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Catalytic reforming of palm kernel shell (PKS) pyrolysis volatile matter was studied using char (Char) and activated carbon (AC) as catalysts under microwaveassisted heating. The impacts of different carbonbased catalysts on the composition of products were studied. The possible reaction pathways during catalytic reforming of PKS pyrolysis volatile matter under microwaveassisted heating were also investigated. During catalytic reforming of pyrolysis volatile matter, the catalyst promoted the yield of gas product, which led to the decrease of biooil yield. Compared with the Char, AC not only has higher catalytic activity to facilitate the conversion of biooil to gas, but also exhibited better selectivity for the formation of singlering aromatic compounds (especially phenol) in biooil. Using the AC catalyst, the concentrations of the singlering aromatic compounds reached 84.25%. The catalyst mainly promoted the secondary reactions such as demethoxylation reaction and dehydrocarbylation reaction.

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在微波辅助加热方式下,分别以半焦(Char)和活性炭(AC)为催化剂,对棕榈壳(PKS)热解挥发分进行催化重整,分析了不同催化剂对产物分布的影响,同时对反应过程中可能发生的反应路径进行分析。结果表明:在Char和AC的作用下,生物油产率减小,气体产物产率增加;与Char相比,AC具有显著的促使生物油向气体转化的催化活性,同时对单环芳香化合物(尤其苯酚)的形成具有更高的选择性;当AC作为催化剂时,单环芳香化合物的相对含量为84.25%; Char和AC催化剂主要促使了脱甲氧基、脱烃基等反应的发生。

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刘说(1977-),女,博士,副教授,研究方向为催化剂的开发与制备及其在能源方面的应用。E-mail:

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刘说(1977-),女,博士,副教授,研究方向为催化剂的开发与制备及其在能源方面的应用。E-mail:

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Bioresource Technology, 2016, 207: 188-196., articleTitle=Production of phenol-rich bio-oil during catalytic fixed-bed and microwave pyrolysis of palm kernel shell, refAbstract=null)], funds=[Fund(id=1154430609272333287, tenantId=1146029695717560320, journalId=1146119893612605453, articleId=1154430574472192858, awardId=null, language=CN, fundingSource=2022年营口市企业博士双创计划:微波催化重整生物质热解挥发分制苯酚和合成气, fundOrder=null, country=null)], companyList=[AuthorCompany(id=1154430605178692501, tenantId=1146029695717560320, journalId=1146119893612605453, articleId=1154430574472192858, xref=1, ext=[AuthorCompanyExt(id=1154430605182886806, tenantId=1146029695717560320, journalId=1146119893612605453, articleId=1154430574472192858, companyId=1154430605178692501, language=EN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=1 College of Chemistry and Environmental Engineering Yingkou Institute of Technology Yingkou 115014 China), 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companyId=1154430605275161496, language=CN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=2 辽宁省化学助剂合成与分离省市共建重点实验室 辽宁 营口 115014)])], figs=[ArticleFig(id=1154430608118899670, tenantId=1146029695717560320, journalId=1146119893612605453, articleId=1154430574472192858, language=EN, label=Fig. 1, caption=Experimental