阅读说明：本技术 一种皮革脱脂剂及其制备方法和应用 (Leather degreasing agent and preparation method and application thereof ) 是由 戴诗媛 马贺伟 陈勇 王泽胜 黄婷 许洁 于 2020-07-23 设计创作，主要内容包括：本发明提供了一种皮革脱脂剂及其制备方法和应用,属于皮革加工领域。本发明提供的皮革脱脂剂,按重量份数计,包括：脂肪酶5～15份,脂肪醇聚氧乙烯醚10～20份,异构醇聚氧乙烯醚5～15份,助溶剂0.5～5份,十二烷基苯磺酸0.1～3份,稳定剂0.2～4份,碱类物质0.2～1.1份,水50～70份。本发明通过稳定剂、助溶剂和碱类物质的协同作用提高脂肪酶的稳定性,降低脂肪酶的活力衰减速率。实施例的结果显示,本发明提供的皮革脱脂剂在10℃、20℃储放12个月,活力损失率低于6％；30℃、40℃储放12个月,活力损失率不超过30％,应用到生皮脱脂工序中,脂肪的残留量明显低。(The invention provides a leather degreasing agent, and a preparation method and application thereof, and belongs to the field of leather processing. The invention provides a leather degreasing agent, which comprises the following components in parts by weight: 5-15 parts of lipase, 10-20 parts of fatty alcohol-polyoxyethylene ether, 5-15 parts of isomeric alcohol-polyoxyethylene ether, 0.5-5 parts of cosolvent, 0.1-3 parts of dodecylbenzene sulfonic acid, 0.2-4 parts of stabilizer, 0.2-1.1 parts of alkali substance and 50-70 parts of water. According to the invention, the stability of the lipase is improved and the activity decay rate of the lipase is reduced through the synergistic effect of the stabilizer, the cosolvent and the alkali substance. The results of the examples show that the leather degreasing agent provided by the invention has the activity loss rate lower than 6% when stored at 10 ℃ and 20 ℃ for 12 months; the skin is stored for 12 months at the temperature of 30 ℃ and 40 ℃, the activity loss rate is not more than 30 percent, and the residual quantity of fat is obviously low when the skin is applied to the process of degreasing the raw skin.)

1. A leather degreasing agent comprises the following components in parts by weight: 5-15 parts of lipase, 10-20 parts of fatty alcohol-polyoxyethylene ether, 5-15 parts of isomeric alcohol-polyoxyethylene ether, 0.5-5 parts of cosolvent, 0.1-3 parts of dodecylbenzene sulfonic acid, 0.2-4 parts of stabilizer, 0.2-1.1 parts of alkali substance and 50-70 parts of water.

2. Leather degreaser according to claim 1 wherein the stabilizer comprises citric acid and succinic acid.

3. The leather degreasing agent according to claim 2, wherein the mass ratio of citric acid to succinic acid is (1-2): (1-2).

4. Leather degreaser according to claim 1, wherein the fatty alcohol-polyoxyethylene ether is AEO-9 and/or MOA-9.

5. Leather degreaser according to claim 1, wherein the iso-alcohol polyoxyethylene ether is iso-tridecanol polyoxyethylene ether with an ethoxy unit number of 7.

6. Leather degreaser according to claim 1, wherein the co-solvent is sodium cumene sulfonate.

7. Leather degreaser according to claim 1, wherein the base is at least one of potassium hydroxide and sodium hydroxide.

8. The method for preparing the leather degreasing agent as claimed in any one of claims 1 to 7, comprising the steps of:

(1) mixing a stabilizer, an alkali substance and part of water, and then mixing the mixture with dodecylbenzene sulfonic acid and a cosolvent to obtain a mixture A;

(2) mixing fatty alcohol-polyoxyethylene ether, isomeric alcohol-polyoxyethylene ether and the rest water to obtain a mixture B;

(3) mixing the mixture A obtained in the step (1) with the mixture B obtained in the step (2), and then mixing with lipase to obtain a leather degreasing agent;

the step (1) and the step (2) have no chronological order.

9. The leather degreasing agent as defined in any one of claims 1 to 7 or the leather degreasing agent prepared by the preparation method as defined in claim 8 is applied to leather processing.

10. Use according to claim 9, wherein the leather degreaser is used in an amount of 0.5 to 2 wt% based on the weight of the hide.

Technical Field

The invention relates to the field of leather processing, in particular to a leather degreasing agent, and a preparation method and application thereof.

Background

In the tanning process, natural fat in the raw hide needs to be removed as much as possible, and a foundation is laid for subsequent operations such as tanning, retanning agent dyeing and the like. If the degreasing effect of the hide is poor, the subsequent quality problems of uneven tanning, color change, oil cream of the finished leather and the like can be caused. Degreasing is therefore an important process step in the tanning process, the degreasing agent used being the key to determine the effectiveness of degreasing.

