废旧轮胎催化裂解研究进展

doi:10.16085/j.issn.1000-6613.2021-1910

摘要/Abstract

摘要：

废旧轮胎因产量高、难降解、污染环境，被称为最难处理的“黑色垃圾”之一。催化裂解是一种处理废旧轮胎的重要手段，可以实现其高效转化与资源化利用，同时得到高附加值的化学产品，如单环芳烃、低碳烯烃与柠檬烯等。本文基于轮胎的物理结构与化学组成、催化裂解过程与裂解产物特征、反应器类型与特征、催化剂类型与作用原理、工艺条件等问题综述了废旧轮胎的催化裂解产物分布规律。通过对比反应器、催化剂与工艺条件对产物分布的影响，进一步分析了当前实现废旧轮胎催化裂解工业化的问题，并基于当前废旧轮胎催化裂解的研究现状，提出应集中设计适应于大规模处理的反应器与配套工艺，同时开发高稳定性与对特定产物高选择性的催化剂，从而实现对废旧轮胎以低能耗、高转化、高价值为特点的资源化利用。

关键词: 废旧轮胎, 热解, 催化裂解, 催化剂, 回收, 环境

Abstract:

Huge amounts of waste tires are difficult to degrade and they pollute the environment. Therefore, waste tires are thought as a kind of black pollution. Catalytic cracking is an important means for the treatment of waste tires, which can not only achieve efficient conversion and resource utilization but also obtain high value-added chemical products, such as monocyclic aromatic hydrocarbons, light olefins and limonene. In this paper, the distribution characteristics of catalytic cracking products of waste tires are discussed from the aspects of physical structure and chemical composition, catalytic cracking process and characteristics of cracking products, reactor types and characteristics, catalyst types and functions, and process conditions. By comparing the effects of reactors, catalysts and process conditions on the product distribution, the existing problems for the industrialization of catalytic cracking of waste tires are further analyzed. According to the current research situation of catalytic cracking of waste tires, it is proposed that reactors and supporting processes suitable for large-scale treatment should be designed, and catalysts with high stability and high selectivity for specific products should be developed at the same time. The resource utilization of waste tires characterized by low energy consumption, high conversion and high added value is then realized.

Key words: waste tires, pyrolysis, catalytic cracking, catalyst, recovery, environment

中图分类号:

X783.3

杨超, 矫庆泽, 冯彩虹, 赵芸. 废旧轮胎催化裂解研究进展[J]. 化工进展, 2022, 41(7): 3877-3889.

YANG Chao, JIAO Qingze, FENG Caihong, ZHAO Yun. Research progress on catalytic cracking of waste tires[J]. Chemical Industry and Engineering Progress, 2022, 41(7): 3877-3889.

图/表 5

表1

表2

表3

表4

轮胎裂解常用固体酸催化剂对裂解产物分布的影响"

