CN112048380B - Method for accurately controlling stearic acid content in soybean oil by adopting mixed filler - Google Patents
Method for accurately controlling stearic acid content in soybean oil by adopting mixed filler Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B3/00—Refining fats or fatty oils
- C11B3/003—Refining fats or fatty oils by enzymes or microorganisms, living or dead
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- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B3/00—Refining fats or fatty oils
- C11B3/008—Refining fats or fatty oils by filtration, e.g. including ultra filtration, dialysis
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- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
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- C11B3/00—Refining fats or fatty oils
- C11B3/02—Refining fats or fatty oils by chemical reaction
- C11B3/06—Refining fats or fatty oils by chemical reaction with bases
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- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B3/00—Refining fats or fatty oils
- C11B3/10—Refining fats or fatty oils by adsorption
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Abstract
The invention belongs to the technical field of medicinal oil refining, and discloses a method for accurately controlling the stearic acid content in soybean oil by adopting mixed filler, which comprises the following steps: A. uniformly mixing lipase, inorganic base, filter aid and adsorbent in a physical mode to form mixed filler, wherein the lipase is Sn-1, 3-site specific lipase; B. and (3) allowing soybean oil to flow through the mixed filler to obtain refined soybean oil. The invention solves the problems that the traditional soybean oil production process can not accurately control the content of stearic acid and can not meet the requirement of preparing high-quality fat emulsion preparation.
Description
Technical Field
The invention relates to the technical field of medicinal oil refining, in particular to a method for accurately controlling the content of stearic acid in soybean oil by adopting mixed filler.
Background
The grease contains a small amount of free fatty acid and a large amount of combined fatty acid, wherein the free fatty acid is easy to remove and control, but the combined fatty acid is one of the components of the grease in the form of ester, cannot be removed and controlled, only depends on the raw material, and the composition ratio of the combined fatty acid has naturalness and randomness.
Soybean oil is natural oil extracted and refined from soybean, and is the main energy component of the conventional parenteral nutrition type fat emulsion injection and the oil phase matrix of the drug-loaded fat emulsion. Soybean oil can provide fatty acids essential to human body, and its main fatty acids include palmitic acid, palmitoleic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, arachidic acid, eicosenoic acid, behenic acid, lignoceric acid, etc. The specification of the content of the soybean oil fatty acid in the Chinese pharmacopoeia is as follows: less than tetradecane, no more than 0.1% of saturated fatty acid, no more than 0.2% of tetradecanoic acid, 9-13% of palmitic acid, no more than 0.3% of palmitoleic acid, 3.0-5.0% of stearic acid, 17.0-30.0% of oleic acid, 48.0-58.0% of linoleic acid, 5.0-11.0% of linolenic acid, no more than 1.0% of arachidic acid, no more than 1.0% of eicosenoic acid and no more than 1.0% of behenic acid.
In recent years, with the evaluation of the consistency of the simulated injection in China, the requirements on the quality and the curative effect of the injection are more and more strict, especially for the complex injections such as fat emulsion, liposome, microspheres and the like. The raw materials and auxiliary materials used by the complex injection are natural source substances with functions and complex components, such as oil and fat products such as soybean oil, olive oil and the like. How to accurately control the consistency of the quality of the raw and auxiliary materials from natural sources currently faces a great challenge to the traditional production process.
The soybean oil has been used for fat emulsion for 60 years, and the rich fatty acid composition of the soybean oil can provide necessary nutritional support for special clinical patients. At present, the traditional production process of medicinal soybean oil only controls impurity components in the oil, cannot change the composition and proportion of fatty acid, mostly keeps the state of natural fatty acid, and does not control the content of a certain fatty acid in the natural oil. Although the traditional production process of soybean oil can meet the quality requirement that the stearic acid content in the soybean oil meets 3-5% of Chinese pharmacopoeia, the stearic acid content is basically 4-5%, mainly depends on the quality of the soybean oil raw material, and cannot be controlled from the production process. At present, more and more preparation enterprises seek soybean oil with stearic acid content of 3-4% to produce higher-quality fat emulsion preparations, but until now, no technical report about controlling stearic acid content in soybean oil exists, and development of the fields of medicinal lipid and fat emulsion in China is hindered.
