55 grams, then plus 385 grams and 30 grams concentrated hydrochloric acids (38%w/w) of methanol, condensation reflux unit, 70 DEG C of water are set
Bath heating is lower to open stirring, after reacting 4.5 hours, filters to obtain methyl 2-keto-L-gulonate solution, isolates tree after collecting filter cake washing
Rouge；
(2) in the methyl 2-keto-L-gulonate solution, convert into 2-KLG molal weight 100% is added 18 grams of magnesia, In
It is filtered by vacuum after being reacted 3 hours under 70 DEG C of water-baths, collects the filtrate containing Vc, filter cake carries out elution drying with equal proportion pure water.
Through detecting, original Vc content is 1.59%, under the catalytic action of calcium oxide, 3 in the methyl 2-keto-L-gulonate solution
Vc% increases to 7.67% in reaction solution after hour, illustrates that magnesia has certain catalytic effect.And filter cake detects after drying
For magnesia solid, it was demonstrated that the recuperability of the base catalyst.The present embodiment overall reaction Vc conversion ratio is 69%.By perfect
Alkali reaction conversion ratio can be improved in optimization experimental program.
Embodiment 3
A kind of ascorbic preparation method is present embodiments provided, specifically:
(1) 120 grams of gulonate are weighed in 2 liters of there-necked flasks, after being added 840 grams of dehydrated alcohol, adds 50 grams of phosphoric acid
(content 85%) is arranged condensate collection device, stirring, after band 2.5 hours of vacuum reaction, mistake is opened under 80 DEG C of oil bath heatings
Filter to obtain Cologne acetate solution；
(2) 200 grams of above-mentioned Cologne acetate solution is taken, 400 grams of OH are added-Type resin, the static reaction 2 under 50 DEG C of water-baths
After hour, Vc solution is filtered to obtain.
Through detecting, original Vc content is 0.41% in the Cologne acetate solution, and Vc% is increased in solution after reaction
2.26%.The present embodiment overall reaction Vc conversion ratio is 51%.Alkali reaction conversion ratio can be improved by improvement and optimization experimental program.
Embodiment 4
A kind of ascorbic preparation method is present embodiments provided, specifically:
(1) 114 grams of gulonate are weighed in 1 liter of there-necked flask, after being added 570 grams of n-butanol, adds 35 grams of concentrated hydrochloric acids
(37%w/w) is arranged condensate collection device, opens stirring under 99 DEG C of oil bath heatings and filter after band 2 hours of vacuum reaction
2-KLG N-butyl solution；
(2) above-mentioned 100 grams of 2-KLG N-butyl solution are taken, 300 grams of OH are added-Type resin, static state is stirred under 50 DEG C of water-baths
After mixing reaction 3 hours, Vc solution is filtered to obtain.
Through detecting, the present embodiment overall reaction Vc conversion ratio is 73%.Alkali reaction can be improved by improvement and optimization experimental program
Conversion ratio.
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 (8)
1. a kind of prepare ascorbic method by the alkali conversion method of raw material of Cologne hydrochlorate, which is characterized in that including walking as follows
It is rapid:
(1) using Cologne hydrochlorate as raw material, esterification is carried out with alcohols material under the action of acidic catalyst, Cologne must be contained
The solution of acid esters；
The combination of inorganic acid or itself and acidic resins of the acidic catalyst not including sulfuric acid；
(2) alkaline non-nitrogen containing catalyst is added in the solution containing Gulonate, carries out lactonization reaction, obtains vitamin
C；
The alkalinity non-nitrogen containing catalyst is solid-state alkaline matter, basic resin or combinations thereof.
2. the method according to claim 1, wherein the Cologne hydrochlorate can by fermentation method, chemical synthesis or
Other approach are made, and are selected from gulonate, 2-KLG calcium, 2-KLG potassium, 2-KLG ammonium or 2-KLG magnesium.
3. the method according to claim 1, wherein the inorganic acid not including sulfuric acid is preferably hydrochloric acid, phosphorus
Acid or boric acid.
4. the method according to claim 1, wherein the alcohols material is to include 1~24 carbon atom
Cell alcohol or polyalcohol preferably include the cell alcohol of 1~4 carbon atom.
5. the method according to claim 1, wherein the solid-state alkaline matter is alkaline metal oxide or alkali
Acid carbonate.
6. according to the method described in claim 5, it is characterized in that, the alkaline metal oxide is preferably magnesia, oxidation
Calcium, barium monoxide or strontium oxide strontia.
7. according to the method described in claim 5, it is characterized in that, the basic carbonate is calcium carbonate and magnesium carbonate.
8. method described in any one according to claim 1~7, which comprises the steps of:
(1) using gulonate as raw material, not including sulfuric acid inorganic acid or its catalytic action combined with acidic resins
It is lower to carry out esterification with the cell alcohol containing 1~4 carbon atom, obtain the solution containing Gulonate；
(2) it is added in magnesia, calcium oxide, magnesium carbonate, calcium carbonate or basic resin in the solution containing Gulonate
One or more combinations, carry out lactonization reaction, obtain vitamin C.
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|---|---|---|---|
| CN201910728734.4A CN110386908A (en) | 2019-08-08 | 2019-08-08 | It is a kind of to prepare ascorbic method by the alkali conversion method of raw material of Cologne hydrochlorate |
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| CN201910728734.4A CN110386908A (en) | 2019-08-08 | 2019-08-08 | It is a kind of to prepare ascorbic method by the alkali conversion method of raw material of Cologne hydrochlorate |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1633425A (en) * | 2002-02-12 | 2005-06-29 | 伊斯曼化学公司 | Process for the preparation of ascorbic acid |
| CN101805319A (en) * | 2010-04-21 | 2010-08-18 | 石药集团维生药业（石家庄）有限公司 | Method for directly converting and preparing sodium ascorbate by using sodium gulonic acid |
-
2019
- 2019-08-08 CN CN201910728734.4A patent/CN110386908A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1633425A (en) * | 2002-02-12 | 2005-06-29 | 伊斯曼化学公司 | Process for the preparation of ascorbic acid |
| CN101805319A (en) * | 2010-04-21 | 2010-08-18 | 石药集团维生药业（石家庄）有限公司 | Method for directly converting and preparing sodium ascorbate by using sodium gulonic acid |
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