CN115197736B - 一种调控塑料垃圾超临界水热液化油品质的方法 - Google Patents
一种调控塑料垃圾超临界水热液化油品质的方法 Download PDFInfo
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- CN115197736B CN115197736B CN202210918980.8A CN202210918980A CN115197736B CN 115197736 B CN115197736 B CN 115197736B CN 202210918980 A CN202210918980 A CN 202210918980A CN 115197736 B CN115197736 B CN 115197736B
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
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- HEILIGJNYTWOHU-UHFFFAOYSA-N ethanol 2-hydroxybenzoic acid Chemical compound CCO.OC(=O)C1=CC=CC=C1O HEILIGJNYTWOHU-UHFFFAOYSA-N 0.000 claims description 6
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- GNFTZDOKVXKIBK-UHFFFAOYSA-N 3-(2-methoxyethoxy)benzohydrazide Chemical compound COCCOC1=CC=CC(C(=O)NN)=C1 GNFTZDOKVXKIBK-UHFFFAOYSA-N 0.000 description 2
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
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Abstract
本发明公开了一种调控塑料垃圾超临界水热液化油品质的方法,包括催化剂的合成、煅烧以及超临界水热液化三个步骤。通过采用本发明提出的方法制备成催化剂,并将其应用在塑料垃圾超临界水热液化油品质的过程中,不但降低了成本,且反应过程得到了优化,使塑料得到了资源化回收利用,降低碳排放,促进了循环经济的发展,功能性强,本发明实用性和功能性强,可广泛应用于塑料垃圾的无害化处理、资源化利用技术领域。
Description
技术领域
本发明涉及塑料垃圾的无害化处理、资源化利用技术领域,具体是指一种调控塑料垃圾超临界水热液化油品质的方法。
背景技术
塑料制品为社会带来了极大的便利,在农业、工业、建筑业等领域得到了广泛的应用,然而同时也造成了大量塑料废弃物的堆积,带来塑料废弃物处置难题。此外,绝大多数塑料都来自化石燃料,因此塑料生产的增加消耗了大量的化石能源。
现有塑料废弃物的处理主要包括传统的土地填埋、机械回收和焚烧。垃圾填埋占用了大量的土地资源,塑料分解周期长,且分解后的微塑料流入土壤、河流,对生态系统构成了威胁。机械回收技术需要根据塑料的类型、颜色和质量等进行分选,存在一定的局限性,回收效率低下。焚烧处置技术简单,能处理大部分塑料,然而塑料焚烧会释放出影响人体健康和污染环境的有毒物质。除了这三种传统塑料废弃物处理方式之外,还有新型热处理方法如热解、汽化和水热液化,该类方法能将塑料废弃物转换为可供二次利用的燃料油以及其他化工产物等,在其处理过程中需要获得较高的反应温度和压力,对设备的性能要求高,能耗也较高,且得到的产物产率欠佳,成分复杂。催化热解是在热解的基础上加入一定量的商业催化剂,降低热解所需要的温度,在一定程度上提高热解油的产率和品质,添加商业催化剂后温度在400℃附近即可发生热解,商业催化剂定价高,成本高。
