CN111593567A - Method for removing protein in starch slurry - Google Patents
Method for removing protein in starch slurry Download PDFInfo
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- CN111593567A CN111593567A CN202010581671.7A CN202010581671A CN111593567A CN 111593567 A CN111593567 A CN 111593567A CN 202010581671 A CN202010581671 A CN 202010581671A CN 111593567 A CN111593567 A CN 111593567A
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- starch
- protein
- slurry
- starch slurry
- desizing
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
- D06M15/03—Polysaccharides or derivatives thereof
- D06M15/11—Starch or derivatives thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
- D06L1/00—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods
- D06L1/12—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods using aqueous solvents
- D06L1/14—De-sizing
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/40—Reduced friction resistance, lubricant properties; Sizing compositions
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention discloses a method for removing protein in starch slurry, belonging to the technical field of textile slurry. The method comprises the steps of firstly, treating starch slurry by adopting a reducing agent so as to destroy protein structures on the surface and inside of starch granules and increase the solubility of protein; and then treating the starch slurry by adopting an organic solvent. The invention utilizes the reduction effect of sodium bisulfite to cut disulfide bonds among protein subunits, destroys the three-dimensional network structure of protein, destroys the protein structure on the surface and inside of starch granules, increases the solubility of protein, weakens the interaction between protein and protein, then uses ethanol solution to dissolve the denatured protein, and finally removes the protein in the starch through washing. The starch treated by the method has the protein content reduced from 0.52% to 0.16% or less, and the effect is better than the sum of the effect of the sodium bisulfite treatment and the ethanol treatment.
Description
Technical Field
The invention relates to a method for removing protein in starch slurry, belonging to the technical field of textile slurry.
Background
Currently, the most energy-saving and environment-friendly desizing method is an enzyme desizing method, wherein the enzyme desizing method is to hydrolyze starch into soluble micromolecular sugar by using amylase to remove the soluble micromolecular sugar. Compared with other desizing methods, the enzyme desizing method has high efficiency, does not damage fabrics, has small pollution to the environment and has wide application prospect. However, the efficiency of the enzymatic desizing method is low, and starch size on the yarn cannot be completely removed, so that the application of the enzymatic desizing method in the textile industry is limited. An important factor that restricts enzymatic desizing of starch slurry is the protein present in the starch. Although the proportion of the alpha-amylase in the starch slurry is small, the alpha-amylase can be prevented from being combined with the starch, and the enzymatic hydrolysis and desizing performance of the starch are greatly influenced. In actual production, the enzyme desizing efficiency of common raw starch and modified starch slurry is often lower than 95% and more than the industry requirement, the requirements of fabric dyeing and finishing can not be met, and the wide application of an enzyme desizing method is hindered. Therefore, it is imperative to remove protein from the slurry and improve the enzymatic desizing efficiency of the starch slurry.
Currently, common methods for removing proteins from slurries are ethanol removal and protease removal. However, the removal of protein by ethanol is poor and cannot remove protein in the starch granules and on most surfaces. The protease removal method can be used for well removing protein in starch, but the cost of the used enzyme is high, the requirement on water quality in the enzymolysis process is high, and the large-scale use in industry cannot be met. Therefore, there is a need to develop a new method for improving the desizing efficiency of starch slurry, which is more economical and effective, non-toxic and harmless.
Disclosure of Invention
In order to solve the problems, the invention utilizes the reduction effect of sodium bisulfite to cut disulfide bonds among protein subunits, destroys the three-dimensional network structure of protein, destroys the protein structure on the surface and inside of starch granules, increases the solubility of the protein, weakens the interaction between the protein and the protein, then uses ethanol solution with the concentration of more than 80 percent to dissolve the denatured protein, and finally removes the protein in the starch through washing. The method combines sodium bisulfite and ethanol solution to treat protein, can effectively remove protein in starch, and improves the enzyme desizing efficiency of starch slurry. On the other hand, the deproteinization method of the invention firstly carries out deproteinization treatment on starch, and then carries out oxidation, phosphorylation, vinyl acetate grafted starch and quaternary ammonium etherification modification; the starch is modified first and then protein is removed, so that the desizing effect of the starch slurry is obviously improved.
