生物质热解催化剂积炭问题的研究进展

doi:10.16085/j.issn.1000-6613.2022-0511

化工进展 ›› 2023, Vol. 42 ›› Issue (1): 236-246.DOI: 10.16085/j.issn.1000-6613.2022-0511

生物质热解催化剂积炭问题的研究进展

李攀¹^,²^,³(), 王彪¹^,²^,³, 徐骏浩¹, 王贤华⁴, 胡俊豪¹^,²^,³(), 宋建德², 白净¹^,²^,³, 常春¹^,²^,³

^1.郑州大学机械与动力工程学院，河南郑州 450001
^2.河南省生物基化学品绿色制造重点实验室，河南濮阳 457000
^3.车用生物燃料技术国家重点实验室，河南南阳 473000
^4.华中科技大学煤燃烧国家重点实验室，湖北武汉 430074

收稿日期:2022-03-29 修回日期:2022-05-20 出版日期:2023-01-25 发布日期:2023-02-20
通讯作者: 胡俊豪
作者简介:李攀（1987—），男，副教授，研究方向为生物质资源化利用。E-mail：lipanhust@163.com。
基金资助:
国家自然科学基金(52006200);煤燃烧国家重点实验室开放基金(FSKLCCA2108);河南省杰出外籍科学家工作室项目(GZS2022007);南阳市协同创新重大专项（郑州大学南阳研究院）(NRIZU2020CIP0006)

Research progress on carbon deposition of catalysts for biomass pyrolysis

LI Pan¹^,²^,³(), WANG Biao¹^,²^,³, XU Junhao¹, WANG Xianhua⁴, HU Junhao¹^,²^,³(), SONG Jiande², BAI Jing¹^,²^,³, CHANG Chun¹^,²^,³

^1.School of Mechanical and Power Engineering, Zhengzhou University, Zhengzhou 450001, Henan, China
^2.Henan Key Laboratory of Green Manufacturing of Biobased Chemicals, Puyang 457000, Henan, China
^3.State Key Laboratory of Motor Vehicle Biofuel Technology, Nanyang 473000, Henan, China
^4.State Key Laboratory of Coal Combustion, Huazhong University of Science and Technology, Wuhan 430074, Hubei, China

Received:2022-03-29 Revised:2022-05-20 Online:2023-01-25 Published:2023-02-20
Contact: HU Junhao

摘要/Abstract

摘要：

生物质催化热解获得生物油等高质产品是最有前途替代传统化石能源的方法之一，但在热解过程中存在着严重的催化剂失活问题，其中积炭是导致催化剂失活的最主要因素。本文对近年来生物质催化热解领域的催化剂积炭问题进行综述，重点介绍催化剂积炭失活原因及表征方法、积炭的影响因素分析（催化剂结构、催化剂酸性与反应温度）、抑制催化剂积炭的方法（催化剂改性、高压反应条件等）以及积炭催化剂再生方法（氧化灼烧再生、臭氧低温再生、非热等离子体再生等），并介绍了近年来新兴的微波催化热解技术对催化剂积炭的抑制和消除作用，然后针对该领域目前所面临的困难和发展方向进行展望，以期为生物质催化热解过程中催化剂积炭问题研究提供理论基础。

关键词: 生物质, 催化剂积炭, 催化热解, 催化剂失活

Abstract:

Biomass catalytic pyrolysis to obtain high-value products such as bio-oil is one of the most promising methods to replace traditional fossil energy. However, there is a serious catalyst deactivation problem in the pyrolysis process, among which carbon deposition is the most important factor leading to catalyst deactivation. This paper reviews the catalyst carbon deposition in the field of biomass catalytic pyrolysis in recent years, focusing on the causes and characterization methods of catalyst carbon deposition deactivation, the analysis of the influencing factors of carbon deposition (catalyst structure, catalyst acidity and reaction temperature), the inhibition of catalyst carbon deposition (catalyst modification, high pressure reaction conditions, etc.) and coke catalyst regeneration methods (oxidative burning regeneration, ozone low-temperature regeneration, non-thermal plasma regeneration, etc.). The new microwave catalytic pyrolysis technology to inhibit and eliminate catalyst carbon deposition is intruduced. The current difficulties and development directions in this field are prospected, in order to provide a theoretical basis for the study of catalyst carbon deposits in the process of biomass catalytic pyrolysis.

