CN115433189A - Extraction process of high-purity folic acid for food and feed and folic acid - Google Patents
Extraction process of high-purity folic acid for food and feed and folic acid Download PDFInfo
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- OVBPIULPVIDEAO-LBPRGKRZSA-N folic acid Chemical compound C=1N=C2NC(N)=NC(=O)C2=NC=1CNC1=CC=C(C(=O)N[C@@H](CCC(O)=O)C(O)=O)C=C1 OVBPIULPVIDEAO-LBPRGKRZSA-N 0.000 title claims abstract description 474
- OVBPIULPVIDEAO-UHFFFAOYSA-N N-Pteroyl-L-glutaminsaeure Natural products C=1N=C2NC(N)=NC(=O)C2=NC=1CNC1=CC=C(C(=O)NC(CCC(O)=O)C(O)=O)C=C1 OVBPIULPVIDEAO-UHFFFAOYSA-N 0.000 title claims abstract description 237
- 229960000304 folic acid Drugs 0.000 title claims abstract description 237
- 235000019152 folic acid Nutrition 0.000 title claims abstract description 237
- 239000011724 folic acid Substances 0.000 title claims abstract description 237
- 235000013305 food Nutrition 0.000 title claims abstract description 35
- 238000000605 extraction Methods 0.000 title claims abstract description 23
- RSKNEEODWFLVFF-UHFFFAOYSA-N sulfuric acid;2,5,6-triamino-1h-pyrimidin-4-one Chemical compound OS(O)(=O)=O.NC1=NC(=O)C(N)=C(N)N1 RSKNEEODWFLVFF-UHFFFAOYSA-N 0.000 claims abstract description 49
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 38
- SMZHKGXSEAGRTI-UHFFFAOYSA-N 1,1,1-trichloropropan-2-one Chemical compound CC(=O)C(Cl)(Cl)Cl SMZHKGXSEAGRTI-UHFFFAOYSA-N 0.000 claims abstract description 32
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims abstract description 30
- 238000007670 refining Methods 0.000 claims abstract description 27
- 235000010262 sodium metabisulphite Nutrition 0.000 claims abstract description 26
- FREULXCEHUTYEQ-HVDRVSQOSA-N OC(=O)[C@@H](N)CCC(O)=O.NC1=CC=C(C(O)=O)C=C1 Chemical compound OC(=O)[C@@H](N)CCC(O)=O.NC1=CC=C(C(O)=O)C=C1 FREULXCEHUTYEQ-HVDRVSQOSA-N 0.000 claims abstract description 24
- 238000001035 drying Methods 0.000 claims abstract description 24
- 229940001584 sodium metabisulfite Drugs 0.000 claims abstract description 20
- 238000007363 ring formation reaction Methods 0.000 claims abstract description 19
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 19
- 239000012043 crude product Substances 0.000 claims abstract description 17
- 238000004806 packaging method and process Methods 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 239000000843 powder Substances 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 238000000746 purification Methods 0.000 claims abstract description 6
- 239000007864 aqueous solution Substances 0.000 claims description 39
- 238000003756 stirring Methods 0.000 claims description 38
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 36
- 230000002572 peristaltic effect Effects 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 239000002808 molecular sieve Substances 0.000 claims description 27
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 27
- 239000008367 deionised water Substances 0.000 claims description 26
- 229910021641 deionized water Inorganic materials 0.000 claims description 26
- 230000001276 controlling effect Effects 0.000 claims description 23
- 239000011148 porous material Substances 0.000 claims description 21
- 239000011259 mixed solution Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- 238000000967 suction filtration Methods 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 230000001105 regulatory effect Effects 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 10
- 238000005303 weighing Methods 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 7
- 239000012295 chemical reaction liquid Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 17
- 229910052710 silicon Inorganic materials 0.000 description 17
- 239000010703 silicon Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 13
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 238000004128 high performance liquid chromatography Methods 0.000 description 8
- GADGMZDHLQLZRI-VIFPVBQESA-N N-(4-aminobenzoyl)-L-glutamic acid Chemical compound NC1=CC=C(C(=O)N[C@@H](CCC(O)=O)C(O)=O)C=C1 GADGMZDHLQLZRI-VIFPVBQESA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 235000013922 glutamic acid Nutrition 0.000 description 4
- 239000004220 glutamic acid Substances 0.000 description 4
- 230000003068 static effect Effects 0.000 description 4
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- DUEPRVBVGDRKAG-UHFFFAOYSA-N carbofuran Chemical compound CNC(=O)OC1=CC=CC2=C1OC(C)(C)C2 DUEPRVBVGDRKAG-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229960004050 aminobenzoic acid Drugs 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- CPNGPNLZQNNVQM-UHFFFAOYSA-N pteridine Chemical compound N1=CN=CC2=NC=CN=C21 CPNGPNLZQNNVQM-UHFFFAOYSA-N 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000009874 alkali refining Methods 0.000 description 1
- -1 aminobenzoic acid glutamic acid Chemical compound 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000002307 glutamic acids Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D475/00—Heterocyclic compounds containing pteridine ring systems
- C07D475/02—Heterocyclic compounds containing pteridine ring systems with an oxygen atom directly attached in position 4
- C07D475/04—Heterocyclic compounds containing pteridine ring systems with an oxygen atom directly attached in position 4 with a nitrogen atom directly attached in position 2
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Saccharide Compounds (AREA)
Abstract
The invention relates to the field of C07D475/04, in particular to an extraction process of high-purity folic acid for food and feed and folic acid. The invention takes 2,4, 5-triamino-6-hydroxypyrimidine sulfate, p-aminobenzoic acid glutamic acid and trichloroacetone as raw materials, performs cyclization reaction in the presence of sodium metabisulfite and sodium carbonate to prepare a folic acid crude product, obtains refined folic acid through two times of refining and purification, and finally obtains the high-purity folic acid through drying, crushing and packaging. The purity and yield of the crude folic acid are improved by controlling the adding sequence of raw materials, the adding amount of the raw materials and the reaction conditions in the cyclization reaction, the crude folic acid is refined and purified by controlling the technological parameters of primary refining and secondary refining and the selection of substances, and orange high-purity folic acid powder is obtained by drying, crushing and packaging, wherein the yield of the folic acid is 82-85 percent, and the purity of the folic acid is 99.5-99.9 percent.
