CN108611188A - A kind of grease processing technique - Google Patents
A kind of grease processing technique Download PDFInfo
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- CN108611188A CN108611188A CN201611129078.9A CN201611129078A CN108611188A CN 108611188 A CN108611188 A CN 108611188A CN 201611129078 A CN201611129078 A CN 201611129078A CN 108611188 A CN108611188 A CN 108611188A
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- grease
- alkali
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- zeranol
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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
- C11B3/02—Refining fats or fatty oils by chemical reaction
- C11B3/06—Refining fats or fatty oils by chemical reaction with bases
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- Chemical Kinetics & Catalysis (AREA)
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- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
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- Organic Chemistry (AREA)
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Abstract
The present invention provides a kind of grease processing techniques can effectively reduce the content of zeranol in grease by using the operation for contacting grease with alkali under the conditions of 3 25 DEG C.There is lower alkali consumption and neutral oil loss, higher production efficiency and more excellent zeranol removal efficiency compared with prior art.
Description
Technical field
The present invention relates to oil processing fields, are related to a kind of oil refining process, and in particular to a kind of to lower red enzyme ketenes
Grease processing technique.
Background technology
Zeranol toxin (Zearalenone, ZEN), also known as zearalenone, F-2 toxin are a kind of with dihydroxy
The compound of yl benzoic acid lactone structure initially comes from the corn for obtaining head blight, it is whole world pollution most commonly used one
Kind biotoxin has the toxic action that can not be ignored to health.The mankind take in for a long time zeranol toxin can cause it is female
Hormonosis causes the form of reproductive organs that lesion and dysfunction occurs, as reproductive organs is extremely red and swollen, symptom of estrus
Persistently occur, be not easy to be pregnant, easy symptoms such as miscarriage, abnormal stillborn foetus frequency of occurrences height.
Zeranol mainly pollutes the cereal such as corn, wheat, rice, barley, millet and oat.The wherein positive inspection of corn
Extracting rate is 45%, and highest toxic amount can reach 2909mg/kg；The recall rate of wheat be 20%, toxic amount be 0.364~
11.05mg/kg.The heat resistance of zeranol is stronger, handles 1 hour at 110 DEG C and is just totally disrupted.Corn oil is from maize
The edible oil squeezed in bud.If corn or maize germ storage are improper, in the dark moist or not good environment of ventilation condition,
Fungi is easily infected, is polluted by zearalenone toxin.Zeranol is macromolecular organic compound, is readily dissolved in oil
In fat, enter in raw corn oil through expressing process.If dealing with improperly, zeranol toxin can not be down in safe range, pole
Easily cause damages to health.With the continuous improvement of people's level of consumption and consumption concept update, grease consumption is more focused on
Nutrition and health make the occupation rate of market of the certain alimentary health-care function corn oil of tool rise year by year.Therefore, how oil is effectively reduced
In fat, the content of zeranol toxin especially in corn oil, it is necessary to be studied.
Currently, having many reports about the research that zeranol toxin in grease removes, removal methods focus primarily upon
Physical, chemical method, bioanalysis.Wherein, Physical includes mainly following manner：1. high-temperature heating.Heating is by mould under high temperature
The grease of pollution is a kind of method of traditional destruction toxin, but this method expends mass energy, and may be to oil
Beneficiating ingredient in fat damages.(screening of Xu Jing zearalenone detoxifying agents and its detoxification mechanism Primary Study [D]
Hua Zhong Agriculture University, 2014:1-41.) 2. irradiation.Irradiation method has certain effect to the removal of zeranol, but can also break simultaneously
The structure of bad nutriment, and irradiation method treating capacity is small, equipment is expensive, is not easy to realize in mass production, therefore produce
Industry application is restricted.(Liu Yongzhen, Zhu Fenghua, peaceful snow is tender to wait zearalenone toxin poison-removing method progress in feeds
[J] China feed, 2013,15:3-13.) 3. absorption method.Absorption is to reach different degrees of by the hydrophobic effect of adsorbent
Remove the effect of zeranol toxin in ground.It, simultaneously may also can be right although the method has certain effect in terms of absorbing toxin
There are suction-operateds for other benefit materials in grease, reduce the nutritive value of grease itself.(Liu Yongzhen, Zhu Fenghua, Ning Xuejiao
Zearalenone toxin poison-removing method progress [J] China feed in equal feeds, 2013,15:3-13.)
Chemical method includes mainly：1. ozone treatment.McKenzie degrades to zearalenone with ozone, in 15s
Time in can be with 100% degradation zeranol.(McKenzie K S,Sarr A B,Mayurak,et
al.Oxidative Degradation and Detoxification of Mycotoxins Using a Novel
Source of Ozone[J].Food Chemical Toxicology,1997,35(8):807-820.) 2. dioxygen water process.
For Abd Alla etc. studies have shown that under conditions of 80 DEG C, the hydrogen peroxide of concentration 10% is reachable to the degradation rate of zeranol
83.9%.(Abd Alla E S.Zearalenone:Toxigenic Fungi and Chemical Decontamination
in Egyptian Cereals[J].Nahrung,1996,41(6):362-365.) degradation of the above oxidizing process to zeranol
It is with obvious effects, but the genotoxic potential of the new product generated after aoxidizing needs further to be studied.3. alkaline process.Alkaline process removing at present is red mould
Ketenes is all made of the mode of high temperature alkali refining.For Pei Yaxiao etc. at 55 DEG C of temperature, addition excess alkali 0.4% carries out corn oil alkali refining,
The result shows that the removal efficiency of zeranol is up to 94.63%.High temperature alkali refining is more apparent to the reducing effect of zeranol, but consumes
Alkali number causes greatly the loss of neutral oil to increase, and production yield is greatly reduced.
