A method for isolating squalene from a plant oil deodorizer distillate

Abstract

The application discloses a method for separating squalene from a plant oil deodorization distillate, which comprises mixing the plant oil deodorization distillate containing squalene with a first solvent to obtain a raw material liquid, and performing fractional extraction on the raw material liquid by taking a second solvent as an extractant and a third solvent as a washing agent, wherein the first solvent is selected from one or more of non-polar solvents and weakly polar solvents, the second solvent is selected from one or more of polar solvents, and the third solvent is selected from one or more of non-polar solvents and weakly polar solvents. The fractional extraction method has the advantages of large processing capacity, high product purity and recovery rate, low energy consumption and cost, easy amplification and the like, and is suitable for industrial production.

Description

[0001] Cross-reference to related applications

[0002] This application claims priority to Chinese patent application No. CN 202311574408.5, filed on November 23, 2023, the entire contents of which are incorporated herein by reference. Technical Field

[0003] This application relates to the field of chemical engineering technology, and specifically to a method for separating squalene from deodorized vegetable oil distillates. Background Technology

[0004] Squalene is a tricarboxyhexaene containing six isoprene unsaturated bonds and belongs to the terpenoid class of compounds. Squalene possesses antioxidant, anticancer, anti-inflammatory, and antidiabetic activities, and is widely used in cosmetics, health products, and pharmaceuticals.

[0005] Deodorized distillate is a byproduct of steam distillation deodorization during vegetable oil refining, and its composition varies depending on the plant source and deodorization process. The main components of vegetable oil deodorization distillate (DD oil) are free fatty acids (30-60%), glycerides (10-20%), vitamin E (1-20%), phytosterols (10-30%), and a small amount of squalene. It is a good raw material for natural vitamin E, phytosterols, and fatty acids / esters; however, the squalene content is relatively low and extraction is difficult. Therefore, developing efficient separation and purification processes to extract squalene from plant deodorized distillates is an effective way to achieve the preparation of squalene from plant sources.

[0006] Currently, methods for separating squalene from deodorized vegetable oil distillates often employ a combination of processes. First, pretreatment methods such as esterification, cold precipitation / pressure filtration, and molecular distillation / multiple distillation (WO / 2010 / 004193 and CN102089263A) are used to separate some active components or impurities, obtaining a squalene-enriched raw material. For example, Chinese patent CN103483305B uses high-pressure crystallization combined with urea encapsulation to achieve rapid impurity removal and partial deacidification; after further deacidification, a mixture with high vitamin E and squalene content is obtained. Chinese patent CN107474093A discloses a method using enzymatic esterification, cold precipitation, and molecular distillation to couple the separation of vitamin E, sterols, methyl esters, glycerol, squalene, and high-boiling-point substances, but the squalene content is only 10-20%. Therefore, it is necessary to develop processes with high separation selectivity for squalene to obtain high-purity squalene.

[0007] Currently, high-purity squalene products can be obtained by multi-stage distillation (WO / 2010 / 004193, CN102089263A), multi-stage rectification (CN202211106716.0), adsorption separation (Chinese patents CN 105949025A, CN 103708992B), extraction (CN101830770B) and other methods. Chinese patent CN202211106716.0 discloses a method for obtaining phytosterols, squalene, natural vitamin E and fatty acid alkyl esters from plant deodorization distillate by esterification, cold separation / pressure filtration and multi-stage rectification. Rectification is a high-energy unit operation, and the rectification column temperature is relatively high (170-210℃), which can produce by-products and affect the yield. Chinese patent CN 105949025 A discloses a method for adsorbing and separating squalene in plant oil deodorization distillate by using D101 macroporous adsorption resin. Chinese patent CN 103708992B discloses a method for extracting squalene from plant oil deodorization distillate by two-stage column chromatography using basic anion exchange resin and silica gel as the fillers of the first and second stage chromatography columns, respectively. However, the squalene content in the product is about 50%, and the purity needs to be improved. Chinese patent CN101830770B uses plant oil deodorization distillate as raw material, and obtains phytosterols, squalene and mixed tocopherols by molecular distillation twice, combined with crystallization and extraction. The extraction section uses a liquid-liquid two-phase system composed of n-hexane and methanol, and the separation efficiency needs to be improved.

[0008] Extraction separation is a commonly used separation method in industry. Patent CN 106588542A discloses a method for separating squalene from valuable acid-free oil by single-stage liquid-liquid extraction of plant deodorization distillate to extract vitamin E and phytosterols, and by single-stage liquid-liquid extraction and decolorization, the squalene in the raffinate phase has a purity of 75-90%; patent CN103804337A uses plant oil deodorization distillate as raw material, and obtains light boiling point components containing vitamin E and squalene by esterification reaction, glycerolysis reaction and short path distillation, and then separates the two by multi-stage countercurrent liquid-liquid extraction, and obtains squalene with a content of 93.5% and a yield of 91.7% by low-temperature crystallization of the squalene-rich raffinate phase. Although the above methods can obtain squalene with improved purity, due to the limitations of single-stage liquid-liquid extraction and countercurrent liquid-liquid extraction operation modes, there are still problems of insufficiently high squalene purity and low yield. Therefore, it is urgent to develop a process route with low energy consumption, high processing capacity, high product yield, high product purity and easy scale-up for separating squalene from plant deodorization distillate. SUMMARY

[0009] In order to solve the problems of high cost, high operating temperature and large consumption of organic solvents in the existing extraction and separation of squalene from plant oil deodorization distillate, the present application provides a method for separating squalene from plant oil deodorization distillate.

