CN113045521A - Preparation method of vitamin C - Google Patents
Preparation method of vitamin C Download PDFInfo
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- CN113045521A CN113045521A CN202110309352.5A CN202110309352A CN113045521A CN 113045521 A CN113045521 A CN 113045521A CN 202110309352 A CN202110309352 A CN 202110309352A CN 113045521 A CN113045521 A CN 113045521A
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- Prior art keywords
- gulonic acid
- vitamin
- gulonate
- sodium
- salt
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- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 title claims abstract description 184
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 229930003268 Vitamin C Natural products 0.000 title claims abstract description 92
- 235000019154 vitamin C Nutrition 0.000 title claims abstract description 92
- 239000011718 vitamin C Substances 0.000 title claims abstract description 92
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- RGHNJXZEOKUKBD-QTBDOELSSA-N L-gulonic acid Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)C(O)=O RGHNJXZEOKUKBD-QTBDOELSSA-N 0.000 claims abstract description 137
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 238000002425 crystallisation Methods 0.000 claims abstract description 41
- 230000008025 crystallization Effects 0.000 claims abstract description 41
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 35
- 239000011734 sodium Substances 0.000 claims abstract description 35
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 35
- 238000005886 esterification reaction Methods 0.000 claims abstract description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- 239000003513 alkali Substances 0.000 claims abstract description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 90
- -1 gulonic acid ester Chemical class 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 30
- 238000001816 cooling Methods 0.000 claims description 25
- 239000007788 liquid Substances 0.000 claims description 19
- 238000000855 fermentation Methods 0.000 claims description 16
- 230000004151 fermentation Effects 0.000 claims description 16
- 239000012528 membrane Substances 0.000 claims description 15
- 230000020477 pH reduction Effects 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 238000000108 ultra-filtration Methods 0.000 claims description 10
- 150000003700 vitamin C derivatives Chemical class 0.000 claims description 10
- 238000005119 centrifugation Methods 0.000 claims description 9
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000012295 chemical reaction liquid Substances 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 4
- 230000001476 alcoholic effect Effects 0.000 claims description 3
- 238000004042 decolorization Methods 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000002585 base Substances 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 239000013078 crystal Substances 0.000 abstract description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 24
- 239000012452 mother liquor Substances 0.000 abstract description 16
- 238000004519 manufacturing process Methods 0.000 abstract description 13
- 230000032050 esterification Effects 0.000 abstract description 12
- 239000012535 impurity Substances 0.000 abstract description 6
- 239000003814 drug Substances 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- 238000001953 recrystallisation Methods 0.000 abstract description 2
- 239000004973 liquid crystal related substance Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 45
- 239000000047 product Substances 0.000 description 42
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 33
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 28
- 238000001914 filtration Methods 0.000 description 21
- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical compound [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 0.000 description 17
- 238000003756 stirring Methods 0.000 description 16
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 13
- 239000012043 crude product Substances 0.000 description 13
- 229910052938 sodium sulfate Inorganic materials 0.000 description 13
- 235000011152 sodium sulphate Nutrition 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 9
- 150000004702 methyl esters Chemical class 0.000 description 8
- 238000004064 recycling Methods 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 6
- 239000003729 cation exchange resin Substances 0.000 description 6
- 238000001471 micro-filtration Methods 0.000 description 4
- 239000003957 anion exchange resin Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000010413 mother solution Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- MIJPAVRNWPDMOR-UHFFFAOYSA-N [2-(1,2-dihydroxyethyl)-3-hydroxy-5-oxo-2h-furan-4-yl] dihydrogen phosphate Chemical compound OCC(O)C1OC(=O)C(OP(O)(O)=O)=C1O MIJPAVRNWPDMOR-UHFFFAOYSA-N 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 239000002535 acidifier Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 235000015424 sodium Nutrition 0.000 description 1
- 235000010378 sodium ascorbate Nutrition 0.000 description 1
- 229960005055 sodium ascorbate Drugs 0.000 description 1
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
The invention relates to the technical field of medicine production, and particularly discloses a preparation method of vitamin C. The preparation method comprises the following steps: sodium gulonate or gulonate esterify and make esterification solution, and make the gulonate crystal without crystal water separate out through the crystallization mode, and unesterified gulonic acid and water and other impurity of the reaction system are all left in the mother liquor, the crystallization makes purification and dewatering of the gulonate finish at the same time, add alkali conversion into anhydrous alcohol with pure gulonate crystal again, realize the high-efficient conversion above 99% of gulonate, and the impurity is few in the vc salt conversion solution obtained, can directly crystallize after acidifying the conversion solution and make the vc product with purity greater than 99%, and need not carry on the step of recrystallization after purifying the vc liquid crystal again, not only simplify the vc production technology, still obviously improve the yield of vc product, the total yield from gulonate fermented solution to vc product can be up to more than 88%, reduce production cost by a wide margin, still realize cleaner production at the same time.
