CN113200835B - Method for removing various harmful substances in capsorubin - Google Patents
Method for removing various harmful substances in capsorubin Download PDFInfo
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- CN113200835B CN113200835B CN202110468130.8A CN202110468130A CN113200835B CN 113200835 B CN113200835 B CN 113200835B CN 202110468130 A CN202110468130 A CN 202110468130A CN 113200835 B CN113200835 B CN 113200835B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
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- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
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- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/786—Separation; Purification; Stabilisation; Use of additives by membrane separation process, e.g. pervaporation, perstraction, reverse osmosis
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Abstract
The invention belongs to the field of extraction of natural products, and particularly relates to a method for removing various hazards in capsorubin. The method comprises the following steps: dissolving capsorubin to be treated in an organic solvent, and separating the harmful substances through an organic solvent-resistant nanofiltration membrane; the organic solvent is one or more of acetone, vegetable oil extraction solvent or ethyl acetate. The method has simple process and high capsorubin yield, and compared with the process without removal, the loss rate is not more than 0.5 percent. The method can simultaneously remove a plurality of harmful components, including removing benzopyrene in the capsorubin from the level of dozens of ppb to less than 10 ppb; removing illegal dyes such as Sudan red, rhodamine B and the like from dozens to hundreds of ppb to below 10 ppb; the pesticide residue is removed from dozens of ppm to below 20ppb, the high-end product quality requirement is met, and the safety is greatly improved.
Description
Technical Field
The invention belongs to the field of extraction of natural products, and particularly relates to a method for removing various hazards in capsorubin.
Background
Capsorubin is an oily liquid obtained by extracting red pepper, and is rich in natural carotenoids such as capsorubin and capsorubin, and the natural carotenoids exist in the form of ester with fatty acid. Therefore, the capsorubin is an excellent fat-soluble pigment and is widely applied to the aspects of food, daily chemicals, medicine coloring and the like at present.
Benzopyrene (Benzoapyrene), chemical formula: c 20 H 12 And the English expression BaP is a pentacyclic polycyclic aromatic hydrocarbon. The crystals were yellow solids, which were produced in an incomplete combustion state at temperatures between 300 and 600 ℃. Benzo (b) isPyrene is present in coal tar, which is found in automobile exhaust, smoke from the combustion of tobacco and wood, and charcoal-roasted food. Benzopyrene is a mutagen and carcinogen, and has been found to be associated with many cancers since the 18 th century. The metabolite of benzopyrene in vivo, dihydroxyepoxybenzopyrene, produces carcinogenic substances. The food seasoning oil requires the limit amount of benzopyrene to be less than 10 ppb. Due to environmental pollution and pollution in the process of packaging material transportation and production processing, benzopyrene in capsorubin is higher than 10ppb and even reaches 100ppb level, and cannot meet the requirements of high-end food.
"Sudan Red" is a chemical coloring agent and is not a food additive. Its chemical composition contains a compound called naphthalene, said material possesses azo structure, and the property of said chemical structure can determine that it possesses carcinogenicity, and possesses obvious toxic action for liver and kidney organs of human body. Sudan red belongs to a chemical coloring agent, is mainly used in petroleum, engine oil and other industrial solvents for coloring and brightening shoes, floors and the like. Due to the wide use of chemical dyes, the capsicum can be polluted by the dyes in the processes of production, transportation, processing, storage and the like, and the polluted capsicum can be transferred to a capsicum red product in the processing process of Sudan red.
