CN113980047B - Preparation method of phytic acid - Google Patents
Preparation method of phytic acid Download PDFInfo
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- CN113980047B CN113980047B CN202111204479.7A CN202111204479A CN113980047B CN 113980047 B CN113980047 B CN 113980047B CN 202111204479 A CN202111204479 A CN 202111204479A CN 113980047 B CN113980047 B CN 113980047B
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- 235000002949 phytic acid Nutrition 0.000 title claims abstract description 85
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 title claims abstract description 83
- 229940068041 phytic acid Drugs 0.000 title claims abstract description 60
- 239000000467 phytic acid Substances 0.000 title claims abstract description 60
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000011347 resin Substances 0.000 claims abstract description 75
- 229920005989 resin Polymers 0.000 claims abstract description 75
- 238000005342 ion exchange Methods 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 30
- 238000000108 ultra-filtration Methods 0.000 claims abstract description 23
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002253 acid Substances 0.000 claims abstract description 16
- 150000001768 cations Chemical class 0.000 claims abstract description 12
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 40
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 23
- 239000012528 membrane Substances 0.000 claims description 20
- 240000008042 Zea mays Species 0.000 claims description 19
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 19
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 19
- 235000005822 corn Nutrition 0.000 claims description 19
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 12
- 239000002002 slurry Substances 0.000 claims description 9
- 102000004169 proteins and genes Human genes 0.000 claims description 8
- 108090000623 proteins and genes Proteins 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- 125000002091 cationic group Chemical group 0.000 claims description 3
- 150000001450 anions Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 10
- 239000011574 phosphorus Substances 0.000 abstract description 10
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 10
- 239000003513 alkali Substances 0.000 abstract description 7
- 238000001556 precipitation Methods 0.000 abstract description 7
- 238000000605 extraction Methods 0.000 abstract description 5
- 150000002500 ions Chemical class 0.000 abstract description 5
- 239000000047 product Substances 0.000 abstract description 4
- 238000004064 recycling Methods 0.000 abstract description 3
- 230000007797 corrosion Effects 0.000 abstract description 2
- 238000005260 corrosion Methods 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 239000010865 sewage Substances 0.000 abstract description 2
- 239000006227 byproduct Substances 0.000 abstract 1
- 239000000460 chlorine Substances 0.000 description 13
- 238000001179 sorption measurement Methods 0.000 description 6
- 241000196324 Embryophyta Species 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 159000000007 calcium salts Chemical class 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 description 2
- 230000009615 deamination Effects 0.000 description 2
- 238000006481 deamination reaction Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000019197 fats Nutrition 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 230000004060 metabolic process Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- -1 phytic acid ammonium salt Chemical class 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- 230000002335 preservative effect Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 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 1
- 208000020154 Acnes Diseases 0.000 description 1
- 206010003210 Arteriosclerosis Diseases 0.000 description 1
- 208000020084 Bone disease Diseases 0.000 description 1
- 206010006956 Calcium deficiency Diseases 0.000 description 1
- 235000019750 Crude protein Nutrition 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- 208000003251 Pruritus Diseases 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 208000011775 arteriosclerosis disease Diseases 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 235000012000 cholesterol Nutrition 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 235000019784 crude fat Nutrition 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000009920 food preservation Methods 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 230000035764 nutrition Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 208000007442 rickets Diseases 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 208000017520 skin disease Diseases 0.000 description 1
- 235000014214 soft drink Nutrition 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/117—Esters of phosphoric acids with cycloaliphatic alcohols
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention provides a preparation method of phytic acid, which comprises pretreatment and Cl ‑ The resin is subjected to continuous ion exchange, stripping, concentration, ultrafiltration and cation resin exchange. The invention shortens the production process, omits the complicated steps of acid extraction and alkali precipitation in the traditional process, adopts the continuous ion exchange one-step extraction process, saves a large amount of acid and alkali use, reduces the pollution of acid and alkali sewage to the environment, saves the production cost and reduces the energy consumption; concentrating and recycling the ion exchange byproducts or concentrating and crystallizing or producing ammonium chloride solid; the phytate concentration reduces the damage to organic phosphorus in the phytic acid, the quality of the product produced by the process is high, the inorganic phosphorus content is far lower than the standard requirement, and other ions are far lower than the standard requirement; the phytate concentration reduces the corrosion to equipment, and the common evaporator equipment can be satisfied with low investment.
