CN102816224B - A kind of hair keratin protein solution for spinning and its preparation method and application - Google Patents

Abstract

The invention relates to a hair protein solution for spinning and its preparation method and application. The protein solution is prepared by the following methods: (1) hair cleaning and impurity removal; (2) adding the hair after cleaning and impurity removal to lye (3) Use dilute hydrochloric acid with a concentration of 15-20%, slowly add it into the hair protein solution dissolved in step (2) while stirring, and neutralize to pH=7.5-8.5; (4) Centrifuge (5) clarification and filtration; (6) ultrafiltration desalination and filtration of small molecular compounds to obtain a hair keratin solution for spinning that meets the requirements for spinning hair keratin composite fibers. The invention adopts the waste-low-grade hair as raw material, dissolves and purifies it to make its keratin solution, which is used for spinning hair keratin composite fiber. In addition, the prepared keratin solution can be directly applied to spinning protein fibers, which has good prospects for development and utilization.

Description

A kind of hair keratin protein solution for spinning and its preparation method and application

technical field

The invention relates to a hair protein solution for spinning, and also relates to a preparation method and application of the protein solution, belonging to the field of comprehensive utilization of hair raw materials.

technical background

Keratin (Keratin), also known as insoluble fibrin, is the horniness of animals, including hair, hair, feathers, nails, horns, hooves, scales, etc. The molecular structure of keratin in hair is very tight, and the molecular chains of the protein are cross-linked horizontally through chemical bonds such as disulfide bonds, which makes it have a network space structure, so it cannot be dissolved in ordinary solvents, showing the characteristics of not being easy to dissolve and not melting. To dissolve hair keratin, it is necessary to first destroy the disulfide bonds and hydrogen bonds between keratin molecules. Generally, strong alkali dissolution, oxidation dissolution, reduction dissolution, etc. can be used.

Contents of the invention

The object of the present invention is to provide a hair protein solution for spinning to reduce cost and improve solubility.

At the same time, the object of the present invention is also to provide a method for preparing the hair protein solution for spinning.

Further, the object of the present invention is to provide an application of the hair protein solution for spinning in spinning protein fibers.

In order to achieve the above purpose, the technical solution of the present invention adopts a hair protein solution for spinning, which is prepared by the following method: (1) hair washing and impurity removal; (2) adding the hair after washing and impurity removal to alkali (3) Use dilute hydrochloric acid with a concentration of 15-20%, slowly add it into the dissolved hair protein solution in step (2) while stirring, and neutralize to pH=7.5-8.5; (4) Centrifuge Separation: Centrifuge the neutralized protein solution to remove solid impurities above 5 μm to obtain a relatively pure hair protein solution; (5) Clarification and filtration: add filter aid to the hair protein solution prepared in step (4) , carry out fine filtration to obtain a clear and transparent protein solution; (6) ultrafiltration desalination and filtration of small molecular compounds: select an ultrafiltration membrane with a molecular weight cut-off of 3,000-10,000 to remove more than 90% of salt and most of the small molecular compounds , so that the protein content in the solution reaches 6-10%, and a hair keratin solution for spinning that meets the requirements for spinning hair keratin composite fibers is obtained.

The hair cleaning and impurity removal described in step (1) is: when the raw material used is pig hair, after drying the pig hair, first remove hoof shells and impurities with heavy sand and stone weight in the pig hair, and then remove The dander and small impurities in the pig hair are finally separated by a ruler machine to separate the bristles with longer size and higher economic value, and the remaining short pig hair is washed by a water beating machine to further remove impurities, that is, Can be used to extract keratin.

0.1-0.5% sodium hydroxide can be added to the water of the water hair-shaving machine to remove lipid impurities in the hair, and the washing water can be recycled after being filtered through quartz sand.

The hair cleaning and impurity removal described in step (1) is: when the raw material used is human hair, it is firstly cleaned, washed, and divided to separate the longer size for wig manufacturing and other purposes, and the remaining size is 20 ~30mm or less have low utilization value and can be directly used to extract keratin.

