CN114456056A - Method for removing impurity molecules influencing ferulic acid smell by using resin process - Google Patents
Method for removing impurity molecules influencing ferulic acid smell by using resin process Download PDFInfo
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- CN114456056A CN114456056A CN202210014655.9A CN202210014655A CN114456056A CN 114456056 A CN114456056 A CN 114456056A CN 202210014655 A CN202210014655 A CN 202210014655A CN 114456056 A CN114456056 A CN 114456056A
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- KSEBMYQBYZTDHS-HWKANZROSA-N ferulic acid Chemical compound COC1=CC(\C=C\C(O)=O)=CC=C1O KSEBMYQBYZTDHS-HWKANZROSA-N 0.000 title claims abstract description 239
- KSEBMYQBYZTDHS-UHFFFAOYSA-N ferulic acid Natural products COC1=CC(C=CC(O)=O)=CC=C1O KSEBMYQBYZTDHS-UHFFFAOYSA-N 0.000 title claims abstract description 208
- KSEBMYQBYZTDHS-HWKANZROSA-M (E)-Ferulic acid Natural products COC1=CC(\C=C\C([O-])=O)=CC=C1O KSEBMYQBYZTDHS-HWKANZROSA-M 0.000 title claims abstract description 207
- 229940114124 ferulic acid Drugs 0.000 title claims abstract description 207
- 235000001785 ferulic acid Nutrition 0.000 title claims abstract description 207
- QURCVMIEKCOAJU-UHFFFAOYSA-N trans-isoferulic acid Natural products COC1=CC=C(C=CC(O)=O)C=C1O QURCVMIEKCOAJU-UHFFFAOYSA-N 0.000 title claims abstract description 207
- 239000011347 resin Substances 0.000 title claims abstract description 111
- 229920005989 resin Polymers 0.000 title claims abstract description 111
- 239000012535 impurity Substances 0.000 title claims abstract description 95
- 238000000034 method Methods 0.000 title claims abstract description 86
- 230000008569 process Effects 0.000 title claims abstract description 39
- 238000001914 filtration Methods 0.000 claims abstract description 62
- YOMSJEATGXXYPX-UHFFFAOYSA-N 2-methoxy-4-vinylphenol Chemical compound COC1=CC(C=C)=CC=C1O YOMSJEATGXXYPX-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000001035 drying Methods 0.000 claims abstract description 38
- 239000000463 material Substances 0.000 claims abstract description 33
- 238000002425 crystallisation Methods 0.000 claims abstract description 25
- 238000001514 detection method Methods 0.000 claims abstract description 25
- 230000008025 crystallization Effects 0.000 claims abstract description 22
- 238000010828 elution Methods 0.000 claims abstract description 21
- 238000011069 regeneration method Methods 0.000 claims abstract description 20
- 238000004806 packaging method and process Methods 0.000 claims abstract description 18
- 230000008929 regeneration Effects 0.000 claims abstract description 18
- 238000005342 ion exchange Methods 0.000 claims abstract description 14
- 238000007873 sieving Methods 0.000 claims abstract description 12
- 238000003916 acid precipitation Methods 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 239000000047 product Substances 0.000 claims description 76
- 238000001179 sorption measurement Methods 0.000 claims description 58
- 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 claims description 47
- 239000003456 ion exchange resin Substances 0.000 claims description 46
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 43
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 229940114123 ferulate Drugs 0.000 claims description 31
- 239000007788 liquid Substances 0.000 claims description 31
- 238000004128 high performance liquid chromatography Methods 0.000 claims description 24
- 239000003513 alkali Substances 0.000 claims description 19
- 239000007787 solid Substances 0.000 claims description 19
- 238000011282 treatment Methods 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 13
- 239000008213 purified water Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000003480 eluent Substances 0.000 claims description 9
- 238000012216 screening Methods 0.000 claims description 9
- 229920006395 saturated elastomer Polymers 0.000 claims description 8
- 239000004744 fabric Substances 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 238000004090 dissolution Methods 0.000 claims description 5
- 238000007689 inspection Methods 0.000 claims description 5
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 239000012467 final product Substances 0.000 claims description 3
- 238000005070 sampling Methods 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 2
- 239000000356 contaminant Substances 0.000 claims 1
- 238000010998 test method Methods 0.000 claims 1
- 239000003205 fragrance Substances 0.000 abstract description 9
- 238000012545 processing Methods 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 5
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 4
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- 239000003153 chemical reaction reagent Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 81
- 230000000694 effects Effects 0.000 description 11
- NCTHNHPAQAVBEB-WGCWOXMQSA-M sodium ferulate Chemical compound [Na+].COC1=CC(\C=C\C([O-])=O)=CC=C1O NCTHNHPAQAVBEB-WGCWOXMQSA-M 0.000 description 10
- 235000013305 food Nutrition 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000000796 flavoring agent Substances 0.000 description 4
- 235000019634 flavors Nutrition 0.000 description 4
- MIYFPRPQXKJXCC-WGCWOXMQSA-M potassium;(e)-3-(4-hydroxy-3-methoxyphenyl)prop-2-enoate Chemical compound [K+].COC1=CC(\C=C\C([O-])=O)=CC=C1O MIYFPRPQXKJXCC-WGCWOXMQSA-M 0.000 description 4
- 230000007480 spreading Effects 0.000 description 4
- 238000003892 spreading Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
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- 230000004048 modification Effects 0.000 description 3
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- 239000000126 substance Substances 0.000 description 3
- 206010028980 Neoplasm Diseases 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
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- 238000000151 deposition Methods 0.000 description 2
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- 230000018109 developmental process Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
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- -1 ion exchanging Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000000144 pharmacologic effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- 206010001029 Acute pulmonary oedema Diseases 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 206010067125 Liver injury Diseases 0.000 description 1
- 235000019774 Rice Bran oil Nutrition 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
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- 201000011510 cancer Diseases 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 208000029078 coronary artery disease Diseases 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
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- 231100000753 hepatic injury Toxicity 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 235000013622 meat product Nutrition 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
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- 230000003647 oxidation Effects 0.000 description 1
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- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 239000001397 quillaja saponaria molina bark Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000008165 rice bran oil Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229930182490 saponin Natural products 0.000 description 1
- 150000007949 saponins Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 208000010110 spontaneous platelet aggregation Diseases 0.000 description 1
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- 210000003556 vascular endothelial cell Anatomy 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 235000015099 wheat brans Nutrition 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/487—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to chemical modification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/47—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
Abstract
The invention belongs to the technical field of separation and purification of ferulic acid, and particularly relates to a method for removing impurity molecules affecting the smell of ferulic acid by using a resin process. The ferulic acid with the content of 4-vinyl-2-methoxyphenol of less than 50ppm and without special fragrance is obtained by nine steps of dissolving and filtering, adsorbing and removing impurities, ion exchange, acid precipitation and crystallization, centrifugal filtering, product drying, crushing and sieving detection, mixed material packaging, finished product detection and elution regeneration. The invention has no addition of any organic reagent in the whole production and processing process, and the product has small organic residue; except for finished products, the materials of the elution part can be recycled, so that the raw material utilization rate is high, and the loss is extremely low; the whole process is simple and convenient, the used equipment is simple, the processing medium is resin which can be repeatedly used, the investment of fixed assets is small, and the mass and large-scale production is easy to realize.