system of catalytic reforming, figureFileSmall=iU2OCqInLj0Jpn6FAlLicA==, figureFileBig=w0GlvHil0pc5r3USy/QMMQ==, tableContent=null), ArticleFig(id=1154430608177619927, tenantId=1146029695717560320, journalId=1146119893612605453, articleId=1154430574472192858, language=CN, label=图 1, caption=催化重整实验装置, figureFileSmall=iU2OCqInLj0Jpn6FAlLicA==, figureFileBig=w0GlvHil0pc5r3USy/QMMQ==, tableContent=null), ArticleFig(id=1154430608248923096, tenantId=1146029695717560320, journalId=1146119893612605453, articleId=1154430574472192858, language=EN, label=Fig. 2, caption=Product yields under different conditions, figureFileSmall=VlTlvkmZfD7Q7wWEBLK4VQ==, figureFileBig=ciR0ZSrYKheXLgB8t4HoIA==, tableContent=null), ArticleFig(id=1154430608307643353, tenantId=1146029695717560320, journalId=1146119893612605453, articleId=1154430574472192858, language=CN, label=图 2, caption=不同条件下的产物产率, figureFileSmall=VlTlvkmZfD7Q7wWEBLK4VQ==, figureFileBig=ciR0ZSrYKheXLgB8t4HoIA==, tableContent=null), ArticleFig(id=1154430608404112346, tenantId=1146029695717560320, journalId=1146119893612605453, articleId=1154430574472192858, language=EN, label=Fig. 3, caption=Composition of bio-oils under different conditions, figureFileSmall=UeAePhcW+FfYfOrCN9SqAw==, figureFileBig=b50aJw6sWJcj1GuDYbhnsw==, tableContent=null), ArticleFig(id=1154430608458638299, tenantId=1146029695717560320, journalId=1146119893612605453, articleId=1154430574472192858, language=CN, label=图 3, caption=不同条件下生物油的组成, figureFileSmall=UeAePhcW+FfYfOrCN9SqAw==, figureFileBig=b50aJw6sWJcj1GuDYbhnsw==, tableContent=null), ArticleFig(id=1154430608504775644, tenantId=1146029695717560320, journalId=1146119893612605453, articleId=1154430574472192858, language=EN, label=Fig. 4, caption=Changes of weight loss of Char and AC before and after catalytic reforming reaction, figureFileSmall=zQzXYsKgj34PyGB+N5/Lbg==, figureFileBig=FYqMj/4i0Ej3D0cQXLgSPQ==, tableContent=null), ArticleFig(id=1154430608567690205, tenantId=1146029695717560320, journalId=1146119893612605453, articleId=1154430574472192858, language=CN, label=图 4, caption=Char 和 AC 在催化重整反应前后失重率的变化, figureFileSmall=zQzXYsKgj34PyGB+N5/Lbg==, figureFileBig=FYqMj/4i0Ej3D0cQXLgSPQ==, tableContent=null), ArticleFig(id=1154430608630604766, tenantId=1146029695717560320, journalId=1146119893612605453, articleId=1154430574472192858, language=EN, label=Fig. 5, caption=Potential reaction paths during catalytic reforming, figureFileSmall=NuMdZ2C2Ko1Vviv+rT/URg==, figureFileBig=5fdemjB2rqUmf6iDtkVSMQ==, tableContent=null), ArticleFig(id=1154430608693519327, tenantId=1146029695717560320, journalId=1146119893612605453, articleId=1154430574472192858, language=CN, label=图 5, caption=催化重整过程中可能发生的反应路径, figureFileSmall=NuMdZ2C2Ko1Vviv+rT/URg==, figureFileBig=5fdemjB2rqUmf6iDtkVSMQ==, tableContent=null), ArticleFig(id=1154430608748045280, tenantId=1146029695717560320, journalId=1146119893612605453, articleId=1154430574472192858, language=EN, label=Table 1, caption=Proximate and ultimate analysis of PKS, figureFileSmall=null, figureFileBig=null, tableContent=