With the more and more intensive research in the field of grease in recent years, researchers find that the distribution of three carbon chains of triglyceride in soybean oil has a certain rule. Research shows that the 1, 3-position fatty acid residues in the soybean oil triglyceride are mainly distributed with saturated fatty acids such as palmitic acid, stearic acid and the like, and the 2-position fatty acids are mainly unsaturated such as oleic acid, linoleic acid, linolenic acid and the like. Although there have been many reports on the results of using lipase to hydrolyze triglyceride for the confirmation of triglyceride, the fatty acid composition of monoglyceride has been studied by substantially using enzymatic hydrolysis to obtain monoglyceride. Researchers have tried to make attempts to control the accuracy of the enzymatic hydrolysis if a lipase hydrolysis step is added to the traditional soybean oil production process, so that the stearic acid content of the final product is drastically reduced and the requirements of fat emulsion preparations cannot be met. If an enzymatic hydrolysis process is introduced in the traditional soybean oil refining process to prepare the soybean oil with the stearic acid content of 3-4%, the soybean oil refining process becomes very long. The conventional soybean oil alone has the following problems in the enzymatic hydrolysis process: firstly, stirring is needed in the hydrolysis process, and the enzyme can be smashed by the strong mechanical energy of industrial mechanical stirring, so that the uncertainty of enzyme activity guarantee is increased; the subsequent enzyme removal procedure is inevitably added by adding the enzyme hydrolysis process, and the working hours are further prolonged; thirdly, because the enzyme is crushed by mechanical energy in the hydrolysis process, the subsequent process verification problem of whether the enzyme can be completely removed and the enzyme residue needs to be added is solved.
Therefore, how to accurately control the stearic acid content in the soybean oil is a problem to be solved urgently in the industry.
Disclosure of Invention
The invention aims to solve the problems that the traditional soybean oil production process cannot accurately control the content of stearic acid and cannot meet the requirement of preparing a high-quality fat emulsion preparation.
In order to solve the technical problems, the invention adopts the following technical scheme:
a method for accurately controlling the stearic acid content in soybean oil by adopting mixed filler comprises the following steps:
A. uniformly mixing lipase, inorganic base, filter aid and adsorbent in a physical mode to form mixed filler, wherein the lipase is Sn-1, 3-site specific lipase;
B. passing a soybean oil through the mixed filler to obtain a refined soybean oil;
the specific gravity of each component of the mixed filler and the soybean oil is as follows: 0.1-5% of lipase, 0.1-5% of solid alkali, 1-20% of filter aid and 1-20% of adsorbent.
From the current pharmacopoeia standards and the standards which can be inquired by various international organizations, the requirements of the current standards on the stearic acid content in the soybean oil are relatively loose, the requirements are generally established according to the natural properties of the local soybean oil (for example, the pharmacopoeia requirements are 3% -5%), and only part of the grease which has larger difference with the local properties or is relatively poor is not accepted. However, in the actual process of cooperation and research and development, especially in the cooperative development and production of medicinal products, the soybean oil, which is a raw material of a common fat emulsion preparation, actually needs to meet the internal standards of enterprises which cannot be known in advance. The internal standards of enterprises are often more strict than the inquired local standards and cannot be generally met, and the main purposes of the internal standards are to reduce competitors and improve the quality of medicinal products.
