简化制革新技术的研究
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摘要
制革是我国具有综合优势的传统产业,近十年来,随着世界产业结构的调整,我国的皮革工业发展迅速,皮革产量约占世界总产量的30%,成为世界制革中心。但是,在我国,制革工业已成为轻工业中的第三污染大户,近年来,随着人们环境意识的增强和国家环保部门新的排放标准的逐渐出台,我国皮革工业的可持续发展正面临着环境污染问题的严峻挑战。
传统的制革过程在很宽的pH范围内进行,包括很多步骤,如浸水、浸灰、复灰、脱灰软化、浸酸、铬鞣、提碱、铬复鞣、碱化、中和、水洗、复鞣、染色、加油、酸固定等,多次进行浸灰-脱灰、浸酸-提碱、中和-酸化等步骤,反复的酸碱作用导致产生大量中性盐和废水,同时也会使皮革本身受到损害。特别是在浸酸过程中,需要加入大量的NaCl来抑制酸膨胀,大量盐的加入会造成裸皮的脱水,使成革扁平、不丰满,同时NaCl的加入会造成环境中盐的污染。
近年来,人们为了减少制革的污染做了很多工作,如无盐浸酸、高pH铬鞣、铬鞣和复鞣染色加脂同浴等,但没有从根本上改变制革过程。
在本论文中,我们研制了一种简化了的制革新技术,该技术利用了脱灰软化后裸皮的pH值(8.0±),其远高于胶原蛋白质的等电点,胶原羧基呈负电性。在这种pH值下,直接加入阴离子复鞣剂、酸性染料及阴离子加脂剂,由于皮革的pH值较高,便于复鞣填充材料的渗透,待渗透均匀后,稍降低pH至4.5-5.0,这样不仅固定了填充材料,也为铬鞣提供了合适的条件,这时,铬分子的渗透和固定将同时发生。并且由于铬盐本身的酸性和铬盐的水解,pH降低,有利于铬盐渗透,无需进行碱化,最后pH达到4.0左右。本工艺避免了反复的酸碱操作对皮革的损坏,一定程度上增大了皮的物理机械性能,同时避免了大量中性盐的产生,降低了污染。整个湿操作只有六步:浸水、浸灰、复灰、脱灰软化、填充/染色/加油、铬鞣等,大大简化了工序,减少了化工材料的使用,节约了时间和能耗。
本论文用浸灰牛皮和绵羊灰皮进行实验,研究了各种填充材料对新技术制作的坯革性能的影响,进行了填充材料的配伍实验,和传统工艺进行了对比,并对制革工序中污染量的降低进行了分析。通过对铬吸收率、坯革的抗张强度、撕裂强度、收缩温度、柔软度及各项感官指标的测定表明,与传统制革工艺相比,本技术可简化工序,大大降低中性盐和废水的产生,减少制革污染,对现有制革技术是一个很大的突破,对实现制革业的清洁化生产和可持续发展具有重要意义。
Tanning is the traditional industry which has comprehensive advantages in our country. In the past 10 years, our country’s leather industry developed rapidly with the adjustment of the world’s industrial structure. The leather production of our country has accounted for about 30% of the world and become the center of the world's tanning industry. However, in China, the tanning industry has the third major pollution in the light industry. With the increase of people's environmental consciousness and the issue of new discharge standards., the sustainable development of the leather industry is facing with severe challenges.
The conventional tanning process has a wide pH range. It involves so many steps such as soaking, liming, reliming, deliming/bating, pickling, chrome tannage, basification, chrome retanning, basify, nueturazation, washing, retanning, dyeing, fatliquoring and acid fixing. It has many acid-base operations such as liming—deliming, pickling—basifycation, nueturazation--acidification, such pH changes demands the usage of acids and alkalis, which leads to the generation of salts and wastewater, at the same time it will damage the leather. Especially, a lot of NaCl are needed to add to control acid swelling in the pickling step. So many salts would cause dehydration of pelt and make leather flat, and the addition of NaCl will cause the salt pollution in the environment.
In order to reduce the environment pollution of leather industry, in recent years, people have done a lot of works, such as pickling without salts, high pH chrome tanning and so on. But all these works have not fundamentally changed the tanning process.
In this paper, we studied a new simplified technology of tanning. The new technology used the pH condition of the delimed/bated pelt, which was 7.0-8.0, and this pH value outclassed the isoelectric point of collagen protein. So the collagen carboxyl was electronegativity. When the anionic retanning agent, acid dyestuff and anionic fatliquor were added in this high pH, the retanning materials could easily penetrate into leather because of the higher pH. After the materials penetrated uniformly, pH value was lowered slightly to 4.5~5.5 to fix these filling materials, and simultaneously the conditions were provided for chrome tanning. Here, the penetration and fixing of chrome molecular would be taken place simultaneously. Without basification, the solution pH value would fit for chromium penetration because of its acidity and hydrolyzation. And the final pH value was 4.0±. With the new technology, the acid-base damages to leather were avoided, the physical-mechanical properties were enhanced in a certain extent and a large number of neutral salt were avoided, the pollution was reduced. There are only six steps in the whole wet operation in the new technology: soaking, liming, reliming, deliming and bating, filling/dyeing /fatliquoring, chromium tanning, etc.. The new technology could greatly simplify the process, reduce the use of chemical materials and save time and energy.
In this paper, we did the experiments by using cow limed hides and sheep limed hides respectively. The various filling materials’influence to the properties of crust leather was studied, the experiments of match of filling materials and the contrast with conventional process were did. At the same time, the analysis of lightening pollutions in the tanning procedures were did. According to the testing results of chromium absorption rate, tensile strength, tear strength, shrinkage temperature, softness and sensory evaluation, the new technology could simplify the process compared to the conventional process. And it also could greatly reduce the quantity of neutral salt and wastewater. The new technology was a major breakthrough to the conventional process, and it had a great significance for achieving the clean production and sustainable development of leather industry.
