CN102272280A - Method for producing vegetable oil - Google Patents
Method for producing vegetable oil Download PDFInfo
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- CN102272280A CN102272280A CN2010800042339A CN201080004233A CN102272280A CN 102272280 A CN102272280 A CN 102272280A CN 2010800042339 A CN2010800042339 A CN 2010800042339A CN 201080004233 A CN201080004233 A CN 201080004233A CN 102272280 A CN102272280 A CN 102272280A
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/12—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by hydrogenation
- C11C3/126—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by hydrogenation using catalysts based principally on other metals or derivates
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Abstract
Disclosed is a method for producing a vegetable oil comprising: step 1 of adding one or more kinds of non-phosphorus surfactants, which are selected from among an anionic surfactant, a cationic surfactant and an amphoteric surfactant, or a solution of the same to a vegetable oil containing a sterol glycoside and a phosphorus compound and mixing by stirring to give a mixture; step 2 of further adding a definite amount of water to the mixture obtained in step 1 and mixing by stirring to give a mixture containing an aggregate; and step 3 of separating the aggregate from the mixture obtained in step 2 to give a vegetable oil from which the sterol glycoside and the phosphorus compound have been removed each at a ratio of 60% or greater.
Description
Technical field
The present invention relates to the manufacture method of vegetables oil.
Background technology
As the oil expression method of vegetables oil, mainly used full milling process, hexane extraction method or squeezing-hexane extraction combined method in the past.In recent years,, the hexane extraction method is reappraised, become the method that solvent is not used in many employings owing to care to security and environment.Contain various impurity in resulting thick oil, the content of impurity is different according to the difference of oil expression method, in order to be used for edible oil purposes and chemical purposes etc., is necessary with refining step combined.
In the process for purification of vegetables oil, roughly there are chemical refining and physics to make with extra care two kinds of methods.The former operation can be divided into come unstuck, alkali depickling, decolouring, deodorization, the latter's operation can be divided into come unstuck, decolouring, deodorization procedures.Degumming Procedures is the refining total operation of chemical refining and physics for removing contained gelationus operation in the crude oil.Particularly, exploitation has method, the method for using enzyme of adding acid, the method for using film etc. (OREO Science, Japanese oiling association, on March 1st, 2006, No. 3, the 6th volume, 3～21 pages).In addition, report has: in grease, add tensio-active agent as degumming agent remove the impurity in the degrease technology (US-A2,525,702), add acid more than two kinds and surfactant mixtures method (WO-A1995/000609) as degumming agent.In addition, in the example 68～70 of JP-A51-112810, put down in writing in the soybean oil that water-process is come unstuck add citric acid solution after, the method for adding the solution of the Sodium Lauryl Sulphate BP/USP that contains 0.5 weight %.In addition, report has: add technology (JP-A2-255896 communique) that egg phospholipids comes unstuck, use technology (JP-A9-501453 communique) that Sodium Lauryl Sulphate BP/USP and edta salt come unstuck with a large amount of water (is 300 weight % with respect to oil), with the come unstuck technology (US-A3 of (except that dewax) of Sodium Lauryl Sulphate BP/USP and phosphoric acid salt, 994,943).
Summary of the invention
The present invention relates to comprise the manufacture method of the vegetables oil of following operation 1～operation 3.
Operation 1: in the vegetables oil that contains steroline and phosphorus compound, add the non-phosphorus more than a kind be selected from anionic surfactant, cationic surfactant and the amphoterics and be tensio-active agent or contain this non-phosphorus the solution that is tensio-active agent, thereby obtain the operation of mixture
Operation 2: in operation 1 resulting mixture, add water, and make the content of the water in this mixture become 0.1～80 weight % of the vegetables oil that uses in the operation 1, thereby obtain containing the operation of the mixture of condensation product,
Operation 3: by separating condensation product from operation 2 resulting mixtures, thereby the rate of removing that obtains steroline and phosphorus compound is respectively the operation of the vegetables oil more than 60%.
In addition, the present invention relates to a kind of manufacture method of ester cpds, wherein, as operation 4, to carry out the ester reaction by the resulting vegetables oil of the method for the invention described above.The invention still further relates to a kind of manufacture method of alkylol cpd, wherein, as operation 5, to carrying out hydrogenation by the resulting ester cpds of the method for the invention described above.
As the impurity in the vegetables oil, known to have with phosphatide be phosphorus compound, steroline (sugared sterol), vitamin-E of main component etc.Yet, do not have so far to find by refining can optionally reduce or remove above-mentioned all or the simple and easy method of certain predetermined substance.At US-A2, in 525,702 the method,, can not reduce other impurity such as steroline (sugared sterol) though can reduce colloid material phosphorus compound.
The object of the present invention is to provide that a kind of to reduce effectively or remove what contain as impurity in vegetables oil be the phosphorus compound of main component, the method for steroline (sugared sterol) with phosphatide from vegetables oil.
In existing Degumming Procedures,, use citric acid or phosphoric acid in order mainly to remove the colloid of phosphatide etc.In the present invention, use tensio-active agent to substitute above-mentioned citric acid or phosphoric acid, significantly improve, can also remove inexpungible sugared sterol in common Degumming Procedures thereby can make phosphoric acid remove efficient.