The first purpose of the invention is to provide a method for removing protein in starch slurry, which comprises the steps of firstly treating the starch slurry by using a reducing agent to destroy the protein structure on the surface and in the starch granules and increase the solubility of protein; and then treating the starch slurry by adopting an organic solvent.
In one embodiment of the invention, the starch slurry is starch or modified starch.
In one embodiment of the invention, the modified starch includes oxidized starch, phosphate starch, vinyl acetate grafted starch, and quaternary ammonium starch.
In one embodiment of the invention, the reducing agent comprises sodium bisulfite, sodium thiosulfate, 2-mercaptoethanol, and sodium sulfide.
In one embodiment of the invention, the organic solvent comprises ethanol, methanol, acetone and acetonitrile.
In one embodiment of the invention, the mass ratio of starch to reducing agent is from 1:5 to 1: 10.
In one embodiment of the invention, the temperature of the starch slurry treated by the reducing agent is 30-40 ℃.
In one embodiment of the invention, the method comprises the steps of:
(1) sodium bisulfite treatment of raw starch slurry: mixing the raw starch slurry with a sodium bisulfite solution, reacting for 2-5 hours at 30-40 ℃, and centrifuging and washing the starch suspension;
(2) dispersing the starch in the step (1) in ethanol, reacting for 3-5 hours, and centrifuging and washing the starch suspension to obtain starch slurry.
In one embodiment of the present invention, in the process (1), the concentration by mass volume of the sodium bisulfite in the sodium bisulfite solution is 0.2% to 0.65%.
In one embodiment of the present invention, the ethanol concentration in the process (2) is 70% or more.
The second purpose of the invention is to provide starch slurry prepared by the method.
A third object of the invention is to improve the use of a starch size as described above in the textile field.
A fourth object of the present invention is to provide a method for improving the sizing performance of a yarn by sizing the yarn using the above starch slashing to improve the sizing performance of the yarn and reduce the mold of the slashing.
The fifth purpose of the invention is to provide a method for improving the desizing efficiency of starch size, which adopts the starch slashing to carry out sizing and enzymatic desizing on yarns so as to improve the desizing efficiency of the enzymatic method.
In one embodiment of the invention, the yarn used for sizing is 36tex cotton yarn.
In one embodiment of the invention, the enzyme used for desizing is an amylase.
In one embodiment of the invention, the desizing temperature is 50-60 ℃.
In one embodiment of the invention, the desizing time is 1 hour.
The invention has the beneficial effects that:
the method of the invention can not only improve the enzymolysis performance of the original starch, but also improve the enzymolysis performance of the modified starch. The protein content of the starch treated by the method is reduced from 0.52% to 0.16% or below, and the starch is superior to the sum of the effects of the sodium bisulfite treatment (protein content is 0.46%) and the ethanol treatment (protein content is 0.35%), which shows that the sodium bisulfite and the ethanol support each other in the aspect of removing protein and have a certain synergistic effect. By using the method, the slashing performance can be improved by over 5% no matter the slashing is processed firstly and then modified, or the slashing is processed firstly and then modified. Besides the quaternary ammonium ether starch, other starch sizing agents can meet the desizing effect required by production (the enzyme desizing efficiency is over 95 percent). The molding probability of the sizing is reduced by about 50 percent in the process of sizing storage.
Detailed Description
The following description of the preferred embodiments of the present invention is provided for the purpose of better illustrating the invention and is not intended to limit the invention thereto.
1. The protein content determination method comprises the following steps:
the protein content in the starch slurry was determined using the kjeldahl method.
2. The desizing efficiency test method comprises the following steps:
the desizing rate was determined using an enzymatic desizing method. The slashing is dipped in alpha-amylase solution with the temperature of 60 ℃ and the temperature is kept for 1 hour after padding. And washing with water to remove the starch slurry after enzymolysis from the yarns.
3. The mildew point test method comprises the following steps:
the sized yarn was placed in a constant temperature and humidity chamber, stored for 15 days, and the number of mold spots on each package was observed.