Bioanalysis, mainly microbial degradation method.Biodegradation refers to the toxophore of mycotoxin molecule by microorganism
The secondary metabolite of generation or secreted intracellular, ectoenzyme are decomposed and are destroyed, while generating the mistake of nontoxic catabolite
Journey.This poison-removing method will not destroy the nutritional ingredients such as vitamin in grease, amino acid, advantageously ensure that later use；It is red mould
Ketenes can be completely degraded into nontoxic product, ensure materials quality, and free from environmental pollution.(Chen Yi mycotoxin Gibberella zeaes
Research [D] the South China Science ＆ Engineering University of ketenes biodegradation key enzyme, 2014,1-71.) microbial degradation zeranol have it is all
More advantages, but it is very stringent to experimental condition requirement, and treating capacity is also difficult to adapt to mass produce, therefore is not easy to realize industry
Industrialization.
The country is also more about the patent of removing zeranol toxin, but mostly based on microbial degradation method.Such as：A kind of drop
Solve the method (CN102406098A) of zearalenone, the microbial degradation method of zearalenone
(CN102550893A), the application (CN105154351A) of one plant of Rhodococcus sp and its degrading zearalenone, efficient degradation are beautiful
The bacillus subtilis of Zearlenone and its application (CN105385616A).Corn is red in a kind of industrialization removal maize germ
It is reported in the method (CN103205311A) of mould ketenes and removes zearalenone toxin during high temperature alkali refining.
Prior art alkali refining removes in the method for zeranol, and it is big to there is alkali consumption, and neutral oil loss is high, production yield
Low problem is also not apparent enough simultaneously for the reducing effect of zeranol.
Invention content
Problems to be solved by the invention
Based on the defect present in the above prior art, technical problem to be solved by the present invention lies in provide a kind of grease
Processing method specifically provides a kind of method reducing zeranol in grease, for solving in current oil and fat refining, especially
It is that alkali consumption is big in alkaline process reduction zeranol technique, neutral oil loss is high, low production efficiency, and zeranol reducing effect is unknown
Aobvious technical problem.
The solution to the problem
The present invention provides a kind of fat processing method, which is characterized in that and include the steps that contacting grease with alkali, it is described to connect
It touches and is carried out at a temperature of 3~25 DEG C.
The present invention also provides a kind of methods of oil alkali refining, which is characterized in that and include the steps that contacting grease with alkali, institute
Contact is stated to carry out at a temperature of 3~25 DEG C.
The present invention also provides a kind of methods of grease detoxification, which is characterized in that and include the steps that contacting grease with alkali, institute
Contact is stated to carry out at a temperature of 3~25 DEG C.
The present invention also provides it is a kind of reduction grease in zeranol toxin method, which is characterized in that including by grease with
The step of alkali contacts, the contact carries out at a temperature of 3~25 DEG C.
In one or more embodiments, the Contact Temperature is 4-15 DEG C.
In one or more embodiments, the Contact Temperature is 4-10 DEG C.
In one or more embodiments, the alkali exists as an aqueous solution, and a concentration of 5~32%.
In one or more embodiments, the concentration of aqueous solution of the alkali is 5-20%.
In one or more embodiments, the concentration of aqueous solution of the alkali is 11-20%.
In one or more embodiments, the dosage of the alkali is the 0.02-0.08% of grease weight.
In one or more embodiments, the dosage of the alkali is the 0.03-0.06% of grease weight.
In one or more embodiments, the dosage of the alkali is the 0.03-0.05% of grease weight.
In one or more embodiments, the time that the grease is contacted with alkali is 1-6 hours.
In one or more embodiments, the time that the grease is contacted with alkali is 2-5 hours.
In one or more embodiments, the time that the grease is contacted with alkali is 2-4 hours.
In one or more embodiments, before the grease is contacted with alkali, the grease temperature is controlled 3~25
℃。
In one or more embodiments, before the grease is contacted with alkali, the grease temperature is controlled 4~25
℃。
In one or more embodiments, before the grease is contacted with alkali, the grease temperature is controlled 4~10
℃。
In one or more embodiments, the alkali is selected from：Sodium hydroxide, potassium hydroxide, lithium hydroxide, hydroxide
Calcium, magnesium hydroxide, potassium carbonate, sodium carbonate, calcium carbonate, magnesium carbonate, saleratus, sodium bicarbonate, potassium methoxide, sodium methoxide, ethyl alcohol
It is one or more in potassium, sodium ethoxide, sodium metasilicate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, ammonium hydroxide.
In one or more embodiments, the grease contains corn oil.
In one or more embodiments, the method further includes the operation being separated by solid-liquid separation.
Further include refining operation before the grease is contacted with alkali in one or more embodiments.
In one or more embodiments, the refining operation is selected from：Degumming, depickling, decoloration, deodorization, takes off dewaxing
It is one or more in fat, precipitation.
The present invention also provides a kind of greases being prepared by an any of the above-described method.
The present invention also provides a kind of grease groups that the zeranol content being prepared such as an any of the above-described method is low
Close object.
In one or more embodiments, in the low fat or oil composition of the zeranol content, in terms of grease weight
Zeranol content is not higher than 600ppb, preferably no greater than 300ppb, is further preferably not higher than 250ppb, more preferably no higher than
150ppb。
The present invention also provides a kind of fat or oil compositions containing above-mentioned grease.