[0010] To achieve the above object, the application provides a method for separating squalene from plant oil deodorization distillate by fractional extraction, which comprises mixing plant oil deodorization distillate containing squalene with a first solvent to obtain a raw material liquid, and performing fractional extraction on the raw material liquid by using a second solvent as an extractant and a third solvent as a washing agent.

[0011] The first solvent is selected from one or more of non-polar solvents and weakly polar solvents, the second solvent is selected from one or more of polar solvents, and the third solvent is selected from one or more of non-polar solvents and weakly polar solvents.

[0012] According to the structural differences between squalene and other components in the plant oil deodorization distillate, and in view of the fact that squalene has a thirty-carbon six-alkene structure and weak polarity, and the other components in the plant oil deodorization distillate such as tocopherol, glyceride, phytosterol and fatty acid contain one or more polar groups such as phenolic hydroxyl, ester group, hydroxyl group and carboxylic acid group, and the polarity of these substances is stronger than that of squalene. Therefore, in a liquid-liquid two-phase system constructed by non / weakly polar-polar solvents, squalene is easily distributed in the non-polar phase, and the components having polar groups are more easily dissolved in the polar solvent, so that selective separation of squalene is achieved. Meanwhile, the fractional extraction is composed of an extraction section and a washing section, and the introduction of the washing section can significantly improve the purity and recovery rate of the product, and is more suitable for industrial production.

[0013] In some embodiments, the application provides a method for separating squalene from plant oil deodorization distillate by fractional extraction, which comprises dissolving the plant oil deodorization distillate in a non-polar solvent, and performing fractional extraction by using a polar solvent as an extractant and the same washing agent as the raw material solvent.

[0014] Compared with the reported distillation / refining method, the extraction method has higher separation selectivity and lower energy consumption; compared with the reported adsorption chromatography method, the extraction method has the advantages of simple operation, easy continuous operation, low consumption of organic solvent and low cost; compared with single-stage liquid-liquid extraction and countercurrent liquid-liquid extraction, the fractional extraction is composed of an extraction section and a washing section, and the introduction of the washing section can significantly improve the purity and recovery rate of the product, and is suitable for industrial production.

[0015] In some embodiments, the plant oil deodorization distillate containing squalene comprises one or more of the following: full components of plant oil deodorization distillate or esterification products thereof, components of plant oil deodorization distillate or esterification products thereof from which tocopherol and / or phytosterol is removed, and components of plant oil deodorization distillate enriched in squalene.

[0016] In some embodiments, the squalene-containing vegetable oil deodorizer distillate is selected from a vegetable oil deodorizer distillate or a fraction of the vegetable oil deodorizer distillate depleted in tocopherols and / or phytosterols or a squalene-enriched vegetable oil deodorizer distillate.

[0017] In some embodiments, the feedstock is a squalene-containing vegetable oil deodorizer distillate, including a whole fraction of a vegetable oil deodorizer distillate, a fraction depleted in tocopherols and / or phytosterols, a squalene-enriched fraction, etc. In some preferred embodiments, to achieve the comprehensive utilization of the vegetable oil deodorizer distillate, the feedstock is one of a fraction depleted in tocopherols and / or phytosterols, a squalene-enriched fraction of a vegetable oil deodorizer distillate or a vegetable oil deodorizer distillate esterification product.

[0018] In some embodiments, the squalene-containing vegetable oil deodorizer distillate has a squalene content of 5 wt% to 50%, such as 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, or any value therebetween.

[0019] In some embodiments, the vegetable oil deodorizer distillate is selected from one or more of a soybean oil deodorizer distillate, a rice bran oil deodorizer distillate, a rapeseed oil deodorizer distillate, a camellia oil deodorizer distillate, and an olive oil deodorizer distillate.

[0020] In some embodiments, the non-polar and / or weakly polar solvent includes one or more of a linear alkane having a carbon number of 5 to 12, a branched alkane having a carbon number of 5 to 12, a cyclic saturated alkane having a carbon number of 5 to 12, a linear alkene having a carbon number of 5 to 12, a branched alkene having a carbon number of 5 to 12, and a cyclic alkene having a carbon number of 5 to 12.

[0021] In some embodiments, the non-polar and / or weakly polar solvent is selected from one or more of cyclopentane, n-hexane, cyclohexane, methylcyclohexane, iso-pentane, n-octane, iso-octane, n-decane, and 1-hexene.

[0022] In some embodiments, the non-polar and / or weakly polar solvent includes one of a linear, branched, and cyclic saturated hydrocarbon, an alkene having a carbon number of 5 to 12. In some preferred embodiments, the solvent is one of cyclopentane, n-hexane, cyclohexane, methylcyclohexane, iso-pentane, n-octane, iso-octane, n-decane, and 1-hexene.

[0023] In some embodiments, the first solvent includes one or more of a linear alkane having a carbon number of 5 to 12, a branched alkane having a carbon number of 5 to 12, a cyclic saturated alkane having a carbon number of 5 to 12, a linear alkene having a carbon number of 5 to 12, a branched alkene having a carbon number of 5 to 12, and a cyclic alkene having a carbon number of 5 to 12.

[0024] In some embodiments, the first solvent is selected from one or more of cyclopentane, n-hexane, cyclohexane, methylcyclohexane, iso-pentane, n-octane, iso-octane, n-decane, and 1-hexene.

[0025] In some embodiments, the first solvent comprises one of linear, branched, and cyclic saturated hydrocarbons, olefins having carbon number of 5-12. In some preferred embodiments, the first solvent is one of cyclopentane, n-hexane, cyclohexane, methylcyclohexane, iso-pentane, n-octane, iso-octane, n-decane, and 1-hexene.