According to the present invention, provide that a kind of to reduce effectively or remove what contain as impurity in vegetables oil be the phosphorus compound of main component, the method for steroline (sugared sterol) with phosphatide.And, in the method for the invention, can in vegetables oil, keep having excellent antioxidant effect and as edible oil or as the useful material vitamin-E of chemical raw material.
Embodiment
The present invention is, in the manufacturing of the vegetables oil that contains steroline and phosphorus compound, adding specific non-phosphorus as operation 1 is tensio-active agent or solution that to contain this non-phosphorus be tensio-active agent, thereby add water in the mode that becomes 0.1～80 weight % with respect to the vegetables oil that uses in the operation 1 condensation product is generated, separate the condensation product that contains impurity as operation 3 as operation 2.Promptly, in operation 1, add specific non-phosphorus and be tensio-active agent or contain this non-phosphorus the solution that is tensio-active agent, in operation 2, the condensation product that contains insoluble composition is generated by adding the quantitative water of regulation, in operation 3 by carry out centrifugation, filtering separation wait reduce or remove the condensation product that contain insoluble composition, thereby make vegetables oil thereafter.
Manufacture method of the present invention is for to carry out the purified method to material plant oil, i.e. the manufacture method of treated oil.Below, sometimes manufacturing treatment process of the present invention is called " making with extra care ".
In addition, the present invention also provides the ester cpds of the vegetables oil that use obtains thus and the manufacture method of alkylol cpd.
＜operation 1 〉
In operation 1, in the vegetables oil that contains steroline and phosphorus compound, add the non-phosphorus more than a kind be selected from anionic surfactant, cationic surfactant and amphoterics and be tensio-active agent or contain this non-phosphorus the solution that is tensio-active agent.
Be not particularly limited as vegetables oil, can list Oleum Cocois, plam oil, palm-kernel oil, palm-kernel palmitin (Palm Kernel Olein), palm-kernel tristearin (Palm Kernel stearin), soybean oil, rapeseed oil, Semen Maydis oil, sunflower seed oil, curcas oil (Jatropha oil), algae wet goods.Be preferably selected from the vegetables oil more than a kind in Oleum Cocois, plam oil, palm-kernel oil, palm-kernel oleic acid, rapeseed oil, sunflower seed oil and the soybean oil, more preferably be selected from the vegetables oil more than a kind in Oleum Cocois, plam oil, palm-kernel oil, the rapeseed oil.Usually, contain the steroline of 1～500ppm degree and the phosphorus compound of 1～1000ppm degree under the state of vegetables oil before refining that above-mentioned vegetables oil especially obtains with complete milling process.
As non-phosphorus is tensio-active agent, and the non-phosphorus more than a kind that is preferably selected from anion surfactant and amphoterics is tensio-active agent, and the non-phosphorus more than a kind that more preferably is selected from amphoterics is tensio-active agent.
As anion surfactant, be not particularly limited, can list alkyl-sulphate, sulfated alkyl ether, alkyl ether carboxy acid salt, alkylbenzene sulfonate etc.The carbonatoms of abovementioned alkyl is preferably 8～18, more preferably 10～16, is preferably 12～14 especially.In addition, the average addition mole number of alkylene oxide in the ether based compound (alkylene oxide) is preferably 2～10, and alkylene oxide can list oxyethylene, propylene oxide.Be preferably the anionic surfactant who is selected from alkyl-sulphate, sulfated alkyl ether and alkylbenzene sulfonate.More preferably be selected from the anionic surfactant of alkyl-sulphate and alkylbenzene sulfonate.
As cationic surfactant, be not particularly limited, (preferred carbonatoms is 8～22 can to list alkyl, more preferably carbonatoms is 10～18, preferred especially carbonatoms is 12～14) trimethyl ammonium chloride, (preferred carbonatoms is 8～22 to alkyl, more preferably carbonatoms is 10～18, preferred especially carbonatoms is 12～14) trimethylammonium bromide, (preferred carbonatoms is 8～18 to dialkyl group, more preferably carbonatoms is 10～16, preferred especially carbonatoms is 12～14) alkyl dimethyl ammonium chloride, (preferred carbonatoms is 8～18 to alkyl, more preferably carbonatoms is 10～16, preferred especially carbonatoms is 12～14) benzyl dimethyl ammonium chloride etc.More preferably be selected from the cationic surfactant of alkyl trimethyl ammonium chloride and alkyl benzyl dimethyl ammonium chloride.
As amphoterics, be not particularly limited, can list the sultaine of alkylamide propyl sultaine, alkyl sultaine, alkyl hydroxy sultaine etc., the carboxybetaine of alkylamide propyl carboxybetaine, alkyl carboxyl trimethyl-glycine etc., alkyl amine oxide etc.Be preferably selected from the amphoterics of carboxybetaine and sultaine.The preferred carbonatoms of abovementioned alkyl is 8～18, more preferably carbonatoms is 10～16, especially preferably carbonatoms is 12～14.
In operation 1, non-phosphorus is tensio-active agent or to contain non-phosphorus be that the condition that the addition of the solution of tensio-active agent satisfies is, with non-phosphorus be tensio-active agent as effective constituent, content of effective is preferably 0.01～10 weight %, more preferably 0.05～5 weight %, further preferred 0.1～1 weight % with respect to vegetables oil.In addition, from reducing or remove the viewpoint consideration of the effect of phosphorus compound and steroline, preferably not using phosphorus in operation 1 is tensio-active agent.Therefore, in operation 1 employed tensio-active agent, non-phosphorus is that the ratio of tensio-active agent is preferably 50～100 weight %, more preferably 90～100 weight %, 100 weight % more preferably.