Description
Technical Field
The invention relates to the technical field of medicine production, in particular to a preparation method of vitamin C.
Background
China is a main world producing vitamin C, and the current production process of vitamin C is mainly as follows: firstly, preparing sodium gulonic acid liquid by fermenting sorbitol through a biological secondary fermentation method, then carrying out membrane ultrafiltration, ion resin exchange acidification and concentration crystallization on the sodium gulonic acid liquid to obtain gulonic acid crystals, carrying out sulfuric acid catalysis on the gulonic acid crystals and methanol to generate gulonic acid methyl ester, then adding alkali to convert the gulonic acid methyl ester to obtain vitamin C sodium salt crude products, dissolving the vitamin C sodium salt crude products in water, then carrying out cation exchange resin acidification, removing sulfuric acid by anion exchange resin, carrying out vacuum concentration crystallization, cooling crystallization and centrifugation to obtain vitamin C crude products, finally dissolving the vitamin C crude products in pure water, adding activated carbon to decolor, cooling crystallization, centrifugation and drying to obtain the vitamin C products.
However, since the esterification reaction of gulonic acid and methanol is a reversible reaction, and gulonic acid itself carries a molecule of crystal water, the water generated by the esterification reaction and the crystal water carried by gulonic acid itself both affect the esterification rate of the esterification reaction and result in a low conversion rate of gulonic acid. In order to improve the conversion rate of gulonic acid, most of the prior vitamin C manufacturers adopt a method of adding multiple times of excessive methanol to improve the esterification rate of gulonic acid to about 92 percent. However, about 8% of gulonic acid in the system is not esterified during the subsequent alkali-adding conversion, and during the subsequent alkali-adding conversion, the unreacted gulonic acid, the catalyst sulfuric acid and the product gulonic acid methyl ester can all react with alkali to generate gulonic sodium, sodium ascorbate and sodium sulfate which are all present in a reaction system, before the crude product of the vitamin C sodium salt is acidified, the crude product is centrifuged and then dissolved in water to prepare a vitamin C sodium water solution, and then the vitamin C sodium water solution is acidified, sodium gulonate and sodium sulfate generated in the acidification process can also be acidified to form gulonic acid or sulfuric acid, the sulfuric acid in the vitamin C solution can be removed by using anion resin, but the alkali consumption is increased and the salt-containing wastewater is discharged, even so, the vitamin C acidizing fluid still contains a large amount of gulonic acid and other impurities, and crude vitamin C dry products are prepared by crystallization, and then the crude vitamin C dry products with higher purity are dissolved in water and recrystallized to prepare vitamin C products. Therefore, the existing vitamin C production process has the defects of long production process, low yield, high consumption and high emission of the vitamin C. Therefore, the development of a vitamin C clean production method which has high vitamin C yield, simple process route, low consumption and low waste discharge is of great significance.
Disclosure of Invention
Aiming at the problems of low yield, long process route, high consumption and high waste discharge of the prior art for preparing the vitamin C, the invention provides a preparation method of the vitamin C.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a preparation method of vitamin C comprises the following steps:
step one, carrying out esterification reaction on gulonic acid salt or gulonic acid and anhydrous alcohol to obtain esterification reaction liquid, and crystallizing and centrifuging the esterification reaction liquid to obtain a dry gulonic acid ester product;
secondly, adding the dried gulonic acid ester into anhydrous alcohol for dissolving to obtain a gulonic acid ester alcohol solution;
adding alkali into the gulonic acid ester alcoholic solution for conversion to obtain a vitamin C salt conversion solution;
step four, acidifying the vitamin C salt conversion solution to obtain a vitamin C solution;
and step five, crystallizing, centrifuging, washing and drying the vitamin C liquid to obtain a vitamin C product.
