CN110294726A - The preparation method of ISOASCORBIC ACID potassium - Google Patents

The preparation method of ISOASCORBIC ACID potassium Download PDF

Info

Publication number
CN110294726A
CN110294726A CN201910689231.0A CN201910689231A CN110294726A CN 110294726 A CN110294726 A CN 110294726A CN 201910689231 A CN201910689231 A CN 201910689231A CN 110294726 A CN110294726 A CN 110294726A
Authority
CN
China
Prior art keywords
keto
gluconate
potassium
isoascorbic acid
preparation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201910689231.0A
Other languages
Chinese (zh)
Inventor
崔凤霞
高莉
秦天苍
曹琳青
周俊俊
张抗
郭金权
刘银霞
曹晓伟
龚舒
史小利
肖媛
刘杉
宋莹莹
李永生
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Xintuoyang Bioengineering Co Ltd
Original Assignee
Xintuoyang Bioengineering Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Xintuoyang Bioengineering Co Ltd filed Critical Xintuoyang Bioengineering Co Ltd
Priority to CN201910689231.0A priority Critical patent/CN110294726A/en
Publication of CN110294726A publication Critical patent/CN110294726A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H1/00—Processes for the preparation of sugar derivatives
    • C07H1/06—Separation; Purification
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H7/00—Compounds containing non-saccharide radicals linked to saccharide radicals by a carbon-to-carbon bond
    • C07H7/02—Acyclic radicals
    • C07H7/027—Keto-aldonic acids

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Biochemistry (AREA)
  • Biotechnology (AREA)
  • General Health & Medical Sciences (AREA)
  • Genetics & Genomics (AREA)
  • Molecular Biology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The present invention relates to a kind of preparation methods of ISOASCORBIC ACID potassium, the preparation method of the ISOASCORBIC ACID potassium is the following steps are included: take 2- keto-D-gluconate fermentation liquid, it is centrifuged and the concentrated sulfuric acid is added in supernatant, acidification clear liquid is obtained by filtration later, acidification clear liquid is used into hollow-fibre ultrafiltration device progress ultrafiltration, ultrafiltrate of the molecular cut off less than 50,000 is concentrated up to 2- keto-D-gluconate concentrate；Alcoholic solvent is added and solid super acid catalyst carries out esterification, alkaline potassium ion donor is added later and carries out conversion reaction, up to ISOASCORBIC ACID potassium after purifying.2- keto-D-gluconate fermentation liquid is pre-processed, so that the material purity of esterification is higher, 2- keto-D-gluconate ester yield is higher, so that subsequent 2- keto-D-gluconate esterification efficiency is higher and to be converted to the yield of ISOASCORBIC ACID higher.