[0026] In some embodiments, the concentration of the plant oil deodorizer distillate in the feedstock solution is from 0.1 g / L to 500 g / L, for example, 1 g / L, 5 g / L, 10 g / L, 20 g / L, 30 g / L, 40 g / L, 50 g / L, 60 g / L, 70 g / L, 80 g / L, 90 g / L, 100 g / L, 110 g / L, 120 g / L, 130 g / L, 140 g / L, 150 g / L, 160 g / L, 170 g / L, 180 g / L, 190 g / L, 200 g / L, 210 g / L, 220 g / L, 230 g / L, 240 g / L, 250 g / L, 260 g / L, 270 g / L, 280 g / L, 290 g / L, 300 g / L, 310 g / L, 320 g / L, 330 g / L, 340 g / L, 350 g / L, 360 g / L, 370 g / L, 380 g / L, 390 g / L, 400 g / L, 410 g / L, 420 g / L, 430 g / L, 440 g / L, 450 g / L, 460 g / L, 470 g / L, 480 g / L, 490 g / L, or any value therebetween.

[0027] In some embodiments, the concentration of the feedstock dissolved in the first solvent, for example, a non-polar solvent, to form the feedstock solution is from 0.1 g / L to 500 g / L, for example, 0.5 g / L, 6 g / L, 20 g / L, 100 g / L, 500 g / L, or any value therebetween. In some preferred embodiments, the concentration of the plant oil deodorizer distillate in the feedstock solution is from 5 g / L to 400 g / L.

[0028] In some embodiments, the method further comprises, after mixing the plant oil deodorizer distillate containing squalene with the first solvent, subjecting the mixture to a cooling process, filtering to obtain a filter cake and a filtrate, drying the filter cake to obtain a phytostanol mixture, and using the filtrate as a feedstock solution for subsequent fractionation extraction.

[0029] In some embodiments, the temperature after the cooling treatment is from -20 °C to 10 °C, for example -15 °C, -10 °C, -5 °C, 0 °C, 1 °C, 2 °C, 3 °C, 4 °C, 5 °C, 6 °C, 7 °C, 8 °C, 9 °C, or any value therebetween. In some embodiments, the temperature after the cooling treatment is from 0 °C to 7 °C.

[0030] In some embodiments, due to the low solubility of phytosterols in the starting material in the non / weak polar solvent, after sufficient stirring of the starting material with the starting material solvent, the starting material cannot be completely dissolved in the non / weak polar solvent. In this case, the insufficiently dissolved starting material solution is cooled to -20 °C to 10 °C, and after standing for 5 to 24 hours, the filtrate is collected for subsequent fractional extraction, and the filter cake is collected and dried to obtain a phytosterol mixture.

[0031] In some embodiments, the second solvent comprises one or more of water, an alcoholic polar solvent, a sulfone polar solvent, a ketone polar solvent, an amide polar solvent, a nitrile polar solvent, and a glyconal.

[0032] In some embodiments, the second solvent comprises a monopolar polar solvent and / or a dipolar polar solvent.

[0033] In some embodiments, the monopolar polar solvent is selected from one of water, an alcoholic polar solvent, a sulfone polar solvent, a ketone polar solvent, an amide polar solvent, a nitrile polar solvent, and a glyconal. In some embodiments, the monopolar polar solvent is selected from one of methanol, dimethyl sulfoxide, sulfolane, N-methyl pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, or furfural.

[0034] In some embodiments, the dipolar polar solvent is selected from any two of an alcoholic polar solvent, a sulfone polar solvent, a ketone polar solvent, an amide polar solvent, a nitrile polar solvent, and a glyconal. In some embodiments, the dipolar polar solvent is selected from two of methanol, dimethyl sulfoxide, sulfolane, N-methyl pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, or furfural.

[0035] In some embodiments, the dipolar polar solvent is selected from a mixed solvent comprising water, the mixed solvent comprising water and any one polar solvent selected from an alcoholic polar solvent, a sulfone polar solvent, a ketone polar solvent, an amide polar solvent, a nitrile polar solvent, and a glyconal.

[0036] In some embodiments, the mole fraction of water in the mixed solvent is less than or equal to 50%. In some embodiments, the binary polar solvent is selected from water and any one of polar solvents selected from methanol, dimethyl sulfoxide, sulfolane, N-methyl pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, and furfural.

[0037] In some embodiments, the polar solvent is selected from a monopolar polar solvent or a binary polar solvent. In some embodiments, the monopolar polar solvent includes water, alcohols, sulfones, ketones, amides, nitriles, furfural, and other organic solvents, and the binary solvent is a mixture of two of the above polar organic solvents or a mixture of one of the above polar organic solvents and water in any ratio. In some preferred embodiments, the monopolar solvent is one of methanol, dimethyl sulfoxide, sulfolane, N-methyl pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, and furfural, and the binary solvent is preferably a mixture of two of the above solvents in any ratio or a mixture of one of the above solvents and water with a mole fraction of water ≤ 50%.

[0038] In some embodiments, the third solvent includes one or more of a linear alkane having a carbon number of 5-12, a branched alkane having a carbon number of 5-12, a cyclic saturated alkane having a carbon number of 5-12, a linear alkene having a carbon number of 5-12, a branched alkene having a carbon number of 5-12, and a cyclic alkene having a carbon number of 5-12.

[0039] In some embodiments, the third solvent is selected from one or more of cyclopentane, n-hexane, cyclohexane, methylcyclohexane, iso-pentane, n-octane, iso-octane, n-decane, and 1-hexene.

