三水磷酸钾耦合CaO对樟木粉热解特性及NO_x前体释放特性的影响
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摘要
利用生物质催化热解生产高附加值化学品具有广阔的应用前景,但热解过程中排放的NO_x会对环境造成不利影响。本文利用热重-质谱联用技术(TG-MS)探究樟木粉热解特性及热解过程中主要NO_x前体的释放特性,对比分析Ca O耦合磷酸盐对樟木粉热解过程中NO_x前体生成的反应过程的影响。实验结果显示,随着三水磷酸钾和Ca O的加入,樟木粉热解过程中挥发性产物的释放量有所增加而固相产物的产率有所减少;同时,混合热解过程中生成的主要NO_x前体的离子流强度曲线有所降低。这表明,三水磷酸钾和Ca O的耦合作用,一方面能够改善樟木粉的热解特性,使热解过程更加彻底;另一方面能够有效抑制樟木粉中含氮化合物的一次裂解,延缓NH_3等NO_x前体的生成、减少HCN等NO_x前体的释放。
Using the biomass to produce high value-added chemicals by catalytic pyrolysis has broad application prospects. But the emission of NO_x in pyrolysis process has adverse effect on the environment. The Thermogravimetric Analysis and Mass Spectrometry(TG-MS)were used to investigate the pyrolysis characteristics of camphor powder and the main characteristics of NO_xprecursor release during pyrolysis,and the interconnection effect of Ca O and phosphate on the formation of NO_x precursors during pyrolysis of camphor powder was studied. The experimental results showed that with the addition of Ca O and tripotassium phosphate trihydrate,,the release of volatile products increased while the yield of solid products decreased in the pyrolysis process of camphor wood powder;meanwhile,the ion flow intensity curve of the main NO_x precursors produced decreased during the mixed pyrolysis process. This showed that the interconnection effect of Ca O and tripotassium phosphate trihydrate could improve the pyrolysis of camphor powder and make it more thoroughly; and the interconnection effect of Ca O and tripotassium phosphate trihydrate could effectively restrain the first cleavage of nitrogen-compounds in the camphor powder,and indirectly reduce the production and release of HCN,HNCO,CH_3 CN; the interconnection effect of Ca O and tripotassium phosphate trihydrate could postpone producing NO_x precursors during pyrolysis of camphor powder.
Using the biomass to produce high value-added chemicals by catalytic pyrolysis has broad application prospects. But the emission of NO_x in pyrolysis process has adverse effect on the environment. The Thermogravimetric Analysis and Mass Spectrometry(TG-MS)were used to investigate the pyrolysis characteristics of camphor powder and the main characteristics of NO_xprecursor release during pyrolysis,and the interconnection effect of Ca O and phosphate on the formation of NO_x precursors during pyrolysis of camphor powder was studied. The experimental results showed that with the addition of Ca O and tripotassium phosphate trihydrate,,the release of volatile products increased while the yield of solid products decreased in the pyrolysis process of camphor wood powder;meanwhile,the ion flow intensity curve of the main NO_x precursors produced decreased during the mixed pyrolysis process. This showed that the interconnection effect of Ca O and tripotassium phosphate trihydrate could improve the pyrolysis of camphor powder and make it more thoroughly; and the interconnection effect of Ca O and tripotassium phosphate trihydrate could effectively restrain the first cleavage of nitrogen-compounds in the camphor powder,and indirectly reduce the production and release of HCN,HNCO,CH_3 CN; the interconnection effect of Ca O and tripotassium phosphate trihydrate could postpone producing NO_x precursors during pyrolysis of camphor powder.
引文
[1]张智博,董长青,叶小宁,等.利用固体磷酸催化热解纤维素制备左旋葡萄糖酮[J].化工学报,2014,65(3):912-920.ZHANG Z B,DONG C Q,YE X N,et al.Preparation of levoglucosenone by catalytic pyrolysis of cellulose over solid phosphoric acid[J].CIESC Journal,2014,65(3):912-920.
[2]FU Q,ARGYROPOULOS D S,TILOTTA D C,et al.Understanding the pyrolysis of CCA-treated wood:PartⅠ.Effect of metal ions[J].Journal of Analytical&Applied Pyrolysis,2008,81(1):60-64.
[3]李凯.木质纤维素类生物质负载氨源及钾盐热解实验研究[D].合肥:中国科学技术大学,2016.LI K.Experimental study on the pyrolysis characteristics of lignocellulosic biomass impregnated with ammonia source and potassium salts[D].Hefei:University of Science&Technology China,2016.
[4]任献涛.生物质催化热解实验研究[D].郑州:郑州大学,2012.REN X T.Study on catalytic pyrolysis of biomass[D].Zhengzhou:Zhengzhou University,2012.
[5]ZHANG Z B,QIANG L,YE X N,et al.Selective production of phenolic-rich bio-oil from catalytic fast pyrolysis of biomass:comparison of K3PO4,K2HPO4,and KH2PO4[J].Bio Resources,2014,9(3):4050-4062.
[6]LU Q,ZHANG Z B,YANG X C,et al.Catalytic fast pyrolysis of biomass impregnated with K3PO4 to produce phenolic compounds:analytical Py-GC/MS study[J].Journal of Analytical&Applied Pyrolysis,2013,104(11):139-145.
[7]HANSSON K M,SAMUELSSON J,TULLIN C,et al.Formation of HNCO,HCN,and NH3 from the pyrolysis of bark and nitrogen-containing model compounds[J].Combustion&Flame,2004,137(3):265-277.
[8]陈吟颖,阎维平,王淑娟.生物质热解后氮元素迁移的试验研究[J].锅炉技术,2010,41(5):75-78.CHEN Y Y,YAN W P,WANG S J.Experimental investigation on N migration of biomass pyrolysis[J].Boiler Technology,2010,41(5):75-78.
