CN104531349A - Method for reducing 3-chlorine-1,2-propylene glycol ester during grease processing - Google Patents
Method for reducing 3-chlorine-1,2-propylene glycol ester during grease processing Download PDFInfo
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- CN104531349A CN104531349A CN201510036523.6A CN201510036523A CN104531349A CN 104531349 A CN104531349 A CN 104531349A CN 201510036523 A CN201510036523 A CN 201510036523A CN 104531349 A CN104531349 A CN 104531349A
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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
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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
- C11B3/001—Refining fats or fatty oils by a combination of two or more of the means hereafter
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- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
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- Fats And Perfumes (AREA)
Abstract
The invention provides a method for reducing 3-chlorine-1,2-propylene glycol ester (called 3-MCPD ester for short) during grease processing. 3-MCPD ester is a harmful substance generated during the grease processing, the control over the content of the 3-MCPD ester in grease and a related food has great significance in maintaining food safety. The idea of the invention is derived from that an iron ion is discovered to have catalytic action on the formation of the 3-MCPD ester in study, and thus the content of the 3-MCPD ester contained in the grease can be controlled by reducing the content of the iron ion. According to the method provided by the invention, the measures of storing the grease by using a non-ferrous container and adding an antioxidant, an iron ion chelating agent and the like during grease storage or processing are adopted, and the measures can both be used for obviously reducing the content of the 3-MCPD ester contained in the grease.
Description
Technical field
The present invention relates to oil and fat chemical field.Concrete, the invention provides a kind of method reducing 3-chlorine-1,2-propylene glycol ester in fats and oils processing.
Background technology
3-chloro-1,2-propylene glycol ester (being called for short 3-MCPD ester) is a kind of objectionable impurities with renal toxicity and carinogenicity produced in oil and fat refining process, finds to exist in bread, cake, biscuit, infant formula, refined vegetable wet goods numerous food at present.2008, German scholar was reported in human milk and 3-chlorine-1,2-propylene glycol ester (30-2195 μ g/kg) detected, shows that 3-glycerin chlorohydrin ester can absorb in human tissue organ, distribute.The harm of 3-chlorine-1,2-propylene glycol ester has caused showing great attention to of European Union, the U.S., Japan and multiple state food enterprise such as Chinese and government at present.
Triglyceride level (triacylglycerol, TAG) is topmost glyceride type compound in grease, and in plam oil, triglyceride level accounts for the 88-96% of whole glyceride type compound.2012, Destaillats etc. compare triglyceride and triglyceride level and chlorine-containing compound and react the yield generating 3-MCPD diester, result shows that triglyceride level reaction generates the yield of 3-MCPD ester higher than triglyceride, shows that triglyceride level is the main producers forming 3-MCPD ester.
The method reducing the generation of 3-MCPD ester in oil and fat refining process mainly contains three kinds: the first is raw material oil handling before refining, washed by washing or ethanol (75%), removing generates the precursor substance of 3-MCPD ester, comprises triglyceride (DAG), monoglyceride (MAG) and muriate etc.; The second is in oil and fat refining process, reduces the generation of 3-MCPD ester by changing processing parameter (as temperature, time and pH); The third removes the 3-MCPD ester generated, and comprises thermal destruction, absorption and enzymolysis.
First method can remove the 3-MCPD ester of 30%-40%, but between different material oil (such as plam oil and soybean oil), difference is very large, also has bigger difference between the different batches of even same stock oil; As for second method, through decades, development reaches optimal condition to oil and fat refining, the rising of such as pH can reduce the production of 3-MCPD ester, but the amount of another kind of objectionable impurities acrylamide obviously raises, and although the reduction of decolouring and deodorization temperature makes the content of 3-MCPD ester reduce, but the effect of decolouring and deodorization declines, need the longer time; There is minimum balance in the third method thermal destruction, not exclusively, sorbent material and enzymolysis, also in exploration, are only in conceptual phase at present in degraded;
Therefore, the better method reducing 3-chlorine-1,2-propylene glycol ester content in fats and oils processing of searching, is not only raising grease and food safety provides scientific basis, can reduce the cost of fats and oils processing enterprise yet.
