CN107245167A - 一种复合橡胶补强剂及其制备方法和应用 - Google Patents
一种复合橡胶补强剂及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种复合橡胶补强剂,由以下重量份的原料组成:垃圾焚烧飞灰20~40份,复合络合剂1~4份,埃洛石30~40份,活性炭30~40份,水4~10份。其制备包括:(1)按配比将复合络合剂溶于水,形成复合络合剂的水溶液,加入配比量的垃圾焚烧飞灰,得到络合垃圾焚烧飞灰;(2)将络合垃圾焚烧飞灰经干燥、粉碎后,加入配比量的埃洛石和活性炭,置于高速混合机中进行复合,复合后粉碎得到复合橡胶补强剂。该复合橡胶补强剂可与炭黑及白炭黑配合使用,改善橡胶料的耐磨性、耐水性、耐油性和耐热性,同时实现焚烧飞灰的废物无害化及资源化再利用。本发明采用高速混合复合工艺,反应过程无废水废气产生,工艺简单、能耗低。
Description
技术领域
本发明属于橡胶填充材料技术领域,具体涉及一种复合橡胶补强剂及其制备方法和应用。
背景技术
近年来,随着我国城镇化的日益推进,与城镇化的增长一起来的还有各种避免的垃圾废弃物,垃圾处理问题已成为我国面临的一个刻不容缓的问题。
垃圾焚烧飞灰来源于垃圾集中焚烧产生的固体废弃物。垃圾焚烧技术能大幅度将废弃物减容、无害化程度高、可利用废热,是目前垃圾资源化、减量化、无害化处理并回收其热量的主要途径,焚烧后垃圾体积减少80%~90%,重量减少70%。垃圾焚烧通常在800~1000℃的高温下使有毒有害有机物质充分热解,获得一定温度和压力蒸汽,再通过发电机组使其转化为电能。然而,由于垃圾焚烧过程中,重金属不被高温破坏,而只是发生转移和转化,垃圾中的部分低熔点盐及所含重金属在高温焚烧过程中会大量挥发,并富集在烟气净化系统的焚烧飞灰上,因而垃圾焚烧飞灰含有重金属物质主要重金属为如Pb、Cr、Cu和Cd等,是一种危险废弃物。若不针对上述污染源进行有效处理,不仅会侵占土地而且容易污染土壤和水体,还会带来巨大的环境压力。因此寻找垃圾焚烧飞灰无害化处理技术至关重要。
国内垃圾焚烧飞灰传统的处理方式主要是填埋或者堆放,由于飞灰中重金属的浓度较高,如遇到酸雨,飞灰中的重金属会较快溶出并渗透到地下水中,对环境造成破坏。为避免飞灰直接填埋带来的环境压力,研究学者还开展了水泥固化垃圾焚烧飞灰及垃圾焚烧飞灰制作建材的利用和研究,见以下参考文献:
①中国发明专利名称为“一种垃圾焚烧飞灰的稳定固化剂及处理城市生活垃圾焚烧飞灰的方法”,申请号为:201510956480.3,该专利公开了一种采用重金属稳定剂、水和水泥作稳定固化剂固化垃圾焚烧飞灰的方法,固化体养护时间为3~28天。养护时间较长,而且由于垃圾焚烧飞灰中Cl与S含量较高,会对水泥的安定性造成影响,导致垃圾焚烧飞灰中重金属的二次溶出。
②中国发明专利名称为“一种垃圾焚烧飞灰再利用生产薄型陶瓷砖的方法”,申请号为:201510276863.6,该专利公开了一种采用垃圾焚烧飞灰为原料制备薄型陶瓷砖的方法,该专利先用烟气碳酸化对垃圾焚烧飞灰进行化学稳定处理,然后将稳定后的垃圾焚烧飞灰与黏土配料,再经球磨、过筛、造粒、成型、施釉和烧成工序,即可生产出4.5~6mm厚的薄型陶瓷砖。该发明需要经过1100℃左右的高温烧结过程,能耗大、对设计要求高,成本高且不利于节能减排。
发明内容
本发明的目的是为了解决上述现有技术中存在的不足,提供一种以垃圾焚烧飞灰为主要原料的复合橡胶补强剂用于弥补上述缺点。
本发明通过以下技术方案实现:
一种复合橡胶补强剂,由以下重量份的原料组成:
