CN101974101A - Polysaccharide metal complex resin with function of hydrolyzing protein - Google Patents
Polysaccharide metal complex resin with function of hydrolyzing protein Download PDFInfo
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- CN101974101A CN101974101A CN 201010513922 CN201010513922A CN101974101A CN 101974101 A CN101974101 A CN 101974101A CN 201010513922 CN201010513922 CN 201010513922 CN 201010513922 A CN201010513922 A CN 201010513922A CN 101974101 A CN101974101 A CN 101974101A
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Abstract
The invention relates to a technology for preparing a polysaccharide metal complex resin with a function of hydrolyzing the protein, belonging to the field of high polymer material and food engineering. The technology comprises the following steps of: modifying a space framework structure provided by chitosan resin by using a carbon and nitrogen heterocyclic compound and then coupling specific metal ions to obtain polysaccharide metal complex resin with a function of hydrolyzing the protein. the resin is easy to prepare, can be recycled and has favorable mechanical performance and reusability; and the resin is superior to the traditional diatomite clearing method when applied ro the wine production, can decompose the protein, prevent the precipitation of the wine caused by the protein and effectively prolong the shelf life of the wine while increasing the content of the amino acid in the wine. the resin can be applied to the field associated with the food production.
Description
Technical field
The present invention relates to a kind of preparation method, belong to macromolecular material and field of food industry with polyose metal complexes resin of protolysate function.
Background technology
Chitosan (Chitosan) is unique a kind of alkaline polysaccharide that nature exists, and it is chitin (Chitin) product behind the hydrolysis deacetylate under alkaline condition.In organic sphere, the year resultant quantity of chitin is 10,000,000,000 tons, is the second largest organic resource except that Mierocrystalline cellulose on the earth, and therefore, chitosan is a kind of wide material sources, Biological resources with low cost.There are a large amount of hydroxyls and amino to be easy to by cooperating, just can prepare chitosan metal complexes on the chitosan molecule with specific function with dissimilar metal ion through the row chemically modified.
In foodstuffs industry, particularly in the course of processing of fruit wine and beer, the protein that is contained in the wine is very big to the quality influence of wine.Thereby excessive albumen can form complex compound to be precipitated with the polyphenol in beer and the fruit wine, when reducing the drinks nutritive value, has also influenced the storage time and the organoleptic quality of wine.It is annual because the financial loss that albumen precipitation causes in the wine is very serious.At present to polyphenol in the wine product and the proteic method that removes many with polyvinylpyrrolidone (PVPP) and diatomite combination treatment, though this method is used for many years, closely become classical pre-treatment means, but because PVPP and diatomite are Powdered, when handling the wine product all is disposable use, and this not only makes and filters the cost increase, and diatomite is non-renewable, and adsorb a large amount of wine bodies, produced a large amount of wastings of resources.In addition, protein is essential nutrient substance, removes by filter the nutrition of also unfavorable wine product.Cooperate plastic resin treatment wine product with chitosan-metal, when getting clarification filtration, utilize this resin to have protein effect in the hydrolysis wine product, can increase in the wine product amino acid whose content to improve nutritive value, and solved the polyphenol-albumen precipitation problem of wine product, have very wide application prospect.
Summary of the invention
The present invention is exactly the novelty solution of a kind of economic environmental protection of proposing at the protein problem in the wine product.
Concrete preparation technology is as follows: chitosan is dissolved in the certain density acetum, under stable temperature, adds whiteruss, class of department, polyoxyethylene glycol, epoxy chloropropane etc. successively, regulate pH, behind the isothermal reaction some hrs, decompress filter, drip washing just obtain the chitosan microball resin.With the abundant swelling of resin, under the organic solvent condition, resin is carried out modification with the carbon nitrogen heterocyclic, resin after the modification and certain density metal ion solution react in shaking table, decompress filter, metal ion, the drying of not complexing removed in distilled water drip washing, just obtains modified chitosan metal and cooperates resin.
Advantage of the present invention is:
(1) chitosan is a kind of natural polysaccharide, and wide material sources are with low cost, and biodegradable under state of nature, can not cause the pollution of environment.
(2) chitosan resin is owing to itself be solid-state, and wine product are easy to separate with the wine sample after clarifying, and this resin can use repeatedly, has the characteristics of economic environmental protection.
(3) relative and natural enzyme protolysate, the cost of this resin is cheaper; Also need specific hydrolysising condition, can under existing foodstuffs industry working condition, carry out unlike the natural enzyme hydrolysis.
Embodiment
The acetum of preparation 1.0% in the acetum that the 100ml that 5.0g chitosan powder is dissolved in prepares, constantly adds class of 1ml department solution under the stirring at 40 ℃, adds polyoxyethylene glycol 15~65ml again, reaction 60min; Add formaldehyde 10ml, reaction 30min; 75 ℃ of attemperation, adding epoxy chloropropane 10~50ml and regulating the pH value is 8.0, continues reaction 3 hours.Decompress filter, respectively with sherwood oil, absolute ethanol washing, last pure water drip washing promptly gets the chitosan microball resin.Measure 15~55ml dimethyl formamide solution, add the carbon nitrogen heterocyclic, make the concentration of the carbon nitrogen heterocyclic of adding reach 1.5~5% (w/v), add chitosan resin, 40~90 ℃ of constant temperature vibrations and resin reaction 3~9 hours, after filtering the unnecessary carbon nitrogen heterocyclic of removal reaction, add magnesium, calcium, copper, zinc or cerium metal solion 40~90ml, concentration is 0.1~0.4mol/L, 10~40 ℃ of couplings 6~12 hours, decompression filters, and is drying to obtain the poly-metal ion match resin of modification shell.