工业分析/% 元素分析/%
水分 灰分 挥发分 固定碳 C H $\mathrm{N}$ S 0
14.90 1.64 64.68 18.78 49.90 5.25 0.36 0.95 43.54
), ArticleFig(id=1154430608852902881, tenantId=1146029695717560320, journalId=1146119893612605453, articleId=1154430574472192858, language=CN, label=表 1, caption=PKS 的工业分析和元素分析, figureFileSmall=null, figureFileBig=null, tableContent=
工业分析/% 元素分析/%
水分 灰分 挥发分 固定碳 C H $\mathrm{N}$ S 0
14.90 1.64 64.68 18.78 49.90 5.25 0.36 0.95 43.54
), ArticleFig(id=1154430608945177571, tenantId=1146029695717560320, journalId=1146119893612605453, articleId=1154430574472192858, language=EN, label=Table 2, caption=Pore structure parameters of the catalysts, figureFileSmall=null, figureFileBig=null, tableContent=
催化剂 孔隙结构参数
比表面积 孔体积 平均孔径/nm
Char 115.19 0.10 1.80
AC 1002.72 0.46 1.02
), ArticleFig(id=1154430609024869348, tenantId=1146029695717560320, journalId=1146119893612605453, articleId=1154430574472192858, language=CN, label=表 2, caption=催化剂的孔隙结构参数, figureFileSmall=null, figureFileBig=null, tableContent=
催化剂 孔隙结构参数
比表面积 孔体积 平均孔径/nm
Char 115.19 0.10 1.80
AC 1002.72 0.46 1.02
), ArticleFig(id=1154430609083589605, tenantId=1146029695717560320, journalId=1146119893612605453, articleId=1154430574472192858, language=EN, label=Table 3, caption=Main compounds and their relative contents of bio-oil, figureFileSmall=null, figureFileBig=null, tableContent=
化合物 相对含量/%
PKS PKS+Char PKS+AC
糠醛 5.72 - -
邻二甲苯 1.90 2.96 2.51
乙苯 1.72 2.31 2.35
苯酚 14.91 48.94 67.44
间乙炔基甲苯 2.04 1.94 -
2-甲氧基苯酚 3.27 - -
3-乙基苯酚 0.73 - -
环丙基甲醇 1.89 - -
醋酸苯酯 3.62 2.99 -
间甲酚 - 4.92 3.59
对甲酚 - 5.81 7.93
2-甲氧基-6-甲基苯酚 2.31 - -
2-甲氧基-5-甲基苯酚 3.42 - -
2-甲氧基-4-甲基苯酚 1.03 - -
2-甲基苯并呋喃 1.06 0.72 0.95
3-羟基十二烷酸 1.64 - -
2-甲氧基-4-丙烯基苯酚 8.12 0.83 -
2-甲氧基-4-乙基苯酚 3.91 - -
2-甲氧基-4-乙烯基苯酚 2.67 - -
2,6-二甲氧基苯酚 3.29 - -
3,4-二甲氧基苯酚 1.22 - -
1,2,4-三甲氧基苯 1.54 1.09 -
1,2,3-三甲氧基-5-甲基苯 1.32 - 0.75
2-甲氧基-5-丙烯基苯酚 2.03 - -
5-叔丁基邻苯三酚 2.23 0.89 -
2,6-二甲氧基-4-丙烯基苯酚 5.26 - -
右旋苯丙胺 4.8 3.22 1.24
0.87 4.03 5.89
1-甲基萘 - 1.33 2.62
联苯烯 - 0.87 -
9-十六烯酸 3.92 - -
2,6-二叔丁基对甲基苯酚 0.88 0.51 -
1,2-苯二甲酸二丁酯 1.83 2.04 0.63
), ArticleFig(id=1154430609150698470, tenantId=1146029695717560320, journalId=1146119893612605453, articleId=1154430574472192858, language=CN, label=表 3, caption=生物油中主要化合物及其相对含量, figureFileSmall=null, figureFileBig=null, tableContent=
化合物 相对含量/%
PKS PKS+Char PKS+AC
糠醛 5.72 - -
邻二甲苯 1.90 2.96 2.51
乙苯 1.72 2.31 2.35
苯酚 14.91 48.94 67.44
间乙炔基甲苯 2.04 1.94 -
2-甲氧基苯酚 3.27 - -
3-乙基苯酚 0.73 - -
环丙基甲醇 1.89 - -
醋酸苯酯 3.62 2.99 -
间甲酚 - 4.92 3.59
对甲酚 - 5.81 7.93
2-甲氧基-6-甲基苯酚 2.31 - -
2-甲氧基-5-甲基苯酚 3.42 - -
2-甲氧基-4-甲基苯酚 1.03 - -
2-甲基苯并呋喃 1.06 0.72 0.95
3-羟基十二烷酸 1.64 - -
2-甲氧基-4-丙烯基苯酚 8.12 0.83 -
2-甲氧基-4-乙基苯酚 3.91 - -
2-甲氧基-4-乙烯基苯酚 2.67 - -
2,6-二甲氧基苯酚 3.29 - -
3,4-二甲氧基苯酚 1.22 - -
1,2,4-三甲氧基苯 1.54 1.09 -
1,2,3-三甲氧基-5-甲基苯 1.32 - 0.75