所述复合络合剂为Na2HPO4、NaH2PO4、Na3PO4、Al(H2PO4)3、Na2S、六偏磷酸钠和三聚磷酸钠的至少一种。
本发明以垃圾焚烧飞灰为主要原料,垃圾焚烧飞灰采用复合络合剂进行特殊表面处理和复合后,产品分散性好,活性强,与胶料的兼容性好。产品相对密度较小,粒径小,粒径均匀,粒径分布较窄,比表面积大。
作为优选,所述的复合橡胶补强剂,由以下重量份的原料组成:
本发明复合络合剂能络合垃圾焚烧飞灰的重金属,减少重金属的浸出;埃洛石具有纤维状结构,与活性炭复配协同发挥补强橡胶的作用,在优选范围内,所得复合橡胶补强剂的雾化参数最优。
作为优选,所述埃洛石和活性炭的粒径为1500~2000目。
本发明还提供了一种所述的复合橡胶补强剂的制备方法,包括以下步骤:
(1)按配比将复合络合剂溶于水中,形成复合络合剂的水溶液,加入配比量的垃圾焚烧飞灰,混合得到络合垃圾焚烧飞灰;
(2)将步骤(1)得到的络合垃圾焚烧飞灰经干燥、粉碎后,加入配比量的埃洛石和活性炭,置于高速混合机中进行复合,复合后粉碎得到所述的复合橡胶补强剂。
本发明复合络合剂能有效实现垃圾焚烧飞灰中的重金属的络合,进而高效降低重金属的浸出。同时,垃圾焚烧飞灰在机械力研磨处理条件下,增大比表面积,增大表面活性,实现改性处理。
步骤(2)中,络合垃圾焚烧飞灰置于干燥箱中于100~120℃下干燥6~10h。
干燥后的络合垃圾焚烧飞灰粉碎置于机械粉碎机中进行粉碎,得到粒径为400~600目的络合垃圾焚烧飞灰。
步骤(2)中,复合时间为0.5~2h,复合后经粉碎机粉碎至1000~1500目即得所述的复合橡胶补强剂。
本发明还提供了一种上述复合橡胶补强剂在橡胶中进行补强的应用,所述的复合橡胶补强剂与炭黑和/或白炭黑配合使用,用以替代部分炭黑和/或白炭黑。
与现有技术相比,本发明具有以下有益效果:
(1)本发明制备的复合橡胶补强剂价格低、可溶性重金属浸出量低、可实现垃圾焚烧飞灰的环保、资源化利用。产品可与炭黑及白炭黑配合使用,部分代替补强的炭黑和白炭黑,不降低聚合物胶料的性能(如拉伸强度、断裂伸长率和回弹性等),而且还能改善聚合物胶料的耐磨性、耐水性、耐油性与耐热性。
(2)本发明制备的复合橡胶补强剂可用于各类橡胶制品,橡胶矿缆、工程橡胶、密封件、密封条、铁路垫片、汽车减震、胶辊、胶管、输送带、汽车橡胶制品、内胎等制品。
(3)本发明制备的复合橡胶补强剂可用于硬质PVC管材、型材,也可用于软质PVC防水卷材、人造革等制品。
(4)本发明不需要高温反应、过程中无废水、废气产生,具有工艺简单、流程短、设备投资小等优点。
附图说明
图1为本发明复合橡胶补强剂的制备工艺流程图。
具体实施方式
下面结合具体实施例对本发明进行进一步描述,但本发明的保护范围并不仅限于此。
本发明复合橡胶补强剂的制备工艺流程如图1所示。
实施例1
(1)称取复合络合剂(由Al(H2PO4)3、Na2S和三聚磷酸钠以质量比为1:1:1复合得到)1份溶解于4份水中配成水溶液后,加入到20份垃圾焚烧飞灰中,置于高速搅拌机中搅拌、混合,得到络合垃圾焚烧飞灰;
(2)将步骤(1)所得的络合垃圾焚烧飞灰置于干燥箱中于100℃干燥6h,然后置于粉碎机中粉碎到400目,得到400目络合垃圾焚烧飞灰;
(3)将步骤(2)中制备的400目络合垃圾焚烧飞灰与埃洛石10份、活性炭10份置于高速混合机中,经过高速混合0.5h,然后经粉碎机粉碎到1250目左右,得到垃圾焚烧飞灰基的复合橡胶补强剂。
实施例2
(1)称取复合络合剂(由Na2S、六偏磷酸钠和三聚磷酸钠以质量比为1:0.8:1复合得到)4份溶解于20份水中配成水溶液后,加入到80份垃圾焚烧飞灰中,置于高速搅拌机中搅拌、混合,得到络合垃圾焚烧飞灰;