Compared with the prior art, the preparation method of the vitamin C provided by the invention has the advantages that sodium gulonate or esterification liquid of gulonic acid esterification reaction is crystallized to separate out gulonic acid ester crystals, unesterified gulonic acid, water of a reaction system and other impurities are remained in mother liquor, so that the purification and the water removal of gulonic acid methyl ester are simultaneously completed, then the gulonic acid ester crystals are added into anhydrous alcohol to be dissolved and then added with alkali for conversion, the high-efficiency conversion of the gulonic acid ester with the purity of more than 99 percent can be realized, the obtained vitamin C salt conversion liquid has less impurities, pure vitamin C liquid basically not containing gulonic acid can be prepared after the conversion liquid is acidified, the vitamin C liquid is directly concentrated, cooled and crystallized to prepare the vitamin C product with the purity of more than 99 percent, the step of recrystallization after the vitamin C liquid is crystallized is not needed, the product yield is obviously improved, and the total yield from the gulonic acid salt fermentation liquid to the vitamin C product can be up to more than 88 percent, meanwhile, the production process for preparing the vitamin C is obviously simplified, the production cost is greatly reduced, and meanwhile, thorough clean production is realized, so that the vitamin C has wide application prospect.
Preferably, in the first step, the salt of gulonic acid is sodium gulonic acid, potassium gulonic acid, ammonium gulonic acid or calcium gulonic acid.
Further preferably, in the first step, the salt of gulonic acid is sodium gulonate.
The sodium gulonate aqueous solution is neutral, can not produce acid conversion when evaporating and concentrating at high temperature, and the low temperature solubility is lower, help to improve the crystalline yield, therefore, the invention prefers the sodium gulonate crystalline dry product to be regarded as the raw materials of the esterification reaction.
Preferably, in the first step and the second step, the anhydrous alcohol is anhydrous C1-C4 alcohol.
More preferably, in the first and second steps, the anhydrous alcohol is anhydrous methanol.
Preferably, the preparation method of the gulonate comprises the following steps: and (3) carrying out membrane ultrafiltration, decoloration, concentration, crystallization and centrifugation on the gulonate fermented liquor obtained by the secondary biological fermentation method to obtain the gulonate, wherein the gulonate is a gulonate crystal containing a crystal water.
Preferably, the preparation method of the gulonic acid comprises the following steps: and (3) carrying out membrane ultrafiltration, acidification, decoloration, concentration, crystallization and centrifugation on the gulonic acid salt fermented liquor obtained by the secondary biological fermentation method to obtain gulonic acid, wherein the gulonic acid is a gulonic acid crystal containing a crystal water.
Further preferably, the acidification step in the preparation process of the gulonic acid crystal is carried out by using a cationic resin.
The preparation of the gulonic acid salt crystals and the gulonic acid crystals is a conventional preparation method in the field, and specific parameters in the preparation process can be adjusted by a person skilled in the art in a conventional way.
Preferably, in the step one, the mass-to-volume ratio of the gulonic acid salt or the gulonic acid to the anhydrous alcohol is 1000: 2-5 in terms of gulonic acid, wherein the unit of mass is Kg, and the unit of volume is m3。
More preferably, in the step one, the mass-to-volume ratio of the gulonic acid salt or the gulonic acid to the anhydrous alcohol is 1000: 3-4 in terms of gulonic acid, wherein the unit of mass is Kg, and the unit of volume is m3。
The optimized proportion is favorable for enabling the gulonic acid and the alcohol to fully react, and the production cost is reduced on the premise of ensuring higher esterification rate.
