TWI419975B - Method of manufacturing protein filling agent by using animal hair - Google Patents

Description

Method for preparing protein filler for leather by using animal hair as raw material

The invention relates to a method for preparing a protein filler for leather making by using animal hair as a raw material, and belongs to the field of utilization of waste residue resources in leather making.

The toxic and harmful substances in tannery wastewater mainly come from the sulfur-containing wastewater generated by the hair removal process. The COD of the tannery wastewater is above 10000 mg/L, accounting for about 40% of the total load of the tannery wastewater, and the sulfur content is above 5500 mg/L, accounting for the total amount of tannery wastewater. About 90% of the sulfur content. Therefore, using the hair removal hair removal method instead of the hair removal hair removal method, the cleaning of the hair removal process is the fundamental reason for reducing the pollution of the tanning industry. However, the current tannery companies are taking great risks in the world. They prefer to insist on ruining the hair and not using the hair removal method. The reason is not that the hair is not clean, but that the hair will be piled up like a mountain. Resource utilization is the bottleneck for the promotion and application of hair removal hair removal.

Although the current hair removal method accounts for a small proportion of leather production, it will eventually become the dominant hair removal method for the hair removal process. There are two reasons for this: First, the widespread use of hair removal and hair removal methods can lead to serious environmental pollution, and human environmental awareness is increasing. The environmental laws and regulations of countries around the world are also more stringent. Secondly, replacing the hair removal and hair removal method with hair removal hair removal method can reduce the cost of wastewater treatment. If the problem of resource utilization of hair is solved, Mao will soon be transformed into a new economic growth point. Thus, turning waste into treasure, killing two birds with one stone Enterprises will be keen to invest in the transformation of existing production processes.

At present, most of the research on the recycling of animal hair is concentrated on wool and pig hair. Wool has special felting properties and excellent spinnability, generally used in Production of felt and wool textiles, and the waste wool produced by leather hair removal has no textile value, can only be used for felting or directly discarded; pig hair is thick and strong, hardness and breaking strength are large, generally used for making brushes, etc.; cattle hair is neither good The spinnability, but not enough strength, so there are very few reports on the use of cattle hair, mostly in the exploration stage, far from the requirements of industrialization. It can be seen that the existing animal hair utilization technology products have low added value, or are discarded without recycling, and seriously pollute the environment. Therefore, finding effective ways to use animal hair and developing high value-added products has become an important issue in the utilization of tannery waste, and it is also a technical premise that can be used by tanners.

The invention provides a method for preparing a protein filler for tanning by using animal hair as a raw material, characterized in that the method comprises the following steps: (1) washing the animal hair with tap water, using a volume of at least 0.01-0.5 which can submerge the hair. M-inorganic acid solution soak for 10-48 hours, then wash the hair to neutral with tap water, drain water, and dry naturally; take 600 parts by weight of the above hair, and reduce it with 2-30 wt% of the volume that can at least drown the hair. Soak the solution for 10-48 hours, drain the water, dry it, and set aside; (2) Put the pre-treated hair into a reaction kettle with a stirrer, thermometer and reflux condenser, and add at least the hair. a volume of 0.5-20 wt% of the alkaline compound solution, heating 50-95 ° C, 2-20 hours of incubation, to obtain a viscous liquid; (3) after cooling the above liquid, adjust the pH to 5-8 with a mineral acid solution A filtrate rich in keratin polypeptide having a solid content of 10-20% is obtained, and concentrated and dried to obtain a protein filler for leather making.

The above and other objects, features and advantages of the present invention will become more apparent from

The object of the present invention is to provide a utilization technology of animal hair based on the hair removal hair removal method according to the deficiencies of the prior art, and hydrolyze the animal hair into a protein filler, and reuse the retanning and filling process for the leather production. Eliminate the worries of using the hair removal and hair removal method instead of the hair removal and hair removal method, and also reduce the difficulty of processing the tannery wastewater.

The object of the present invention is achieved by the following technical measures, wherein the parts of the raw materials are all parts by weight unless otherwise specified.

The method for preparing the protein filler for tanning by using animal hair comprises the following steps: 1. Washing the animal hair with tap water, soaking for 10 to 48 hours with a volume of 0.01-0.5 M inorganic acid solution capable of submerging the hair, and then using Tap water to wash the hair to neutral, drain the water, and dry naturally; take 600 parts of the above hair, soak for 2 to 48 hours with a 2-30 wt% reducing agent solution that can at least submerge the hair, drain the water, and dry Dry, standby; 2. The above pretreated hair is placed in a reaction vessel equipped with a stirrer, a thermometer and a reflux condenser, and a basic compound solution of at least 0.5-20 wt% capable of submerging the hair is added. Heating at 50-95 ° C, holding for 2-20 hours, to obtain a viscous liquid; 3. After cooling the above liquid, adjust the pH to 5-8 with a mineral acid solution to obtain a keratin-rich polypeptide having a solid content of 10-20%. The filtrate is concentrated and dried to obtain a protein filler for leather making.

The animal hair is any one of waste cow hair, waste wool or waste pig hair obtained by the hair removal hair removal method in the leather making process.

The inorganic acid is hydrochloric acid or sulfuric acid.

The reducing agent is at least one of sulfhydrylethanol, sodium thioacetate, Na ₂ S ₂ O ₃ , NaHSO ₃ , and Na ₂ SO ₃ .