Description

The preparation method of ISOASCORBIC ACID potassium
Technical field
The invention belongs to ISOASCORBIC ACID potassium production technical fields, and in particular to a kind of preparation method of ISOASCORBIC ACID potassium.
Background technique
The alternative sodium isoascorbate of ISOASCORBIC ACID potassium is applied in multiple fields.For example, ISOASCORBIC ACID potassium can be used as food Additive application in field of food, primarily serve it is fresh-keeping, help color, antioxygen, corrosion-resistant effect.The synthesis side of ISOASCORBIC ACID potassium with The synthetic method of sodium isoascorbate is similar.The synthetic method of ISOASCORBIC ACID potassium are as follows: make 2- ketone group-glucose using catalyst It is esterified in acid, alkaline potassium ion donor is added later, obtains ISOASCORBIC ACID potassium by purification after reaction.Meeting in purification process A part of mother liquor is generated, contains a large amount of potassium ion in mother liquor, potash fertilizer can be converted into, wastewater treatment expense is saved and can produce Economic benefit.
Currently, the 2- keto-D-gluconate that synthesis ISOASCORBIC ACID potassium uses is mostly from zymotechnique, completion of fermenting 2- keto-D-gluconate fermentation liquid is directly used in synthesis ISOASCORBIC ACID potassium, but contains in 2- keto-D-gluconate fermentation liquid A large amount of spent acid, mycoprotein, carbohydrate etc., if do not purified to 2- keto-D-gluconate fermentation liquid, a large amount of impurity Adverse effect can be caused to synthesis ISOASCORBIC ACID potassium, reduce the yield of ISOASCORBIC ACID potassium, and make the different dimension ultimately generated raw Plain C potassium is not easy to purify.
In the prior art, there is the method purified using ion exchange resin to 2- keto-D-gluconate fermentation liquid, such as Application publication number is that the patent of invention of CN102329226A discloses a kind of process for separation and purification of 2- keto-D-gluconate, should Method will be the following steps are included: inorganic acid radical ion, 2-KDG content will be removed as 18.37g/100mL, pH is 1.59 fermentation liquid flows through the 130mL WDA918 weak-base anion-exchange resin bed regenerated with the flow velocity of 2BV/h, works as stream The content of the 2-KDG of liquid is stops inhaling handing over out when 18.18g/100mL, shared fermentation liquid 540mL, and collection pH < 3.0,2-KDG average content is the total 405mL of efflux of 10.60g/100mL；With the deionized water of 260mL Eject 2-KDG unadsorbed in resin bed；Successively with 52% methanol aqueous solution 65mL, 73% methanol Aqueous solution 65mL and industrial methanol 195mL flows through resin bed with the flow velocity of 3.0BV/h, removes the water in resin bed；Successively use H2SO4The H that volume fraction is 5%2SO4-CH3OH solution 195mL, H2SO4The H that volume fraction is 3%2SO4-CH3OH solution 260mL elutes resin, and first gradient eluent flow rate is 1.5BV/h, and the second gradient elution flow velocity is 1.0BV/h； Above-mentioned eluent is stirred to react 2h after steaming 300mL methanol at 66-70 DEG C, and isolated purity is 97.2%HPLC method 2-KDG methyl esters 36.86g, pure 35.82g, desorption and two step total recovery of esterification are 91.4%.This method Directly 2- keto-D-gluconate fermentation liquid is purified using ion exchange resin, the macromoleculars such as carbohydrate and protein compared with Hardly possible removes and ion exchange resin is not easy to regenerate, while production cost is higher, only rests on laboratory stage at present, it is more difficult to big rule Mould production.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of ISOASCORBIC ACID potassium, which is made ISOASCORBIC ACID potassium yield it is higher.
In order to achieve the goal above, the technical scheme adopted by the invention is as follows: the preparation method of ISOASCORBIC ACID potassium, including with Lower step:
1) 2- keto-D-gluconate fermentation liquor pretreatment: taking 2- keto-D-gluconate fermentation liquid, is centrifuged and in supernatant The middle addition concentrated sulfuric acid, is obtained by filtration acidification clear liquid later, and acidification clear liquid is carried out ultrafiltration, retention using hollow-fibre ultrafiltration device Ultrafiltrate of the molecular weight less than 50,000 is concentrated up to 2- keto-D-gluconate concentrate；
2) 2- keto-D-gluconate concentrate is taken, alcoholic solvent is added and solid super acid catalyst carries out esterification, it Alkaline potassium ion donor is added afterwards and carries out conversion reaction, up to ISOASCORBIC ACID potassium after purifying.
