CN105779122A - Technology for controlling or reducing plasticizers in grease and grease obtained through same - Google Patents
Technology for controlling or reducing plasticizers in grease and grease obtained through same Download PDFInfo
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- CN105779122A CN105779122A CN201410830706.0A CN201410830706A CN105779122A CN 105779122 A CN105779122 A CN 105779122A CN 201410830706 A CN201410830706 A CN 201410830706A CN 105779122 A CN105779122 A CN 105779122A
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Abstract
The invention relates to a technology for controlling or reducing plasticizers in grease and the grease obtained through the same, and belongs to the field of grease processing.According to the technology, the content of phthalate plasticizers in the grease can be reduced to be within the allowed maximum residue limit range by adding amino adsorbing agents and/or specific acid substances.In addition, the technology is easy to implement, the technological processes are simplified, and the cost is saved.
Description
Technical field
The application relates to a kind of technique controlling plasticiser, particularly phthalate plasticiser in oils and fats and the oils and fats thus obtained, and belongs to fats and oils processing field.
Background technology
Plasticiser is also referred to as plasticizer, and it is the industrial macromolecular material auxiliary agent being widely used, and adds this material in plastic processing, it is possible to make plastics pliability strengthen, it is easy to processing.This commercial auxiliaries is forbidden in food.The plasticiser detected in food is mainly phthalate plasticiser, including: phthalic acid two (2-ethylhexyl) ester (DEHP), diisononyl phthalate (DINP), dinoctyl phthalate (DNOP), dibutyl phthalate (DBP), dimethyl phthalate (DMP), diethyl phthalate (DEP) etc..
Phthalate plasticiser is to be insoluble in water, is soluble in the colourless transparent oil liquid of organic solvent.
Owing to plasticiser can endanger male reproductive function and promotes female precocious puberty, long-term huge uptake can cause hepatocarcinoma, and child is in the hormonal system Development of Reproductive System phase, so the potential hazard that child is brought by plasticiser can be bigger.Now, phthalate plasticiser is all successively listed in the list of the pollutant of priority acccess control by European Union, the U.S., Japan, China, phthalic acid two (2-ethylhexyl) ester (DEHP) allowed in the food of China and food additive, diisononyl phthalate (DINP), dibutyl phthalate (DBP) maximum residue limit respectively 1.5mg/Kg, 9.0mg/Kg, 0.3mg/Kg.
In view of the toxicity of phthalate plasticiser is more serious than tripolycyanamide, and extensively remain in oils and fats, for the food safety of broad masses of the people, it is necessary to find a kind of production technology phthalate plasticiser effectively to remove in oils and fats.
The article (" allowing grain and oil goods away from plasticiser " delivered at present, Wang Ruiyuan, Jin Qingzhe, An Jun, " Grain in China economy ", 3rd phase in 2013) it is proposed by improving packaged form and material, edible vegetable oil processing enterprise can use polyethylene terephtalate, PE, PP etc. without the plastic package material adding plasticiser.
PeterRoslev, KatrinVorkampetal, Degradationofphthalateestersinanactivatedsludgewastewate rtreatmengplant, WaterResearch [J] .2007,41:969-976 have studied the removal effect of DMP, DBP, BBP in Sewage Plant (butyl benzyl phthalate), DEHP.
SatoshiKaneco, HideyukiKatsumata, TohruSuzuki, etc.TitaniumDioxidemediatedphotocatalyticdegradationofdi butylphthalateinaqueoussolutionkinetics, mineralizationandreactionmechanism [J] .ChemicalEngineering, the PAE resin (phthalate resin) that 2006,125:59-66 thinks in water by experiment can use TiO2Photoactivation after its pretreatment is degraded by solution, and the method is impracticable in oil-soluble oils and fats.
NAdhoum, L.Moeser, RemovalofPhthalateinmodifiedaetivatedcarbon:applicationt othetreatmentofindustricalwastewater [J] .PurifyTechnol, 2004,38:233-239 research shows that activated carbon powder foot couple phthalic acid has certain removal effect.S.VenkataMohan, S.Shailaja, M.RamaKrishna, etc.Adsorptiveremovalofphthalateesterfromaqueousphasebya ctiveatedcarbon:Akineticstudy.JournalofHazardousMaterial s [J] .2007,146:278-282 is found through experiments activated carbon and DEP has certain absorbability, but for other plasticiser DeGrains such as DEHP, DBP, DINP, there is certain limitation.
