烘焙脱氧毛竹与高密度聚乙烯共催化热解制备轻质芳烃

朱亮; 黄明; 丁紫霞; 马中青

doi:10.19906/j.cnki.JFCT.2022014

烘焙脱氧毛竹与高密度聚乙烯共催化热解制备轻质芳烃

doi: 10.19906/j.cnki.JFCT.2022014

浙江农林大学化学与材料工程学院国家木质资源综合利用工程技术研究中心, 浙江杭州 311300

基金项目: 浙江省“尖兵”“领雁”研发攻关计划（2022C03092），浙江省自然科学基金（LY21E060001），浙江省属高校基本科研业务费专项资金资助（2020YQ006)，中国科协“青年人才托举工程”项目（2018QNRC001)，国家林业和草原局科技创新青年拔尖人才项目（2019132617)和浙江大学能源清洁利用国家重点实验室开放基金（ZJU-CEU2020021）资助

详细信息

作者简介:
朱亮（1997—），男，硕士研究生，zhuliang19970913@163.com

通讯作者:
E-mail: mazq@zafu.edu.cn

中图分类号: TK6
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出版历程
- 收稿日期: 2022-01-04
- 修回日期: 2022-02-22
- 录用日期: 2022-02-27
- 网络出版日期: 2022-03-08
- 刊出日期: 2022-08-26

Production of light bio-aromatics from co-catalytic fast pyrolysis of torrefied bamboo and high-density polyethylene

College of Chemistry and Materials Engineering, National Engineering Research Center of Wood-based Resources Comprehensive Utilization, Zhejiang A & F University, Hangzhou 311300, China

Funds: The project was supported by the Key R & D Program of Zhejiang Province (2022C03092), Natural Science Foundation of Zhejiang Province (LY21E060001), the Fundamental Research Funds for the Provincial Universities of Zhejiang (2020YQ006), the Young Elite Scientists Sponsorship Program by CAST (2018QNRC001), the Youth Talent Support Program by National Forestry and Grassland Administration (2019132617) and the Open Foundation from the State Key Laboratory of Clean Energy Utilization (ZJU-CEU2020021).

摘要

摘要: 轻质芳烃是化工领域重要的基础有机原料，可通过生物质和废塑料共催化热解技术路线制取。首先，采用烘焙预处理对毛竹进行脱氧改性提质；其次，通过Na₂CO₃溶液对微孔HZSM-5进行碱扩孔预处理，制备多级孔分子筛催化剂，最后通过烘焙毛竹和高密度聚乙烯（HDPE）共催化热解制取轻质芳烃，研究烘焙温度、Na₂CO₃浓度、原料共混比例、热解温度等因素对轻质芳烃产率的影响。结果表明，毛竹经烘焙脱氧预处理后，碳元素显著增加，氧元素显著下降，氧脱除率达到40.3%，高位热值从17.47 MJ/kg增加至25.64 MJ/kg；微孔HZSM-5经Na₂CO₃溶液碱扩孔预处理后，介孔容积、总孔容和平均孔径均增加，表明经过碱扩孔后HZSM-5形成了一定程度的介孔结构，使其转变为具有微-介孔结构的多级孔分子筛；烘焙毛竹热解产生的呋喃类含氧中间产物和HDPE热解产生的轻烯烃中间产物会发生“双烯合成”反应，成为轻质芳烃生成的关键协同催化反应，当烘焙温度为250 ℃、Na₂CO₃浓度为0.6 mol/L、烘焙毛竹和HDPE质量比为1∶2和热解温度为800 ℃时，BTX（苯、甲苯和二甲苯）等轻质芳烃产率达到最大值，为3.05×10⁸ p.a./mg。
- 生物质 /
- 烘焙脱氧预处理 /
- 高密度聚乙烯 /
- 多级孔分子筛 /
- 共催化热解 /
- 轻质芳烃
Abstract: Light aromatics are extremely important building blocks in the chemical industry which can be produced from the co-catalytic fast pyrolysis (Co-CFP) of biomass and waste plastics. In this work, torrefaction pretreatment was first employed to remove the oxygen element from bamboo for improving the the quality of bamboo. Then, the hierarchical HZSM-5 was prepared by alkali pretreatment of HZSM-5 using Na₂CO₃ solution. At last, the optimal operation condition was investigated during Co-CFP of bamboo and high-density polyethylene (HDPE). Results showed that during torrefaction pretreatment process, the carbon content of bamboo gradually increased with the increase of torrefaction temperature, while the oxygen content decreased. The oxygen removal rate and HHV reached their maximum value of 40.3% and 25.64 MJ/kg at 300 ℃, respectively. The specific surface area, pore volume of mesopore, and average pore size of HZSM-5 increased after alkali pretreatment, indicating the development of the micro-mesoporous hierarchical structure in HZSM-5. The Diels-Alder reaction between the furans from pyrolysis of bamboo and the light olefins from pyrolysis of HDPE was the most important synergistic catalytic reaction which could highly promote the formation of light aromatics. The maximum yield of BTX (benzene, toluene, and xylene) was 3.05×10⁸ p.a./mg when the torrefaction temperature, the concentration of Na₂CO₃, the mass ratio of torrefied bamboo and HDPE, and the pyrolysis temperature were 250 ℃, 0.6 mol/L, 1∶2, and 800 ℃, respectively.
- biomass /
- torrefaction deoxygenation pretreatment /
- high-density polyethylene /
- co-catalytic fast pyrolysis /
- hierarchical zeolite /
- light aromatics

HTML全文

FIG. 1769. FIG. 1769.