因此,如何清洁、高效、低成本处理塑料废弃物成为了一个亟待解决的问题,也成为了国内外研究的热点。通过加入催化剂,可以降低活化能,促进塑料废物的裂解和液体油的生产,液体油热值高、性能优良,具有替代石油、柴油等化石能源的潜力。和其他处理方式相比,水热液化本身就具有很大的优势,通过合成制备低成本的催化剂添加到水热液化中,进一步促进塑料转化为油、且定向调控有品质有着重要的现实意义和理论价值。
发明内容
针对以上问题,本发明提出了一种在超临界溶剂中定向调控塑料液化油品质的方法,降低了塑料处理的能耗,提高了液化油的产率和品质,低碳经济。
本发明提供的技术方案为:
一种调控塑料垃圾超临界水热液化油品质的方法,包括催化剂的合成、煅烧以及超临界水热液化三个步骤。
优选地,在催化剂的合成过程中,包括以下子步骤:
1.1)将含有Cu2+、Zn2+、Fe2+中的至少一种的盐类化合物,与含有Mg2+、Al3+的盐溶液共沉淀,且共沉淀的过程在0.5~2M的Na2CO3或0.8~3M的NaHCO3水溶液中进行;
1.2)在反应过程中添加0~1M的NaOH溶液或0~3M的NH4·H2O溶液,用于调节反应环境的pH值为10~12;
1.3)在反应过程中将温度恒定在65~75℃之间,且进行搅拌,搅拌速度为100~300rpm,沉淀形成后继续养护8~24h;
1.4)将沉淀物清洗至中性,而后在0~2M的水杨酸乙醇溶液中浸渍8~24h;
1.5)浸渍结束后,按照过滤、洗涤、烘干的顺序进行后续处理,从而得到催化剂。
优选地,在煅烧过程中,设定的工艺条件为:煅烧过程升温速率为10℃~30℃/min;煅烧最终温度为450~700℃;煅烧氛围为空气环境,煅烧时间为4~24h。
优选地,所述超临界水热液化中的溶剂是水、甲醇、乙醇、甲苯、丙酮、醋酸中的一种,水热液化温度为240~500℃,反应时间为0~4h,所述催化剂与塑料垃圾的质量比为0~0.1,塑料垃圾与溶剂的质量比为0.1~1。
优选地,所述塑料垃圾为一种、两种或多种塑料类型的混合物。
优选地,对于未完全转化的塑料垃圾,通过重力沉降、离心、压滤中的一种或多种的组合实现油的分离。
本发明与现有技术相比的优点在于:
本发明提出的催化剂方法,与现有催化剂相比成本制作更低,且催化效果佳;
本发明将催化剂加入到超临界水热液化过程中,降低了反应所需的温度,减少了设备的使用负担,延长了设备的工作寿命,能耗低,并且极大加速了塑料垃圾转化为高品质油的反应进程;
本发明提出的方法无二次污染物排放,能有效解决塑料垃圾堆积的问题,使塑料垃圾得到资源化回收利用,降低碳排放,促进循环经济的发展,具有理论和现实意义,应用前景良好。
附图说明
图1是本发明实施例中不同的催化剂与塑料质量比降解后的效果图。
具体实施方式
下面结合实施例对本发明做进一步的详细说明。
结合附图1,本发明提出的技术方案为:
一种调控塑料垃圾超临界水热液化油品质的方法,包括催化剂的合成、煅烧以及超临界水热液化三个步骤。
在催化剂的合成过程中,包括以下子步骤:
1.1)将含有Cu2+、Zn2+、Fe2+中的至少一种,与含有Mg2+、Al3+的盐溶液共沉淀,且共沉淀的过程在0.5~2M的Na2CO3或0.8~3M的NaHCO3的水溶液中进行;
1.2)在反应过程中添加0~1M的NaOH溶液或0~3M的NH4·H2O溶液,用于调节反应环境的pH值为10~12;
1.3)在反应过程中将温度恒定在65~75℃之间,且进行搅拌,搅拌速度为100~300rpm,沉淀形成后继续养护8~24h;
1.4)将沉淀物清洗至中性,而后在0~2M的水杨酸乙醇溶液中浸渍8~24h;
1.5)浸渍结束后,按照过滤、洗涤、烘干的顺序进行后续处理,从而得到催化剂。
过滤的具体操作为:将浸渍后的沉淀物转置于放有滤纸的漏斗中过滤;洗涤的具体操作为:向漏斗中注入少量水,使水浸过沉淀物,等水滤出后再次加入少量水洗涤,洗涤3次;烘干的具体操作为:将洗涤后的沉淀物置于105℃的烘箱中烘干直至质量不再减少。
