WO2020133849A1 - Adsorbant hybride et son application, et procédé et équipement de traitement d'acide gras polyinsaturé - Google Patents

Adsorbant hybride et son application, et procédé et équipement de traitement d'acide gras polyinsaturé Download PDF

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WO2020133849A1
WO2020133849A1 PCT/CN2019/084573 CN2019084573W WO2020133849A1 WO 2020133849 A1 WO2020133849 A1 WO 2020133849A1 CN 2019084573 W CN2019084573 W CN 2019084573W WO 2020133849 A1 WO2020133849 A1 WO 2020133849A1
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molecular sieve
column
adsorption column
ultrasonic
copper
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Chinese (zh)
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甄明
廖炜程
霍明娟
王海彬
胡泽君
王晓东
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内蒙古金达威药业有限公司
厦门金达威集团股份有限公司
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/12—Naturally occurring clays or bleaching earth
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/16—Alumino-silicates
    • B01J20/18—Synthetic zeolitic molecular sieves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/34—Regenerating or reactivating
    • B01J20/3441—Regeneration or reactivation by electric current, ultrasound or irradiation, e.g. electromagnetic radiation such as X-rays, UV, light, microwaves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/34—Regenerating or reactivating
    • B01J20/345—Regenerating or reactivating using a particular desorbing compound or mixture
    • B01J20/3475—Regenerating or reactivating using a particular desorbing compound or mixture in the liquid phase
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C1/00—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids
    • C11C1/08—Refining

Definitions

  • the invention belongs to the field of polysaturated fatty acid treatment, and specifically discloses a mixed adsorbent and its application and polyunsaturated fatty acid treatment method and equipment.
  • Unsaturated fatty acids such as DHA and ARA are mainly derived from fish oil and algae oil. Most of them exist in the form of ethyl ester in fish oil, and most of them exist in the form of triglyceride in algae oil. Utilization, safety, stability and other aspects have great advantages.
  • the use of microbial fermentation to produce algae oil overcomes the shortcomings of traditional deep-sea fish oil sources such as limited resources, low yield, and vulnerability to pollution. It has the advantages of easy large-scale fermentation and culture, easy separation and purification, short production cycle, and high polyunsaturated fatty acid content. At present, the microbial cell oil produced by biological fermentation engineering technology is already an ideal substitute for fish oil. Marine microbes such as Schizochytrium, Thraustochytrium, Schizochytrium kotsui have become several major strains of unsaturated fatty acid production.
  • Commonly used methods of decolorization of unsaturated fatty acid esters include: physical adsorption, chemical decolorization, membrane decolorization, light energy decolorization, ultrasonic assisted decolorization, etc.
  • the high-temperature stirring physical adsorption method commonly uses white clay with a small amount of activated carbon for decolorization. It has a large amount of decolorizing agent, a long decolorizing time, low utilization of the decolorizing agent, high temperature produces other harmful substances that affect product quality, and excessive use of decolorizing agent causes trace nutrients in oil Many problems such as material loss and poor stability.
  • the chemical decolorization method generally also has problems such as high requirements for reagents, narrow application range, cumbersome removal of impurities after decolorization, and hidden dangers of residual chemical substances.
  • the membrane decolorization method is clean and efficient, but its selectivity is not strong, the equipment cost is high, the regeneration is relatively difficult, and maintenance and maintenance are time-consuming and laborious, which is not conducive to large-scale long-term stable production.
  • the light energy decolorization method has a better effect on specific pigments, but the application range is narrower and the light energy quality requirements are higher. At present, it has not reached the standard for large-scale application. Ultrasound can play the role of decolorization of grease to a certain extent.
  • Microalgae have high pigment content, and the crude oil extracted from microalgae usually has a higher red light and appears brownish red.
  • DHA hair oil uses Lovibond colorimetric detection red value up to 15.0 or more.
  • the physical adsorption method is used to decolorize DHA hair oil, in order to obtain refined oils with lighter color and better quality, it is often adopted to increase the amount of decolorizing agent, extend the time of decolorization, increase the temperature of decolorization, increase the number of decolorization, etc. Traditional means.
