CN111138584A - 一种酸洗废液再生剂及其制备方法 - Google Patents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
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Abstract
本发明为一种酸洗废液再生剂,该再生剂由以下原料通过水溶液调节共聚制备而成,其物料组成即配比包括:不饱和酸:10‑20;不饱和酸酯:10‑20;分子量调节剂:0.5‑5;引发剂:0.1‑2.0;水:100。该抑尘剂采用不饱和酸、不饱和酸酯,通过水溶液调节共聚技术制备,通过配位、交联金属离子,促使各种金属离子絮凝、沉降,分离之后的絮凝物可用作工业原料,回收的酸液就地返回再利用,本发明的制备工艺简单,综合性能好,安全环保。
Description
技术领域
本发明涉及金属加工液体废弃物回收领域的再生剂,特别是一种水溶性聚合物再生剂及其制备方法。
背景技术
钢铁金属制品在电镀之前一个必不可少的环节是酸洗,通常采用盐酸清除金属表面的氧化物和油渍。盐酸提高了金属电镀的效率和制品表面的质量,但也产生了大量的盐酸废液:盐酸浓度低于6%、氯化亚铁浓度高于10%,这对周边环境造成了巨大的潜在危害。
液体废酸的回收处理普遍采用浓缩、水解技术。盐酸废液的处理,一部分在再生机组用于吸收氯化氢气体生成再生酸,其余部分采用中和沉淀脱水工艺生成氢氧化亚铁,曝气氧化后加入絮凝剂沉淀氢氧化铁,泥浆脱水形成的固态废渣做掩埋处理;清水盐分较高,脱盐后才有利用价值,否则直接排放亦造成水系盐碱化,对环境产生破坏。CN107098529公开了一种盐酸酸洗废液的无排放处理方法及其装置,先利用氧化铁砂中和酸洗后的盐酸废水、过滤有机物质和固态杂质,然后向滤液中加入混凝剂、分离;溢清流液经反渗透处理后,浓缩废液送入酸再生系统热水解,再生的盐酸回用至酸洗生产线。CN106222681公开了一种钢铁酸洗废水回收处理方法,先加入阳离子表面活性剂,然后在隔膜电解槽中进行电解,阴极析出高纯铁,阳极废酸得到再生。高纯铁经破碎、退火还原得到高纯铁粉;阳极再生后的废酸返回至钢铁酸洗步骤重复利用。该回收处理方法工艺简单,铁回收率高,可得到高纯铁,不产生二次污染,回收处理后不降低废水酸度,可将酸洗废水再生重复利用,并且适用于对pH小于2的钢铁酸洗废水进行处理,但需要隔膜电解槽设备投资,电能消耗较大。CN107417007提出了一种电镀废酸和稀酸废水的树脂法回收工艺,第一步将排出的废酸水经过滤脱除固体颗粒类杂质;第二步通过阳离子交换树脂和螯合树脂脱除废水中的铝、铁、铅等金属离子,该工艺可循环操作、回收效率高、节能环保、安全程度高,但混合树脂需要再生处理,容易产生二次污染。
本专利发明了一种酸洗废液再生剂及其制备方法。该再生剂由不饱和酸、不饱和酸酯通过水溶液调节共聚技术制备,以絮凝的方式沉降、分离铁盐,回收的酸液就地返回再利用。
发明内容
本发明的目的在于提供一种酸洗废液再生剂及其制备方法。该再生剂采用不饱和酸、不饱和酸酯,通过水溶液调节共聚技术制备,通过配位、交联金属离子,促使各种金属离子絮凝、沉降,分离之后的絮凝物可用作工业原料,回收的酸液就地返回再利用。本发明的制备工艺简单,综合性能好,安全环保。
本发明的技术方案实现为:
一种再生剂,通过水溶液共聚制备而成,其物料组成即配比包括:
所述的不饱和酸为丙烯酸、甲基丙烯酸、衣康酸、乙烯基磺酸、2-丙烯酰胺-2-甲基丙磺酸和其钠盐中的一种或两种。
所述的不饱和酸酯为丙烯酸甲酯、丙烯酸羟乙酯和丙烯酸羟丙酯中的一种或两种。
所述的分子量调节剂为巯基乙酸、巯基丙酸、十二烷基硫醇中的一种或两种。
所述的引发剂为过硫酸铵、过硫酸钾和过氧化氢/亚硫酸钠中的一种或两种,以水溶液形式加入,所述的引发剂溶液的质量浓度为5~10%。
所述的水为蒸馏水或自来水。
所述的再生剂的制备方法,包括如下步骤:
(1)将不饱和酸、不饱和酸酯与分子量调节剂混合,作为原料混合液备用;
(2)向装有搅拌器、温度计、滴液漏斗和氮气导管的反应器中加入水,开启搅拌,氮气或氩气置换10~30分钟后,水浴加热升温;
(3)升温到60-90℃时,加入引发剂,再加入原料混合液;原料混合液的加入方式为分批加入或连续滴加;
(4)原料混合液完全加入之后,在60-100℃保温0.5-2.5小时;