Further, the concentration is that the 2- ketone group-glucose for being 80~90% for solid content is concentrated in ultrafiltrate Sour concentrate, using vacuum distillation when concentration.
Further, the solid super acid catalyst is SO4 2-/TiO2Or SO4 2-/ZrO2。
Further, the alcoholic solvent is methanol or ethyl alcohol.
Further, the volume of the alcoholic solvent of every kilogram of 2- keto-D-gluconate concentrate addition is 3~5L；Every thousand Gram 2- keto-D-gluconate concentrate addition solid super acid catalyst quality be 50~70g.
Further, the ultrafiltrate is concentrated again later using resin cation purification, the resin cation that ultrafiltration uses For 732# cation exchange resin column.
Further, the esterification uses rectifying and dewatering device, and the 2- keto-D-gluconate of formula ratio is concentrated In liquid, alcoholic solvent and solid super acid catalyst investment reactor tank, alcoholic solvent is flowed back by rectifying column, reaction time of esterification 3 ~4h after esterification, is filtered to remove solid super acid catalyst.
Further, the alkaline potassium ion donor is the mixture of potassium carbonate or potassium hydroxide solution and alcohol, potassium carbonate Or the ratio of potassium hydroxide solution and alcohol is the corresponding 1~2g potassium carbonate of every 25mL alcohol or potassium hydroxide solution, addition alkalescence potassium from Reaction solution is adjusted to alkalinity after sub- donor, conversion reaction uses rectifying and dewatering device, and the conversion reaction time is 0.5~1h.
Further, the purifying is the reaction solution cooling for terminating conversion reaction and filters, and it is thick to obtain ISOASCORBIC ACID potassium ISOASCORBIC ACID potassium crude salt is dissolved in water later by salt, and oxalic acid and active carbon removal of impurities is added.
Further, the additional amount of the oxalic acid and activated carbon is the 0.4~0.6% of ISOASCORBIC ACID potassium crude salt quality, Temperature is 50~70 DEG C when removal of impurities.
Beneficial effects of the present invention:
The preparation method of ISOASCORBIC ACID potassium of the invention pre-processes 2- keto-D-gluconate fermentation liquid, so that The material purity of esterification is higher, and 2- keto-D-gluconate ester yield is higher, so that subsequent 2- keto-D-gluconate is esterified Reaction efficiency is higher and to be converted to the yield of ISOASCORBIC ACID higher.When pretreatment, the addition concentrated sulfuric acid removes calcium ion, makes later The macromoleculars such as mycoprotein, undecomposed carbohydrate and protein when fermenting are removed with ultrafiltration, molecular cut off 50,000 with Under ultrafiltrate, obtain more pure 2- keto-D-gluconate, carry out esterification after concentration, purification process is relatively simple And it can effectively remove heteroacid, mycoprotein, carbohydrate etc. in 2- keto-D-gluconate fermentation liquid.
The preparation method of ISOASCORBIC ACID potassium of the invention, is catalyzed using solid super acid catalyst, improves 2- ketone Conversion ratio when the esterification reaction of base-gluconic acid, and it is subsequent can by being directly filtered to remove solid super acid catalyst, method compared with It is simple.
The preparation method of ISOASCORBIC ACID potassium of the invention, before it is concentrated, using resin cation to 2- ketone group-grape Saccharic acid concentrate, which carries out purifying, can further improve the purity of 2- keto-D-gluconate.
The preparation method of ISOASCORBIC ACID potassium of the invention, esterification use rectifying and dewatering device, during the reaction, Water improves the conversion ratio of 2- keto-D-gluconate by other than discharge system in time.
Specific embodiment
Below in conjunction with embodiment, the invention will be further described.
Embodiment 1
The preparation method of the ISOASCORBIC ACID potassium of the present embodiment, comprising the following steps:
1) 2- keto-D-gluconate fermentation liquor pretreatment: 2- keto-D-gluconate fermentation liquid is taken, is carried out using centrifuge Centrifugation, centrifugal rotational speed 1000r/min.The concentrated sulfuric acid is added in obtained supernatant, so that calcium ions precipitate, is centrifuged simultaneously later Filtering, centrifugal rotational speed 600r/min remove calcium sulfate, obtain acidification clear liquid.Acidification clear liquid is used into hollow fiber ultrafiltration membrane Carry out ultrafiltration, ultrafiltrate of the molecular cut off less than 50,000.Ultrafiltrate is purified using cation exchange resin, removes part sun It is concentrated after ion.Concentration is using vacuum distillation, and temperature is 50 DEG C, the 2- keto-D-gluconate concentrate being concentrated to get Solid content be 80%.