  • the color index of the final product can be qualified, it will inevitably lead to low product refining yield, low utilization rate of decolorizing agent, excessive loss of beneficial nutrients (microtocopherol, sterol), harmful substances (hydroperoxidation products, trans fatty acids) , Polycyclic aromatic hydrocarbons, glycidyl esters, 3-MCPD, etc.) have problems such as enrichment, which affect the nutritional quality and food safety of oils and fats, which is contrary to the proper processing of edible oils and fats.
  • Unsaturated fatty acids generally have a quality risk, that is, they are easily oxidized, causing the oil to deteriorate too quickly and produce an unpleasant odor.
  • the generation of unpleasant odors can be basically attributed to the formation of aldehyde ketone quinone oxidation products.
  • Aldehyde quinone compounds can destroy the normal physiological functions of human cells, promote blood pressure increase, reduce the absorption efficiency of fat-soluble vitamins of the human body, and are very easy to cause cancer.
  • the presence of aldehyde quinone compounds in oils has brought great health to human health Impact.
  • the aldehyde ketone quinones in fats and oils can be classified as "volatile” or "non-volatile".
  • oils and fats Because the primary oxidation product produced by the oxidation of oils and fats is the main source of volatile aldehyde ketone quinone, its content in oils and fats can be expressed in terms of peroxide value, and volatile aldehyde ketone quinones can be obtained through standard refining processes such as deodorization processes well known in the industry Remove.
  • the non-volatile aldehyde ketone quinone has a relatively high boiling point, so it is more difficult to remove in fats and oils, which may cause durability problems.
  • the anisidine value of oils and fats is a standard measure for evaluating the content of oil and fat secondary oxidation products (aldehyde ketone quinone).
  • chromatography packings are various types of silica gel, but there are still fillers (silica gel) that are expensive and excessive adsorption performance leads to the loss and operation of trace nutrients in oils and fats. There are many problems such as harsh conditions (high operating pressure) and high equipment cost.
  • the deep red light has a limited ability to remove oil pigments
  • the use of fillers such as silica gel
  • the excess adsorption performance leads to the loss of oil and fat micronutrients (the product stability becomes poor)
  • the adsorption column pressure is high (Equipment cost is higher)
  • the regenerative performance of adsorbent is generally low in reuse rate.
  • CN101497026A discloses a decolorizer that reduces the anisidine value of soybean oil for injection.
  • the decolorizer has a high decolorization rate, but the ability to reduce the anisidine value using traditional high-temperature adsorption methods is limited, and it is difficult to deal with oils with anisidine value higher than 15.0. At high temperatures, there is still a risk of other harmful substances, and the decolorizer cannot be reused after use.
  • CN105542951A discloses the use of graphitized carbon as a solid-phase extraction column, which can effectively decolorize microalgal oil at normal temperature, avoiding the risks caused by traditional high-temperature adsorption, but its ability to handle the oil anisidine value is limited.
  • CN106978254A discloses a bleaching technology that incorporates chemical substances such as glycerol or potassium glycerol, which has a high efficiency of removing red light from oils and fats, but the chemical method requires multiple washings of the product after bleaching, which takes time and effort, and There are still hidden dangers to other aspects of product quality, and the ability to handle the anisidine value of oils and fats is also limited.
  • CN101879436A discloses a method for decolorizing DHA normal temperature column. It uses activated silica gel, diatomaceous earth, activated carbon and sucrose as a column to fill the column, and uses a solvent to elute at room temperature. This method can effectively reduce oil color and peroxide Value, but the processing raw material is alkaline refining, its color is relatively light, the decolorizing agent does not contain materials that absorb red light efficiently, the pressure is high when processing crude oil, it does not reflect the effect on the anisidine value, and the decolorizing agent is used It cannot be reused later.