Rhodamine B (Rhodamine B), also called rhodamine B, Rose Bengal B, and alkaline Rose Bengal C 28 H 31 C l N 2 O 3 Is an artificially synthesized dye with bright pink color. Is easily soluble in water and ethanol, and slightly soluble in acetone, chloroform, hydrochloric acid and sodium hydroxide solution. The fluorescent powder is red to violet powder, the aqueous solution is blue-red, strong fluorescence is generated after dilution, and the alcoholic solution has red fluorescence. The fluorescent dye is often used as a cell fluorescent dye in a laboratory, and is widely applied to industries such as colored glass, special fireworks and crackers and the like. Rhodamine B is also an artificially synthesized raw material, is derived from Sudan red and is polluted by dye in the processes of production, transportation, processing, storage and the like, and the polluted pepper is transferred to a pepper red product by the rhodamine B in the processing process
Pesticide residues (Pesticide residues) after the Pesticide is usedA general term for a trace amount of agricultural chemicals, toxic metabolites, degradants and impurities which are not decomposed and remain in an organism, harvested materials, soil, water body, atmosphere within a period of time. The pesticide applied to the crops is partially attached to the crops, partially scattered in the environment such as soil, atmosphere and water, and part of the pesticide remained in the environment can be absorbed by the plants. Triazophos is a broad-spectrum organic phosphorus insecticide, acaricide, nematicide, and is mainly used for preventing and controlling lepidoptera pests, pest mites, fly larvae, underground pests and the like on fruit trees, cotton and grain crops. The pure product of ethion is colorless or amber liquid with a boiling point of 164-165 ℃ (40 Pa). Slightly soluble in water, soluble in most common solvents, and highly toxic. The organophosphorus insecticide and acaricide available in the 50 s of 20 th century can be prepared by reacting diethoxy dithiophosphate with dibromomethane. Can be used for preventing and treating aphid, scale insect and mite. The preparation can be granule, wettable powder, emulsion, etc. Chlorpyrifos, O-diethyl-O- (3,5, 6-trichloro-2-pyridyl) thiophosphoric acid with molecular formula C 9 H 11 Cl 3 NO 3 PS is white crystal, has slight mercaptan smell, is a non-systemic broad-spectrum insecticide and acaricide, and has high volatility in the land. During the growth process of the pepper, pesticide residues exist on pepper fruits due to the use of pesticides, and during the production process, the pesticide residues are not easy to volatilize and degrade, so that the pepper red product contains pesticide residues.
In the prior art, benzopyrene, total Sudan red and rhodamine B are usually removed by adsorption of an adsorbent, common adsorbents comprise activated clay, activated carbon or fired special adsorbents and adsorption resin, and the like, the adsorbents have the characteristics that pigments can be adsorbed while hazards are adsorbed, different adsorbents have different adsorption effects on different hazards, and if similar technologies are adopted to directly adsorb and remove the hazards to capsorubin related products, a large amount of adsorption loss of capsorubin can be caused, and at present, no adsorbent which only adsorbs the hazards without adsorbing capsorubin is found. In the process of removing pesticide residues, the pesticide residues in capsanthin are mainly enriched to a light phase in a molecular distillation mode at the present stage, so that the heavy phase pesticide residues are reduced, but the temperature in the molecular distillation process is high, the pigment loss is serious, and the energy consumption is high.
Therefore, the development of a method which is suitable for removing various hazards in capsorubin and does not lose capsorubin has very important practical significance.
Disclosure of Invention
In view of the above problems in the prior art, the present invention provides a method for removing various noxious substances from capsorubin by membrane filtration.
The method comprises the steps of dissolving capsorubin to be treated in an organic solvent, and separating noxious substances through an organic solvent-resistant nanofiltration membrane; the organic solvent is one or more of acetone, vegetable oil extraction solvent or ethyl acetate.
The invention discovers that the harmful components in the capsorubin can be effectively separated and removed by the organic solvent resistant nanofiltration membrane after the capsorubin is dissolved in the solvent.
Preferably, the organic solvent resistant nanofiltration membrane is a composite membrane and comprises a base membrane and a separation layer, wherein the base membrane is made of polyacrylonitrile, and the separation layer is an organic silicone coating coated on the surface of the base membrane. The organic solvent resistant nanofiltration membrane has obvious difference in adsorption force on capsorubin and harmful components therein, and can effectively realize separation of capsorubin and various harmful components therein.
Preferably, the operating pressure of the organic solvent resistant nanofiltration membrane treatment process is 1.3-2.8 MPa.
Further preferably, the operation pressure of the organic solvent resistant nanofiltration membrane treatment process is 1.6-2.0 MPa. Under the pressure condition, the material can be ensured to ideally pass through the filter membrane, the separation effect is not ideal due to the over-low pressure, and the membrane is not damaged due to the over-high pressure.