Non-phosphorus is that tensio-active agent can directly make an addition in the vegetables oil, perhaps, makes an addition in the vegetables oil with the form that contains the solution that non-phosphorus is tensio-active agent and other composition (below, being also referred to as non-phosphorus is surfactant soln, or abbreviates solution as).Under the situation of solution, non-phosphorus is that the content (active constituent content) of tensio-active agent is preferably more than the 5 weight % and less than 100 weight %.The big viewpoint of thing amount is considered from operation, more preferably 10 weight % above, more preferably 15 weight % above, more preferably 20 weight % above, more preferably more than the 25 weight %.On the other hand, the viewpoint of the operability from operation considers, more preferably less than 100 weight %, more preferably below the 80 weight %, more preferably below the 65 weight %, more preferably below the 50 weight %.Consider from the viewpoint of actual operation, be preferably 10～80 weight %, more preferably 20～65 weight %, 25～50 weight % more preferably.
In addition, as being the composition that can contain in the surfactant soln, can enumerate water outlet, methyl alcohol, ethanol, Virahol, acetone, hexane etc. at non-phosphorus.
In addition, directly using non-phosphorus is under the tensio-active agent situation, and its use form can be any one of liquid or solid.In addition, also can use non-phosphorus is the dispersion liquid (preferably water dispersion liquid) of the emulsification of tensio-active agent, outstanding absurd creature etc.In addition, also can use the non-phosphorus that contains solid state is the solid state mixture of tensio-active agent and other solids component.In addition, use form as under the solid situation, the preferred powder powder composition.Use form as the solid situation under, as the composition that can contain in this mixture, can list salt, water, alcohol etc.
Consider that from the viewpoint of operability preferably using non-phosphorus is the solution of tensio-active agent, the especially aqueous solution.Using non-phosphorus is under the situation of solution of tensio-active agent, can be in the final total amount that will add of adding once, and also can portion-wise addition.In addition, can add continuously, also can add off and on.In addition, be accompanied by the interpolation of water phase surfactant mixture and the amount of the water that adds with respect to employed vegetables oil be preferably below the 80 weight %, more preferably below the 10 weight %, further more preferably below the 1 weight %.
In operation 1, preferably to add non-phosphorus under 30～90 ℃ the state be that tensio-active agent or non-phosphorus are surfactant soln in that vegetables oil is heated to.In addition, preferably adding non-phosphorus under the state that stirs vegetables oil is that tensio-active agent or non-phosphorus are surfactant soln.
In operation 1, consider from the viewpoint of operability, adding above-mentioned non-phosphorus in above-mentioned vegetables oil is after tensio-active agent or non-phosphorus are surfactant soln, preferably 30～90 ℃, more preferably 40～90 ℃, further carry out the operation of operation 2 after mixing 1 minute～10 hours under preferred 50～90 ℃ of temperature condition.Here,, consider, be preferably more than 3 minutes, more preferably more than 5 minutes from the viewpoint of usability and operability about the time of mixing, in addition, be preferably 5 hours with interior, more preferably 1 hour with interior, in more preferably 30 minutes.
In addition, during mixing in the operation 1, can together use batch-type and continous way.
＜operation 2 〉
In operation 2, in operation 1 resulting mixture, add water, thereby obtain containing the mixture of condensation product.In operation 2, the amount of the water that adds in operation 1 resulting mixture is, is 0.1～80 weight % with respect to the vegetables oil that uses in the operation 1.Here, lower value be preferably 0.5 weight % above, more preferably 1 weight % above, more preferably 2 weight % above, further more preferably 3 weight % above, be preferably more than the 5 weight % especially.On the other hand, higher limit be preferably 75 weight % following, more preferably 50 weight % following, more preferably below the 20 weight %.The viewpoint of the operability from actual operation considers that in operation 2, the amount of the water that adds is, is 0.1～80 weight % with respect to the vegetables oil that uses in the operation 1 in operation 1 resulting mixture.Water can use deionized water or tap water etc., can contain other composition (sterilization component etc.) with the amount of the degree that do not influence cohesion in the water.
In addition, the addition of the water in the operation 2 is preferably 0.1～80 weight % with respect to the vegetables oil that uses in the operation 1, more preferably 2 weight % above, more preferably 3 weight % above, more preferably more than the 5 weight %, in addition, more preferably 50 weight % following, more preferably below the 20 weight %.
The temperature of operation 1 resulting mixture is preferably 30～90 ℃, more preferably 50～90 ℃ when adding water, in addition, after adding after water injection, preferably 30～90 ℃, more preferably 40～90 ℃, more preferably mixed 5 minutes～5 hours under 50～90 ℃ of temperature condition.Here, consider, be preferably more than 10 minutes in the time of mixing under this temperature, more preferably more than 20 minutes from coherent viewpoint.In addition, consider from the viewpoint of economy, be preferably below 3 hours in the time of mixing under this temperature, more preferably below 1 hour, more preferably below 30 minutes.In addition, consider from the viewpoint of operability, under this temperature, preferably mix 5～30 minutes, more preferably mixed 10～30 minutes.At this moment, stirring condition is preferably batch-type or continous way.The interpolation of water can final add once the total amount that will add, also can portion-wise addition.In addition, can add continuously, also can add off and on.In addition, can use the means identical in the mixing in operation 2 with operation 1.