  • CN103908946A discloses a method for preparing a mixed adsorbent, which can prepare a low anisidine value, low absorbance and low 3-MCPD oil for injection, wherein the raw materials used are lower anisidine value ( ⁇ 5.0) and low Absorbent grease (less than 0.1), which has a higher pressure when processing crude oil; the silica gel used is relatively expensive, the amount of adsorbent used is large, and cannot be reused; processing grease requires higher pressure, and the equipment requirements are higher when scaling up mass production ; The oxidation stability of the treated oil is relatively poor; therefore, the cost is higher in the mass production process of edible oil, and the application is more difficult.
  • the present invention aims to provide a new mixed adsorbent and its application and processing method and equipment for polyunsaturated fatty acids, so as to realize the physical reduction of the red light value and anisidine value of polyunsaturated fatty acids under normal temperature conditions, while ensuring the treatment
  • the cost is low and the difficulty of large-scale production and application is small.
  • Alumina and silica gel are commonly used strong polar adsorption fillers for chromatography purification. Compared with silica gel, alumina is cheap, easy to regenerate, and easy to control activity. However, the separation and purification of fatty acids is not suitable for the use of basic alumina; under neutral or slightly acidic conditions, the use of non-polar solvent elution, the comprehensive adsorption effect of silica gel is stronger than neutral or acidic alumina, so silica gel The removal ability of small molecule aldehyde ketone quinone is slightly stronger than alumina. But at the same time, silica gel has a stronger adsorption and retention effect on other nutrients (such as tocopherol) in the oil and fat will cause the loss of nutrients, and the adsorption performance of neutral or acidic alumina is relatively weak.
  • nutrients such as tocopherol
  • Activated clay is the decolorizing agent with the best oil decolorization effect on the market, but its large single batch dosage and relatively large viscosity make it difficult to filter, and the regeneration of clay is also difficult.
  • the zeolite molecular sieve used in the present invention is modified with a copper salt to carry a metal center adsorption site. After ultrasonic activation, it can produce strong adsorption and local catalysis for some active pigments and has a very strong processing ability for oil red light. It can reach the equivalent level of activated clay, and after multiple regenerations, the adsorbent still has the same level of treatment capacity for red light.
  • the column pressure is smaller than that of clay, which is an excellent substitute for clay.
  • the inventor of the present invention has surprisingly found that the use of copper salt modified zeolite molecular sieve in combination with neutral and/or acidic alumina, supplemented by ultrasonic activation, can greatly enhance the adsorption of aldehyde ketone quinone and The ability to remove red light (comparable to silica gel), at the same time has the advantages of low price, easy regeneration, small loss of other nutrients, and excellent product stability. Based on this, the present invention has been completed.
  • the present invention provides a mixed adsorbent, wherein the mixed adsorbent contains alumina and a copper salt modified zeolite molecular sieve, and the alumina is neutral alumina and/or acidic alumina.
  • the copper salt content in terms of copper oxide is 0.1-8.0 wt%.
  • the copper salt-modified zeolite molecular sieve is prepared according to the following method: the copper-containing compound is attached to the inner and outer surfaces of the porous zeolite molecular sieve, dried at 80 to 120°C, and then baked at 400 to 600°C for 2 to 10 hour.
  • the method of attaching the copper-containing compound to the inner and outer surfaces of the porous zeolite molecular sieve is a dipping method or an ion exchange method.
  • the copper-containing compound is selected from at least one of copper nitrate, copper sulfate, copper acetate and copper acetylacetonate.
  • the porous zeolite molecular sieve is selected from at least one of natural clinoptilolite molecular sieve, activated zeolite molecular sieve, sodium zeolite molecular sieve, high-silicon ZSM molecular sieve and mercerized molecular sieve.
  • the mixed adsorbent further contains at least one of clay, attapulgite, silica and activated carbon.
  • the content of alumina in the mixed adsorbent is 10-40 parts by weight
  • the content of the copper salt modified zeolite molecular sieve is 2-10 parts by weight
  • the contents of clay, attapulgite, silica, and activated carbon are each independent
  • the ground is 0.2 to 5 parts by weight.