Preferably, the temperature of the feed liquid is controlled to be 0-40 ℃ in the membrane separation process. The membrane does not swell at the above temperature, and the separation effect is not affected.
Further preferably, the temperature in the membrane separation process is controlled to be 30-35 ℃. At which temperature the desired separation efficiency and separation effect can be ensured.
Preferably, the mass volume ratio of the capsorubin to be treated to the organic solvent is 1: 6-30.
Further preferably, the mass volume ratio of the capsorubin to be treated to the organic solvent is 1: 10-20. At the above mass-to-volume ratio, sufficient removal of harmful substances can be ensured, and reduction of separation efficiency due to excessive use of solvent is avoided.
Preferably, the organic solvent is a mixed solution of a vegetable oil extraction solvent and acetone or ethyl acetate, and the volume ratio of the vegetable oil extraction solvent to the acetone is 1-4: 1. The organic solvent has high extraction yield and good harmful substance removing effect in the membrane separation process.
More preferably, the organic solvent is a mixed solution of a vegetable oil extraction solvent and acetone, and the volume ratio of the vegetable oil extraction solvent to the acetone is 1-3: 1.
Preferably, the hazardous component comprises one or more of benzopyrene, Sudan red, rhodamine B or pesticide residue.
Preferably, the organic solvent resistant nanofiltration membrane is a composite membrane and comprises a base membrane and a separation layer, wherein the base membrane is made of polyacrylonitrile, and the separation layer is an organic silicone coating coated on the surface of the base membrane; the operating pressure in the organic solvent resistant nanofiltration membrane treatment process is 1.6-2.0 Mpa; the mass volume ratio of the capsorubin to be treated to the organic solvent is 1: 10-20; the organic solvent is acetic ester or a mixed solution of a vegetable oil extraction solvent and acetone, and the volume ratio of the vegetable oil extraction solvent to the acetone is 1-4: 1.
Preferably, the capsorubin includes capsorubin obtained by solvent extraction, oil extraction, and supercritical extraction.
As a preferable operation mode, the organic solvent-resistant nanofiltration membrane is used for separating to obtain a permeate and a retentate, the retentate is concentrated to obtain the capsorubin without the hazardous substances, and the permeate is rectified by a rectifying tower to obtain the solvent without hazardous components.
As a preferable operation mode, in order to ensure the removal effect of the harmful components, the solvent can be added into the system for a plurality of times after one separation is completed for a plurality of times of separation.
The mass-to-volume ratio of the present invention includes standard units such as kg and g, and standard units such as L, ml.
The invention has the following beneficial effects:
(1) the method can simultaneously remove a plurality of harmful components, including effectively removing benzopyrene in capsorubin from the level of dozens of ppb to less than 10 ppb; removing illegal dyes such as Sudan red, rhodamine B and the like, wherein dozens to hundreds of ppb of the illegal dyes are removed to be below 10 ppb; the pesticide residue is removed from dozens of ppm to below 20ppb, the high-end product quality requirement is met, and the safety is greatly improved.
(2) The method of the invention has less capsorubin loss, and the capsorubin loss rate is not more than 0.5%.
(3) The method of the invention has no solid waste discharge, only needs a very small amount of sewage to be treated, and can be reused after the solvent is recovered.
(4) The method is simple to operate and is suitable for large-scale industrial production.
Detailed Description
The process of the invention is described below by means of specific embodiments. In addition, the embodiments should be considered illustrative, and not restrictive, of the scope of the invention, which is defined solely by the claims.
The organic solvent-resistant nanofiltration membranes used in the examples were PMP nanofiltration membranes purchased from winning specialty chemicals (shanghai) ltd.
The vegetable oil extraction solvent used in the examples was purchased from Yufeng chemical Co., Ltd, Liaoning.
The color number described in the examples is the absorbance of capsorubin per mass at 1% concentration in a 1cm cuvette at its maximum absorption peak. Directly measuring by an ultraviolet spectrophotometer. The calculation method comprises the following steps: and the color value is Af/100m, wherein A is the absorbance of the measured sample, and f is the dilution multiple m and is the mass of the sample.
The calculation method of the color value retention rate comprises the following steps: (raw material mass raw material color number)/(product mass product color number) the data of example 1 are used as an example: (995.3 × 145.1)/(1000 × 145.2) × 100% ═ 99.46%.
