改性石墨烯对典型生物质热解产物分布作用影响
|
摘要
为解决固体废物处理、处置过程中可再生能源的转化与废物的利用问题,本课题利用热裂解-色谱质谱联用仪(Py-GC/MS)研究分别以氧化石墨烯与石墨烯分散液为原料制备Ni改性石墨烯对生物质热解产物的影响。结果显示:改性石墨烯促进了纤维素热解主要产物1,6-脱水吡喃葡萄糖的生成,随负载量增加效果更明显;C1—C4烃类产率受改性石墨烯影响很大,C5—C8烃类产率略有提高;经改性石墨烯催化木质素热解产物中酚类产率明显提高,经6%Ni-GO催化酚类产率达最大;醇类产率下降,酚类产率上升表明改性石墨烯对羟基的脱除与重组具有一定影响。此外,改性石墨烯还促进了结构较为简单的长碳链产物生成。
To solve the problem occurs during renewable energy conversion and waste utilization in the process of solid waste treatment and disposal, the effect of Ni-modified graphene on pyrolysis products components of typical combustible solid waste were studied, by pyrolysis-chromatography mass spectrometry(Py-GC/MS). Graphene oxide and dispersion liquid of reduced graphene oxide were selected for preparation of catalysts. The results show that, the modified graphene promoted the formation of 1,6-dehydrated glucose, the main product of cellulose pyrolysis, and the effect was more obvious with the increase of the loading amount. The modified grapheme gave higher selectivity toward C1—C4 hydrocarbons and slightly to C5—C8 hydrocarbons. Catalyzed by the modified grapheme, lignin produced more phenol during pyrolysis, and the yield of phenol reached the highest when adding 6%Ni-RGO. The yield of alcohols decreased, while the yield of phenols increased, indicating the modified graphene played a certain role in removal and recombination of hydroxyl groups. In addition, the modified graphene promoted the production of long carbon chain products with simple structure.
To solve the problem occurs during renewable energy conversion and waste utilization in the process of solid waste treatment and disposal, the effect of Ni-modified graphene on pyrolysis products components of typical combustible solid waste were studied, by pyrolysis-chromatography mass spectrometry(Py-GC/MS). Graphene oxide and dispersion liquid of reduced graphene oxide were selected for preparation of catalysts. The results show that, the modified graphene promoted the formation of 1,6-dehydrated glucose, the main product of cellulose pyrolysis, and the effect was more obvious with the increase of the loading amount. The modified grapheme gave higher selectivity toward C1—C4 hydrocarbons and slightly to C5—C8 hydrocarbons. Catalyzed by the modified grapheme, lignin produced more phenol during pyrolysis, and the yield of phenol reached the highest when adding 6%Ni-RGO. The yield of alcohols decreased, while the yield of phenols increased, indicating the modified graphene played a certain role in removal and recombination of hydroxyl groups. In addition, the modified graphene promoted the production of long carbon chain products with simple structure.
引文
[1]KAWAI K,TASAKI T.Revisiting estimates of municipal solid waste generation per capita and their reliability[J].Journal of Material Cycles&Waste Management,2016,18(1):1-13.
[2]ZAMAN A U.Life cycle environmental assessment of municipal solid waste to energy technologies[J].International Journal of Environmental Research,2009,3(3):155-163.
[3]孟光范,孙来芝,陈雷,等.生物质催化热解技术研究进展[J].山东科学,2016,29(4):50-54.MENG Guangfan,SUN Laizhi,CHEN Lei,et al.Research progress of biomass catalytic pyrolysis technology[J].Shandong Science,2016,29(4):50-54.
[4]NONGBE M C,EKOU T,EKOU L,et al.Biodiesel production from palm oil using sulfonated graphene catalyst[J].Renewable Energy,2017,106:135-141.
[5]CHENG J,QIU Y,ZHANG J,et al.Conversion of lipids from wet microalgae into biodiesel using sulfonated graphene oxide catalysts[J].Bioresource Technology,2017,244:569-574.
[6]LIU H B,LIU Z L.Recycling utilization patterns of coal mining waste in China[J].Resources Conservation&Recycling,2010,54(12):1331-1340.
[7]蒋振亚.功能化石墨烯合成及在单糖催化中的应用[D].合肥:中国科技大学,2015:28-56.JIANG Zhenya.Functionalized graphene synthesis and its application in monosaccharide catalysis[D].Hefei:University of Science and Technology of China,2015:28-56.
[8]宋焕萌.金属氧化物及其负载石墨烯催化生物质制备5-羟甲基糠醛[D].天津:天津工业大学,2015:47-54.SONG Huanmeng.Metal oxides and their support for graphene-catalyzed biomass preparation of 5-hydroxymethylfurfural[D].Tianjin:Tianjin Polytechnic University,2015:47-54.