According to the invention, by adopting the method of using the mixed filler for accurately controlling the stearic acid content in the soybean oil, three effects of deacidification, enzyme hydrolysis and adsorption impurity removal can be simultaneously realized. And lipase, solid alkali, filter aid and adsorbent are mixed together by physical mixing to be uniformly dispersed, free fatty acid in the soybean oil and the solid alkali are subjected to neutralization reaction, deacidification is carried out, and water is generated; the Sn-1, 3-site specific lipase carries out positioning hydrolysis on triglyceride in the soybean oil by utilizing water generated in the deacidification process to generate free fatty acid; the free fatty acids are neutralized again by the solid base, forming a microcirculation process. The filter aid mixed in the filter aid can effectively avoid the problem of difficult filtration caused by the saponin generated in the alkali refining process. If the filter aid is lacked, the saponin produced in the alkali refining process can increase the flow resistance of the soybean oil, and the soybean oil is difficult to flow through even the mixed filler, so that the hydrolysis degree of the soybean oil is difficult to control, and meanwhile, the duration of the refining process is greatly prolonged. Lipase, solid alkali, filter aid and adsorbent, wherein the lipase, the solid alkali, the filter aid and the adsorbent are uniformly mixed and supplement each other, neutralization and hydrolysis form a microcirculation reaction, saponin formed in the alkali refining process is blocked by the filter aid, and impurities such as diester, monoester, oxide and the like generated by hydrolysis are timely adsorbed by the adsorbent, so that the accurate control of the stearic acid content in the soybean oil is possible. On the basis, the accurate control of the process can be realized by controlling the temperature, controlling the pressure of equipment and controlling the contact time of the raw materials and the filler, so that the accurate control of the stearic acid content in the soybean oil within a very narrow range is finally realized, and different medicinal requirements can be met.
For the process of reducing stearic acid content in soybean oil, the preferred amounts are as follows for the specific gravity of the components of the mixed filler with soybean oil: 0.1-5% of lipase, 0.1-5% of solid alkali, 1-20% of filter aid and 1-20% of adsorbent, wherein the content of stearic acid in the soybean oil can be controlled to be slowly reduced, and the acid value, the peroxide value and the like are controlled within a reasonable range until the requirements of refining the soybean oil are met.
Preferably, the stearic acid content of the refined soybean oil is 3-4%; the peroxide number of the refined soybean oil is less than 1.
The invention relates to a soybean oil fat emulsion preparation, which has great influence on the quality of a soybean oil fat emulsion preparation and is the stearic acid content in soybean oil, wherein the stearic acid content in the soybean oil is mainly controlled by utilizing the characteristic that stearic acid is mainly distributed at 1 and 3 sites of triglyceride in the soybean oil, lipase which has selectivity on the 1 and 3 sites of the triglyceride is selected to hydrolyze the soybean oil, and impurities such as diester, monoester, oxide and the like are removed through solid alkali deacidification and adsorbent adsorption, so that the stearic acid content is reduced, and the stearic acid content is controlled within the range of 3-4%. The method can control the stearic acid content of soybean oil from any source within a very narrow range of 3-4%, and simultaneously control the peroxide value below 1, so that the dependence of the research on the soybean oil source of the fat emulsion preparation is eliminated, and the research on medicaments is greatly influenced.
Preferably, the standard deviation of the mixing uniformity of the mixed filler is not more than 0.05%; the particle sizes of the lipase, the inorganic base, the filter aid and the adsorbent are all less than 250 micrometers.
The filler particles of lipase, inorganic base, filter aid and adsorbent should be controlled to be approximately same in size and less than 250 μm in particle size, and if the filler particles are different in particle size, the purpose of uniform mixing is difficult to achieve. Meanwhile, the filler is controlled in a smaller particle size range, so that the contact area of the raw material and the filler can be increased, and the contact efficiency is improved. The smaller the particle size, the more beneficial the 4 components of lipase, inorganic base, filter aid and adsorbent to be mixed and take effect synergistically. Under the condition that the standard deviation of the mixing uniformity is not more than 0.05 percent, the soybean oil can have the smoothest microcirculation reaction in the mixed filler without retardation, and is in a more ideal mixing state.
Preferably, the step a further comprises: and filling the mixed filler into a chromatographic column.
Preferably, the operation of step B is: and the soybean oil enters the chromatographic column, and the refined soybean oil is obtained after the soybean oil flows out.
Preferably, the temperature of the chromatographic column is 30-60 ℃, the pressure is 0.02-0.5 MPa, and the contact time with the soybean oil is 1-10 h; and the soybean oil circularly enters the chromatographic column for 1-10 times.
Preferably, the Sn-1, 3-position specific Lipase comprises one or more of TLIM, 435 Lipase, Lipase Lipase and RMIM Lipase.
Preferably, the solid base comprises one or more of sodium hydroxide, potassium hydroxide and calcium hydroxide.
