CN103409308A - Treating method for plasticizer in liquor - Google Patents
Treating method for plasticizer in liquor Download PDFInfo
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- CN103409308A CN103409308A CN2013103551482A CN201310355148A CN103409308A CN 103409308 A CN103409308 A CN 103409308A CN 2013103551482 A CN2013103551482 A CN 2013103551482A CN 201310355148 A CN201310355148 A CN 201310355148A CN 103409308 A CN103409308 A CN 103409308A
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Abstract
The invention provides a treating method for a plasticizer in liquor. The method comprises the following steps: adding 0.2 to 0.35% by mass of active carbon with a bore diameter of less than 100 A DEG into liquor; carrying out sealing and full stirring at a temperature of 30 to 40 DEG C; and successively carrying out standing and filtering. With the treating method, the plasticizer in the liquor can be effectively absorbed, the content of the plasticizer is lower than plasticizer content prescribed in limit standards of China, and the treated liquor has taste slightly different from that of an original sample.
Description
Technical field
The present invention relates to the treatment process of fluidizer in a kind of purifying method of white wine, particularly white wine.
Background technology
Liquor industry is Chinese conventional column industry, in food service industry, has at home very important effect.Yet, due to fluidizer event in white wine, cause whole industry to be pushed to the teeth of the storm of food-safety problem.In 2011 No. 551 files of the special issue of national health department, the limit standard of three kinds of materials in clear food, be respectively DEHP:1.5mg/kg, DIBP:9.0mg/kg, DBP:0.3mg/kg.Wherein, in white wine, exceeding standard is the most also DBP(dibutyl phthalate the most generally), according to investigation, find that in a lot of old base liquors, content of plasticizing agent is quite high, be about ten times that national standard is limited the quantity of.The food that long-term edible fluidizer exceeds standard, can damage male reproductive function, impels female precocious puberty and immunity system and Digestive tract are damaged, and even can poison Human genome.
In dibutyl phthalate (DBP), diisobutyl phthalate (DIBP), phthalic acid two (2-ethyl) own ester (DEHP) and diisononyl phthalate (DINP), first three kind is material the most common in white wine and that content is the highest, and its molecular structural formula is as follows:
Wherein, formula 1 is the DBP structural formula, and formula 2 is the DIBP structural formula, and formula 3 is the DEHP structural formula.
According to structural formula, can find out, these three kinds of material things contain identical agent structure, and remaining part also is saturated carbochain, and just arranged dividing of side chain and straight chain.The phthalate material, owing between substituting group and phenyl ring, producing π-π electrophilic conjugative effect, makes the molecular structure quite stable, is not easy to decompose.In addition, two side chains of fluidizer molecule are on the phenyl ring ortho position, make molecule have certain moment of dipole, belong to polar molecule.But because side chain is longer, between two groups above ortho position, have larger sterically hinderedly, make intramolecular moment of dipole diminish, finally cause the fluidizer molecule to present the state of low-pole.Water is strong polar material, and alcohol is the low-pole material, is subject to simultaneously the impact of the intramolecular conjugative effect of fluidizer, makes three kinds of materials water insoluble, but can be dissolved in alcohol.The white wine main component is alcohol and water, and this mixed system is along with the rising of alcoholic strength, and the solvent integral polarity reduces gradually, so the also increase thereupon of the solubleness of fluidizer, makes it in wine, be in the uneven distribution state but be subject to the water molecules impact.This brings larger difficulty to plasticizer treats on the one hand, also causes on the other hand the detection data of fluidizer to have larger random error.
Prior art adopts heavily steams and the method such as reverse osmosis is removed fluidizer in white wine, and wherein heavily steaming sample can effectively reduce content of plasticizing agent, but sense organ is tasted and appraised result and shown that this sample and former state have larger difference and the rate of recovery to only have 68.2%.Reverse-osmosis treated has all been got rid of the molecular weight in wine at the material more than 100 basically, processes white wine later and basically only has water and part alcohol, and the flavour ingredient loss is serious.And physisorphtion is method more elementary in current separation method, usually be applied to require lower primary separation.In addition, the impact because alcohol and fluidizer are low-pole and are subject to water molecules uneven distribution state in alcohol, it is believed that by physisorphtion and be difficult to be up to state standards.In addition, people generally believe that this simple separation method of physical adsorption also can not realize in absorption during fluidizer and retain the local flavor of wine, and make people abandon trial and the research of physisorphtion, so research direction is placed on the methods such as distillation that separation accuracy is higher and reverse osmosis.