Example 1: method for removing protein in starch slurry
A method of removing protein from a starch slurry, the method comprising the steps of:
(1) process of sodium bisulfite treatment of raw starch slurry: preparing a mixed solution from the raw starch slurry and a sodium bisulfite solution according to the proportion of 1:15, maintaining the temperature of a reaction solution at 40 ℃, stirring for 4 hours, and centrifuging and washing a starch suspension;
(2) dispersing the starch in the step (1) in 90% ethanol, mechanically stirring for a certain time, and centrifuging and washing the starch suspension. The protein content of the starch slurry is changed from 0.52% to 0.16% by Kjeldahl method.
Example 2: method for removing protein in modified starch slurry
With reference to the process of example 1, except that the starch slurry was replaced with a modified starch slurry, the other conditions were the same as in example 1, the process comprising the steps of:
(1) modifying the pretreated starch slurry: modifying the original starch by oxidation, phosphorylation, vinyl acetate grafted starch, quaternary ammonium etherification and the like;
(2) sodium bisulfite treatment of modified starch slurry: preparing a mixed solution of the modified starch slurry and sodium bisulfite according to the ratio of 1:15, maintaining the temperature of a reaction solution at 40 ℃, stirring for 4 hours, and centrifuging and washing the starch suspension;
(3) dispersing the starch in the step (2) in 90% ethanol, mechanically stirring for a certain time, and centrifuging and washing the starch suspension. The protein content of the starch slurry was changed from 0.52% to 0.15% or less as measured by Kjeldahl method.
Example 3:
referring to the method of example 2, except that the modification sequence was adjusted to perform deproteinization of the raw starch slurry and then to perform modification, the other conditions were the same as in example 2, and the method includes the following steps:
(1) process of sodium bisulfite treatment of raw starch slurry: preparing a mixed solution from the original starch slurry and sodium bisulfite according to the ratio of 1:15, maintaining the temperature of a reaction solution at 40 ℃, stirring for 4 hours, and centrifuging and washing the starch suspension;
(2) dispersing the starch in the step (1) in 90% ethanol, mechanically stirring for a certain time, and centrifuging and washing the starch suspension;
(3) modifying the pretreated starch slurry: and (3) carrying out phosphorylation modification on the starch treated in the step (1). The protein content of the starch slurry was changed from 0.52% to 0.14% or less by Kjeldahl method.
The results of examples 2 and 3 show that the starch treated with sodium bisulfite and ethanol, whether modified after treatment or modified after treatment, can achieve better deproteinization effect with little influence on the structure of the starch.
Example 4: method for improving starching performance of starch slurry
A method for improving the sizing performance of a starch slurry, the method comprising:
the starch size obtained by the treatment of the embodiment 1-3 is adopted to size the yarn, and the specific steps are as follows: the starch size is processed by the method, the size before and after being processed is pasted at high temperature (the concentration is 6 percent), and a single-yarn sizing machine is adopted to size 36tex cotton yarns. The prepared slashing is stored in a constant temperature and humidity chamber for balancing. The slashing breaking strength and elongation were measured using an electronic strength meter.
The sizing performance of the oxidized starch, the phosphated starch, the vinyl acetate grafted starch and the quaternary ammonium ether starch is improved by 5 percent.
Example 5: method for improving enzyme desizing efficiency of corn starch slurry
The starch size obtained by the treatment of the embodiment 1-3 is adopted to carry out sizing and enzymatic desizing on the yarn, and the specific steps are as follows: the starch size is processed by the method, the size before and after being processed is pasted at high temperature (the concentration is 6 percent), and a single-yarn sizing machine is adopted to size 36tex cotton yarns. And storing the prepared slashing in a constant temperature and humidity chamber for balancing for later use. The slashing is dipped in alpha-amylase solution with the temperature of 60 ℃ and the temperature is kept for 1 hour after padding. And (4) washing with water to remove the starch size subjected to enzymolysis from the yarns. And (3) measuring the starch content change on the yarns before and after enzymolysis, and evaluating the desizing effect of various slashes by taking the ratio of the residual starch quality to the starch quality on the slashes as the desizing rate.
The desizing rates of the oxidized starch, the phosphated starch and the vinyl acetate grafted starch are all over 95 percent and above, and the desizing rate of the quaternary ammonium ether starch is improved from 87 percent to 93 percent, and the results are shown in Table 2.
Example 6: method for reducing slashing mildew point
The starch size obtained by the treatment of example 1-3 was used to size the yarn, and the sized yarn was placed in a constant temperature and humidity chamber and stored for 15 days, and the number of mold spots on each package was observed.