在煅烧过程中,设定的工艺条件为:煅烧过程升温速率为10℃~30℃/min;煅烧最终温度为450~700℃;煅烧氛围为空气氛围,煅烧时间为4~24h。
超临界水热液化中的溶剂是水、甲醇、乙醇、甲苯、丙酮、醋酸中的一种,水热液化温度为240~500℃,反应时间为0~4h,催化剂与塑料垃圾的质量比为0~0.1,塑料与溶剂的质量比为0.1~1。
塑料垃圾为一种、两种或多种塑料类型的混合物。
对于未完全转化的塑料垃圾,其通过重力沉降、离心、压滤中的一种或多种的组合实现油的分离。
结合附图1,分别给出了催化剂与塑料垃圾比为0、0.05、0.1以及0.15过程中得到的降解产物的分布规律。从图1中可知,在利用本发明提出的技术方案对塑料垃圾降解的过程中,利用本发明中提出的方法制备成的催化剂在催化塑料垃圾的过程中,能够得到不同的含碳有机物,从而实现了降解的目的。
下面通过具体的实施例来对本发明进行进一步的说明。
下面具体阐述下本发明提出的技术方案的操作步骤。
催化剂的合成方法,具体操作步骤如下:
a)基础溶液配制:将盐类化合物溶解于去离子水中得到金属溶液,将NaOH或NaHCO3溶解于去离子水中得到碱性溶液,将不同量的Na2CO3或NaHCO3溶解于去离子水中得到沉淀溶液和平衡溶液;
b)混合搅拌:将步骤a)中配制的金属溶液和碱性溶液加入到沉淀溶液中,并充分搅拌形成混合物,温度和pH分别严格控制在10℃和55℃;
c)结晶:将步骤b)中得到的混合物搅拌结晶24h,得到混合物;
d)沉淀:过滤步骤c)中得到的混合物,并将其分散在平衡溶液中搅拌1h,再次过滤,得到沉淀物;
e)浸渍:将步骤d)中得到的沉淀物需清洗至中性,然后在0~2M的水杨酸乙醇溶液中浸渍8~24h;
f)将步骤e)中浸渍后的沉淀物过滤、洗涤、烘干;
g)煅烧:将经步骤f)处理后的沉淀物置于马弗炉中煅烧,得到块状催化剂;
h)研磨:将步骤g)中得到的块状催化剂在研磨钵中研磨成粉末状,得到最终催化剂。
在上述步骤a)中金属溶液中金属离子与去离子水的质量比为1:70~1:80,碱性溶液中碱与去离子水的质量比为1:20~1:30,沉淀溶液中Na2CO3或NaHCO3与去离子水的质量比为1:70~1:80,平衡溶液中Na2CO3或NaHCO3与去离子水的质量比为1:50~1:60。
在上述步骤b)、c)中搅拌温度均为65~75℃,搅拌速度为100~300rpm。
在上述步骤f)中烘干温度为105℃。
在上述步骤g)中煅烧过程升温速率10℃~30℃/min,煅烧最终温度为450~700℃,煅烧氛围为空气氛围,煅烧时间为4~24h。
超临界水热液化,具体操作步骤:
a)混合搅拌:将废弃塑料破碎成小颗粒,向其中加入一定量的溶剂和催化剂,搅拌混合均匀,形成混合物;塑料垃圾可以是一种、两种或者多种塑料的混合物。溶剂可以是水、甲醇、乙醇、甲苯、丙酮、醋酸中的任一种;
b)水热处理:将步骤a)中配置好的混合物转移到高压反应釜中,设置目标温度,保温、搅拌,完成超临界水热处理过程;
c)固液分离:将步骤b)中处理后得到的固液混合物通入固液分离设备完成固液分离;
d)产品:步骤c)得到的液体经蒸馏或萃取后得到油产品。
在上述步骤a)中进料装置内的催化剂与塑料垃圾的质量比为0~0.1,塑料与溶剂的质量比为0.1~1。
在上述步骤b)中进料混合物在水热处理设备中的目标温度为240~500℃,反应时间为0~4h。
在上述步骤c)中如果有未完全转化的塑料,可以采用重力沉降、离心、压滤中的一种或多种的组合实现油的分离。
在上述步骤d)中固液分离后得到的液体根据所选溶剂类别,增加蒸馏或萃取步骤,去除残留溶剂,得到提质后的油产品。
具体实施例:
实施例一:以超临界水热液化聚丙烯为例:
步骤一:按金属离子与去离子水的质量比为1:70称取或量取Cu(NO3)2·3H2O、Mg(NO3)2·6H2O和Al(NO3)3·9H2O溶解于去离子水中;
步骤二:向步骤一中得到的溶液中加入1M的NaOH溶液,调节反应环境的pH值为10,充分搅拌结晶24h,再将得到的混合物过滤并分散到1M的Na2CO3水溶液中并搅拌1h后过滤;