[0040] In some embodiments, the washing agent includes one or more of a linear alkane having a carbon number of 5-12, a branched alkane having a carbon number of 5-12, a cyclic saturated alkane having a carbon number of 5-12, a linear alkene having a carbon number of 5-12, a branched alkene having a carbon number of 5-12, and a cyclic alkene having a carbon number of 5-12.

[0041] In some embodiments, the washing agent is selected from one or more of cyclopentane, n-hexane, cyclohexane, methylcyclohexane, iso-pentane, n-octane, iso-octane, n-decane, and 1-hexene.

[0042] In some embodiments, the washing agent is the same as the first solvent.

[0043] In some embodiments, in the fractional extraction, the flow ratio of the feed liquid to the extractant is 1:(0.1-30), for example 1:0.5, 1:1, 1:3, 1:5, 1:7, 1:10, 1:11, 1:13, 1:15, 1:17, 1:20, 1:21, 1:23, 1:25, 1:27, or any value therebetween.

[0044] In some embodiments, in the fractional extraction, the flow ratio of the feed liquid to the washing agent is 1:(0.01-10), for example 1:0.03, 1:0.05, 1:0.07, 1:0.1, 1:0.3, 1:0.5, 1:0.7, 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, 1:5, 1:5.5, 1:6, 1:6.5, 1:7, 1:7.5, 1:8, 1:8.5, 1:9, 1:9.5, or any value therebetween. In some embodiments, in the fractional extraction, the flow ratio of the feed liquid to the washing agent is 1:(0.01-5). In some embodiments, in the fractional extraction, the flow ratio of the feed liquid to the washing agent is 1:(0.01-1).

[0045] In some embodiments, in the fractional extraction, the flow ratio of the feed liquid, the extractant, and the washing agent is 1:(0.1-30):(0.01-10) in consideration of the purity of the product, the recovery rate, the production cost, and the like. In some preferred embodiments, the flow ratio of the feed liquid, the extractant, and the washing agent is 1:(1-20):(0.05-5). In some preferred embodiments, the flow ratio of the feed liquid, the extractant, and the washing agent is 1:(1-20):(0.05-1).

[0046] The flow ratio in the present application refers to the volume ratio of each component.

[0047] In some embodiments, the operation temperature of the fractional extraction is 20-70°C, for example 20°C, 30°C, 40°C, 50°C, 60°C, 70°C, or any value therebetween. If the temperature is too low, the viscosity of the feed liquid is large at the concentration, and the mass transfer rate is reduced; if the temperature is too high, the solvent volatilizes seriously, and the separation effect is affected. It is worth noting that the operation temperature cannot be higher than the boiling point of the selected non / weak polar solvent and polar solvent.

[0048] In some embodiments, the method further comprises concentrating the raffinate of the fractional extraction, and the liquid phase obtains the recyclable feed first solvent and / or washing agent, and the solid phase, after drying, obtains squalene.

[0049] In some embodiments, the method further comprises subjecting the raffinate of the fractional extraction to a separation process selected from vacuum concentration, flash evaporation, or back extraction to obtain recyclable extractant and squalene-depleted plant oil deodorizer distillate.

[0050] In some embodiments, the method further comprises subjecting the raffinate of the fractional extraction to vacuum concentration, drying to obtain squalene; subjecting the extract of the fractional extraction to vacuum concentration / flash evaporation / back extraction with the same solvent as the feedstock solvent and the washing agent to recover the extractant and recycle it.

[0051] In some embodiments, the fractional extraction is a multi-stage fractional extraction. In some embodiments, the fractional extraction is performed in a fractional extraction setup. In some embodiments, the fractional extraction setup comprises an extraction section and a washing section.

[0052] In some embodiments, the extraction section has a theoretical stage number of 4-20 stages, such as 5 stages, 6 stages, 7 stages, 8 stages, 9 stages, 10 stages, 11 stages, 12 stages, 13 stages, 14 stages, 15 stages, 16 stages, 17 stages, 18 stages, or 19 stages. In some embodiments, the washing section has a theoretical stage number of 2-15 stages, such as 2 stages, 3 stages, 4 stages, 5 stages, 6 stages, 7 stages, 8 stages, 9 stages, 10 stages, 11 stages, 12 stages, 13 stages, or 14 stages.

[0053] In some embodiments, the extractant enters the fractional extraction system from the first stage of the extraction section, the feedstock enters the fractional extraction system from the last stage of the extraction section, the washing agent enters the fractional extraction system from the first stage of the washing section, the feedstock from the last stage of the extraction section is combined and enters the extraction section at the last stage of the extraction section, the extraction phase and the washing phase are subjected to multi-stage countercurrent contact, the raffinate enriched in squalene flows out from the first stage of the extraction section, the raffinate is collected, and the raffinate is preferably subjected to vacuum concentration-drying to obtain squalene and recyclable non-polar / weakly polar solvent (the first solvent and / or the washing agent); the extract enriched in other components of the plant oil deodorizer distillate flows out from the first stage of the washing section, and the extract is preferably subjected to vacuum concentration / flash evaporation / back extraction to recover the extractant and recycle it.

[0054] In some embodiments, the squalene obtained by the method has an absolute purity and a yield of >92 wt.%, and in some preferred embodiments, the squalene obtained has an absolute purity and a yield of >95 wt.%.

