CN110358875A - 一种以羧基多肽物为基的无铵脱灰剂制造方法 - Google Patents
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Abstract
本发明提供了一种以羧基多肽物为基的无铵脱灰剂制造方法,包括将含有100份蛋白多肽以固体或水溶液的形式置入反应器内,在搅拌下加入80~100份的小分子卤代羧酸、酸酐、酰氯化合物,加入8~10份相应的催化剂,升温至60℃~90℃,反应3h,降温,加水、用盐酸或氢氧化钠调整pH为3.2~3.5,获得35%水溶液。本发明可以利用制革废弃蛋白进行降解、改性再用,不仅降低的成本,减少使用毒性物,产物可以降解,是一种环境友好的技术方案,有利于大力推广和使用。
Description
技术领域
本发明涉及一种以多肽物为基的无铵脱灰剂制造方法,属于皮革制造领域尤其涉及废弃物再生资源化应用。
背景技术
制革清洁化生产技术是关系到制革工业可持续发展的关键技术。
由于钙盐极易与在浸酸时所用的硫酸产生硫酸钙沉淀而沉积于纤维结构中,不利于后城鞣制工段鞣剂的渗入和结合。
脱灰,顾名思义是除去皮内固态及液态的石灰,其次是降低皮内的pH以帮助后续酶软化的要求。通过pH值调整,中和皮中的灰或碱,避免pH值的剧烈变化而导致的皮纤维组织变性和受损。随着脱灰过程的进行,溶液和裸皮的pH值逐渐下降,皮的膨胀状态消失,充水量减少,处于一种平细松弛的状态,为软化、浸酸等工段创造最适条件。
传统上都是采用硫酸铵或氯化铵进行脱灰生产。百年来硫酸铵或氯化铵无论从效果还是成本角度讲都是最为理想的材料。只有当废水排放的NH3-N指标被控制时,以硫酸铵或氯化铵功能为基础的广泛筛选开始。不少酸性材料自然成为实验应用的目标,利用无铵材料对灰(碱)皮作用,中和皮内的灰(碱),降低pH达到后继工序要求,如酸性盐,无机酸和有机酸。但是,用于生产的脱灰剂应该具备以下几个条件:
1)能够形成可溶性钙盐,使钙从裸皮中脱除;
2)温和地降低裸皮pH,脱灰过程中不会出现因急剧或过低的pH引起裸皮的酸膨胀。因此,目前许多商品化的脱灰剂的主要成分就为非膨胀性酸;
3)良好的缓冲特征及不影响后继工序中蛋白酶的使用条件及酶的活性;
4)不产生新的污染引起废水的毒性;
5)生产可接受的成本;
6)良好的储存性及可溶性。
无氨脱灰剂的功能要求给材料的选择带来了新挑战。大量研究表明:
1)无机酸脱灰剂。硫酸、盐酸、磷酸都可以用于脱灰,但因过低的pH及酸膨胀性使得无法直接选用。硼酸可以用于脱灰,但受最终成革及废水中限量要求无法使用。
2)有机酸脱灰剂。一些酸如甲酸、乙酸、丙酸可以用于脱灰,但因过低的pH、酸的胶解与膨胀作用使得无法直接选用;另一些酸如草酸、柠檬酸可以脱灰,但因与钙形成弱溶解性钙盐导致脱除钙不良。
3)酸性盐脱灰剂。正如硫酸铵及氯化铵那样,无氨的中性、酸性盐也可以成为脱灰材料,如磷酸二氢钠、硫酸氢钠等,但因价格及储存稳定性问题难以单独形成产品。
氨基酸与多肽具有较低的等电点,与裸皮有良好的相容性。为了提高脱灰效率,对氨基酸及多肽进行改性。作为缓冲性有机酸,进一步消除氨基,相对增加羧基,降低了缓冲pH,不仅提高降低裸皮pH的能力,也可以保证脱灰安全性。从技术上获得创新,在科学上具有很好的意义。
制革过程有大量的蛋白废弃物,循环利用是重要的天然资源有效利用及减小排污的措施。该脱灰剂的原料采用制革废弃胶原蛋白、角蛋白进行化学或生物降解处理,然后进行适当改性,使脱灰效果大大增强。
发明内容
本发明的目的在于提供一种以羧基多肽物为基的无铵脱灰剂制造方法,其目的在于氨基酸与多肽的物理化学特征,利用废弃蛋白降解、改性后再生利用,减小排放。
本发明是这样实现的,一种以羧基多肽物为基的无铵脱灰剂制造方法,包括以下步骤:
一种以羧基多肽物为基的无铵脱灰剂制造方法,包括以下步骤:
将含有100份蛋白多肽以固体或水溶液的形式置入反应器内,在搅拌下加入80~100份的小分子卤代羧酸、酰氯、酸酐化合物,加入8~10份相应的催化剂,升温至60℃~90℃,反应3h,降温,加水、用盐酸或氢氧化钠调整pH为3.2~3.5,获得35%水溶液。
其中所述的蛋白多肽是胶原蛋白的水解物、毛蛋白水解物或植物蛋白水解物,这些水解物是通过用酸、碱及酶对所述蛋白进行水解获得,平均分子量为500~2000。