催化剂	催化方式	催料比	反应器	轮胎粉粒径	（热解/催化温度）/℃	裂解产物组成（质量分数）/%				参考文献
催化剂	催化方式	催料比	反应器	轮胎粉粒径	（热解/催化温度）/℃	气体	液体	固体	其他	参考文献
ZSM-5	先热解，再催化	0.5	常压固定床	1cm	500/400		44.66		烷基苯系物：24.99	［46］
USY	先热解，再催化	0.5	常压固定床	1cm	500/400		32.66		烷基苯系物：46.10
热解	―	―	常压固定床	1cm	500		51.98		烷基苯系物：83.28
ZSM-5	共同催化热解	2g/min	流化床	―	500	19.32	约46.68	约34	芳香族（<C₁₀）：13.00	［43］
HY	共同催化热解	2g/min	流化床	―	500	2.49	约62.51	约35	芳香族（<C₁₀）：22.67
热解	―	―	流化床	―	500	3.25	约38.25	约35	芳香族（<C₁₀）：7.77
HBeta	先热解，再催化	0.25	常压固定床	20~40目	500/350	8	51	41.5	气体中硫：22	［50］
HY	先热解，再催化	0.25	常压固定床	20~40目	500/350	10	51.5	41.5	气体中硫：29
HMOR	先热解，再催化	0.25	常压固定床	20~40目	500/350	11	48	41	气体中硫：27
Cu/Hβ	先热解，再催化	0.25	常压固定床	20~40目	500/350	11.5	47.5	41	气体中硫：20
Cu/HY	先热解，再催化	0.25	常压固定床	20~40目	500/350	12	47	41	气体中硫：22
Cu/HMOR	先热解，再催化	0.25	常压固定床	20~40目	500/350	11	47.5	41.5	气体中硫：18
热解	―	―	常压固定床	20~40目	500/350	11.5	46.5	42	气体中硫：20
Ni/Hβ	先热解，再催化	0.25	常压固定床	―	500/350	8	49	43	气体中硫：20	［53］
Ni/HMOR	先热解，再催化	0.25	常压固定床	―	500/350	10	46	44	气体中硫：18
Ni/HY	先热解，再催化	0.25	常压固定床	―	500/350	7	51	42	气体中硫：12
Ni/HZSM-5	先热解，再催化	0.25	常压固定床	―	500/350	12	44	44	气体中硫：15
热解	―	―	常压固定床	―	500/350	12	47.5	40.5	气体中硫：29
Fe/KL	先热解，再催化	0.25	常压固定床	―	500/350	12.1	42.9	42.5	BTEX：58	［52］
Fe/HMOR	先热解，再催化	0.25	常压固定床	―	500/350	13.3	42	42.4	BTEX：52
Fe/Hβ	先热解，再催化	0.25	常压固定床	―	500/350	11.4	43.6	41.7	BTEX：13
Fe/HZSM-5	先热解，再催化	0.25	常压固定床	―	500/350	16.2	39	41.8	BTEX：23
热解	―	―	常压固定床	―	500	11.6	46.0	42.4	BTEX：20
Ru/MCM-41	先热解，再催化	0.25	常压固定床	―	500/350	30	25.5	44.5	C₁~C₄：29.1	［54］
MCM-41	先热解，再催化	0.25	常压固定床	―	500/350	15	38	47	C₁~C₄：11.8
热解	―	―	常压固定床	―	500	11	47	42	C₁~C₄：8
Cu/ZSM-5	先热解，再催化	0.25	常压固定床	1~3mm	430/500	30	65	5	气体中硫：66	［56］
Zn/ZSM-5	先热解，再催化	0.25	常压固定床	1~3mm	430/500	28.5	66	5.5	气体中硫：65
Cu/MCM-41	先热解，再催化	0.25	常压固定床	1~3mm	430/500	27	67.5	5.5	气体中硫：62
Zn/MCM-41	先热解，再催化	0.25	常压固定床	1~3mm	430/500	27.5	68	4.5	气体中硫：75
热解	―	―	常压固定床	1~3mm	430/500	25	71	4	气体中硫：67
Hβ	共同催化热解	0.3	常压固定床	3~5mm	550	32.5	34	33.5	―	［68］
HUSY	共同催化热解	0.3	常压固定床	3~5mm	550	32	33	35	―
TiO₂	共同催化热解	0.3	常压固定床	3~5mm	550	30.5	26.5	43	―
热解	―	―	常压固定床	3~5mm	550	28.5	28.5	43	―

表4

表5

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方法	主要内容	特点
燃烧	热值与天然气相当，约为36MJ/kg，可作为燃料使用	尾气含有二??英、酚类等致癌物质
热解		产物分布宽、操作温度高
常规热解	在缺氧或惰性气体中高温（500~600℃）降解，可产生气、油及固体残渣
熔融盐热解	在氯化锂/氯化钾共熔混合物中分解
微波解聚	在氮气和微波条件下，炭黑吸收微波，促进橡胶裂解
共热解	与导热剂（如生物质等）共混热解，可降低热解温度，减少积炭和结焦
气化	在一定温度下与气化剂共混降解，目标产物是合成气	气化剂昂贵、成本高、气体产率低
炭化	在高温（>1000℃）下，降解形成高品质炭和其他产物	实现高温难度大、对工艺设备要求高
超临界水氧化	在水的超临界（T_c=374.3℃， p_c=22.05MPa）和亚临界状态下，以过氧化氢为氧化剂对废旧轮胎颗粒降解，产物以燃料油和固体炭黑为主	操作条件要求高、装置复杂
催化裂解	在隔氧和催化剂的作用下，可降解形成气、液、固体残渣	产物分布窄、资源化利用率高