Preferably, the adsorbent comprises one or more of alumina, silica gel, clay, and gel.
Preferably, the filter aid comprises one or more of diatomaceous earth and bentonite.
A refined soybean oil product obtained by the method for accurately controlling the stearic acid content in soybean oil by adopting the mixed filler.
Compared with the prior art, the implementation of the invention has the following beneficial effects:
1. the invention realizes three effects of enzyme hydrolysis, acid reduction and impurity removal through one-step reaction, and realizes the effects of removing diglyceride, monoglyceride, free fatty acid, oxide and the like by controlling the temperature and pressure of equipment provided with mixed filler and the contact time of raw materials and filler. Greatly reducing the defect of complicated industrial steps.
2. Various indexes of the low-stearic acid soybean oil prepared by the invention meet the standards of Chinese pharmacopoeia, and the stearic acid content of the soybean oil can be strictly controlled to be 3-4% by the process. The stearic acid content fluctuation caused by the difference of starting materials of the soybean oil is avoided, the specific raw material requirement of domestic preparation enterprises for the soybean oil with the stearic acid content of 3-4% is met, and further the fat emulsion preparation with higher quality can be produced. The process can solve the problem of soybean oil dependence on the starting material.
3. In order to ensure the operability of the process, the invention adopts the method of adding the filter aid into the uniformly dispersed mixed filler formed by physically mixing the lipase, the solid alkali and the adsorbent, so that the problem that the whole system cannot be subjected to smooth chromatography due to the saponin formed in the alkali refining process is avoided, and the three effects of enzyme hydrolysis, deacidification and impurity removal are further realized by a further operation method.
4. The lipase, solid alkali, filter aid and adsorbent are physically mixed to be uniformly dispersed, and the lipase realizes the positioned hydrolysis of triglyceride in the soybean oil by using water generated in the deacidification process. The temperature and the equipment pressure can be controlled, the contact time of the raw materials and the filler is controlled to realize the accurate control of the process, and finally, the accurate control of the stearic acid content in the soybean oil within a narrow range is realized.
Drawings
FIG. 1 is a schematic illustration of a hybrid packing of the present invention;
FIG. 2 is a graph showing the results of investigation of column passage time by the mixed packing method;
FIG. 3 is a schematic view of a filler of comparative example 1;
FIG. 4 is a graph showing the results of examining column passage time by the packing method of comparative example 1;
FIG. 5 is a schematic view of a comparative example 2 filler;
FIG. 6 is a graph showing the results of examining column passage time by the packing method of comparative example 2;
FIG. 7 is a schematic view of a filler of comparative example 3;
FIG. 8 is a graph showing the results of examining column passage time by the packing method of comparative example 3;
FIG. 9 is a graph showing the results of examining the lipase and the solid base used in comparative example 4.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings.
Example 1
Weighing 1g of Sn-1, 3-site specific lipase 435 lipase 1g, 1g of sodium hydroxide, 10g of kieselguhr and 10g of alumina, physically mixing uniformly, and adding into a chromatographic column. Taking 1kg edible soybean oil, performing column chromatography operation with the mixed filler, controlling the column temperature at 50 + -2 deg.C, controlling the pressure at 0.04 + -0.02 mPa, and passing the column for 10 h. And detecting the acid value, the anisidine value, the peroxide value and the stearic acid content of the edible soybean oil and the refined soybean oil after column chromatography. The measurement results are shown in table 1 (wherein the acid value, peroxide value, and anisidine value were measured and calculated according to the methods shown in pharmacopoeia).
Table 1 example 1 determination results of key indexes before and after refining of edible soybean oil
Example 2
Weighing 10g of Sn-1, 3-site specific Lipase Lipase Lipase, 10g of sodium hydroxide, 50g of kieselguhr and 50g of silica gel, physically mixing uniformly, and adding into a chromatographic column. Taking 1kg edible soybean oil, performing column chromatography operation with the mixed filler, controlling column temperature at 40 + -2 deg.C, controlling pressure at 0.1 + -0.02 mPa, and passing column for 5 h. And detecting the acid value, the anisidine value, the peroxide value and the stearic acid content of the edible soybean oil and the refined soybean oil after column chromatography. The measurement results are shown in table 2 (wherein the acid value, peroxide value, and anisidine value were measured and calculated according to the methods shown in pharmacopoeia).