Description
Technical Field
The invention relates to the field of C07D475/04, in particular to an extraction process of high-purity folic acid for food and feed and folic acid.
Background
Folic acid is a general name of a group of compounds with similar chemical structures and biochemical characteristics, and is formed by combining pteridine, p-aminobenzoic acid and 1 or more glutamic acids, namely, the folic acid is formed by connecting a-amino-4-hydroxyperidine with p-aminobenzoic acid and then connecting the pteridine with glutamic acid by an-NH-CO-bond. Folic acid is unstable in an acidic environment, is easily decomposed under illumination and high temperature conditions, is particularly easily damaged by ultraviolet rays, and can cause great loss when stored at normal temperature. At present, the folic acid synthesis process in China is relatively mature, but the problems of low yield, more byproducts, large wastewater amount, serious environmental pollution and the like exist.
Chinese patent CN105440035A discloses a low-energy-consumption preparation method for synthesizing high-purity folic acid, which comprises using 2,4,5 triamino-6-hydroxypyrimidine sulfate, N-p-aminobenzoyl glutamic acid and trichloroacetone as main raw materials, shortening reaction time by butt-joint reaction, acid washing and alkali refining, reducing energy consumption, but the product yield and purity need to be further improved; chinese patent CN108676006A discloses a refining method of high-purity folic acid, which comprises the steps of mixing a folic acid crude product, an organic solvent and concentrated hydrochloric acid, heating to dissolve the mixture, adding activated carbon for hot filtration, cooling and carrying out suction filtration to obtain a folic acid finished product, wherein the yield of the folic acid is 62.3-74.5%, and the purity of the folic acid is 99.37-99.8%, but the folic acid synthesis and the folic acid refining both directly influence the yield and the purity of the folic acid.
Therefore, the extraction process of the high-purity folic acid for the food and the feed is provided, the extraction process route is simple, the production efficiency is improved, the waste water amount and the byproducts in the production process are reduced, the folic acid with high yield, high purity and long retention time is prepared, and the method is particularly suitable for application in the fields of food and feed.
Disclosure of Invention
In order to solve the problems, the invention provides an extraction process of high-purity folic acid for food and feed, which takes 2,4, 5-triamino-6-hydroxypyrimidine sulfate, p-aminobenzoic acid glutamic acid and trichloroacetone as raw materials, performs cyclization reaction in the presence of sodium metabisulfite and sodium carbonate to obtain orange folic acid precipitate, then performs refining and purification twice to obtain folic acid, and finally obtains the high-purity folic acid by drying, crushing and packaging.
As a preferred technical scheme, the extraction process of the high-purity folic acid at least comprises the following steps:
s1, pretreatment: adding 2,4, 5-triamino-6-hydroxypyrimidine sulfate into a container, and introducing hydrogen at a certain temperature and under a certain pressure to ensure that the 2,4, 5-triamino-6-hydroxypyrimidine sulfate is fully contacted with the hydrogen for 40-60min to obtain 2,4, 5-triamino-6-hydroxypyrimidine sulfate containing dissolved hydrogen;
s2, cyclization reaction: (1) Dissolving p-aminobenzoic acid glutamic acid in deionized water at 60-65 ℃, controlling the rotating speed and temperature, adding sodium pyrosulfite, stirring for 5-10min, adding trichloroacetone, and stirring for reacting for 20-30min; (2) Adjusting the temperature, and adding the 2,4, 5-triamino-6-hydroxypyrimidine sulfate obtained in the step S1 for reaction; (3) Regulating the rotation speed, dropwise adding a sodium carbonate aqueous solution by using a peristaltic pump, regulating the pH of the system, keeping the temperature for 40-60min after the pH is stable, and performing suction filtration and washing for 3-5 times after the reaction liquid is cooled to room temperature to obtain a folic acid crude product;
s3, primary refining: (1) Weighing the wet weight of the folic acid crude product obtained in the step S2, marking as M1, adding a certain mass of sulfuric acid aqueous solution, and stirring for 5-10min to obtain a mixed solution A; (2) Dropwise adding the mixed solution A into deionized water with a certain mass by using a peristaltic pump, controlling the temperature at 35 ℃ and the rotating speed at 200-300rpm, stirring for 15-20min, standing, performing suction filtration, and washing to obtain primary refined folic acid;
s4, secondary refining: (1) Weighing the wet weight of the primary refined folic acid obtained in the step S3 as M2, adding a certain mass of deionized water, and stirring for 5-10min under the conditions that the temperature is controlled to be 75-83 ℃ and the rotating speed is 300-500rpm to obtain a mixed solution B; (2) Dropwise adding the sodium hydroxide aqueous solution into the mixed solution B by using a peristaltic pump, adjusting the pH =8.8-9.3 of the solution B, and stirring for 20-30min; (3) Adding inorganic porous material with certain mass, and stirring for 20-30min; (4) Controlling the flow rate of a peristaltic pump to be 1-2mL/min, dropwise adding hydrochloric acid to adjust the pH of the system to be =2.5-3, keeping the temperature for 10-15min, and performing suction filtration and washing while the solution is hot to obtain secondary refined folic acid;
s5, drying: placing the secondary refined folic acid obtained in the step S4 in a vacuum drying oven, and drying for a certain time to obtain high-purity folic acid;
s6, crushing: and (3) crushing the high-purity folic acid into high-purity folic acid powder with the particle size of 300-450 meshes by using a crusher, and packaging to obtain the high-purity folic acid for the food and the feed.
In order to improve the conversion rate of the 2,4, 5-triamino-6-hydroxypyrimidine sulfate and further improve the yield and the purity of folic acid, the 2,4, 5-triamino-6-hydroxypyrimidine sulfate is pretreated before cyclization reaction, and as a preferable technical scheme, a container in the step S1 is a static mixer; the temperature in the step S1 is 60-80 ℃; the pressure in the step S1 is 1.8-2.2MPa; is beneficial to improving the content of dissolved hydrogen in the 2,4, 5-triamino-6-hydroxypyrimidine sulfate, and further improves the cyclization reaction efficiency.