Chinese patent application CN102961416A discloses and a kind of removes the residual of plasticiser in Ganoderma spore powder raw material and the method polluted, it removes the plasticiser in Ganoderma spore powder raw material by the method for supercritical carbon dioxide extraction, the method is relatively costly, and treating capacity is less, it is not suitable for oil prodution industryization and produces.Chinese patent application CN102586022A discloses and a kind of removes the method for plasticiser in plants essential oil, but its relatively low molecular distillation temperature (40～80 DEG C) can not remove each plasticiser to large extent, clearance is relatively low, wherein the content of n-butyl phthalate (DBP) can not be removed to below 0.3mg/kg, and molecular distillation equipment and technology require higher, relatively costly, production capacity is limited.Chinese patent CN102295989B and Chinese patent application CN102304418A discloses to use and can dissolve and adsorb the solvent of phthalate material as the back washing agent phthalate material to remove in oils and fats, but its anti-extraction process of 2～5 times and bigger back washing agent make consumption (maximum make consumption be oils and fats 8 times, weight ratio), significantly increase the weight of to remove complexity and the production cost of phthalate material, and increase the weight of the burden of subsequent recovery back washing agent.
There is presently no and find to use the oil refining process optimized to reduce the report of the phthalate plasticiser of residual in oils and fats.
Summary of the invention
The problem that invention to solve
The application aims to provide a kind of by oil and fat refining, the technique reducing the phthalate plasticiser of residual in oils and fats and the oils and fats prepared by this technique.
For solving the scheme of problem
The application provides a kind of and controls or reduce the technique of plasticiser in oils and fats, comprising:
In oils and fats, based on oils and fats weighing scale, add the amino acids adsorbent that part by weight is 0.1-30% and/or the acid of 10-5000ppm not Nitrogen element, after heated and stirred, obtain the oils and fats that content of plasticizing agent reduces.
According to technique described herein, it is characterized in that, one or more in threonine, glycine, serine, cysteine, tyrosine, agedoite, the glutamine of described amino acids adsorbent, it is preferable that one or more in threonine, glycine, serine, cysteine, tyrosine.
According to technique described herein, it is characterised in that oils and fats adds at least two amino acids adsorbent.
According to technique described herein, it is characterised in that oils and fats adds at least one amino acids adsorbent and the acid of at least one not Nitrogen element.
According to technique described herein, it is characterised in that one or more in phosphoric acid, citric acid, malic acid, tartaric acid, lactic acid, the succinic acid of the acid of described not Nitrogen element, it is preferable that one or more in phosphoric acid, citric acid.
According to technique described herein, it is characterised in that based on oils and fats weighing scale, the additional proportion of described amino acids adsorbent is 0.1%-20%, it is preferred to 0.1%-10%, more preferably 2%-8%, it is most preferred that 5%；And/or, the additional proportion of the acid of described not Nitrogen element is 10-1000ppm, it is preferred to 10-500ppm, it is most preferred that for 50-100ppm.
According to technique described herein, it is characterised in that heating-up temperature is 60-130 DEG C, and/or, mixing time is 15-60 minute.
The application also provides for the oils and fats prepared according to above-mentioned technique.
A kind of technique removing plasticiser provided herein, it is characterised in that including:
In the sample of plasticiser to be removed, based on described example weight meter, add the amino acids adsorbent that part by weight is 0.1-30%, and/or the acid of 10-5000ppm not Nitrogen element, obtain after heated and stirred content of plasticizing agent reduce sample, the acid of described amino acids adsorbent and described not Nitrogen element not with or substantially not with described example reaction；Described sample is preferably medicine, cosmetics, health product, food.
The application also provides for the acid of amino acids adsorbent and/or not Nitrogen element in the application reducing or controlling plasticiser in oils and fats or in other sample.
The effect of invention
By the technique of the application, the content of plasticiser in oils and fats can be effectively reduced, especially can the content of phthalate plasticiser in oils and fats be reduced in the scope of the maximum residue limit allowed, in addition, this technological operation is simple, only namely can reach the effect of intended reduction phthalate content of plasticizing agent by adding specific material, simplify technological process, saved cost.
Detailed description of the invention
Oils and fats described herein, it is possible to selected from animal oil or Vegetable oil lipoprotein, or through modified oils and fats, or the emulsus wet goods that oils and fats and water are formed.Technique in the application, the oils and fats that all phthalate plasticisers are exceeded standard, in control or minimizing oils and fats in phthalate plasticiser, having identical effect, the acid of the amino acids adsorbent that adds in the application and not Nitrogen element can by filtering and/or deodorize be removed.Based on identical removal principle, the method in the present invention can be used for removing the plasticiser in other sample, the acid of wherein said aminoacid and not Nitrogen element not with or substantially not with the example reaction of plasticiser to be removed.Wherein said sample source contacts in production with transporting procedures and uses the material containing plasticiser material, all can be removed by the method in the application.Described sample, it is preferred that, it is possible to deriving from food, health product, medicine and/or cosmetics, its non-limitative example includes: drinking water, beverage, fruit wine, skin care item, Chinese liquor, wine, soy sauce, milk, health product, oral liquid, various medicaments etc..
