CN103842420A - 塑料废弃物的热解聚方法 - Google Patents

塑料废弃物的热解聚方法 Download PDF

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CN103842420A
CN103842420A CN201280046012.7A CN201280046012A CN103842420A CN 103842420 A CN103842420 A CN 103842420A CN 201280046012 A CN201280046012 A CN 201280046012A CN 103842420 A CN103842420 A CN 103842420A
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沙姆斯·巴哈尔·民·莫汉德·诺尔
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Abstract

本发明涉及一种基于塑料废弃物(10)生产液态运输燃料(15)的方法，包括下述步骤：提供(S101)熔融形式的塑料废弃物(10)；使用石灰石催化剂(20)在1Bar的正常大气压力条件下，在420℃到450℃的温度范围内解聚(S103)进入反应室的熔融塑料废弃物(10)；和引导(S106)气态解聚产物(25)进入蒸馏单元使气态解聚产物(25)分馏和冷凝成液态运输燃料(15)。

Description

塑料废弃物的热解聚方法
技术领域
本发明涉及废弃塑料物的催化热解聚方法，尤其涉及使用固体催化剂在低温下将塑料废弃物转化为高品质的液态燃料并且不影响其产量。
背景技术
在大多数传统的废弃塑料处理方法中，塑料废弃物一般采用焚烧，掩埋或填埋，对由此带来的环境和健康问题的逐步认识驱动当代的科学家和发明家研究出对环境更友好的废弃物管理处理方案一裂解和解聚塑料废弃物。
与当前的废弃塑料处理方法不同，裂解和解聚方法能够从废弃塑料中成功地回收特定的资源、原油和/或天然气。因此，这样的废弃物处理方法能够使得废弃塑料重新利用而不是在自然界中降解，在自然界降解依旧没有解决塑料填埋处理导致其数量越来越多的问题。
与废弃塑料热解相关的现有技术包括美国专利US2003047437(A1)，其公开了一种两阶段的热解方法，将破碎的废弃塑料在300-600℃之间通过流化床热循环颗粒状惰性载热体引入惰性气体从而初步熔化和热解成烃油。在接下来的步骤中，未转化的废弃塑料、载热体、引入的惰性气体从热解产物中分离并进入流化床完成热解。第一步和第二步的热解产物进行分级分离并冷凝成液态运输燃料。
这样的废弃塑料热解方法，如本领域技术人员所理解的那样，成功地减轻了在流化床工艺中通常观察到的限制，例如热解产物的逆向混合、流化床的不均匀，更重要的是有价值的芳香烃类和高分子烃类的低产量。然而，由于该方法是一个多步骤过程，需要在高温高压条件下完全分解废弃塑料转化成烃油，因此这种技术相当昂贵。此外，还需要额外的步骤，例如通过在600到900℃燃烧去除沉积在流化床中的焦炭，这导致了高昂的维护成本。
因此，与高温分解方法相比，在温和的温度条件下进行的催化热解聚废弃塑料以获得其原始单体的方法在本领域是更优选的。美国专利申请5369215即公开了这样的热催化解聚方法。在该文献中，在解聚来自废旧轮胎和橡胶的废弃塑料的工艺中使用金属盐催化剂，这些废旧轮胎和橡胶优选是在高温和低压的条件下已经暴露于臭氧。尽管臭氧化的聚合物易受热从而使废塑料能在相当低的温度下完全分解，但臭氧气体的有害作用不应被忽视。
因此，本发明的主要目的是提供一种环境上可接受的和经济上可行的塑料废弃物的热解聚方法以克服上述传统塑料废弃物处理方法的局限性。
本发明的另一个目的是提供一种新的催化剂，能够在相当低的温度下，尤其是在低于460℃的条件下进行塑料解聚并且不影响产量。
本发明的还一个目的是提供一种热解聚方法，能够从塑料废弃物中回收高品质的液态运输燃料同时不形成副产物，尤其是含碳物质或焦炭。
发明概述
一方面，本发明提供了一种热解聚方法，通过使用石灰石催化剂催化增强废弃塑料到其单体成分的分解，又可容易地在正常气压、低于460℃地条件下转换成液态运输燃料。