The addition sequence and the addition amount of the raw materials directly influence the yield and the purity of folic acid, and as a preferable technical scheme, in the step S2, the raw materials comprise 3.8-4.1 parts by weight of p-aminobenzoic acid glutamic acid, 2.7-2.9 parts by weight of sodium metabisulfite, 3.5-3.7 parts by weight of trichloroacetone, 3.5-3.7 parts by weight of 2,4, 5-triamino-6-hydroxypyrimidine sulfate and 145-153 parts by weight of water; preferably, 4.0 parts of p-aminobenzoic acid glutamic acid, 2.85 parts of sodium metabisulfite, 3.6 parts of trichloroacetone, 3.6 parts of 2,4, 5-triamino-6-hydroxypyrimidine sulfate and 150 parts of water in the step S2 are calculated by weight, so that the prepared folic acid has high yield and high purity;
the p-aminobenzoic acid glutamic acid has a CAS number of 4271-30-1 and a purity (HPLC) of 99%, and is purchased from Jinan Luxin chemical technology Co., ltd; the sodium metabisulfite has CAS number of 7681-57-4, purity (AR) of 96.0%, and is purchased from Shanghai Michelin Biotech, inc.; the CAS number of the trichloroacetone is 921-03-9, the purity (GC) is more than 80.0 percent, and the trichloroacetone is purchased from Taixi (Shanghai) formation industry development limited company; the 2,4, 5-triamino-6-hydroxypyrimidine sulfate has a CAS number of 35011-47-3 and a purity (HPLC) of 95% and is available from Shanghai Ji to Biochemical technology, inc.;
as a preferable technical scheme, the rotation speed in the step S2 (1) is 150-220rpm, the temperature in the step S2 (1) is 40-42 ℃, p-aminobenzoic acid glutamic acid is firstly reacted with trichloroacetone in the presence of sodium metabisulfite to generate an intermediate, and the rotation speed and the temperature are controlled to avoid excessive by-product generation caused by overhigh reaction temperature and excessively fast reaction; in order to ensure the normal operation of the cyclization reaction, as a preferred technical scheme, the temperature in the step S2 (2) is 35-40 ℃, and the reaction time in the step S2 (2) is 30-40min; as a preferable technical solution, the rotation speed in the step S2 (3) is 100-150rpm, the flow rate of the peristaltic pump in the step S2 (3) is 2-4mL/min, the concentration of the sodium carbonate aqueous solution in the step S2 (3) is 12-16wt%, the system pH in the step S2 (3) is 3.0-4.0, and the yield and purity of the crude folic acid can be improved by controlling the flow rate and the rotation speed of the peristaltic pump and adjusting the system pH to 3.0-4.0 by using the sodium carbonate aqueous solution with the concentration of 12-16wt%, so as to provide a basis for the subsequent preparation of high-purity and high-yield folic acid;
in the step S2, the yield of the crude folic acid is 72.3-75.1%, and the purity of the crude folic acid is 83.6-85.5%;
the purity of the primary refined folic acid is closely related to the type and concentration of acid adopted in the primary refining process, and as a preferable technical scheme, the concentration of the sulfuric acid aqueous solution in the step S3 (1) is 20-28%; the mass ratio of the sulfuric acid aqueous solution to the crude folic acid in the step S3 (1) is (1-1.5): 1; as a preferable technical scheme, the flow rate of the peristaltic pump in the step S3 (2) is 4-6mL/min, and the mass ratio of the deionized water to the crude folic acid in the step S3 (2) is (8-12): 1; on the basis of ensuring the effect of primary purification, the use amounts of the sulfuric acid aqueous solution and the deionized water are reduced as much as possible, and the generation of a large amount of wastewater in the production process of folic acid is reduced from the source.
The yield of the first refined folic acid in the step S3 is 76.8 to 80.1 percent, and the purity of the first refined folic acid is 90.6 to 92.5 percent;
in the secondary refining process of folic acid, the type of alkali and the pH value of a system are adopted to directly influence the further refining and purifying effect of the subsequent inorganic porous material on folic acid, so that the yield and the quality of the product are influenced, and as a preferable technical scheme, the mass ratio of deionized water to the primary refined folic acid in the step S4 (1) is (10-15): 1; as a preferable technical scheme, the concentration of the sodium hydroxide aqueous solution in the step S4 (2) is 10-15wt%; in the step S4 (2), the flow rate of the peristaltic pump is 1-3mL/min, so that on one hand, the using amount of the sodium hydroxide aqueous solution is reduced on the basis of ensuring the full dissolution of the primary refined folic acid, on the other hand, the dissolution time of the primary refined folic acid can be shortened, and the production efficiency is improved; as a preferable technical solution, the mass ratio of the inorganic porous material to the primary purified folic acid in the step S4 (3) is (0.1-0.15): 100, respectively; as a preferred technical solution, in the step S4 (3), the inorganic porous material is selected from at least one of zeolite and molecular sieve; preferably, the inorganic porous material in the step S4 (3) is a molecular sieve; the molecular sieve is a mesoporous silicon-based molecular sieve; the aperture of the mesoporous silicon-based molecular sieve is 7-11nm, and the specific surface area is 550-650m < 2 >/g; the impurity adsorption effect of the inorganic porous material is ensured to the maximum extent, the using amount of the inorganic porous material is reduced, and the influence of other impurities on the quality of final folic acid is avoided;
the CAS number of the mesoporous silicon-based molecular sieve is 12173-28-3, the model is J & K533339, and the mesoporous silicon-based molecular sieve is purchased from Beijing carbofuran technology GmbH;
in order to remove the moisture in the secondarily purified folic acid as much as possible and prolong the storage time of the folic acid, as a preferable technical scheme, the temperature of the vacuum drying oven in the step S5 is set to be 35-45 ℃, and the drying time in the step S5 is 2-3h, so that the moisture in the secondarily purified folic acid is sufficiently removed, the purity of the folic acid is further improved, and the storage time of the folic acid is prolonged.
The invention provides high-purity folic acid prepared by the extraction process of the high-purity folic acid for food and feed, wherein the high-purity folic acid is orange powder, the yield of the high-purity folic acid is 82-85%, and the purity of the high-purity folic acid is 99.7-99.9%.