In addition, using non-phosphorus in operation 1 is under the situation of the aqueous solution of tensio-active agent or aqueous dispersions, in the total by the amount (W2) of the water that is added in the amount (W1) of the water that this aqueous solution or aqueous dispersions added and the operation 2 in the operation 1, it is above and less than 100 weight %, more preferably more than the 70 weight % and less than 100 weight % that the ratio of W2 is preferably 50 weight %.
In the present invention, for the rate of removing that obtains steroline and phosphorus compound is respectively vegetables oil more than 60%, be preferably: the non-phosphorus that adds in the operation 1 is that tensio-active agent or non-phosphorus are that the condition that the amount of surfactant soln satisfies is, with non-phosphorus is that tensio-active agent is as effective constituent, this effective constituent (is heated to and is preferably 40～90 ℃ with respect to vegetables oil, the vegetables oil of 50～90 ℃ state more preferably) be 0.01～10 weight %, adding with respect to vegetables oil in operation 2 is the water of 1～1000 weight %, at 30～90 ℃ keep 5 minute～5 hour, preferably under whipped state, keep thereafter.Agitation condition in the operation 2 is preferably batch-type or continous way.
＜operation 3 〉
In operation 3, by separating condensation product from operation 2 resulting mixtures, thereby the rate of removing that obtains steroline and phosphorus compound is respectively the vegetables oil more than 60%.Here, the rate of removing of steroline be preferably more than 70%, more preferably more than 80%, more preferably more than 90%, more preferably more than 95%.In addition, the rate of removing of phosphorus compound be preferably more than 70%, more preferably more than 80%, more preferably more than 90%, more preferably more than 95%.
In addition, in the present invention, the rate of removing (%) of steroline and phosphorus compound is tried to achieve according to following formula.In addition, the content of steroline in the vegetables oil (crude oil and treated oil) and phosphorus compound is to measure with the method for embodiment described later.
The rate of removing (%) of steroline=[1-(the steroline content in the vegetables oil behind the separation condensation product)/(the steroline content in the vegetables oil (crude oil))] * 100
The rate of removing (%) of phosphorus compound=[1-(the phosphorus compound content in the vegetables oil behind the separation condensation product)/(the phosphorus compound content in the vegetables oil (crude oil))] * 100
Usually, the vegetables oil of process operation 1,2 generates the condensation product that contains insoluble composition, comprises steroline and phosphorus compound in this condensation product.In addition, the condensation product that relates to is insoluble in vegetables oil, but the specific non-phosphorus of selecting among the present invention is the existence of tensio-active agent, makes the dispersive ability excellence of described condensation product in water, therefore infers that its distribution to aqueous phase becomes easy.Therefore, in operation 3, remove described condensation product as the known method of separation means, thereby the rate of removing that can access steroline and phosphorus compound is respectively the vegetables oil more than 60% by what adopt solid-liquid or liquid-liquid etc.
As concrete separation method, can list the combination of centrifugation, standing separation, filtration or aforesaid method.Use under the situation of centrifugation, can 40～100 ℃, be preferably 40～70 ℃, 1,000～100,000G, be preferably 5,000～50, carry out under the condition of 000G.
Vegetables oil through operation 3 can be handled according to common process for purification.
In addition,, compare, can keep more vitamin-E (not losing) with usual method for the situation that contains vitamin-E through the vegetables oil of above-mentioned operation 1～3.Here, the conservation rate of vitamin-E be preferably more than 80%, more preferably more than 90%, more preferably more than 95%.
In addition, in the present invention, the conservation rate of vitamin-E (%) is tried to achieve according to following formula.In addition, the content of the vitamin-E in the vegetables oil (crude oil and treated oil) is to measure with the method for embodiment described later.
The conservation rate of vitamin-E (%)=[(content of vitamin E in the vegetables oil behind the separation condensation product)/(content of vitamin E in the vegetables oil (crude oil))] * 100
In addition, the invention provides a kind of manufacture method of ester cpds, wherein,, the vegetables oil that obtains with above-mentioned method of the present invention is carried out the ester reaction as operation 4.The ester reaction of operation 4 can enough known method be implemented.Reaction can utilize any one reaction form of continuous mode or batch mode, but under the situation of making a large amount of esters, successive reaction is favourable.As catalyzer, usually use the homogeneous phase alkaline catalysts of sodium hydroxide or potassium hydroxide, sodium alkoxide etc., but also can make spent ion exchange resin or oxidizing aqueous zirconium, aluminum phosphate, support the vitriolic zirconium white, the solid catalyst of titanium silicon (titanosilicate) etc.Use under the situation of homogeneous phase alkaline catalysts, under following condition, react usually.Temperature of reaction is 30～90 ℃, is preferably 40～80 ℃ that reaction pressure is the scope of normal pressure～0.5MPa, preferably carries out under normal pressure.
In addition, provide a kind of manufacture method of alkylol cpd in the present invention, wherein,, the ester cpds that obtains with above-mentioned method of the present invention is carried out hydrogenation as operation 5.As operation 5, can list, the ester cpds of use fatty acid ester etc. is as raw material, and the use hydrogenation catalyst carries out the method for hydrogenation.As hydrogenation catalyst, use common known copper to be, or the precious metal series catalysts of palladium, platinum etc. etc.As Cu-series catalyst, can enumerate copper-chromium, copper-zinc, copper-iron-aluminium, copper-silicon-dioxide etc.In the presence of above-mentioned any catalyzer, can carry out hydrogenation by normally used any reactive modes such as liquid phase suspensoid method or fixed bed processes.