Summary of the invention
The object of the invention is the content by reducing iron ion in course of oil processing thus reduce the content of 3-chlorine-1,2-propylene glycol ester (3-MCPD ester) in grease.
A first aspect of the present invention provides a kind of method reducing 3-chlorine-1,2-propylene glycol ester in grease (being called for short 3-MCPD ester) content, and described method comprises step:
A () provides a kind of grease containing triglyceride level or raw material;
B () reduces concentration or the content of free iron in described grease or raw material, thus reduce 3-chlorine-1,2-propylene glycol ester in grease (being called for short 3-MCPD ester) content.
In another preference, in step (b), the reduction concentration of free iron or the method for content comprise one or more steps being selected from lower group:
I () adopts non-ferric container to hold described grease or raw material;
(ii) from described grease or raw material, free iron is removed;
(iii) in described grease or raw material, sequestrant is added.
In another preference, described method also comprises: in described grease or raw material, add antioxidant.
In another preference, described method also comprises step between step (a) and (b): the concentration or the content that measure the free iron in described grease or raw material, and when free iron observed value is higher than limit value, carry out step (b).
In another preference, described limit value refers to that Fe ionic concn is 135-140mg/L when sodium stearate is tested.
In another preference, described method also comprises step:
C () processes described grease or raw material, obtain the product through processing;
D () measures the content of described 3-MCPD ester in the product of processing.
In another preference, the processing conditions in step (c) comprises: nitrogen protection and under rough vacuum condition, 240 DEG C of heating 1h.
In another preference, in the process, non-ferric container is adopted to hold described grease or raw material all the time.Preferably, in step (a)-(d), adopt non-ferric container to hold described grease or raw material, and process in non-ferric container.
In another preference, described iron ion comprises Fe
2+, Fe
3+or its combination.
In another preference, the addition of described sequestrant is 1-5 times (mol ratio) of iron ion content.
In another preference, the addition of described sequestrant is lower than national Specification value or conventional value.
In another preference, described triglyceride level comprises the ester that the lipid acid such as stearic acid, oleic acid, linolic acid, palmitinic acid, linolenic acid and combination and glycerine thereof are formed.
In another preference, described non-ferric container is selected from lower group: non-ferrous metal container, non-ferric plastic containers and non-ferric Glass Containers.
In another preference, described iron chelator is selected from lower group: EDTA, citric acid.
In another preference, described in the ratio of the iron chelator that adds and iron ion be 1:1-15:1, being preferably 4:1, is more preferably 10:1.
A second aspect of the present invention provides a kind of method of fats and oils processing being carried out to quality control, and described method comprises step:
A () measures in described course of oil processing, the concentration of the free iron in glyceride stock to be processed or content obtain the observed value of iron ion;
B () compares when the observed value of described iron ion and limit value, wherein, when described free iron observed value is lower than limit value, do not carry out the operation reducing iron ion; When described free iron observed value is higher than carrying out the operation reducing iron ion during limit value;
(c) optionally, after the operation having carried out reducing iron ion, repeating step (a) and (b) one or many;
D () measures the 3-MCPD ester content in the oil and fat product of processing.
In another preference, the operation of described reduction iron ion comprises one or more methods being selected from lower group:
I () adopts non-ferric container to hold described grease or raw material;
(ii) from described grease, free iron is removed;
(iii) in described grease or raw material, sequestrant is added.
In another preference, described method also comprises: in described grease or raw material, add antioxidant.
A third aspect of the present invention provides a kind of method reducing 3-chlorine-1,2-propylene glycol ester (being called for short 3-MCPD ester) in grease storage or processing, and described method comprises the one or more steps being selected from lower group:
I () grease stores or adopts non-ferric container in the course of processing;
(ii) store at grease or add antioxidant in the course of processing;
(iii) store at grease or add iron chelator in the course of processing.