  • the content of alumina in the mixed adsorbent is 25 to 35 parts by weight
  • the content of the copper salt modified zeolite molecular sieve is 3 to 9 parts by weight
  • the contents of clay, attapulgite, silica and activated carbon are independent of each other
  • the ground is 0.5 to 3 parts by weight.
  • the particle size of the alumina is 50-1000 mesh, more preferably 70-300 mesh.
  • the particle sizes of the copper salt-modified zeolite molecular sieve, clay, attapulgite, silica, and activated carbon are each independently 40 to 600 mesh, and more preferably each independently are 100 to 300 mesh.
  • the invention also provides the application of the mixed adsorbent as a decolorizing agent for polyunsaturated fatty acids and an anisidine value reducing agent.
  • the present invention also provides a method for processing polyunsaturated fatty acids.
  • the polyunsaturated fatty acids have a red light value of 4 or more and anisidine value of 3 or more determined by the Rovibond colorimetric method.
  • the method includes mixing the above
  • the adsorbent is subjected to ultrasonic activation pretreatment, and the resulting active adsorbent is used to decolorize the polyunsaturated fatty acid and reduce the anisidine value.
  • the method for processing polyunsaturated fatty acids includes the following steps:
  • Sample loading and elution dissolve the polyunsaturated fatty acids in a diluted solvent to prepare a sample loading solution, and then use the sample loading solution to load the active adsorption column under ultrasonic conditions The solvent in the active adsorption column is separated to obtain an effluent. After the sample is loaded, the elution solvent is used to elute the eluent, and the effluent and the eluent are mixed and then concentrated.
  • the total ultrasonic power is 20-100 w/L column volume
  • the ultrasonic frequency is 15-100 kHz
  • the temperature of the activation pretreatment is 30-60° C.
  • the time is 20-60 min .
  • the total ultrasonic power is 30-60 w/L column volume
  • the ultrasonic frequency is 20-60 kHz
  • the temperature of the activation pretreatment is 35-50° C.
  • the time is 30-40 min .
  • the weight ratio of the polyunsaturated fatty acid used in the preparation process of the loading liquid to the dilution solvent is 1: (0.5-3).
  • step (2) the solvent in the active adsorption column is separated by increasing the pressure in the active adsorption column to 0.02 to 0.2 MPa.
  • the total ultrasound power is 15-100 w/L column volume, and the ultrasound frequency is 15-100 kHz.
  • the column temperature of the active adsorption column is controlled at 30-60°C.
  • the amount of the elution solvent used is 1.2-4.0 times the column volume.
  • the dilution solvent is selected from at least one of n-hexane, cyclohexane, isohexane, isopentane, n-pentane and petroleum ether.
  • the elution solvent is selected from at least one of n-hexane, n-pentane and petroleum ether.
  • the polyunsaturated fatty acid processing method further includes a step of regenerating the adsorption column after the sample loading and elution steps.
  • the regeneration method includes: washing the adsorption column with a polar solvent under a pressure of 0.03 to 0.2 MPa under ultrasonic conditions.
  • the amount of the polar solvent is 1 to 4 times the column volume.
  • the polar solvent is at least one of acetone, methyl ethyl ketone, tetrahydrofuran and ethyl acetate, or a mixture of at least one of acetone, methyl ethyl ketone, tetrahydrofuran and ethyl acetate and the elution solvent.
  • the ultrasound conditions include a total power of 20-100 w/L column volume and a frequency of 15-100 kHz.
  • the temperature of the column washing is 15-65°C.
  • the present invention also provides a processing apparatus for polyunsaturated fatty acids, wherein the processing apparatus includes an adsorption column and a jacket disposed around the adsorption column, and there is a certain gap between the adsorption column and the jacket It is used to set an ultrasonic rod and store an ultrasonic medium.
  • the adsorption medium filled in the adsorption column is the above mixed adsorbent.
  • the ratio of the height of the adsorption medium filled in the adsorption column to the inner diameter of the adsorption column is (4-25):1.