(2)将步骤(1)所得的络合垃圾焚烧飞灰置于干燥箱中于120℃干燥10h,然后置于粉碎机中粉碎到600目,得到600目络合垃圾焚烧飞灰;
(3)将步骤(2)中制备的600目络合垃圾焚烧飞灰与埃洛石40份、活性炭40份置于高速混合机中,经过高速混合2h,然后经粉碎机粉碎到1250目左右,得到垃圾焚烧飞灰基的复合橡胶补强剂。
实施例3
(1)称取复合络合剂(由Al(H2PO4)3、Na2S和六偏磷酸钠以质量比为1:0.9:0.6复合得到)2份溶解于10份水中配成水溶液后,加入到50份垃圾焚烧飞灰中,置于高速搅拌机中搅拌、混合,得到络合垃圾焚烧飞灰;
(2)将步骤(1)所得的络合垃圾焚烧飞灰置于干燥箱中于110℃干燥8h,然后置于粉碎机中粉碎到400目,得到400目络合垃圾焚烧飞灰;
(3)将步骤(2)中制备的400目络合垃圾焚烧飞灰与埃洛石30份、活性炭30份置于高速混合机中,经过高速混合1h,然后经粉碎机粉碎到1250目左右,得到垃圾焚烧飞灰基的复合橡胶补强剂。
浸出测试实验
重金属浸出实验以《固体废弃物浸出毒性浸出方法——水平震荡法》(HJ557-2009)为参比数据。具体步骤为:称取干基重量为100g的试样,置于2L提取瓶中,加入1L水后盖紧瓶盖,然后垂直固定在水平振荡装置上,在室温下振荡8h后取下提取瓶,静置16h,取浸出液体经微孔滤膜过滤后经等离子体原子发射光谱测试。实验结果如表1所示。
表1实施例样品的检测分析结果
通过表1中实施例1~3的检测分析结果可知,实施例1~3样品在水溶液中震荡浸出8h、静置16h后,实施例1~3中重金属Cr,Cu,Cd与Pb等浸出率都明显低于工业污水排放标准,说明实施例1~3样品都具有良好的对垃圾焚烧飞灰中重金属的固化能力。
Claims (8)
1.一种复合橡胶补强剂,其特征在于,由以下重量份的原料组成:
所述复合络合剂为Na2HPO4、NaH2PO4、Na3PO4、Al(H2PO4)3、Na2S、六偏磷酸钠和三聚磷酸钠的至少一种。
2.根据权利要求1所述的复合橡胶补强剂,其特征在于,由以下重量份的原料组成:
所述复合络合剂为Na2HPO4、NaH2PO4、Na3PO4、Al(H2PO4)3、Na2S、六偏磷酸钠和三聚磷酸钠的至少一种。
3.一种根据权利要求1或2所述的复合橡胶补强剂的制备方法,其特征在于,包括以下步骤:
(1)按配比将复合络合剂溶于水中,形成复合络合剂的水溶液,加入配比量的垃圾焚烧飞灰,混合得到络合垃圾焚烧飞灰;
(2)将步骤(1)得到的络合垃圾焚烧飞灰经干燥、粉碎后,加入配比量的埃洛石和活性炭,置于高速混合机中进行复合,复合后粉碎得到所述的复合橡胶补强剂。
4.根据权利要求3所述的复合橡胶补强剂的制备方法,其特征在于,步骤(2)中,络合垃圾焚烧飞灰置于干燥箱中于100~120℃下干燥6~10h。
5.根据权利要求3所述的复合橡胶补强剂的制备方法,其特征在于,干燥后的络合垃圾焚烧飞灰粉碎置于机械粉碎机中进行粉碎,得到粒径为400~600目的络合垃圾焚烧飞灰。
6.根据权利要求3所述的复合橡胶补强剂的制备方法,其特征在于,步骤(2)中,复合时间为0.5~2h,复合后经粉碎机粉碎至1000~1500目即得所述的复合橡胶补强剂。
7.一种根据权利要求1或2所述的复合橡胶补强剂在橡胶中进行补强的应用。
8.根据权利要求7所述的复合橡胶补强剂在橡胶中进行补强的应用,其特征在于,所述的复合橡胶补强剂与炭黑和/或白炭黑配合使用。
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