Description
Technical Field
The invention belongs to the technical field of separation and purification of ferulic acid, and particularly relates to a method for removing impurity molecules influencing the smell of ferulic acid by using a resin process.
Background
Ferulic acid, chemical name 3-methoxy-4-hydroxycinnamic acid, is mainly obtained from plants, such as corn bran, wheat bran, rice bran oil saponin, etc. At present, the main preparation method of ferulic acid adopts an alkaline hydrolysis method, and the method has the advantages of low cost, high yield, mature and stable process and suitability for large-scale production.
Ferulic acid is used as a natural antioxidant, not only has the functions of resisting oxidation and removing free radicals, but also has the pharmacological effects of preventing and treating coronary heart disease, resisting cancer and the like, and the characteristic ensures that the ferulic acid has great value and market development prospect in the fields of foods, cosmetics and the like. For example, the addition of ferulic acid, which is a natural preservative, to meat products is a relatively novel technique. At present, ferulic acid is gradually applied to products in parts of mainstream meat food enterprises in europe, north america and the like, and is vigorously popularized as a 'green label'. Some derivatives of ferulic acid have good lipid solubility and stability, are one of research hotspots, not only have pharmacological actions such as platelet aggregation resistance, tumor resistance and anti-inflammatory action, but also have actions such as liver injury protection, vascular endothelial cell protection and acute pulmonary edema protection, and have great development potential.
The adsorption resin is a resin adsorbent which has the characteristic of adsorption and has a porous three-dimensional structure. It is a new porous resin in the polymer field in recent years, and can be widely used in the fields of water treatment, separation, purification and the like; the ion exchange resin is a high molecular spherical particulate compound having a network structure, having active groups for exchanging ions, and having insolubility. In industrial production application, the ion exchange resin has the advantages of large processing capacity, wide decolorization range, high capacity, capability of removing various ions, repeated regeneration and use and long service life. The adsorption resin and the ion exchange resin are matched for operation, so that extremely high separation and purification effects can be achieved.
Along with the increasing concern of people on health and health care problems, the demand of ferulic acid is also increasing, and meanwhile, the demand of people on the ferulic acid with standardized production and high quality is also higher. However, almost most ferulic acid finished products in the market have a special fragrance due to the influence of factors such as production and preparation processes of ferulic acid, raw material sources and the like, the odor cannot influence the use of ferulic acid under most conditions, and the odor inspection is an important quality index for high-quality ferulic acid products. Meanwhile, for some special foods which utilize ferulic acid as a food additive, the special fragrance can change the original flavor of the foods and influence the use effect of the ferulic acid; in the aspect of medicine application, the aroma molecules can also be an impurity, and the using effect of the medicine is influenced. Through a large number of analysis and identification, the special odor is mainly a substance called 4-vinyl guaiacol and has a chemical name of 4-vinyl-2-methoxyphenol; based on the purposes of improving the quality of ferulic acid products and increasing the use ways of ferulic acid, a method for removing impurities with special fragrance brought by 4-vinyl-2-methoxyphenol in ferulic acid is urgently needed.
Disclosure of Invention
The invention provides a method for removing impurity molecules influencing the odor of ferulic acid by using a resin process, and aims to provide a method for removing impurities with special fragrance brought by 4-vinyl-2-methoxyphenol in the ferulic acid, so as to solve the problem that the ferulic acid has special odor caused by the 4-vinyl-2-methoxyphenol.
In order to achieve the purpose, the invention adopts the technical scheme that:
a method for removing impurity molecules affecting ferulic acid odor by resin process comprises the following steps,
the method comprises the following steps: dissolution filtration
Firstly, ferulic acid with odor impurities exceeding the standard reacts with alkali liquor to generate corresponding ferulate solution and is filtered;
step two: removing impurities by adsorption
Adsorbing the ferulate solution filtered in the step one by using adsorption resin, and collecting the liquid adsorbed by the resin;
step three: ion exchange
Enabling the liquid collected in the second step to pass through ion exchange resin, and collecting the liquid after passing through the ion exchange resin;
step four: acid precipitation crystallization
Adding an acid solution into the liquid obtained in the third step, and standing until solid ferulic acid is separated out by crystallization;
step five: centrifugal filtration
Filtering or centrifuging the solid ferulic acid separated out in the step four to obtain ferulic acid with the water content of less than 35%;
step six: drying the product
Dividing the ferulic acid product obtained in the step five into small blocks, and uniformly paving the small blocks in a drying appliance for drying to obtain ferulic acid with the water content of less than 0.4%;
step seven: crushing and sieving detection
Crushing the ferulic acid dried in the sixth step, screening and detecting to obtain a ferulic acid product with the particle size of 80 meshes;
step eight: mixing material packaging and finished product detection
Mixing the sieved materials, and then packaging according to a preset specification to obtain a finished product ferulic acid; performing content and impurity content sampling inspection on the finished product ferulic acid;
step nine: elution regeneration
And (3) respectively carrying out elution regeneration treatment on the saturated adsorption resin and the saturated ion exchange resin to obtain ferulic acid containing more impurities, and returning the part of material to the first step for treatment until the part of material completely reaches the preset standard.