  • the inner diameter of the jacket is 2 to 20 times the outer diameter of the adsorption column.
  • the ultrasonic rods are arranged around the adsorption column, and the number of the ultrasonic rods is 2-6.
  • the ultrasonic medium is selected from at least one of water, ethanol and thermal oil.
  • the mixed adsorbent provided by the present invention is used to treat polyunsaturated fatty acids, which can effectively reduce the red color of the crude oil under high temperature conditions, and greatly reduce the high boiling aldehyde ketone quinone in the crude oil (represented by anisidine value).
  • the advantages are as follows: (1) It still has strong processing capacity for high red light (Rovibon colorimetric method ⁇ 15.0) and high anisidine value ( ⁇ 15.0), and it has a wide universality; ( 2) It has good selectivity to pigments and high-boiling aldehyde ketone quinones, and can still retain trace amounts of tocopherols and sterols in some fats and oils to improve the stability of decolorized fats and oils; (3) The process pressure is lower, and the processing efficiency is higher.
  • FIG. 1 is a schematic structural diagram of a polyunsaturated fatty acid processing device provided by the present invention
  • FIG. 2 is a graph of the results of accelerated oxidation experiments of Examples 1 to 7 and Comparative Example 4, Comparative Example 6, and Comparative Example 7.
  • FIG. 2 is a graph of the results of accelerated oxidation experiments of Examples 1 to 7 and Comparative Example 4, Comparative Example 6, and Comparative Example 7.
  • the mixed adsorbent provided by the present invention contains alumina and a copper salt modified zeolite molecular sieve, and preferably further contains at least one of clay, attapulgite, silica and activated carbon.
  • the alumina is neutral alumina and/or Or acid alumina.
  • the mixed adsorbent may be used after uniformly mixing the components, or the components may be used in a layered and tiled manner.
  • the copper salt-modified zeolite molecular sieve uses porous zeolite molecular sieve as a raw material, and is a porous molecular sieve rich in divalent copper obtained after modification.
  • the divalent copper is preferably present in the form of copper oxide.
  • the copper salt-modified zeolite molecular sieve is prepared according to the following method: the copper-containing compound is attached to the inner and outer surfaces of the porous zeolite molecular sieve, and the molecular sieve is optionally washed with water until colorless, and then It is dried at 80 to 120°C, and then baked at 400 to 600°C for 2 to 10 hours.
  • the method of attaching the copper-containing compound to the inner and outer surfaces of the porous zeolite molecular sieve may be a dipping method or an ion exchange method.
  • the copper-containing compound may be organic copper or inorganic copper, and specific examples thereof include, but are not limited to, at least one of copper nitrate, copper sulfate, copper acetate, and copper acetylacetonate.
  • the porous zeolite molecular sieve has an extremely high internal surface area, and specific examples thereof include but are not limited to: at least one of natural clinoptilolite molecular sieve, activated zeolite molecular sieve, sodium zeolite molecular sieve, high-silicon ZSM molecular sieve, and mercerized molecular sieve Species.
  • the content of copper salt in terms of copper oxide is preferably 0.1 to 8.0% by weight.
  • the mixed adsorbent preferably contains 10 to 40 parts by weight of alumina, 2 to 10 parts by weight of copper salt-modified zeolite molecular sieve, and further contains 0.2 to 5 parts by weight of clay and/or 0.2 to 5 parts by weight of attapulgite. And/or 0.2 to 5 parts by weight of silica, and/or 0.2 to 5 parts by weight of activated carbon.
  • the mixed adsorbent contains 10 to 40 parts by weight of alumina, 2 to 10 parts by weight of copper salt modified zeolite molecular sieve, and further contains 0.5 to 5 parts by weight of clay, and/or 0.5 to 5 parts by weight of unevenness Clay soil, and/or 0.2 to 3 parts by weight of silica, and/or 0.2 to 5 parts by weight of activated carbon.