Description
Technical Field
The invention relates to a preparation method of phytic acid, and belongs to the technical field of phytic acid purification.
Background
Phytic acid is a natural organic compound containing phosphorus, is largely present in fruit and plant seeds, is the main storage form of phosphorus in cereals, beans and oilseeds, and accounts for 60% of the phosphorus content in the whole seeds, and plays an important role in normal growth of the seeds. The most remarkable feature of phytic acid is its extremely strong complexation with metal ions and oxidation resistance, which makes it widely used. For example: in the food industry, it is widely used as a preservative for foods, a preservative, and a stabilizer for synthetic and natural pigments because it has excellent oxidation resistance and is safe and nontoxic. By utilizing the chelating property of phytic acid, the metal ions in the wine and soft drink can be removed, and the refreshing taste can be improved. In the pharmaceutical industry, can be used for treating calcium deficiency, rickets, bone diseases and other symptoms, and can improve cell nutrition and be beneficial to metabolism of human bodies. The phytic acid can inhibit the generation of free radicals, promote the fat metabolism in the organism, reduce the blood fat and inhibit the generation of cholesterol, can be prepared into an anti-arteriosclerosis medicine, and has good curative effects on treating kidney, liver and the like. The skin care product can regulate the pH value of skin, keep the moisture of skin, remove horny layer on the skin, remove skin itch and peculiar smell, make the skin more glossy, and reduce the occurrence of skin diseases such as some acnes. At present, the domestic phytic acid market is smaller, but the prospect is better, the price is higher, the phytic acid is mainly applied to food preservation and industrial cleaning, the application amount of the phytic acid in the washing articles is improved in recent years, and the medical industry is monopoly abroad.
The production methods of phytic acid mainly comprise three methods: chemical synthesis, microbial fermentation, solvent extraction, precipitation, and membrane separation. At present, the precipitation and membrane separation method is a method for mainly producing phytic acid in China.
The existing acid extraction and alkali precipitation process route is as follows: corn water-strong base resin adsorption-hydrochloric acid liberation-resin chlorine conversion-phytic acid and hydrochloric acid mixed solution-neutralization precipitation (calcium hydroxide) -plate frame filtration-acidolysis-filtration-ion exchange impurity removal-concentration
The existing process route for purifying phytic acid by a membrane method comprises the following steps: corn water-strong base resin adsorption-hydrochloric acid release-resin chlorine conversion-phytic acid and hydrochloric acid mixed solution-membrane filtration and concentration.
Extracting phytic acid from solid material soaking liquid under acidic condition, precipitating phytic acid under alkaline condition by calcium salt method or other metal salt, refining and purifying the precipitate, dissolving with strong acid, filtering, extracting phytic acid by cation exchange resin in single column fixed bed, decolorizing, and concentrating. Although multiple acid-soluble and alkaline precipitations can effectively increase the concentration of phytic acid, there are several drawbacks in this process. Firstly, the process requires a large amount of acid-base solution, and cannot be recycled, so that serious environmental problems are caused; secondly, the single column fixed bed ion exchange process is discontinuous, and the filling amount of the fixed bed resin is large (generally 20 m), so that the resin utilization rate is low, the adsorption to the phytic acid is incomplete, and the content of organic phosphorus and chloride ions in the phytic acid is high.
The membrane method is that after resin adsorption and analysis, the nanofiltration membrane is directly used for separating phytic acid from other substances to obtain purer phytic acid, and the process has the advantages of simple process, poor membrane separation precision and large fluctuation of the membrane separation precision along with the service cycle of the membrane; impurities in corn water are easily adsorbed by resin, so that a membrane is easy to block, the membrane is frequently cleaned, the membrane loss is serious, and the separation precision is reduced rapidly; the divalent or more ions in the phytic acid have high content, and the quality of the product cannot be ensured; in the membrane operation process, impurities are required to be dialyzed, the concentration is greatly diluted, an expensive titanium alloy evaporator is required to be used for concentrating and preparing phytic acid, and the investment cost is high.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method of phytic acid, which realizes the following aims: avoiding the generation of wastewater, improving the purity and yield of phytic acid, and reducing the content of divalent ions and ions above.