The dissolving and filtering method in the first step comprises the following steps: preparing purified water according to the mass-volume ratio of ferulic acid to purified water in alkali liquor of 1: 10-1: 20, adding alkali into the purified water to fully dissolve the ferulic acid, and slowly adding the ferulic acid to be treated according to the ratio until the ferulic acid is completely dissolved, so that the pH value is 6.5-7; the alkali is NaOH or KOH.
The method for removing impurities by adsorption in the second step comprises the following steps: the flow rate of the ferulate solution passing through the adsorption resin is 1.0-2.0 times of the column volume, and the volume ratio of the ferulate solution to the adsorption resin is 80:1-100: 1; the type of the adsorption resin is HPD-5000 or DM1300 or XDA-200.
The ion exchange method in the third step comprises the following steps: the flow rate of the ferulate solution passing through the adsorption resin is 1.0-2.0 times of column volume, and the volume ratio of the ferulate solution to the ion exchange resin is 10:1-20: 1; the type of the ion exchange resin is LKA-53 or D201 or D296.
The acid precipitation crystallization method in the fourth step comprises the following steps: adding 10-15% HCL solution or H into the ferulate solution after ion exchange resin2SO4The solution is kept until the pH value of the solution is kept between 2.5 and 4.5, the crystallization temperature is kept between 15 and 25 ℃, and the duration is 4 to 8 hours.
The method for centrifugal filtration in the fifth step comprises the following steps: filtering or centrifuging the ferulic acid obtained by crystallization by using a filtering device or a centrifuge, wherein the precision of filtering paper or filtering cloth is 200-400 meshes, the filtering pressure is-0.08-0.1 Mpa, or the working rotating speed of the centrifuge is 4500-6000rpm, and the centrifuging time is 20-40min, so that the water content of the ferulic acid product is less than 35%.
The method for drying in the sixth step comprises the following steps: and (3) putting the filtered or centrifuged raw material into a vacuum drying oven for drying treatment at the drying temperature of 60-80 ℃ for 8-12h, wherein the moisture content is less than 0.4% after drying.
The method for crushing, sieving and detecting in the seventh step comprises the following steps: after being crushed by a crusher, ferulic acid passing through a sieve of 80 meshes is detected, mixed and packaged to obtain a final product, and the detection targets are that the HPLC content of the ferulic acid is more than 98 percent and the HPLC content of 4-vinyl-2-methoxyphenol impurity is less than 50 ppm.
The elution regeneration method in the ninth step comprises the following steps: passing the eluent through adsorption resin or ion exchange resin at flow rate of 1.5-3.0 times of column volume and elution regeneration volume of 3-5 times of column volume.
The eluent used for the adsorption resin is alcohol or alkali solution, and the eluent used for the ion exchange resin is absolute ethyl alcohol or HCL solution or H2SO4A solution; wherein the concentration of the alkali or acid is 3-5 vol%％。
Has the advantages that:
1. the invention further processes the finished product or crude product of ferulic acid containing 4-vinyl-2-methoxyphenol exceeding standard by nine steps of dissolving and filtering, adsorbing and removing impurities, ion exchanging, acid depositing and crystallizing, centrifugal filtering, product drying, crushing and sieving detection, mixed material packaging, finished product detection and elution regeneration, and obtains the finished product of ferulic acid with 4-vinyl-2-methoxyphenol content less than 50ppm and without special fragrance.
2. The ferulic acid treated by the technical scheme of the invention has low impurity content and no fragrance source, can be widely used in industries such as food, and compared with untreated ferulic acid, the ferulic acid can better retain the flavor of food, has wider application range and higher market acceptance degree, and meanwhile, the finished product has lower impurity content, can also be widely used in pharmaceutical industry, and has higher market value and application prospect.
3. The invention has no addition of any organic reagent in the whole production and processing process of the ferulic acid, and the product has small organic residue.
4. The invention can recycle the materials of the elution part except the finished product, and has high utilization rate of raw materials and extremely low loss.
5. The invention has simple and convenient integral process and simple used equipment, the processing medium is resin which can be repeatedly used, the investment of fixed assets is small, and the mass and large-scale production is easy to realize.
The foregoing is merely an overview of the technical solutions of the present invention, and in order to make the technical solutions of the present invention more clearly understood and to be implemented in accordance with the content of the description, the following is a detailed description of preferred embodiments of the present invention.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIG. 1 is a flow chart of the present invention.
The foregoing is only an overview of the technical solutions of the present invention, and in order to make the technical solutions of the present invention more clear and clear, and to implement them in accordance with the content of the description, the following is a detailed description of preferred embodiments of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The first embodiment is as follows:
referring to fig. 1, a method for removing foreign molecules affecting the odor of ferulic acid by using a resin process includes the steps of,
the method comprises the following steps: dissolution filtration
Firstly, ferulic acid with odor impurities exceeding the standard reacts with alkali liquor to generate corresponding ferulate solution and is filtered;
step two: removing impurities by adsorption
Adsorbing the ferulate solution filtered in the step one by using adsorption resin, and collecting the liquid adsorbed by the resin;
step three: ion exchange
Enabling the liquid collected in the second step to pass through ion exchange resin, and collecting the liquid after passing through the ion exchange resin;
step four: acid precipitation crystallization
Adding an acid solution into the liquid obtained in the third step, and standing until solid ferulic acid is separated out by crystallization;
step five: centrifugal filtration
Filtering or centrifuging the solid ferulic acid separated out in the step four to obtain ferulic acid with the water content of less than 35%;
step six: drying the product
Dividing the ferulic acid product obtained in the step five into small blocks, and uniformly paving the small blocks in a drying appliance for drying to obtain ferulic acid with the water content of less than 0.4%;
step seven: crushing and sieving detection
Crushing the ferulic acid dried in the sixth step, screening and detecting to obtain a ferulic acid product with the particle size of 80 meshes;
step eight: mixing material packaging and finished product detection
Mixing the sieved materials, and then packaging according to a preset specification to obtain a finished product ferulic acid; performing content and impurity content sampling inspection on the finished product ferulic acid;
step nine: elution regeneration
And (3) respectively carrying out elution regeneration treatment on the saturated adsorption resin and the saturated ion exchange resin to obtain ferulic acid containing more impurities, and returning the part of material to the first step for treatment until the part of material completely reaches the preset standard.