Accompanying drawing explanation
Fig. 1. show the relation between the mol ratio of EDTA-2Na and Fe ion and the relative percentage content of 3-MCPD diester, wherein control group does not add EDTA-2Na.
Fig. 2 shows the relation between the mol ratio of EDTA-2Na and Fe ion and the relative percentage content of 3-MCPD monoesters.
Embodiment
The present inventor is through extensive and deep research, by a large amount of screening and test, surprisingly find that iron ion is to the katalysis generating 3-chlorine-1,2-propylene glycol ester, the method of 3-chlorine-1,2-propylene glycol ester content in fats and oils processing is reduced according to this thinking concentration established by reducing iron ion.Complete the present invention on this basis.
Preferably, the reduction grease that the present invention takes stores or in processing, the measure of 3-chlorine-1,2-propylene glycol ester (being called for short 3-MCPD ester) comprising:
I () grease stores or adopts non-ferric container in the course of processing;
(ii) store at grease or add antioxidant in the course of processing;
(iii) store at grease or add iron chelator in the course of processing.
The measure taked of the method store for reducing grease and in course of oil processing iron ion content thus finally reach the object reducing 3-MCPD ester content.
Major advantage of the present invention comprises:
I () effectively reduces the content of 3-MCPD ester in oil and fat product;
(ii) can complete in oil and fat refining step (deodorization), not need to increase plant and instrument and production stage;
(iii) EDTA-2Na is the foodstuff additive of country's license, safe and effective.
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.The experimental technique of unreceipted actual conditions in the following example, usually conveniently condition, or according to the condition that manufacturer advises.Unless otherwise indicated, otherwise per-cent and number are weight percent and parts by weight.
Embodiment 1
Added by 2mL iron(ic) chloride in 5mL Tristearoylglycerol solution, described strength of solution is 0.5mg/mL, and solvent is n-hexadecane.Sonic oscillation, after 30 minutes, adds the EDTA-2Na (1.2,2.3,4.6,9.2,23.0mg) of a series of different content, itself and FeCl
3molar ratio be respectively 0.5:1,1:1,2:1,4:1,10:1.Control group does not add as EDTA-2Na.Reaction system continuously stirring at 120 DEG C, after 20 minutes, is cooled to room temperature.The reaction solution methyl alcohol of 50 times: Virahol=1:1 (v/v) solution dilution, analyzes with UPLC-Q-TOF MS after filtering.
The content of the 3-MCPD diester that above-mentioned experiment generates as shown in Figure 1.Experimental result shows, and along with the rising of EDTA-2Na and iron(ic) chloride ratio, the 3-MCPD ester content generated in reaction product significantly reduces.As EDTA-2Na and FeCl
3molar ratio when being respectively 1:1, the 3-MCPD diester of generation is only 32% of blank; As EDTA-2Na and FeCl
3molar ratio when being respectively 4:1, the 3-MCPD diester of generation is only 18% of blank.
Embodiment 2
By 400mg FeCl
3join in 80g refined palm oil, supersound process 5min, then add 0.938g and 4.655g EDTA-2Na respectively, blank group does not add EDTA-2Na.Then under nitrogen protection, make pressure maintain 5mbar with oil pump, at 240 DEG C, heat 1h.Continue to pass into nitrogen after reaction terminates, when temperature is lower than 100 DEG C, pressure can return to normal atmosphere (An), gets 10 μ L sample isopropanol 100 times, through 0.2 μm of GHP membrane filtration, detect 3-MCPD ester concentration (detection method is identical with embodiment 1).
The content of the 3-MCPD ester that above-mentioned experiment generates as shown in Figure 2.Along with the rising of EDTA-2Na and iron(ic) chloride ratio, the 3-MCPD ester content generated in reaction product significantly reduces.