Has the beneficial effects that:
1. the invention takes 2,4, 5-triamino-6-hydroxypyrimidine sulfate, p-aminobenzoic acid glutamic acid and trichloroacetone as raw materials, under the condition that sodium pyrosulfite and sodium carbonate exist, cyclization reaction is carried out to prepare folic acid crude product, refined folic acid is obtained through two times of refining and purification, and high-purity folic acid with the yield of 82-85 percent and the purity of 99.5-99.9 percent is obtained through drying, crushing and packaging;
2. a cyclization reaction step: sequentially adding aminobenzoic acid glutamic acid, sodium pyrosulfite, trichloroacetone and 2,4, 5-triamino-6-hydroxypyrimidine sulfate to perform cyclization reaction; controlling the adding temperature, stirring speed and time of the raw materials, dropwise adding a sodium carbonate aqueous solution by using a peristaltic pump, and adjusting the pH of the system to obtain a folic acid crude product with the yield of 72.3-75.1% and the purity of 83.6-85.5%;
3. a primary refining step: by adopting a sulfuric acid aqueous solution with the concentration of 20-28%, and controlling the mass ratio of the sulfuric acid aqueous solution to the crude folic acid to be (1-1.5): 1, refining the folic acid crude product for one time; adjusting the flow rate of a peristaltic pump to be 4-6mL/min, and controlling the mass ratio of the deionized water to the crude folic acid to be (8-12): 1, preparing primary refined folic acid with uniform texture, wherein the yield of the primary refined folic acid is 76.8-80.1 percent, and the purity of the primary refined folic acid is 90.6-92.5 percent;
4. a secondary refining step; the pH =8.8-9.3 of a system is controlled by adopting a 10-15wt% sodium hydroxide aqueous solution, an inorganic porous material mesoporous silicon-based molecular sieve is used as an adsorbing material, and the mass ratio of the inorganic porous material to the first-time refined folic acid is controlled to be (0.1-0.15): 100, further improving the purity of the primary refined folic acid;
5. drying and crushing: and drying, crushing and packaging the secondary refined folic acid to obtain the high-purity folic acid for the food and the feed.
Drawings
FIG. 1 is a diagram showing the actual production of high-purity folic acid produced in example 1 of the present invention.
Detailed Description
Example 1
The embodiment 1 of the invention provides an extraction process of high-purity folic acid for food and feed, which comprises the steps of taking 2,4, 5-triamino-6-hydroxypyrimidine sulfate, p-aminobenzoic acid glutamic acid and trichloroacetone as raw materials, carrying out cyclization reaction in the presence of sodium metabisulfite and sodium carbonate to obtain orange folic acid precipitate, refining and purifying twice to obtain folic acid, drying, crushing and packaging to obtain the high-purity folic acid.
The extraction process of the high-purity folic acid comprises the following steps:
s1, pretreatment: adding 2,4, 5-triamino-6-hydroxypyrimidine sulfate into a container, introducing hydrogen at a certain temperature and under a certain pressure, and fully contacting the 2,4, 5-triamino-6-hydroxypyrimidine sulfate with the hydrogen for 50min to obtain 2,4, 5-triamino-6-hydroxypyrimidine sulfate containing dissolved hydrogen;
s2, cyclization reaction: (1) Dissolving p-aminobenzoic acid glutamic acid in deionized water at 62 ℃, controlling the rotating speed and the temperature, adding sodium metabisulfite, stirring for 8min, adding trichloroacetone, and stirring for reacting for 25min; (2) Adjusting the temperature, and adding the 2,4, 5-triamino-6-hydroxypyrimidine sulfate obtained in the step S1 for reaction; (3) Regulating the rotation speed, dropwise adding a sodium carbonate aqueous solution by using a peristaltic pump, regulating the pH of the system, keeping the temperature for 50min after the pH is stable, and performing suction filtration and washing for 5 times after the reaction liquid is cooled to room temperature to obtain a folic acid crude product;
s3, primary refining: (1) Weighing the wet weight of the folic acid crude product obtained in the step S2, and recording the wet weight as M 1 Adding a certain mass of sulfuric acid aqueous solution, and stirring for 10min to obtain a mixed solution A; (2) Dropwise adding the mixed solution A into deionized water with a certain mass by using a peristaltic pump, controlling the temperature at 35 ℃ and the rotating speed at 280rpm, stirring for 18min, standing, performing suction filtration, and washing to obtain primary refined folic acid;
s4, secondary refining: (1) Weighing the wet weight of the primary refined folic acid obtained in the step S3 as M 2 Adding deionized water with a certain mass, controlling the temperature at 80 ℃, and stirring for 8min at the rotating speed of 400rpm to obtain a mixed solution B; (2) Dropwise adding a sodium hydroxide aqueous solution into the mixed solution B by using a peristaltic pump, adjusting the pH =9.0 of the solution B, and stirring for 25min; (3) adding an inorganic porous material with a certain mass, and stirring for 25min; (4) Controlling the flow rate of a peristaltic pump to be 1.5mL/min, dropwise adding hydrochloric acid to adjust the pH of the system to be =3, keeping the temperature for 15min, and performing suction filtration and washing while the solution is hot to obtain secondary refined folic acid;
s5, drying: placing the secondary refined folic acid obtained in the step S4 in a vacuum drying oven, and drying for a certain time to obtain high-purity folic acid;
s6, crushing: and (3) crushing the high-purity folic acid by a crusher to high-purity folic acid powder with the particle size of 400 meshes, and packaging to obtain the high-purity folic acid for the food and the feed.