The hair cleaning and impurity removal described in step (1) is: when the raw material used is poultry feathers: first air and dry, then loosen and winnow to remove heavy sand and stone impurities, and then go through a water dehairing machine to remove impurities. Washing to further remove impurities can be used to extract keratin.

The hair described in the step (1) can be leftovers from wool spinning mills and ground wool short fluff, and can be directly used to extract keratin without removing impurities.

The lye in step (2) is prepared by the following method: add sodium hydroxide to water to prepare 2.5-5% lye, then add sulfite or/and mercapto compound with 2-10% dry weight of hair, and heat up To 80 ~ 98 ℃ can be.

Described sulfite is any one in sodium sulfite, sodium bisulfite, potassium sulfite, potassium bisulfite.

The mercapto compound can be selected from any one of thioglycolic acid, sodium thioglycolate, mercaptoethanol and cysteine.

The dissolution of hair in step (2) is: the amount of lye added is 5 to 10 times the dry weight of the hair. After the solution is added, the temperature should be kept at 80-85°C. After 5-10 minutes, the hair begins to dissolve. Stir to dissolve for 30 minutes. ~120 minutes.

The filter aid in (5) is diatomite or perlite, and the amount of diatomite or perlite added to the protein solution is 20-150 g/L.

The technical solution of the present invention also adopts a method for preparing a hair protein solution for spinning, which includes the following steps: (1) hair cleaning and impurity removal; (2) adding the hair after cleaning and impurity removal to lye Dissolve; (3) Use dilute hydrochloric acid with a concentration of 15-20%, slowly add it into the hair protein solution dissolved in step (2) while stirring, and neutralize to pH=7.5-8.5; (4) Centrifugal separation: The neutralized protein solution is centrifuged to remove solid impurities above 5 μm to obtain a relatively pure hair protein solution; (5) clarification and filtration: add filter aid to the hair protein solution prepared in step (4) for fine (6) Ultrafiltration desalting and filtering out small molecular compounds: select an ultrafiltration membrane with a molecular weight cut-off of 3,000 to 10,000 to remove more than 90% of salt and most of the small molecular compounds, making the solution The protein content in the method reaches 6-10%, and a hair keratin solution for spinning that meets the requirements for spinning hair keratin composite fibers is obtained.

The technical scheme of the present invention also adopts the application of a hair protein solution for spinning as protein fiber.

The invention adopts the waste-low-grade hair as raw material, dissolves and purifies it to make its keratin solution, which is used for spinning hair keratin composite fiber. Hair raw materials include: pig short hair after bristle extraction, human hair slag, woolen mill waste (floor hair), poultry feathers, etc. These raw materials have poor performance and low economic value, and the keratin solution made from them can be directly applied to Spinning protein fibers has good prospects for development and utilization.

By adopting the method of the present invention, the protein solution after ultrafiltration can be directly used for spinning hair keratin composite fibers, which reduces the process of protein dissolution and filtration, reduces production costs, and due to high purification precision, can be used for spinning hair When keratin is combined with fibers, it can improve the stability of the stock solution, reduce the number of filter and spinneret replacements, improve the utilization of the stock solution, and finally increase the yield of the product, which can obtain better economic benefits.

The method of the invention is simple and practical, adopts the method of preparing keratin solution by alkali dissolution and UF membrane separation with low cost, and the prepared protein solution can be directly used for spinning keratin composite fiber. Use low-grade hair as raw material, dissolve it and further process and utilize it. Hair raw materials include: pig short hair after bristle extraction, human hair slag, wool spinning mill waste (floor hair), poultry feathers, etc. These raw materials have poor performance and low economic value, which greatly reduces the cost.