The invention further processes the finished product or crude product of ferulic acid containing 4-vinyl-2-methoxyphenol exceeding standard by nine steps of dissolving and filtering, adsorbing and removing impurities, ion exchanging, acid depositing and crystallizing, centrifugal filtering, product drying, crushing and sieving detection, mixed material packaging, finished product detection and elution regeneration, and obtains the finished product of ferulic acid with 4-vinyl-2-methoxyphenol content less than 50ppm and without special fragrance.
The ferulic acid treated by the technical scheme of the invention has low impurity content and no fragrance source, can be widely used in industries such as food, and compared with untreated ferulic acid, the ferulic acid can better retain the flavor of food, has wider application range and higher market acceptance degree, and meanwhile, the finished product has lower impurity content, can also be widely used in pharmaceutical industry, and has higher market value and application prospect.
The invention has no addition of any organic reagent in the whole production and processing process of the ferulic acid, and the product has small organic residue.
The invention can recycle the materials of the elution part except the finished product, and has high utilization rate of raw materials and extremely low loss. The invention has simple and convenient integral process and simple used equipment, the processing medium is resin which can be repeatedly used, the investment of fixed assets is small, and the mass and large-scale production is easy to realize.
The preset standard in the step nine means that the HPLC detection content of 4-vinyl-2-methoxyphenol in the finished ferulic acid is less than 50ppm, and the special flavor brought by the 4-vinyl-2-methoxyphenol in the ferulic acid completely disappears from the sense of sense.
The mechanism of the invention for removing impurity molecules affecting the odor of ferulic acid is as follows:
ferulic acid is difficult to dissolve in water at normal temperature, 4-vinyl-2-methoxyphenol is also difficult to dissolve in water at normal temperature, the pH value is weak acid and is close to neutral, the acidity of the ferulic acid is stronger than that of 4-vinyl-2-methoxyphenol, therefore, when the pH value is about 6.5, the ferulic acid is firstly reacted with an alkali solution to generate corresponding ferulate, the 4-vinyl-2-methoxyphenol is hardly reacted with the alkali, 4-vinyl-2-methoxyphenol ferulate solution passes through adsorption resin which is a molecular material combining the adsorption and molecular sieve principles, and the 4-vinyl-2-methoxyphenol in the solution is easily adsorbed as an organic matter due to Van der Waals attraction and the porous structure of the resin, and the ferulate solution is not easily adsorbed, so that the 4-vinyl-2-methoxyphenol can be adsorbed by the adsorption resin; the metal cation contained in the aqueous solution in the ion exchange resin action environment and the acid group H of the cation exchange resin+Ion exchange is carried out so that cations in the solution are transferred to the resin and H on the resin+Na exchanged into sodium ferulate solution+H from acidic groups of the resin+Exchange to form ferulic acid, Na+Then the ferulic acid is adsorbed on the resin, and meanwhile, an acid solution is added into the collected effluent to maintain the pH of the solution at 2.5-4.5, so that the ferulic acid is dissolved in a smaller amount in an acid environment and is more easily separated out to form a solid.
Example two:
referring to fig. 1, a method for removing impurity molecules affecting ferulic acid odor by using a resin process is disclosed, wherein on the basis of the first embodiment, the dissolution filtration method of the first step is as follows: preparing purified water according to the mass-volume ratio of the ferulic acid to the purified water in the alkali liquor of 1: 10-1: 20, adding alkali into the purified water to fully dissolve the ferulic acid, and slowly adding the ferulic acid to be treated according to the ratio until the ferulic acid is completely dissolved, so that the pH value is 6.5-7.
Further, the alkali is NaOH or KOH.
In practical use, ferulic acid with overproof odor impurities is reacted with a NaOH or KOH aqueous solution according to a proportion. During treatment, NaOH or KOH solid particles are added according to a ratio to be fully dissolved, ferulic acid to be treated is slowly added to generate a sodium ferulate solution and is filtered, the pH value is 6.5-7, and then filtering is carried out with the filtering precision of more than 200 meshes.
Through the process, the ferulic acid solid which is difficult to dissolve in water can react with the alkali solution to generate sodium salt or potassium salt solution which is easy to dissolve in water, so that the subsequent treatment is convenient.
Example three:
referring to fig. 1, a method for removing impurity molecules affecting ferulic acid odor by using a resin process is described in the second step, based on the first embodiment, as follows: the flow rate of the ferulate solution passing through the adsorption resin is 1.0-2.0 times of the column volume, and the volume ratio of the ferulate solution to the adsorption resin is 80:1-100: 1; the type of the adsorption resin is HPD-5000 or DM1300 or XDA-200.
In actual use, the flow rate is set to be 1.0 to 2.0 times of the column volume, so that the contact between the ferulate solution and the resin is more sufficient and the adsorption is more complete; the volume ratio of the ferulate solution to the adsorption resin is 80:1-100:1 to avoid the loss of adsorption effect caused by the saturation of the resin adsorption capacity.
The adopted adsorption resin with the model of HPD-5000, DM1300 or XDA-200 can not only meet the adsorption requirement, but also has lower cost.
Example four:
referring to fig. 1, a method for removing impurity molecules affecting ferulic acid odor by using a resin process is disclosed, and on the basis of the first embodiment, the ion exchange method in the third step is as follows: the flow rate of the ferulate solution passing through the adsorption resin is 1.0-2.0 times of column volume, and the volume ratio of the ferulate solution to the ion exchange resin is 10:1-20: 1.
Further, the ion exchange resin is LKA-53 or D201 or D296.