  • the mixed adsorbent contains 25 to 35 parts by weight of alumina, 3 to 9 parts by weight of copper salt modified zeolite molecular sieve, and further contains 0.5 to 3 parts by weight of white clay, and/or 0.5 to 3 parts by weight of unevenness Clay soil, and/or 0.5 to 3 parts by weight of silica, and/or 0.5 to 3 parts by weight of activated carbon.
  • the mixed adsorbent preferably contains 25 to 35 parts by weight of alumina, 3 to 9 parts by weight of copper salt modified zeolite molecular sieve, and further contains 1 to 3 parts by weight of white clay, and/or 1 to 3 parts by weight Attapulgite, and/or 1 to 2 parts by weight of silica, and/or 0.5 to 2 parts by weight of activated carbon.
  • the particle size of each component in the mixed adsorbent is not particularly limited.
  • the particle size of the alumina may be 50-1000 mesh, preferably 70-300 mesh.
  • the particle size of the copper salt-modified zeolite molecular sieve, clay, attapulgite, silica, and activated carbon may each independently be 40 to 600 mesh, preferably each independently be 100 to 300 mesh.
  • the invention also provides the application of the mixed adsorbent as a decolorizing agent for polyunsaturated fatty acids and an anisidine value reducing agent.
  • the present invention also provides a method for processing polyunsaturated fatty acids.
  • the polyunsaturated fatty acids have a red light value of 4 or more (preferably 7 to 40) and an anisidine value of 3 or more (preferably 8 to 30), wherein the method includes subjecting the mixed adsorbent to ultrasonic activation pretreatment, and using the obtained active adsorbent to decolor the polyunsaturated fatty acid and reduce the anisidine value.
  • the method for processing polyunsaturated fatty acids includes the following steps:
  • Sample loading and elution dissolve the polyunsaturated fatty acids in a diluted solvent to prepare a sample loading solution, and then use the sample loading solution to load the active adsorption column under ultrasonic conditions The solvent in the active adsorption column is separated to obtain an effluent. After the sample is loaded, the elution solvent is used to elute the eluent, and the effluent and the eluent are mixed and then concentrated.
  • the method for loading the mixed adsorbent into the adsorption column may be dry packing or wet packing.
  • the solvent used therein may be, for example, at least one of n-hexane, cyclohexane, isohexane, isopentane, n-pentane, and petroleum ether.
  • the ratio of the adsorption medium filled in the adsorption column to the inner diameter of the adsorption column may be (4-25):1, preferably (5-10):1.
  • step (1) when the mixed adsorbent is infiltrated with a solvent, ultrasound is turned on to perform activation pretreatment on the mixed adsorbent.
  • the total power of the ultrasound is calculated according to the volume of the adsorbent column, preferably 20 to 100 w/L column volume, more preferably 30 to 60 w/L column volume.
  • the ultrasonic frequency is preferably controlled at 15-100 kHz, and more preferably 20-60 kHz.
  • the temperature of the activation pretreatment is preferably 30 to 60°C, more preferably 35 to 50°C; the time is preferably 20 to 60 min, and more preferably 30 to 40 min.
  • step (2) most of the pigments in the polyunsaturated fatty acids, aldehyde ketone quinone, and a small amount of other nutrients will be adsorbed on the active adsorption column after loading, and after elution, a small part of the pigment and aldehyde Ketone quinone and almost all other nutrients will be desorbed from the active adsorption column, while most of the pigment and aldehyde ketone quinone will remain on the active adsorption column.
  • the weight ratio of the polyunsaturated fatty acid used in the preparation process of the loading liquid to the dilution solvent may be 1:((0.5-3).
  • Specific examples of the dilution solvent used here include but are not limited to : At least one of n-hexane, cyclohexane, isohexane, isopentane, n-pentane, and petroleum ether.
  • the method of separating the solvent in the active adsorption column may be standing for a long time to allow the solvent to flow naturally Dry, it can also be (using a metering pump or air pressure method) to increase the pressure in the active adsorption column to 0.02 ⁇ 0.2MPa, preferably to 0.03 ⁇ 0.1MPa to accelerate the flow of solvent out of the adsorption column, the latter is preferred to save time
  • the total ultrasonic power is calculated according to the adsorption column volume, preferably 15-100w/L column volume, more preferably 30-60w/L column volume.