The solvent method and the emulsification method are the two most commonly used degreasing methods, and therefore a solvent (e.g., kerosene) and an emulsifier (surfactant) become the main components of the degreasing agent. However, the solvent method causes serious environmental pollution and operation danger (flammability), and some surfactants (such as alkylphenol ethoxylates) used in the emulsion method have problems of poor biodegradability, difficult demulsification and the like, thereby increasing the burden of sewage treatment, and the environmental problems generated by the method are receiving increasing social attention. Therefore, the development of the environment-friendly and efficient leather degreasing agent is always pursued by the leather industry.

The lipase has the advantages of good degreasing effect and no introduction of chemical pollution, but the permeability of the lipase is poor and no emulsifying property exists, so the lipase needs to be matched with other components to form a synergistic effect to exert good degreasing capability, and the lipase is usually compounded with a surfactant to obtain a liquid degreasing agent product containing the lipase, such as patents CN106350620A, CN102296312A and CN 102296316A. However, although the lipase degreasing agent provided by the above patent has a good degreasing effect, the activity of lipase in a liquid state is attenuated quickly, the activity of lipase is reduced with the time, and the lipase degreasing agent is not immediately used after being prepared, and is often stored for a period of time, and the activity of lipase is gradually reduced in the period of time, so that the degreasing effect is poor.

Based on the above problems, it is a problem to be solved to provide a degreasing agent capable of ensuring that the lipase activity is not significantly attenuated during regular storage.

Disclosure of Invention

The leather degreasing agent provided by the invention has a good effect of stabilizing lipase, so that the lipase can be stored for a longer time, and meanwhile, residual fat in the raw hide can be effectively removed, and the leather degreasing agent has a better degreasing effect.

In order to achieve the above object, the present invention provides the following technical solutions:

the invention provides a leather degreasing agent, which comprises the following components in parts by weight: 5-15 parts of lipase, 10-20 parts of fatty alcohol-polyoxyethylene ether, 5-15 parts of isomeric alcohol-polyoxyethylene ether, 0.5-5 parts of cosolvent, 0.1-3 parts of dodecylbenzene sulfonic acid, 0.2-4 parts of stabilizer, 0.2-1.1 parts of alkali substance and 50-70 parts of water.

Preferably, the stabilizer comprises citric acid and succinic acid.

Preferably, the mass ratio of the citric acid to the succinic acid is (1-2): (1-2).

Preferably, the fatty alcohol-polyoxyethylene ether is AEO-9 and/or MOA-9.

Preferably, the isomeric alcohol polyoxyethylene ether is isomeric tridecanol polyoxyethylene ether with the ethoxy unit number of 7.

Preferably, the cosolvent is sodium cumene sulfonate.

Preferably, the alkali substance is at least one of potassium hydroxide and sodium hydroxide.

The invention provides a preparation method of the leather degreasing agent in the technical scheme, which comprises the following steps:

(1) mixing a stabilizer, an alkali substance and part of water, and then mixing the mixture with dodecylbenzene sulfonic acid and a cosolvent to obtain a mixture A;

(2) mixing fatty alcohol-polyoxyethylene ether, isomeric alcohol-polyoxyethylene ether and the rest water to obtain a mixture B;

(3) mixing the mixture A obtained in the step (1) with the mixture B obtained in the step (2), and then mixing with lipase to obtain a leather degreasing agent;

the step (1) and the step (2) have no chronological order.

The invention provides the leather degreasing agent in the technical scheme or the application of the leather degreasing agent prepared by the preparation method in leather processing.

Preferably, the amount of the leather degreasing agent is 0.5-2 wt% of the weight of the raw hide.

The invention provides a leather degreasing agent, which comprises the following components in parts by weight: 5-15 parts of lipase, 10-20 parts of fatty alcohol-polyoxyethylene ether, 5-15 parts of isomeric alcohol-polyoxyethylene ether, 0.5-5 parts of cosolvent, 0.1-3 parts of dodecylbenzene sulfonic acid, 0.2-4 parts of stabilizer, 0.2-1.1 parts of alkali substance and 50-70 parts of water. The leather degreasing agent provided by the invention takes lipase as a functional component and can hydrolyze fat; the stabilizing agent improves the stability of the lipase at higher temperature, reduces the activity decay rate of the lipase at higher temperature and prolongs the storage time of the lipase; the cosolvent can play a synergistic role with the stabilizer to stabilize the lipase and promote the compatibility of the lipase and the emulsifier; the alkaline substance adjusts the pH value of the degreasing agent, so that the pH value is stabilized in a proper range, the stability of the lipase is improved, and the lipase is ensured to have higher biological activity; the raw materials used in the invention are degradable, and the organic matters in the wastewater generated in the degreasing process can be gradually degraded and disappear, so that the environment can not be polluted, and the requirements of China on environmental protection are met. The results of the examples show that the lipase activity of the leather degreasing agent provided by the invention is not obviously attenuated (the activity loss rate is lower than 6%) when the leather degreasing agent is stored at a lower temperature (10 ℃ and 20 ℃) for 12 months; the animal hide defatting enzyme has the advantages that the animal hide defatting enzyme is stored at a high temperature (30 ℃ and 40 ℃) for 12 months, the enzyme activity loss rate is not more than 30%, the enzyme activity loss rate has a good effect of stabilizing lipase, and when the animal hide defatting enzyme is applied to a hide defatting process, the residual amount of fat in the hide after defatting is obviously low, the residual fat in the hide is effectively removed, and a better defatting effect is endowed to the defatting process.