The container in the step S1 is a static mixer; the temperature in the step S1 is 70 ℃; the pressure in the step S1 is 2.0MPa;
4.0 parts of p-aminobenzoic acid glutamic acid, 2.85 parts of sodium metabisulfite, 3.6 parts of trichloroacetone, 3.6 parts of 2,4, 5-triamino-6-hydroxypyrimidine sulfate and 150 parts of water in the step S2 by weight;
the para aminobenzoic acid glutamic acid has CAS number of 4271-30-1 and purity (HPLC) of 99%, and is purchased from Jinan Luxin chemical technology Co., ltd; the sodium metabisulfite has CAS number of 7681-57-4, purity (AR) of 96.0%, and is purchased from Shanghai Michelin Biotech, inc.; the CAS number of the trichloroacetone is 921-03-9, the purity (GC) is more than 80.0 percent, and the trichloroacetone is purchased from Taixi (Shanghai) formation industry development limited company; the 2,4, 5-triamino-6-hydroxypyrimidine sulfate has a CAS number of 35011-47-3 and a purity (HPLC) of 95% and is available from Shanghai Ji to Biochemical technology, inc.;
the rotating speed in the step S2 (1) is 200rpm, and the temperature in the step S2 (1) is 40 ℃; the temperature in the step S2 (2) is 38 ℃, and the reaction time in the step S2 (2) is 35min; the rotation speed in the step S2 (3) is 120rpm, the flow rate of the peristaltic pump in the step S2 (3) is 3mL/min, the concentration of the sodium carbonate aqueous solution in the step S2 (3) is 15wt%, and the pH of the system in the step S2 (3) is 3.5;
in the step S2, the yield of the crude folic acid is 75.1 percent, and the purity of the crude folic acid is 85.5 percent;
the concentration of the sulfuric acid aqueous solution in the step S3 (1) is 25%; the mass ratio of the sulfuric acid aqueous solution to the crude folic acid in the step S3 (1) is 1.2:1; the flow rate of the peristaltic pump in the step S3 (2) is 5mL/min, and the mass ratio of the deionized water to the crude folic acid in the step S3 (2) is 10:1;
the yield of the once refined folic acid in the step S3 is 80.1 percent, and the purity of the once refined folic acid is 92.5 percent;
the mass ratio of the deionized water to the primary refined folic acid in the step S4 (1) is 12:1; the concentration of the sodium hydroxide aqueous solution in the step S4 (2) is 12wt%; in the step S4 (2), the flow rate of the peristaltic pump is 2mL/min; the mass ratio of the inorganic porous material to the primary refined folic acid in the step S4 (3) is 0.12:100; in the step S4 (3), the inorganic porous material is a molecular sieve; the molecular sieve is a mesoporous silicon-based molecular sieve; the aperture of the mesoporous silicon-based molecular sieve is 7-11nm, and the specific surface area is 550-650m 2 /g；
The CAS number of the mesoporous silicon-based molecular sieve is 12173-28-3, the model number is J & K533339, and the mesoporous silicon-based molecular sieve is purchased from Beijing Bailingwei science and technology Limited company;
the temperature of the vacuum drying oven in the step S5 is set to be 40 ℃; the drying time in the step S5 is 2.5h.
In another aspect, embodiment 1 of the present invention provides high-purity folic acid prepared by an extraction process of high-purity folic acid for food and feed, wherein the high-purity folic acid is orange powder, the high-purity folic acid yield is 85%, and the high-purity folic acid purity is 99.9%.
Example 2
The embodiment 2 of the invention provides an extraction process of high-purity folic acid for food and feed, which comprises the steps of taking 2,4, 5-triamino-6-hydroxypyrimidine sulfate, p-aminobenzoic acid glutamic acid and trichloroacetone as raw materials, carrying out cyclization reaction in the presence of sodium metabisulfite and sodium carbonate to obtain orange folic acid precipitate, refining and purifying twice to obtain folic acid, drying, crushing and packaging to obtain the high-purity folic acid.
The extraction process of the high-purity folic acid comprises the following steps:
s1, pretreatment: adding 2,4, 5-triamino-6-hydroxypyrimidine sulfate into a container, introducing hydrogen at a certain temperature and under a certain pressure, and fully contacting the 2,4, 5-triamino-6-hydroxypyrimidine sulfate with the hydrogen for 50min to obtain 2,4, 5-triamino-6-hydroxypyrimidine sulfate containing dissolved hydrogen;
s2, cyclization reaction: (1) Dissolving p-aminobenzoic acid glutamic acid in deionized water at 62 ℃, controlling the rotating speed and the temperature, adding sodium metabisulfite, stirring for 8min, adding trichloroacetone, and stirring for reacting for 25min; (2) Adjusting the temperature, and adding the 2,4, 5-triamino-6-hydroxypyrimidine sulfate obtained in the step S1 for reaction; (3) Regulating the rotation speed, dropwise adding a sodium carbonate aqueous solution by using a peristaltic pump, regulating the pH of the system, keeping the temperature for 50min after the pH is stable, and performing suction filtration and washing for 5 times after the reaction liquid is cooled to room temperature to obtain a folic acid crude product;
s3, primary refining: (1) Weighing the wet weight of the folic acid crude product obtained in the step S2, and recording the wet weight as M 1 Adding a certain mass of sulfuric acid aqueous solution, and stirring for 10min to obtain a mixed solution A; (2) Dropwise adding the mixed solution A into deionized water with a certain mass by using a peristaltic pump, controlling the temperature at 35 ℃ and the rotating speed at 280rpm, stirring for 18min, standing, performing suction filtration, and washing to obtain primary refined folic acid;
s4, secondary refining: (1) Weighing the wet weight M of the primary refined folic acid obtained in the step S3 2 Adding a certain mass of deionized water, controlling the temperature to be 80 ℃,stirring for 8min under the condition that the rotating speed is 400rpm to obtain a mixed solution B; (2) Dropwise adding a sodium hydroxide aqueous solution into the mixed solution B by using a peristaltic pump, adjusting the pH =9.0 of the solution B, and stirring for 25min; (3) adding an inorganic porous material with a certain mass, and stirring for 25min; (4) Controlling the flow rate of a peristaltic pump to be 1.5mL/min, dropwise adding hydrochloric acid to adjust the pH of the system to be =3, keeping the temperature for 15min, and obtaining secondary refined folic acid after hot suction filtration and washing;
s5, drying: placing the secondary refined folic acid obtained in the step S4 in a vacuum drying oven, and drying for a certain time to obtain high-purity folic acid;
s6, crushing: and (3) crushing the high-purity folic acid by a crusher to high-purity folic acid powder with the particle size of 400 meshes, and packaging to obtain the high-purity folic acid for the food and the feed.