2) esterification: take 2- keto-D-gluconate concentrate in the step 1) of 1kg, 3L industrial anhydrous methanol with And the solid super acid catalyst SO of 55g4 2-/TiO2, put into reactor tank and carry out esterification, entire reaction unit is using essence Dehydration device is evaporated, methanol is flowed back by rectifying column, and the time of esterification is 3h, and temperature is 80 DEG C, mistake after esterification Solid super acid catalyst is filtered out, 2- keto-D-gluconate methyl esters is obtained.
3) conversion reaction: taking the 2- keto-D-gluconate methyl esters in step 2), and the mixing of solution of potassium carbonate and methanol is added Object, reaction time 1h, reaction temperature are 60 DEG C, obtain ISOASCORBIC ACID nak response liquid after reaction.Solution of potassium carbonate and methanol Mixture in every 25mL alcohol correspond to 2g solution of potassium carbonate, the mass concentration of solution of potassium carbonate is 60%.
4) it purifies: taking the ISOASCORBIC ACID nak response liquid cooling in step 3) but and filter, obtain ISOASCORBIC ACID potassium crude salt.It ISOASCORBIC ACID potassium crude salt is dissolved in water afterwards, and oxalic acid and active carbon removal of impurities is added.The additional amount of oxalic acid and activated carbon is different dimension The 0.4% of raw element C potassium crude salt quality, temperature is 70 DEG C when removal of impurities.
Embodiment 2
The preparation method of the ISOASCORBIC ACID potassium of the present embodiment, comprising the following steps:
1) 2- keto-D-gluconate fermentation liquor pretreatment: 2- keto-D-gluconate fermentation liquid is taken, is carried out using centrifuge Centrifugation, centrifugal rotational speed 1000r/min.The concentrated sulfuric acid is added in obtained supernatant, so that calcium ions precipitate, is centrifuged simultaneously later Filtering, centrifugal rotational speed 600r/min remove calcium sulfate, obtain acidification clear liquid.Acidification clear liquid is used into hollow fiber ultrafiltration membrane Carry out ultrafiltration, ultrafiltrate of the molecular cut off less than 50,000.Ultrafiltrate is purified using cation exchange resin, removes part sun It is concentrated after ion.Concentration is using vacuum distillation, and temperature is 55 DEG C, the 2- keto-D-gluconate concentrate being concentrated to get Solid content be 80%.
2) the industrial anhydrous methanol of 2- keto-D-gluconate concentrate in the step 1) of 1kg, 3.5L esterification: are taken And the solid super acid catalyst SO of 55g4 2-/ZrO2, put into reactor tank and carry out esterification, entire reaction unit uses Rectifying and dewatering device, methanol are flowed back by rectifying column, and the time of esterification is 3h, and temperature is 85 DEG C, after esterification It is filtered to remove solid super acid catalyst, obtains 2- keto-D-gluconate methyl esters.
3) conversion reaction: taking the 2- keto-D-gluconate methyl esters in step 2), and the mixing of solution of potassium carbonate and methanol is added Object, reaction time 0.5h, reaction temperature are 60 DEG C, obtain ISOASCORBIC ACID nak response liquid after reaction.Solution of potassium carbonate and first Every 25mL alcohol corresponds to 1.5g solution of potassium carbonate in the mixture of alcohol, and the mass concentration of solution of potassium carbonate is 60%.
4) it purifies: taking the ISOASCORBIC ACID nak response liquid cooling in step 3) but and filter, obtain ISOASCORBIC ACID potassium crude salt.It ISOASCORBIC ACID potassium crude salt is dissolved in water afterwards, and oxalic acid and active carbon removal of impurities is added.The additional amount of oxalic acid and activated carbon is different dimension The 0.5% of raw element C potassium crude salt quality, temperature is 55 DEG C when removal of impurities.
Embodiment 3
The preparation method of the ISOASCORBIC ACID potassium of the present embodiment, comprising the following steps:
1) 2- keto-D-gluconate fermentation liquor pretreatment: 2- keto-D-gluconate fermentation liquid is taken, is carried out using centrifuge Centrifugation, centrifugal rotational speed 1000r/min.The concentrated sulfuric acid is added in obtained supernatant, so that calcium ions precipitate, is centrifuged simultaneously later Filtering, centrifugal rotational speed 600r/min remove calcium sulfate, obtain acidification clear liquid.Acidification clear liquid is used into hollow fiber ultrafiltration membrane Carry out ultrafiltration, ultrafiltrate of the molecular cut off less than 50,000.Ultrafiltrate is purified using cation exchange resin, removes part sun It is concentrated after ion.Concentration is using vacuum distillation, and temperature is 50 DEG C, the 2- keto-D-gluconate concentrate being concentrated to get Solid content be 85%.