  • the ultrasound frequency is preferably controlled at 15-100kHz, more preferably at 20- 60kHz.
  • the column temperature of the active adsorption column is preferably controlled at 30 to 60°C, more preferably at 40 to 50°C.
  • the elution solvent used Specific examples include, but are not limited to: at least one of n-hexane, n-pentane, and petroleum ether.
  • the amount of the elution solvent used is preferably 1.2 to 4.0 column volumes, and more preferably 1.5 to 2.5 column volumes.
  • the effluent and eluent are mixed and concentrated to remove the organic solvent, and then the target oil is obtained.
  • the method of concentration can be, for example, evaporation and concentration.
  • the eluted solvent can be collected and used for next sample loading. Adsorption.
  • the method for processing polyunsaturated fatty acids provided by the present invention preferably further includes the step of regenerating the adsorption column after the sample loading and elution steps.
  • the regeneration method includes: washing the adsorption column with a polar solvent under a pressure of 0.03 to 0.2 MPa under ultrasonic conditions.
  • the amount of the polar solvent is preferably 1 to 4 times the column volume, and more preferably 2 to 3 times the column volume.
  • the temperature of the column washing is preferably controlled at 15 to 65°C, more preferably at 30 to 50°C.
  • the total ultrasonic power is calculated according to the adsorption column volume, preferably 20 to 100 w/L column volume, more preferably 30 to 60 w/L column volume.
  • the ultrasonic frequency is preferably controlled at 15-100 kHz, and more preferably 20-60 kHz.
  • the polar solvent may be at least one of acetone, methyl ethyl ketone, tetrahydrofuran, and ethyl acetate, or a mixture of at least one of acetone, methyl ethyl ketone, tetrahydrofuran, and ethyl acetate, and the elution solvent.
  • the total amount of acetone, methyl ethyl ketone, tetrahydrofuran and ethyl acetate in the polar solvent is preferably 50-100 wt%, more preferably 60-90 wt%.
  • the processing equipment for polyunsaturated fatty acids provided by the present invention includes an adsorption column 1 and a jacket 2 disposed on the periphery of the adsorption column 1. There is a certain distance between the adsorption column 1 and the jacket 2 The gap is used for setting the ultrasonic rod 3 and storing the ultrasonic medium 4, and the adsorption medium 5 filled in the adsorption column 1 is the above mixed adsorbent.
  • the ratio of the height of the adsorption medium filled in the adsorption column 1 to the inner diameter of the adsorption column is preferably (4-25):1, and more preferably (5-10):1.
  • the inner diameter of the jacket is preferably 2 to 20 times the outer diameter of the adsorption column, and more preferably 10 to 18 times.
  • the ultrasonic rods are arranged around the adsorption column, and the number of the ultrasonic rods is preferably 2-6. When the number of the ultrasonic rods is more than 3, multiple ultrasonic rods are preferably distributed at equal intervals around the adsorption column.
  • the ultrasonic medium may be, for example, at least one selected from water, ethanol, and thermal oil, preferably water.
  • This preparation example is used to explain the preparation method of the copper salt modified zeolite molecular sieve provided by the present invention.
  • the natural clinoptilolite molecular sieve was immersed in an aqueous solution of copper nitrate with a concentration of 0.10 mol/L, and the molecular sieve was washed with deionized water to be colorless, then dried at 80°C, and then baked at 400°C for 10 hours to obtain copper Salt modified zeolite molecular sieve, referred to as S1.
  • the copper salt content in terms of copper oxide is 0.26 wt%.
  • This preparation example is used to explain the preparation method of the copper salt modified zeolite molecular sieve provided by the present invention.