The basic compound is at least one of MgO, CaO, NaOH, KOH, Na ₂ CO ₃ , and NaHCO ₃ .

The invention has the following advantages: 1. The invention creates conditions for replacing the hair removal and hair removal method by the hair removal and hair removal method in the leather production, and fundamentally reduces the pollutant content of the tannery wastewater, which is beneficial to the treatment of the integrated wastewater and the discharge of the standard.

2. The invention provides a simple and easy way of utilizing animal hair, and the method of recycling the hair into protein for recycling and filling in the tanning not only solves the problem of waste pollution, but also increases the added value of the product. With significant environmental and economic benefits.

3. The protein filler prepared by the invention not only has good retanning filling function, but also has certain dyeing performance, and the product performance reaches the standard of foreign equivalent protein filler.

detailed description

The present invention will be described in detail below with reference to the accompanying drawings. The content makes some non-essential improvements and adjustments.

Example 1:

600 g of waste cow hair obtained by hair removal hair removal method was washed with tap water, soaked in 1200 g of 0.01 M hydrochloric acid solution for 48 hours, then washed with boiled water to neutrality, drained with water, and 30 wt% Na ₂ S Soak the ₂ O ₃ solution in 3000 ml for 48 hours, drain the water, and dry it. Place the pre-treated bovine hair into the reaction vessel with a stirrer, thermometer and reflux condenser, and add 0.5 wt% NaOH solution to 3000 ml. Hydrolyzed at a temperature of 95 ° C for 20 hours to obtain a viscous liquid; after cooling the hydrolyzate, the pH was adjusted to 5 with a sulfuric acid solution to obtain 3200 ml of a hydrolyzate having a solid content of 10%, and the protein filler for tanning was obtained by concentration and drying. .

Example 2:

Wash 600 g of waste wool obtained by hair removal method with tap water, soak it in 1000 g of 0.5 M sulfuric acid solution for 10 hours, then wash the wool to neutral with tap water, drain water, and use 15% sulfhydryl ethanol. Soaked in 12 ml of 12% sodium thioacetate solution for 10 hours, drained water, and air-dried; put the above pretreated wool into a reaction kettle with a stirrer, thermometer and reflux condenser, add 12 wt % Na ₂ CO ₃ and 7 wt% NaHCO ₃ solution 2000 ml, hydrolyzed at 70 ° C for 2 hours to obtain a viscous liquid; after cooling the hydrolyzate, adjust the pH to 7 with hydrochloric acid solution to obtain a solid content of 20% The 1800 ml of the hydrolyzate was concentrated and dried to obtain a protein filler for tanning.

Example 3:

Wash 600 g of waste pig hair obtained by hair removal method with tap water, soak it in 1500 g of 0.3 M hydrochloric acid solution for 24 hours, then wash the pig hair to neutral with tap water, drain water, use 2% Na ₂ Soak the SO ₃ solution in 2500 ml for 30 hours, drain off the water, and dry it. Place the pre-treated pig hair into a reaction vessel equipped with a stirrer, a thermometer and a reflux condenser, and add 2500 ml of 20 wt% KOH solution. The mixture was hydrolyzed at a temperature of 50 ° C for 6 hours to obtain a viscous liquid; after the hydrolyzate was cooled, the pH was adjusted to 8 with a hydrochloric acid solution to obtain 2,600 ml of a hydrolyzate having a solid content of 15%, and the protein filler for tanning was obtained by concentration and drying.

While the present invention has been described in its preferred embodiments, the present invention is not intended to limit the invention, and the present invention may be modified and modified without departing from the spirit and scope of the invention. The scope of protection is subject to the definition of the scope of the patent application.

Claims (3)

A method for preparing a protein filler for tanning by using animal hair as a raw material, characterized in that the method comprises the following steps: (1) washing the animal hair with tap water, using a volume of 0.01-0.5M inorganic acid solution capable of submerging at least the hair. Soak for 10 to 48 hours, then wash the hair to neutral with tap water, drain the water, and let it dry naturally; take 600 parts by weight of the above hair, soak it with a 2-30 wt% reducing agent solution that can at least submerge the hair. 48 hours, drain water, air dry, spare; (2) put the pre-treated hair into a reaction kettle with a stirrer, thermometer and reflux condenser, add 0.5- of the volume that can at least drown the hair 20wt% alkaline compound solution, heating 50-95 ° C, holding 2-20 hours, to obtain a viscous liquid; (3) after cooling the above liquid, adjust the pH to 5-8 with a mineral acid solution to obtain a solid content of 10 The -20% keratin polypeptide-rich filtrate is concentrated and dried to obtain a protein filler for tanning, wherein the inorganic acid is hydrochloric acid or sulfuric acid, and the reducing agent is sulfhydryl alcohol, sodium thioacetate, Na ₂ S ₂ O ₃ , at least one of NaHSO ₃ and Na ₂ SO ₃ , and the basic compound is At least one of MgO, CaO, NaOH, KOH, Na ₂ CO ₃ , and NaHCO ₃ . The method for preparing a protein filler for tanning by using animal hair as a raw material according to the first aspect of the patent application, characterized in that the animal hair is any one of waste cow hair, waste wool or waste pig hair obtained by the hair removal hair removal method in the leather making process. . A protein filler for tanning, which is prepared by the method described in claim 1 of the patent application.