In practical use, the flow rate of the ferulate solution passing through the ion exchange resin is 1.0-2.0 times of column volume, so that the ferulate solution is more fully contacted with the resin and the reaction is more complete, and the volume ratio of the ferulate solution to the ion exchange resin is 10:1-20:1, so as to avoid the problem that the exchange capacity of the resin is saturated and the exchange effect is lost.
The ion exchange resin with the type LKA-53 or D201 or D296 is adopted, not only can the separation and removal effect be achieved, but also the ion exchange resin is a common type in the market, and is relatively higher in practicability and low in cost.
Example five:
referring to fig. 1, a method for removing impurity molecules affecting ferulic acid odor by using a resin process, on the basis of the first embodiment, the acid precipitation crystallization method of the fourth step is as follows: adding 10-15% HCL solution or H into the ferulate solution after ion exchange resin2SO4The solution is kept until the pH value of the solution is kept between 2.5 and 4.5, the crystallization temperature is kept between 15 and 25 ℃, and the duration is 4 to 8 hours.
In practical use, the acid solution is added into the solution which passes through the ion exchange resin until the pH range of the solution is maintained between 2.5 and 4.5, the crystallization temperature is kept between 15 and 25 ℃, and the duration is 4 to 8 hours, so that the solubility of the ferulic acid in water is minimized and the ferulic acid is more sufficiently separated out.
Example six:
referring to fig. 1, a method for removing impurity molecules affecting ferulic acid odor by using a resin process is as follows, on the basis of the first embodiment: filtering or centrifuging the ferulic acid obtained by crystallization by using a filtering device or a centrifuge, wherein the precision of filtering paper or filtering cloth is 400 meshes, the filtering pressure is-0.08-0.1 Mpa, or the working rotating speed of the centrifuge is 4500-6000rpm, and the centrifuging time is 20-40min, so that the water content of the ferulic acid product is less than 35%.
In actual use, the water content in the ferulic acid product is reduced as much as possible by centrifugation or filtration, so as to shorten the time of subsequent drying treatment.
Example seven:
referring to fig. 1, a method for removing impurity molecules affecting ferulic acid odor by using a resin process is disclosed, wherein on the basis of the first embodiment, the six-step drying method comprises the following steps: and (3) putting the filtered or centrifuged raw material into a vacuum drying oven for drying treatment, wherein the drying temperature is 60-80 ℃, the drying time is 8-12h, and the moisture content after drying is less than 0.4%.
When the ferulic acid is actually used, the ferulic acid product is dried, so that the subsequent packaging and storage are facilitated.
Example eight:
referring to fig. 1, a method for removing impurity molecules affecting ferulic acid odor by using a resin process is based on the first embodiment, and the method for detecting crushing and sieving in the seventh step is as follows: after being crushed by a crusher, ferulic acid passing through a sieve of 80 meshes is detected, mixed and packaged to obtain a final product, and the detection targets are that the HPLC content of the ferulic acid is more than 98 percent and the HPLC content of 4-vinyl-2-methoxyphenol impurity is less than 50 ppm.
In actual use, the finished ferulic acid product meeting the product requirements is obtained by screening with a 80-mesh screen. The quality of the finished ferulic acid is ensured by inspection.
Example nine:
referring to fig. 1, a method for removing impurity molecules affecting ferulic acid odor by using a resin process is as follows, on the basis of the first embodiment: passing the eluent through adsorption resin or ion exchange resin at flow rate of 1.5-3.0 times of column volume and elution regeneration volume of 3-5 times of column volume.
Further, the eluent used for adsorbing the resin is alcohol or alkali solution used for ion-pairThe eluent of the exchange resin is absolute ethyl alcohol or HCL solution or H2SO4The solution has a concentration of 3% to 5% by volume of a base or acid.
When the adsorption resin is actually used, the ferulic acid which is remained on the adsorption resin and the ion exchange resin and contains more impurities is eluted and then enters the circulation treatment by adopting the technical scheme, so that the waste of materials is avoided to the maximum extent.
Example ten:
a method for removing impurity molecules affecting ferulic acid smell by resin process comprises the following steps,
1. dissolving and filtering: reacting ferulic acid (the content of ferulic acid is 83.2 percent, the content of impurity molecules is 4-vinyl-2-methoxyphenol is 513.7ppm) with odor and impurities exceeding the standard with a NaOH aqueous solution, wherein the mass-to-volume ratio of the ferulic acid to purified water in the NaOH solution is 1:10, firstly adding NaOH solid particles to fully dissolve the ferulic acid, then slowly adding ferulic acid to be treated to generate a sodium ferulate solution, filtering, wherein the dissolving temperature is 25 ℃, the stirring speed is 100rpm, the pH value is 6.5, and the filtering precision is 200 meshes.
2. Adsorbing and removing impurities: passing the filtered sodium ferulate solution through adsorption resin HPD-5000 and collecting the liquid passing through the resin column at a flow rate of 1.5 times the volume of the resin column, wherein the volume ratio of the sodium ferulate solution to the adsorption resin HPD-5000 is 80: 1.
3. Ion exchange: and (3) passing the collected liquid passing through the adsorption resin HPD-5000 through ion exchange resin LKA-53, collecting the liquid, wherein the flow rate is 1.5 times of the volume of the resin column, and the volume ratio of the liquid to the ion exchange resin LKA-53 is 10: 1.
4. Acid precipitation and crystallization: and (3) adding a 10% HCL solution into the liquid which is obtained in the step (3) and passes through the ion exchange resin LKA-53 until the pH value is 2.5, reducing the temperature to 15 ℃, standing for 4 hours, and crystallizing to separate out ferulic acid meeting the requirements.
5. Centrifugal filtration: filtering or centrifuging ferulic acid obtained by crystallization with a filter device or centrifuge, with the precision of filter paper or filter cloth of 200 mesh, the filtering pressure of-0.1 Mpa, or the working speed of the centrifuge of 4500rpm, and centrifuging for 30min to obtain solid ferulic acid
6. Drying a product: dividing the finished ferulic acid into small pieces, uniformly spreading in a drying apparatus, and drying in a vacuum drying oven at 75 deg.C under-0.1 Mpa for 8 hr to obtain ferulic acid product with water content of less than 0.4%;
7. and (3) crushing, sieving and detecting: crushing the dried ferulic acid, screening and detecting to obtain a qualified product with the particle size of 80 meshes;
8. material mixing and packaging and finished product detection: mixing the sieved batch materials, then packaging according to the specification of 25 kg/barrel to obtain a finished product ferulic acid, and detecting the content and impurity content of the finished product, wherein the content of ferulic acid is 99.32% by HPLC (high performance liquid chromatography), and the content of impurity molecules 4-vinyl-2-methoxyphenol is reduced to 20.4 ppm.