Detailed ways

Example 1

The hair protein solution for spinning of the present embodiment is prepared by the following method:

Taking 1000kg of wet pig hair after cleaning, cleaning and dehydration as an example, the average moisture content is about 33-34%, and the pure pig hair content is about 65%, which is 650kg. The keratin extraction method is as follows:

1) Preparation of lye: Add 4000 liters of water (6.15 times the dry weight of pig hair) to a 10,000-liter lye preparation tank, then add 120kg of sodium hydroxide and 30kg of sodium sulfite to prepare a solution with a sodium hydroxide content of 2.9%, and heat Heat up to 95°C;

2) Hair dissolving: Add 1000kg of impurity-removed and cleaned wet pig hair into the hair dissolving tank, and then add all the above mixed solutions. After the solution is added, the temperature is kept at 80°C. After 10 minutes, the hair begins to dissolve. Turn on the stirring device for stirring. After dissolving for 30 minutes, take a sample and observe until the pig hair is basically completely dissolved (more than 90% is dissolved);

3) Neutralization: Use dilute hydrochloric acid with a concentration of 15%, slowly add it into the above-mentioned dissolved hair protein solution while stirring, and neutralize to pH=7.5;

4) Centrifugal separation: The neutralized protein solution is centrifuged with a decanter centrifuge with a separation factor of more than 3000 to remove solid impurities of more than 5 μm and obtain a relatively pure hair protein solution of about 4600 liters; the filtrate can be placed at room temperature for 1 day.

5) Clarification and filtration: Add 200kg of diatomite filter aid to the protein solution, perform fine filtration with a diatomite filter, remove impurities, and obtain a clear and transparent protein solution;

6) Ultrafiltration desalting and filtering out small molecular compounds: use the W-UF tangential flow ultrafiltration system, select ultrafiltration membranes with a molecular weight cut-off of 5000, and remove more than 90% of salt and most of the small molecular compounds, making the solution The protein content reaches 8%, and a hair keratin solution meeting the requirements for spinning hair keratin composite fibers is obtained.

Example 2

The hair protein solution for spinning of the present embodiment is prepared by the following method:

Take 1000kg wet human hair after impurity removal, cleaning and dehydration as an example, the average moisture content is about 31-32%, and the pure human hair content is about 67%, which is 670kg. The keratin extraction method is as follows:

1) Alkaline preparation: Add 4000 liters of water (5.97 times the dry weight of human hair) to a 10,000-liter lye preparation tank, then add 120kg of sodium hydroxide and 30kg of sodium thioglycolate to prepare a solution with a sodium hydroxide content of 2.9% , heated up to 90°C;

2) Hair dissolving: Add 1000kg of impurity-removed and cleaned wet human hair into the hair dissolving tank, and then add all the above mixed solutions. After the solution is added, the temperature is kept at 78°C. After 10 minutes, the hair begins to dissolve, and the stirring device is turned on for stirring. After dissolving for 30 minutes, take a sample and observe until the human hair is basically completely dissolved (more than 90% is dissolved);

Other steps are the same as in Example 1.

Example 3

The hair protein solution for spinning of the present embodiment is prepared by the following method:

Taking 1250kg of wet poultry feathers after cleaning, cleaning and dehydration as an example, the average moisture content is about 42-45%, and the pure feather content is about 52%, which is 650kg. The keratin extraction method is as follows:

1) Alkali preparation: Add 3600 liters of water (6.15 times the dry weight of feathers) to a 10,000-liter lye preparation tank, then add 120kg of sodium hydroxide and 30kg of sodium bisulfite to prepare a solution with a sodium hydroxide content of 3.3%. , heated up to 98°C;

2) Hair dissolving: Add 1250kg of impurity-removed and cleaned wet feathers into the hair dissolving tank, and then add all the above mixed solutions. After the solution is added, the temperature is kept at 78°C. After 10 minutes, the hair begins to dissolve. Turn on the stirring device to stir and dissolve After 30 minutes, take a sample and observe until the feathers are basically completely dissolved (about 90% dissolved);

Other steps are the same as in Example 1.

