CN107652999A - 一种微波辅助双床层催化快速共热解竹废料与废弃轮胎制备生物质基车用柴油的方法 - Google Patents
一种微波辅助双床层催化快速共热解竹废料与废弃轮胎制备生物质基车用柴油的方法 Download PDFInfo
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Abstract
一种微波辅助双床层催化快速共热解竹废料与废弃轮胎制备生物质基车用柴油的方法,1)按1:1~1:10的质量比,称取竹废料与废弃轮胎混匀;2)按HZSM‑5分子筛催化剂:竹废料与废弃轮胎混合物=1:1~1:10的质量比,将催化剂置于与石英双口瓶热解蒸汽出口连接的U型石英管内,将微波吸收剂加入石英杯中;3)将石英双口瓶及U型石英管埋入石英杯中,置于微波热解仪器中,加热至450~650℃,快速添加竹废料和废弃轮胎混合物至石英双口瓶,产生的热解蒸汽经过U型石英管催化剂催化重整,通过冷凝管冷凝成富烃生物质基车用柴油。本发明大大缩短了碳化时间,提高了生物油产率和品质;显著提高了富烃生物油中烷烃、芳烃的含量。
Description
技术领域
本发明属于生物质能源转化技术领域,主要涉及一种竹废料与废弃轮胎制备生物质基车用柴油的方法。
背景技术
随着化石燃料的急剧消耗以及环境的恶化,生物质快速热解制备可再生燃油技术受到了研究者越来越多的重视。但该技术所得的生物油含氧量高、热值低、热稳定性差、粘度高、酸度大、腐蚀性强,因此其进一步的应用受到了较大限制。值得注意的是,这些缺点都和生物油中含氧量高密切相关。为了提高生物油品质,微波快速催化热解生物质制备富烃生物油技术应运而生,通过将快速热解和催化重整制油技术相结合,以在生物油冷凝前提升其品质,降低生物油含氧量、提高烃类含量。该技术以较低的成本、连续化的生产工艺将低能量密度的生物质转化为高能量密度的富烃生物油,减少了生物质的体积,便于储存和运输。
我国可开发的生物质资源潜力巨大,现有农林生物质废弃物、生活垃圾及有机废弃物每年总量超过10亿吨,其中可利用的生物质资源总量每年约4.6亿吨标准煤,目前已利用约2200万吨标准煤,还有约4.4亿吨可利用。同时由于汽车变成日常的交通工具,对人们的生活水平有着极大的提高和改善。但出现了大量的废弃轮胎。随着我国社会发展、生态文明建设和农林业的进一步发展,生物质利用潜力将进一步增大。将生物质废弃物高效炼制替代化石燃料,生产能源、化工产品和生物材料的低碳型工业模式,是社会经济实现可持续发展的重大战略需求。
目前,微波作为一种新型加热方式在生物质快速催化热解技术中开始得到应用。作为电磁波谱中的一个有限频带,微波位于红外线和特高频无线电波之间,其频率范围为0.3-30 GHz,波长范围为1 mm-1 m。微波具有极强的穿透性,物料内外受微波辐射时会通过偶极子极化介电响应实现电磁能向热能的转换(微波介电加热)。具体而言,物料中的极性分子或极性部分在微波作用下极化形成偶极子,偶极子随微波交变电场作高频振荡,并互相摩擦碰撞挤压而生热,导致物料内外同时迅速升温。微波加热的本质是微波在物料中的能量耗散。与传统加热方式相比,微波加热具有如下优势:微波加热具有如下优势:(1)加热均匀:微波加热时能量利用率高,物料升温非常迅速,且微波穿透性强,能对物料进行内外均衡体加热,也无需对物料进行粉碎加工;(2)节约能耗:微波发生器和微波加热器与物料不直接接触,物料无需流化等操作;(3)无滞后效应:关闭微波发射源后便再无能量转换;(4)便与操作:微波加热响应迅速,对物料温度可以精确控制,也便于自动化控制;(5)安全无污染。目前微波加热技术发展迅速,工业许多领域都用到了该技术。
但是值得注意的是,尽管生物质微波快速热解制油技术能够均匀加热物料、促进烃类生成,但该技术在原料、催化剂、传热效果、生物油品质等方面仍存在一系列突出的问题,如生物质是缺氢多氧的原料,从源头上决定了制得的生物油中烃类含量不足、含氧化合物过多,因此需要设法从源头上对原料进行补氢,物质与多氢原料(废弃轮胎/塑料、厨余垃圾和地沟油)微波加热催化共热解研究,解决生物质原料少氢的缺陷。
发明内容
本发明的目的是克服现有生物质热解技术所得的生物油含氧量高、热值低、热稳定性差、粘度高、酸度大、腐蚀性强的不足,提供了一种微波辅助双床层催化快速共热解竹废料与废弃轮胎制备生物质基车用柴油的方法,该方法工艺简单,热解快速,所得热解生物油含氧量低,含烃类量高,稳定性强,热值高,性质与0#柴油相似,可直接与车用柴油按比例混合使用。
本发明是通过以下技术方案实现的。
本发明所述的一种微波辅助双床层催化快速共热解竹废料与废弃轮胎制备生物质基车用柴油的方法,包括以下步骤。
(1)按竹废料﹕废弃轮胎=1:1~1:10的质量比,称取竹废料与废弃轮胎并混合均匀。