结构	组成及功能
胎面（tread）	成分为天然或合成橡胶，具有优良的耐摩擦性和热稳定性
带层（belts）	包括冠带层与带束层等，一般由橡胶、钢和帘子布等多种材料制成，为外层提供结构支撑
胎侧（sidewalls）	由橡胶制成，主要用来缓冲来自路面的颠簸，同时保证轮胎结构的完整性
胎体层（carcass）	由涂有天然橡胶的金属制成，支撑轮胎的内部结构
内衬层（inner line）	成分为低透气性的（卤）丁基橡胶，具有存气、稳压等作用
胎圈（beads）	主要由钢丝与橡胶制成，具有高的拉伸强度，确保轮胎和轮辋之间的连接
胎圈填料（beads filler）	保证了胎圈线的刚性部分和内衬之间的过渡连接

类型	反应器	操作温度/℃	传热速率/℃·min^-1	气体停留时间/s	特点
慢速裂化反应器	固定床	350~600	5~40	10~40	间歇操作，处理量小
	回转窑	400~600	约100	约30	固体停留时间可控
	微波反应器	400~700	1~150	20~60	气体停留时间较长，不易工业化放大
	螺旋窑	400~550	100~1000	5~30	传热速率范围大
快速裂化反应器	流化床	350~800	>10000	1~5	连续操作，易于工业放大
快速裂化反应器	喷泉床	400~600	>10000	0.03~0.5	气体停留时间短，裂解油产率高

催化剂	催化方式	催料比	反应器	轮胎粉粒径	（热解/催化温度）/℃	裂解产物组成（质量分数）/%				参考文献
催化剂	催化方式	催料比	反应器	轮胎粉粒径	（热解/催化温度）/℃	气体	液体	固体	其他	参考文献
MgO	先热解，再催化	0.03	常压固定床	2~3mm	550/550	20	38	42	固体中S元素的残余：2.68	［58］
Al₂O₃	先热解，再催化	0.03	常压固定床	2~3mm	550/550	33	26	41	固体中S元素的残余：2.63
CaCO₃	先热解，再催化	0.03	常压固定床	2~3mm	550/550	37	23	40	固体中S元素的残余：2.00
ZSM-5	先热解，再催化	0.03	常压固定床	2~3mm	550/550	25	35	40	固体中S元素的残余：2.59
热解	―	―	常压固定床	2~3mm	550/550	19	36	45	固体中S元素的残余：2.70
CaO	共同催化热解	―	真空固定床	20~60目	520	14.9	48.84	36.26	H₂S：60	［62］
ZnO	共同催化热解	―	真空固定床	20~60目	520	12.16	47.49	36.56	H₂S：25
CaO/TiO₂	共同催化热解	―	真空固定床	20~60目	520	18.46	45.24	36.30	H₂S：55
ZnO/TiO₂	共同催化热解	―	真空固定床	20~60目	520	24.82	39.98	35.20	H₂S：35
热解	―	―	真空固定床	20~60目	520	16.72	45.96	37.32	H₂S：195
Al₂O₃	共同催化热解	―	常压固定床	5~10mm	400	21	23.2	55.8	轻质油的相对密度：0.8288	［69］
SiO₂	共同催化热解	―	常压固定床	5~10mm	400	15.5	28.2	56.3	轻质油的相对密度：0.799
Al₂O₃+SiO₂	共同催化热解	―	常压固定床	5~10mm	400	5	14.8	80.2	轻质油的相对密度：0.7575
CaC₂	共同催化裂解	0.2	常压固定床	5~10mm	400	29.6	38.4	32	―	［70］
热解	―	―	常压固定床	5~10mm	400	37	22.8	40.2	―	［70］
Na₂CO₃	共同催化裂解	0.03	真空固定床	20~60目	500	14.6	47.8	37.6	低热值：18.1	［16］
NaOH	共同催化裂解	0.03	真空固定床	20~60目	500	13.3	48.1	38.6	低热值：16.9
热解	―	―	真空固定床	20~60目	500	21.8	42.1	26.1	低热值：20.7

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