[0055] In some embodiments, the method comprises the following steps:

[0056] (1) The plant oil deodorization distillate containing squalene is mixed with a raw material solvent (first solvent) to form a raw material solution. If the raw material cannot be completely dissolved, the mixture is cooled and filtered, and the filtrate is collected for subsequent fractional extraction. Fractional extraction is carried out using a monopolar or bipolar polar solvent as an extractant and the same solvent as the raw material solvent as a washing agent. The fractional extraction is divided into an extraction section and a washing section. The extractant enters the fractional extraction system from the first stage of the extraction section, and the raw material solution enters the fractional extraction system from the last stage of the extraction section. The washing agent enters the fractional extraction system from the first stage of the washing section. The raw material solution is combined with the extractant and enters the extraction section from the last stage of the extraction section. The extraction phase and the washing phase are in multi-stage countercurrent contact. The squalene-enriched raffinate flows out from the first stage of the extraction section, and the extraction liquid enriched in other components of the plant oil deodorization distillate flows out from the first stage of the washing section.

[0057] (2) The raffinate in step (1) is vacuum concentrated and dried to obtain squalene and recyclable raw material solvent. The extraction liquid in step (1) is vacuum concentrated / flash evaporated / counter-extracted with the same solvent as the raw material solvent and the washing agent to obtain recyclable extractant and squalene-removed plant oil deodorization distillate.

[0058] The advantages of the present application are:

[0059] 1. The present application is based on the polarity difference caused by the structural difference of squalene and phytosterols, tocopherols, and fatty esters in plant oil deodorization distillate. Fractional extraction is carried out in a liquid-liquid two-phase system composed of non / weak polar solvent-polar solvent, which has good separation selectivity for weakly polar squalene.

[0060] 2. The process route proposed in the present application has a simple process flow, low energy consumption, high recovery rate and purity of squalene, large processing capacity, and is easy to scale up.

[0061] 3. The present application preferably uses plant oil deodorization distillate waste with removed tocopherols and / or phytosterols as raw material. High-purity squalene is obtained, and phytosterols in plant oil distillate can be recovered, realizing the comprehensive utilization of plant oil deodorization distillate. DETAILED DESCRIPTION

[0062] The present application provides a method for separating squalene from plant oil deodorization distillate with large processing capacity, simple process flow, high product purity and recovery rate. The method is based on the polarity difference of squalene and other components, and constructs a liquid-liquid two-phase system composed of non / weak polar solvent and polar solvent for fractional extraction. Weakly polar squalene is enriched in the non / weak polar solvent phase, and other components with higher polarity are enriched in the polar solvent phase, realizing molecular recognition separation of squalene in plant oil deodorization distillate.

[0063] The present application will be further described in conjunction with specific examples. It should be understood that these examples are only used to illustrate but not to limit the scope of protection of the present application.

[0064] In the following examples, high performance liquid chromatography (HPLC) was used to analyze the concentration of each component in the plant oil deodorization distillate. The specific HPLC analysis conditions were as follows: Waters Sunfire C18 column (4.6 mm x 250 mm, particle size 5 μm), column temperature 30 °C, mobile phase methanol: isopropanol: formic acid = 9:1:0.001 (volume ratio), flow rate 1 mL / min; detector ultraviolet detector and / or universal electrospray detector (Thermo Fisher), wherein the ultraviolet detector wavelength was set to 205 nm and 292 nm, which were the maximum ultraviolet absorption wavelengths of squalene and tocopherol, respectively.

[0065] In the following examples, the calculation method of the purity and recovery of squalene was as follows:

[0066] Purity = mass of squalene in product / total mass of product x 100%

[0067] Yield = total mass of squalene in product / total mass of squalene in raw material x 100%

[0068] Example 1

[0069] Using the deodorization distillate of soybean oil from which tocopherol was removed (squalene content 26.0 wt%) as raw material, the raw material was mixed with n-hexane to form a raw material solution of 50 g / L. The raw material was not completely dissolved. The raw material solution was cooled to 4 °C and stood for 12 hours. After filtration, the filter cake was washed twice with a small amount of ice n-hexane and then vacuum dried to obtain phytosterol.

[0070] The filtrate was collected. Dimethyl sulfoxide was used as the extractant and n-hexane as the washing agent. The flow ratio of the raw material solution, the extractant and the washing agent was 1:8.1:0.3 (v / v / v). Fractionation extraction was carried out at 30 °C. The theoretical stage number of the extraction section and the washing section was 8 and 4, respectively. The extractant entered the fractionation extraction device from the first stage of the extraction section, the raw material solution entered the last stage of the extraction section, and the washing agent entered the first stage of the washing section. The squalene-rich raffinate flowed out from the first stage of the extraction section, and the extract liquid rich in other components flowed out from the first stage of the washing section. The extract liquid and the raffinate were collected separately.

[0071] The raffinate was vacuum concentrated. The solvent (raw material solvent) was collected for recycling. The solid phase was collected and dried to obtain squalene product. The purity of squalene was 96.3 wt% and the recovery was 94.4%. The extract liquid was vacuum concentrated. The organic solvent (extractant) was collected for recycling.

[0072] Example 2

[0073] Example 1

[0074] The raffinate was concentrated under vacuum, and the solvent (the solvent of the raw material) was collected for recycling. The solid phase was collected and dried to obtain the squalene product. The purity of the squalene was 93.1 wt%, and the recovery rate was 92.5%. The extract was concentrated under vacuum, and the organic solvent (the extractant) was collected for recycling.