Example 1
The embodiment relates to removal of harmful components in capsorubin, which comprises the following steps:
dissolving 1000g of capsorubin (color value 145.2, 26ppb of benzopyrene, 200ppb of total Sudan red (Sudan red I-IV), 65ppb of rhodamine B, 36ppm of ethion, 12ppm of chlorpyrifos and 21ppm of triazophos) into 10000ml of a mixed solution of a vegetable oil extraction solvent and acetone (the vegetable oil extraction solvent: acetone is 3:2), filtering to remove solid insoluble substances, putting the feed liquid into a feed liquid tank of an organic solvent-resistant nanofiltration membrane device, starting a power supply, operating the device, keeping the temperature of the feed liquid at 30-35 ℃ in the separation process, circulating the feed liquid at the upstream side of the membrane under the operating pressure of 1.6-2.0MP in the downstream, collecting primary permeate liquid in the downstream, and closing the device when the collection amount of the primary permeate liquid is 7L; supplementing 7.5L of mixed solution of vegetable oil extraction solvent and acetone (vegetable oil extraction solvent: acetone: 3:2) into the feed liquid tank, performing secondary separation, starting the device, keeping the temperature at 30-35 deg.C and the operating pressure at 1.6-2.0MPa, collecting secondary permeate at downstream, and closing the device when the collection amount of the secondary permeate is 7L; supplementing 6L of mixed solution of vegetable oil extraction solvent and acetone (vegetable oil extraction solvent: acetone: 3:2) to the feed liquid tank, carrying out three-time separation, starting the device, keeping the temperature at 30-35 ℃, operating the pressure at 1.6-2.0MPa, collecting three-time permeate liquid at the downstream, closing the device when the collection amount of the three-time permeate liquid is 6L, discharging trapped liquid, concentrating the trapped liquid to obtain the final material, wherein the trapped liquid is 995.3g (the color value is 145.1, the benzopyrene content is 4.1ppb, the total Sudan red is 18.9ppb, the rhodamine B5.0ppb, the ethion P19.1 ppb, the chlorpyrifos is less than 10ppb, and the triazophos is less than 10 ppb). The benzopyrene removal rate is 84.30%, the total Sudan red removal rate is 90.59%, the rhodamine removal rate, the ethion removal rate, the chlorpyrifos removal rate and the triazophos removal rate are more than or equal to 99.9%, the color value retention rate is 99.46%, the permeation solution is directly fed into a tower evaporator, the hot water heating is carried out at the temperature of 60 ℃, the solvent is recovered by normal pressure distillation, and the detection solvent is continuously recycled without detecting any harmful component.
After repeating the above experiment 50 times, the tower evaporator uses 1000ml of sodium hydroxide aqueous solution with concentration of 15% to drip the wall of the evaporation kettle, collects the cleaning waste liquid, and washes with 300ml of clear water for 2-3 times, and all the waste water is put into a sewage treatment system for treatment.