The present invention also provides a kind of food, above-mentioned grease and/or fat or oil composition are contained in the food.
The effect of invention
The invention reduces the dosage and concentration of alkali in alkali refining operation, and/or uses more conventional alkali refining more
Low temperature, and/or the reaction time is controlled, the content of zeranol in grease can be significantly reduced.
Specific implementation mode
Below in conjunction with specific embodiment, the invention will be further described.It should be understood that following preferred embodiment is only used for
It illustrates rather than for limiting the scope of the present invention.
In the following examples, the experimental methods for specific conditions are not specified, usually measures according to national standards.If without corresponding
National standard, then carry out according to general international standard, normal condition or according to the normal condition proposed by manufacturer.
Unless otherwise defined or described herein, all professional and scientific terms used herein and those skilled in the art institute
Known meaning is identical.In addition any method and material similar or impartial to described content all can be applied to the method for the present invention
In.
In the present invention, term " containing " or " comprising " indicate that various composition can be applied to the mixture or group of the present invention together
It closes in object.Therefore, term " mainly by ... form " and " consist of " are included in term " containing " or " comprising ".
" range " disclosed herein is in the form of lower and upper limit.Can be respectively one or more lower limits and one
Or multiple upper limits.Given range is defined by selecting a lower limit and a upper limit.Selected lower and upper limit limit
The boundary of special range is determined.All ranges that can be defined in this way comprising and can combine, i.e., any lower limit
It can combine to form a range with any upper limit.For example, if the minimum zone value 1 and 2 listed, and if list maximum
Value range 3,4 and 5, then below range can all expect：1-3,1-4,1-5,2-3,2-4 and 2-5.
In the present invention, unless otherwise indicated, between the content range of each component of composition and its preferred scope
It can be combined with each other to form new technical solution.
In the present invention, unless otherwise indicated, " a combination thereof " indicates the multicomponent mixture of each element, such as two
Kind, three kinds, four kinds and until maximum possible multicomponent mixture.
In the present invention, unless otherwise indicated, own " part " and percentage (%) all refers to weight percent.
In the present invention, unless otherwise indicated, the sum of percentage of each component is 100% in all compositions.
In the present invention, unless otherwise indicated, the arbitrary reality of endpoint is included between numberical range " a-b " expression a to b
The breviary that array is closed indicates that wherein a and b are real numbers.Such as numberical range " 0-5 " expression has all listed herein
Whole real numbers between " 0-5 ", " 0-5 " are that the breviary of these combinations of values indicates.
If be not specifically stated, the term "an" used in this specification refers to "at least one".
In the present invention, if without particularly illustrating, all embodiments mentioned in this article and preferred implementation side
Formula can be combined with each other to form new technical solution.
In the present invention, if without particularly illustrating, all technical characteristics and preferred feature mentioned in this article can
New technical solution is formed to be combined with each other.
Grease
The present invention by control grease and alkali Contact Temperature, to realize the object of the invention.
In a specific embodiment, the grease includes but not limited to：Palm oil, palm-kernel oil, soybean oil are high
Oleic soybean oil, low linolenic soybean oil, rape oil, Canola Oil, high oleic acid rapeseed oil, seed oil of sunflower, high stearic acid vegetable seed
Oil, high oleic acid seed oil of sunflower, peanut oil, high oleic acid peanut oil, coconut oil, cottonseed oil, linseed oil, safflower seed oil, perilla herb oil, oil
Tea-seed oil, castor oil, olive oil, tallowseed oil, sesame oil, corn oil, Rice oil, walnut oil, grape seed oil, wild pepper seed
Oil, algal oil, peony seed oil, pumpkin seed oil, tomato seed oil, fiery flaxseed oil, cape jasmine oil, wheat-germ oil, amygdalus pedunculata pall oil, text
It is preced with fruit oil, bancoul nuts oil, Chinese torreya seed oil, samara oil, eucommia ulmoides seed oil, acer truncatum seed oil, oil and fat of sacha inchi, smooth bark Lai wood oils, mountain paulownia
Seed oil, hemp seed oil, dogwood oil, rhus glabra oil, cashew nut oil, avocado fruit oil, large-fruited hodgsonia fruit oil, big fruit melon chestnut fruit oil, butter
Fruit oil, shea butter, fat prok oil, macadimia nut oil, talisai oil, shuttle fruit oil, the wooden peanut oil, sinopimelodendron kwangsiense oil, rag wood
Oil, almond oil, hazelnut oil, pine-seed oil, rubber seed oil, oenothera seed oil, walnut oil, linseed oil, borage seed oil, sea-buckthorn
Seed is oily, one or more in tea seed oil.
In a specific embodiment, the grease further include optionally it is above-mentioned state vegetable oil it is modified processing obtain
Grease.
In a specific embodiment, the modification include be not limited to esterification, hydrolysis, transesterification, divide carry, hydrogen
The operations such as change, desaturation.
In a specific embodiment, the grease contains corn oil or is made of corn oil.
In a specific embodiment, the grease is polished fat.
In a specific embodiment, the grease is the grease without refining treatment.
In a specific embodiment, the grease is by one or more refining treatment steps.
In a specific embodiment, the refining operation is selected from：Degumming, depickling, decoloration, deodorization, takes off dewaxing
It is one or more in fat, precipitation.
In a specific embodiment, the grease is handled by degumming, depickling.
In a specific embodiment, the content of zeranol is less than 10000ppb in the grease, preferably smaller than
8000ppb is further preferably no larger than 7000ppb.
Method
The present invention by control grease and alkali Contact Temperature, to achieve the object of the present invention.