[0075] Example 3

[0076] The soybean oil deodorization distillate (in which the squalene content was 26.0 wt%) was used as the raw material, and was mixed with 1-octene to prepare a raw material solution with a concentration of 5 g / L. The raw material was completely dissolved. Acetonitrile was used as the extractant, and 1-octene was used as the washing agent. The flow ratio of the raw material solution, the extractant, and the washing agent was 1:18.2:0.08 (v / v / v). Fractional extraction was performed at 20°C. The theoretical stage number of the extraction section and the washing section was 15 and 2, respectively. The extractant entered the fractional extraction device from the first stage of the extraction section, the raw material solution entered the fractional extraction device from the last stage of the extraction section, and the washing agent entered the fractional extraction device from the first stage of the washing section. The raffinate rich in squalene flowed out from the first stage of the extraction section, and the extract rich in other components flowed out from the first stage of the washing section. The extract and the raffinate were collected separately.

[0077] The raffinate was concentrated under vacuum, and the solvent (the solvent of the raw material) was collected for recycling. The solid phase was collected and dried to obtain the squalene product. The purity of the squalene was 95.3 wt%, and the recovery rate was 94.0%. The extract was concentrated under vacuum, and the organic solvent (the extractant) was collected for recycling.

[0078] Example 4

[0079] Example 1

[0080] The raffinate was concentrated under vacuum, and the solvent (the solvent of the raw material) was collected for recycling. The solid phase was collected and dried to obtain the squalene product. The purity of the squalene was 94.6 wt%, and the recovery rate was 95.2%. The extract was concentrated under vacuum, and the organic solvent (the extractant) was collected for recycling.

[0081] Example 5

[0082] The squalene-enriched amaranth oil deodorization distillate (in which the squalene content was 40.3 wt%) was used as the raw material, which was mixed with methylcyclohexane to form a raw material solution of 200 g / L, and the raw material was completely dissolved. Furfural was used as the extractant, and methylcyclohexane was used as the washing agent. The flow ratio of the raw material solution, the extractant, and the washing agent was 1:11:1 (v / v / v). Fractional extraction was carried out at 25°C. The theoretical stage number of the extraction section and the washing section was 16 and 12, respectively. The extractant entered the fractional extraction device from the first stage of the extraction section, the raw material solution entered the last stage of the extraction section, and the washing agent entered the first stage of the washing section. The squalene-rich raffinate flowed out from the first stage of the extraction section, and the extract solution rich in other components flowed out from the first stage of the washing section. The extract solution and the raffinate were collected separately.

[0083] The raffinate was concentrated under vacuum, and the solvent (the solvent of the raw material) was collected for recycling. The solid phase was collected and dried to obtain the squalene product. The purity of the squalene was 94.6 wt%, and the recovery rate was 95.2%. The extract was concentrated under vacuum, and the organic solvent (the extractant) was collected for recycling.

[0084] Example 6

[0085] The raw material was the phytosterol-removed rice bran oil deodorization distillate (in which the squalene content was 24.0 wt%). The raw material was mixed with n-octane to form a raw material solution of 400 g / L, and the raw material was not completely dissolved. The raw material solution was cooled to 4°C, and then stood for 12 hours. After filtration, the filter cake was washed twice with a small amount of ice n-octane, and then vacuum dried to obtain phytosterol.

[0086] The filtrate was collected, and the aqueous acetonitrile solution with a water mole fraction of 5% was used as the extractant, and n-octane was used as the washing agent. The flow ratio of the raw material solution, the extractant, and the washing agent was 1:20:0.7 (v / v / v). Fractional extraction was carried out at 55°C, and the theoretical stage number of the extraction section and the washing section was 19 and 6, respectively. The extractant entered the fractional extraction device from the first stage of the extraction section, the raw material solution entered the fractional extraction device from the last stage of the extraction section, and the washing agent entered the fractional extraction device from the first stage of the washing section. The raffinate rich in squalene flowed out from the first stage of the extraction section, and the extract rich in other components flowed out from the first stage of the washing section. The extract and the raffinate were collected, respectively.

[0087] The raffinate was concentrated under vacuum, and the solvent (the raw material solvent) was collected for recycling. The solid phase was collected and dried to obtain the squalene product. The purity of the squalene was 93.1 wt%, and the recovery rate was 93.4%. The extract was concentrated under vacuum, and the organic solvent (the extractant) was collected for recycling.

[0088] Example 7

[0089] The soybean oil deodorization distillate from which tocopherols were removed (the squalene content of which was 24.0 wt%) was used as the raw material, and the raw material solution was prepared by mixing the raw material with n-hexane to a concentration of 400 g / L. The raw material was not completely dissolved. The raw material solution was cooled to 4°C, and was allowed to stand for 12 hours. Filtration was performed, and the filter cake was washed twice with a small amount of ice n-hexane and was then dried under vacuum to obtain phytosterols.

[0090] The filtrate was collected, and the aqueous acetonitrile solution with a water mole fraction of 5% was used as the extractant, and n-hexane was used as the washing agent. The flow ratio of the raw material solution, the extractant, and the washing agent was 1:20:1 (v / v / v). Fractional extraction was carried out at 30°C. The theoretical stage number of the extraction section and the washing section was 19 and 6, respectively. The extractant entered the fractional extraction device from the first stage of the extraction section, the raw material solution entered the fractional extraction device from the last stage of the extraction section, and the washing agent entered the fractional extraction device from the first stage of the washing section. The raffinate rich in squalene flowed out from the first stage of the extraction section, and the extract rich in other components flowed out from the first stage of the washing section. The extract and the raffinate were collected, respectively.

[0091] The raffinate was concentrated under vacuum, and the solvent (the raw material solvent) was collected for recycling. The solid phase was collected and dried to obtain the squalene product. The purity of the squalene was 92.7 wt%, and the recovery rate was 94.5%. The extract was concentrated under vacuum, and the organic solvent (the extractant) was collected for recycling.