Table 2 example 2 determination results of key indexes before and after refining edible soybean oil
Example 3
Weighing 100g of Sn-1, 3-site specific lipase RMIM lipase, 100g of calcium hydroxide, 50g of bentonite and 750g of clay, fully mixing physically, and adding into a chromatographic column. 5kg of edible soybean oil is taken and passes through a mixed filler chromatographic column, the column temperature is controlled at 40 +/-2 ℃, the pressure is controlled at 0.3 +/-0.02 mPa, and the column passing time is 5 hours. And detecting the acid value, the anisidine value, the peroxide value and the stearic acid content of the edible soybean oil and the refined soybean oil after column chromatography. The measurement results are shown in table 3 (wherein the acid value, peroxide value, and anisidine value were measured and calculated according to the methods shown in pharmacopoeia).
Table 3 example 3 determination results of key indexes before and after refining edible soybean oil
Example 4
Weighing 300g of Sn-1, 3-site specific lipase TLIM lipase, 400g of sodium hydroxide, 1000g of kieselguhr and 1500g of gel, fully mixing physically, and adding into a chromatographic column. 10kg of edible soybean oil is taken and passes through a mixed filler chromatographic column, the column temperature is controlled at 30 +/-2 ℃, the pressure is controlled at 0.4 +/-0.02 mPa, and the column passing time is 1.5 h. And detecting the acid value, the anisidine value, the peroxide value and the stearic acid content of the edible soybean oil and the refined soybean oil after column chromatography. The measurement results are shown in table 4 (wherein the acid value, peroxide value, and anisidine value were measured and calculated according to the methods shown in pharmacopoeia).
Table 4 example 4 determination results of key indexes before and after refining of edible soybean oil
Example 5
Weighing 750g of Sn-1, 3-site specific lipase 435 lipase, 750g of calcium hydroxide, 3000g of kieselguhr and 3000g of silica gel, fully mixing physically, and adding into a chromatographic column. Taking 30kg of edible soybean oil, passing through a mixed filler chromatographic column, controlling the column temperature at 35 +/-2 ℃, controlling the pressure at 0.5 +/-0.02 mPa, and allowing the soybean oil to pass through the column for 1 h. And detecting the acid value, the anisidine value, the peroxide value and the stearic acid content of the edible soybean oil and the refined soybean oil after column chromatography. The measurement results are shown in table 5 (wherein the acid value, peroxide value, and anisidine value were measured and calculated according to the methods shown in pharmacopoeia).
Table 5 example 5 determination results of key indexes before and after refining of edible soybean oil
Example 6
Weighing 3kg of Sn-1, 3-site specific lipase 435 lipase 3kg, 3kg of calcium hydroxide, 30kg of kieselguhr and 30kg of silica gel, fully mixing physically, and adding into a chromatographic column. Taking 3000kg of edible soybean oil, passing through a mixed filler chromatographic column, controlling the column temperature at 35 +/-2 ℃, controlling the pressure at 0.5 +/-0.02 mPa, passing through the column for 1h, circulating for 5 times, and detecting the acid value, the anisidine value, the peroxide value and the stearic acid content of the edible soybean oil and the refined soybean oil after passing through the column. The measurement results are shown in table 6 (wherein the acid value, peroxide value, and anisidine value were measured and calculated by the method shown in pharmacopoeia).
Table 6 example 6 determination results of key indexes before and after refining of edible soybean oil
Example 7
Weighing 50g of Sn-1, 3-position specific lipase 435 lipase, 50g of calcium hydroxide, 200g of kieselguhr and 200g of silica gel, fully mixing physically, and adding into a chromatographic column. Taking 1kg of edible soybean oil, passing through a mixed filler chromatographic column, controlling the column temperature at 40 +/-2 ℃, controlling the pressure at 0.5 +/-0.02 mPa and the column passing time at 5h, and detecting the acid value, the anisidine value, the peroxide value and the stearic acid content of the edible soybean oil and the refined soybean oil after column passing. The measurement results are shown in table 7 (wherein the acid value, peroxide value, and anisidine value were measured and calculated according to the methods shown in pharmacopoeia).