The mildew number of oxidized starch, phosphated starch and vinyl acetate grafted starch is reduced by more than 50 percent, and the mildew number of quaternary ammonium ether starch is reduced by more than 30 percent.
Example 7:
referring to the method of example 1, except for adjusting the reaction time, temperature and other conditions as in example 1, the method includes the following steps:
(1) sodium bisulfite treatment to modify the native starch size: mixing the raw starch slurry and sodium bisulfite according to the proportion of 1:15, maintaining the temperature of the reaction solution at 30, 40 and 50 ℃, stirring for 3, 4 and 5 hours, and centrifuging and washing the starch suspension;
(3) dispersing the starch in the step (2) in ethanol with the concentration of 70%, mechanically stirring for a certain time, and then centrifuging and washing the starch suspension. And measuring the protein content change of the starch slurry by a Kjeldahl method. With the increase of the reaction temperature, the nitrogen content of the starch slurry is gradually reduced, but the starch is easy to gelatinize at 50 ℃ and is not beneficial to later use, so that the starch slurry is not preferable. In addition, the nitrogen content of the starch slurry gradually decreases with increasing reaction time.
Comparative example 1:
the raw starch slurry was treated according to the method of example 1, except that step (2) was omitted, i.e., the starch slurry was treated with only sodium bisulfite of step (1), and the protein content of the resulting starch slurry was 0.46%.
Comparative example 2:
the raw starch slurry was processed according to the method of example 1, except that step (1) was omitted, i.e., the starch slurry was processed with only ethanol of step (2), and the protein content of the resulting starch slurry was 0.38%.
TABLE 1
TABLE 2
As can be seen from Table 1, comparative example 1, which used sodium bisulfite alone, reduced the protein content from 0.52% to 0.46%, with a protein removal rate of 11.54%; comparative example 2 the protein content was reduced from 0.52% to 0.38% with a protein removal of 26.92% by ethanol treatment alone; however, in example 1, the protein content is reduced from 0.52% to 0.16% by using the combination of sodium bisulfite and ethanol, the protein removal rate is as high as 69.23%, which is superior to the sum (38.46%) of the effects of the sodium bisulfite treatment and the ethanol treatment, which indicates that the sodium bisulfite and the ethanol support each other in the aspect of removing protein and have a certain synergistic effect.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. The method for removing the protein in the starch slurry is characterized in that the starch slurry is treated by adopting a reducing agent, and then the protein in the starch slurry is removed by adopting an organic solvent.
2. The method of claim 1, wherein the starch slurry is starch or modified starch.
3. The method of claim 2, wherein the modified starch comprises oxidized starch, phosphate starch, vinyl acetate grafted starch, and quaternary ammonium starch.
4. The method of any one of claims 1 to 3, wherein the reducing agent comprises sodium bisulfite solution, sodium thiosulfate, 2-mercaptoethanol, and sodium sulfide.
5. The method of any one of claims 1-4, wherein the organic solvent comprises ethanol solution, methanol, acetone, and acetonitrile.
6. The method according to any one of claims 1 to 5, wherein the mass ratio of the starch slurry to the reducing agent is from 1:5 to 1: 10.
7. Starch slurry obtainable by the process according to any one of claims 1 to 6.
8. Use of the starch size according to claim 7 in the textile field.
9. A method of improving the sizing performance of a yarn by sizing the yarn with the starch size of claim 7.
10. A method for improving the desizing efficiency of a starch size, characterized in that the method is used for sizing and enzymatic desizing of a yarn by using the starch slashing according to claim 7.
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| CN202010581671.7A CN111593567A (en) | 2020-06-23 | 2020-06-23 | Method for removing protein in starch slurry |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115232219A (en) * | 2022-08-19 | 2022-10-25 | 上海交通大学 | Preparation method of deproteinized toughened modified starch |
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| CN115232219A (en) * | 2022-08-19 | 2022-10-25 | 上海交通大学 | Preparation method of deproteinized toughened modified starch |
| CN115232219B (en) * | 2022-08-19 | 2023-08-22 | 上海交通大学 | Preparation method of deproteinized and toughened modified starch |
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