9. Elution and regeneration: respectively eluting saturated adsorption resin HPD-5000 and ion exchange resin LKA-53 with anhydrous ethanol and 4% HCl solution to obtain ferulic acid containing more impurities, and treating the part of material again until completely meeting the standard.
In the embodiment, by adopting the technical scheme of the invention, the impurity exceeding product with the ferulic acid HPLC content of 83.2% and the impurity molecule 4-vinyl-2-methoxyphenol content of 513.7ppm is prepared into the high-quality product with the ferulic acid HPLC detection content of 99.32% and the impurity molecule 4-vinyl-2-methoxyphenol content of 20.4 ppm.
Example eleven:
a method for removing impurity molecules affecting ferulic acid smell by resin process comprises the following steps,
1. dissolving and filtering: reacting ferulic acid (the ferulic acid content is 83.2%, the impurity molecule 4-vinyl-2-methoxyphenol content is 513.7ppm) with odor and impurities exceeding the standard with a KOH aqueous solution, wherein the mass-to-volume ratio of the ferulic acid to purified water in the KOH solution is 1:15, firstly adding KOH solid particles to fully dissolve the solid particles, then slowly adding ferulic acid to be treated to generate a potassium ferulate solution, filtering, wherein the dissolving temperature is 25 ℃, the stirring speed is 50rpm, the pH value is 6.5, and the filtering precision is 200 meshes.
2. Adsorbing and removing impurities: passing the filtered potassium ferulate solution through adsorption resin HPD-5000 and collecting the liquid passing through the resin column at a flow rate of 1.5 times the volume of the resin column, wherein the volume ratio of the ferulate solution to the resin HPD-5000 is 80: 1.
3. Ion exchange: passing the collected liquid through adsorption resin HPD-5000 through ion exchange resin LKA-53, and collecting the liquid; the flow rate was 1.5 times the volume of the resin column, and the ratio of liquid to resin LKA-53 was 10:1 by volume.
4. Acid precipitation and crystallization: and (3) adding a 10% HCL solution into the liquid which is obtained in the step 3 and passes through the ion exchange resin LKA-53 until the pH value is 2.5, reducing the temperature to 15 ℃, standing for 4 hours, and crystallizing out ferulic acid meeting the requirements.
5. Centrifugal filtration: filtering or centrifuging ferulic acid obtained by crystallization with a filter device or centrifuge, with the precision of filter paper or filter cloth of 200 mesh, the filtering pressure of-0.1 Mpa, or the working speed of the centrifuge of 4500rpm, and centrifuging for 30min to obtain solid ferulic acid
6. Drying a product: dividing the finished ferulic acid into small pieces, uniformly spreading in a drying apparatus, and drying in a vacuum drying oven at 75 deg.C under-0.1 Mpa for 8 hr to obtain ferulic acid product with water content of less than 0.4%;
7. and (3) crushing, sieving and detecting: crushing the dried ferulic acid, screening and detecting to obtain a qualified product with the particle size of 80 meshes;
8. material mixing and packaging and finished product detection: mixing the sieved batch materials, then packaging according to the specification of 25 kg/barrel to obtain a finished product ferulic acid, and detecting the content and impurity content of the finished product, wherein the content of ferulic acid is 98.83% by HPLC (high performance liquid chromatography), and the content of impurity molecules 4-vinyl-2-methoxyphenol is reduced to 32.6 ppm.
9. Elution and regeneration: respectively eluting saturated adsorption resin HPD-5000 and ion exchange resin LKA-53 with anhydrous ethanol and 4% hydrochloric acid solution for regeneration treatment to obtain ferulic acid containing more impurities, and treating the part of material again until completely meeting the standard.
In the embodiment, by adopting the technical scheme of the invention, the high-quality product with the ferulic acid HPLC detection content of 98.83% and the impurity molecule 4-vinyl-2-methoxyphenol content of 32.6ppm is prepared from the impurity exceeding product with the ferulic acid HPLC content of 83.2% and the impurity molecule 4-vinyl-2-methoxyphenol content of 513.7 ppm.
Example twelve:
a method for removing impurity molecules affecting ferulic acid smell by resin process comprises the following steps,
1. dissolving and filtering: reacting ferulic acid (the content of ferulic acid is 83.2 percent, the content of impurity molecules is 4-vinyl-2-methoxyphenol is 513.7ppm) with odor and impurities exceeding the standard with a NaOH aqueous solution, wherein the mass-to-volume ratio of the ferulic acid to purified water in the NaOH solution is 1:20, firstly adding NaOH solid particles to fully dissolve the ferulic acid, then slowly adding ferulic acid to be treated to generate a sodium ferulate solution, filtering, wherein the dissolving temperature is 25 ℃, the stirring speed is 100rpm, the pH value is 7.0, and the filtering precision is 200 meshes.
2. Adsorbing and removing impurities: passing the filtered sodium ferulate solution through adsorption resin DM1300 and collecting the liquid passing through the resin column at a flow rate of 2.0 times the volume of the resin column, wherein the volume ratio of the sodium ferulate solution to the adsorption resin DM1300 is 100: 1.
3. Ion exchange: passing the collected liquid through the adsorption resin DM1300 through an ion exchange resin D201 and collecting the liquid; the flow rate was 2 times the volume of the resin column and the volume ratio of liquid to ion exchange resin D201 was 15: 1.
4. Acid precipitation and crystallization: adding 15% of H into the liquid which is obtained in the step 3 and passes through the ion exchange resin LKA-532SO4And (3) reducing the temperature to 15 ℃ until the pH of the solution is 3.0, standing for 6 hours, and crystallizing to separate out the ferulic acid meeting the requirement.