Under the situation of reacting with liquid phase suspensoid method, catalytic amount is preferably 0.1～20 weight % with respect to the ester cpds of fatty acid ester etc.; According to temperature of reaction or reaction pressure, can in the scope that can access practical reaction yield, select arbitrarily.Temperature of reaction is preferably 160～350 ℃, more preferably 200～280 ℃.Reaction pressure is preferably 0.1～35MPa, 3～30MPa more preferably.
Under the situation of reacting continuously in the fixed bed mode, catalyzer uses and is configured as cylindric or particulate state, spherical etc. object.Temperature of reaction is preferably 130～300 ℃, more preferably 150～270 ℃, and reaction pressure is preferably 0.1～30MPa.Consider productivity and reactivity, can be according to reaction conditions arbitrary decision LHSV.
Embodiment
Following embodiment is the explanation to enforcement of the present invention.Embodiment is the explanation that illustration of the present invention is carried out, and does not limit the present invention.
The scale of the phosphorus compound (ppm) that the vegetables oil (crude oil) that uses in following embodiment and the comparative example is contained, steroline (ppm), vitamin-E (ppm) is shown in the following table 1.In addition, the phosphorus compound content in vegetables oil (crude oil) and the treated oil thereof is based on that standard grease analytical test method 2.4.11-2003 (phosphorus) (Japanese oiling association compiles, version in 2003) measures.In addition, the content of the steroline in vegetables oil (crude oil) and the treated oil thereof is to use Lipids, and the method for record is measured in 34 (11), 1231 (1999) [U.S. oiling association (the American Oil Chemists ' Society) distribution].In addition, the content of vitamin-E is based on that standard grease analytical test method 2.4.10-2003 (tocopherol) (Japanese oiling association compiles, version in 2003) measures.
Table 1
| Phosphorus compound (ppm) | Steroline (ppm) | Vitamin-E *(ppm) | |
| Coconut crude oil | ?31 | ?45 | Less than 50 |
| Palm crude oil | ?21 | ?23 | ?720 |
| Soy bean oil | ?130 | ?25 | ?1330 |
| Vegetable seed crude oil | ?206 | ?54 | ?850 |
| Sunflower seeds crude oil | ?43 | ?26 | ?772 |
*Vitamin-E is represented the aggregate value of tocopherol and tocotrienols.
Embodiment 1
Reaction vessel uses the length dimension 500cc removable flask bigger than width.Stir on one side and (stir the stainless steel wing of 6 pieces of blades that uses mechanical stirrer, diameter 60mm.Revolution is 580 rev/mins) 200g coconut crude oil is warming up to 60 ℃ on one side, and add 30% (weight %, below same) the laurylamide propyl group carboxybetaine aqueous solution of 1.2g and under 60 ℃ condition, stirred 5 minutes for water phase surfactant mixture., add 20g water, under 60 ℃ condition, continue stirring in 30 minutes again, obtain comprising the mixture of condensation product thereafter.With 15,000G carries out centrifugation in 10 minutes operation (HITACHI himac CR22F) to the mixture that obtains under 60 ℃ condition, separates the water that comprises condensation product by decant, obtains cochin oil.Measure phosphorus compound content and steroline content in the cochin oil, compare with coconut crude oil, thereby try to achieve the rate of removing.
Comparative example 1
In embodiment 1, the intensification temperature of coconut crude oil is 40 ℃, adds the 30% laurylamide propyl group carboxybetaine aqueous solution of 1.2g and the mixture of 20g water, stirs 30 minutes.From the mixture that obtains, separate glue according to mode similarly to Example 1, obtain cochin oil.According to the trans rate of removing of trying to achieve steroline and phosphorus compound similarly to Example 1.The result is shown in the table 2.
Comparative example 2
Except the intensification temperature with coconut crude oil changes to 60 ℃, according to obtaining cochin oil with the same mode of comparative example 1.Try to achieve the rate of removing of steroline and phosphorus compound according to mode similarly to Example 1.The result is shown in the table 2.
Table 2
| Embodiment 1 | Comparative example 1 | Comparative example 2 | |
| Steroline is removed rate (%) | ?80 | ?42 | ?46 |
| Phosphorus compound is removed rate (%) | ?98 | ?95 | ?95 |
As shown in table 2, in comparative example 1 and comparative example 2, can not fully remove steroline, remove rate and in embodiment 1, can reach height for steroline and phosphorus compound both.
Embodiment 2～4 and comparative example 3～5
Except using 98% lauryl sodium sulfate aqueous solution (embodiment 2, comparative example 3), 26% sodium dodecyl benzene sulfonate aqueous solution (embodiment 3, comparative example 4), the 50% dodecylbenzyl alkyl dimethyl ammonium chloride aqueous solution (embodiment 4, comparative example 5) to replace the 30% laurylamide propyl group carboxybetaine aqueous solution among the embodiment 1 as tensio-active agent, make with extra care according to mode similarly to Example 1 for embodiment 2～4, for comparative example 3～5 according to making with extra care with the same mode of comparative example 1, thereby obtain cochin oil.Try to achieve the rate of removing of steroline and phosphorus compound according to mode similarly to Example 1.The result is shown in the table 3.