In a specific embodiment, the Contact Temperature of grease and alkali is 3-25 DEG C, preferably 4-15 DEG C, further excellent
Select 4-10 DEG C.
In a specific embodiment, before grease is contacted with alkali, the grease temperature is controlled at 3~25 DEG C, it is excellent
Select 4-15 DEG C, further preferred 4-10 DEG C.
The present invention can compared with conventional alkali refining removes the method for zeranol by reducing the Contact Temperature of grease and alkali
Significantly to reduce the content of zeranol in grease the removal efficiency of 30 DEG C of zeranols is especially more than when temperature is higher than 25 DEG C
It is relatively low, and when less than 3 DEG C, process operation cost will be dramatically increased, filtering load is dramatically increased, filtration difficulty, and not
The removal efficiency of zeranol can be caused further to be promoted, so as to cause the waste of the energy.And in the temperature model of the present invention
In enclosing, the removal efficiency of zeranol can at least reach 85% or more or even 90% or more in grease.
In a specific embodiment, the time that grease is contacted with alkali be 1-6 hours, preferably 2-5 hours, further
It is preferred that 2-4 hours.
Inventor is found surprisingly that, identical in caustic dosage, with the progress in reaction time, is initially
Based on alkali destruction zeranol structure, zeranol content reduces, but continues to extend the time, and alkali can carry out soap with neutral oil
Change, reaction system pH is caused to decline, the ester bond congregation of zeranol is looped back to self structure.It is red when being 6 hours between when reacted
The content of mould ketenes is minimum, is 286.7ppb, and reaction time control is relatively good at 6 hours or so, unsuitable long, and the reaction time
When less than 1 hour, zeranol removing is incomplete, and 2-6 hours best results, 2-4 hours further wherein, more preferable 2-3
Hour.Therefore by further controlling the time of contact of grease and alkali, to realize further zeranol removing effect
Fruit effectively prevents the rise of the content of zeranol.
In a specific embodiment, the alkali is not particularly limited, i.e., can be in alkalinity in aqueous solution, or with
Water contact can generate [OH-] ion substance.
In a specific embodiment, the alkali is selected from the oxide of alkali or alkaline earth metal, hydroxide, weak
Hydrochlorate, alkoxide, ammonium hydroxide it is one or more.
In a specific embodiment, the alkali be selected from sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide,
Magnesium hydroxide, barium hydroxide, potassium carbonate, sodium carbonate, calcium carbonate, magnesium carbonate, saleratus, sodium bicarbonate, potassium methoxide, methanol
It is one or more in sodium, potassium ethoxide, sodium ethoxide, sodium metasilicate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, ammonium hydroxide.
In a specific embodiment, the preferred sodium hydroxide of the alkali, potassium hydroxide, lithium hydroxide, calcium hydroxide,
One kind or more in potassium carbonate, sodium carbonate, saleratus, sodium bicarbonate, potassium methoxide, sodium methoxide, potassium ethoxide, sodium ethoxide, ammonium hydroxide
Kind.
In a specific embodiment, the alkali exists for liquid form, preferably exists as an aqueous solution.
In a specific embodiment, the concentration of aqueous solution of the alkali is 5-32%, the preferred aqueous slkali of 5-20%,
The aqueous slkali of further preferred 11-20%.
In a specific embodiment, the dosage of the alkali is the 0.02-0.08%, preferably 0.03- of grease weight
0.06%, further preferred 0.03-0.05%.
In a specific embodiment, very high for free fatty (Free Fatty Acid, FFA) content
Grease needs to convert the alkali consumption needed for its FFA, and required alkali consumption is needed for alkali consumption needed for FFA is contacted with zeranol
The sum of alkali number.
The present invention be further discovered that concentration of lye, reaction time under the same conditions, caustic dosage is higher, zeranol
Content is lower, and when caustic dosage is more than in 0.06% and oil, the content of zeranol tends towards stability substantially, but with the increasing of caustic dosage
The loss of neutral oil is added to be consequently increased, and when caustic dosage is less than 0.02%, one side zeranol removal efficiency is insufficient, another party
The loss of face neutral oil is also relatively high.Therefore the present invention realizes neutral oil minimum by further controlling caustic dosage
Loss late and the maximum removal efficiency of zeranol.
In a specific embodiment, further include the operation being separated by solid-liquid separation after grease is contacted with alkali.
In a specific embodiment, it is described be separated by solid-liquid separation operation includes centrifugation, filtering, filter, be decanted in one
Kind is a variety of.
In a specific embodiment, further include refining operation before the grease is contacted with alkali.
In a specific embodiment, the refining operation is selected from：Degumming, depickling, dewaxing, decoloration, deodorization, precipitation
In it is one or more.
In a specific embodiment, it is stirred during grease is contacted with alkali.
In a specific embodiment, the mixing speed be no more than 40r/min, preferably no greater than 30r/min,
Further preferably it is not more than 20r/min, more preferably no more than 15r/min.
In a specific embodiment, without stir process during grease is contacted with alkali.
In a specific embodiment, ultrasonication, shear treatment are used during grease is contacted with alkali and/or are passed through
Inert gas.
In a specific embodiment, the inert gas is selected from：Nitrogen, carbon dioxide, argon gas, helium, hydrogen
In it is one or more.
The grease of low zeranol content
The present invention also provides a kind of greases being prepared by the above method.