Example 2
This example relates to the removal of harmful components from capsorubin, which is different from example 1 in the amount of organic solvent, and comprises the following steps:
dissolving 1000g of capsorubin (color value 145.2, 26ppb of benzopyrene, 200ppb of total Sudan red (Sudan red I-IV), 65ppb of rhodamine B, 36ppm of ethion, 12ppm of chlorpyrifos and 21ppm of triazophos) into 20000ml of a mixed solution of a vegetable oil extraction solvent and acetone (the vegetable oil extraction solvent: acetone is 3:2), filtering to remove solid insoluble substances, putting the feed liquid into a feed liquid tank of an organic solvent-resistant nanofiltration membrane device, starting a power supply, operating the device, keeping the temperature of the feed liquid at 30-35 ℃ in the separation process, keeping the operating pressure at 1.6-2.0MPa, circulating the feed liquid at the upstream side of the membrane, collecting primary permeate liquid at the downstream, and closing the device when the collection amount of the primary permeate liquid is 14L; adding 14L of mixed solution of vegetable oil extraction solvent and acetone into the feed liquid tank (vegetable oil extraction solvent: acetone: 3:2), carrying out secondary separation, starting the device, keeping the temperature at 30-35 ℃, operating the pressure at 1.6-2.0MPa, collecting secondary permeate at the downstream, and closing the equipment when the collection amount of the secondary permeate is 14L; supplementing 12L of mixed solution of vegetable oil extraction solvent and acetone (vegetable oil extraction solvent: acetone: 3:2) to a feed liquid tank, carrying out three-time separation, starting a device, keeping the temperature at 30-35 ℃, operating pressure at 1.6-2.0MPa, collecting three-time permeate liquid at the downstream, closing the device when the collection amount of the three-time permeate liquid is 12L, discharging trapped liquid, and concentrating the trapped liquid to obtain the final material, wherein the trapped liquid is 993.6g (color value is 144.8, benzopyrene content is 2.3ppb, total Sudan red is less than 10ppb, rhodamine B is less than 3ppb, ethion is less than 10ppb, chlorpyrifos is less than 10ppb, and triazophos is less than 10 ppb). The benzopyrene removal rate is 87.9 percent, the total Sudan red removal rate is more than or equal to 95 percent, the rhodamine removal rate, the ethion removal rate, the chlorpyrifos removal rate and the triazophos removal rate are more than or equal to 99.9 percent, and the color value retention rate is 99.09 percent. And (3) allowing the permeate to enter a tower evaporator, heating with hot water at 60 ℃, distilling at normal pressure to recover the solvent, detecting that no harmful component is detected in the solvent, and continuously recycling.
After repeating the above experiment for 25 times, the evaporator uses 1000ml of sodium hydroxide aqueous solution with concentration of 15% to wash the wall of the evaporation kettle, the cleaning waste liquid is collected and washed 2-3 times by using 300ml of clear water, and all the waste water is put into a sewage treatment system for treatment.
Example 3
The difference compared to example 1 is that the organic solvent is ethyl acetate.
The embodiment relates to removal of harmful components in capsorubin, which comprises the following steps:
1) dissolving 1000g of capsorubin (color value 145.2, 26ppb of benzopyrene, 200ppb of total Sudan red (Sudan red I-IV), 65ppb of rhodamine B, 36ppm of ethion, 12ppm of chlorpyrifos and 21ppm of triazophos) into 10000ml of ethyl acetate, filtering to remove solid insoluble substances, putting the feed liquid into a feed liquid tank of organic solvent resistant nanofiltration membrane equipment, starting a power supply, operating the device, and keeping the temperature of the feed liquid at 30-35 ℃ and the operating pressure at 1.6-2.0MPa in the separation process. The feed liquid circulates at the upstream side of the membrane, primary permeate is collected at the downstream side, and the equipment is closed when the collection amount of the primary permeate is 7L; adding 7.5L of ethyl acetate into the feed liquid tank, performing secondary separation, starting the device, keeping the temperature at 30-35 ℃, operating pressure at 1.6-2.0MPa, collecting secondary permeate at the downstream, and closing the equipment when the collection amount of the secondary permeate is 7L; supplementing 6L of ethyl acetate into the feed liquid tank, carrying out three-time separation, starting a device, keeping the temperature at 30-35 ℃, keeping the operating pressure at 1.6-2.0MPa, collecting three-time permeate liquid at the downstream, closing the device when the collection amount of the three-time permeate liquid is 6L, discharging trapped fluid, and concentrating the trapped fluid to obtain a final material, wherein the trapped fluid is 992.1g (the color value is 144.9, the benzopyrene content is 4.3ppb, the total Sudan red is 22.5ppb, the rhodamine B7.2 ppb, the ethion is 21.2ppb, the chlorpyrifos is 10.2ppb, and the triazophos is 15.5 ppb). The removal rate of benzopyrene is 83.59%, the removal rate of total Sudan red is 88.84%, the removal rate of rhodamine is 89.01%, the removal rate of ethion and other pesticide residues is more than or equal to 99.0%, and the retention rate of color number is 99.00%. The permeate liquid is directly heated by a tower evaporator with hot water at 60 ℃, the solvent is recovered by normal pressure distillation, and no harmful component is detected in the solvent for continuous recycling.