所述的热解聚方法优选包括如下步骤：提供熔融形式的废弃塑料；在1Bar的正常气压条件和420℃-450℃的温度范围内使用石灰石催化剂解聚进入反应室的熔融废弃塑料；将气态的解聚产物引入到蒸馏单元使解聚产物分馏和冷凝成液态运输燃料。
需要注意的是，本发明所用的石灰石催化剂来自固体组合物的烧结产物，该固体组合物包括39％到41％的氧化铝(Al2O3)；30％到32％的氧化钙(CaO)；0.09％到0.12％的一氧化硅(SiO)；0.01％到0.03％的氧化镁。
附图概述
图1是流程图，详细显示了热解聚废弃塑料材料得到液态烃，尤其是运输燃料的过程。
发明详述
参照下述给出的详述的实施例可以更好的理解本发明的目的、构造、特征和功能。
本发明涉及一种废弃材料，尤其是塑料废弃物(10)通过使用石灰石(20)作为催化剂转变成液态运输燃料(15)的热解聚方法(100)。本发明所述的废弃塑料(10)是市政和/或工业废料，包括但不限于聚乙烯，聚丙烯和聚氯乙烯。
在本发明的一个实施例中，石灰石催化剂(20)由下述固体组合物烧结得到，该固体组合物含有：39％到41％的氧化铝(Al2O3)；30％到32％的氧化钙(CaO)；0.09％到0.12％的一氧化硅(SiO)；0.01％到0.03％的氧化镁。优选的，固体组合物含有40.6％±0.1的氧化铝(Al2O3)；31.7％±0.1的氧化钙(CaO)；0.15％±0.01的一氧化硅(SiO)；和0.03±0.01氧化镁(MgO)。
需要注意的是，除了促进解聚以外，石灰石催化剂(20)还能使得塑料废弃物在低温，优选低于460℃，和1Bar的正常气压条件下解聚成高级烯烃(C4-C25)。可以理解，碳化处理会形成分解残留物或焦炭结晶和不可接受的环境危害，例如温室气体，二恶英和呋喃，在低的操作温度下能抑制这种情况。采用石灰石催化剂进行的塑料废弃物热解聚毫无疑问的更具有经济上的可行性和环境上的可接受性。
图1详细显示了塑料废弃物(10)到有价值的化学品，尤其是液态运输燃料(20)的热解聚过程。所述方法包括在1bar的正常气压条件和420℃-450℃的温度范围内使用本发明的石灰石催化剂(15)在反应室内解聚(S103)熔融塑料废弃物(10)的步骤。需要注意的是，熔融塑料废弃物(10)可以通过在加热室中在低于250℃的温度下加热(S101)固体塑料废弃物(10)来制备。在进入热熔融挤出机(S101)之前可以切碎固体塑料废弃物(10)并消除其中的水分。
如前所述，石灰石催化剂通过烧结(S102)固体组合物的步骤得到，该固体组合物含有：39％到41％的氧化铝(Al2O3)；30％到32％的氧化钙(CaO)；0.09％到0.12％的一氧化硅(SiO)；0.01％到0.03％的氧化镁。在一优选实施例中，对含有40.6％±0.1的氧化铝(Al2O3)；31.7％±0.1的氧化钙(CaO)；0.15％±0.01的一氧化硅(SiO)；和0.03±0.01氧化镁(MgO)的固体组合物进行粉碎和烧结(S102)以形成本发明的石灰石催化剂(15)。
解聚产物(25)，优选为气态烃的混合物，进入蒸馏单元从而使气态烃(25)被分馏和冷凝(S106)成液态运输燃料(20)，如柴油，煤油和汽油。在分馏过程(S106)之前，气态烃(25)的混合物优选在1Bar的正常大气压力条件下，在420℃到450℃的温度范围内破碎(S104)。为了获得更高产量的高品质液态燃料，对解聚烃(25)执行清洗步骤(S105)以消除气溶胶和颗粒。所述清洗步骤(S105)优选的包括通过高速旋流引导解聚烃(25)进入压力密封容器从而在分馏之前去除不需要的成分。
如上所述，本发明的解聚方法(100)，不仅可以通过采用有效的催化剂在420℃到450℃的温度范围之间分解塑料衍生的废弃材料(10)，而且能够从废弃塑料材料(10)中成功地回收十六烷值高于55和0-50PPM含硫量的高品质机动车燃料(20)。
尽管参照优选实施方案和实施例描述了本发明，但是对于本领域的技术人员而言，在不背离本发明范围的情况下进行各种修改和改变是显而易见的是，本发明的保护范围由所附权利要求限定。

