光电离质谱法在典型固体燃料热解研究中的应用进展

Title

Recent contributions of photoionization mass spectrometry in the study of typical solid fuel pyrolysis
作者

沈洋崔存浩刘浩然任海荣蔡江淮周忠岳齐飞
Author

SHEN Yang;CUI Cunhao;LIU Haoran;REN Hairong;CAI Jianghuai;ZHOU Zhongyue;QI Fei
单位

上海交通大学机械与动力工程学院福建省能源材料科学与技术创新实验室（IKKEM）固体表面物理化学国家重点实验室厦门大学化学化工学院厦门大学福建航空航天学院
Organization

School of Mechanical Engineering, Shanghai Jiao Tong University
Innovation Laboratory for Sciences and Technologies of Energy Materials of Fujian Province (IKKEM)
State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University
School of Aerospace Engineering, Xiamen University
摘要

通过热解将固体燃料在热化学上转化为运输燃料和增值化学品是实现固体燃料高效利用的最为切实可行和兼顾经济性的途径之一。由于热解反应产物的复杂性，对固体燃料热解的中间产物和最终产物在分子水平上进行全面阐明对于理解热解反应机理至关重要，同时对提高热解过程的可持续性具有积极意义。光电离质谱（PIMS）技术被普遍认为是一种高度通用的过程分析技术，通过对热解气相产物中的离子进行实时检测和分析，为热解提供了实时的信息。为此，本工作综述了近年来PIMS技术在固体燃料（包括煤、生物质和固体推进剂）热解领域的应用，并对不同实验和模型的进展进行了概述。这些进展相互促进，有助于学者加深对热解固体燃料复杂过程的理解，并为未来深入研究热解机理提供有力支持。
Abstract

Pyrolysis, an economically viable method, thermochemically converts solid fuel into transportation fuels and value-added chemicals, such as clean gas, liquid fuels, and chemicals, alongside undesirable by-products. Photoionization mass spectrometry (PIMS) is a versatile technique for real-time process analysis, offering ‘soft’ ionization for complex analytes, detecting and analyzing ions during in-situ pyrolysis. This review focuses on recent applications of PIMS during pyrolysis of solid fuels (i.e. coal, biomass and energetic materials). It summarizes studies on mass spectrometric analysis combined with different reactors and highlights the benefits through online PIMS as a diagnostic tool for in-situ analysis. It provides an overview of interplay between experimental advancements and models and discusses future perspectives, potential applications in support of mechanistic studies.
关键词

热解光电离质谱法煤炭生物质能固体推进剂在线分析
KeyWords

pyrolysis;photoionization mass spectrometry;coal;biomass;solid propellants;on-line analysis
DOI

10.1016/S1872-5813(23)60411-6
引用格式

沈洋, 崔存浩, 刘浩然, 任海荣, 蔡江淮, 周忠岳, 齐飞. 光电离质谱法在典型固体燃料热解研究中的应用进展[J]. 燃料化学学报（中英文）, 2024, 52(7): 921-944.
Citation

SHEN Yang, CUI Cunhao, LIU Haoran, REN Hairong, CAI Jianghuai, ZHOU Zhongyue, QI Fei. Recent contributions of photoionization mass spectrometry in the study of typical solid fuel pyrolysis[J]. Journal of Fuel Chemistry and Technology, 2024, 52(7): 921-944.

图表

Energy of ionization for certain organic compounds (with permission from International Union of Crystallography)

Proposed mechanism for the pyrolysis of model compounds featuring C−C bonds (with permission from Elsevier)

Mass spectra profiles of volatile products from Huainan coal pyrolysis (with permission from American Chemical Society)

The influence of catalysts on the relative content of typical coal pyrolysis products (with permission from Elsevier)

Relative content of primary volatiles from PC (a), HDPE (b) and their mixture PC/HDPE (7:3) pyrolysis (c) (with permission from Elsevier)

Mass spectra of in situ APPI combined with fixed-bed reactor during the catalytic pyrolysis of lignin[−]((a): Schematic diagram of experimental set-up; (b): Results of model compounds at 673 K)(with permission from American Chemical Society and

(a) Schematic representation of iPEPICO setup ; (b) PI spectrum of fulvenone ketene from catalytic pyrolysis of 2-methoxy acetophenone ; (c) Fast pyrolysis of guaiacol over H-USY and results from the mass spectrum of iPEPICO at 10.5 eV photon energy (with

Pyrolysis of furanic compounds over zeolite catalyst with mass spectrometric analysis ((a): Schematic diagram of experimental set-up; (b): Proposed pathways)(with permission from American Chemical Society)

The pyrolysis of major constituents at 350 °C(a): Microcrystalline cellulose; (b): Birch hemicellulose; (c): Miscanthus lignin (photon energy 9.5 eV). (with permission from Royal Society of Chemistry)

Typical pyrolysis products of hemicellulose model compounds (a): xylose at 280 °C; (b): xylobiose at 280 °C; (c): xylan at 250 °C.(with permission from Elsevier)

Comparison of zeolite catalysts with different structures for catalytic pyrolysis of Oka in a fluidized bed at 500 °C (a): blank test; (b): the first injected of the fresh HZSM-5; (c): the 14th injected of the coked HZSM-5; (d): the first injec

The results obtained by online PIMS in pyrolysis experiments[−] (a): the total intensity of different products of NTO; (b): Products evolution of NTO with temperature; (c): the total intensity of different products of FOX-7; (d): Products evolu