After repeating the above experiment 50 times, the evaporator uses 1000ml of sodium hydroxide aqueous solution with concentration of 15% to wash the wall of the evaporation kettle, the cleaning waste liquid is collected and washed 2-3 times by using 300ml of clear water, and all the waste water is put into a sewage treatment system for treatment.
Example 4
The difference compared to example 1 is that the volume ratio of the vegetable oil extraction solvent to acetone was 4: 1.
The embodiment relates to removal of harmful ingredients in capsorubin, and the method comprises the following steps of:
dissolving 1000g of capsorubin (color value 145.2, 26ppb of benzopyrene, 200ppb of total Sudan red (Sudan red I-IV), 65ppb of rhodamine B, 36ppm of ethion, 12ppm of chlorpyrifos and 21ppm of triazophos) into 10000ml of mixed solution of a vegetable oil extraction solvent and acetone (the vegetable oil extraction solvent: acetone is 4:1), filtering to remove solid insoluble substances, putting the feed liquid into a feed liquid tank of organic solvent-resistant nanofiltration membrane equipment, starting a power supply, operating the device, and keeping the temperature of the feed liquid at 30-35 ℃ and the operating pressure at 1.6-2.0MPa in the separation process. The feed liquid circulates at the upstream side of the membrane, primary permeate is collected at the downstream side, and the equipment is closed when the collection amount of the primary permeate is 7L; supplementing 7.5L of mixed solution of vegetable oil extraction solvent and acetone (vegetable oil extraction solvent: acetone is 4:1) to the feed liquid tank, performing secondary separation, starting the device, keeping the temperature at 30-35 ℃, operating the pressure at 1.6-2.1MPa, collecting secondary permeate at the downstream, and closing the device when the collection amount of the secondary permeate is 7L; supplementing 6L of mixed solution of vegetable oil extraction solvent and acetone (vegetable oil extraction solvent: acetone is 4:1) to a feed liquid tank, carrying out three-time separation, starting a device, keeping the temperature at 30-35 ℃, keeping the operating pressure at 1.6-2.0MPa, collecting three-time permeate liquid at the downstream, closing the device when the collection amount of the three-time permeate liquid is 6L, discharging trapped liquid, and concentrating the trapped liquid to obtain a final material, wherein the trapped liquid is 991.2g (the color value is 145, the benzopyrene content is 4.2ppb, the total Sudan red is 21.3ppb, the rhodamine B7.5ppb, the ethion P22.1 ppb, the chlorpyrifos is 11.2ppb, and the triazophos is 14.5 ppb). The removal rate of benzopyrene is 83.98 percent, the removal rate of total Sudan red is 89.44 percent, the removal rate of rhodamine is 88.56, the removal rate of ethion and other pesticide residues is more than or equal to 99.0 percent, and the retention rate of color value is 98.98 percent. The permeate liquid is directly heated by a tower evaporator with hot water at 60 ℃, the solvent is recovered by normal pressure distillation, and no harmful component is detected in the solvent for continuous recycling.
After repeating the above experiment 50 times, the evaporator uses 1000ml of sodium hydroxide aqueous solution with concentration of 15% to wash the wall of the evaporation kettle, the cleaning waste liquid is collected and washed 2-3 times by using 300ml of clear water, and all the waste water is put into a sewage treatment system for treatment.
Comparative example 1
Compared with example 1, the difference is that the harmful components are not separated and removed by using an organic filter membrane, but are removed by adding activated carbon for adsorption.
1000g of capsorubin (color value 145.2, 26ppb of benzopyrene, 200ppb of total Sudan red (Sudan red I-IV), 65ppb of rhodamine B, 36ppm of ethion, 12ppm of chlorpyrifos and 21ppm of triazophos) is dissolved in 20000ml of a mixed solution of a vegetable oil extraction solvent and acetone (vegetable oil extraction solvent: 90:10), solid insoluble substances are removed by filtration, 50g of powdered activated carbon is added into the solution system, after sufficient stirring and adsorption, the activated carbon is removed by filtration, and after the filtrate is subjected to vacuum concentration, 958.8g (color value 145.3, benzopyrene content 8.3ppb, total Sudan red 154.5ppb, rhodamine B13.2ppb, ethion 28ppm, chlorpyrifos 10ppm and triazophos) is obtained. The color value retention rate is 95.95%, although a plurality of harmful components are adsorbed to different degrees, only benzopyrene reaches below 10ppb and meets the food requirement, the removal effect of other harmful components does not meet the requirements of European Union and the like, and the activated carbon obviously adsorbs capsorubin, so that the color value retention rate is reduced.