2) industrial alcohol and 60g of 2- keto-D-gluconate concentrate in the step 1) of 1kg, 5L esterification: are taken Solid super acid catalyst SO4 2-/TiO2, put into reactor tank and carry out esterification, entire reaction unit uses rectifying and dewatering Device, ethyl alcohol are flowed back by rectifying column, and the time of esterification is 3.5h, and temperature is 80 DEG C, are crossed and are filtered out after esterification Solid super acid catalyst is removed, 2- keto-D-gluconate methyl esters is obtained.
3) conversion reaction: taking the 2- keto-D-gluconate methyl esters in step 2), and the mixed of potassium hydroxide solution and ethyl alcohol is added Object, reaction time 1h are closed, reaction temperature is 60 DEG C, obtains ISOASCORBIC ACID nak response liquid after reaction.Potassium hydroxide solution with Every 25mL alcohol corresponds to 1g potassium hydroxide solution in the mixture of ethyl alcohol, and the mass concentration of potassium hydroxide solution is 60%.
4) it purifies: taking the ISOASCORBIC ACID nak response liquid cooling in step 3) but and filter, obtain ISOASCORBIC ACID potassium crude salt.It ISOASCORBIC ACID potassium crude salt is dissolved in water afterwards, and oxalic acid and active carbon removal of impurities is added.The additional amount of oxalic acid and activated carbon is different dimension The 0.6% of raw element C potassium crude salt quality, temperature is 60 DEG C when removal of impurities.
Embodiment 4
The preparation method of the ISOASCORBIC ACID potassium of the present embodiment, comprising the following steps:
1) 2- keto-D-gluconate fermentation liquor pretreatment: 2- keto-D-gluconate fermentation liquid is taken, is carried out using centrifuge Centrifugation, centrifugal rotational speed 1000r/min.The concentrated sulfuric acid is added in obtained supernatant, so that calcium ions precipitate, is centrifuged simultaneously later Filtering, centrifugal rotational speed 600r/min remove calcium sulfate, obtain acidification clear liquid.Acidification clear liquid is used into hollow fiber ultrafiltration membrane Carry out ultrafiltration, ultrafiltrate of the molecular cut off less than 50,000.Ultrafiltrate is purified using cation exchange resin, removes part sun It is concentrated after ion.Concentration is using vacuum distillation, and temperature is 50 DEG C, the 2- keto-D-gluconate concentrate being concentrated to get Solid content be 83%.
2) the industrial anhydrous methanol of 2- keto-D-gluconate concentrate in the step 1) of 1kg, 4.5L esterification: are taken And the solid super acid catalyst SO of 70g4 2-/TiO2, put into reactor tank and carry out esterification, entire reaction unit uses Rectifying and dewatering device, methanol are flowed back by rectifying column, and the time of esterification is 4h, and temperature is 83 DEG C, after esterification It is filtered to remove solid super acid catalyst, obtains 2- keto-D-gluconate methyl esters.
3) conversion reaction: taking the 2- keto-D-gluconate methyl esters in step 2), and the mixing of solution of potassium carbonate and methanol is added Object, reaction time 1h, reaction temperature are 60 DEG C, obtain ISOASCORBIC ACID nak response liquid after reaction.Solution of potassium carbonate and methanol Mixture in every 25mL alcohol correspond to 1.8g solution of potassium carbonate, the mass concentration of solution of potassium carbonate is 60%.
4) it purifies: taking the ISOASCORBIC ACID nak response liquid cooling in step 3) but and filter, obtain ISOASCORBIC ACID potassium crude salt.It ISOASCORBIC ACID potassium crude salt is dissolved in water afterwards, and oxalic acid and active carbon removal of impurities is added.The additional amount of oxalic acid and activated carbon is different dimension The 0.5% of raw element C potassium crude salt quality, temperature is 65 DEG C when removal of impurities.
Embodiment 5
The preparation method of the ISOASCORBIC ACID potassium of the present embodiment, comprising the following steps:
1) 2- keto-D-gluconate fermentation liquor pretreatment: 2- keto-D-gluconate fermentation liquid is taken, is carried out using centrifuge Centrifugation, centrifugal rotational speed 1000r/min.The concentrated sulfuric acid is added in obtained supernatant, so that calcium ions precipitate, is centrifuged simultaneously later Filtering, centrifugal rotational speed 600r/min remove calcium sulfate, obtain acidification clear liquid.Acidification clear liquid is used into hollow fiber ultrafiltration membrane Carry out ultrafiltration, ultrafiltrate of the molecular cut off less than 50,000.Ultrafiltrate is purified using cation exchange resin, removes part sun It is concentrated after ion.Concentration is using vacuum distillation, and temperature is 50 DEG C, the 2- keto-D-gluconate concentrate being concentrated to get Solid content be 86%.