[9]李云霞,魏子栋,赵巧玲,等.石墨烯负载Pt催化剂的制备及催化氧还原性能[J].物理化学学报,2011,27(4):858-862.LI Yunxia,WEI Zidong,ZHAO Qiaoling,et al.Preparation of graphene-supported Pt catalysts and catalytic oxygen reduction performance[J].Journal of Physical Chemistry,2011,27(4):858-862.
[10]朱宏文,段正康,张蕾,等.氧化石墨烯的制备及结构研究进展[J].材料科学与工艺,2017,25(6):82-88.ZHU Hongwen,DUAN Zhengkang,ZHANG Lei,et al.Progress in preparation and structure of graphene oxide[J].Material Science and Technology,2017,25(6):82-88.
[11]WU Z S,REN W,GAO L,et al.Synthesis of high quality graphene with a pre-determined number of layers[J].Carbon,2009,47(2):493-499.
[12]李林.热解生产1,6-脱水-β-D-吡喃葡萄糖的研究[D].北京:中国科学院,2004:34-35.LI Lin.Pyrolytic production of 1,6-anhydro-β-D-glucopyranose[D].Key Laboratory of Environmental Biotechnology,2004:34-35.
[13]闫伦靖,孔晓俊,白永辉,等.Mo和Ni改性的HZSM-5催化剂对煤热解焦油的改质[J].燃料化学学报,2016,44(1):30-36.YAN Lunjing,KONG Xiaojun,BAI Yonghui,et al.Catalytic upgrading of gaseous tar from coal pyrolysis over Mo and Ni-modified HZSM-5[J].Journal of Fuel Chemistry and Technology,2016,44(1):30-36.
[2]ZAMAN A U.Life cycle environmental assessment of municipal solid waste to energy technologies[J].International Journal of Environmental Research,2009,3(3):155-163.
[3]孟光范,孙来芝,陈雷,等.生物质催化热解技术研究进展[J].山东科学,2016,29(4):50-54.MENG Guangfan,SUN Laizhi,CHEN Lei,et al.Research progress of biomass catalytic pyrolysis technology[J].Shandong Science,2016,29(4):50-54.
[4]NONGBE M C,EKOU T,EKOU L,et al.Biodiesel production from palm oil using sulfonated graphene catalyst[J].Renewable Energy,2017,106:135-141.
[5]CHENG J,QIU Y,ZHANG J,et al.Conversion of lipids from wet microalgae into biodiesel using sulfonated graphene oxide catalysts[J].Bioresource Technology,2017,244:569-574.
[6]LIU H B,LIU Z L.Recycling utilization patterns of coal mining waste in China[J].Resources Conservation&Recycling,2010,54(12):1331-1340.
[7]蒋振亚.功能化石墨烯合成及在单糖催化中的应用[D].合肥:中国科技大学,2015:28-56.JIANG Zhenya.Functionalized graphene synthesis and its application in monosaccharide catalysis[D].Hefei:University of Science and Technology of China,2015:28-56.
[8]宋焕萌.金属氧化物及其负载石墨烯催化生物质制备5-羟甲基糠醛[D].天津:天津工业大学,2015:47-54.SONG Huanmeng.Metal oxides and their support for graphene-catalyzed biomass preparation of 5-hydroxymethylfurfural[D].Tianjin:Tianjin Polytechnic University,2015:47-54.
[9]李云霞,魏子栋,赵巧玲,等.石墨烯负载Pt催化剂的制备及催化氧还原性能[J].物理化学学报,2011,27(4):858-862.LI Yunxia,WEI Zidong,ZHAO Qiaoling,et al.Preparation of graphene-supported Pt catalysts and catalytic oxygen reduction performance[J].Journal of Physical Chemistry,2011,27(4):858-862.
[10]朱宏文,段正康,张蕾,等.氧化石墨烯的制备及结构研究进展[J].材料科学与工艺,2017,25(6):82-88.ZHU Hongwen,DUAN Zhengkang,ZHANG Lei,et al.Progress in preparation and structure of graphene oxide[J].Material Science and Technology,2017,25(6):82-88.
[11]WU Z S,REN W,GAO L,et al.Synthesis of high quality graphene with a pre-determined number of layers[J].Carbon,2009,47(2):493-499.
[12]李林.热解生产1,6-脱水-β-D-吡喃葡萄糖的研究[D].北京:中国科学院,2004:34-35.LI Lin.Pyrolytic production of 1,6-anhydro-β-D-glucopyranose[D].Key Laboratory of Environmental Biotechnology,2004:34-35.
[13]闫伦靖,孔晓俊,白永辉,等.Mo和Ni改性的HZSM-5催化剂对煤热解焦油的改质[J].燃料化学学报,2016,44(1):30-36.YAN Lunjing,KONG Xiaojun,BAI Yonghui,et al.Catalytic upgrading of gaseous tar from coal pyrolysis over Mo and Ni-modified HZSM-5[J].Journal of Fuel Chemistry and Technology,2016,44(1):30-36.