The container in the step S1 is a static mixer; the temperature in the step S1 is 80 ℃; the pressure in the step S1 is 2.2MPa;
4.1 parts of p-aminobenzoic acid glutamic acid, 2.9 parts of sodium metabisulfite, 3.7 parts of trichloroacetone, 3.7 parts of 2,4, 5-triamino-6-hydroxypyrimidine sulfate and 153 parts of water in parts by weight in the step S2;
the p-aminobenzoic acid glutamic acid has a CAS number of 4271-30-1 and a purity (HPLC) of 99%, and is purchased from Jinan Luxin chemical technology Co., ltd; the sodium metabisulfite has CAS number of 7681-57-4, purity (AR) of 96.0%, and is purchased from Shanghai Michelin Biochemical technology Co., ltd; the CAS number of the trichloroacetone is 921-03-9, the purity (GC) is more than 80.0 percent, and the trichloroacetone is purchased from Taixi (Shanghai) formation industry development limited company; the 2,4, 5-triamino-6-hydroxypyrimidine sulfate has a CAS number of 35011-47-3 and a purity (HPLC) of 95% and is available from Shanghai Ji to Biochemical technology, inc.;
the rotating speed in the step S2 (1) is 200rpm, and the temperature in the step S2 (1) is 40 ℃; the temperature in the step S2 (2) is 38 ℃, and the reaction time in the step S2 (2) is 35min; the rotation speed in the step S2 (3) is 150rpm, the flow rate of the peristaltic pump in the step S2 (3) is 4mL/min, the concentration of the sodium carbonate aqueous solution in the step S2 (3) is 16wt%, and the pH of the system in the step S2 (3) is 3.5;
in the step S2, the yield of the crude folic acid is 73.6 percent, and the purity of the crude folic acid is 84.3 percent;
the concentration of the sulfuric acid aqueous solution in the step S3 (1) is 28%; the mass ratio of the aqueous sulfuric acid solution to the crude folic acid product in the step S3 (1) is 1:1; the flow rate of the peristaltic pump in the step S3 (2) is 6mL/min, and the mass ratio of the deionized water to the crude folic acid in the step S3 (2) is 10:1;
the yield of the primary refined folic acid in the step S3 is 78.5 percent, and the purity of the primary refined folic acid is 91.2 percent;
the mass ratio of the deionized water to the primary refined folic acid in the step S4 (1) is 12:1; the concentration of the sodium hydroxide aqueous solution in the step S4 (2) is 12wt%; in the step S4 (2), the flow rate of the peristaltic pump is 2mL/min; the mass ratio of the inorganic porous material to the primary refined folic acid in the step S4 (3) is 0.15:100; in the step S4 (3), the inorganic porous material is a molecular sieve; the molecular sieve is a mesoporous silicon-based molecular sieve; the aperture of the mesoporous silicon-based molecular sieve is 7-11nm, and the specific surface area is 550-650m 2 /g；
The CAS number of the mesoporous silicon-based molecular sieve is 12173-28-3, the model is J & K533339, and the mesoporous silicon-based molecular sieve is purchased from Beijing carbofuran technology GmbH;
the temperature of the vacuum drying oven in the step S5 is set to be 45 ℃; the drying time in the step S5 is 2h.
In another aspect, embodiment 2 of the present invention provides high-purity folic acid prepared by an extraction process of high-purity folic acid for food and feed, wherein the high-purity folic acid is orange powder, the high-purity folic acid yield is 84%, and the high-purity folic acid purity is 99.8%.
Example 3
In an aspect, embodiment 3 of the present invention provides an extraction process of high purity folic acid for food and feed, wherein 2,4, 5-triamino-6-hydroxypyrimidine sulfate, p-aminobenzoic acid glutamic acid, and trichloroacetone are adopted as raw materials, cyclization is performed in the presence of sodium metabisulfite and sodium carbonate to obtain an orange folic acid precipitate, then folic acid is obtained through two refining and purification processes, and finally, folic acid is obtained through drying, crushing, and packaging.
The extraction process of the high-purity folic acid comprises the following steps:
s1, pretreatment: adding 2,4, 5-triamino-6-hydroxypyrimidine sulfate into a container, introducing hydrogen at a certain temperature and under a certain pressure, and fully contacting the 2,4, 5-triamino-6-hydroxypyrimidine sulfate with the hydrogen for 50min to obtain 2,4, 5-triamino-6-hydroxypyrimidine sulfate containing dissolved hydrogen;
s2, cyclization reaction: (1) Dissolving p-aminobenzoic acid glutamic acid in deionized water at 62 ℃, controlling the rotating speed and the temperature, adding sodium metabisulfite, stirring for 8min, adding trichloroacetone, and stirring for reacting for 25min; (2) Adjusting the temperature, and adding the 2,4, 5-triamino-6-hydroxypyrimidine sulfate obtained in the step S1 for reaction; (3) Regulating the rotation speed, dropwise adding a sodium carbonate aqueous solution by using a peristaltic pump, regulating the pH of the system, keeping the temperature for 50min after the pH is stable, and performing suction filtration and washing for 5 times after the reaction liquid is cooled to room temperature to obtain a folic acid crude product;
s3, primary refining: (1) Weighing the wet weight of the folic acid crude product obtained in the step S2, and recording the wet weight as M 1 Adding a certain mass of sulfuric acid aqueous solution, and stirring for 10min to obtain a mixed solution A; (2) Dropwise adding the mixed solution A into deionized water with a certain mass by using a peristaltic pump, controlling the temperature at 35 ℃ and the rotating speed at 280rpm, stirring for 18min, standing, performing suction filtration, and washing to obtain primary refined folic acid;
s4, secondary refining: (1) Weighing the wet weight of the primary refined folic acid obtained in the step S3 as M 2 Adding deionized water with a certain mass, controlling the temperature at 80 ℃, and stirring for 8min at the rotating speed of 400rpm to obtain a mixed solution B; (2) Dropwise adding a sodium hydroxide aqueous solution into the mixed solution B by using a peristaltic pump, adjusting the pH =9.0 of the solution B, and stirring for 25min; (3) adding an inorganic porous material with a certain mass, and stirring for 25min; (4) Controlling the flow rate of a peristaltic pump to be 1.5mL/min, dropwise adding hydrochloric acid to adjust the pH of the system to be =3, keeping the temperature for 15min, and performing suction filtration and washing while the solution is hot to obtain secondary refined folic acid;
s5, drying: placing the secondary refined folic acid obtained in the step S4 in a vacuum drying oven, and drying for a certain time to obtain high-purity folic acid;
s6, crushing: and (3) crushing the high-purity folic acid into high-purity folic acid powder with the particle size of 400 meshes by adopting a crusher, and packaging to obtain the high-purity folic acid for the food and the feed.