2-甲氧基-5-丙烯基苯酚 2.03 - -
5-叔丁基邻苯三酚 2.23 0.89 -
2,6-二甲氧基-4-丙烯基苯酚 5.26 - -
右旋苯丙胺 4.8 3.22 1.24
0.87 4.03 5.89
1-甲基萘 - 1.33 2.62
联苯烯 - 0.87 -
9-十六烯酸 3.92 - -
2,6-二叔丁基对甲基苯酚 0.88 0.51 -
1,2-苯二甲酸二丁酯 1.83 2.04 0.63
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催化重整棕榈壳热解挥发分制备单环芳香化合物
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刘说 1, 2 , 安杨 1 , 寇巍 1, 2 , 张莹莹 1
可再生能源 | 2024,42(4): 427-432
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可再生能源 | 2024, 42(4): 427-432
催化重整棕榈壳热解挥发分制备单环芳香化合物
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刘说1, 2 , 安杨1, 寇巍1, 2, 张莹莹1
作者信息
  • 1 营口理工学院 化学与环境工程学院 辽宁 营口 115014
  • 2 辽宁省化学助剂合成与分离省市共建重点实验室 辽宁 营口 115014
  • 刘说(1977-),女,博士,副教授,研究方向为催化剂的开发与制备及其在能源方面的应用。E-mail:

Catalytic reforming of palm kernel shell pyrolysis volatile matter for single-ring aromatic compounds production
Shuo Liu1, 2 , Yang An1, Wei Kou1, 2, Yingying Zhang1
Affiliations
  • 1 College of Chemistry and Environmental Engineering Yingkou Institute of Technology Yingkou 115014 China
  • 2 Key Laboratory of Chemical Additives Synthesis and Separation of Liaoning Province Yingkou 115014 China
出版时间: 2024-04-20
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在微波辅助加热方式下,分别以半焦(Char)和活性炭(AC)为催化剂,对棕榈壳(PKS)热解挥发分进行催化重整,分析了不同催化剂对产物分布的影响,同时对反应过程中可能发生的反应路径进行分析。结果表明:在Char和AC的作用下,生物油产率减小,气体产物产率增加;与Char相比,AC具有显著的促使生物油向气体转化的催化活性,同时对单环芳香化合物(尤其苯酚)的形成具有更高的选择性;当AC作为催化剂时,单环芳香化合物的相对含量为84.25%; Char和AC催化剂主要促使了脱甲氧基、脱烃基等反应的发生。

生物质热解  /  催化重整  /  炭基催化剂  /  微波辅助加热  /  单环芳香化合物

Catalytic reforming of palm kernel shell (PKS) pyrolysis volatile matter was studied using char (Char) and activated carbon (AC) as catalysts under microwaveassisted heating. The impacts of different carbonbased catalysts on the composition of products were studied. The possible reaction pathways during catalytic reforming of PKS pyrolysis volatile matter under microwaveassisted heating were also investigated. During catalytic reforming of pyrolysis volatile matter, the catalyst promoted the yield of gas product, which led to the decrease of biooil yield. Compared with the Char, AC not only has higher catalytic activity to facilitate the conversion of biooil to gas, but also exhibited better selectivity for the formation of singlering aromatic compounds (especially phenol) in biooil. Using the AC catalyst, the concentrations of the singlering aromatic compounds reached 84.25%. The catalyst mainly promoted the secondary reactions such as demethoxylation reaction and dehydrocarbylation reaction.

biomass pyrolysis  /  catalytic reforming  /  carbon-based catalyst  /  microwave-assisted heating  /  single-ring aromatic compounds
刘说, 安杨, 寇巍, 张莹莹. 催化重整棕榈壳热解挥发分制备单环芳香化合物. 可再生能源, 2024 , 42 (4) : 427 -432 .
Shuo Liu, Yang An, Wei Kou, Yingying Zhang. Catalytic reforming of palm kernel shell pyrolysis volatile matter for single-ring aromatic compounds production[J]. Renewable Energy Resources, 2024 , 42 (4) : 427 -432 .