[0092] Example 8

[0093] The soybean oil deodorization distillate from which tocopherols were removed (the squalene content of which was 24.0 wt%) was used as the raw material, and the raw material solution was prepared by mixing the raw material with n-hexane to a concentration of 400 g / L. The raw material was not completely dissolved. The raw material solution was cooled to 4°C, and was allowed to stand for 12 hours. Filtration was performed, and the filter cake was washed twice with a small amount of ice n-hexane and was then dried under vacuum to obtain phytosterols.

[0094] The filtrate was collected, and the aqueous acetonitrile solution with a water mole fraction of 5% was used as the extractant, and n-hexane was used as the washing agent. The flow ratio of the raw material solution, the extractant, and the washing agent was 1:10:0.7 (v / v / v), and the fractional extraction was carried out at 30°C. The theoretical stage number of the extraction section and the washing section was 19 and 6, respectively. The extractant entered the fractional extraction device from the first stage of the extraction section, the raw material solution entered the last stage of the extraction section, and the washing agent entered the first stage of the washing section. The raffinate rich in squalene flowed out from the first stage of the extraction section, and the extract rich in other components flowed out from the first stage of the washing section. The extract and the raffinate were collected, respectively.

[0095] The raffinate was concentrated under vacuum, the solvent (the raw material solvent) was collected for recycling, and the solid phase was collected and dried to obtain the squalene product. The purity of the squalene was 90.1 wt%, and the recovery rate was 98.6%. The extract was concentrated under vacuum, and the organic solvent (the extractant) was collected for recycling.

[0096] Example 9

[0097] The filtrate was collected, and the aqueous acetonitrile solution with a water mole fraction of 5% was used as the extractant, and n-hexane was used as the washing agent. The flow ratio of the raw material solution, the extractant, and the washing agent was 1:10:0.7 (v / v / v), and the fractional extraction was carried out at 30°C. The theoretical stage number of the extraction section and the washing section was 19 and 6, respectively. The extractant entered the fractional extraction device from the first stage of the extraction section, the raw material solution entered the last stage of the extraction section, and the washing agent entered the first stage of the washing section. The raffinate rich in squalene flowed out from the first stage of the extraction section, and the extract rich in other components flowed out from the first stage of the washing section. The extract and the raffinate were collected, respectively.

[0098] The filtrate was collected, and the aqueous acetonitrile solution with a water mole fraction of 5% was used as the extractant, and n-hexane was used as the washing agent. The flow ratio of the raw material solution, the extractant, and the washing agent was 1:10:0.7 (v / v / v), and the fractional extraction was carried out at 30°C. The theoretical stage number of the extraction section and the washing section was 19 and 6, respectively. The extractant entered the fractional extraction device from the first stage of the extraction section, the raw material solution entered the last stage of the extraction section, and the washing agent entered the first stage of the washing section. The raffinate rich in squalene flowed out from the first stage of the extraction section, and the extract rich in other components flowed out from the first stage of the washing section. The extract and the raffinate were collected, respectively.

[0099] The raffinate was concentrated under vacuum, the solvent (the raw material solvent) was collected for recycling, and the solid phase was collected and dried to obtain the squalene product. The purity of the squalene was 92.0 wt%, and the recovery rate was 94.5%. The extract was concentrated under vacuum, and the organic solvent (the extractant) was collected for recycling.

[0100] Example 10

[0101] The phytosterol was obtained from the tocol-removed soybean oil deodorization distillate (squalene content 24.0 wt%) by dissolving it in n-hexane to form a feed solution of 400 g / L, the feed solution was cooled to 4 ℃ and stood for 12 hours, then filtered, the filter cake was washed twice with a small amount of ice n-hexane and dried under vacuum.

[0102] The filtrate was collected, and the water solution of acetonitrile with a mole fraction of water of 5% was used as the extractant, n-hexane was used as the washing agent, the flow ratio of the feed solution, the extractant and the washing agent was 1:20:0.7 (v / v / v), and the fractional extraction was carried out at 30 ℃. The theoretical stage number of the extraction section and the washing section was 12 and 8 respectively. The extractant entered the fractional extraction device from the first stage of the extraction section, the feed solution entered the last stage of the extraction section, and the washing agent entered the first stage of the washing section. The raffinate rich in squalene flowed out from the first stage of the extraction section, and the extract rich in other components flowed out from the first stage of the washing section. The extract and the raffinate were collected respectively.

[0103] The raffinate was concentrated under vacuum, the solvent (the feed solvent) was collected for recycling, the solid phase was collected and dried to obtain the squalene product, the purity of the squalene was 93.0 wt%, and the recovery rate was 90.6%. The extract was concentrated under vacuum, and the organic solvent (the extractant) was collected for recycling.

[0104] Example 11

[0105] The phytosterol was obtained from the tocol-removed soybean oil deodorization distillate (squalene content 24.0 wt%) by dissolving it in n-hexane to form a feed solution of 400 g / L, the feed solution was cooled to 4 ℃ and stood for 12 hours, then filtered, the filter cake was washed twice with a small amount of ice n-hexane and dried under vacuum.

[0106] The filtrate was collected, and the water solution of acetonitrile with a mole fraction of water of 5% was used as the extractant, n-hexane was used as the washing agent, the flow ratio of the feed solution, the extractant and the washing agent was 1:20:0.7 (v / v / v), and the fractional extraction was carried out at 30 ℃. The theoretical stage number of the extraction section and the washing section was 12 and 8 respectively. The extractant entered the fractional extraction device from the first stage of the extraction section, the feed solution entered the last stage of the extraction section, and the washing agent entered the first stage of the washing section. The raffinate rich in squalene flowed out from the first stage of the extraction section, and the extract rich in other components flowed out from the first stage of the washing section. The extract and the raffinate were collected respectively.