Table 7 example 7 determination results of key indexes before and after refining of edible soybean oil
It can be seen from this example that even though the quality of the raw material of edible soybean oil is poor (the stearic acid content is 5.10%), after the process treatment of the present invention, the stearic acid content can still be accurately controlled within the range of 3-4%, which meets the requirements for preparing high-quality fat emulsion preparations (wherein, the acid value, the peroxide value, and the anisidine value are determined and calculated according to the methods shown in pharmacopoeia).
Example 8
Weighing 1.1g of Sn-1, 3-site specific lipase RMIM lipase, 1g of sodium hydroxide, 10g of kieselguhr and 12g of alumina, physically mixing uniformly, and adding into a chromatographic column. Taking 1kg edible soybean oil, performing column chromatography operation with the above mixed filler, controlling column temperature at 45 + -2 deg.C, controlling pressure at 0.05 + -0.02 mPa, and allowing the column to pass for 8 h. And detecting the acid value, the anisidine value, the peroxide value and the stearic acid content of the edible soybean oil and the refined soybean oil after column chromatography. The measurement results are shown in table 8 (wherein the acid value, peroxide value, and anisidine value were measured and calculated by the method shown in pharmacopoeia).
Table 8 example 8 determination results of key indexes before and after refining of edible soybean oil
It can be seen from this example that even though the quality of the raw material of edible soybean oil is poor (the stearic acid content is 5.96%), after the process treatment of the present invention, the stearic acid content can still be accurately controlled within the range of 3-4%, which meets the requirements for preparing high-quality fat emulsion preparations (wherein, the acid value, the peroxide value, and the anisidine value are determined and calculated according to the methods shown in pharmacopoeia).
Effect example 1
A plurality of data sets were tested by physically mixing lipase, solid base, filter aid, and adsorbent to form a mixed packing, a schematic of which is shown in FIG. 1. The conditions, filler ratio and amount of soybean oil were as in example 1, and the test results were integrated into a line graph as shown in fig. 2.
As can be seen from figure 2, by adopting the technical scheme of the invention, the stearic acid content can be effectively controlled to be 3-4%, and meanwhile, as no external water is required to be introduced, the adsorption effect of the silica gel is ensured, and the peroxide adsorption capacity of the silica gel is not damaged. Within 1-10 h of column passing time, the stearic acid content of the soybean oil can be guaranteed to be 3-4%, and the peroxide value can meet the requirements of pharmacopoeia standards.
In addition to the technical scheme of the invention, a comparison test of the layered packing is also carried out, and when the layered packing test scheme is designed, in order to ensure the comparability of test results, the positions of the filter aid and the adsorbent are required to be fixed. In order to ensure the permeability of the soybean oil flowing through the chromatographic column, the filter aid is arranged below the saponin formation to ensure the filtering effect, and simultaneously, in order to ensure the refining effect of the soybean oil flowing through the chromatographic column, the adsorbent is arranged at the bottom layer. Thus, the test protocols of comparative examples 1 and 2 were designed based on the effect of the filter aid and the adsorbent in the column.
Comparative example 1
A method for forming layered packing by adding lipase, solid alkali, filter aid and adsorbent into the same chromatographic column and sequentially packing the lipase, the solid alkali, the filter aid and the adsorbent from top to bottom is adopted to carry out a plurality of groups of data tests, and the detailed schematic diagram of the packing is shown in figure 3. The conditions, filler ratio and amount of soybean oil were as in example 1, and the test results were integrated into a line graph as shown in fig. 4.
As can be seen from FIG. 4, the preparation of soybean oil with stearic acid content of 3-4% by using a method of forming layered filler by using lipase, solid alkali, filter aid and adsorbent can make the stearic acid content uncontrollable. This is probably because when the soybean oil passes through the enzyme layer, the first process of enzymatic hydrolysis occurs, which tends to over-hydrolyze the triglycerides. In addition, by adopting the layered filling method, because water is needed to participate in the enzymatic hydrolysis process, the enzyme layer needs to be wetted before being extracted with water with a proper proportion, and the introduced water can cause the effect of adsorbing peroxide by the subsequent silica gel to be poor. By adopting a layered filling method, the content of stearic acid is directly lower than 3 percent, and the requirements of 3-5 percent in pharmacopoeia are not met. From the peroxide value measurement result, in order to meet the pharmacopoeia standard, the column passing time is more than 4h to meet the requirement.