In the detailed description of the invention of the application, described amino acids adsorbent is selected from two or more aminoacid.In a preferred embodiment, described amino acids adsorbent is selected from glycine and serine.Other is alternatively preferably combined as: threonine and serine；Threonine and glycine；Glycine and cysteine；Tyrosine and cysteine；Tyrosine and glycine；Etc..
In the detailed description of the invention of the application, oils and fats or sample add the acid of at least one described amino acids adsorbent and at least one not Nitrogen element.In a preferred embodiment, described amino acids adsorbent is selected from one or more in threonine, glycine, serine, cysteine, tyrosine, agedoite, glutamine.The acid of described not Nitrogen element is selected from one or more in phosphoric acid, citric acid, malic acid, tartaric acid, lactic acid, succinic acid.In the application, synergist effect is not played in the acid of Nitrogen element.
In the detailed description of the invention of the application, described amino acids adsorbent can also be selected from the aminoacid of more than three kinds.In a preferred embodiment, the non-limitative example of described amino acids adsorbent includes: glycine, serine and threonine；Glycine, cysteine and tyrosine；Serine, threonine and tyrosine；Etc..
In the detailed description of the invention of the application, described oils and fats or the heating-up temperature of sample are 60-130 DEG C, it is preferred to 80-120 DEG C.Without being bound by any theory, in the detailed description of the invention of the application, all can reduce the effect of plasticiser in oils and fats or other sample when heating, in temperature range in this application, there is more excellent effect.
In the detailed description of the invention of the application, the process time of described oils and fats is 15-60 minute.
Embodiment
In following embodiment, the glyceride stock before refine is the oils and fats that phthalate plasticiser exceeds standard, it is to adopt the Oleum Brassicae campestris that market is bought to be mixed into phthalic acid two (2-ethylhexyl) ester (DEHP), diisononyl phthalate (DINP), dibutyl phthalate (DBP), and become the oils and fats that phthalate plasticiser exceeds standard, detect it according to GBT21911-2008 and contain 39.45ppmDEHP, 46.93ppmDINP, 26.21ppmDBP, also referred to as non-polished fat under this oils and fats.
Embodiment 1-35
Take the oils and fats that 200 grams of above-mentioned phthalate plasticisers exceed standard, the initial content of phthalate plasticiser that will comprise in the oils and fats measured according to GBT21911-2008, it is listed in the table below in 1.
Then, weighing scale based on oils and fats, the acid of addition amino acids adsorbent shown in table 1 below and/or not Nitrogen element, heating is to 110 DEG C and stirs 35 minutes, obtain the oils and fats after refine, measure the content of phthalate plasticiser in oils and fats according to GBT21911-2008, be listed in the following table.
The acid of the amino acids adsorbent that uses in embodiment and/or not Nitrogen element is all material known in the art, it is possible to commercially available from the market.
Table 1 below illustrates the amino acids adsorbent added in the initial content of the phthalate plasticiser comprised in oils and fats, each embodiment and/or the not kind of the acid of Nitrogen element and quantity and the content of phthalate plasticiser in the oils and fats after refine.Wherein the refine object of embodiment 1 (matched group) is the oils and fats (Ji Wei polished fat) that phthalate plasticiser exceeds standard, and is not added with the acid of amino acids adsorbent and/or not Nitrogen element before refine.All the other embodiment 2-35 all with the addition of the material described in table 1 in glyceride stock.In table 1, plasticiser numerical value corresponding to embodiment 1-35 is the content of plasticizing agent in the oils and fats after refine.
Wherein, DEHP refers to that phthalic acid two (2-ethylhexyl) ester, DINP refer to that diisononyl phthalate, DBP refer to dibutyl phthalate.