Summary of the invention
The invention provides and a kind ofly can effectively remove the fluidizer in white wine, keep simultaneously the method for the theme local flavor of white wine.
The present invention mainly realizes by the following method:
A kind of plasticizer treats method in white wine is characterized in that: in white wine, add aperture to be less than
Gac sealing fully stir, standing rear filtration.
Further, described sorbent material add-on is that ten thousand of quality of white spirit/20 are to 35/10000ths.
Further, adding charcoal absorption is to carry out in white wine production terminal operation.
Further, described gac is to add absorption in batches in batches.
Further, carboxyl, lactone group and phenylol are contained in described activated carbon surface and inside, space.
Further, described adsorption temp is 30-40 ℃.
Further, the pH value in described when absorption is between 3.3-4.5.
Further, described gac is Powdered.
Beneficial effect of the present invention is: the applicant, through lot of experiments, have been surprisingly found that, when adopting aperture to be less than
Charcoal absorption the time, content of plasticizing agent in wine is up to state standards, changed traditional understanding, and the method compares raw material with reverse osmosis and is easy to get with heavily steaming, easy to operate, cost is low.
The accompanying drawing explanation
Fig. 1 is the relation between gac add-on and fluidizer adsorption effect.
Embodiment
Below describe for example the present invention in detail.
The different separation method contrasts of embodiment 1
In order to study the characteristics of heavily steaming, reverse osmosis and physical adsorption, respectively three kinds of methods are contrasted.
Heavily steam: 100 ℃ of Heating temperatures, normal pressure water-cooled.
Reverse osmosis: Tao Shi BW30-400 type reverse osmosis membrane, by LG-DOW company, to be produced, supercharging pressure is 1.0Mpa, carries out reverse-osmosis treated.
Physical adsorption: adopt aperture to be
Ball shape active carbon, 6.003g, sealing was stirred 1.5 hours, filtered after standing 24 hours.
Detect respectively after treatment three kinds of content of plasticizing agents in wine.Simultaneously, five teacher of sampling wine estimate its mouthfeel.It the results are shown in Table 1.
Table 1 is processed rear content of plasticizing agent in different ways
Found through experiments, three kinds of modes all can reach certain treatment effect, but have drawback separately.Can effectively to reduce the content of plasticizing agent rate of recovery low but heavily steam sample, and sense organ is tasted and appraised result and shown that this sample and former state have larger difference simultaneously.Although select the absorption treatment effect not as heavily steaming and reverse osmosis, also can reduce content of plasticizing agent, and substantially keep the original style and characteristic of wine body.Reverse-osmosis treated has all been got rid of the molecular weight in wine at the material more than 100 basically, processes white wine later and basically only has water and part alcohol.Therefore, guarantee that the white wine main style is not affected, adopt physical adsorption way better.But it is research emphasis that its plasticizer treats amount is up to state standards.
The impact in embodiment 2 different activities charcoal apertures
Under the same conditions, adopt the processing to fluidizer in white wine A (DIBP, DBP, DEHP content are 1.5mg/kg) of gac that different pore size further features are identical, abundant experimental results is as shown in table 2.
The impact of table 2 micropore size on the fluidizer adsorption effect
Result shows that pore size has considerable influence to the adsorption effect of fluidizer, and the less treatment effect for fluidizer in aperture is more obvious.But micropore size can not be too little, otherwise the inner resistance to mass transfer strengthened that exists causes internal diffusion and interior back diffusion effect to be a greater impact, and has both reduced processing efficiency and has also had influence on adsorption effect simultaneously.As can be known from Table 2, the aperture of gac is for being less than
The time white wine after processing in content of plasticizing agent can be up to standard, be less than
The time adsorption effect best.After processing, the difference of the mouthfeel of white wine and raw sample is less.
The impact of embodiment 3 activated carbon dosage on adsorption effect
In the alcohol that contains fluidizer (DIBP, DBP, DEHP content are 2.5mg/kg), add same aperture
The powdered carbon of difference amount, 30-40 ℃ of lower seal stirs, standing rear filtration detects respectively the adsorptive capacity of fluidizer in each filtrate, result such as Fig. 1.