单环芳香化合物(如苯、苯酚、甲苯、甲酚等) 是重要的化工原料,被广泛应用于制药、材料、有机合成等行业。传统单环芳香化合物主要由化石能源产生,然而,化石能源濒临枯竭,并且单环芳香化合物的生产过程常伴随着污染物的排放。因此, 寻找清洁可再生的原料替代化石能源生产单环芳香化合物势在必行。
木质纤维素类生物质是一类重要的生物质资源,主要由木质素、半纤维素和纤维素构成,具有碳中性、可再生、来源广等特性。木质素与半纤维素通过醚键、酯键等共价键连接形成网络结构, 纤维素与半纤维素主要通过氢键或分子间作用力连接 [ 1 - 3 ] 。构成木质素的 3 种单体(愈创木基结构、 紫丁香基结构、对羟基苯基结构)均具有单环芳香结构, 且 3 种单体间主要通过键能较低的醚键进行连接,在低温条件下易发生裂解反应 [ 4 , 5 ] 。因此, 木质纤维素类生物质代替化石能源制备单环芳香化合物具有明显的化学结构方面的优势。
热解是一种能将木质纤维素类生物质转化为单环芳香化合物的有前景的热化学方法, 但由于生物质化学结构的特点, 导致其在热解过程中发生裂解反应的同时也容易发生副反应, 这为定向制备高附加值单环芳香化合物带来了一定的挑战 [ 6 , 7 ] 。针对挥发分进行催化重整是一种可调控产物品质的途径, 其中催化剂类型是影响催化重整反应过程的重要因素,与金属催化剂、 分子筛催化剂相比,炭基催化剂(如半焦、活性炭等)具有活性高、制备方便、再生简单、成本低等优点 [ 3 , 8 - 11 ] 。Hu D D [ 12 ] 研究了半焦对松木屑热解挥发分的催化重整,发现重整后气体产物的产率和品质均有所提高。杨殿才 [ 13 ] 研究了生物质挥发分催化重整后的产物组成, 发现炭基催化剂可使气体产物中的 ${\mathrm{H}}_{2}$ 含量提高 ${12.4}\%$ 。加热方式是影响催化重整反应的另一重要因素, 近年来, 微波辅助加热技术及其在生物质转化方面的使用引起了人们的高度关注。与常规加热方式 (如电加热、蒸汽加热等)相比,微波辅助加热方式具有更快的升温速率、更均匀的宏观温度场、温度易调控、清洁无污染等优势 [ 14 ] 。因此,利用微波辅助加热方式对生物质挥发分进行催化重整,有利于提高产物的可控性和选择性。
然而, 以往针对催化重整挥发分的研究, 主要以脱除生物油后制备高附加值气体产物(如氢气或合成气等)为目的,致使生物油中潜在的精细化学品(如苯酚等单环芳香化合物)得不到利用。因此, 本文以一种木质纤维素类生物质为原料, 选择半焦和活性炭为催化剂, 在微波辅助加热的条件下对挥发分进行催化重整,重点考察催化剂对产物分布的影响, 同时通过单环芳香化合物种类和含量的变化推断可能的反应路径和机制。
选用的棕榈壳(PKS)取自马来西亚地区, 其工业分析和元素分析见 表 1 。利用粉碎机粉碎并用研钵研磨 PKS,然后在 ${105}^{\circ }\mathrm{C}$ 烘箱中烘 12 h,最后筛取粒径小于 $1\mathrm{\;{mm}}$ 的颗粒作为实验原料。碳化硅(SiC)作为微波吸收剂,在高纯氮气的惰性气氛下,将 $\mathrm{{SiC}}$${800}{}^{\circ }\mathrm{C}$ 的马弗炉中煅烧 $3\mathrm{\;h}$ ,待冷却后筛选粒径小于 $1\mathrm{\;{mm}}$ 的颗粒待用。
称取 ${20}\mathrm{\;g}$ PKS 或活性炭(购于天津登科化学试剂有限公司)置于马弗炉中, 在高纯氮气 (100 $\mathrm{{mL}}/\mathrm{{min}}$ )的氛围下,炉温由室温升高至 ${800}^{\circ }\mathrm{C}$ ,恒温 $3\mathrm{\;h}$ 后停止加热,冷却至室温后,获得半焦催化剂(Char)或活性炭催化剂(AC)。
催化重整实验是在下段热解上段催化重整的两段石英反应器中进行的,实验装置见 图 1
微波炉的输出功率为 ${1000}\mathrm{\;W}$ ,微波炉的结构包括微波发射场、控温系统和测温系统。为了比较催化剂对挥发分的催化重整效果, 分别进行了 PKS 直接热解的空白实验和催化重整 PKS 热解挥发分的实验,具体实验方案如下。