2) esterification: take 2- keto-D-gluconate concentrate in the step 1) of 1kg, 4L industrial anhydrous methanol with And the solid super acid catalyst SO of 65g4 2-/ZrO2, put into reactor tank and carry out esterification, entire reaction unit is using essence Dehydration device is evaporated, methanol is flowed back by rectifying column, and the time of esterification is 3.5h, and temperature is 80 DEG C, after esterification It is filtered to remove solid super acid catalyst, obtains 2- keto-D-gluconate methyl esters.
3) conversion reaction: taking the 2- keto-D-gluconate methyl esters in step 2), and the mixed of potassium hydroxide solution and ethyl alcohol is added Object, reaction time 0.5h are closed, reaction temperature is 60 DEG C, obtains ISOASCORBIC ACID nak response liquid after reaction.Potassium hydroxide solution 1.2g potassium hydroxide solution corresponding with 25mL alcohol every in the mixture of ethyl alcohol, the mass concentration of potassium hydroxide solution are 60%.
4) it purifies: taking the ISOASCORBIC ACID nak response liquid cooling in step 3) but and filter, obtain ISOASCORBIC ACID potassium crude salt.It ISOASCORBIC ACID potassium crude salt is dissolved in water afterwards, and oxalic acid and active carbon removal of impurities is added.The additional amount of oxalic acid and activated carbon is different dimension The 0.6% of raw element C potassium crude salt quality, temperature is 50 DEG C when removal of impurities.
Embodiment 6
The preparation method of the ISOASCORBIC ACID potassium of the present embodiment, comprising the following steps:
1) 2- keto-D-gluconate fermentation liquor pretreatment: 2- keto-D-gluconate fermentation liquid is taken, is carried out using centrifuge Centrifugation, centrifugal rotational speed 1000r/min.The concentrated sulfuric acid is added in obtained supernatant, so that calcium ions precipitate, is centrifuged simultaneously later Filtering, centrifugal rotational speed 600r/min remove calcium sulfate, obtain acidification clear liquid.Acidification clear liquid is used into hollow fiber ultrafiltration membrane Carry out ultrafiltration, ultrafiltrate of the molecular cut off less than 50,000.Ultrafiltrate is purified using cation exchange resin, removes part sun It is concentrated after ion.Concentration is using vacuum distillation, and temperature is 50 DEG C, the 2- keto-D-gluconate concentrate being concentrated to get Solid content be 88%.
2) esterification: take 2- keto-D-gluconate concentrate in the step 1) of 1kg, 3.5L industrial alcohol and The solid super acid catalyst SO of 58g4 2-/TiO2, put into reactor tank and carry out esterification, entire reaction unit uses rectifying Dehydration device, ethyl alcohol are flowed back by rectifying column, and the time of esterification is 4h, and temperature is 80 DEG C, are filtered after esterification Solid super acid catalyst is removed, 2- keto-D-gluconate methyl esters is obtained.
3) conversion reaction: taking the 2- keto-D-gluconate methyl esters in step 2), and the mixing of solution of potassium carbonate and ethyl alcohol is added Object, reaction time 0.5h, reaction temperature are 60 DEG C, obtain ISOASCORBIC ACID nak response liquid after reaction.Solution of potassium carbonate and second Every 25mL alcohol corresponds to 1.6g solution of potassium carbonate in the mixture of alcohol, and the mass concentration of solution of potassium carbonate is 60%.
4) it purifies: taking the ISOASCORBIC ACID nak response liquid cooling in step 3) but and filter, obtain ISOASCORBIC ACID potassium crude salt.It ISOASCORBIC ACID potassium crude salt is dissolved in water afterwards, and oxalic acid and active carbon removal of impurities is added.The additional amount of oxalic acid and activated carbon is different dimension The 0.4% of raw element C potassium crude salt quality, temperature is 70 DEG C when removal of impurities.
Comparative example 1
This comparative example provides a kind of preparation method of ISOASCORBIC ACID potassium, the difference from embodiment 1 is that: it saves to 2- The ultrafiltration of keto-D-gluconate fermentation liquid and the processing step of cation exchange resin.
The yield of ISOASCORBIC ACID potassium and purity are as shown in table 1 in embodiment 1-6.
The yield and purity of ISOASCORBIC ACID potassium in 1 embodiment 1-6 of table
Sample number into spectrum Yield (%) Purity (%)
Embodiment 1 99.52 99.65
Embodiment 2 99.24 99.43
Embodiment 3 98.35 99.12
Embodiment 4 99.15 99.36
Embodiment 5 99.41 99.15
Embodiment 6 98.66 98.96
Comparative example 70.25 75.65
Seen from table 1, by 2- keto-D-gluconate fermentation liquid after ultrafiltration and cation exchange resin processing, different dimension is raw The yield of plain C potassium significantly improves.When using methanol as pure solvent, the yield of ISOASCORBIC ACID potassium is higher.

