CN111592904A - 一种利用固废碳基双金属材料去除焦油的方法 - Google Patents
一种利用固废碳基双金属材料去除焦油的方法 Download PDFInfo
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Abstract
本发明公开了一种利用固废碳基双金属材料去除焦油的方法，本发明的固废碳基双金属材料以固体热解碳为材料载体，利用湿式浸渍法将两种金属物质均匀的负载在载体的表面，通过协同作用，使固废碳基双金属材料在热解时去除焦油方面的能力明显提升，焦油去除效率可达到83％；同时所使用的固废原材料种类多源，应用范围广泛。
Description
技术领域：
本发明涉及固体废弃物处理技术领域，具体涉及一种利用固废碳基双金属材料去除焦油的方法。
背景技术：
热解技术是实现固体废弃物能源化、资源化利用的方法之一，热解方法可以将固废能源转化为各种化工产品和气体产品，能够缓解能源短缺并减少污染物排放等问题。热解过程主要产生固态碳、液态焦油和热解气三种产物，产物焦油是一种高芳香度的碳氢化合物的复杂混合物，绝大部分为带侧链或不带侧链的多环、稠环化合物和含氧、硫、氮的杂环化合物，其具有高粘稠度和毒性，在反应中会造成管路的堵塞和腐蚀，如何有效的去除焦油使其转化为更多的有用气体是热解方法中的关键技术问题。
发明内容：
本发明的目的是提供一种利用固废碳基双金属材料去除焦油的方法，该固废碳基双金属材料以固体热解碳为材料载体，利用湿式浸渍法将两种金属物质均匀的负载在载体的表面，通过协同作用，使固废碳基双金属材料在热解过程中去除焦油方面的能力明显提升。
本发明是通过以下技术方案予以实现的：
一种利用固废碳基双金属材料去除焦油的方法，该方法包括以下步骤：
(1)惰性气氛下，固体废弃物600-900℃热解处理1-3h得到固废热解碳；所述的固体废弃物包括但不限于生活垃圾固体废弃物、农林固体废弃物、工业固体废弃物，市政污泥、畜禽粪便等；
(2)湿式浸渍法在固废热解碳上进行两种活性金属的负载，活性金属选自Cu、Ni、Fe、Ca中的任意两种，含有金属和热解碳的溶液经过烘干处理后得到前驱体，前驱体在惰性气氛下600-900℃二次煅烧1～3h，得到固废碳基双金属材料；
(3)将步骤(2)得到的固废碳基双金属材料应用于热解过程中去除焦油。
所述前驱体制作的具体步骤为：两种金属盐溶于水中得到混合物溶液，称取步骤(1)中的固废热解碳溶于混合溶液中并搅拌，搅拌后的溶液进行烘干处理既得到前驱体；其中两种活性金属的总质量与固废热解碳的质量比为0.1:1～0.3:1。
优选地，金属盐选自金属的氯化物或硝酸盐。
优选地，步骤(3)中所述热解过程为可燃固废的热解过程，原料包括但不限于生活垃圾、农林废物、工业废物，市政污泥、畜禽粪便等；固体废弃物与催化剂材料的添加质量比例为0.1:1～1:1，热解温度为600-900℃。
本发明的有益效果如下：本发明的固废碳基双金属材料以固体热解碳为材料载体，利用湿式浸渍法将两种金属物质均匀的负载在载体的表面，通过协同作用，使固废碳基双金属材料在热解过程中去除焦油方面的能力明显提升，焦油去除效率可达到83％；同时所使用的固废原材料种类多源，应用范围广泛。
附图说明：
图1是实施例1制备固废炭基双金属材料的SEM照片。
具体实施方式：
以下是对本发明的进一步说明，而不是对本发明的限制。
实施例1：
(1)取农林固体废弃物稻壳为原料，在900℃下氮气气氛下下进行1h的热解，得到固废热解碳；