[0107] The raffinate was concentrated under vacuum, the solvent (the feed solvent) was collected for recycling, the solid phase was collected and dried to obtain the squalene product, the purity of the squalene was 93.0 wt%, and the recovery rate was 90.6%. The extract was concentrated under vacuum, and the organic solvent (the extractant) was collected for recycling.

[0108] Comparative Example 1

[0109] The squalene content of the deodorized soya oil distillate was 26.0 wt%. The distillate was dissolved in n-hexane to form a feed solution with a concentration of 50 g / L. The feed solution was cooled to 4°C and allowed to stand for 12 hours. The solution was filtered and the filter cake was washed twice with a small amount of ice-cold n-hexane and then dried under vacuum to obtain the phytosterols.

[0110] The filtrate was collected and subjected to fractional extraction with dimethyl sulfoxide as the extractant at 30°C. The flow ratio of the feed solution to the extractant was 1:8.1 (v / v). The theoretical stage number of the extraction section was 8. The extractant entered the extraction section at the first stage and the feed solution entered the extraction section at the last stage. The raffinate rich in squalene flowed out of the first stage of the extraction section and the extract rich in other components flowed out of the last stage of the extraction section. The extract and the raffinate were collected separately.

[0111] The raffinate was concentrated under vacuum and the solvent (the feed solvent) was collected for recycling. The solid phase was collected and dried to obtain the squalene product. The purity of the squalene was 90.1 wt% and the recovery rate was 70.1%. The extract was concentrated under vacuum and the organic solvent (the extractant) was collected for recycling.

[0112] The above examples are only used to illustrate the technical solutions of the present application, and not to limit the present application; although the present application has been described in detail with reference to the above examples, those skilled in the art should understand that they can still modify the technical solutions described in the above examples, or make equivalent replacements for part or all of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the present application.

Claims

1. A method for separating squalene from deodorized vegetable oil distillate, comprising mixing the squalene-containing deodorized vegetable oil distillate with a first solvent to obtain a feed liquid, and fractionally extracting the feed liquid using a second solvent as an extractant and a third solvent as a washing agent. in, The first solvent is selected from one or more of cyclopentane, n-hexane, cyclohexane, methylcyclohexane, isopentane, n-octane, isooctane, n-decane, and 1-hexene. The second solvent includes a monoprotic polar solvent and / or a binary polar solvent. The monoprotic polar solvent is selected from one of dimethyl sulfoxide, sulfolane, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, or furfural. The binary polar solvent is selected from two of methanol, dimethyl sulfoxide, sulfolane, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, or furfural. Alternatively, the binary polar solvent is selected from a mixture of water and acetonitrile. The third solvent is selected from one or more of cyclopentane, n-hexane, cyclohexane, methylcyclohexane, isopentane, n-octane, isooctane, n-decane, and 1-hexene; The squalene-containing deodorized vegetable oil distillate is the component of the deodorized vegetable oil distillate or its esterification product from which tocopherols or both tocopherols and phytosterols have been removed.

2. The method according to claim 1, characterized in that, The deodorized vegetable oil distillate is selected from one or more of the following: soybean oil deodorized distillate, rice bran oil deodorized distillate, rapeseed oil deodorized distillate, camellia oil deodorized distillate, and olive oil deodorized distillate.

3. The method according to any one of claims 1-2, characterized in that, The concentration of the deodorized vegetable oil distillate in the feed liquid is 0.1 g / L-500 g / L.

4. The method according to any one of claims 1-2, characterized in that, The concentration of the deodorized vegetable oil distillate in the feed liquid is 5 g / L-400 g / L.

5. The method according to any one of claims 1-2, characterized in that, The method further includes mixing the deodorized distillate of vegetable oil containing squalene with a first solvent, then cooling and filtering it to obtain a filter cake and a filtrate. The filter cake is dried to obtain a mixture of phytosterols, and the filtrate is used as a raw material for subsequent fractional distillation and extraction.

6. The method according to claim 5, characterized in that, The temperature after the cooling treatment is -20℃ to 10℃.

7. The method according to claim 5, characterized in that, The temperature after the cooling treatment is 0°C to 7°C.

8. The method according to any one of claims 1-2, characterized in that, In the mixed solvent, the molar fraction of water is less than or equal to 50%.

9. The method according to any one of claims 1-2, characterized in that, The third solvent is the same as the first solvent.

10. The method according to any one of claims 1-2, characterized in that, In the fractional extraction, the flow ratio of the feed liquid, extractant, and detergent is 1:(0.1-30):(0.01-10).

11. The method according to any one of claims 1-2, characterized in that, In the fractional extraction, the flow ratio of the feed liquid, extractant, and detergent is 1:(1-20):(0.05-5).

12. The method according to any one of claims 1-2, characterized in that, The operating temperature for the fractionation extraction is 20℃-70℃.

13. The method according to any one of claims 1-2, characterized in that, The method further includes: The raffinate from the fractional extraction is concentrated, and the liquid phase yields a recyclable first solvent and / or detergent. The solid phase is dried to obtain squalene; and / or The extract from the fractionation extraction is separated to obtain a recyclable extractant and a deodorized vegetable oil distillate free of squalene. The separation process is selected from vacuum concentration, flash evaporation, or back extraction.

14. The method according to claim 13, characterized in that, In the back-extraction, the extractant is selected from the same solvent as the first solvent and / or detergent.