  • the mercerized molecular sieve Immerse the mercerized molecular sieve in an aqueous solution of copper nitrate with a concentration of 0.20 mol/L, rinse the molecular sieve with deionized water until it is colorless, then dry at 120°C, and then roast at 600°C for 2 hours to obtain a copper salt Zeolite molecular sieve, which is referred to as S2. Based on the total weight of the copper salt-modified zeolite molecular sieve, the copper salt content in terms of copper oxide is 2.13 wt%.
  • This preparation example is used to explain the preparation method of the copper salt modified zeolite molecular sieve provided by the present invention.
  • Sodium zeolite molecular sieve was immersed in 0.12mol/L copper nitrate aqueous solution, and then the molecular sieve was washed with deionized water to be colorless, then dried at 100 °C, and then baked at 500 °C for 6 hours to obtain copper Salt modified zeolite molecular sieve, referred to as S3.
  • the copper salt content in terms of copper oxide is 1.34 wt%.
  • 20g activated silica gel, 5g mixture 1, 5g mixture 2, and 20g activated silica gel were packed in a wet order from the bottom to the top of the column in the above order. The column was washed with a pressure of 0.05MPa to compact the packing to obtain a decolorized column.
  • the oil and fat treatment method provided by the present invention can reduce the DHA/ARA crude oil Luoweipeng red light with red light and anisidine value of 15.0 or more to less than 0.5, and the anisidine value to within 3.0
  • the mixed adsorbent still has high adsorption activity.
  • the column pressure during adsorption and elution is only at the level of 0.03 ⁇ 0.05MPa.
  • the theoretical column pressure does not exceed 1.0MPa, and the general low-pressure chromatography equipment can meet the production requirements. .
  • the adsorption column pressure is better than that of the comparative example using a large amount of silica gel and clay.
  • the comprehensive performance of the three indicators of the treatment of oils in Examples 1-7 is significantly better than the three indicators of anisidine value, red light and stability.
  • Comparative examples 1-7 The change trend of the total oxidation value of the treated oil of Comparative Example 4 was significantly more dramatic, and the oxidation stability after 24 hours was significantly worse than that of Example 1, which was due to the excessive removal of micronutrients (such as tocopherol) in the oil and fat using silicone gel, resulting in the oil Relatively poor stability during long-term storage.
  • micronutrients such as tocopherol

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Abstract

La présente invention concerne le domaine du traitement d'acides gras polyinsaturés, et concerne ainsi un adsorbant hybride et une application de celui-ci, et un procédé et un équipement pour traiter un acide gras polyinsaturé. Ledit adsorbant hybride contient de l'oxyde d'aluminium et des tamis moléculaires à zéolite modifiés par un sel de cuivre, et contient de préférence en outre au moins l'un de l'argile, de l'attapulgite, du dioxyde de silicium et du charbon actif. L'oxyde d'aluminium est un oxyde d'aluminium neuronal et/ou un oxyde d'aluminium acide. L'adsorbant hybride fourni par la présente invention est complété par une activation ultrasonore, et par conséquent est comparable à un gel de silice dans les aspects de décoloration et d'élimination de cétone aldéhyde cétone, et ne conduira pas fondamentalement à la perte d'autres composants nutritionnels dans la graisse. En même temps, les avantages de faible coût, de régénération facile et de bonne stabilité du produit sont encore conservés.
PCT/CN2019/084573 2018-12-29 2019-04-26 Adsorbant hybride et son application, et procédé et équipement de traitement d'acide gras polyinsaturé WO2020133849A1 (fr)

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CN109569516B (zh) * 2018-12-29 2020-09-15 内蒙古金达威药业有限公司 一种混合吸附剂及其应用和多不饱和脂肪酸的处理方法和设备
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CN111534373B (zh) * 2020-03-24 2023-07-14 吉林省百利生物科技有限公司 一种降低植物油茴香胺值的方法
CN113150863A (zh) * 2021-02-04 2021-07-23 吉林省百利生物科技有限公司 一种采用大孔吸附树脂降低油脂茴香胺值的方法
CN115487780B (zh) * 2022-08-02 2023-09-22 山东省农业科学院作物研究所 一种小麦麸皮的综合利用方法

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