When the raw material of esterification is gulonic acid salt, acid is added for acidification before esterification, so that the gulonic acid is hydrochlorinated into the gulonic acid, namely, concentrated sulfuric acid added during esterification is used as an acidifier and a catalyst. When the raw material is gulonic acid, the esterification reaction is directly carried out, and the amount of the concentrated sulfuric acid added is only the amount of the catalyst. Preferably, the catalyst for the acidification and esterification is 98% concentrated sulfuric acid.
When the raw material of the esterification reaction is gulonate, the addition amount of concentrated sulfuric acid is equal to the acid amount for acidification of the gulonate plus the acid amount of the esterification catalyst; when the esterification reaction raw material is gulonic acid, the esterification catalyst amount is only added into concentrated sulfuric acid: the esterification catalyst amount is 98% concentrated sulfuric acid volume/anhydrous alcohol volume is 1% -2%.
Preferably, in the first step, the temperature of the esterification reaction is 60-65 ℃, and the time of the esterification reaction is 2-3 hours.
Optionally, in the step one, the mass-volume ratio of the gulonic acid salt or the gulonic acid to the anhydrous alcohol is 1000Kg to 2m3And cooling crystallization is adopted as the crystallization, and the crystallization temperature is-5-0 ℃. In the first step, the mass-volume ratio of the gulonic acid salt or the gulonic acid to the anhydrous alcohol is 1000Kg to 3-5 m3And then, the crystallization is vacuum concentration crystallization and cooling crystallization, and the temperature of the cooling crystallization is-5-0 ℃.
Preferably, in the second step, the mass-to-volume ratio of the gulonic acid ester dry product to the anhydrous alcohol is 1000: 3-6, wherein the unit of mass is Kg, and the unit of volume is m3。
More preferably, in the second step, the mass-to-volume ratio of the dried gulonate to the anhydrous alcohol is 1000:4, wherein the unit of mass is Kg and the unit of volume is m3。
Preferably, in the third step, the alkali is sodium carbonate, sodium bicarbonate or sodium methoxide.
Preferably, in the third step, the temperature of the conversion reaction is 65-68 ℃, and the time of the conversion reaction is 2-3 hours.
Optionally, in the fourth step, the vitamin C salt conversion solution may be acidified directly by adding strong acid to adjust the pH, or a method may be used in which a crude vitamin C salt obtained by centrifuging the vitamin C salt conversion solution is dissolved in water and then acidified by using cation exchange resin. The method for directly acidifying by adding strong acid to adjust the pH is preferably adopted, the preferable strong acid is 50 wt% of dilute sulfuric acid, the addition amount is based on the pH of the adjusting solution being 2.10-2.30, and the preferable pH is 2.15-2.20.
In the fourth step, the step of filtering the sodium sulfate after acidification is further included, so that vitamin C liquid and high-purity sodium sulfate solid are obtained.
According to the invention, because the purity of the vitamin C salt synthesized by conversion is high, not only can pure vitamin C liquid be obtained after acidification, but also high-purity sodium sulfate solid can be obtained, and the sodium sulfate solid can be used as a raw material of high-quality glass and sold as industrial salt, so that waste materials are changed into valuable things, the cost of environmental pollution and hazardous waste treatment caused by a large amount of salt-containing wastewater is avoided, and the enterprise profit is improved.
Preferably, in the fifth step, the crystallization is vacuum concentration crystallization and cooling crystallization, and the temperature of the cooling crystallization is-5 to 0 ℃.
The fifth step is specifically as follows: adding activated carbon into the vitamin C solution for decolorization, fine filtering, vacuum concentration and crystallization, cooling and crystallization, centrifugation, alcohol washing and drying to obtain a vitamin C product.
The mother solution after the vitamin C liquid crystallization is concentrated and can be recovered to prepare a finished vitamin C product, and the mother solution can also be directly used as a raw material for preparing the finished vitamin C phosphate, so that the yield of the vitamin product is further improved, and the enterprise profit is improved.