①PKS 直接热解空白实验:称取 ${10}\mathrm{\;g}$ PKS 与 $2\mathrm{\;g}\mathrm{{SiC}}$ 混合均匀,然后放进反应器下段热解区, 热解温度为 ${600}^{\circ }\mathrm{C}$
②催化重整 PKS 热解挥发分实验:称取 ${10}\mathrm{\;g}$ PKS 与 $2\mathrm{\;g}$ SiC 混合均匀,然后添加到反应器的下段热解区,再称取 $5\mathrm{\;g}$ 催化剂(Char 或 AC)添加到反应器的上段催化重整区,重整温度为 ${600}^{\circ }\mathrm{C}$
高纯 ${\mathrm{N}}_{2}$ (流量为 ${400}\mathrm{\;{mL}}/\mathrm{{min}}$ )为载气,实验前通入 ${30}\mathrm{\;{min}}$${\mathrm{N}}_{2}$ 排空反应体系内的空气。在催化重整实验中, 待上层催化重整段达到目标温度并稳定后,下层生物质热解段开始进行热解,热解时间为 ${30}\mathrm{\;{min}}$ 。利用盛有 ${\mathrm{{CH}}}_{2}{\mathrm{{Cl}}}_{2}$ 的冷凝装置收集生物油,然后经蒸馏分离获得生物油并称重,利用气相色谱质谱联用仪(GC-MS)对生物油成分进行分析检测, 检测条件可参照文献[ 4 ]。在反应器冷却后, 利用称量法获得固体产物(热解半焦) 质量,通过差量法得到气体产物质量。气体产物质量、固体产物(热解半焦)产率、生物油产率、气体产物产率的计算式分别为
$ m\text{气体}= {m}_{0}- m\text{半焦}- m\text{生物油}$
$ Y\text{半焦}= \frac{{m}_{\text{半焦 }}}{{m}_{0}}\times {100}\%$
$ Y\text{生物油}= \frac{{m}_{\text{生物油 }}}{{m}_{0}}\times {100}\%$
$ Y\text{气体}= \frac{{m}_{\text{气体 }}}{{m}_{0}}\times {100}\%$
式中: ${m}_{0},{m}_{\text{半焦 }},{m}_{\text{生物油 }},{m}_{\text{气体分别为生物质原料、热}}$ 解半焦、生物油、气体产物的质量, $\mathrm{g};Y$ 半焦, $Y$ 生物油, $Y$ 气体分别为热解半焦、生物油、气体产率,%。
利用美国 Perkine Elmer 公司的 Pyris Diamond TG-DTG SII 型热重分析仪对催化剂反应前后的积碳情况进行分析。实验条件:样品用量为 5~10 $\mathrm{{mg}}$ ,温度从室温升高至 ${800}^{\circ }\mathrm{C}$ 并维持 ${30}\mathrm{\;{min}}$ ,升温速率为 ${10}^{\circ }\mathrm{C}/\mathrm{{min}}$ ,吹扫气为 ${200}\mathrm{\;{mL}}/\mathrm{{min}}$ 的高纯氮气,采样频率为 $2\mathrm{\;s}$
不同条件下的产物产率分布见 图 2 。从 图 2 可以看出:PKS 直接热解的半焦、生物油和气体产率分别为 ${39.13}\%,{17.82}\%$${42.15}\%$ ;与 PKS 直接热解相比,催化重整不影响半焦产率。由于 SiC 是一种化学惰性微波吸收剂,不参与热解反应 [ 15 ] ,因此,半焦产率只与热解温度有关。
与 PKS 直接热解相比, 在 Char 和 AC 的催化作用下, 生物油产率均明显降低, 分别降至 10.16%和 7.25%,而气体产率分别增加至 51.08% 和 53.68%。由此可见, Char 和 AC 均可以将部分生物油催化裂解为气体产物,并且 $\mathrm{{AC}}$ 表现出更高的催化活性。这是由于, 和 Char 相比, AC 具有较大的孔体积和比表面积 ( 表 2 ),较大的孔体积和比表面积不仅有助于活性金属的分布, 也有利于对生物油组分的吸附。催化剂床层延长了生物油分子在体系中的停留时间, 在活性金属的催化作用下,生物油组分被裂解为更多的气体产物 [ 16 ]
