塑料催化热解制备高附加值产品的研究进展

doi:10.11949/0438-1157.20220624

摘要/Abstract

摘要：

塑料催化热解技术可定向或联产制备低碳烯烃、单环芳烃、碳纳米管（CNTs）和氢气等能源产品，其调控过程简单，且产物选择性好、附加值高，因而受到了广泛的关注。在较短的停留时间（＜1 s）和较高的反应温度（＞800℃）下，塑料热解可得到较高产率的烯烃单体，而芳烃产物的形成更依赖催化剂的酸位点和孔结构。Fe、Co、Ni基催化剂可将塑料热解产生的含碳挥发分转为CNTs和富氢气，其CNTs产率和氢转化效率可分别达到30%（质量）和90%以上。总结了塑料催化热解制备高附加值能源化工产品的研究进展，讨论总结了温度、停留时间、催化剂等因素对产物分布和品质的作用机制，并对各类产物形成机理和制备方法分别进行了回顾与展望。

关键词: 废塑料, 催化热解, 碳纳米管, 氢, 芳烃, 低碳烯烃

Abstract:

Catalytic pyrolysis of plastics can be directional preparation or cogeneration of energy products such as light olefins, aromatics, carbon nanotubes (CNTs), and hydrogen. It has the advantages of simple control process, good product selectivity and high-added value, thus become widely attractive. At shorter residence time (<1 s) and higher reaction temperature (>800℃), plastic pyrolysis can yield higher yields of olefin monomers, while the formation of aromatic products is more dependent on catalyst acid sites and pore structure. Fe, Co, and Ni-based catalysts can convert the gaseous carbon source generated by plastic pyrolysis into CNTs and hydrogen-rich gas, and the CNTs yield and hydrogen conversion efficiency can reach more than 30%(mass) and 90%, respectively. This article summarizes the research progress of plastic catalytic pyrolysis to produce high value-added energy products, discusses the mechanism of temperature, residence time, catalyst and other factors on product distribution and quality, the formation mechanism and preparation methods of various products were reviewed and prospected respectively.

Key words: plastic waste, catalytic pyrolysis, carbon nanotubes, hydrogen, aromatics, light olefins

中图分类号:

TQ 028.8

肖皓宇, 杨海平, 张雄, 陈应泉, 王贤华, 陈汉平. 塑料催化热解制备高附加值产品的研究进展[J]. 化工学报, 2022, 73(8): 3461-3471.

Haoyu XIAO, Haiping YANG, Xiong ZHANG, Yingquan CHEN, Xianhua WANG, Hanping CHEN. Recent progress of catalytic pyrolysis of plastics to produce high value-added products[J]. CIESC Journal, 2022, 73(8): 3461-3471.

图/表 4

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序号	原料	温度和反应时间	催化剂	反应器	目标产物	产物分布/%(质量)			文献
序号	原料	温度和反应时间	催化剂	反应器	目标产物	气	液	固	文献
1	HDPE	850℃，0.6~1.7 s	无	流化床	低碳烯烃	83.8~88.6	11.4~16.2		[10]
2	PE+PP+PVC+PET	700℃，15 s	无	流化床	低碳烯烃	68.8	18.4		[11]
3	PP	500℃	HZSM-5	锥形喷床反应器	60%(质量)低碳烯烃	71.6	28.4		[12]
4	PE	450~515℃，10~12 s	FCC	流化床	39%~40.9%(质量)低碳烯烃，8.8%(质量)芳烃	48.3~51.8	37.1~38.3		[13]
5	LDPE	380℃，360 min	MCM-41	搅动反应器	低碳烯烃	37.3	23.2		[14]
6	PS	780℃	无	螺旋热解+流化床	26.3%(质量) BTEX+26%(质量)苯乙烯	13.8	86.0		[15]
7	PE	280℃，24 h	Pt/γ-Al₂O₃	搅动式反应釜	50%(mol)芳烃		80		[16]
8	PP	400℃	ZSM-5	等离子体热解反应器	4.19 mmol/g H₂+85% BTX	47	53		[17]
9	PE	430℃	ZSM-5	固定床	低碳烯烃+芳烃	44.3	49.8		[18]
10	PE+PP+PS+PET+PVC	500℃	赤泥	半连续式反应器	35.4%(质量) C₁~C₄ +42.3% (area)苯乙烯	41.3	57	1.7	[19]
11	PP	300℃+720℃	无	活化器+流化床	52%(质量)低碳烯烃+ 芳烃92%(质量)	71.3	28	0.8	[20]
12	HDPE	600℃	Y型分子筛	两段式固定床	80%~95% (area)芳烃	36	45		[21]
13	PP+PE+PS	500℃	Zn-生物炭	管式炉	42.4%芳烃	42.2	54.7	3.1	[22]
14	PP	800℃	Fe-Al₂O₃	两段式固定床	82 mg H₂+337 mg CNTs	50		42	[23]
15	PP+PE+PS	300℃	FeAlO _x	微波反应器	55.6 mmol/g_plastic H₂+ 620 mg/g_plastic CNTs	27		73	[24]
16	PS	800℃	Fe-Al₂O₃	两段式固定床	富氢气+芳烃+CNTs	17.2	26.1	48.7	[25]
17	真实废塑料	800℃	FeNi-Al₂O₃	两段式固定床	富氢气+CNTs	39.4	8.8	50.9	[26]