Table 3
| Table 3a | Embodiment 2 | Comparative example 3 |
| Steroline is removed rate (%) | Greater than 99 | ?36 |
| Phosphorus compound is removed rate (%) | ?93 | ?92 |
| Table 3b | Embodiment 3 | Comparative example 4 |
| Steroline is removed rate (%) | ?92 | ?26 |
| Phosphorus compound is removed rate (%) | ?94 | ?93 |
| Table 3c | Embodiment 4 | Comparative example 5 |
| Steroline is removed rate (%) | ?82 | ?34 |
| Phosphorus compound is removed rate (%) | ?88 | ?77 |
As shown in table 3, in comparative example 3～5, can not fully remove steroline, remove rate and in embodiment 2～4, can reach height for steroline and phosphorus compound both.
Embodiment 5～7
Except use palm crude oil (embodiment 5), vegetable seed crude oil (embodiment 6), sunflower seeds crude oil (embodiment 7) as glyceride stock, obtain treated oil according to similarly to Example 1 mode.Try to achieve the rate of removing of steroline and phosphorus compound according to mode similarly to Example 1.In addition, measure the conservation rate of vitamin-E.The result is shown in the table 4.
Table 4
| Embodiment 5 | Embodiment 6 | Embodiment 7 | |
| Steroline is removed rate (%) | Greater than 99 | Greater than 99 | Greater than 99 |
| Phosphorus compound is removed rate (%) | ?86 | ?76 | ?96 |
| Vitamin-E conservation rate (%) | ?96 | ?98 | ?99 |
As can be known from the results of Table 4, method of the present invention also can be finished the operation of effectively removing impurity for plam oil, rapeseed oil and sunflower seed oil, in addition, can keep the useful component vitamin-E extremely effectively.
Embodiment 8
Using the addition of soy bean oil, tensio-active agent as glyceride stock is that the addition of 0.3 weight % (effective constituent), water is 20 weight % (40g) with respect to oil with respect to oil, in addition, obtains treated oil according to similarly to Example 1 mode.Try to achieve the rate of removing of steroline and phosphorus compound according to mode similarly to Example 1.In addition, according to trying to achieve the conservation rate of vitamin-E with the same mode of embodiment 5 grades.The result is shown in the table 5.
Table 5
| Embodiment 8 | |
| Steroline is removed rate (%) | 71 |
| Phosphorus compound is removed rate (%) | 71 |
| Vitamin-E conservation rate (%) | Greater than 99 |
As can be known from the results of Table 5, method of the present invention also can be finished the operation of effectively removing impurity for soybean oil, in addition, can keep the useful component vitamin-E extremely effectively.
Embodiment 9
Be warming up to 40 ℃ while stirring 200g coconut crude oil, add the 30% laurylamide propyl group carboxybetaine aqueous solution of 1.2g, and under 40 ℃ condition, stirred 5 minutes., add 20g water, under 40 ℃ condition, continue stirring in 3 hours more thereafter.With 15,000G carries out centrifugation in 10 minutes operation to the mixture that obtains, and separates glue by decant, obtains cochin oil.Try to achieve the rate of removing of steroline and phosphorus compound according to mode similarly to Example 1.The result is shown in the table 6.
Table 6
| Embodiment 9 | |
| Steroline is removed rate (%) | ?90 |
| Phosphorus compound is removed rate (%) | ?92 |
As can be known from the results of Table 6, in operation 2 by under 40 ℃ of temperature condition, carrying out 3 hours stirring, thereby show the rate of removing of high steroline and phosphorus compound.
Embodiment 10
Be warming up to 90 ℃ while stirring 200g coconut crude oil, add the 30% laurylamide propyl group carboxybetaine aqueous solution of 1.2g, and under 90 ℃ condition, stirred 5 minutes., add 20g water, under 90 ℃ condition, continue stirring in 1 hour more thereafter.With 15,000G carries out centrifugation in 10 minutes operation to the mixture that obtains, and separates glue by decant, obtains cochin oil.Try to achieve the rate of removing of steroline and phosphorus compound according to mode similarly to Example 1.The result is shown in the table 7.
Table 7
| Embodiment 10 | |
| Steroline is removed rate (%) | 89 |
| Phosphorus compound is removed rate (%) | 98 |
As can be known from the results of Table 7, in operation 2 by under 90 ℃ of temperature condition, carrying out 1 hour stirring, thereby show the rate of removing of high steroline and phosphorus compound.
Embodiment 11～16
Except using the 30% AMONYL 380LC aqueous solution (embodiment 11), the 26% dodecyl carboxybetaine aqueous solution (embodiment 12), the 26% stearyl carboxybetaine aqueous solution (embodiment 13), 40% 2-dodecyl-N-carboxymethyl-N-hydroxyethyl imidazole quinoline aqueous solutions of betaine (embodiment 14), the 30% dodecyl hydroxyl sulfo betaine aqueous solution (embodiment 15), 30% cocamidopropyl propyl amide amine oxide aqueous solution (embodiment 16) replaces beyond the 30% laurylamide propyl group carboxybetaine aqueous solution as tensio-active agent among the embodiment 1, obtains cochin oil according to similarly to Example 1 mode.Try to achieve the rate of removing of steroline and phosphorus compound according to mode similarly to Example 1.In addition, according to trying to achieve the conservation rate of vitamin-E with the same mode of embodiment 5 grades.The result is shown in table 8, the table 9.