As can be seen from Figure 1 along with the increase of add-on, the adsorptive capacity of fluidizer also increases thereupon, but is not to present linear increasing always.This is that the dispersion effect when additional proportion is larger in solution is affected because gac is Powdered on the one hand.On the other hand, vying each other of adsorption and desorption when the content of plasticizing agent in solution drops to a certain degree, occurred, especially this phenomenon is particularly evident in the alcohol system.In addition, can find out this for the DEHP adsorption rate apparently higher than DBP and DIBP.Therefore, as can be known according to Fig. 1, when add-on, can reach best treatment effect 35/20/10000ths to ten thousand the time.When in sample, content of plasticizing agent is higher, can adopt the mode in batches added, can obviously improve processing efficiency.
The impact of embodiment 4 differing tempss on adsorption effect
In 4 stainless steel casks that fill 4.0kg white wine A, add respectively the 6.000g aperture
Gac, then be placed in respectively the super thermostat of 10 ℃, 20 ℃, 30 ℃, 40 ℃, 50 ℃, shake continuously after 1 hour and filter, measure content of plasticizing agent in filtered liquid, result is as shown in table 3.
Adsorption effect under table 3 differing temps
As can be seen from Table 3, temperature has certain influence for the adsorption effect of fluidizer, when temperature during at 30-40 ℃ adsorption effect best.This is mainly the process of a running balance that is actually due to solid-liquid absorption.When temperature is low, along with the rising of temperature, the absorption dominate; An equilibrium system when temperature reaches 40 ℃, occurs, now adsorbed the state that reached capacity; When temperature surpassed 40 ℃, desorption was leading by occupying gradually.Therefore in actual mechanical process, select as much as possible adsorption effect to account for leading temperature range and process.
The impact of embodiment 5 solvent effects on adsorption effect
Found through experiments, the treatment effect of higher its fluidizer of alcoholic strength is poorer, and this is mainly because the fluidizer molecule has larger solubleness in wine, has weakened the reactive force between fluidizer molecule and adsorbent surface, thereby has reduced equilibrium adsorption capacity.In actual process, in order to reduce solvent effect, be generally after white spirit mixing completes, to carry out again adsorption treatment.The impact of embodiment 6 acidity on adsorption effect
Preparation contains the spirituous solution of DBP, DEHP and DIBP respectively, adopts acetic acid that the pH value is adjusted into respectively to pH=2.5,3,3.5,4,5, then adds respectively the equivalent aperture
Powdered carbon, filter after 1 hour in vibration under 30 ℃, detects content of plasticizing agent in filtrate.Experimental result shows that the pH value has a certain impact for the absorption of fluidizer, the too low and too high adsorption process that all is unfavorable for of acidity, and adsorption effect is best when the pH value is between 3.3-4.5.In actual process, be the terminal process mode due to what adopt, although can not control acidity, under the reason condition, the acidity of white wine all, near 4.0, has guaranteed the final effect of processing.
The impact of embodiment 7 activated carbon surface character on treatment effect
Differing materials is adopted respectively in experiment,
It is as shown in table 4 that the powdered carbon in aperture is processed its effect to white wine A.Simultaneously, adopt the Boehm method, detect carboxyl, lactone group and phenylol that three kinds of activated carbon surfaces and inside, space are contained.Concrete grammar is: respectively by 0.1000mol/L NaOH, Na
2CO
3And NaHCO
3Each 25mL of solution adds in three ground Erlenmeyer flasks that the 5.0g gac is housed, under 30 ℃ of conditions, 150 times/min constant temperature oscillation absorption 24h, get supernatant liquid and using 0.1000mol/L HC1 solution as titrating solution, with the tropeolin-D agent of giving instruction, carry out back titration, detected result is as shown in table 4.NaHCO wherein
3With in carboxyl react, Na
2CO
3With carboxyl and lactone group, react NaOH and carboxyl, lactone group and phenylol reaction.From the difference of measurement result, can determine carboxyl, lactone group, phenolic hydroxyl group in upper quantitative relation.
Table 4 unlike material adsorption effect and functional group content
As can be seen from Table 4, the number of surface group has a certain impact for adsorption efficiency, and the rich 1# gac of selecting is all higher due to lactone group, carboxyl and phenolic group, so that treatment effect also obviously is better than is common.
The impact of embodiment 8 gac profiles on the plasticizer treats effect
Select aperture to be
Be only the gac that profile is different, under identical condition, fluidizer in Wine Sample A processed, its experimental result is as shown in table 5.Data results by table 5 is as can be known, and the gac of different profiles has certain influence to the adsorptive power of fluidizer, and its magnitude relationship is powdery>particulate state>indefinite form>ball-type>cylindrical.This is mainly because powdery has larger specific surface area, and simultaneously the proportion in the wine body is less, in mixing process sedimentation slow, be convenient to and the wine body between abundant contact, make the adsorption effect of fluidizer molecule obviously improve.