生物油是由众多化合物组成的复杂混合物, 目前,研究者主要利用 GC-MS 并结合化合物结构对生物油组分分布进行分析, 每类组分的相对含量通常用 GC-MS 相对峰面积表示 [ 17 , 18 ] 。基于化合物结构的分析, 将生物油中的主要组分分为呋喃类、单环芳香化合物、多环芳香化合物、脂肪烃类、羧酸类、醇类、醛酮类、酯类等。 图 3 为不同条件下生物油的组成。从 图 3 可以看出:当 PKS 直接热解时, 单环芳香化合物是生物油中含量最高的组分, 其含量为 61.41%; 相比 PKS 直接热解, 催化重整后生物油成分发生了明显变化, 催化重整提高了单环芳香化合物在生物油中的占比,在 Char 和 AC 的作用下, 单环芳香化合物含量分别增加至 76.98%和 84.25%,较 PKS 直接热解时的含量分别增高了 15.57%和 22.84%。
图 3 可知, 在催化重整后的生物油中, 羧酸类、醇类、醛酮类、酯类等组分的相对含量均显著降低, 炭基催化剂表现出优异的脱氧性能, 这可能是由于催化剂的添加促进了脱羰和脱羧等脱氧反应的发生 [ 3 ] 。在催化剂的作用下,羧酸类、醇类等含氧化合物经过一系列的脱氧、脱水、环化、芳构化反应会形成单环芳香化合物。糠醛等呋喃类化合物主要来自纤维素和半纤维素的解聚反应 [ 3 ] , 催化重整后其含量也明显降低。Char 和 AC 催化剂不仅催化生物油组分分解为低分子量化合物和气体产物, 也促进了产物间的聚合反应(如乙炔的氢提取加成反应),多环芳烃化合物的相对含量在催化重整后也明显增加。
生物油中主要化合物及其相对含量见 表 3
表 3 可知, 苯酚是 PKS 直接热解生物油中含量最高的化合物(14.91%),其中木质素的裂解可导致酚类化合物的产生 [ 5 , 19 ] 。催化重整后生物油组分的复杂程度显著降低, 生物油组分趋于向结构简单、分子量小的化合物转化, 使生物油产物有一定的轻质化, 其中苯酚的含量显著升高, 在 Char 和 AC 的催化作用下,苯酚的含量分别增加到 48.94%和 67.44%。与 Char 相比, AC 表现出更高的促进苯酚形成的催化作用,因此,以 AC 为催化剂催化重整生物质热解挥发分是一种高效制备单环芳香化合物(如苯酚)的有效途径。
生物油中化合物的聚合反应可能会导致催化剂产生积碳。 图 4 为 Char 和 AC 催化剂在催化重整反应前后的失重率变化。由 图 4 可以看出:在催化重整反应前, Char 和 AC 催化剂的失重率分别为 0.96%和 1.04%,这主要来源于催化剂中水分的失重;在催化重整反应后, Char 和 AC 催化剂的失重率分别为 6.71% 和 7.39%, 这说明催化剂在催化重整过程中产生了积碳。积碳是催化剂活性降低的主要原因,通常可利用气化的方式对活性降低或失活的炭基催化剂进行活化或再生处理。
Char 和 AC 不仅是催化活性较高的催化剂, 也是具有较好微波吸收能力的微波吸收剂 [ 20 ] 。在微波存在的情况下, 由于 Char 和 AC 表面存在活性金属,表面电荷和电子会发生分离和移动,从而促使局部热点效应和瞬态电子空穴对的产生, 最终导致 Char 和 AC 催化剂具有较强的亲电能力 [ 3 , 11 ] 。通过对 PKS 直接热解生物油中主要化合物的结构分析可知, 生物油中主要化合物的结构中包含甲氧基、羟基、烃基等基团。相比之下,甲氧基基团具有较强的供电子能力, 易与形成的电子空穴对相结合,在较高的热解温度下会发生分解反应, 因此, 甲氧基基团的脱除反应可能是主要的重整反应。与 Char 相比, AC 催化剂较大的比表面积有利于活性位点的分布和对甲氧基基团组分的吸附,因此,添加 $\mathrm{{AC}}$ 催化剂时更易发生脱甲氧基反应。
图 5 列出了催化重整 PKS 热解挥发分过程中可能发生的反应路径。从 图 5 可以看出, 在 PKS 直接热解生物油中,2-甲氧基苯酚、2,6-二甲氧基苯酚和 3,4-二甲氧基苯酚是化学结构中侧链仅含有若干个甲氧基基团的酚类化合物, 当这类化合物经过催化剂床层时, 甲氧基会与电子空穴对结合, 由于电子空穴对形成的同时伴随温度较高的热点存在, 由此促进了脱甲氧基反应的发生, 进而导致此类化合物分解形成苯酚自由基、甲基自由基和氧自由基,最终与反应体系中游离的氢自由基反应分别形成苯酚、 ${\mathrm{{CH}}}_{4}$${\mathrm{H}}_{2}\mathrm{O}\left({\mathrm{R}1}\right)$ 。