Key words: biomass, catalyst carbon deposition, catalyst pyrolysis, catalyst deactivation

中图分类号:

李攀, 王彪, 徐骏浩, 王贤华, 胡俊豪, 宋建德, 白净, 常春. 生物质热解催化剂积炭问题的研究进展[J]. 化工进展, 2023, 42(1): 236-246.

LI Pan, WANG Biao, XU Junhao, WANG Xianhua, HU Junhao, SONG Jiande, BAI Jing, CHANG Chun. Research progress on carbon deposition of catalysts for biomass pyrolysis[J]. Chemical Industry and Engineering Progress, 2023, 42(1): 236-246.

图/表 10

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催化剂	生物质原料	处理方法	结论	参考文献
ZSM-5	呋喃	催化热解	部分积炭具有催化活性为活性积炭，ZSM-5容易积炭	[28]
多层纳米ZSM-5片，HZSM-5	纤维素	蒸汽热解	积炭沉积在催化剂的微孔阻碍活性位点，可以通过增加中孔降低失活率	[34]
La、Pr、Ce、Y、Gd、Zr改性Ni	木质纤维素	快速催化热解	La改性Ni催化剂具有较大孔径、适度酸性和最佳的抗积炭性能	[35]
ZSM-5	木质素	催化热解	H₂氛围中，催化剂积炭较少	[36]
USY	半纤维素	催化热解	USY酸性较强，孔道狭窄易积炭，但在高压反应条件下促进物质扩散，减少积炭生成	[37]
HZSM-5	柳枝稷和聚乙烯	催化共热解	聚乙烯衍生的烃蒸气有助于减少积炭的形成，HZSM-5积炭严重，脱氧率高	[38]
镍/渣（镁渣钢渣、高炉渣、黄铁矿渣、硅酸钙渣）	松锯末	热解催化重整	在催化剂测试中负载在镁渣上的镍活性最高，反应过程中生成石墨碳和无定形碳	[31]
白云石	松木	催化热解	白云石不易积炭，但催化性能较弱，生物油等产品产率低	[39]
碳基催化剂	纤维素	微波催化热解	微波与碳基催化剂的协同作用可以有效抑制积炭生成，但碳基催化剂本身易积炭失活	[40]
整体式催化剂	牛粪	催化热解	积炭沉积在外表面，目标产物产率更高，催化剂回收、再生效率更高	[41]
CoO、Cr₂O₃、CuO、Fe₂O₃、 Mn₂O₃、NiO、TiO₂、V₂O₅和CeO₂	白杨	催化热解	不同的金属氧化物，积炭行为不同，V-、Mn-、Cu-和Co-基容易形成积炭	[42]