Example 1: get chitosan powder 5.0g and be dissolved in 100ml, in 1.0% the acetum, 40 ℃ are constantly stirred the 80 solution 1.0ml of class of adding department down, add polyoxyethylene glycol 15ml, reaction 60min; Adjust the temperature to 65 ℃, add formaldehyde 10ml, reaction 30min; Attemperation is 75 ℃, and adding epoxy chloropropane 10ml and regulating the pH value is 8.0, reacts 3 hours, and decompress filter respectively with sherwood oil, absolute ethanol washing, obtains the chitosan microball resin after the pure water drip washing.Get the 8.0g chitosan resin, adding 20ml carbon nitrogen heterocyclic concentration is 1.0% dimethyl formamide solution, 40 ℃ of constant temperature vibration activated resin 5 hours, filter and remove remaining organic solvent, add copper ion solution 50ml, concentration is 0.1mol/L, and 20 ℃ of couplings decompression in 7 hours filters, and is drying to obtain modified chitosan metal ionic complex resin.
Example 2: get chitosan powder 5.0 and be dissolved in 150ml, in 1.0% the acetum, 40 ℃ are constantly stirred the 80 solution 1.0ml of class of adding department down, add polyoxyethylene glycol 35ml, reaction 60min; 80 ℃ of attemperation add formaldehyde 10ml, reaction 30min; Adjust the temperature to 75 ℃, adding epoxy chloropropane 30ml and regulating pH value is 8.0, continues to react 3 hours, and decompress filter respectively with sherwood oil, acetone, water washing, promptly gets the chitosan microball resin after repeatedly.Get the 8.0g chitosan resin, adding 15.0ml carbon nitrogen heterocyclic concentration is 3.0% dimethyl formamide solution, 80 ℃ of constant temperature vibration activated resin 8 hours, add the 75ml ionic calcium soln aqueous solution after filtering removal carbon nitrogen heterocyclic, concentration is 0.3mol/L, 30 ℃ of couplings decompression in 9 hours filters water, ethanol and ultrapure water drip washing successively, promptly gets modified chitosan metal ionic complex resin after the drying.
Claims (4)
- One kind can protein hydrolysate the polyose metal complexes resin, it is characterized in that this resin utilizes polymer chitosan to be skeleton, again by after the modification of carbon azepine and the coupling transition metal ion, finally realize the function of protein hydrolysate.Its technical process is as follows: chitosan is dissolved in the acetum, and controlled temperature adds whiteruss, class of department, polyoxyethylene glycol, formaldehyde, epoxy chloropropane respectively, regulate pH, reacted 4 hours, and decompress filter, used sherwood oil, ethanol and pure water drip washing successively, promptly obtain the chitosan microball resin.The organic solution that adds the carbon nitrogen heterocyclic again continues reaction 6 hours, removes the remaining carbon nitrogen heterocyclic of dereaction solution, the solution that adds transition metal ion, reacted 6~12 hours, decompress filter, pure water washing final vacuum drying promptly get modified chitosan metal ionic complex resin.
- 2. in the technical process of modified chitosan metal complexes resins according to claim 1, it is 5.0~15.0% that the adding polyoxyethylene glycol makes its concentration, and the concentration of epoxy chloropropane is 2.0~10.0%.
- 3. in the technical process of modified chitosan metal complexes resins according to claim 1, the organic solution of described carbon nitrogen heterocyclic is 1,4,7,10-four aza-dodecanes, 1,7-diaza dodecane or 18 is preced with a kind of six ethers or with above-mentioned 3 kinds of mixed solutions by any mixed, its concentration is 2.0~8.0%.
- 4. in the technical process of modified chitosan metal complexes resins according to claim 1, described transition metal ion is meant that magnesium, calcium, copper, zinc or cerium metal ionic are a kind of or by the multiple metal ion of any mixed, its concentration is 0.1~1.0mol/L.
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106629922A (en) * | 2017-01-07 | 2017-05-10 | 内蒙古民族大学 | Organics degrading agent and preparation method thereof |
Citations (4)
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US5336415A (en) * | 1993-02-10 | 1994-08-09 | Vanson L.P. | Removing polyvalent metals from aqueous waste streams with chitosan and halogenating agents |
US20040137041A1 (en) * | 2003-01-09 | 2004-07-15 | Jakwang Co., Ltd. | Water-soluble natural film and its preparing method |
CN101591445A (en) * | 2008-05-30 | 2009-12-02 | 中国海洋大学 | The preparation technology of magnetic chitosan metal composition particles |
CN101747449A (en) * | 2008-11-28 | 2010-06-23 | 北京大学 | Nano chitosan derivative affinity matrix and preparation method and application thereof |
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2010
- 2010-10-11 CN CN 201010513922 patent/CN101974101A/en active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5336415A (en) * | 1993-02-10 | 1994-08-09 | Vanson L.P. | Removing polyvalent metals from aqueous waste streams with chitosan and halogenating agents |
US20040137041A1 (en) * | 2003-01-09 | 2004-07-15 | Jakwang Co., Ltd. | Water-soluble natural film and its preparing method |
CN101591445A (en) * | 2008-05-30 | 2009-12-02 | 中国海洋大学 | The preparation technology of magnetic chitosan metal composition particles |
CN101747449A (en) * | 2008-11-28 | 2010-06-23 | 北京大学 | Nano chitosan derivative affinity matrix and preparation method and application thereof |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106629922A (en) * | 2017-01-07 | 2017-05-10 | 内蒙古民族大学 | Organics degrading agent and preparation method thereof |
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Application publication date: 20110216 |