In order to solve the technical problems, the invention adopts the following technical scheme:
a preparation method of the phytic acid comprises pretreatment and Cl - The resin is subjected to continuous ion exchange, stripping, concentration, ultrafiltration and cation resin exchange.
The following is a further improvement of the above technical scheme:
the pretreatment, namely, filtering the corn soaking liquid through a plate frame and ultrafiltering to obtain corn slurry; the corn steep liquor comprises 0.9-1.2wt% of phytic acid and 2.3-2.7wt% of protein.
The plate and frame is filtered, and the pressure of the plate and frame is 0.55-0.65Mpa;
the ultrafiltration pressure is 2.8-3.2Mpa, and the molecular weight cut-off of the ultrafiltration membrane is 1500 daltons.
The Cl - Resin continuous ion exchange, introducing the corn slurry into Cl - In the resin, the flow rate is 45-55L/h; the Cl - The resin is a weakly basic anionic resin, the particle size of the resin is more than 95 percent, and the particle diameter of the resin is 0.5mm.
The Cl after the phytic acid is adsorbed by the release - The resin is released by ammonia water in a releasing zone to obtain a soluble ammonium phytate releasing solution; the mass concentration of the ammonia water is 5.5-6.5g/dL, and the flow rate of the ammonia water flowing through the resin is 3-3.5L/h.
The resin after release is OH - The resin was regenerated with hydrochloric acid to give Cl - And (3) resin, wherein the hydrochloric acid is regenerated, the concentration of the hydrochloric acid is 6.3-6.7g/dL, and the flow rate is 3.8-4.2L/h.
And concentrating the ammonium phytate stripping solution to 68-72wt percent.
The ultrafiltration is carried out, the concentrated ammonium phytate solution is removed, the temperature is controlled to be less than 40 ℃, and the ammonium phytate solution is obtained through ultrafiltration; the ultrafiltration adopts an ultrafiltration membrane with the molecular weight cut-off of 1500 daltons.
The cation resin is exchanged, the ammonium phytate solution enters a continuous ion exchange system filled with the cation resin, the flow rate is 1.8-2.2L/H, and the ammonium phytate solution is mixed with H in a feeding area + The resin is subjected to ion exchange to obtain 48-52wt% phytic acid solution.
The resin is strong acid cation type resin, the model is D317, and the granularity is 5-7mm and is more than or equal to 95%.
After the feeding of the ammonium phytate solution is finished, hydrochloric acid is used for regeneration, and the concentration of the hydrochloric acid is as follows: 6.3-6.7g/dL, and the flow rate is 5.2-5.6L/h.
In the invention, a plate frame and an ultrafiltration membrane are adopted for pretreatment, a CL-type resin continuous ion exchange method is adopted, ammonia water is released, ammonium phytate of a release solution is obtained, the ammonium phytate is concentrated by MVR, the concentration is 70%, excessive protein substances are separated out at the moment, the ammonium phytate is filtered again by the ultrafiltration membrane, the ammonium phytate solution after filtration is subjected to continuous ion exchange deamination by a strong acid cation resin, the phytic acid is directly obtained, the high-purity phytic acid is obtained after vacuum concentration, and the ammonium chloride is obtained after the hydrochloric acid is released, is concentrated and recycled or is concentrated and crystallized to produce ammonium chloride solid. The process has the main advantages that the phytic acid ammonium salt is prepared by single set of continuous ion exchange, chlorine-type adsorption ammonia water is released, the solubility of the phytic acid ammonium salt is high, common MVR equipment directly concentrates to 70 percent concentration, all proteins are salted out, the proteins are removed by ultrafiltration, and NH is removed by continuous ion exchange 4 + No waste water is produced in the process, and all water can be used in production.
Compared with the prior art, the invention has the beneficial effects that:
1. the method shortens the production process, omits the complicated steps of acid extraction and alkali precipitation in the traditional process, adopts the continuous ion exchange one-step extraction process, saves a large amount of acid and alkali use, reduces the pollution of acid and alkali sewage to the environment, saves the production cost and reduces the energy consumption.