步骤三:将步骤二中得到的沉淀物用去离子水清洗至中性,然后在1M的水杨酸乙醇溶液中浸渍8h,其中,水杨酸乙醇溶液按照0-2m的比例溶解而成,在溶解过程中采用搅拌棒进行搅拌,以加快溶解速率;
步骤四:将经步骤三处理后得到的沉淀物过滤、洗涤、烘干,置于马弗炉中煅烧,煅烧温度为500℃,煅烧12h,最后将煅烧好的催化剂研磨成粉末状,得到最终催化剂;
步骤五:将催化剂与聚丙烯按质量比为1:10、聚丙烯与水按质量比为1:10混合作为原料;
步骤六:将步骤五中的混合原料加入到反应釜中,使混合原料在400℃下水热处理1h;
步骤七:将步骤六中处理后得到的固液混合物通入固液分离设备完成固液分离;
步骤八:得到的液体即为油产品。
实施例二:以超临界甲醇液化聚丙烯为例。
在本实施例中的操作步骤与实施例一相同,从而得到了对应的高品质油。
实施例三:以超临界甲醇液化聚乙烯、聚丙烯混合物为例。
在本实施例中的操作步骤与实施例一相同,从而得到了对应的高品质油。
综上,通过采用本发明提出的技术方案,不但提出了一种制作成本低的催化剂,而且在实施的过程中催化效果佳;
本发明将催化剂加入到超临界水热液化过程中,降低了反应所需的温度,降低了设备的使用负担,延长了工作寿命,能耗低,并且极大促进塑料转化为高品质油的反应进程;
本发明提出的方法无二次污染物排放,能有效解决塑料物堆积的问题,使塑料得到资源化回收利用,降低碳排放,促进了循环经济的发展,应用前景良好;
通过采用本发明提出的方法制备成相应的催化剂,并将其加入到超临界水热液化过程中,降低了塑料降解及小分子重组过程中部分反应的活化能,从而降低了反应的所需温度条件,提高了油产率,使油富含碳原子分布集中的碳氢化合物,达到了定向调控塑料垃圾超临界水热液化油品质的效果。
以上对本发明及其实施方式进行了描述,这种描述没有限制性,实施例中所示的也只是本发明的实施方式之一,实际的内容并不局限于此。总而言之如果本领域的普通技术人员受其启示,在不脱离本发明创造宗旨的情况下,不经创造性的设计出与该技术方案相似的实施例,均应属于本发明的保护范围。
Claims (3)
1.一种调控塑料垃圾超临界水热液化油品质的方法,其特征在于:包括催化剂的合成、超临界水热液化两个步骤;
在催化剂的合成过程中,包括以下子步骤:
1.1)将含有Cu2+、Zn2+、Fe2+中的至少一种,与含有Mg2+、Al3+的盐溶液共沉淀,且共沉淀的过程在0.5~2M的Na2CO3或0.8~3M的NaHCO3的水溶液中进行;
1.2)在反应过程中添加0~1M的NaOH溶液或0~3M的NH4·H2O溶液,用于调节反应环境的pH值为10~12;
1.3)在反应过程中将温度恒定在65~75℃之间,且进行搅拌,搅拌速度为100~300rpm,沉淀形成后继续养护8~24h;
1.4)将沉淀物清洗至中性,而后在0~2M的水杨酸乙醇溶液中浸渍8~24h;
1.5)浸渍结束后,按照过滤、洗涤、烘干的顺序进行后续处理,从而得到沉淀物;
1.6)煅烧:将烘干处理后的沉淀物置于马弗炉中煅烧,得到块状催化剂;
在煅烧过程中,设定的工艺条件为:煅烧过程升温速率为10℃~30℃/min;煅烧最终温度为450~700℃;
煅烧氛围为空气氛围,煅烧时间为4~24h;
超临界水热液化中的溶剂是水、甲醇、乙醇、甲苯、丙酮、醋酸中的一种,水热液化温度为240~500℃,反应时间为0~4h,催化剂与塑料垃圾的质量比为0~0.1,塑料与溶剂的质量比为0.1~1。
2.根据权利要求1所述的一种调控塑料垃圾超临界水热液化油品质的方法,其特征在于:所述塑料垃圾为一种、两种或多种塑料类型的混合物。
3.根据权利要求2述的一种调控塑料垃圾超临界水热液化油品质的方法,其特征在于:对于未完全转化的塑料垃圾,通过重力沉降、离心、压滤中的一种或多种的组合方式实现油的分离;针对固液分离后得到的液体,采用蒸馏或萃取方式,从而去除残留溶剂,得到提质后的油产品。
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