Claims (11)

1.一种基于塑料废弃物(10)生产液态运输燃料(15)的方法，包括下述步骤；提供熔融形式的废弃塑料(10)；在1Bar的正常气压条件和低于460℃的温度下使用石灰石催化剂解聚进入反应室的熔融塑料废弃物(10)；和将气态的解聚产物(25)引入到蒸馏单元使解聚产物(25)分馏和冷凝成液态运输燃料(15)。
2.根据权利要求1的基于塑料废弃物(10)生产液态运输燃料(15)的方法，其中所述石灰石催化剂(20)由包含氧化铝(Al2O3)、氧化钙(CaO)、一氧化硅(SiO)和氧化镁(MgO)的固体组合物烧结而成。
3.根据权利要求1的基于塑料废弃物(10)生产液态运输燃料(15)的方法，其中所述固体组合物优选的包含39％到41％的氧化铝(Al2O3)；30％到32％的氧化钙(CaO)；0.09％到0.12％的一氧化硅(SiO)；0.01％到0.03％的氧化镁。
4.根据权利要求2的基于塑料废弃物(10)生产液态运输燃料(15)的方法，其中所述固体组合物优选的包含40.6％±0.1的氧化铝(Al2O3)；31.7％±0.1的氧化钙(CaO)；0.15％±0.01的一氧化硅(SiO)；和0.03±0.01氧化镁(MgO)。
5.根据权利要求2的基于塑料废弃物(10)生产液态运输燃料(15)的方法，其中固体组合物在烧结之前进行粉碎。
6.根据权利要求1的基于塑料废弃物(10)生产液态运输燃料(15)的方法，其中提供熔融形式塑料废弃物(10)的步骤包括以下步骤：除去封闭在固体塑料废弃物(10)中的水分；将干燥的固体塑料废弃物(10)粉碎成小块；和在加热室中在低于250℃的温度下加热干燥和粉碎的固体塑料废弃物(10)。
7.根据权利要求1的基于塑料废弃物(10)生产液态运输燃料(15)的方法，其中解聚熔融塑料废弃物(10)优选在1Bar的正常大气压力条件下，在420℃到450℃的温度范围内进行。
8.根据权利要求1的基于塑料废弃物(10)生产液态运输燃料(15)的方法，其中进一步包括在进入分馏过单元之前，在1Bar的正常大气压力条件下，在420℃到450℃的温度范围内破碎气态解聚产物(25)的步骤。
9.根据权利要求1的基于塑料废弃物(10)生产液态运输燃料(15)的方法，其中进一步包括在分馏之前去除气态解聚产物(25)气溶胶和颗粒的步骤。
10.根据权利要求8的基于塑料废弃物(10)生产液态运输燃料(15)的方法，其中气态解聚产物(25)中不需要的成分通过高速旋流引导气态解聚产物(25)进入压力密封容器去除。
11.根据权利要求1的基于塑料废弃物(10)生产液态运输燃料(15)的方法，其中所述液态运输燃料(15)的十六烷值高于55，含硫量在0-50PPM之间。
CN201280046012.7A 2011-07-22 2012-07-23 塑料废弃物的热解聚方法 Pending CN103842420A (zh)

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