Table 8
| Embodiment 11 | Embodiment 12 | Embodiment 13 | Embodiment 14 | |
| Steroline is removed rate (%) | 95 | 94 | 95 | Greater than 99 |
| Phosphorus compound is removed rate (%) | 99 | 98 | 98 | 99 |
| Vitamin-E conservation rate (%) | Greater than 99 | Greater than 99 | Greater than 99 | Greater than 99 |
Table 9
| Embodiment 15 | Embodiment 16 | |
| Steroline is removed rate (%) | 88 | 92 |
| Phosphorus compound is removed rate (%) | 98 | 94 |
| Vitamin-E conservation rate (%) | Greater than 99 | Greater than 99 |
From the result of table 8 and table 9 as can be known, by using amphoterics, can show the rate of removing of high steroline and phosphorus compound.In addition, can keep the useful component vitamin-E extremely effectively.
Comparative example 6
Except using 99% 2 palmitoyl phosphatidylcholine (comparative example 6) to replace the 30% laurylamide propyl group carboxybetaine aqueous solution among the embodiment 1, obtain cochin oil according to similarly to Example 1 mode as tensio-active agent.Try to achieve the rate of removing of steroline and phosphorus compound according to mode similarly to Example 1.The result is shown in the table 10.
Table 10
| Comparative example 6 | |
| Steroline is removed rate (%) | ?55 |
| Phosphorus compound is removed rate (%) | ?80 |
As shown in table 10, in comparative example 6, can not fully remove steroline.
Comparative example 7
Except using 99% dilauryl phosphoric acid ester (comparative example 7) to replace the 30% laurylamide propyl group carboxybetaine aqueous solution among the embodiment 1, obtain cochin oil according to similarly to Example 1 mode as tensio-active agent.Try to achieve steroline according to mode similarly to Example 1 and remove rate.The result is shown in the table 11.In addition, the content of in table 11, representing phosphorus compound in the lump.
Table 11
As shown in table 11, in comparative example 7, can not fully remove steroline.In addition, because the dilauryl phosphoric acid ester of using as tensio-active agent remains in the treated oil, therefore, can not fully remove phosphorus compound.
Comparative example 8
Except in embodiment 1, the water yield of adding being increased to 100 weight %, obtain cochin oil according to similarly to Example 1 mode.Try to achieve steroline according to mode similarly to Example 1 and remove rate.The result is shown in the table 12.In addition, the rate of removing of in table 12, representing phosphorus compound in the lump.
Table 12
| Comparative example 8 | |
| Steroline is removed rate (%) | ?35 |
| Phosphorus compound is removed rate (%) | ?98 |
As shown in table 12, in the many comparative examples 8 of the water yield, can not fully remove steroline.
Embodiment 17
Except in embodiment 1, the water yield of adding in the operation 2 being changed to 0.2g, obtain cochin oil according to similarly to Example 1 mode.Try to achieve steroline and phosphorus compound is removed rate according to mode similarly to Example 1.The result is shown in the table 13.
Table 13
| Embodiment 17 | |
| Steroline is removed rate (%) | 88 |
| Phosphorus compound is removed rate (%) | 97 |
As shown in table 13, the rate of removing that can obtain steroline and phosphorus compound in embodiment 17 similarly to Example 1 is respectively the vegetables oil more than 60%.
Claims (9)
1. the manufacture method of a vegetable oil, it comprises following operation 1～operation 3,
Operation 1: in the vegetables oil that contains steroline and phosphorus compound, add the non-phosphorus more than a kind be selected from anionic surfactant, cationic surfactant and the amphoterics and be tensio-active agent or contain this non-phosphorus the solution that is tensio-active agent, thereby obtain the operation of mixture
Operation 2: in operation 1 resulting mixture, add water, and make the content of the water in this mixture become 0.1～80 weight % of the vegetables oil that uses in the operation 1, thereby obtain containing the operation of the mixture of condensation product,
Operation 3: by separating condensation product from operation 2 resulting mixtures, thereby the rate of removing that obtains steroline and phosphorus compound is respectively the operation of the vegetables oil more than 60%.
2. the manufacture method of vegetables oil as claimed in claim 1, wherein,
Described non-phosphorus be tensio-active agent be selected from the anionic surfactant that forms by alkyl-sulphate, sulfated alkyl ether and alkylbenzene sulfonate and the amphoterics formed by carboxybetaine and sultaine in the non-phosphorus more than a kind be tensio-active agent.
3. the manufacture method of vegetables oil as claimed in claim 1 or 2, wherein,
Described vegetables oil is the vegetables oil more than a kind that is selected from Oleum Cocois, palm-kernel oil, palm-kernel palmitin, palm-kernel tristearin, plam oil, rapeseed oil, sunflower seed oil, soybean oil, curcas oil and the algae oil.
4. as the manufacture method of each described vegetables oil in the claim 1～3, wherein,
In operation 1, after the described non-phosphorus of interpolation is tensio-active agent or the solution that contains this tensio-active agent in described vegetables oil, after 30～90 ℃ mix 1 minute～10 hours, carry out the operation of operation 2.