(2)按HZSM-5分子筛催化剂﹕竹废料与废弃轮胎混合物=1:1~1:10的质量比,称取催化剂,置于与石英双口瓶热解蒸汽出口连接的U型石英管内作为催化剂床层,另称取5~10kg微波吸收剂加入石英杯中作为微波吸收床层。
(3)将石英双口瓶以及与其连接装有催化剂的U型石英管埋入装有微波吸收剂的石英杯中,置于微波热解仪器中,加热至450~650℃,快速添加竹废料和废弃轮胎混合物至石英双口瓶,产生的热解蒸汽在抽气泵作用下,经过U型石英管催化剂催化重整,最终通过冷凝管冷凝成富烃生物质基车用柴油。
本发明所述的HZSM-5分子筛催化剂的硅铝比为20~100。
本发明所述的微波吸收剂为碳化硅。
本发明比较已有的热解技术,具有以下优点。
(1)通过提高原料H/Ceff(有效氢碳比)来提高目标产物产率,选用高H/Ceff物质(废弃轮胎)与生物质(竹废料)共催化热解是提高烃类产率以及减少催化剂失活速率。
(2)微波吸收床层的热传递和反应物料吸波双重加热效果,使反应物快速升到目标温度,大大缩短了碳化时间,提高了富烃生物油的产率和品质,石英双口瓶热解蒸汽出口连接的U型石英管内催化剂床层的引入充分发挥了外部催化的优势,对了热解气体进行有效催化重整,显著提高了生物油中烃类的含量。
(3)微波吸收剂与热解蒸汽不接触,减少了二次热解反应。
具体实施方式
本发明将通过以下实施例作进一步说明。
实施例1。
将8kg碳化硅加入石英杯,20g HZSM-5分子筛催化剂(直径5mm,Si/Al=50,比表面积640m2/g)置于与石英双口瓶连接装的U型石英管中,将石英双口瓶以及与其连接装有催化剂的U型石英管埋入装有微波吸收剂的石英杯中,置于微波热解仪器中,固定功率升温至550℃,从进料口快速添加100g竹废料废弃轮胎混合物(按竹废料:废弃轮胎=1:1的质量比)至石英双口瓶,继续保持550℃催化热解至反应完全,产生的热解蒸汽在抽气泵作用下,经过U型石英管催化剂催化重整,最终通过冷凝管冷凝得到富烃生物油55g,GC-MS分析得出富烃生物油中烃类含量达到90.7%。
实施例2。
将8kg碳化硅加入石英杯,10g HZSM-5分子筛催化剂(直径5mm,Si/Al=50,比表面积640m2/g)置于与石英双口瓶连接装的U型石英管中,将石英双口瓶以及与其连接装有催化剂的U型石英管埋入装有微波吸收剂的石英杯中,置于微波热解仪器中,固定功率升温至500℃,从进料口快速添加100g竹废料废弃轮胎混合物(按竹废料:废弃轮胎=1:1.5的质量比)至石英双口瓶,继续保持500℃催化热解至反应完全,产生的热解蒸汽在抽气泵作用下,经过U型石英管催化剂催化重整,最终通过冷凝管冷凝得到富烃生物油52g, GC-MS分析得出富烃生物油中烃类含量达到86.1%。
实施例3。
将8kg碳化硅加入石英杯,20g HZSM-5分子筛催化剂(直径5mm,Si/Al=50,比表面积640m2/g)置于与石英双口瓶连接装的U型石英管中,将石英双口瓶以及与其连接装有催化剂的U型石英管埋入装有微波吸收剂的石英杯中,置于微波热解仪器中,固定功率升温至550℃,从进料口快速添加100g竹废料废弃轮胎混合物(按竹废料:废弃轮胎=1:2的质量比)至石英双口瓶,继续保持550℃催化热解至反应完全,产生的热解蒸汽在抽气泵作用下,经过U型石英管催化剂催化重整,最终通过冷凝管冷凝得到富烃生物油50g, GC-MS分析得出富烃生物油中烃类含量达到88.4%。
Claims (3)
1.一种微波辅助双床层催化快速共热解竹废料与废弃轮胎制备生物质基车用柴油的方法,其特征是包括以下步骤:
(1)按竹废料:废弃轮胎=1:1~1:10的质量比,称取竹废料与废弃轮胎并混合均匀;
(2)按HZSM-5分子筛催化剂﹕竹废料与废弃轮胎混合物=1:1~1:10的质量比,称取催化剂,置于与石英双口瓶热解蒸汽出口连接的U型石英管内作为催化剂床层,另称取5~10kg微波吸收剂加入石英杯中作为微波吸收床层;
(3)将石英双口瓶以及与其连接装有催化剂的U型石英管埋入装有微波吸收剂的石英杯中,置于微波热解仪器中,加热至450~650℃,快速添加竹废料和废弃轮胎混合物至石英双口瓶,产生的热解蒸汽在抽气泵作用下,经过U型石英管催化剂催化重整,最终通过冷凝管冷凝成富烃生物质基车用柴油。
2.根据权利要求1所述的一种微波辅助双床层催化快速共热解竹废料与废弃轮胎制备生物质基车用柴油的方法,其特征是所述的HZSM-5分子筛催化剂的硅铝比为20~100。
3.根据权利要求1所述的一种微波辅助双床层催化快速共热解竹废料与废弃轮胎制备生物质基车用柴油的方法,其特征是所述的微波吸收剂为碳化硅。
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