王彩云, 王焦飞, 张玉洁, 柯梅容, 宋旭东, 苏暐光, 白永辉, 吕鹏, 于广锁. CaO/HZSM-5复合催化剂调控水稻秸秆和PVC共热解产物的协同作用研究[J]. 燃料化学学报（中英文）. DOI: 10.1016/S1872-5813(24)60484-6
引用本文: 王彩云, 王焦飞, 张玉洁, 柯梅容, 宋旭东, 苏暐光, 白永辉, 吕鹏, 于广锁. CaO/HZSM-5复合催化剂调控水稻秸秆和PVC共热解产物的协同作用研究[J]. 燃料化学学报（中英文）. DOI: 10.1016/S1872-5813(24)60484-6
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WANG Caiyun, WANG Jiaofei, ZHANG Yujie, KE Meirong, SONG Xudong, SU Weiguang, BAI Yonghui, LÜ Peng, YU Guangsuo. Study on the synergistic effect of CaO/HZSM-5 composite catalyst in regulating the co-pyrolysis products of rice straw and PVC[J]. Journal of Fuel Chemistry and Technology. DOI: 10.1016/S1872-5813(24)60484-6
Citation: WANG Caiyun, WANG Jiaofei, ZHANG Yujie, KE Meirong, SONG Xudong, SU Weiguang, BAI Yonghui, LÜ Peng, YU Guangsuo. Study on the synergistic effect of CaO/HZSM-5 composite catalyst in regulating the co-pyrolysis products of rice straw and PVC[J]. Journal of Fuel Chemistry and Technology. DOI: 10.1016/S1872-5813(24)60484-6
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CaO/HZSM-5复合催化剂调控水稻秸秆和PVC共热解产物的协同作用研究

Study on the synergistic effect of CaO/HZSM-5 composite catalyst in regulating the co-pyrolysis products of rice straw and PVC

    摘要
  • 摘要: 生物质与废旧塑料共热解是实现两者资源化利用的潜在技术之一，不仅能制备高附加值的富烃生物油，还可实现废弃物的洁净资源化利用，减轻环境污染。然而，产物的复杂性限制了共热解技术的进一步应用。本研究以农作废弃物水稻秸秆(RS)和聚氯乙烯塑料(PVC)为研究对象，采用热重-质谱联用仪(TG-MS)和热裂解-气相色谱/质谱联用仪(Py-GC/MS)研究两者单独及共热解特性，并考察CaO和HZSM-5复合催化剂对热解产物的协同调控规律。结果表明，PVC和RS在共热解过程中具有相互作用，促进了芳烃化合物的产生。生物油中烃类化合物的相对含量高达66.78%。其中，芳烃的相对含量达到64.17%。相较于RS单独热解，共热解焦油组分中含氧化合物的含量下降62.05%，有效提高了生物油的氧化稳定性。CaO/HZSM-5复合催化剂相较于CaO、HZSM-5单独催化剂，热解产物油中C4−C10烃类化合物的相对含量分别增加2.81%、5.06%，表现出更好的轻质芳烃选择性。在CaO/HZSM-5复合催化剂协同作用下，生物油中单环芳烃的相对含量为34.34%，大于理论计算值33.03%。而多环芳烃的相对含量为28.21%，小于理论计算值31.22%，表现出较好的单环芳烃选择性。此外，CaO/HZSM-5复合催化剂促进大量氯元素以CaCl2等氯化物的形式固定在半焦中，显著降低了Cl元素的气相释放。

     

    Abstract: Co-pyrolysis of biomass and waste plastics is one of the potential technologies to achieve the resourceful utilization of both, not only to prepare high value-added hydrocarbon-rich bio-oil, but also to achieve clean resourceful utilization of wastes and reduce environmental pollution. However, the complexity of the products limits the further application of co-pyrolysis technology. In this study, rice straw (RS), an agricultural waste, and polyvinyl chloride plastic (PVC) were used to investigate the individual and co-pyrolysis characteristics of them by thermogravimetric-mass spectrometry (TG-MS) and pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS), and the synergistic regulation law of the pyrolysis products by CaO and HZSM-5 composite catalyst. The results showed that PVC and RS had interactions during the co-pyrolysis process, which promoted the production of aromatic compounds. The relative content of hydrocarbon compounds in bio-oil is as high as 66.78%. The relative content of aromatics reached 64.17%. Compared with RS pyrolysis, the content of oxygenated compounds in the co-pyrolysis bio-oil fraction decreased by 62.05%, which effectively improved the oxidative stability of the bio-oil. The relative content of C4−C10 hydrocarbons in the pyrolysis product oil increased by 2.81% and 5.06%, respectively, with the CaO/HZSM-5 composite catalyst showing better light aromatic selectivity compared with the individual addition of CaO and HZSM-5 catalysts. Under the synergistic effect of CaO/HZSM-5 composite catalyst, the relative content of monocyclic aromatic hydrocarbons (PAHs) in the bio-oil was 34.34%, which was larger than the theoretical calculated value of 33.03%. And the relative content of PAHs was 28.21%, which was smaller than the theoretically calculated value of 31.22%, showing the better selectivity of monocyclic aromatic hydrocarbons. In addition, the CaO/HZSM-5 composite catalyst promoted the immobilisation of a large amount of elemental chlorine in the form of chlorides such as CaCl2 in the semicoke, which significantly reduced the gas-phase release of elemental Cl.

     

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