2. The phytate concentration reduces the damage to organic phosphorus in the phytic acid, the quality of the product produced by the process is high, the inorganic phosphorus content is far lower than the standard requirement, and other ions are far lower than the standard requirement; the phytate concentration reduces the corrosion to equipment, and the common evaporator equipment can be satisfied with low investment.
3. The method has the advantages that the yield of the phytic acid is 91%, the purity of the prepared phytic acid is 99.5%, inorganic phosphorus is less than 0.015%, chloride (calculated by Cl) is less than 0.02%, sulfate (calculated by SO 4) is less than 0.02%, and calcium salt (calculated by Ca) is less than 0.02%, and all the requirements of the national standard GB 1886.237-2016 of the phytic acid are met.
4. The continuous ion exchange of adsorption and deamination can realize the closed-loop operation from adsorption to desorption, and the production process has no three wastes and no influence on the environment. And (3) recycling the ammonium chloride solution in the ion exchange stripping solution or concentrating and crystallizing to produce ammonium chloride solid.
Detailed Description
The following description of the preferred embodiments of the present invention is provided for the purpose of illustration and explanation only and is not intended to limit the present invention.
Example 1
(1) Pretreatment of
The corn steep liquor contains 1wt% of organic components such as phytic acid, 2.5wt% of protein, starch residues and the like, corn slurry is obtained through plate and frame filtration and ultrafiltration, organic matters with complex components such as crude protein, crude fat and other insoluble inorganic matters are filtered out, and the filtered matters can be recycled to a fertilizer production workshop for reuse.
The plate frame is filtered, and the pressure of the plate frame is 0.6Mpa;
the ultrafiltration pressure is 3Mpa, and the molecular weight cut-off of the ultrafiltration membrane is 1500 daltons.
（2）Cl - Resin continuous ion exchange
The corn slurry obtained after pretreatment of the corn soaking liquid enters a continuous ion exchange system, and phytic acid in the corn slurry and Cl in a feeding area - The resin has ion exchange effect, the phytic acid is adsorbed by the resin, and Cl - And (3) putting the plant acid into a column, wherein the high-concentration phase after extracting the plant acid contains a large amount of soluble proteins and other substances, and the plant acid can be recycled to a raw material workshop.
The Cl-resin is weak alkaline anion resin, the particle diameter of the resin is 0.5mm, the particle size of the resin is more than 95%, the filling amount of the resin is 650ml in each ion exchange column, the total amount is 19.5L, and the flow rate of the corn slurry flowing through the resin is 50L/h.
(3) Release from
The resin after adsorbing the phytic acid is desorbed by ammonia water in a desorption area, and the phytic acid radical is led down to column and NH 4 + And combining to obtain the soluble ammonium phytate stripping solution.
The mass concentration of the ammonia water is 6.0g/dL, and the flow rate of the ammonia water flowing through the resin is 3.2L/h.
The invention adopts a continuous ion exchange system, and can realize continuous and uninterrupted operation from the adsorption to the release of the corn soaking water.
At this time the resin is OH - Resin, regenerated with hydrochloric acid to obtain CL - And (3) resin. Experiments show that CL - The resin only adsorbs a small amount of protein, so that the production efficiency is improved, and the cost is reduced.
The hydrochloric acid is regenerated, the concentration of the hydrochloric acid is 6.5g/dL, the flow rate is 4L/h, and the temperature does not need to be controlled.
(4) Concentrating
The ammonium phytate stripping solution is concentrated by MVR to 70wt percent.
(5) Ultrafiltration
And (3) concentrating the ammonium phytate stripping solution, controlling the temperature to be 35 ℃, and carrying out ultrafiltration to obtain an ammonium phytate solution.
The ultrafiltration membrane is selected from ultrafiltration membranes with molecular weight cut-off of 1500 daltons.
(6) Cation resin exchange
The ammonium phytate solution enters a continuous ion exchange system filled with cationic resin, the flow rate is 2L/H, and the ammonium phytate solution is mixed with H in a feeding area + Ion exchange of resin, NH 4 + Adsorbing by resin, and placing the plant acid radical on a column to obtain 50wt% of phytic acid dilute solution. In the process, NH is removed 4 + The rate reaches 99.99 percent.