5. Centrifugal filtration: filtering or centrifuging ferulic acid obtained by crystallization with a filter device or centrifuge, with the precision of filter paper or filter cloth of 200 mesh, the filtering pressure of-0.1 Mpa, or the working speed of the centrifuge of 5000rpm, and centrifuging for 25min to obtain solid ferulic acid
6. Drying a product: dividing the finished ferulic acid into small pieces, uniformly spreading in a drying device, and drying in a vacuum drying oven at 65 deg.C under-0.1 Mpa for 12 hr to obtain ferulic acid product with water content of less than 0.4%;
7. and (3) crushing, sieving and detecting: crushing the dried ferulic acid, screening and detecting to obtain a qualified product with the particle size of 80 meshes;
8. material mixing and packaging and finished product detection: mixing the sieved batch materials, then packaging according to the specification of 25 kg/barrel to obtain a finished product ferulic acid, and detecting the content and impurity content of the finished product, wherein the content of ferulic acid is 98.97% by HPLC (high performance liquid chromatography), and the content of impurity molecules 4-vinyl-2-methoxyphenol is reduced to 39.7 ppm.
9. Elution and regeneration: respectively using anhydrous ethanol and 5% H for saturated adsorption resin DM1300 and ion exchange resin D2012SO4Eluting and regenerating the solution to obtain ferulic acid with more impurities, and treating the part of the material again until the part of the material completely meets the standard.
In the embodiment, by adopting the technical scheme of the invention, the impurity exceeding product with the ferulic acid HPLC content of 83.2% and the impurity molecule 4-vinyl-2-methoxyphenol content of 513.7ppm is prepared into the high-quality product with the ferulic acid HPLC detection content of 98.97% and the impurity molecule 4-vinyl-2-methoxyphenol content of 39.7 ppm.
Example thirteen:
a method for removing impurity molecules affecting ferulic acid smell by resin process comprises the following steps,
1. dissolving and filtering: reacting ferulic acid (the ferulic acid content is 83.2%, the impurity molecule 4-vinyl-2-methoxyphenol content is 513.7ppm) with odor and impurities exceeding the standard with a KOH aqueous solution, wherein the mass-to-volume ratio of the ferulic acid to purified water in the KOH solution is 1:20, firstly adding KOH solid particles to fully dissolve the solid particles, then slowly adding ferulic acid to be treated to generate a potassium ferulate solution, filtering, wherein the dissolving temperature is 25 ℃, the stirring speed is 100rpm, the pH value is 7.0, and the filtering precision is 200 meshes.
2. Adsorbing and removing impurities: passing the filtered potassium ferulate solution through adsorption resin DM1300 and collecting the liquid passing through the resin column at a flow rate of 2.0 times the volume of the resin column, wherein the volume ratio of the ferulate solution to the DM1300 resin is 100: 1.
3. Ion exchange: passing the collected liquid through the adsorption resin DM1300 through an ion exchange resin D201 and collecting the liquid; the flow rate was 1.5 times the volume of the resin column, and the ratio of the volume of liquid to the volume of resin D201 was 15: 1.
4. Acid precipitation and crystallization: adding 15% H into the solution obtained in step 3 and passed through ion exchange resin LKA-532SO4And (3) reducing the temperature to 15 ℃ until the pH value of the solution is 3.0, then standing for 6 hours, and crystallizing to separate out the ferulic acid meeting the requirement.
5. Centrifugal filtration: filtering or centrifuging ferulic acid obtained by crystallization with a filter device or centrifuge, wherein the precision of filter paper or filter cloth is 200 mesh, the filtering pressure is-0.1 Mpa, or the working speed of the centrifuge is 5000rpm, and the centrifuging time is 25min to obtain solid ferulic acid
6. Drying a product: dividing the finished ferulic acid into small pieces, uniformly spreading in a drying device, and drying in a vacuum drying oven at 65 deg.C under-0.1 Mpa for 12 hr to obtain ferulic acid product with water content of less than 0.4%;
7. and (3) crushing, sieving and detecting: crushing the dried ferulic acid, screening and detecting to obtain a qualified product with the particle size of 80 meshes;
8. material mixing and packaging and finished product detection: mixing the sieved batch materials, then packaging according to the specification of 25 kg/barrel to obtain a finished product ferulic acid, and detecting the content and impurity content of the finished product, wherein the content of ferulic acid is 98.58% by HPLC (high performance liquid chromatography), and the content of impurity molecules 4-vinyl-2-methoxyphenol is reduced to 43.9 ppm.
9. Elution and regeneration: respectively using absolute ethyl alcohol and 3% H to make saturated adsorption resin DM1300 and ion exchange resin D201 use2SO4Eluting and regenerating the solution to obtain ferulic acid containing more impurities,this portion of material is processed again until it is fully within standards.
In the embodiment, by adopting the technical scheme of the invention, the impurity exceeding product with the ferulic acid HPLC content of 83.2% and the impurity molecule 4-vinyl-2-methoxyphenol content of 513.7ppm is prepared into the high-quality product with the ferulic acid HPLC detection content of 98.58% and the impurity molecule 4-vinyl-2-methoxyphenol content of 43.9 ppm.
In summary, it can be seen from the tenth to thirteenth embodiments that the present invention has better effect of removing foreign molecules affecting ferulic acid odor by using the adsorption resin of HPD-5000 and the ion exchange resin of LKA-53, better effect of removing foreign molecules affecting ferulic acid odor by using NaOH than by using KOH, and better effect of removing HCL than by using H2SO4. Comprehensively, NaOH solution and ferulic acid react to generate sodium ferulate solution, the sodium ferulate solution passes through HPD-5000 adsorption resin and LKA-53 ion exchange resin in sequence, and finally HCL is used for acid-adjusting and crystallizing, so that the removal effect of impurity molecules 4-vinyl-2-methoxyphenol is best, the content of ferulic acid is highest, the HPLC detection content of ferulic acid can reach 99.32% at most, and the content of impurity molecules 4-vinyl-2-methoxyphenol can be reduced to 20.4ppm at least.