Comparative example 2
A method for forming layered packing by adding solid alkali, filter aid, lipase and adsorbent into the same chromatographic column and sequentially packing the solid alkali, the filter aid, the lipase and the adsorbent from top to bottom is adopted to carry out a plurality of groups of data tests, and the detailed schematic diagram of the packing is shown in figure 5. The conditions, filler ratio and amount of soybean oil were as in example 1, and the test results were integrated into a line graph as shown in fig. 6.
As can be seen from FIG. 6, the preparation of soybean oil with stearic acid content of 3-4% by using a method of forming layered filler by using solid alkali, filter aid, lipase and adsorbent causes no obvious reduction of stearic acid content. Probably because the water generated after the reaction of soybean oil and solid alkali is absorbed by the filter aid, the enzyme layer has insufficient activity due to the lack of water, so that the stearic acid content of the soybean oil is not obviously changed. In order to ensure the catalytic activity of the enzyme, if the adsorbent is wetted with water in advance, the activity of the adsorbent is affected, and the oxidation index of the soybean oil is unqualified.
Comparative example 3
In addition to comparative examples 1 and 2, the design of the scheme of comparative example 3 was also designed. The method is characterized in that lipase and solid alkali are fully mixed, and a filter aid and an adsorbent are layered and filled, so that the effect of reducing the stearic acid content in soybean oil is observed. The schematic diagram of the fillers is shown in fig. 7, the condition control, the proportion and the amount of the fillers are shown in example 1, and the test results are integrated into a line chart, which is shown in fig. 8.
As can be seen from fig. 8, the stearic acid content of soybean oil still cannot be controlled by the scheme of comparative example 3, and the main reason for the abrupt decrease of stearic acid content may be that a large amount of saponin is formed in the mixed layer of lipase and solid base, so that the soybean oil is hindered from flowing through the mixed layer, resulting in excessively high contact degree of soybean oil and lipase per unit time and excessive hydrolysis.
Comparative example 4
Except for comparative examples 1-3, a single-factor variable control method is adopted to carry out multi-group tests on the dosage ranges of lipase and solid alkali, and two experimental groups are designed: the dosages of the lipase in the experimental group 1 are respectively 0.1%, 0.5%, 1%, 2.5%, 5% and 7.5%, the contact time is 1h, and the other materials are used in the same proportion and under the same condition as those in the example 1; experimental group 2 solid base dosage is 0.1%, 0.5%, 1%, 2.5%, 5%, 7.5%, contact time is 1h, other material proportion and condition control for the same as example 1. The results of the study are shown in FIG. 9.
From the results of the measurement of stearic acid and peroxide value in the experimental group 1 in fig. 9, the stearic acid content reduction rate and the lipase amount are generally inversely related on the premise that the amounts of other components are not changed, and the stearic acid content is reduced more as the lipase amount is increased. However, when the amount of the lipase is more than 5%, the stearic acid content of the soybean oil can be rapidly reduced to below 3.0% even if the contact time is only 1h, which does not meet the requirement of Chinese pharmacopoeia on the stearic acid content of the soybean oil. Such a reduction rate is too fast, and is extremely disadvantageous for accurate control. As can be seen from fig. 9, the effect of the amount of other components on the stearic acid content is roughly divided into 3 stages, the amount of the solid base is in excess relative to the amount of the lipase in the process, when the soybean oil flows through the mixed filler, the alkali refining effect is dominant, so that the stearic acid content reduction effect is relatively slight, and also, the alkali refining process generates moisture, which affects the adsorption effect of the adsorbent to a certain extent, so that the methoxyaniline peroxide value is relatively high; when the dosage of the lipase is 1-5%, when soybean oil flows through the mixed filler, alkali refining and hydrolysis interact, so that the stearic acid content is obviously reduced, and meanwhile, as the alkali refining and hydrolysis processes are fully exerted, less water is absorbed by the adsorbent, so that the adsorption effect of the adsorbent is not greatly influenced, and the effect of reducing the peroxide value of the anisidine value is obvious; with the further increase of the dosage of the lipase, the hydrolysis degree of the soybean oil is gradually increased, and when the dosage of the lipase exceeds 5%, the stearic acid content of the soybean oil is reduced to be below 3.0%, which does not meet the requirement of Chinese pharmacopoeia on the stearic acid content of 3.0-5.0% in the soybean oil. Therefore, the lipase dosage of 0.1-5% is the better choice.