(2)取7.2gFeCl3·6H2O和6gNi(NO3)2溶于500mL水中得到混合溶液，称取步骤(1)得到的10g固废热解碳溶于混合溶液中，在转速为700rmp条件下搅拌3h；将搅拌后的溶液置于105℃的干燥箱里进行烘干24h，烘干后的材料前驱体在氮气气氛下900℃进行二次煅烧1h，即得到固废炭基双金属材料，其中两种金属的总负载比例为30wt％；对得到的固废碳基双金属材料进行表征，如图1所示，所得的材料表面为聚合的纳米粒子形态，表面粒子大小均一、分布均匀，粗糙的表面使得材料具有较大的比表面积，在反应中增大了与焦油的接触面积，增加了焦油去除的概率；
(3)取市政污泥10g和步骤(2)中所得固废炭基双金属材料8g进行充分的混合，混合物氮气气氛下800℃热解处理2h，以市政污泥单独热解产生的焦油量为基础数据，添加双金属材料进行热解对焦油的去除率为83％。
对比例1
(1)取农林固体废弃物稻壳为原料，在900℃下氮气气氛下下进行1h的热解，得到固废热解碳；
(2)取14.4gFeCl3·6H2O溶于500mL水中得到混合溶液，称取步骤(1)得到的10g固废热解碳溶于混合溶液中，在转速为700rmp条件下搅拌3h，将搅拌后的溶液置于105℃的干燥箱里进行烘干24h，烘干后的材料前驱体在氮气气氛下900℃进行二次煅烧1h，即得到固废炭基单金属材料，其中金属的负载比例为30wt％；
(3)取市政污泥10g和步骤(2)中所得固废炭基单金属材料8g进行充分的混合，混合物氮气气氛下800℃热解处理2h，以市政污泥单独热解产生的焦油量为基础数据，添加单金属材料进行热解对焦油的去除率为58％。
对比例2
(1)取农林固体废弃物稻壳为原料，在900℃下氮气气氛下下进行1h的热解，得到固废热解碳；
(2)取12gNi(NO3)2溶于500mL水中得到混合溶液，称取步骤(1)得到的10g固废热解碳溶于混合溶液中，在转速为700rmp条件下搅拌3h；将搅拌后的溶液置于105℃的干燥箱里进行烘干24h，烘干后的材料前驱体在氮气气氛下900℃进行二次煅烧1h，即得到固废炭基单金属材料，其中金属的负载比例为30wt％。
(3)取市政污泥10g和步骤(2)中所得固废炭基单金属材料8g进行充分的混合，混合物氮气气氛下800℃热解处理2h，以市政污泥单独热解产生的焦油量为基础数据，添加单金属材料进行热解对焦油的去除率为60％。
实施例2
(1)取固体废弃物煤底灰为原料，在800℃下氮气气氛下下进行2h的热解，得到固废热解碳；
(2)取9.6gFeCl3·6H2O和5.8gCuCl2·2H2O溶于500mL水中得到混合溶液，称取步骤(1)得到的10g固废热解碳溶于混合溶液中，在转速为800rmp条件下搅拌3h；将搅拌后的溶液置于105℃的干燥箱里进行烘干24h，烘干后的材料前驱体在氮气气氛下800℃进行二次煅烧2h，即得到固废炭基双金属材料，其中两种金属的总负载比例为30wt％。
(3)取生活垃圾10g和步骤(2)中所得固废炭基双金属材料1g进行充分的混合，混合物氮气气氛下700℃热解处理2h，以生活垃圾单独热解产生的焦油量为基础数据，添加双金属材料进行热解对焦油的去除率为79％。
实施例3
(1)取工业固体废弃物木材为原料，在600℃下氦气气氛下下进行3h的热解，得到固废热解碳；
(2)取1.4gCaCl2和2.9gCuCl2·2H2O溶于500mL水中得到混合溶液，称取步骤(1)得到的10g固废热解碳溶于混合溶液中，在转速为900rmp条件下搅拌1h；将搅拌后的溶液置于105℃的干燥箱里进行烘干24h，烘干后的材料前驱体在氦气气氛下600℃进行二次煅烧3h，即得到固废炭基双金属材料，其中两种金属的总负载比例为10wt％。