Claims (10)

1. the preparation method of ISOASCORBIC ACID potassium, which comprises the following steps:
1) 2- keto-D-gluconate fermentation liquor pretreatment: taking 2- keto-D-gluconate fermentation liquid, is centrifuged and adds in supernatant Enter the concentrated sulfuric acid,
Acidification clear liquid is obtained by filtration later, acidification clear liquid is subjected to ultrafiltration using hollow-fibre ultrafiltration device, molecular cut off is small In 50,000 ultrafiltrate, it is concentrated up to 2- keto-D-gluconate concentrate；
2) 2- keto-D-gluconate concentrate is taken, alcoholic solvent is added and solid super acid catalyst carries out esterification, Zhi Houjia Enter alkaline potassium ion donor and carry out conversion reaction, up to ISOASCORBIC ACID potassium after purifying.
2. the preparation method of ISOASCORBIC ACID potassium according to claim 1, which is characterized in that the concentration is by ultrafiltrate Concentration be 2- keto-D-gluconate concentrate that solid content is 80~90%, using being evaporated under reduced pressure when concentration.
3. the preparation method of ISOASCORBIC ACID potassium according to claim 1, which is characterized in that the solid superacid as catalyst Agent is SO4 2-/TiO2Or SO4 2-/ZrO2。
4. the preparation method of ISOASCORBIC ACID potassium according to claim 1, which is characterized in that the alcoholic solvent be methanol or Ethyl alcohol.
5. the preparation method of ISOASCORBIC ACID potassium according to claim 1, which is characterized in that every kilogram of 2- ketone group-grape The volume of the alcoholic solvent of saccharic acid concentrate addition is 3~5L；The solid of every kilogram of 2- keto-D-gluconate concentrate addition is super The quality of strong acid catalyst is 50~70g.
6. the preparation method of ISOASCORBIC ACID potassium according to claim 1, which is characterized in that the ultrafiltrate using sun from It is concentrated again after sub- resin purification, the resin cation that ultrafiltration uses is 732# cation exchange resin column.
7. the preparation method of ISOASCORBIC ACID potassium according to claim 1, which is characterized in that the esterification uses essence Dehydration device is evaporated, the 2- keto-D-gluconate concentrate, alcoholic solvent and solid super acid catalyst of formula ratio are put into reactor tank In, alcoholic solvent is flowed back by rectifying column, and reaction time of esterification is 3~4h, after esterification, is filtered to remove solid super-strong acid Catalyst.
8. the preparation method of ISOASCORBIC ACID potassium according to claim 1, which is characterized in that the alkaline potassium ion donor It is every 25mL alcohol pair for the ratio of potassium carbonate or the mixture of potassium hydroxide solution and alcohol, potassium carbonate or potassium hydroxide solution and alcohol 1~2g potassium carbonate or potassium hydroxide solution are answered, is added after alkaline potassium ion donor and reaction solution is adjusted to alkalinity, conversion reaction is adopted With rectifying and dewatering device, the conversion reaction time is 0.5~1h.
9. the preparation method of ISOASCORBIC ACID potassium according to claim 1, which is characterized in that the purifying is will to convert instead The reaction solution that should terminate is cooling and filters, and obtains ISOASCORBIC ACID potassium crude salt, ISOASCORBIC ACID potassium crude salt is dissolved in water later, and add Enter oxalic acid and active carbon removal of impurities.
10. the preparation method of ISOASCORBIC ACID potassium according to claim 9, which is characterized in that the oxalic acid and activated carbon Additional amount is the 0.4~0.6% of ISOASCORBIC ACID potassium crude salt quality, and temperature is 50~70 DEG C when removal of impurities.
CN201910689231.0A 2019-07-29 2019-07-29 The preparation method of ISOASCORBIC ACID potassium Pending CN110294726A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910689231.0A CN110294726A (en) 2019-07-29 2019-07-29 The preparation method of ISOASCORBIC ACID potassium