From the results of the measurement of stearic acid and peroxide value in experimental group 2 in fig. 9, the stearic acid content decreasing rate is negatively correlated to the solid alkali dosage on the whole under the premise that the dosage of other components is not changed, and the stearic acid content decreases more as the solid alkali dosage increases, but the peroxide value is positively correlated to the solid alkali dosage. At the beginning, because the lipase in the mixed filler system is relatively excessive, but because the solid alkali content is less, the water generated in the alkali refining process is relatively less, and the hydrolysis performance of the lipase and the adsorption performance of silica gel are slightly influenced, the stearic acid content reduction effect is not obvious, and meanwhile, the adsorption effect of the adsorbent is higher, and the peroxide value is smaller; with the increase of the solid alkali consumption, the water generated in the alkali refining process is increased, the lipase hydrolysis effect is improved, and the adsorption performance of the adsorbent is less influenced by the water because the alkali refining water just provides a hydrolysis environment for the lipase; with the further increase of the solid alkali dosage, the mixed filler system is changed into an alkali excess environment, so that the excessive water in the alkali refining process obviously influences the adsorption performance of the adsorbent, and when the solid alkali dosage exceeds 5%, the peroxide value of the soybean oil finally flowing through the mixed filler layer exceeds the internal control standard of 1.0. Therefore, the solid alkali dosage of 0.1-5% is the preferred choice.
From a series of examination results of experimental group 1 and experimental group 2 of comparative example 4, when the lipase or solid alkali content exceeds 5%, it is impossible to simultaneously control the stearic acid content and the oxidation number within a reasonable range, and the final soybean oil product cannot meet the standard requirements.
The above disclosure is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the scope of the present invention, therefore, the present invention is not limited by the appended claims.
Claims (3)
1. A method for accurately controlling the stearic acid content in soybean oil by adopting mixed filler is characterized by comprising the following steps:
A. uniformly mixing lipase, solid alkali, a filter aid and an adsorbent in a physical mode to form a mixed filler, and filling the mixed filler into a chromatographic column, wherein the lipase is Sn-1, 3-site specific lipase;
B. allowing the soybean oil to enter the chromatographic column, flowing through the mixed filler, and flowing out to obtain refined soybean oil;
the specific gravity of each component of the mixed filler and the soybean oil is as follows: 0.1-5% of lipase, 0.1-5% of solid alkali, 1-20% of filter aid and 1-20% of adsorbent; the stearic acid content of the refined soybean oil is 3-4%; the peroxide value of the refined soybean oil is less than 1; the temperature of the chromatographic column is 30-60 ℃, the pressure is 0.02-0.5 MPa, and the contact time of the chromatographic column and the soybean oil is 1-10 h; the soybean oil circularly enters the chromatographic column for 1-10 times; the Sn-1,3 site specific lipase comprises one or more of TLIM lipase and RMIM lipase; the solid alkali comprises one or more of sodium hydroxide, potassium hydroxide and calcium hydroxide; the adsorbent comprises one or more of alumina, silica gel, argil and gel; the filter aid comprises one or more of diatomite and bentonite.
2. The method for precisely controlling the content of stearic acid in soybean oil by using the mixed filler according to claim 1, wherein the standard deviation of the mixing uniformity of the mixed filler is not more than 0.05%; the particle sizes of the lipase, the solid alkali, the filter aid and the adsorbent are all less than 250 micrometers.
3. A refined soybean oil product obtained by the method of claim 1 using a mixed filler to precisely control the amount of stearic acid in soybean oil.
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