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, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
In the case of no conflict, a person skilled in the art may combine the related technical features in the above examples according to actual situations to achieve corresponding technical effects, and details of various combining situations are not described herein.
It should be noted that all the directional indicators (such as up, down, left, right, front, and rear … …) in the embodiment of the present invention are only used to explain the relative position relationship between the components, the movement situation, etc. in a specific posture (as shown in the drawing), and if the specific posture is changed, the directional indicator is changed accordingly.
The foregoing is illustrative of the preferred embodiments of the present invention, and the present invention is not to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein. Any simple modification, equivalent change and modification of the above embodiments according to the technical spirit of the present invention still fall within the scope of the technical solution of the present invention.
Claims (10)
1. A method for removing impurity molecules affecting ferulic acid odor by using a resin process is characterized by comprising the following steps,
the method comprises the following steps: dissolution filtration
Firstly, ferulic acid with odor impurities exceeding the standard reacts with alkali liquor to generate corresponding ferulate solution and is filtered;
step two: removing impurities by adsorption
Adsorbing the ferulate solution filtered in the step one by using adsorption resin, and collecting the liquid adsorbed by the resin;
step three: ion exchange
Enabling the liquid collected in the second step to pass through ion exchange resin, and collecting the liquid after passing through the ion exchange resin;
step four: acid precipitation crystallization
Adding an acid solution into the liquid obtained in the third step, and standing until solid ferulic acid is separated out by crystallization;
step five: centrifugal filtration
Filtering or centrifuging the solid ferulic acid separated out in the step four to obtain a ferulic acid product with the water content of less than 35%;
step six: drying the product
Dividing the ferulic acid product obtained in the step five into small blocks, and uniformly paving the small blocks in a drying appliance for drying to obtain ferulic acid with the water content of less than 0.4%;
step seven: crushing and sieving detection
Crushing the ferulic acid dried in the sixth step, screening and detecting to obtain a ferulic acid product with the particle size of 80 meshes;
step eight: mixing material packaging and finished product detection
Mixing the sieved materials, and then packaging according to a preset specification to obtain a finished product ferulic acid; performing content and impurity content sampling inspection on the finished product ferulic acid;
step nine: elution regeneration
And (3) respectively carrying out elution regeneration treatment on the saturated adsorption resin and the saturated ion exchange resin to obtain ferulic acid containing more impurities, and returning the part of material to the first step for treatment until the part of material completely reaches the preset standard.
2. The method for removing impurity molecules affecting the odor of ferulic acid by using a resin process as claimed in claim 1, wherein the dissolution filtration method of the first step is: preparing purified water according to the mass-volume ratio of ferulic acid to purified water in alkali liquor of 1: 10-1: 20, adding alkali into the purified water to fully dissolve the ferulic acid, and slowly adding the ferulic acid to be treated according to the ratio until the ferulic acid is completely dissolved, so that the pH value is 6.5-7; the alkali is NaOH or KOH.
3. The method for removing impurity molecules affecting the odor of ferulic acid by using a resin process as claimed in claim 1, wherein the second adsorption impurity removal method comprises: the flow rate of the ferulate solution passing through the adsorption resin is 1.0-2.0 times of the column volume, and the volume ratio of the ferulate solution to the adsorption resin is 80:1-100: 1; the type of the adsorption resin is HPD-5000 or DM1300 or XDA-200.
4. The method for removing impurity molecules affecting ferulic acid odor by using resin process as claimed in claim 1, wherein the step three ion exchange method is: the flow rate of the ferulate solution passing through the adsorption resin is 1.0-2.0 times of column volume, and the volume ratio of the ferulate solution to the ion exchange resin is 10:1-20: 1; the type of the ion exchange resin is LKA-53 or D201 or D296.
5. The method for removing impurity molecules affecting the odor of ferulic acid by using a resin process as claimed in claim 1, wherein the acid precipitation crystallization method of the fourth step is: adding 10-15% HCL solution or H into the ferulate solution after ion exchange resin2SO4The solution is kept until the pH value of the solution is kept between 2.5 and 4.5, the crystallization temperature is kept between 15 and 25 ℃, and the duration is 4 to 8 hours.
6. The method for removing impurity molecules affecting the odor of ferulic acid by using a resin process as claimed in claim 1, wherein the step five centrifugal filtration method comprises: filtering or centrifuging the ferulic acid obtained by crystallization by using a filtering device or a centrifuge, wherein the precision of filtering paper or filtering cloth is 400 meshes, the filtering pressure is-0.08-0.1 Mpa, or the working rotating speed of the centrifuge is 4500-6000rpm, and the centrifuging time is 20-40min, so that the water content of the ferulic acid product is less than 35%.
7. The method for removing impurity molecules affecting the odor of ferulic acid by using a resin process as claimed in claim 1, wherein the six-step drying method comprises: and (3) putting the filtered or centrifuged raw material into a vacuum drying oven for drying treatment at the drying temperature of 60-80 ℃ for 8-12h, wherein the moisture content is less than 0.4% after drying.
8. The method for removing impurity molecules affecting ferulic acid odor by using resin process as claimed in claim 1, wherein the step seven crushing and screening test method comprises: after being crushed by a crusher, ferulic acid passing through a sieve of 80 meshes is detected, mixed and packaged to obtain a final product, and the detection targets are that the HPLC content of the ferulic acid is more than 98 percent and the HPLC content of 4-vinyl-2-methoxyphenol impurity is less than 50 ppm.
9. The method for removing impurity molecules affecting ferulic acid odor by using resin process as claimed in claim 1, wherein the step nine elution regeneration method is: passing the eluent through adsorption resin or ion exchange resin at flow rate of 1.5-3.0 times of column volume and elution regeneration volume of 3-5 times of column volume.
10. The method of claim 9, wherein the resin process is used to remove contaminant molecules affecting ferulic acid odor, comprising the steps of: the eluent used for the adsorption resin is alcohol or alkali solution, and the eluent used for the ion exchange resin is absolute ethyl alcohol or HCL solution or H2SO4The solution has a concentration of 3% to 5% by volume of a base or acid.
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