Claims (9)

1. a hair protein matter solution for spinning, is characterized in that: by following methods, prepared: (1) hair cleans and removal of impurities; (2) hair after cleaning and removal of impurities is joined in alkali lye and dissolved; (3) with the dilute hydrochloric acid of concentration 15～20%, slowly join while stirring in the hair protein matter solution that step (2) dissolved, be neutralized to pH=7.5～8.5; (4) centrifugation: the protein liquid after neutralization is carried out to centrifugation, remove solid impurities more than 5 μ m, obtain purer hair protein matter solution; (5) clarification filtration: add flocculating aids in the hair protein matter solution making in step (4), carry out essence filter, obtain the protein soln of clear; (6) ultrafiltration desalination and filtering micromolecular compound: the ultra-filtration membrane of selecting molecular weight cut-off 3000～10000, remove more than 90% salinity and most micromolecular compound, make protein content in solution reach 6～10%, be met the hair-keratin matter solution for spinning of spinning hair-keratin matter conjugated fibre requirement;

Described alkali lye is prepared by following methods: in water, add sodium hydroxide to be mixed with 2.5～5% alkali lye, then add the sulphite of hair dry weight 2～10% or/and sulfhydryl compound is heated to 80～98 ℃.

2. a preparation method for hair protein matter solution for spinning, is characterized in that: comprise the following steps:

(1) hair cleans and removal of impurities;

(2) hair after cleaning and removal of impurities is joined in alkali lye and dissolved;

(3) with the dilute hydrochloric acid of concentration 15～20%, slowly join while stirring in the hair protein matter solution that step (2) dissolved, be neutralized to pH=7.5～8.5;

(4) centrifugation: the protein liquid after neutralization is carried out to centrifugation, remove solid impurities more than 5 μ m, obtain purer hair protein matter solution;

(5) clarification filtration: add flocculating aids in the hair protein matter solution making in step (4), carry out essence filter, obtain the protein soln of clear;

(6) ultrafiltration desalination and filtering micromolecular compound: the ultra-filtration membrane of selecting molecular weight cut-off 3000～10000, remove more than 90% salinity and most micromolecular compound, make protein content in solution reach 6～10%, be met the hair-keratin matter solution for spinning of spinning hair-keratin matter conjugated fibre requirement;

Alkali lye in step (2) is prepared by following methods: in water, add sodium hydroxide to be mixed with 2.5～5% alkali lye, then add the sulphite of hair dry weight 2～10% or/and sulfhydryl compound is heated to 80～98 ℃.

3. the preparation method of hair protein matter solution for spinning according to claim 2, it is characterized in that: the described hair of step (1) cleans and removal of impurities is: when adopted raw material is pig hair, after pig hair is dried, first remove the coffin in pig hair, the impurity that sandstone weight is larger, scurf in removing pig hair, impurity that sandy soil are tiny again, finally by length classifying machine, isolate longer dimension, bristles that economic worth is higher, remaining pig undercoat, through water unhairing machine, beat and wash again, further remove impurity, for extracting keratin protein.

4. the preparation method of hair protein matter solution for spinning according to claim 2, it is characterized in that: the described hair of step (1) cleans and removal of impurities is: when adopted raw material is human hair, first through removal of impurities, cleaning, minute chi, that isolates longer dimension manufactures purposes for wig, the utility value of remaining size below 20～30mm is lower, is directly used in extraction keratin protein.

5. the preparation method of hair protein matter solution for spinning according to claim 2, it is characterized in that: the described hair of step (1) cleans and removal of impurities is: when adopted raw material is poultry feather: after first dryness in the sun, economy-combat pine, selection by winnowing are removed the sandstone impurity that weight is larger, through water unhairing machine, beat and wash again, further remove impurity, for extracting keratin protein.

6. the preparation method of hair protein matter solution for spinning according to claim 2, is characterized in that: described sulphite is any in S-WAT, sodium bisulfite, potassium sulfite, Potassium hydrogen sulfite.

7. the preparation method of hair protein matter solution for spinning according to claim 2, is characterized in that: described sulfhydryl compound is selected any in Thiovanic acid, Thioglycolic acid sodium salt, mercaptoethanol, halfcystine.

8. the preparation method of hair protein matter solution for spinning according to claim 2, it is characterized in that: in step (2), the dissolving of hair is: the add-on of alkali lye is 5～10 times of hair dry weight, after adding, solution should make temperature remain on 80-85 ℃, after 5-10 minute, hair starts to dissolve, stirring and dissolving 30～120 minutes.

9. spinning as claimed in claim 1 application as spinning protein fibre aspect with hair protein matter solution.