The treatment effect of the different profiles of table 5 to fluidizer
The impact of embodiment 9 other factors on adsorption effect
Experiment is also inquired into churning time, time of repose and filter type respectively, and result shows that these factors can be ignored on the impact of adsorption effect as long as guaranteeing to stir fully and in filtration procedure can not produce secondary pollution again.
Conclusion: by factors such as the acidity on gac kind, material and consumption and processed system, temperature and solvent effects, the impact of adsorption effect is analyzed, result shows that the gac aperture has the greatest impact to adsorption effect, when adopting aperture to be less than
Charcoal absorption the time, content of plasticizing agent in wine is up to state standards, employing is less than
Adsorption effect of activated carbon in water the best.Temperature is controlled 30-40 ℃, and the pH value is between 3.3-4.5, the rich 1# gac of employing 35/20/10000ths to ten thousand (
Powdered carbon) can be issued to the optimum handling effect in the situation that guarantees wine phosphor bodies style.
Claims (9)
1. plasticizer treats method in a white wine, is characterized in that: in white wine, add aperture to be less than
Gac sealing fully stir, standing rear filtration.
2. treatment process as claimed in claim 1, it is characterized in that: described sorbent material add-on is that ten thousand of quality of white spirit/20 are to 35/10000ths.
3. treatment process as claimed in claim 2, it is characterized in that: described gac aperture is for being not more than
4. as described treatment process one of in claim 1-3, it is characterized in that: adding charcoal absorption is to carry out in white wine production terminal operation.
5. as described treatment process one of in claim 1-3, it is characterized in that: described gac is to add absorption in batches in batches.
6. as described treatment process one of in claim 1-3, it is characterized in that: carboxyl, lactone group and phenylol are contained in described activated carbon surface and inside, space.
7. as described treatment process one of in claim 1-3, it is characterized in that: described adsorption temp is 30-40 ℃.
8. as described treatment process one of in claim 1-3, it is characterized in that: the pH value during described absorption is between 3.3-4.5.
9. as described treatment process one of in claim 1-3, it is characterized in that: described gac is Powdered.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104071460A (en) * | 2014-07-07 | 2014-10-01 | 扬州大学 | Method for removing plasticizer in liquid food |
| CN107014937A (en) * | 2017-04-10 | 2017-08-04 | 新疆农业科学院农业质量标准与检测技术研究所 | A kind of filter and its application |
| CN109289307A (en) * | 2018-10-26 | 2019-02-01 | 劲牌生物医药有限公司 | A kind of method of plasticiser in removing extract |
| CN114082220A (en) * | 2021-11-04 | 2022-02-25 | 杨凌萃健生物工程技术有限公司 | Device and process for removing plasticizer from cowberry extract |
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| DE4413982A1 (en) * | 1994-04-21 | 1995-10-26 | Bernd Gogol | Use of column filter to filter uncooled alcoholic drinks during prodn. |
| CN101314473A (en) * | 2008-02-20 | 2008-12-03 | 四川省林业科学研究院 | Bamboo absorbent charcoal for wine |
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2013
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4413982A1 (en) * | 1994-04-21 | 1995-10-26 | Bernd Gogol | Use of column filter to filter uncooled alcoholic drinks during prodn. |
| CN101314473A (en) * | 2008-02-20 | 2008-12-03 | 四川省林业科学研究院 | Bamboo absorbent charcoal for wine |
Non-Patent Citations (2)
| Title |
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| 刘辉，等: "4种活性炭吸附典型内分泌干扰物DBP的特性", 《华南师范大学学报（自然科学版）》 * |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104071460A (en) * | 2014-07-07 | 2014-10-01 | 扬州大学 | Method for removing plasticizer in liquid food |
| CN107014937A (en) * | 2017-04-10 | 2017-08-04 | 新疆农业科学院农业质量标准与检测技术研究所 | A kind of filter and its application |
| CN109289307A (en) * | 2018-10-26 | 2019-02-01 | 劲牌生物医药有限公司 | A kind of method of plasticiser in removing extract |
| CN109289307B (en) * | 2018-10-26 | 2020-12-22 | 劲牌生物医药有限公司 | Method for removing plasticizer from extract |
| CN114082220A (en) * | 2021-11-04 | 2022-02-25 | 杨凌萃健生物工程技术有限公司 | Device and process for removing plasticizer from cowberry extract |
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Application publication date: 20131127 |