The container in the step S1 is a static mixer; the temperature in the step S1 is 60 ℃; the pressure in the step S1 is 1.8MPa;
3.8 parts of p-aminobenzoic acid glutamic acid, 2.7 parts of sodium metabisulfite, 3.5 parts of trichloroacetone, 3.5 parts of 2,4, 5-triamino-6-hydroxypyrimidine sulfate and 145 parts of water in parts by weight in the step S2;
the para aminobenzoic acid glutamic acid has CAS number of 4271-30-1 and purity (HPLC) of 99%, and is purchased from Jinan Luxin chemical technology Co., ltd; the sodium metabisulfite has CAS number of 7681-57-4, purity (AR) of 96.0%, and is purchased from Shanghai Michelin Biotech, inc.; the CAS number of the trichloroacetone is 921-03-9, the purity (GC) is more than 80.0 percent, and the trichloroacetone is purchased from Chixi (Shanghai) chemical industry development limited company; the 2,4, 5-triamino-6-hydroxypyrimidine sulfate has a CAS number of 35011-47-3 and a purity (HPLC) of 95% and is purchased from Shanghai Ji to Biochemical technology, inc.;
the rotating speed in the step S2 (1) is 200rpm, and the temperature in the step S2 (1) is 40 ℃; the temperature in the step S2 (2) is 38 ℃, and the reaction time in the step S2 (2) is 35min; the rotation speed in the step S2 (3) is 100rpm, the flow rate of the peristaltic pump in the step S2 (3) is 2mL/min, the concentration of the sodium carbonate aqueous solution in the step S2 (3) is 12wt%, and the pH of the system in the step S2 (3) is 3.5;
in the step S2, the yield of the crude folic acid is 72.3 percent, and the purity of the crude folic acid is 83.6 percent;
the concentration of the sulfuric acid aqueous solution in the step S3 (1) is 20%; the mass ratio of the aqueous sulfuric acid solution to the crude folic acid product in the step S3 (1) is 1.5:1; the flow rate of the peristaltic pump in the step S3 (2) is 4mL/min, and the mass ratio of the deionized water to the crude folic acid in the step S3 (2) is 10:1;
the yield of the once refined folic acid in the step S3 is 76.8 percent, and the purity of the once refined folic acid is 90.6 percent;
the mass ratio of the deionized water to the primary refined folic acid in the step S4 (1) is 12:1; the concentration of the sodium hydroxide aqueous solution in the step S4 (2) is 12wt%; in the step S4 (2), the flow rate of the peristaltic pump is 2mL/min; in the step S4 (3), the mass ratio of the inorganic porous material to the primary refined folic acid is 0.1:100; in the step S4 (3), the inorganic porous material is a molecular sieve; the molecular sieve is a mesoporous silicon-based molecular sieve; the aperture of the mesoporous silicon-based molecular sieve is 7-11nm, and the specific surface area is 550-650m 2 /g；
The CAS number of the mesoporous silicon-based molecular sieve is 12173-28-3, the model is J & K533339, and the mesoporous silicon-based molecular sieve is purchased from Beijing carbofuran technology GmbH;
the temperature of the vacuum drying oven in the step S5 is set to be 35 ℃; the drying time in the step S5 is 3h.
In another aspect, embodiment 1 of the present invention provides high-purity folic acid prepared by an extraction process of high-purity folic acid for food and feed, wherein the high-purity folic acid is orange powder, the high-purity folic acid yield is 82%, and the high-purity folic acid purity is 99.7%.
Comparative example 1
The invention provides an extraction process of high-purity folic acid for food and feed in comparative example 1, which is implemented in the same way as in example 1, except that the addition sequence is adjusted, and the step S2 and the cyclization reaction step are specifically as follows: (1) Dissolving p-aminobenzoic acid glutamic acid and 2,4, 5-triamino-6-hydroxypyrimidine sulfate in deionized water at 62 ℃, controlling the rotating speed and the temperature, adding sodium pyrosulfite, stirring for 8min, adding trichloroacetone, stirring and reacting for 25min; (2) Regulating the rotation speed, dropwise adding a sodium carbonate aqueous solution by using a peristaltic pump, regulating the pH of the system, keeping the temperature for 50min after the pH is stable, and performing suction filtration and washing for 5 times after the reaction liquid is cooled to room temperature to obtain a folic acid crude product.
Comparative example 2
Comparative example 2 of the present invention provides an extraction process of high purity folic acid for food and feed, which is carried out in the same manner as in example 1 except that in step S2, 4.0 parts by weight of p-aminobenzoic acid glutamic acid, 2.85 parts by weight of sodium metabisulfite, 2.7 parts by weight of trichloroacetone, 3.6 parts by weight of 2,4, 5-triamino-6-hydroxypyrimidine sulfate, and 150 parts by weight of water are used.
Comparative example 3
Comparative example 3 of the present invention provides an extraction process of high purity folic acid for food and feed, which is carried out in the same manner as in example 1 except that the temperature in step S2 (2) is 45 ℃ and the reaction time in step S2 (2) is 35min.
Comparative example 4
Comparative example 4 of the present invention provides a process for extracting high-purity folic acid for food and feed, which is the same as example 1 except that the aqueous solution of sulfuric acid in step S3 is a 15wt% aqueous solution of hydrochloric acid.
Comparative example 5
Comparative example 5 of the present invention provides an extraction process of high purity folic acid for food and feed, which is the same as example 1 except that the aqueous sodium hydroxide solution in step S4 is 10wt% ammonia.
Performance test method
The contents of folic acid in the folic acid crude products, the first refined folic acid and the second refined folic acid prepared in the examples and the comparative examples were measured by a high performance liquid chromatograph, and the purity and the yield of folic acid were further calculated by the following formulas.