According to the preparation method of the vitamin C, provided by the invention, esterification reaction liquid is crystallized to prepare a gulonic acid ester dry product, the gulonic acid ester alcoholic solution is used for carrying out alkali conversion, the conversion rate of the gulonic acid ester is obviously improved and can reach more than 99%, the prepared vitamin C salt conversion solution almost contains no impurities, and a vitamin C product with the purity of more than 99% can be directly prepared through acidification, concentration and crystallization.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
A method for preparing vitamin C comprises:
step one, preparing 10L of gulonic acid sodium solution (containing 10% of gulonic acid) by a two-step fermentation method, ultrafiltering by an ultrafiltration membrane, filtering and decoloring by activated carbon, concentrating, crystallizing and centrifuging to obtain a gulonic acid sodium crystal containing crystal water, recycling mother liquor to prepare the gulonic acid crystal, and preparing 1174.6g of the gulonic acid sodium crystal, wherein the gulonic acid sodium content is 91% and the yield is 96%;
step two, adding all the prepared gulonic sodium crystals into 4L of anhydrous methanol, adding 175mL of 98% concentrated sulfuric acid, heating to 60 ℃, reacting for 3 hours under a stirring condition, adding activated carbon after the reaction is finished, decoloring and filtering in a filter to obtain a clear gulonic acid methyl ester methanol solution, concentrating the gulonic acid methyl ester methanol solution in vacuum, cooling to 0-minus 5 ℃ for crystallization, centrifuging to obtain pure anhydrous gulonic acid methyl ester crystals, recovering mother liquor to prepare the gulonic acid methyl ester crystals, and obtaining 999.1g of gulonic acid methyl ester crystals with the content of 99% and the yield of 96.1%;
step three, completely adding the prepared anhydrous gulonic acid methyl ester crystals into 4L of methanol, heating to 65 ℃, stirring and dissolving for 0.5h, adding 257g of sodium carbonate in a flowing manner, stirring and preserving heat for reaction for 2h to obtain a vitamin C sodium salt conversion solution, wherein the conversion rate is 99.5%, cooling to below 30 ℃, adding 50% of dilute sulfuric acid, adjusting the pH value to 2.15-2.20, settling for 2h, filtering to remove sodium sulfate to obtain a clear vitamin C solution, and washing the sodium sulfate obtained by filtering with methanol to recover the vitamin C;
and step four, decoloring the vitamin C liquid by using activated carbon, finely filtering by using a microfiltration membrane, carrying out vacuum concentration crystallization, cooling to 0-5 ℃ for crystallization, centrifuging, washing by using methanol, carrying out vacuum drying to obtain a vitamin C product, recycling mother liquor, and preparing the vitamin C product into 808.4g of the vitamin C product, wherein the content is 99.8%, and the yield is 96.4%.
The total yield from the sodium gulonate fermentation broth to the vitamin C product was 88.93%.
Example 2
A method for preparing vitamin C comprises:
step one, preparing 10L of gulonic acid sodium solution (containing 10% of gulonic acid) by a two-step fermentation method, ultrafiltering by an ultrafiltration membrane, acidifying by cation exchange resin to prepare gulonic acid solution, filtering and decoloring by activated carbon, then carrying out vacuum concentration, crystallization and centrifugation on the gulonic acid solution to obtain a gulonic acid crystal containing a crystal water, recycling mother liquor to prepare the gulonic acid crystal, and preparing 1048.8g of the gulonic acid crystal with the content of 90.1% and the yield of 94.5%;
step two, adding all the prepared gulonic acid crystals into 4L of anhydrous methanol, adding 40mL of 98% concentrated sulfuric acid, heating to 60 ℃, reacting for 2 hours under a stirring condition, adding activated carbon after the reaction is finished, decoloring and filtering in a filter to obtain a clear gulonic acid methyl ester methanol solution, concentrating the gulonic acid methyl ester methanol solution in vacuum, cooling to-5-0 ℃, crystallizing, centrifuging to obtain anhydrous gulonic acid methyl ester crystals, recovering mother liquor to prepare gulonic acid methyl ester crystals, and obtaining 986.7g of gulonic acid methyl ester crystals with the content of 99.4% and the yield of 96.8%;
step three, completely adding the prepared anhydrous gulonic acid methyl ester crystals into 4L of methanol, heating to 65 ℃, stirring and dissolving for 0.5h, adding 404g of sodium bicarbonate in a flowing manner, stirring and preserving heat for reaction for 2h to obtain a vitamin C sodium salt conversion solution, wherein the conversion rate is 99.6%, cooling to below 30 ℃, centrifuging to obtain a vitamin C sodium crude product, adding the vitamin C sodium crude product into pure water with the mass of 4 times of that of the vitamin C sodium salt crude product, stirring and dissolving, acidifying by using cation exchange resin, and removing sulfuric acid by using anion exchange resin to obtain a vitamin C aqueous solution;
and step four, decoloring the vitamin C clear liquid by using activated carbon, finely filtering by using a microfiltration membrane, carrying out vacuum concentration crystallization, cooling to the temperature of minus 5-0 ℃ for crystallization, centrifuging, washing by using methanol, carrying out vacuum drying to obtain a vitamin C product, recycling mother liquor, and preparing the vitamin C product into 801.6g of the vitamin C product, wherein the content of the vitamin C product is 99.9%, and the yield of the vitamin C product is 96.5%.