(5)冷却至室温,出料,即为本发明的再生剂。
所述的步骤(3)中,聚合反应的温度,优选70-90℃。
所述的步骤(3)中,原料混合液的加入时间为1.0-4.0小时。
所述的步骤(4)中,保温的温度,优选80-95℃。
本发明的有益效果是:
(1)本发明的再生剂采用丙烯酸等反应性原料,通过水溶液调节共聚技术将其聚合。不含乙酸、乙二醇等挥发性低分子有机物,没有二次污染,环境安全性良好。其中,共聚温度避免了产品出现凝胶(失去水溶性、流动性)或组成不稳定。
(2)本发明的再生剂通过工艺优化,实现了杂质金属离子配位、交联的高效协同,提高了杂质分离效率和再生酸液的质量。
(3)本发明的再生剂可以沉降铁、锌、铝、钴、镍、铜、硅、砷、铅、铊、镉、锰、钒、钙、铬等离子。
(4)本发明的再生剂处理酸洗废液,回收的酸液可以就地返回再利用,降低企业成本,提高资源利用率,改善环境效益。
(5)本发明所采用的制备工艺,不涉及高温高压,没有三废排放,适于大规模推广使用。
具体实施方式
下面结合实施例进一步说明本发明:
实施例一
质量份数以克计,20克丙烯酸作为不饱和酸物料,2.5克丙烯酸甲脂作为不饱和酸酯物料,0.5克巯基乙酸作为分子量调节剂物料,按比例混合为原料混合液备用。向装有搅拌器、温度计、滴液漏斗和氮气导管的反应器中加入100克蒸馏水,开启搅拌,以氩气置换15分钟,水浴加热至80℃时,加入3克质量浓度为10%的过硫酸铵水溶液。10分钟之后,以滴液漏斗连续滴加前述的原料混合液,控制滴加速度,在2.5小时内滴加完毕。将体系升温至85℃,保温1.5小时。在搅拌的作用下将体系降到室温,出料,即为本发明的一种再生剂。
性能评价:60升酸洗槽中加入50升盐酸废液,在机械搅拌下向酸洗槽中缓慢加入100克再生剂。搅拌20分钟后,过滤酸洗废液。滤液补加10升新购盐酸,混合均匀后进一步用于酸洗。离子滴定分析结果表明,铁、锌、铬等金属离子的浓度降低60%。
实施例二
质量份数以克计,以12克丙烯酸和5克甲基丙烯酸作为不饱和酸物料,与20克水配制水溶液,冷却到室温。2.5克丙烯酸羟乙酯作为不饱和酸酯物料,1.3克巯基丙酸作为分子量调节剂物料,与不饱和酸物料混合为原料混合液,备用。向装有搅拌器、温度计、滴液漏斗和氮气导管的反应器中加入80克蒸馏水,开启搅拌,以氮气置换20分钟,水浴加热至80℃时,加入6克质量浓度为3%的过硫酸钾水溶液。10分钟之后,以滴液漏斗连续滴加前述的原料混合液,控制滴加速度,在2.5小时内滴加完毕。将体系升温至85℃,保温1.5小时。在搅拌的作用下将体系降至室温,出料,即为本发明的一种再生剂。
性能评价方法同实施例一,杂质金属离子的浓度降低43%。
以上内容是结合具体的优选实施方式对本发明所作的进一步详细说明,不能认定本发明的具体实施方式仅限于此,对于本发明所属技术领域的普通技术人员来说,在不脱离本发明构思的前提下,还可以做出若干简单的推演或替换,都应当视为属于本发明由所提交的权利要求书确定专利保护范围。
本发明未尽事宜为公知技术。
Claims (7)
2.如权利要求1所述的不饱和酸酯为丙烯酸甲酯、丙烯酸羟乙酯和丙烯酸羟丙酯中的一种或两种。
3.如权利要求1所述的再生剂,基特征为所述的分子量调节剂为巯基乙酸、巯基丙酸、十二烷基硫醇中的一种或两种。
4.如权利要求1所述的再生剂的制备方法,其特征为包括如下步骤:
(1)将不饱和酸、不饱和酸酯与分子量调节剂混合,作为原料混合液备用;
(2)向装有搅拌器、温度计、滴液漏斗和氮气导管的反应器中加入水,开启搅拌,氮气或氩气置换10~30分钟后,水浴加热升温;
(3)升温至60-90℃时,加入引发剂,再加入原料混合液;原料混合液的加入方式为分批加入或连续滴加;
(4)原料混合液完全加入之后,在60-100℃保温0.5-2.5小时;
(5)冷却至室温,以碱性中和剂调节反应体系的pH值至6.0-9.0,出料,即为本发明的再生剂。
5.如权利要求4所述的再生剂的制备方法,其特征为所述的步骤(3)中,聚合反应的温度,优选70-90℃。
6.如权利要求4所述的再生剂的制备方法,其特征为所述的步骤(3)中,原料混合液的加入时间为1.0-4.0小时。
7.如权利要求4所述的再生剂的制备方法,其特征为所述的步骤(4)中,保温的温度,优选80-95℃。
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