序号	原料	温度和反应时间	催化剂	反应器	目标产物	产物分布/%(质量)			文献
序号	原料	温度和反应时间	催化剂	反应器	目标产物	气	液	固	文献
1	HDPE	850℃，0.6~1.7 s	无	流化床	低碳烯烃	83.8~88.6	11.4~16.2		[10]
2	PE+PP+PVC+PET	700℃，15 s	无	流化床	低碳烯烃	68.8	18.4		[11]
3	PP	500℃	HZSM-5	锥形喷床反应器	60%(质量)低碳烯烃	71.6	28.4		[12]
4	PE	450~515℃，10~12 s	FCC	流化床	39%~40.9%(质量)低碳烯烃，8.8%(质量)芳烃	48.3~51.8	37.1~38.3		[13]
5	LDPE	380℃，360 min	MCM-41	搅动反应器	低碳烯烃	37.3	23.2		[14]
6	PS	780℃	无	螺旋热解+流化床	26.3%(质量) BTEX+26%(质量)苯乙烯	13.8	86.0		[15]
7	PE	280℃，24 h	Pt/γ-Al₂O₃	搅动式反应釜	50%(mol)芳烃		80		[16]
8	PP	400℃	ZSM-5	等离子体热解反应器	4.19 mmol/g H₂+85% BTX	47	53		[17]
9	PE	430℃	ZSM-5	固定床	低碳烯烃+芳烃	44.3	49.8		[18]
10	PE+PP+PS+PET+PVC	500℃	赤泥	半连续式反应器	35.4%(质量) C₁~C₄ +42.3% (area)苯乙烯	41.3	57	1.7	[19]
11	PP	300℃+720℃	无	活化器+流化床	52%(质量)低碳烯烃+ 芳烃92%(质量)	71.3	28	0.8	[20]
12	HDPE	600℃	Y型分子筛	两段式固定床	80%~95% (area)芳烃	36	45		[21]
13	PP+PE+PS	500℃	Zn-生物炭	管式炉	42.4%芳烃	42.2	54.7	3.1	[22]
14	PP	800℃	Fe-Al₂O₃	两段式固定床	82 mg H₂+337 mg CNTs	50		42	[23]
15	PP+PE+PS	300℃	FeAlO _x	微波反应器	55.6 mmol/g_plastic H₂+ 620 mg/g_plastic CNTs	27		73	[24]
16	PS	800℃	Fe-Al₂O₃	两段式固定床	富氢气+芳烃+CNTs	17.2	26.1	48.7	[25]
17	真实废塑料	800℃	FeNi-Al₂O₃	两段式固定床	富氢气+CNTs	39.4	8.8	50.9	[26]

产物	市场价格/(CNY/kg)	催化剂原料价格^①/(CNY/t)	产率/%(质量)	文献
碳纳米管	865.1	Fe(NO₃)₃·9H₂O: 3300 Al₂O₃: 2400	34~62	[23-24, 71]
氢气	27.6	Fe(NO₃)₃·9H₂O: 3300 Al₂O₃: 2400	8~11	[23-24, 72]
苯	4.9~6.4	ZSM-5: 45000~75000 FCC: 22000	30~53 (BTX)	[16, 57, 73-74]
甲苯	4.1~5.8
二甲苯	4.2~6
乙烯丙烯	4.8~7.6 4.8~8.9	ZSM-5: 45000~75000 Y型分子筛：10000~25000	63~75 (低碳烯烃)	[36, 42, 57, 68]

产物	市场价格/(CNY/kg)	催化剂原料价格^①/(CNY/t)	产率/%(质量)	文献
碳纳米管	865.1	Fe(NO₃)₃·9H₂O: 3300 Al₂O₃: 2400	34~62	[23-24, 71]
氢气	27.6	Fe(NO₃)₃·9H₂O: 3300 Al₂O₃: 2400	8~11	[23-24, 72]
苯	4.9~6.4	ZSM-5: 45000~75000 FCC: 22000	30~53 (BTX)	[16, 57, 73-74]
甲苯	4.1~5.8
二甲苯	4.2~6
乙烯丙烯	4.8~7.6 4.8~8.9	ZSM-5: 45000~75000 Y型分子筛：10000~25000	63~75 (低碳烯烃)	[36, 42, 57, 68]

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