In a specific embodiment, in the grease being prepared by the above method, the red mould alkene in terms of grease weight
Ketone content is not higher than 600ppb, preferably no greater than 300ppb, is further preferably not higher than 250ppb, more preferably no higher than
150ppb。
In a specific embodiment, have in the grease that the above method is prepared, the red mould alkene in terms of grease weight
Ketone content not higher than 600ppb, 550ppb, 500ppb, 450ppb, 400ppb, 350ppb, 300ppb, 290ppb, 280ppb,
270ppb、260ppb、250ppb、240ppb、230ppb、220ppb、210ppb、200ppb、190ppb、180ppb、170ppb、
160ppb, 150ppb, 140ppb, 130ppb, 120ppb, or in the interval range that is made of above-mentioned any two number.
In a specific embodiment, the content of the low zeranol refer to red enzyme ketenes in terms of grease weight not
Higher than 600ppb, preferably no greater than 300ppb, it is further preferably not higher than 250ppb, more preferably no higher than 150ppb.
The present invention also provides a kind of fat or oil compositions containing above-mentioned grease.
The present invention also provides a kind of food, above-mentioned grease and/or fat or oil composition are contained in the food.
In following embodiments of the present invention, the raw material and facility information used is as follows：
Zeranol content assaying method：1. extraction：It weighs 40g oil samples (being accurate to 0.01g) and is placed in 250ml conical flasks
In, 4g sodium chloride and 100ml acetonitrile-waters (9+1) is added, 2min is extracted with homogenizer high-speed stirred, by folding fast qualitative
Filter paper filters, and pipettes 10ml filtrates and 40ml water dilution mixing is added, filtered 2 times through glass fiber filter paper, until after filtrate clarification
Carry out immune affinity column purification run；Immune affinity column is connected under 20ml glass syringes, 10ml extractions are accurately pipetted
Filtrate, in implantation glass syringe, adjusting pressure makes solution slow transit through immune affinity column with the flow velocity of 1 drop -2 drops/s, until
There is partial air to pass through cylinder.With 10ml water wash pillar 2 times, whole effluxes are discarded, and partial air is made to pass through cylinder.It is accurate
The elution of 1.5ml methanol is really added, flow velocity 1ml/min collects eluent in teat glass, for liquid chromatogram measuring；2. surveying
It is fixed：Liquid phase chromatogram condition：C18 columns, 150mm × 4.6mm (internal diameter), 4 μm of granularity；Mobile phase：Acetonitrile-water-methanol (46+46+
8)；Flow velocity：1ml/min；Detection wavelength：Excitation wavelength 274nm, launch wavelength 440nm；Sample size：100μl；Column temperature：Room temperature；
Chromatographic determination：Separately sampled liquid and each 100 μ l injections high performance liquid chromatograph of standard solution are measured, fixed with retention time
Property, peak area quantification；Blank control is done simultaneously, i.e., in addition to being not added with sample, presses above-mentioned steps and carries out.3. result calculates：By outer
Mark method calculates the content of zeranol in sample, and result of calculation deducts plain pape, and formula is as follows：In formula：The content of zeranol in X- samples, in unit ppb, A- sample liquid
The peak area of zeranol, the peak area of zeranol in A0- blank sample liquids, zeranol is dense in c- standard working solutions
Degree, unit are the final constant volume of μ g/ml, V- sample liquids, the sample size representated by the final sample liquids of unit ml, m-, unit g,
The peak area of zeranol in As- standard working solutions.
Saponified matter content detection method：Acetone 70ml is taken, bromophenol blue color developing agent 1ml is added, is titrated with the KOH aqueous solutions of 0.1mol
To blue, it then is titrated to yellow with the HCl/water solution of 0.01mol, 10g oil samples is weighed in the above solution, continues to use
The HCl/water solution of 0.01mol titrates, and changes to yellow by blue, record titrates the HCl solution volume needed, and saponified matter content calculates
Formula：X- saponified matter contents, unit ppm, V- titrate sample solution consumption salt
The volume of sour standard solution, the volume of unit ml, V0- titration blank sample solution consumption hydrochloric acid standard solution, unit ml,
The concentration of N- hydrochloric acid standard solutions, unit mol/L, m- oil sample quality, the matter of unit every mM of enuatrol of g, 0.304-
Amount, unit g/mmol.
Content of wax quantity measuring method:1. the purification of dewaxed oil：The oil sample thoroughly to dewax is slowly dropped to room temperature, is placed in refrigerator
Then oil temperature is down to 10 DEG C by 4d, kept for 10 DEG C and filtered in Bush's funnel with one layer of filter paper, obtain the oil sample of the not content of wax.With
This oil makees base oil configuration standard sample.2. the purification of wax：The gatch 200g with filter aid is taken, is rinsed with the petroleum ether of 10 times of volumes
The grease of useless filter aid, mixture is gone to be put into 4 DEG C of refrigerators 17 hours, wax and filter aid filter together, and filter cake is put into cable-styled pumping
In drawer device, petroleum ether is used to carry out drawer 12 hours as solvent, removes solvent, the preparation of 3. standard curves：With the above basic oil
The normal concentration for preparing 50,100,150,200,250,300,450ppm uses turbidity unit reading NTU for ordinate, the content of wax
It is abscissa to measure (ppm), makes a standard curve；4. sample measures；Oil sample is heated to 130 DEG C of removing micro-moistures, so
After make sample pass through 4# filter paper to be filtered removing insoluble impurities, after being cooled to room temperature, add it to one and contain 15ml third
In the colorimetric bottle of ketone, fill it up with to scale 30ml, be then sufficiently mixed, then colorimetric bottle is put into hot water be heated to it is transparent, then
It puts it into and accurately places 5min in ice-water bath, by colorimetric bottle wiped clean (being sure not to shake), finally use Hach2100a nephelometers
Measure its turbidity NTU；4. result of calculation：Paraffin content (ppm)=19.211NTU-9.5168
Zeranol removal efficiency computational methods：X is removal efficiency, %；M is zeranol before processing
Content, n are zeranol content after processing；
Neutral oil loss rate computational methods： Oil product FFA wherein used controls the FFA after 0.08%, reaction, and substantially 0.015%, i.e. △ FFA% are 0.065%；
The front and back H of reaction2O% contents are constant；Experiment oil p contents used are in 3ppm hereinafter, i.e. P × 0.00317 can be ignored substantially；
Soap is the soap that reaction generates；40% is soap cake residual oil content.