催化剂	生物质原料	处理方法	结论	参考文献
ZSM-5	呋喃	催化热解	部分积炭具有催化活性为活性积炭，ZSM-5容易积炭	[28]
多层纳米ZSM-5片，HZSM-5	纤维素	蒸汽热解	积炭沉积在催化剂的微孔阻碍活性位点，可以通过增加中孔降低失活率	[34]
La、Pr、Ce、Y、Gd、Zr改性Ni	木质纤维素	快速催化热解	La改性Ni催化剂具有较大孔径、适度酸性和最佳的抗积炭性能	[35]
ZSM-5	木质素	催化热解	H₂氛围中，催化剂积炭较少	[36]
USY	半纤维素	催化热解	USY酸性较强，孔道狭窄易积炭，但在高压反应条件下促进物质扩散，减少积炭生成	[37]
HZSM-5	柳枝稷和聚乙烯	催化共热解	聚乙烯衍生的烃蒸气有助于减少积炭的形成，HZSM-5积炭严重，脱氧率高	[38]
镍/渣（镁渣钢渣、高炉渣、黄铁矿渣、硅酸钙渣）	松锯末	热解催化重整	在催化剂测试中负载在镁渣上的镍活性最高，反应过程中生成石墨碳和无定形碳	[31]
白云石	松木	催化热解	白云石不易积炭，但催化性能较弱，生物油等产品产率低	[39]
碳基催化剂	纤维素	微波催化热解	微波与碳基催化剂的协同作用可以有效抑制积炭生成，但碳基催化剂本身易积炭失活	[40]
整体式催化剂	牛粪	催化热解	积炭沉积在外表面，目标产物产率更高，催化剂回收、再生效率更高	[41]
CoO、Cr₂O₃、CuO、Fe₂O₃、 Mn₂O₃、NiO、TiO₂、V₂O₅和CeO₂	白杨	催化热解	不同的金属氧化物，积炭行为不同，V-、Mn-、Cu-和Co-基容易形成积炭	[42]

元素分析	积炭的碳、氢、硫、氮含量，氢碳原子比
TGA	积炭含量、类型
TGA+IR	积炭分解情况
TPO	积炭类型、部位
TEOM	积炭失重动力学
IR、Raman	积炭组成（脂肪碳、芳香碳），酸中心失活情况
UV-Vis	积炭组成（烯烃碳、碳正离子）
FTIR	积炭结构和组成
¹H NMR	积炭组成（脂肪碳、芳香碳）
¹³C MAS NMR	积炭组成（脂肪碳、芳香碳）
ESR	积炭组成、自由基信息
SEM、TEM	积炭部分及分布
XPS	积炭部分（表面）、形貌
XRD	积炭晶形
索氏抽提+GC/MS	可溶性积炭的化学组成
分子筛酸溶解法+GC/MS	积炭的化学组成
液氮物理吸附+孔容分析	积炭部位（孔道内分布）

元素分析	积炭的碳、氢、硫、氮含量，氢碳原子比
TGA	积炭含量、类型
TGA+IR	积炭分解情况
TPO	积炭类型、部位
TEOM	积炭失重动力学
IR、Raman	积炭组成（脂肪碳、芳香碳），酸中心失活情况
UV-Vis	积炭组成（烯烃碳、碳正离子）
FTIR	积炭结构和组成
¹H NMR	积炭组成（脂肪碳、芳香碳）
¹³C MAS NMR	积炭组成（脂肪碳、芳香碳）
ESR	积炭组成、自由基信息
SEM、TEM	积炭部分及分布
XPS	积炭部分（表面）、形貌
XRD	积炭晶形
索氏抽提+GC/MS	可溶性积炭的化学组成
分子筛酸溶解法+GC/MS	积炭的化学组成
液氮物理吸附+孔容分析	积炭部位（孔道内分布）

催化剂	原料	表征方法	结论	参考文献
ZSM-5	呋喃	原位漫反射傅里叶变换红外光谱（DRIFTS）	在呋喃热解中，活性积炭的主要成分是聚甲基苯甲醛	[28]
Ni/HZSM-5	典型塑料	扫描电镜（SEM）	失活催化剂表面粗糙、模糊，沟壑丛生，团聚现象明显	[48]
Ni/MCM-41	木屑	透射电镜（TEM）	MCM-41具有长而有序的中孔结构，Ni颗粒均匀分散在MCM-41载体中	[49]
Ni/CeO_2-Al₂O₃	生物油/生物甘油混合物	X射线衍射（XRD）	Ni呈现最强峰，贵金属的掺入没有影响催化剂尺寸；Ni/CeO_2-Al₂O₃是更耐失活和积炭的催化剂	[50]
Ni/La₂O₃-α-Al₂O₃	松木屑	氧化程序升温（TPO）	沉积在Ni/La₂O₃-α-Al₂O₃的积炭主要有两种包封状积炭和丝状积炭	[51]
Ni/ZSM-5，Ni/MCF，Ni/ZrO₂	纤维素	热重分析（TG）	Ni/ZrO的积炭量比Ni/ZSM-5、Ni/MCF少两倍，积炭量最小。并在400~600℃时，大部分积炭被除去	[52]