Comparative example 2
Compared with example 1, the difference is that the method is used for removing the noxious substances according to the technology introduced in the patent CN101747660B, and the removal effect and the yield of the noxious substance capsorubin are compared.
1000g of capsorubin (theoretical color value 145.2, theoretical benzopyrene of 26ppb, total Sudan red (Sudan red I-IV) of 200ppb, rhodamine B65ppb, ethion 36ppm, chlorpyrifos of 12ppm and triazophos of 21ppm) was subjected to supercritical removal of the harmful components of capsorubin in the manner described in example 1 of CN101747660B patent to obtain 835.7g (color value 162.6, benzopyrene content 27.3ppb, total Sudan red of 30.2ppb, rhodamine B19.2ppb, ethion of 3ppm, chlorpyrifos of 0.6ppm and triazophos of 2 ppm). The color value retention rate is 93.58%, several harmful components are adsorbed in different degrees, the removal rate of the Sudan red is high, three pesticide residues and rhodamine also have certain removal rates, but the benzopyrene cannot be removed basically, the overall removal effect does not meet the requirements of European Union and the like, and the supercritical separation removes the harmful components and simultaneously separates partial capsorubin, so that the yield is reduced.
Comparative example 3
The difference from example 1 is that the organic solvent was selected by changing the choice of organic solvent and methanol was selected to dissolve capsanthin.
Dissolving 100g of capsorubin (the color value is 145.2, the benzopyrene is 26ppb, the total Sudan red (Sudan red I-IV) is 200ppb, the rhodamine B65ppb, the ethion is 36ppm, the chlorpyrifos is 12ppm and the triazophos is 21ppm) into 10000ml of methanol, filtering to remove solid insoluble substances, putting the feed liquid into a feed liquid tank of organic solvent resistant nanofiltration membrane equipment, starting a power supply, operating the device, keeping the temperature of the feed liquid at 30-35 ℃ in the separation process, circulating the feed liquid at the upstream side of the membrane under the operating pressure of 1.3-1.8MP, collecting primary permeate liquid at the downstream, and closing the equipment when the collection amount of the primary permeate is 7L; supplementing 7.5L of methanol to the feed liquid tank, performing secondary separation, starting the device, keeping the temperature at 30-35 ℃, operating pressure at 1.3-1.8MPa, collecting secondary permeate at the downstream, and closing the equipment when the collection amount of the secondary permeate is 7L; supplementing 6L of methanol to a feed liquid tank, carrying out three-time separation, starting a device, keeping the temperature at 30-35 ℃, keeping the operating pressure at 1.3-1.8MPa, collecting three-time permeate liquid at the downstream, closing the device when the collection amount of the three-time permeate liquid is 6L, discharging trapped liquid, and concentrating the trapped liquid to obtain a final material, wherein the trapped liquid is 98.3g (the color value is 145.1, the benzopyrene content is 15ppb, the total Sudan red 138ppb, the rhodamine B51.3ppb, the ethion is 13ppm, the chlorpyrifos is 5ppm, and the triazophos is 10 ppm). The benzopyrene removal rate is 56.71%, the total Sudan red removal rate is 67.83%, the rhodamine removal rate is 77.58%, the ethion is 39.50%, the chlorpyrifos is 40.96%, the triazophos is 46.81%, and the color value retention rate is 98.23%. From the above, it can be seen that methanol solution cannot effectively remove various harmful components, and capsorubin is also lost to some extent.
Comparative example 4
Compared with the example 1, the ceramic membrane with the membrane aperture of 20nm is adopted to separate the materials.