2-甲氧基-4-甲基苯酚、2-甲氧基-5-甲基苯酚、2-甲氧基-6-甲基苯酚等化合物是侧链同时含有若干个甲氧基和烃基的组分, 其会通过甲氧基和烃基的脱除反应产生苯酚自由基、烃基自由基和氧自由基,进而主要转化为苯酚、低碳烃类(如 ${\mathrm{{CH}}}_{4}$ , ${\mathrm{C}}_{2}{\mathrm{H}}_{6},{\mathrm{C}}_{2}{\mathrm{H}}_{4},{\mathrm{C}}_{3}{\mathrm{H}}_{6}$ 等) 和 ${\mathrm{H}}_{2}\mathrm{O}$ ,而苯酚自由基也可能与甲基自由基结合转化生成甲酚(如间甲酚、对甲酚等)(R2)。因此, Char 和 AC 催化脱甲氧基反应和脱烃基反应是苯酚含量升高的主要原因。
单环芳香化合物含量的升高不仅是由于酚类化合物含量的增加,也归因于苯的同系物(如苯、 甲苯等)的产生。一方面,糠醛首先经脱羰反应形成呋喃中间产物, 然后经过脱水反应后与体系中的低碳烃类通过芳构化作用形成苯的同系物 (R3);另一方面,1,2,4-三甲氧基苯,1,2,3-三甲氧基-5-甲基苯等侧链仅包含若干个甲氧基基团的苯的衍生物, 会经过脱甲氧基反应导致苯同系物的产生 (R4)。此外,在较高热点温度的作用下, 苯、甲苯、乙苯、邻二甲苯等苯的同系物会通过聚合反应导致多环芳香化合物的形成(R5)。
①Char 和 AC 催化重整 PKS 热解挥发分后, 生物油产率有所降低,气体产率增加。与 Char 相比, $\mathrm{{AC}}$ 具有更高的催化生物油转化为气体产物和轻质化合物的能力。与 PKS 直接热解相比, 使用 AC 作为催化剂时,生物油产率降低了 10.57%。
②催化重整促使生物油组分趋向于结构简单、分子量小的化合物转化,尤其对苯酚等单环芳香化合物的形成表现出较高选择性。在 Char 和 $\mathrm{{AC}}$ 的催化作用下,苯酚在生物油中的相对含量分别提高了 34.03%和 52.53%。
③在微波辅助加热的条件下,催化剂主要通过促进脱甲氧基反应和脱烃基等反应提高单环芳香化合物的含量。
  • 2022年营口市企业博士双创计划:微波催化重整生物质热解挥发分制苯酚和合成气
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2024年第42卷第4期
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  • 接收时间:2023-09-08
  • 首发时间:2025-07-22
  • 出版时间:2024-04-20
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  • 收稿日期:2023-09-08
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2022年营口市企业博士双创计划:微波催化重整生物质热解挥发分制苯酚和合成气
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    1 营口理工学院 化学与环境工程学院 辽宁 营口 115014
    2 辽宁省化学助剂合成与分离省市共建重点实验室 辽宁 营口 115014
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2种不同金属材料的力学参数

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种数
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Percentage of
total species (%)

Genus
种数
Number of
species
占总种数比例
Percentage of total
species (%)
鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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