Detailed Description

The invention provides a leather degreasing agent, which comprises the following components in parts by weight: 5-15 parts of lipase, 10-20 parts of fatty alcohol-polyoxyethylene ether, 5-15 parts of isomeric alcohol-polyoxyethylene ether, 0.5-5 parts of cosolvent, 0.1-3 parts of dodecylbenzene sulfonic acid, 0.2-4 parts of stabilizer, 0.2-1.1 parts of alkali substance and 50-70 parts of water.

The leather degreasing agent comprises 5-15 parts by weight of lipase, preferably 10 parts by weight of lipase. In the invention, the lipase can hydrolyze fat as a functional component, so that the degreasing effect of the degreasing agent is improved.

The leather degreasing agent provided by the invention comprises 10-20 parts of fatty alcohol-polyoxyethylene ether by weight of 5-15 parts of lipase, preferably 15 parts. In the invention, the fatty alcohol-polyoxyethylene ether is preferably AEO-9 and/or MOA-9. In the invention, the fatty alcohol-polyoxyethylene ether is used as a surfactant, so that grease and fatty acid can be emulsified, the degreasing effect of the degreasing agent is improved, and meanwhile, the fatty alcohol-polyoxyethylene ether has good biodegradability and can avoid pollution to the environment.

The leather degreasing agent provided by the invention comprises 5-15 parts of isomeric alcohol polyoxyethylene ether by weight of 5-15 parts of lipase, preferably 10 parts. In the invention, the isomeric alcohol polyoxyethylene ether is preferably isomeric tridecanol polyoxyethylene ether with the ethoxy unit number of 7. In the degreasing agent, the isomeric alcohol polyoxyethylene ether and the fatty alcohol polyoxyethylene ether can play a synergistic effect to further emulsify grease and fatty acid, so that the degreasing effect of the degreasing agent is improved, and meanwhile, the isomeric alcohol polyoxyethylene ether has good biodegradability and can avoid pollution to the environment.

The leather degreasing agent provided by the invention comprises 0.5-5 parts of cosolvent by weight, preferably 2 parts by weight of lipase by weight of 5-15 parts. In the present invention, the cosolvent is preferably sodium cumene sulfonate. In the invention, the cosolvent and the stabilizer play a synergistic role in stabilizing the lipase and promoting the compatibility of the lipase and the emulsifier.

The leather degreasing agent provided by the invention comprises, by weight, 5-15 parts of lipase, 0.1-3 parts of dodecylbenzene sulfonic acid, and preferably 1 part. In the invention, the dodecyl benzene sulfonic acid, the fatty alcohol-polyoxyethylene ether and the isomeric alcohol-polyoxyethylene ether have a synergistic effect, so that the effect of emulsifying the grease is enhanced.

The leather degreasing agent provided by the invention comprises 0.2-4 parts of stabilizer by weight of 5-15 parts of lipase, preferably 2.5-3.5 parts of lipase. In the present invention, the stabilizer preferably includes citric acid and succinic acid, more preferably a mixture of citric acid and succinic acid; the mass ratio of the citric acid to the succinic acid is preferably (1-2): (1-2). In the invention, the stabilizing agent compounded by citric acid and succinic acid is used, and the proportion is limited in the range, so that the citric acid and the succinic acid can play a synergistic effect, the stability of the lipase at higher temperature is further improved, the activity decay rate of the lipase is reduced, and the storage time of the lipase is prolonged.

The leather degreasing agent provided by the invention comprises 0.2-1.1 parts of alkali substances, preferably 0.5 part, by weight of 5-15 parts of lipase. In the present invention, the alkali substance is preferably at least one of potassium hydroxide and sodium hydroxide, and more preferably potassium hydroxide. In the invention, the alkaline substance adjusts the pH value of the degreasing agent, so that the pH value is stabilized in a proper range, and the lipase is ensured to have higher biological activity.