5. as the manufacture method of each described vegetables oil in the claim 1～4, wherein,
The non-phosphorus that contains in the operation 1 is that the solution of tensio-active agent is, is tensio-active agent as effective constituent, contains more than this effective constituent 5 weight % and less than the solution of 100 weight % with non-phosphorus.
6. as the manufacture method of each described vegetables oil in the claim 1～5, wherein,
The non-phosphorus that contains in the operation 1 is that the solution of tensio-active agent is, is tensio-active agent as effective constituent, contains more than this effective constituent 20 weight % and less than the solution of 100 weight % with non-phosphorus.
7. as the manufacture method of each described vegetables oil in the claim 1～6, wherein,
In operation 1, described non-phosphorus is tensio-active agent or to contain non-phosphorus be that the addition of the solution of tensio-active agent is to be tensio-active agent becomes 0.01～10 weight % with respect to described vegetables oil as effective constituent, this effective constituent amount with described non-phosphorus.
8. the manufacture method of an ester cpds wherein, as operation 4, is reacted carried out ester by the resulting vegetables oil of each described method in the claim 1～7.
9. the manufacture method of an alkylol cpd, wherein, as operation 5, to carrying out hydrogenation by the resulting ester cpds of the method described in the claim 8.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009-033570 | 2009-02-17 | ||
| JP2009033570 | 2009-02-17 | ||
| JP2010-006499 | 2010-01-15 | ||
| JP2010006499A JP5412301B2 (en) | 2009-02-17 | 2010-01-15 | Vegetable oil refining and manufacturing method |
| PCT/JP2010/000823 WO2010095396A1 (en) | 2009-02-17 | 2010-02-10 | Method for producing vegetable oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102272280A true CN102272280A (en) | 2011-12-07 |
| CN102272280B CN102272280B (en) | 2014-03-19 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201080004233.9A Expired - Fee Related CN102272280B (en) | 2009-02-17 | 2010-02-10 | Method for producing vegetable oil |
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| Country | Link |
|---|---|
| JP (1) | JP5412301B2 (en) |
| CN (1) | CN102272280B (en) |
| BR (1) | BRPI1007435A2 (en) |
| MY (1) | MY156956A (en) |
| WO (1) | WO2010095396A1 (en) |
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| JP5875140B2 (en) * | 2011-06-14 | 2016-03-02 | 中国電力株式会社 | Method for refining jatropha oil |
| CN114292702B (en) * | 2021-12-31 | 2023-06-16 | 河南省商业科学研究所有限责任公司 | Method for extracting peony essential oil by using surfactant aqueous solution and solid alkali |
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| CN1209160A (en) * | 1995-12-29 | 1999-02-24 | 伊斯曼化学公司 | Polyunsaturated fatty acid and fatty acid easter mixture free of sterols and phosphorous compound |
| JP2001509836A (en) * | 1997-01-31 | 2001-07-24 | カーギル，インコーポレーテッド | Method for removing sterols from fats and oils using phospholipids |
| JP2002233398A (en) * | 2001-02-09 | 2002-08-20 | Ikeda Shokken Kk | Method for producing sterol fatty acid ester for food |
| JP2002543088A (en) * | 1999-04-27 | 2002-12-17 | フォーブス メディ−テック インコーポレーテッド | Process for purifying phytosterols from wood or plant-derived sources and compositions resulting therefrom |
| CN1668631A (en) * | 2002-01-31 | 2005-09-14 | 酶学技术有限公司 | Fractionation of phytosterol esters in oil |
-
2010
- 2010-01-15 JP JP2010006499A patent/JP5412301B2/en not_active Expired - Fee Related
- 2010-02-10 BR BRPI1007435A patent/BRPI1007435A2/en not_active Application Discontinuation
- 2010-02-10 WO PCT/JP2010/000823 patent/WO2010095396A1/en active Application Filing
- 2010-02-10 CN CN201080004233.9A patent/CN102272280B/en not_active Expired - Fee Related
- 2010-02-10 MY MYPI2011003821A patent/MY156956A/en unknown
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| CN1209160A (en) * | 1995-12-29 | 1999-02-24 | 伊斯曼化学公司 | Polyunsaturated fatty acid and fatty acid easter mixture free of sterols and phosphorous compound |
| JP2000502740A (en) * | 1995-12-29 | 2000-03-07 | イーストマン ケミカル カンパニー | Mixture of polyunsaturated fatty acids and fatty acid esters without sterol and phosphorus compounds |
| JP2001509836A (en) * | 1997-01-31 | 2001-07-24 | カーギル，インコーポレーテッド | Method for removing sterols from fats and oils using phospholipids |
| JP2002543088A (en) * | 1999-04-27 | 2002-12-17 | フォーブス メディ−テック インコーポレーテッド | Process for purifying phytosterols from wood or plant-derived sources and compositions resulting therefrom |
| JP2002233398A (en) * | 2001-02-09 | 2002-08-20 | Ikeda Shokken Kk | Method for producing sterol fatty acid ester for food |
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Also Published As
| Publication number | Publication date |
|---|---|
| MY156956A (en) | 2016-04-15 |
| WO2010095396A1 (en) | 2010-08-26 |
| JP5412301B2 (en) | 2014-02-12 |
| BRPI1007435A2 (en) | 2016-02-16 |
| CN102272280B (en) | 2014-03-19 |
| JP2010215896A (en) | 2010-09-30 |
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