Table 1
ND=does not detect, LOQ (content limit)=0.25mg/Kg
Can be seen that from the above, oils and fats is individually added into amino acids adsorbent, can effectively reduce the content (embodiment 4-8) of phthalate plasticiser, the amplitude that DEHP reduces is more than 30%, the reduction amplitude of DINP is more than 20%, and the reduction amplitude of DBP is more than 8%.Oils and fats adds the combination (embodiment 9-19) of the combination with the acid of a kind of not Nitrogen element of a kind of amino acids adsorbent or addition two seed amino acid class adsorbents, the amplitude that DEHP reduces is more than 55%, the reduction amplitude of DINP is more than 55%, the reduction amplitude of DBP is more than 30%, and in oils and fats, add the combination of three seed amino acid class adsorbents or add combination (the embodiment 20-24 of two seed amino acid class adsorbents and the acid of a kind of not Nitrogen element, 28-30), the amplitude that DEHP reduces is more than 82%, the reduction amplitude of DINP is more than 70%, the reduction amplitude of DBP is more than 60%, above example all can reduce the content of phthalate plasticiser further.
Especially, if add the combination of three seed amino acid class adsorbents and the acid of a kind of not Nitrogen element in oils and fats or add amino acid classes four kinds different, phthalate content of plasticizing agent (embodiment 25-27,31-34) can be reduced to a greater degree.
On the contrary, oils and fats adds other kinds of adsorbent, for instance activated carbon (embodiment 35), then cannot reduce phthalate content of plasticizing agent.
Oils and fats phthalate plasticiser exceeded standard when the above-mentioned detailed description of the invention adopted in the present invention or its combination processes, for the oils and fats of the content of different phthalate plasticisers, the method in the present invention can be adopted to be removed to the limitation requirement of Ministry of Public Health plasticizer.For the oils and fats that phthalate plasticiser exceeds standard in a large number, it would however also be possible to employ technical solutions according to the invention are repeated processing or adopt the preferred embodiment in the present invention to be removed, until it reaches food requirement standard.
Claims (10)
1. one kind controls or reduces the technique of plasticiser in oils and fats, it is characterised in that including:
In oils and fats, based on oils and fats weighing scale, add the amino acids adsorbent that part by weight is 0.1-30% and/or the acid of 10-5000ppm not Nitrogen element, after heated and stirred, obtain the oils and fats that content of plasticizing agent reduces.
2. technique according to claim 1, it is characterized in that, one or more in threonine, glycine, serine, cysteine, tyrosine, agedoite, the glutamine of described amino acids adsorbent, it is preferable that one or more in threonine, glycine, serine, cysteine, tyrosine.
3. technique according to claim 1 and 2, it is characterised in that add at least two amino acids adsorbent in oils and fats.
4. the technique according to any one of claim 1-3, it is characterised in that add at least one amino acids adsorbent and the acid of at least one not Nitrogen element in oils and fats.
5. the technique according to any one of claim 1-4, it is characterised in that one or more in phosphoric acid, citric acid, malic acid, tartaric acid, lactic acid, the succinic acid of the acid of described not Nitrogen element, it is preferable that one or more in phosphoric acid, citric acid.
6. the technique according to any one of claim 1-5, it is characterised in that based on oils and fats weighing scale, the additional proportion of described amino acids adsorbent is 0.1%-20%, it is preferred to 0.1%-10%, more preferably 2%-8%, it is most preferred that 5%；And/or, the additional proportion of the acid of described not Nitrogen element is 10-1000ppm, it is preferred to 10-500ppm, it is most preferred that for 50-100ppm.
7. the technique according to any one of claim 1-6, it is characterised in that heating-up temperature is 60-130 DEG C, and/or, mixing time is 15-60 minute.
8. the oils and fats that prepared by the technique according to aforementioned any one of claim.
9. the technique removing plasticiser, it is characterised in that including:
In the sample of plasticiser to be removed, based on described example weight meter, add the amino acids adsorbent that part by weight is 0.1-30%, and/or the acid of 10-5000ppm not Nitrogen element, obtain after heated and stirred content of plasticizing agent reduce sample, the acid of described amino acids adsorbent and described not Nitrogen element not with or substantially not with described example reaction；Described sample is preferably medicine, cosmetics, health product, food.
10. the acid of amino acids adsorbent and/or not Nitrogen element is in the application reducing or controlling plasticiser in oils and fats or in other sample.
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| CN201410830706.0A CN105779122B (en) | 2014-12-22 | 2014-12-22 | Control reduces the technique of plasticiser and thus obtained grease in grease |
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| CN201410830706.0A CN105779122B (en) | 2014-12-22 | 2014-12-22 | Control reduces the technique of plasticiser and thus obtained grease in grease |
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Cited By (1)
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| CN113122377A (en) * | 2019-12-30 | 2021-07-16 | 丰益(上海)生物技术研发中心有限公司 | Method for removing plasticizer in oil refining process |
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| CN113122377A (en) * | 2019-12-30 | 2021-07-16 | 丰益(上海)生物技术研发中心有限公司 | Method for removing plasticizer in oil refining process |
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