The leather degreasing agent provided by the invention comprises 50-70 parts of water, preferably 60 parts of water, by weight of 5-15 parts of lipase.

The specific source of the raw materials in the leather degreasing agent is not particularly limited in the invention, and the raw materials can be obtained from commercial products well known in the field.

The leather degreasing agent provided by the invention is stored for 12 months at a lower temperature (10 ℃, 20 ℃), and the activity of lipase in the product is not obviously attenuated (the activity loss rate is lower than 6%); the skin-care active protein is stored for 12 months at a higher temperature (30 ℃ and 40 ℃), the loss rate of the enzyme activity is not more than 30%, the good effect of stabilizing lipase is achieved, and when the skin-care active protein is applied to a hide degreasing process, the residual amount of fat in the degreased hide is obviously low, the residual fat in the hide is effectively removed, and the better degreasing effect is achieved in the degreasing process; the raw materials used in the invention are degradable, and the organic matters in the wastewater generated in the degreasing process can be gradually degraded and disappear, so that the environment can not be polluted, and the requirements of China on environmental protection are met.

The invention provides a preparation method of the leather degreasing agent in the technical scheme, which comprises the following steps:

(1) mixing a stabilizer, an alkali substance and part of water, and then mixing the mixture with dodecylbenzene sulfonic acid and a cosolvent to obtain a mixture A;

(2) mixing fatty alcohol-polyoxyethylene ether, isomeric alcohol-polyoxyethylene ether and the rest water to obtain a mixture B;

(3) mixing the mixture A and the mixture B, and then mixing the mixture A and the mixture B with lipase to obtain a leather degreasing agent;

the step (1) and the step (2) have no chronological order.

The equipment used in the preparation process is not particularly limited, and a conventional container with a stirrer is adopted. In the present invention, the mixing is preferably performed under stirring conditions. The invention has no special limit on the mixing speed and time, and can uniformly mix all the components without splashing materials.

The invention mixes the stabilizer, the alkali substance and part of water, and then mixes the mixture with dodecylbenzene sulfonic acid and the cosolvent to obtain a mixture A. In the invention, the mass part of the part of water is preferably 10 to 20 parts by weight based on 50 to 70 parts by weight of water in the raw materials.

According to the invention, water is preferably mixed with the stabilizer, the alkali substance, the dodecylbenzene sulfonic acid and the cosolvent in sequence to obtain the mixture A. According to the invention, through the mixing process, the components can be uniformly mixed, and the formed emulsion does not have large particles.

According to the invention, fatty alcohol-polyoxyethylene ether, heterogeneous alcohol-polyoxyethylene ether and the rest water are mixed to obtain a mixture B. In the invention, the mass part of the residual water is preferably 40-50 parts by weight based on 50-70 parts by weight of water in the raw materials.

Preferably, the rest part of water is sequentially mixed with the fatty alcohol-polyoxyethylene ether and the isomeric alcohol-polyoxyethylene ether to obtain a mixture B. Through the mixing process, the components can be uniformly mixed, and larger particles in the formed emulsion are avoided.

After the mixture A and the mixture B are obtained, the mixture A and the mixture B are mixed and then mixed with lipase to obtain the leather degreasing agent.

According to the invention, the mixture A is preferably slowly added into the mixture B, and the slow addition time is preferably 10-15 min. The invention limits the mixing mode within the range, can control the rate of adding the mixture A into the mixture B, prevents the occurrence of gel reaction, avoids the occurrence of precipitate insoluble substances, and ensures that the degreasing agent with the performance meeting the requirements is obtained.

After mixing with lipase, the invention preferably performs standing, qualification testing and filtering on the mixed product in sequence. In the invention, the standing time is preferably 30-90 min, and more preferably 60 min; the eligibility detection index is preferably: the solution is colorless or light yellow transparent, and the pH value is 7-8. The filtration method is not particularly limited in the present invention, and a filtration process known to those skilled in the art may be used. The invention can deposit the particles in the microemulsion below by standing and filtering the product, then remove the redundant solution and improve the quality of the degreasing agent.

The preparation process of the invention can reduce the influence of each component on the particle size of the particles in the degreasing agent emulsion, improve the stability of the degreasing agent, and prevent the phenomena of precipitation, turbidity and the like by limiting the mixing sequence of each component.

The invention provides the application of the leather degreasing agent in the technical scheme or the leather degreasing agent prepared by the preparation method in the technical scheme in leather processing.

In the invention, the amount of the leather degreasing agent is 0.5-2 wt%, preferably 1 wt% of the weight of the raw hide.

Compared with the existing product (BCN-60), the leather degreasing agent is used for degreasing the rawhide, so that the residual amount of fat in the degreased rawhide is lower, the residual fat in the rawhide is effectively removed, and a better degreasing effect is achieved in a degreasing process.

The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.