The total yield from the sodium gulonate fermentation broth to the vitamin C product was 88.27%.
Example 3
A method for preparing vitamin C comprises:
step one, preparing 10L of gulonic acid sodium solution (containing 10% of gulonic acid) by a two-step fermentation method, ultrafiltering by an ultrafiltration membrane, filtering and decoloring by activated carbon, concentrating, crystallizing and centrifuging to obtain a gulonic acid sodium crystal containing crystal water, recycling mother liquor to prepare the gulonic acid sodium crystal, and preparing 1178.1g of the gulonic acid sodium crystal, wherein the content of the gulonic acid sodium is 91.2%, and the yield is 96.5%;
step two, adding the prepared gulonic acid sodium crystals into 2L of anhydrous methanol, adding 165mL of 98% concentrated sulfuric acid, heating to 65 ℃, reacting for 2 hours under a stirring condition, adding activated carbon after the reaction is finished, decoloring and filtering in a filter to obtain a clear gulonic acid methyl ester methanol solution, cooling the gulonic acid methyl ester methanol solution to-5-0 ℃, crystallizing, centrifuging to obtain anhydrous gulonic acid methyl ester crystals, recovering mother liquor to prepare gulonic acid methyl ester crystals, and obtaining 1007.4g of gulonic acid methyl ester crystals with the content of 98.8% and the yield of 96.2%;
step three, completely adding the prepared anhydrous gulonic acid methyl ester crystals into 6L of methanol, heating to 68 ℃, stirring and dissolving for 0.5h, adding 260g of sodium carbonate in a flowing manner, stirring and preserving heat for reaction for 2h to obtain a vitamin C sodium salt conversion solution, wherein the conversion rate is 99.7%, cooling to below 30 ℃, adding 50% of dilute sulfuric acid, adjusting the pH value to 2.15-2.20, settling sodium sulfate for 2h, filtering to remove the sodium sulfate to obtain a clear vitamin C solution, and washing the filtered sodium sulfate with methanol to recover the vitamin C;
and step four, decoloring the vitamin C liquid, finely filtering the vitamin C liquid by using a microfiltration membrane, carrying out vacuum concentration and crystallization, cooling the liquid to the temperature of minus 5-0 ℃ for crystallization, centrifuging, washing by using methanol, carrying out vacuum drying to obtain a vitamin C product, recycling mother liquor to prepare the vitamin C product, and finally obtaining 811.8g of the vitamin C product with the content of 99.9% and the yield of 96.3%.
The total yield from the sodium gulonate fermentation broth to the vitamin C product was 89.4%.