Dissolving 1000g of capsorubin (color value 145.2, 26ppb of benzopyrene, 200ppb of total Sudan red (Sudan red I-IV), 65ppb of rhodamine B, 36ppm of ethion, 12ppm of chlorpyrifos and 21ppm of triazophos) into 10000ml of a mixed solution of a vegetable oil extraction solvent and acetone (the vegetable oil extraction solvent: acetone is 3:2), filtering to remove solid insoluble substances, putting the feed liquid into a feed liquid tank of an organic solvent-resistant nanofiltration membrane device, starting a power supply, operating the device, keeping the temperature of the feed liquid at 30-35 ℃ in the separation process, circulating the feed liquid at the upstream side of the membrane under the operating pressure of 1.6-2.1MP in the downstream, collecting primary permeate liquid, and closing the device when the collection amount of the primary permeate liquid is 7L; supplementing 7.5L of mixed solution of vegetable oil extraction solvent and acetone (vegetable oil extraction solvent: acetone: 3:2) to the feed liquid tank, performing secondary separation, starting the device, keeping the temperature at 30-35 ℃, operating the pressure at 1.6-2.1MPa, collecting secondary permeate at downstream, and closing the device when the collection amount of the secondary permeate is 7L; supplementing 6L of mixed solution of vegetable oil extraction solvent and acetone (vegetable oil extraction solvent: acetone: 3:2) to the feed liquid tank, carrying out three-time separation, starting the device, keeping the temperature at 30-35 ℃, keeping the operating pressure at 1.6-2.1MPa, collecting three-time permeate liquid at the downstream, closing the device when the collection amount of the three-time permeate liquid is 6L, discharging trapped fluid, and concentrating the trapped fluid to obtain the final material, wherein the trapped fluid is 331.0g (the color value is 145.1, the benzopyrene content is 25.3ppb, the total Sudan red is 63.4ppb, the rhodamine B4.9 ppb, the ethion, 36.5ppm, the chlorpyrifos, 12ppm and the triazophos are 21 ppm). As can be seen from the above, the ceramic membrane is adopted to separate the materials, so that the ceramic membrane has no separation effect on benzopyrene, ethion, chlorpyrifos and triazophos, and can cause serious loss of capsorubin.
Claims (9)
1. A method for removing various hazards in capsorubin is characterized by comprising the operation of dissolving capsorubin to be treated in an organic solvent and then separating the hazards through an organic solvent-resistant nanofiltration membrane; the organic solvent is one or more of acetone, a vegetable oil extraction solvent or ethyl acetate;
the organic solvent resistant nanofiltration membrane is a composite membrane and comprises a base membrane and a separation layer, wherein the base membrane is made of polyacrylonitrile, and the separation layer is an organic silicone coating coated on the surface of the base membrane;
the operating pressure in the organic solvent resistant nanofiltration membrane treatment process is 1.3-2.8 Mpa; the temperature of the feed liquid is controlled to be 0-40 ℃ in the process of membrane separation.
2. The method according to claim 1, wherein the operating pressure in the organic solvent-resistant nanofiltration membrane treatment process is 1.6-2.0 MPa.
3. The method according to claim 1 or 2, wherein the temperature of the feed liquid is controlled to be 30-35 ℃ during the membrane separation process.
4. The method according to claim 1, wherein the mass-to-volume ratio of the capsorubin to be treated to the organic solvent is 1:6 to 30.
5. The method according to claim 4, wherein the mass-to-volume ratio of the capsorubin to be treated to the organic solvent is 1: 10-20.
6. The method according to claim 1, wherein the organic solvent is ethyl acetate or a mixed solution of a vegetable oil extraction solvent and acetone, and the volume ratio of the vegetable oil extraction solvent to the acetone is 1-4: 1.
7. The method of any one of claims 1, 2, 4-6, wherein the hazardous component comprises one or more of benzopyrene, Sudan Red, rhodamine B, or pesticide residue.
8. The method of claim 3, wherein the hazardous component comprises one or more of benzopyrene, Sudan Red, rhodamine B, or a pesticide residue.
9. The method according to claim 1, wherein the process operation pressure of the organic solvent resistant nanofiltration membrane treatment is 1.6-2.0 MPa; the mass volume ratio of the capsorubin to be treated to the organic solvent is 1: 10-20; the organic solvent is ethyl acetate or a mixed solution of a vegetable oil extraction solvent and acetone, and the volume ratio of the vegetable oil extraction solvent to the acetone is 1-4: 1.
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