(3)取工业废物木材10g和步骤(2)中所得固废炭基双金属材料10g进行充分的混合，混合物氦气气氛下600℃热解处理3h，以工业废物木材单独热解产生的焦油量为基础数据，添加双金属材料进行热解对焦油的去除率为82％。
实施例4
(1)取畜禽粪便为原料，在700℃下氮气气氛下下进行2h的热解，得到固废热解碳；
(2)取4.8gFeCl3·6H2O和2.9gCuCl2·2H2O溶于500mL水中得到混合溶液，称取步骤(1)得到的10g固废热解碳溶于混合溶液中，在转速为600rmp条件下搅拌2h；将搅拌后的溶液置于105℃的干燥箱里进行烘干24h，烘干后的材料前驱体在氮气气氛下700℃进行二次煅烧2h，即得到固废炭基双金属材料，其中两种金属的总负载比例为15wt％。
(3)取废旧塑料10g和步骤(2)中所得固废炭基双金属材料3g进行充分的混合，混合物氮气气氛下900℃热解处理1h，以废旧塑料单独热解产生的焦油量为基础数据，添加双金属材料进行热解对焦油的去除率为78％。
实施例5
(1)取农业固体废弃物秸秆为原料，在800℃下氩气气氛下下进行2h的热解，得到固废热解碳；
(2)取4.8gFeCl3·6H2O和2.8gCaCl2溶于500mL水中得到混合溶液，称取步骤(1)得到的10g固废热解碳溶于混合溶液中，在转速为800rmp条件下搅拌2h；将搅拌后的溶液置于105℃的干燥箱里进行烘干24h，烘干后的材料前驱体在氩气气氛下800℃进行二次煅烧2h，即得到固废炭基双金属材料，其中两种金属的总负载比例为20wt％。
(3)取废旧轮胎10g和步骤(2)中所得固废炭基双金属材料7g进行充分的混合，混合物氩气气氛下800℃热解处理2h，以废旧轮胎单独热解产生的焦油量为基础数据，添加双金属材料进行热解对焦油的去除率为76％。
以上仅是本发明的优选实施方式，应当指出的是，上述优选实施方式不应视为对本发明的限制，本发明的保护范围应当以权利要求所限定的范围为准。对于本技术领域的普通技术人员来说，在不脱离本发明的精神和范围内，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。
Claims (4)
1.一种利用固废碳基双金属材料去除焦油的方法，其特征在于，该方法包括以下步骤：
(1)惰性气氛下，固体废弃物600-900℃热解处理1-3h得到固废热解碳；所述的固体废弃物包括生活垃圾固体废弃物、农林固体废弃物、工业固体废弃物，市政污泥、畜禽粪便；
(2)湿式浸渍法在固废热解碳上进行两种活性金属的负载，活性金属选自Cu、Ni、Fe、Ca中的任意两种，含有金属和热解碳的溶液经过烘干处理后得到前驱体，前驱体在惰性气氛下600-900℃二次煅烧1～3h，得到固废碳基双金属材料；
(3)将步骤(2)得到的固废碳基双金属材料应用于热解过程中去除焦油。
2.根据权利要求1所述利用固废碳基双金属材料去除焦油的方法，其特征在于，所述前驱体制作的具体步骤为：两种金属盐溶于水中得到混合物溶液，称取步骤(1)中的固废热解碳溶于混合溶液中并搅拌，搅拌后的溶液进行烘干处理既得到前驱体；其中两种活性金属的总质量与固废热解碳的质量比为0.1:1～0.3:1。
3.根据权利要求2所述利用固废碳基双金属材料去除焦油的方法，其特征在于，金属盐选自金属的氯化物或硝酸盐。
4.根据权利要求1所述利用固废碳基双金属材料去除焦油的方法，其特征在于，步骤(3)中所述热解过程为可燃固废的热解过程，原料包括生活垃圾、农林废物、工业废物，市政污泥、畜禽粪便；固体废弃物与催化剂材料的添加质量比例为0.1:1～1:1，热解温度为600-900℃。
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