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910689231.0A CN110294726A (en) 2019-07-29 2019-07-29 The preparation method of ISOASCORBIC ACID potassium

Publications (1)

Publication Number Publication Date
CN110294726A true CN110294726A (en) 2019-10-01

Family

ID=68032081

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910689231.0A Pending CN110294726A (en) 2019-07-29 2019-07-29 The preparation method of ISOASCORBIC ACID potassium

Country Status (1)

Country Link
CN (1) CN110294726A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110642817A (en) * 2019-10-22 2020-01-03 新拓洋生物工程股份有限公司 Isovitamin C potassium refining method
CN110759880A (en) * 2019-12-12 2020-02-07 新拓洋生物工程股份有限公司 Preparation method of potassium isoascorbate

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101029036A (en) * 2006-02-28 2007-09-05 凯能高科技工程（上海）有限公司 Process for producing isovitamine C by membrane-resin method
CN105603018A (en) * 2016-03-15 2016-05-25 山东省食品发酵工业研究设计院 Method for indirectly preparing D-sodium erythorbate
CN108129427A (en) * 2017-12-29 2018-06-08 郑州拓洋生物工程有限公司 ISOASCORBIC ACID potassium and its preparation method and application

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101029036A (en) * 2006-02-28 2007-09-05 凯能高科技工程（上海）有限公司 Process for producing isovitamine C by membrane-resin method
CN105603018A (en) * 2016-03-15 2016-05-25 山东省食品发酵工业研究设计院 Method for indirectly preparing D-sodium erythorbate
CN108129427A (en) * 2017-12-29 2018-06-08 郑州拓洋生物工程有限公司 ISOASCORBIC ACID potassium and its preparation method and application

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
杨永久等: "超滤法提纯异维生素C钠发酵液的研究", 《河南化工》 *
王健祥等: "固体超强酸SO42-/SiO2-TiO2催化合成异维生素C钠", 《应用化学》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110642817A (en) * 2019-10-22 2020-01-03 新拓洋生物工程股份有限公司 Isovitamin C potassium refining method
CN110759880A (en) * 2019-12-12 2020-02-07 新拓洋生物工程股份有限公司 Preparation method of potassium isoascorbate

Similar Documents

Publication Publication Date Title
US9133229B2 (en) Economic process for producing xylose from hydrolysate using electrodialysis and direct recovery method
CN104529755B (en) A kind of method being separated α-ketoglutaric acid from conversion fluid
CN102363594B (en) Method for separating and purifying succinic acid from fermentation broth
CN102040476B (en) Method for separating and purifying 1,3-propylene glycol from fermentation liquor
CN101306993B (en) Refine process of L-lactic acid of polymerization grade
CN101407454B (en) Process for preparing citrate salt from mother liquor for citric acid production
CN111320558B (en) Method for synthesizing taurine
CN110294726A (en) The preparation method of ISOASCORBIC ACID potassium
CN114014341A (en) Device and method for preparing high-lithium solution from raw halogen
CN104693250B (en) Method for purifying acarbose from acarbose-containing solution
CN111302932A (en) Method for recycling sodium phenylacetate
CN109553650B (en) Water phase extraction method of erythromycin fermentation liquor
CN101747301B (en) Method for preparing vitamin C with low consumption
CN110759959A (en) Vitamin B is separated and extracted from fermentation liquor12Method (2)
CN107417749A (en) A kind of resin extender separation method of DPN
CN116606192A (en) Method for producing inositol and byproducts by using corn steep liquor at low cost
CN106966945A (en) A kind of full embrane method extracting method of L hydroxyprolines zymotic fluid
WO2023109027A1 (en) Method for desalting and purifying 1,3-propanediol fermentation broth
CN112679526B (en) Method for recovering D-7-ACA from D-7-ACA crystallization mother liquor
CN109836468A (en) A method of the purifying citicoline sodium from microbial fermentation solution
CN104313071B (en) The biological synthesis method of high-purity L alpha amino acids
CN102212157B (en) Preparation process of aqueous solution of acrylamide containing no polymerization inhibitor
CN105801474A (en) Method for refining 3, 6-clopyralid
CN101492369A (en) Separation purification method for benzoic anhydride sour water and production process for allomaleic acid
CN111620774A (en) Production method for preparing high-purity solid malonic acid from calcium malonate

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20191001

RJ01 Rejection of invention patent application after publication