The all documents mentioned in the present invention are quoted as a reference all in this application, are just quoted separately as a reference as each section of document.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read above-mentioned teachings of the present invention, these equivalent form of values fall within the application's appended claims limited range equally.
Claims (7)
1. reduce a method for 3-chlorine-1,2-propylene glycol ester in fats and oils processing (being called for short 3-MCPD ester) content, it is characterized in that, the method comprising the steps of:
A () provides a kind of grease containing triglyceride level or raw material;
B () reduces concentration or the content of free iron in described grease, thus reduce 3-chlorine-1,2-propylene glycol ester in grease (being called for short 3-MCPD ester) content.
2. the method for claim 1, is characterized in that, in described step (b), the reduction concentration of free iron or the method for content comprise one or more steps being selected from lower group:
I () adopts non-ferric container to hold described grease or raw material;
(ii) from described grease, free iron is removed;
(iii) in described grease or raw material, sequestrant is added.
3. method as claimed in claim 2, it is characterized in that, non-ferric container is selected from lower group: non-ferrous metal container, non-ferric plastic containers and non-ferric Glass Containers.
4. method as claimed in claim 2, is characterized in that, iron chelator is selected from lower group: EDTA, citric acid.
5. method as claimed in claim 2, it is characterized in that, the iron chelator added and the ratio of iron ion are 1:1-15:1.
6. fats and oils processing is carried out to a method for quality control, it is characterized in that, comprise step:
A () measures in described course of oil processing, in glyceride stock to be processed, the concentration of free iron or content, obtain the observed value of iron ion;
B () compares when the observed value of described iron ion and limit value, wherein, when described free iron observed value is lower than limit value, do not carry out the operation reducing iron ion; When described free iron observed value is higher than carrying out the operation reducing iron ion during limit value;
(c) optionally, after the operation having carried out reducing iron ion, repeating step (a) and (b) one or many;
D () measures the 3-MCPD ester content in the oil and fat product of processing.
7. reduce a method for 3-chlorine-1,2-propylene glycol ester in grease storage or processing, it is characterized in that, the method comprises the one or more steps being selected from lower group:
I () grease stores or adopts non-ferric container in the course of processing;
(ii) store at grease or add antioxidant in the course of processing;
(iii) store at grease or add iron chelator in the course of processing.
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| CN201510036523.6A CN104531349A (en) | 2015-01-23 | 2015-01-23 | Method for reducing 3-chlorine-1,2-propylene glycol ester during grease processing |
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| CN201510036523.6A CN104531349A (en) | 2015-01-23 | 2015-01-23 | Method for reducing 3-chlorine-1,2-propylene glycol ester during grease processing |
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| CN106281672A (en) * | 2015-05-28 | 2017-01-04 | 丰益(上海)生物技术研发中心有限公司 | A kind of reduce trichloropropanol or the method for its ester content in oils and fats |
| CN113166677A (en) * | 2018-12-12 | 2021-07-23 | 日本水产株式会社 | Composition containing highly unsaturated fatty acid or alkyl ester thereof and method for producing same |
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Cited By (4)
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| CN106281672A (en) * | 2015-05-28 | 2017-01-04 | 丰益(上海)生物技术研发中心有限公司 | A kind of reduce trichloropropanol or the method for its ester content in oils and fats |
| CN105802731A (en) * | 2016-06-03 | 2016-07-27 | 上海交通大学 | Method for removing 3-monochloropropanediol ester |
| CN113166677A (en) * | 2018-12-12 | 2021-07-23 | 日本水产株式会社 | Composition containing highly unsaturated fatty acid or alkyl ester thereof and method for producing same |
| US11898120B2 (en) | 2018-12-12 | 2024-02-13 | Nissui Corporation | Composition containing highly unsaturated fatty acid or alkyl ester thereof and a method for producing the same |
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Application publication date: 20150422 |