传统的制革过程在很宽的pH范围内进行,包括很多步骤,如浸水、浸灰、复灰、脱灰软化、浸酸、铬鞣、提碱、铬复鞣、碱化、中和、水洗、复鞣、染色、加油、酸固定等,多次进行浸灰-脱灰、浸酸-提碱、中和-酸化等步骤,反复的酸碱作用导致产生大量中性盐和废水,同时也会使皮革本身受到损害。特别是在浸酸过程中,需要加入大量的NaCl来抑制酸膨胀,大量盐的加入会造成裸皮的脱水,使成革扁平、不丰满,同时NaCl的加入会造成环境中盐的污染。
近年来,人们为了减少制革的污染做了很多工作,如无盐浸酸、高pH铬鞣、铬鞣和复鞣染色加脂同浴等,但没有从根本上改变制革过程。
在本论文中,我们研制了一种简化了的制革新技术,该技术利用了脱灰软化后裸皮的pH值(8.0±),其远高于胶原蛋白质的等电点,胶原羧基呈负电性。在这种pH值下,直接加入阴离子复鞣剂、酸性染料及阴离子加脂剂,由于皮革的pH值较高,便于复鞣填充材料的渗透,待渗透均匀后,稍降低pH至4.5-5.0,这样不仅固定了填充材料,也为铬鞣提供了合适的条件,这时,铬分子的渗透和固定将同时发生。并且由于铬盐本身的酸性和铬盐的水解,pH降低,有利于铬盐渗透,无需进行碱化,最后pH达到4.0左右。本工艺避免了反复的酸碱操作对皮革的损坏,一定程度上增大了皮的物理机械性能,同时避免了大量中性盐的产生,降低了污染。整个湿操作只有六步:浸水、浸灰、复灰、脱灰软化、填充/染色/加油、铬鞣等,大大简化了工序,减少了化工材料的使用,节约了时间和能耗。
本论文用浸灰牛皮和绵羊灰皮进行实验,研究了各种填充材料对新技术制作的坯革性能的影响,进行了填充材料的配伍实验,和传统工艺进行了对比,并对制革工序中污染量的降低进行了分析。通过对铬吸收率、坯革的抗张强度、撕裂强度、收缩温度、柔软度及各项感官指标的测定表明,与传统制革工艺相比,本技术可简化工序,大大降低中性盐和废水的产生,减少制革污染,对现有制革技术是一个很大的突破,对实现制革业的清洁化生产和可持续发展具有重要意义。
Tanning is the traditional industry which has comprehensive advantages in our country. In the past 10 years, our country’s leather industry developed rapidly with the adjustment of the world’s industrial structure. The leather production of our country has accounted for about 30% of the world and become the center of the world's tanning industry. However, in China, the tanning industry has the third major pollution in the light industry. With the increase of people's environmental consciousness and the issue of new discharge standards., the sustainable development of the leather industry is facing with severe challenges.
The conventional tanning process has a wide pH range. It involves so many steps such as soaking, liming, reliming, deliming/bating, pickling, chrome tannage, basification, chrome retanning, basify, nueturazation, washing, retanning, dyeing, fatliquoring and acid fixing. It has many acid-base operations such as liming—deliming, pickling—basifycation, nueturazation--acidification, such pH changes demands the usage of acids and alkalis, which leads to the generation of salts and wastewater, at the same time it will damage the leather. Especially, a lot of NaCl are needed to add to control acid swelling in the pickling step. So many salts would cause dehydration of pelt and make leather flat, and the addition of NaCl will cause the salt pollution in the environment.
In order to reduce the environment pollution of leather industry, in recent years, people have done a lot of works, such as pickling without salts, high pH chrome tanning and so on. But all these works have not fundamentally changed the tanning process.
In this paper, we studied a new simplified technology of tanning. The new technology used the pH condition of the delimed/bated pelt, which was 7.0-8.0, and this pH value outclassed the isoelectric point of collagen protein. So the collagen carboxyl was electronegativity. When the anionic retanning agent, acid dyestuff and anionic fatliquor were added in this high pH, the retanning materials could easily penetrate into leather because of the higher pH. After the materials penetrated uniformly, pH value was lowered slightly to 4.5~5.5 to fix these filling materials, and simultaneously the conditions were provided for chrome tanning. Here, the penetration and fixing of chrome molecular would be taken place simultaneously. Without basification, the solution pH value would fit for chromium penetration because of its acidity and hydrolyzation. And the final pH value was 4.0±. With the new technology, the acid-base damages to leather were avoided, the physical-mechanical properties were enhanced in a certain extent and a large number of neutral salt were avoided, the pollution was reduced. There are only six steps in the whole wet operation in the new technology: soaking, liming, reliming, deliming and bating, filling/dyeing /fatliquoring, chromium tanning, etc.. The new technology could greatly simplify the process, reduce the use of chemical materials and save time and energy.
In this paper, we did the experiments by using cow limed hides and sheep limed hides respectively. The various filling materials’influence to the properties of crust leather was studied, the experiments of match of filling materials and the contrast with conventional process were did. At the same time, the analysis of lightening pollutions in the tanning procedures were did. According to the testing results of chromium absorption rate, tensile strength, tear strength, shrinkage temperature, softness and sensory evaluation, the new technology could simplify the process compared to the conventional process. And it also could greatly reduce the quantity of neutral salt and wastewater. The new technology was a major breakthrough to the conventional process, and it had a great significance for achieving the clean production and sustainable development of leather industry.
引文
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