The resin is strong acid cation type resin, the model is D317, and the granularity is 5-7mm and is more than or equal to 95%.
Regenerating the resin with hydrochloric acid, and converting the resin into H again + And (3) resin, and obtaining an ammonium chloride solution, and concentrating, recycling or concentrating and crystallizing to produce ammonium chloride solid. In the continuous ion exchange production process, only hydrochloric acid, ammonia water and a small amount of clear water are needed to be supplemented, and no three wastes are generated in the production process, so that the method has no influence on the environment.
The hydrochloric acid concentration is as follows: 6.5g/dL, the flow rate was 5.4L/h, and the temperature was not limited.
The method has the advantages that the yield of the phytic acid is 91%, the purity of the phytic acid is 99.5%, the inorganic phosphorus is less than 0.015%, the chloride (calculated by Cl) is less than 0.02%, the sulfate (calculated by SO 4) is less than 0.02%, and the calcium salt (calculated by Ca) is less than 0.02%, which all meet the requirements of the national standard GB 1886.237-2016 of the phytic acid.
The percentages stated in the present invention are mass percentages unless otherwise indicated.
Claims (7)
1. A preparation method of the phytic acid is characterized in that: the preparation method comprises pretreatment and Cl - Resin continuous ion exchange, release, concentration, ultrafiltration and cation resin exchange;
the pretreatment is that corn steep liquor is filtered by a plate frame and ultrafiltered to obtain corn slurry;
the Cl - The resin is a weak alkaline anion resin; the Cl - Resin continuous ion exchange to introduce the corn slurry into Cl - Performing continuous ion exchange in the resin;
the release is Cl after the phytic acid is adsorbed - The resin is released by ammonia water in a releasing zone to obtain a soluble ammonium phytate releasing solution;
concentrating the ammonium phytate stripping solution to 68-72wt%;
the ultrafiltration is to remove the concentrated ammonium phytate solution, the temperature is controlled to be less than 40 ℃, and the ammonium phytate solution is obtained through ultrafiltration; the ultrafiltration adopts an ultrafiltration membrane with the molecular weight cut-off of 1500 daltons;
in the cation resin exchange, the ammonium phytate solution enters a continuous ion exchange system filled with the cation resin, the flow rate is 1.8-2.2L/H, and the ammonium phytate solution is mixed with H in a feeding area + The resin is subjected to ion exchange to obtain 48-52wt% of phytic acid diluted solution.
2. The method for preparing the phytic acid according to claim 1, wherein: the corn steep liquor contains 0.9-1.2wt% of phytic acid and 2.3-2.7wt% of protein.
3. The method for preparing the phytic acid according to claim 1, wherein: the Cl - In the resin continuous ion exchange, corn is treatedIntroducing the slurry into Cl - In the resin, the flow rate is 45-55L/h; the particle size of the resin was 0.5mm with a particle fraction > 95%.
4. The method for preparing the phytic acid according to claim 1, wherein: the mass concentration of the ammonia water is 5.5-6.5g/dL, and the flow rate of the ammonia water flowing through the resin is 3-3.5L/h.
5. The method for preparing the phytic acid according to claim 1, wherein: the resin after release is OH - The resin was regenerated with hydrochloric acid to give Cl - And (3) resin, wherein the hydrochloric acid is regenerated, the concentration of the hydrochloric acid is 6.3-6.7g/dL, and the flow rate is 3.8-4.2L/h.
6. The method for preparing the phytic acid according to claim 1, wherein:
the cationic resin is strong acid cationic resin, the model is D317, and the particle size is 5-7mm and is more than or equal to 95%.
7. The method for preparing the phytic acid according to claim 1, wherein: after the cation resin exchange is finished, the resin is regenerated by hydrochloric acid, and the concentration of the hydrochloric acid is as follows: 6.3-6.7g/dL, the flow rate is 5.2-5.6L/h, and the obtained ammonium chloride solution is recycled or concentrated and crystallized to produce ammonium chloride solid.
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