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图 1 烘焙前后毛竹和HDPE的红外光谱谱图（a）和X射线衍射谱图（b）

Figure 1 FT-IR (a) and XRD (b) analysis of raw and torrefied bamboo HDPE

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图 2 烘焙前后毛竹和HDPE的TG（a）和DTG（b）曲线

Figure 2 TG (a) and DTG (b) curves of raw and torrefied bamboo HDPE

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图 3 碱改性前后HZSM-5催化剂的氮气吸附-脱附等温曲线（a）和孔径分布（b）

Figure 3 N₂ adsorption-desorption isotherm curve (a) and pore size distribution curve (b) of the parent and alkali pretreated hierarchical HZSM-5

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图 4 碱改性前后HZSM-5催化剂的NH₃-TPD谱图

Figure 4 NH₃-TPD spectra of the parent and alkali pretreated hierarchical HZSM-5

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图 5 HZSM-5和0.6 mol /L Na₂CO₃溶液扩孔处理后的HZSM-5的扫描电镜图（（a）–（b））和透射电子显微镜图（（c）–（f））

Figure 5 SEM and TEM images of the parent and 0.6 mol /L Na₂CO₃ pretreated hierarchical HZSM-5

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图 6 烘焙温度对共催化热解生物油组分的影响

Figure 6 Effect of torrefaction temperature on the compound distribution of bio-oil

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图 7 Na₂CO₃浓度对共催化热解生物油组分的影响

Figure 7 Effect of Na₂CO₃ concentration on the compound distribution of bio-oil

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图 8 烘焙毛竹与HDPE共混比例对共催化热解生物油组分的影响

Figure 8 Effect of the mass ratio of torrefied bamboo and HDPE on the compound distribution of bio-oil

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图 9 催化热解温度对共催化热解生物油组分的影响

Figure 9 Effect of catalytic fast pyrolysis temperature on the compound distribution of bio-oil

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表 1 烘焙前后毛竹和HDPE的基本特性分析

Table 1 Basic properties of raw and torrefied bamboo, HDPE

Sample	Mass yield/ %	Ultimate analysis/% （dry and ash free basis）					Proximate analysis/% （dry basis）			Q_HHV/ （MJ·kg⁻¹）	H/C_eff	Energy yield/ %	Oxygen removal efficiency/%
Sample	Mass yield/ %	C	H	O	N	S	V	FC	A	Q_HHV/ （MJ·kg⁻¹）	H/C_eff	Energy yield/ %	Oxygen removal efficiency/%
Bamboo	−	47.44	6.63	45.16	0.24	0.53	82.66	16.45	0.89	17.47	0.25	−	−
BT-200	92.37	49.52	6.39	43.67	0.24	0.17	80.66	18.56	1.18	18.10	0.22	95.73	3.29
BT-225	85.62	51.42	6.17	41.64	0.29	0.49	76.49	21.91	1.6	18.79	0.23	92.09	7.81
BT-250	76.24	54.56	6.10	39.01	0.24	0.09	72.84	25.53	1.63	20.22	0.27	88.27	13.63
BT-275	62.62	57.59	5.82	36.24	0.24	0.12	62.62	35.50	1.88	21.34	0.27	76.51	19.76
BT-300	45.99	67.27	5.37	26.96	0.34	0.07	41.78	52.32	1.90	25.64	0.36	67.50	40.30
HDPE	−	85.16	14.48	0.31	0.02	0.03	99.85	0.06	0.09	49.63	2.03	−	−

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表 2 碱改性前后HZSM-5催化剂的孔结构特征

Table 2 Textual properties of the parent and alkali pretreated hierarchical HZSM-5 catalysts

Textual properties	HZSM-5	H-0.2	H-0.4	H-0.6	H-0.8
S_BET /(m²·g⁻¹)	308.05	298.72	296.28	310.63	295.60
v_total /(cm³·g⁻¹)	0.183	0.193	0.193	0.208	0.196
v_micro /(cm³·g⁻¹)	0.144	0.131	0.131	0.134	0.129
v_meso /(cm³·g⁻¹)	0.039	0.062	0.062	0.074	0.067
d_pore/nm	2.421	2.631	2.660	2.725	2.715

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表 3 碱改性前后HZSM-5催化剂的酸量

Table 3 Acid amount of the parent and alkali pretreated hierarchical HZSM-5

Acid amount	HZSM-5	H-0.2	H-0.4	H-0.6	H-0.8
Weak acid/(mmol·g⁻¹)	0.376	0.360	0.382	0.339	0.400
Strong acid/(mmol·g⁻¹)	0.356	0.343	0.345	0.338	0.340
Total acid/(mmol·g⁻¹)	0.732	0.703	0.727	0.737	0.721

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