Example 4
A method for preparing vitamin C comprises:
step one, preparing 10L of gulonic acid sodium solution (containing 10% of gulonic acid) by a two-step fermentation method, ultrafiltering by an ultrafiltration membrane, decoloring by active carbon, concentrating, crystallizing and centrifuging to obtain a gulonic acid sodium crystal containing crystal water, recycling mother liquor to prepare the gulonic acid crystal, and preparing 1181.8g of gulonic acid sodium crystal, wherein the content of the gulonic acid sodium is 91.2%, and the yield is 96.8%;
step two, adding the prepared gulonic acid sodium crystal into 5L of anhydrous methanol, adding 180mL of 98% concentrated sulfuric acid, heating to 65 ℃, reacting for 2 hours under a stirring condition, adding activated carbon after the reaction is finished, decoloring and filtering in a filter to obtain a clear gulonic acid methyl ester methanol solution, concentrating the gulonic acid methyl ester methanol solution in vacuum, cooling to-5-0 ℃, crystallizing, centrifuging to obtain the anhydrous gulonic acid methyl ester crystal, recovering mother liquor to prepare the gulonic acid methyl ester crystal, and obtaining 1012.8g of the gulonic acid methyl ester crystal, wherein the content is 99.5%, and the yield is 97.1%;
step three, completely adding the prepared anhydrous gulonic acid methyl ester crystals into 3L of methanol, heating to 68 ℃, stirring and dissolving for 0.5h, adding 262g of sodium carbonate in a flowing manner, stirring and preserving heat for reaction for 2h to obtain a vitamin C sodium salt conversion solution, wherein the conversion rate is 99.2%, cooling to below 30 ℃, adding 50% of dilute sulfuric acid, adjusting the pH value to 2.20-2.25, settling for 2h, filtering to remove sodium sulfate to obtain a clear vitamin C solution, and washing the sodium sulfate obtained by filtering with methanol to recover the vitamin C;
and step four, decoloring the vitamin C solution, finely filtering the vitamin C solution by using a microfiltration membrane, concentrating the vitamin C solution in vacuum, cooling the vitamin C solution to the temperature of minus 5 to 0 ℃ for crystallization, centrifuging the product, washing the product by using methanol, drying the product in vacuum to obtain a vitamin C product, recovering mother liquor, and preparing the vitamin C product into 821.1g of the vitamin C product with the content of 99.9 percent and the yield of 96.2 percent.
The total yield from the sodium gulonate fermentation broth to the vitamin C product was 90.4%.
Comparative example 1
The comparative example provides a preparation method of vitamin C, which has the same preparation process as the example 2 except that in the second step, the specific operation steps are as follows:
step one, preparing 10L of gulonic acid sodium solution (containing 10% of gulonic acid) by a two-step fermentation method, ultrafiltering by an ultrafiltration membrane, filtering by activated carbon to remove protein and pigment, acidifying by cation exchange resin to prepare gulonic acid solution, carrying out vacuum concentration, crystallization and centrifugation on the gulonic acid solution to obtain a gulonic acid crystal containing a crystal water, recycling mother liquor to prepare the gulonic acid crystal, and preparing 1054.9g of the gulonic acid crystal with the content of 89.3% and the yield of 94.2%;
step two, adding all the prepared gulonic acid crystals into 5L of anhydrous methanol, adding 50mL of 98% concentrated sulfuric acid, heating to 65 ℃, reacting for 3 hours under stirring, adding 568g of sodium bicarbonate, stirring, keeping the temperature and reacting for 3 hours at 68 ℃ to obtain a vitamin C sodium salt conversion solution, cooling to below 30 ℃, centrifuging to obtain a vitamin C sodium crude product, adding the vitamin C sodium salt crude product into pure water with the mass of 4 times that of the vitamin C sodium salt conversion solution, stirring for dissolving, acidifying by cation exchange resin, removing sulfuric acid by anion exchange resin to obtain a vitamin C aqueous solution, adding activated carbon, filtering for decolorization, vacuum concentrating, cooling to-5-0 ℃, crystallizing, and centrifuging to obtain 796.3g of the vitamin C crude product, wherein the content is 98.2%, and the yield is 91.5%;
step four, adding the vitamin C crude product into 790mL of 68 ℃ purified water, removing filter pressing and decoloring by active carbon, finely filtering by a micro-membrane, then putting the mixture into a crystallizing tank, adding seed crystals, cooling to 28 ℃, adding 200mL of 95% antiscale ethanol, centrifuging when the crystallization temperature is reduced to-3 to-2 ℃, washing by methanol, drying in vacuum to obtain a vitamin C product, recovering mother liquor to prepare the vitamin C product, and finally obtaining 753g of the vitamin C product with the content of 99.9% and the yield of 96.2%.