Influence of the embodiment 1-6 temperature to removing zeranol toxic effect
It takes 6 parts of refining level-one corn oil 200mL of same batch (zeranol content is 2567ppb) in beaker, is placed in control
On warm mixing platform, reaction temperature is adjusted to 50,40,30,25,15,3 DEG C, a concentration of 11% NaOH aqueous solutions, caustic dosage is added
For 0.03% (being calculated as 0.055g with NaOH) of grease weight, it is stirred to react 60min, is filtered respectively, sample and measures red mould alkene
The content of ketone, experimental result are as follows：
Influence of 1 temperature of table to removing zeranol effect
As shown in Table 1, identical in caustic dosage, alkali concentration and alkali refining time, the content of zeranol is with alkali
It refines the reduction of temperature and reduces, and reacted oil product saponified matter content is reduced with the reduction of alkali refining temperature；Alkali refining temperature is 25
DEG C or less when, the content of ZEN can be down to Europe superscript range (400ppb) hereinafter, removal efficiency of zeranol is under the conditions of this
89.10% or more.
Influence of the example 7-16 reaction time to zeranol reducing effect
By the test result of table 1, low temperature adds alkali to have preferable effect to the reduction of zeranol.Selection 6 DEG C, 20
Influence of the reaction time to zeranol reducing effect is studied at DEG C.
It takes 4 parts of refining level-one corn oil 200mL of same batch (zeranol content is 3287ppb) in beaker, is placed in control
On warm mixing platform, reaction temperature is adjusted to 6 DEG C, a concentration of 20% NaOH aqueous solutions are added, and caustic dosage is grease weight
0.03% (being calculated as 0.055g with NaOH), according to the following table reaction time, filters respectively, samples and measures every portion of corn oil after processing
The content of middle zeranol, experimental result are as follows：
Influence of the reaction time to zeranol reducing effect under the conditions of 26 DEG C of table
| Embodiment is numbered | Reaction time | ZEN contents (ppb) | Saponified matter content (ppm) | Neutral oil loss % |
| Embodiment 7 | 0 hour | 3287 | 24 | - |
| Embodiment 8 | 6 hours | 286.7 | 692.3 | 0.132% |
| Embodiment 9 | 12 hours | 773.2 | 961.8 | 0.158% |
| Embodiment 10 | 18 hours | 965.8 | 1018.7 | 0.164% |
As shown in Table 2, caustic dosage, alkali concentration under the same conditions, it is red with the extension in reaction time under the conditions of 6 DEG C
The content of mould ketenes can gradually go up, and illustrate the progress with the reaction time, be initially with alkali destroy zeranol structure based on,
Zeranol content reduces, but continues to extend the time, and alkali can carry out saponification with neutral oil, and reaction system pH is caused to decline, red mould
The ester bond congregation of ketenes is looped back to self structure.When being 6 hours between when reacted, the content of zeranol is minimum, is
286.7ppb, reaction time control is relatively good at 6 hours or so, unsuitable long；Under conditions of the temperature and caustic dosage, saponified matter content
Control is relatively good within 700ppm.
It takes 6 parts of refining level-one corn oil 200mL of same batch (zeranol content is 3287ppb) in beaker, is placed in control
On warm mixing platform, reaction temperature is adjusted to 20 DEG C, a concentration of 20% NaOH aqueous solutions are added, and caustic dosage is grease weight
0.03% (being calculated as 0.055g with NaOH), is stirred to react, according to the following table reaction time, filters respectively, after sampling and measuring processing
The content of zeranol, experimental result are as follows in every portion of corn oil：
Influence of the reaction time to zeranol reducing effect under the conditions of 3 20 DEG C of table
| Embodiment is numbered | Reaction time | ZEN contents (ppb) | Saponified matter content (ppm) | Neutral oil loss % |
| Embodiment 11 | 0 | 3287 | 24 | - |
| Embodiment 12 | 1 hour | 451.8 | 342.1 | 0.098% |
| Embodiment 13 | 2 hours | 342.3 | 483.3 | 0.117% |
| Embodiment 14 | 4 hours | 247.2 | 678.9 | 0.131% |
| Embodiment 15 | 6 hours | 392.3 | 887.2 | 0.152% |
| Embodiment 16 | 8 hours | 723.6 | 1092.3 | 0.171% |
As shown in Table 2, caustic dosage, alkali concentration under the same conditions, under the conditions of 20 DEG C, with the extension in reaction time,
Zeranol content is gradually reducing in front 4 hours, but after having spent 4 hours, and zeranol content is being gone up, 6 hours
When can still meet our requirement, after having spent 6 hours, have been over the range of 400ppb, therefore, under this condition, most
The long reaction time is 6 hours.Under the conditions of the temperature and caustic dosage, saponification number control is within 890ppm conducive to the de- of zeranol
It removes.