APPI HRMS in situ mass spectra of CL-20 decomposition products (a): Full pyrolysis product spectrum; (b): enlarged spectrum in the m/z 300−430 range (The signal of the CL-20 molecule is represented by a down triangle symbol, while the produc

Early lumped kinetic models for coal pyrolysis, biomass pyrolysis and polymer pyrolysis

Tar, char and gases predicted by lumped kinetic models (with permission from Taylor & Francis Informa Group)

Experimental and simulated light gases yield by coal pyrolysis with the improved CPD model (with permission from Royal Society of Chemistry)

Table1

表 1 Main characteristics of various raw biomass catalytic pyrolysis with PIMS

Feedstocks	Pyrolysis temperatures	Methods		Catalyst	Key findings	Ref.
Feedstocks	Pyrolysis temperatures	reactor	light source	Catalyst	Key findings	Ref.
Spruce/fir mixture, beech	300−560 °C	TG	VUV lamp	−	at 300 °C, there were mainly phenolic and furanic products, and the oxidation process of oxygenated compounds existed at high temperatures (＞500 °C)	[42]
Beech, a mixture of spruce and fir, and coarse colza meal	250−500 °C	TG	VUV lamp	−	aliphatic hydrocarbons were found. alkaline biomass showed a strong signal of nitrogen-containing substances	[22]
Poplar	300–700 °C	a tubular reactor	SVUV	−	as a typical hardwood, the signal strength of pyrolysis products' syringyl subunits first increased and then decreased with the increase of temperature, while guaiacyl subunits continued to decrease	[89]
Micro-crystalline cellulose, xylan from birch, cellulose and lignin extracted from miscanthus and oak	350，450， 550 °C	a tubular reactor	SVUV	−	a typical intermediate product of cellulose pyrolysis was found to be a possible precursor of the furanone-based species, and hydroxyacetaldehyde was the product of secondary reactions	[78]
Pine wood	300−700 °C	a tubular reactor	SVUV	−	as a typical softwood, polycyclic aromatic hydrocarbon (PAH) growth mechanism was demonstrated	[90]
Chrysophanol, emodin, rhein and aloe-emodin	373−973 K	a PYR-2A pyrolyzer	SVUV	−	the principal pyrolysis pathways for rhein involved the elimination reactions of CO, CO₂ and HCOOH	[91]
Miscanthus, Douglas fir and oak	400 or 500 °C	MFBR^a	VUV lamp	−	typical pyrolysis products of miscanthus, Douglas fir and oak were 4-vinylphenol, 4-methylguaiacol and 2,6-dimethoxy-4-(2-propenyl)-phenol	[92]
Miscanthus, oak and Douglas fir	200−500 °C	a fixed-bed reactor	VUV lamp	−	the most critical parameter affecting the chemical mechanisms during pyrolysis was the presence of inorganic constituents within the native biomass	[82]
Heartwood, sapwood, and bark (from Douglas fir and oak)	500 °C	MFBR^a	Laser	−	the variation in pyrolysis products can largely be attributed to the mineral content as a primary factor	[86]
Douglas and oak	400 or 500 °C	fixed bed reactor and MFBR^a	VUV lamp	−	the temporal evolution of key tar is indicated during both slow and fast pyrolysis conditions	[93]
Elm	500−700 °C	MFBR^a	SVUV	−	the main factor impacting the change of primary tar during secondary reactions was the reaction temperature. At temperatures above 700 °C, the aerosols were primarily composed of large PAHs with over three rings	[87]
Elm	500−700 °C	MFBR^a	aPPI	−	in secondary reactions, the primary mechanisms for transforming heavy compounds were deoxygenation and aromatization	[88]
Oak	500 or 600 °C	MFBR^a	laser	hierarchical zeolite	desilicated zeolite was better than microporous zeolite for producing single aromatic compounds and was more stable when coke deposits formed	[94]
Xylan	300 °C	a homemade tubular furnace	SVUV	Na₂CO₃ and K₂CO₃	alkali metal ions encouraged the creation of both char and lighter substances	[23]
Oka	500 °C	MFBR^a	FT-ICR with ESI and APPI sources	microporous and hierarchical zeolites	the mesopores HZSM-5 catalyst increased aromaticity and reduced oxygen-contenting products	[95]
Nannochloropsis, Spirulina, and Sargasso	500 °C	a double micro-fixed-bed reactor	SVUV	HZSM-5 zeolite	for algae, the product of monocyclic aromatic hydrocarbons was mainly derived from protein	[96]
Cellulose and polyethylene	50−700 °C	TG	VUV lamp	HZSM-5	the co-feeding approach resulted in a notable enhancement in the generation of aromatic compounds	[97]
Cellulose and polyethylene	50−700 °C	TG	VUV lamp	MgO	the utilization of the MgO catalyst exhibited the capability to enhance the cellulose pyrolysis process and facilitate the cleavage of C–C bonds in polyethylene (PE)	[98]
Bamboo sawdust and polyethylene	50−650 °C	fixed bed reactor	VUV lamp	−	MgO catalyst can promote the Diels-Alder reaction in co-feeding pyrolysis, thus promoting aromatics production	[99]
Lignin and polyethylene	550 °C	TG	VUV lamp	Cu-modified HZSM-5	Cu₂O has better dehydrogenation activity and CuO has better selectivity of monocyclic aromatic hydrocarbons	[41]
^a: A microfluidized bed reactor (MFBR).

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