(1) Crude folic acid purity = (folic acid mass in crude folic acid/crude folic acid mass) × 100%;
yield of crude folic acid = (crude folic acid mass/2,4, 5-triamino-6-hydroxypyrimidine sulfate, p-aminobenzoic acid glutamic acid, and trichloroacetone total mass) × 100%;
(2) Primary refined folic acid purity = (folic acid mass in primary refined folic acid/primary refined folic acid mass) × 100%; yield of once refined folic acid = (mass of once refined folic acid/mass of crude folic acid) × 100%;
(3) High purity folic acid purity = (folic acid mass in high purity folic acid/high purity folic acid mass) × 100%;
high-purity folic acid yield = (mass of high-purity folic acid/mass of once refined folic acid) × 100%.
Performance test data
The performance of folic acid prepared by the specific process of examples 1 to 3 and comparative examples 1 to 4 was evaluated.
Referring to table 1, table 1 shows folic acid performance test data obtained by a specific process in examples 1 to 3 and comparative examples 1 to 4.
Claims (10)
1. An extraction process of high-purity folic acid for food and feed is characterized in that 2,4, 5-triamino-6-hydroxypyrimidine sulfate, p-aminobenzoic acid glutamic acid and trichloroacetone are used as raw materials, cyclization reaction is carried out in the presence of sodium pyrosulfite and sodium carbonate to obtain orange folic acid precipitate, folic acid is obtained through two times of refining and purification, and finally, the folic acid is dried, crushed and packaged to obtain the high-purity folic acid.
2. The process for extracting high-purity folic acid for food and feed according to claim 1, wherein the process for extracting high-purity folic acid for food and feed at least comprises the following steps:
s1, pretreatment: adding 2,4, 5-triamino-6-hydroxypyrimidine sulfate into a container, introducing hydrogen at a certain temperature and under a certain pressure, and allowing the 2,4, 5-triamino-6-hydroxypyrimidine sulfate to contact with the hydrogen for 40-60min to obtain 2,4, 5-triamino-6-hydroxypyrimidine sulfate containing dissolved hydrogen;
s2, cyclization reaction: (1) Dissolving p-aminobenzoic acid glutamic acid in deionized water at 60-65 ℃, controlling the rotating speed and temperature, adding sodium pyrosulfite, stirring for 5-10min, adding trichloroacetone, and stirring for reacting for 20-30min; (2) Adjusting the temperature, and adding the 2,4, 5-triamino-6-hydroxypyrimidine sulfate obtained in the step S1 for reaction; (3) Regulating the rotation speed, dropwise adding a sodium carbonate aqueous solution by using a peristaltic pump, regulating the pH of the system, keeping the temperature for 40-60min after the pH is stable, and performing suction filtration and washing for 3-5 times after the reaction liquid is cooled to room temperature to obtain a folic acid crude product;
s3, primary refining: (1) Weighing the wet weight of the folic acid crude product obtained in the step S2, recording the wet weight as M1, adding a certain mass of sulfuric acid aqueous solution, and stirring for 5-10min to obtain a mixed solution A; (2) Dropwise adding the mixed solution A into deionized water with a certain mass by using a peristaltic pump, controlling the temperature at 35 ℃ and the rotating speed at 200-300rpm, stirring for 15-20min, standing, performing suction filtration, and washing to obtain primary refined folic acid;
s4, secondary refining: (1) Weighing the wet weight of the primary refined folic acid obtained in the step S3 as M2, adding a certain mass of deionized water, and stirring for 5-10min under the conditions that the temperature is controlled to be 75-83 ℃ and the rotating speed is 300-500rpm to obtain a mixed solution B; (2) Dropwise adding the sodium hydroxide aqueous solution into the mixed solution B by using a peristaltic pump, adjusting the pH =8.8-9.3 of the solution B, and stirring for 20-30min; (3) Adding inorganic porous material with certain mass, and stirring for 20-30min; (4) Controlling the flow rate of a peristaltic pump to be 1-2mL/min, dropwise adding hydrochloric acid to adjust the pH of the system to be =2.5-3, keeping the temperature for 10-15min, and performing suction filtration and washing while the solution is hot to obtain secondary refined folic acid;
s5, drying: placing the secondary refined folic acid obtained in the step S4 in a vacuum drying oven, and drying for a certain time to obtain high-purity folic acid;
s6, crushing: and (3) crushing the high-purity folic acid into high-purity folic acid powder with the particle size of 300-450 meshes by using a crusher, and packaging to obtain the high-purity folic acid for the food and the feed.
3. The process for extracting high-purity folic acid for foods and feeds according to claim 2, wherein the temperature in the step S1 is 60-80 ℃.
4. The process for extracting high-purity folic acid for foods and feeds according to claim 2, wherein 3.8 to 4.1 parts by weight of p-aminobenzoic acid glutamic acid, 2.7 to 2.9 parts by weight of sodium metabisulfite, 3.5 to 3.7 parts by weight of trichloroacetone, 3.5 to 3.7 parts by weight of 2,4, 5-triamino-6-hydroxypyrimidine sulfate, and 145 to 153 parts by weight of water are added in the step S2.
5. The process for extracting high-purity folic acid for food and feed according to claim 2, characterized in that the temperature in the step S2 (2) is 35-40 ℃, and the reaction time in the step S2 (2) is 30-40min.
6. The process for extracting high-purity folic acid for food and feed according to claim 2, characterized in that the mass ratio of the aqueous sulfuric acid solution to the crude folic acid in the step S3 (1) is (1-1.5): 1.
7. the process for extracting high-purity folic acid for food and feed according to claim 2, wherein the mass ratio of the inorganic porous material to the primarily refined folic acid in the step S4 (3) is (0.1-0.15): 100.
8. the process of claim 2, wherein the inorganic porous material in step S4 (3) is at least one selected from zeolite and molecular sieve.
9. The process for extracting high-purity folic acid for food and feed according to claim 2, characterized in that the temperature of a vacuum drying oven is set to 35-45 ℃ in the step S5; the drying time in the step S5 is 2-3h.
10. The process for extracting high-purity folic acid for food and feed according to any one of claims 1 to 9, wherein the high-purity folic acid is orange powder, the yield of the high-purity folic acid is 82 to 85 percent, and the purity of the high-purity folic acid is 99.7 to 99.9 percent.
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