生物质热解催化剂积炭问题的研究进展

Research progress on carbon deposition of catalysts for biomass pyrolysis

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催化剂	生物质原料	处理方法	结论	参考文献
ZrO₂改性ZSM-5挤出物	橡木	热解和蒸汽升级催化	积炭沉积为蛋壳空间分布，起初积炭在B酸上形成，促进深度脱氧和裂解，然后积炭沉积在外表面，在ZrO₂上形成更多富氢积炭	[17]
Ni/La₂O₃-Al₂O₃、Ni/Al₂O₃和商业镍催化剂（G90-LDP）	松木废料	热解催化重整	生成无定形积炭，La₂O₃使积炭气化，其碱性和吸水能力可抑制积炭生成	[50]
Ni/镁渣和Ni/γ-Al₂O₃	松锯末	热解催化重整	Ni/镁渣的积炭率、石墨化程度较低，抗积炭能力较强	[51]
MCM-41/ZSM-5	纤维素、木质素和向日葵茎	生物油原位催化升级	MCM-41作为积炭沉积的牺牲层降低了 ZSM-5的失活率	[60]
Na、Mg、La改性Ni/SiO₂	愈创木酚	蒸汽重整	La改性Ni/SiO₂催化剂后积炭量最低	[80]
HZSM-5、Fe/ZSM-5、Ni/ZSM-5和FeNi/ZSM-5	软木锯末	热解和蒸汽升级催化	积炭形成取决于酸性位点强度和金属，FeNi/ZSM-5催化时产品的芳烃产率高，积炭量少	[81]
酸脱铝、化学液相沉积改性ZSM-5	松锯末	热解催化重整	改性后催化剂积炭重要前驱体生成量减少40%左右，有效抑制积炭的生成	[76]
化学液相沉积改性HZSM-5	竹子	微波催化热解	催化剂比表面积增加10%，积炭量明显减少	[82]
HF脱铝HZSM-5	纤维素	快速催化热解	脱铝过程中布朗斯台德酸位点的减少，积炭量大幅减少，芳烃产率增加44.9%	[83]
碱洗HZSM-5减弱酸度、增加介孔结构	稻壳	微波催化热解	碱洗后，催化剂外表面强酸位点减少，内表面为弱酸环境，积炭生成量减少4.6%	[84]
CaO、碱洗HZSM-5	竹子和废旧轮胎	共热解	双重催化显著提升目标产物相对含量，并抑制因酸性过强而产生的积炭等不良产物	[85]

催化剂	再生方法	结论	参考文献
ZSM-5	臭氧低温再生	失活催化剂上几乎97.4%的积炭完全去除；催化剂骨架保持良好	[93]
工业废弃催化剂	溶剂萃取方法	可在低温下有效除去催化剂孔道中的积炭，再生活性高	[94]
Pt-Sn/γ-Al₂O₃	氢气、氮气吹扫	氢气再生，去除积炭的低密度组分，积炭流动性更高，活性位点可及性更强	[95]
MnO _x -CeO₂	NO₂氛围灼烧	积炭在350~400℃时被除去，比常规空气灼烧再生低200℃左右	[96]
BaZr/Fe	CO₂氛围灼烧	催化剂内部和表面的积炭被部分去除，再生的催化剂恢复部分活性，稳定性较好	[97]
沸石催化剂	非热等离子体再生	低能量的非热等离子体在293K温度下实现催化剂完全再生，去除积炭	[98]

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