The total yield from the sodium gulonate fermentation broth to the vitamin C product was 82.9%.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents or improvements made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. The preparation method of vitamin C is characterized by comprising the following steps:
step one, carrying out esterification reaction on gulonic acid salt or gulonic acid and anhydrous alcohol to obtain esterification reaction liquid, and crystallizing and centrifuging the esterification reaction liquid to obtain a dry gulonic acid ester product;
secondly, adding the dried gulonic acid ester into anhydrous alcohol for dissolving to obtain a gulonic acid ester alcohol solution;
adding alkali into the gulonic acid ester alcoholic solution for conversion to obtain a vitamin C salt conversion solution;
step four, acidifying the vitamin C salt conversion solution to obtain a vitamin C solution;
and step five, crystallizing, centrifuging, washing and drying the vitamin C liquid to obtain a vitamin C product.
2. The method of claim 1, wherein in step one, the salt of gulonic acid is sodium, potassium, ammonium or calcium gulonic acid; and/or
In the first step and the second step, the anhydrous alcohol is anhydrous C1-C4 alcohol.
3. The method of claim 1, wherein in step one, the salt of gulonic acid is sodium gulonate; and/or
In the first step and the second step, the anhydrous alcohol is anhydrous methanol.
4. The method of claim 1, wherein the gulonate is prepared by a process comprising the steps of: carrying out membrane ultrafiltration, decolorization, concentration, crystallization and centrifugation on the gulonate fermented liquor obtained by the secondary biological fermentation method to obtain gulonate;
the preparation method of the gulonic acid comprises the following steps: and (3) carrying out membrane ultrafiltration, acidification, decoloration, concentration, crystallization and centrifugation on the gulonic acid salt fermented liquor obtained by the secondary biological fermentation method to obtain the gulonic acid.
5. The method according to claim 1, wherein in the first step, the mass-to-volume ratio of the salt of gulonic acid or the salt of gulonic acid to the anhydrous alcohol is 1000:2 to 5 in terms of gulonic acid, wherein the unit of mass is Kg and the unit of volume is m3。
6. The method of claim 1, wherein the esterification reaction temperature is 60-65 ℃ and the esterification reaction time is 2-3 hours in the first step.
7. Such asThe process according to claim 1, wherein in the second step, the mass-to-volume ratio of the dried gulonic acid ester to the anhydrous alcohol is 1000:3 to 6, wherein the unit of mass is Kg and the unit of volume is m3。
8. The method of claim 1, wherein the base is sodium carbonate, sodium bicarbonate or sodium methoxide in step three.
9. The method for preparing vitamin C according to claim 1, wherein in the third step, the temperature of the conversion reaction is 65-68 ℃ and the time of the conversion reaction is 2-3 h.
10. The method for preparing vitamin C according to claim 1, wherein in the fifth step, the crystallization is vacuum concentration crystallization and cooling crystallization, and the temperature of the cooling crystallization is-5 to 0 ℃.
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| CN114712451A (en) * | 2022-04-08 | 2022-07-08 | 江门海关技术中心 | Additive solution for preventing poultry digestive tract bacterial diseases and preparation method thereof |
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| CN101747301A (en) * | 2010-01-26 | 2010-06-23 | 河北维尔康制药有限公司 | Method for preparing vitamin C with low consumption |
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| CN102351699A (en) * | 2011-10-28 | 2012-02-15 | 安徽泰格生物技术股份有限公司 | Gulonate and preparation method thereof |
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| GB428814A (en) * | 1933-10-25 | 1935-05-20 | Tadeus Reichstein | Process for the manufacture of laevo-ascorbic acid (vitamin-c) |
| CN101284824A (en) * | 2008-06-06 | 2008-10-15 | 郑州拓洋实业有限公司 | Preparation method of cenolate |
| CN101747301A (en) * | 2010-01-26 | 2010-06-23 | 河北维尔康制药有限公司 | Method for preparing vitamin C with low consumption |
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| CN114712451A (en) * | 2022-04-08 | 2022-07-08 | 江门海关技术中心 | Additive solution for preventing poultry digestive tract bacterial diseases and preparation method thereof |
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