Influence of the embodiment 17-21 caustic dosages to zeranol reducing effect
It takes 5 parts of refining level-one corn oil 200mL of same batch (zeranol content is 2567ppb) in beaker, is placed in control
On warm mixing platform, reaction temperature is adjusted to 6 DEG C, a concentration of 20% NaOH aqueous solutions are added by 4 caustic dosage of table, are stirred to react 6
Hour, it filters respectively, samples and measure the content of zeranol in every portion of corn oil after processing, experimental result is as follows：
Influence of the 46 DEG C of caustic dosages of table to zeranol reducing effect
As shown in Table 4, concentration of lye, reaction time under the same conditions, caustic dosage is higher, and the content of zeranol is got over
Low, when caustic dosage is more than in 0.3kg/t and oil, the content of zeranol tends towards stability substantially, but in the increase of caustic dosage
Property oil loss be consequently increased.
Influence of the embodiment 22-27 alkali concentrations to zeranol reducing effect
It takes 6 parts of refining level-one corn oil 200mL of same batch (zeranol content is 2567ppb) in beaker, is placed in control
On warm mixing platform, reaction temperature is adjusted to 6 DEG C, NaOH aqueous solutions are added by 5 alkali concentration of table, caustic dosage is grease weight
0.03% (being calculated as 0.055g with NaOH), is stirred to react 6 hours, filters respectively, samples and measures after processing in every portion of corn oil
The content of zeranol, experimental result are as follows：
Influence of the alkali concentration to zeranol reducing effect under the conditions of 56 DEG C of table
As shown in Table 4, caustic dosage, reaction time under the same conditions, with the increase of concentration of lye, zeranol
Changes of contents is little, can be maintained at relatively low range.
Low temperature adds influence of the alkali to reduction zeranol effect in embodiment 28-30 producing lines
It takes in 3 parts of corns of same batch and oily crude oil 1300t (zeranol content is 6000ppb) is in reaction kettle, this is anti-
It is 20t oil samples to answer kettle capacity, and speed of agitator 15r/min adjusts reaction temperature to 6 DEG C, is added by 4 caustic dosage of table a concentration of
20% NaOH aqueous solutions are stirred to react 6 hours, filter respectively, sample and measure after processing zeranol in every portion of corn oil
Content, experimental result is as follows：
Low temperature adds influence of the alkali to zeranol reducing effect in 6 producing line of table
By producing line test result it is found that when caustic dosage is adjusted to 0.06%, the content of zeranol is reduced to 168ppb, takes off
Except rate is up to 97.20%, oil weight 1275.3t, yield 98.1% after reaction filtering.
Influence while embodiment 31-34 low temperature adds alkali to remove zeranol to wax content
It takes 4 parts of refining level-one corn oil 200mL of same batch (starting corn oil paraffin content is 420ppm) in beaker, is placed in
On temperature control stirring platform, reaction temperature is adjusted by table 7, while a concentration of 20% NaOH aqueous solutions being added by 7 caustic dosage of table, stirring
Reaction 6 hours, is filtered respectively, samples and measure the content of wax in every portion of corn oil after processing, and experimental result is as follows：
Add influence of the alkali to corn oil paraffin content under the conditions of 76 DEG C of table
| Embodiment is numbered | Caustic dosage | Reaction temperature | Saponified matter content/ppm | Grease paraffin content (ppm) | Neutral oil loss % |
| Embodiment 31 | 0 | 6℃ | - | 38 | - |
| Embodiment 32 | 0.03% | 6℃ | 726 | 35 | 0.135% |
| Embodiment 33 | 0 | 20℃ | - | 418 | - |
| Embodiment 34 | 0.03% | 20℃ | 1254 | 416 | 0.186% |
Experiment finds that at 6 DEG C and 20 DEG C plus alkali, the wax content of oil product lower there is no apparent；Illustrate, in the temperature section, to add
Alkali does not play facilitation to dewaxing, and there are significant differences with dewaxing operation.
Influence of other alkali of embodiment 35-37 to removing zeranol
It takes 3 parts of refining level-one corn oil 200mL of same batch (zeranol content is 2567ppb) in beaker, is placed in control
On warm mixing platform, reaction temperature is adjusted to 6 DEG C, the aqueous solution of a concentration of 20% alkali is added by the type of alkali described in table 8, adds alkali
Amount is 0.03% (being calculated as 0.055g with NaOH) of grease weight, is stirred to react 6 hours, filters respectively, samples and measure processing
Afterwards in every portion of corn oil zeranol content, experimental result is as follows：
Influence of the embodiment 38-40 present invention to red enzyme ketenes in other greases
Weigh 200mL in beaker by glyceride stock described in table 9, be placed on temperature control stirring platform, adjust reaction temperature to 6 DEG C,
A concentration of 20% NaOH aqueous solutions are added, caustic dosage is 0.03% (being calculated as 0.055g with NaOH) of grease weight, and stirring is anti-
It answers 6 hours, filters respectively, sample and measure the content of zeranol in every portion of corn oil after processing, experimental result is as follows：
Claims (10)
1. a kind of fat processing method, which is characterized in that be included at 3~25 DEG C, preferably at 4-15 DEG C, further preferably exist
The step of grease and alkali are contacted at 4-10 DEG C.
2. a kind of method reducing zeranol toxin in grease, which is characterized in that be included at 3~25 DEG C, preferably in 4-15
At DEG C, the step of grease and alkali are contacted further preferably at 4-10 DEG C.
3. method as claimed in claim 1 or 2, which is characterized in that the alkali exists as an aqueous solution, a concentration of 5~
32%, preferably 5-20%, further preferably 11-20%.