其中所述的小分子氯代羧酸、酰氯、酸酐类化合物中,所述的卤代羧酸类化合物为一氯代乙酸或2-氯代丙酸,相应的催化剂可以是碳酸钠,碳酸氢钠,氢氧化钠;所述的酰氯类化合物是草酰氯或磺酰氯,相应的催化剂可以是碳酸钠、碳酸氢钠或氢氧化钠;所述的酸酐类化合物是乙酸酐或马来酸酐,相应的催化剂为苯磺酸或甲苯磺酸。
其中所述的采用小分子氯代羧酸、酸酐类化合物进行蛋白多肽改性时,蛋白多肽以50%的水溶液置入立式反应器进行合成,相应的催化剂为固体。
其中所述的采用小分子酰氯类化合物进行蛋白多肽改性时,蛋白多肽以固体的形式置入滚筒式反应器进行合成,相应的催化剂为液体。
通过上述技术方案,本发明的有益效果为:本发明可以利用制革废弃蛋白进行降解、改性再用,不仅降低的成本,减少使用毒性物,产物可以降解,是一种环境友好的技术方案,有利于大力推广和使用。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白,以下结合实施例,对本发明进行进一步详细说明。应当理解,此处所描述的具体实施例仅仅用以解释本发明,并不用于限定本发明。
实施1:一种以羧基多肽物为基的无铵脱灰剂制造方法,包括如下步骤:
将含有100份由废弃胶原碱-酶联合降解获得的蛋白多肽,平均分子质量为500~2000,调制成含量50%的水溶液置入反应器内,在搅拌下加入80份的氯代乙酸,加入8份碳酸钠,升温至80℃,反应3h,降温,加水、用盐酸调整pH为3.2~3.5,获得35%水溶液。
实施2:一种以羧基多肽物为基的无铵脱灰剂制造方法,包括如下步骤:
将含有100份由废弃毛蛋白通过碱降解获得的蛋白多肽,平均分子质量为500~2000,将粉状蛋白多肽粉置入反应器内,在搅拌下慢慢加入100份的磺酰氯,加入10份乙酸,升温至60℃,反应3h,降温,加水、用氢氧化钠调整pH为3.2~3.5,获得35%水溶液。
实施3:一种以羧基多肽物为基的无铵脱灰剂制造方法,包括如下步骤:
将含有100份由大豆蛋白通过碱-酶降解获得的蛋白多肽,平均分子质量为500~2000,调制成含量50%的水溶液置入反应器内,在搅拌下慢慢加入100份的马来酸酐,加入10份苯磺酸,升温至85℃,反应3h,降温,加水、用氢氧化钠调整pH为3.2~3.5,获得35%水溶液。
以上对本发明的具体实施方式进行了描述,但本发明并不限于以上描述。对于本领域的技术人员而言,任何对本技术方案的同等修改和替代都是在本发明的范围之中。因此,在不脱离本发明的精神和范围下所作的均等变换和修改,都应涵盖在本发明的范围内。
Claims (5)
1.一种以羧基多肽物为基的无铵脱灰剂制造方法,其特征在于,包括以下步骤:
将含有100份蛋白多肽以固体或水溶液的形式置入反应器内,在搅拌下加入80~100份的小分子卤代羧酸、酸酐、酰氯化合物,加入8~10份相应的催化剂,升温至60℃~90℃,反应3h,降温,加水、用盐酸或氢氧化钠调整pH为3.2~3.5,获得35%水溶液。
2.如权利要求1所述的一种以多肽物为基的无铵脱灰剂制造方法,其特征在于:所述的蛋白多肽为胶原蛋白的水解物、毛蛋白水解物或植物蛋白水解物,上述水解物是通过用酸、碱及酶对所述蛋白进行水解获得,平均分子量为500~2000。
3.如权利要求1所述的一种以多肽物为基的无铵脱灰剂制造方法,其特征在于:
所述的小分子卤代羧酸类化合物为一氯代乙酸或2-氯代丙酸,相应的催化剂是碳酸钠、碳酸氢钠或氢氧化钠;
所述的小分子酰氯类化合物为草酰氯或磺酰氯,相应的催化剂是甲酸、乙酸或丙酸;
所述的小分子酸酐类化合物为乙酸酐或马来酸酐,相应的催化剂为苯磺酸或甲苯磺酸。
4.如权利要求1所述的一种以多肽物为基的无铵脱灰剂制造方法,其特征在于: 采用小分子氯代羧酸、酸酐类化合物进行蛋白多肽改性时,蛋白多肽以50%的水溶液置入立式反应器进行合成,相应的催化剂为固体。
5.如权利要求1所述的一种以多肽物为基的无铵脱灰剂制造方法,其特征在于:采用小分子酰氯类化合物进行蛋白多肽改性时,蛋白多肽以固体的形式置入滚筒式反应器进行合成,相应的催化剂为液体。
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