4. method as claimed in any one of claims 1-3, which is characterized in that the time that the grease is contacted with alkali is 1-6
Hour, preferably 2-5 hours, further preferably 2-4 hours.
5. the method as described in any one of claim 1-4, which is characterized in that the dosage of the alkali is grease weight
0.02-0.08%, preferably 0.03-0.06%, further preferably 0.03-0.05%.
6. the method as described in any one of claim 1-5, which is characterized in that before being contacted with the alkali, by the grease temperature
Degree control is at 3~25 DEG C, preferably at 4-15 DEG C, further preferably at 4-10 DEG C.
7. the method as described in any one of claim 1-6, which is characterized in that the alkali is selected from：Sodium hydroxide, hydroxide
Potassium, lithium hydroxide, calcium hydroxide, magnesium hydroxide, potassium carbonate, sodium carbonate, calcium carbonate, magnesium carbonate, saleratus, sodium bicarbonate,
It is one or more in potassium methoxide, sodium methoxide, potassium ethoxide, sodium ethoxide, sodium metasilicate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, ammonium hydroxide.
8. a kind of fat or oil composition, which is characterized in that the oil being prepared containing any one of such as claim 1-7 the methods
Fat, or the grease being prepared by any one of such as claim 1-7 the methods form.
9. low fat or oil composition, special such as the zeranol content that any one of claim 1-7 the methods are prepared
Sign is, in terms of fat or oil composition weight, zeranol content is not higher than 600ppb in the fat or oil composition, preferably no greater than
300ppb is further preferably not higher than 250ppb, more preferably no higher than 150ppb.
10. a kind of food, it is characterised in that contain the fat or oil composition as described in claim 8 and/or 9.
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| CN116948744A (en) * | 2023-09-20 | 2023-10-27 | 曲阜良友食品有限公司 | Corn oil moderate processing technology |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1147011A (en) * | 1994-12-21 | 1997-04-09 | 中国科学院福建物资结构研究所 | Peanut oil refining method |
| CN102452929A (en) * | 2010-11-03 | 2012-05-16 | 李家波 | Production process for preparing high-purity alpha-linolenic acid by taking perilla seeds as raw materials |
| CN103205311A (en) * | 2013-05-06 | 2013-07-17 | 国家粮食局科学研究院 | Method for industrially removing zearalenone out of maize germ |
| CN103284023A (en) * | 2013-05-20 | 2013-09-11 | 江南大学 | Application of food-grade microorganism in degradation of zearalenone |
| CN104212634A (en) * | 2014-09-04 | 2014-12-17 | 青岛海智源生命科技有限公司 | DHA (docosahexaenoic acid) oil low-temperature refining method |
| CN105038979A (en) * | 2015-07-16 | 2015-11-11 | 山东三星玉米产业科技有限公司 | Method for removal of zearalenone in corn oil |
| CN105087444A (en) * | 2015-09-02 | 2015-11-25 | 国家粮食局科学研究院 | Bacillus amyloliquefaciens capable of degrading ZEN (zearalenone) efficiently and application of bacillus amyloliquefaciens |
| CN105385616A (en) * | 2015-09-02 | 2016-03-09 | 国家粮食局科学研究院 | Bacillus subtilis for effectively degrading zearalenone and application thereof |
| CN106010771A (en) * | 2016-06-04 | 2016-10-12 | 河南工业大学 | Corn germ pretreatment processing technology to eliminate mycotoxin in corn oil |
-
2016
- 2016-12-09 CN CN201611129078.9A patent/CN108611188B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1147011A (en) * | 1994-12-21 | 1997-04-09 | 中国科学院福建物资结构研究所 | Peanut oil refining method |
| CN102452929A (en) * | 2010-11-03 | 2012-05-16 | 李家波 | Production process for preparing high-purity alpha-linolenic acid by taking perilla seeds as raw materials |
| CN103205311A (en) * | 2013-05-06 | 2013-07-17 | 国家粮食局科学研究院 | Method for industrially removing zearalenone out of maize germ |
| CN103284023A (en) * | 2013-05-20 | 2013-09-11 | 江南大学 | Application of food-grade microorganism in degradation of zearalenone |
| CN104212634A (en) * | 2014-09-04 | 2014-12-17 | 青岛海智源生命科技有限公司 | DHA (docosahexaenoic acid) oil low-temperature refining method |
| CN105038979A (en) * | 2015-07-16 | 2015-11-11 | 山东三星玉米产业科技有限公司 | Method for removal of zearalenone in corn oil |
| CN105087444A (en) * | 2015-09-02 | 2015-11-25 | 国家粮食局科学研究院 | Bacillus amyloliquefaciens capable of degrading ZEN (zearalenone) efficiently and application of bacillus amyloliquefaciens |
| CN105385616A (en) * | 2015-09-02 | 2016-03-09 | 国家粮食局科学研究院 | Bacillus subtilis for effectively degrading zearalenone and application thereof |
| CN106010771A (en) * | 2016-06-04 | 2016-10-12 | 河南工业大学 | Corn germ pretreatment processing technology to eliminate mycotoxin in corn oil |
Non-Patent Citations (1)
| Title |
|---|
| 裴娅晓，等: "碱炼脱除玉米油中玉米赤霉烯酮(ZEN)的研究", 《中国油脂》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116948744A (en) * | 2023-09-20 | 2023-10-27 | 曲阜良友食品有限公司 | Corn oil moderate processing technology |
| CN116948744B (en) * | 2023-09-20 | 2023-12-08 | 曲阜良友食品有限公司 | Corn oil moderate processing technology |
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