[9]GIRODS P,ROGAUME Y,DUFOUR A,et al.Low-temperature pyrolysis of wood waste containing urea–formaldehyde resin[J].Renewable Energy,2008,33(4):648-654.
[10]苟进胜,常建民,任学勇.生物质热解过程中氮元素迁移规律研究进展[J].科技导报,2012,30(14):70-74.GOU J S,CHANG J M,REN X Y.A review on the release characterization of nitrogen speicies during biomass pyrolysis[J].Science&Technology Review,2012,30(14):70-74.
[11]张军.微波热解污水污泥过程中氮转化途径及调控策略[D].哈尔滨:哈尔滨工业大学,2013.ZHANG J.Nitrogen conversation and control of nitrogen compounds during microwave pyrolysis of sewage sludge[D].Harbin:Harbin Institute of Technology,2013.
[12]LIU H,ZHANG Q,HU H,et al.Catalytic role of conditioner Ca O in nitrogen transformation during sewage sludge pyrolysis[J].Proceedings of the Combustion Institute,2014,35(3):2759-2766.
[13]孙来芝,张晓东,陈雷,等.Ca O作用下生物质三组分快速热解实验研究[C]//第二届能源转化化学与技术研讨会.太原:2015.SUN L Z,ZHANG X D,CHEN L,et al.Study on rapid pyrolysis of three components of biomass under the action of Ca O[C]//Second Symposium on Energy Conversion Chemistry and Technology.Shanxi,Taiyuan,2015.
[14]HAYHURST A N,LAWRENCE A D.The effect of solid Ca O on the production of NOx,and N2O in fluidized bed combustors:studies using pyridine as a prototypical nitrogenous fuel[J].Combustion&Flame,1996,105(4):511-527.
[15]夏海岸,黄彩燕,肖媛媛,等.磷酸铁催化热解纤维素制备左旋葡萄糖酮[J].广东化工,2013,40(18):15-16.XIA H A,HUANG C Y,XIAO Y Y,et al.Catalytic pyrolysis of cellulose into levoglucosenone using Fe PO4 as catalyst[J].Guangdong Chemical Industry,2013,40(18):15-16.
[16]柏继松.生物质燃烧过程氮和硫的迁移、转化特性研究[D].杭州:浙江大学,2012.BAI J S.Nitrogen and sulfur conversion mechanism during biomass combustion[D].Hangzhou:Zhejiang University,2012.
[17]LI C Z,LI L T.Formation of NOx and SOx precursors during the pyrolysis of coal and biomass.PartⅢ.Further discussion on the formation of HCN and NH3 during pyrolysis[J].Fuel,2000,79(15):1899-1906.
[18]郝菊芳,郭吉兆,谢复炜,等.不同裂解条件对天冬酰胺主要裂解产物的影响[J].分析测试学报,2013,32(5):519-526.HAO J F,GUO J Z,XIE F W,et al.Influences of pyrolysis conditions on the major pyrolytic products of asparagine[J].Journal of Instrumental Analysis,2013,32(5):519-526.
[19]沈洪浩,金晶,林郁郁,等.Ca O对大豆蛋白热解特性及NH3等含氮化合物释放的影响[J].化工进展,2016,35(7):2263-2267.SHEN H H,JIN J,LIN Y Y,et al.Influence of Ca O on soybean protein pyrolysis characteristics and NH3 and other nitrogenous compounds release[J].Chemical Industry and Engineering Progress,2016,35(7):2263-2267.
[20]任强强,赵长遂,梁财,等.麦秆热解过程中氮迁移特性的试验研究[J].中国电机工程学报,2008,28(23):99-104.REN Q Q,ZHAO C S,LIANG C,et al.Experimental research on formation behavior of fuel-nitrogen during wheat straw pyrolysis[J].Proceedings of the CSEE,2008,28(23):99-104.
[2]FU Q,ARGYROPOULOS D S,TILOTTA D C,et al.Understanding the pyrolysis of CCA-treated wood:PartⅠ.Effect of metal ions[J].Journal of Analytical&Applied Pyrolysis,2008,81(1):60-64.
[3]李凯.木质纤维素类生物质负载氨源及钾盐热解实验研究[D].合肥:中国科学技术大学,2016.LI K.Experimental study on the pyrolysis characteristics of lignocellulosic biomass impregnated with ammonia source and potassium salts[D].Hefei:University of Science&Technology China,2016.
[4]任献涛.生物质催化热解实验研究[D].郑州:郑州大学,2012.REN X T.Study on catalytic pyrolysis of biomass[D].Zhengzhou:Zhengzhou University,2012.
[5]ZHANG Z B,QIANG L,YE X N,et al.Selective production of phenolic-rich bio-oil from catalytic fast pyrolysis of biomass:comparison of K3PO4,K2HPO4,and KH2PO4[J].Bio Resources,2014,9(3):4050-4062.
[6]LU Q,ZHANG Z B,YANG X C,et al.Catalytic fast pyrolysis of biomass impregnated with K3PO4 to produce phenolic compounds:analytical Py-GC/MS study[J].Journal of Analytical&Applied Pyrolysis,2013,104(11):139-145.
[7]HANSSON K M,SAMUELSSON J,TULLIN C,et al.Formation of HNCO,HCN,and NH3 from the pyrolysis of bark and nitrogen-containing model compounds[J].Combustion&Flame,2004,137(3):265-277.
[8]陈吟颖,阎维平,王淑娟.生物质热解后氮元素迁移的试验研究[J].锅炉技术,2010,41(5):75-78.CHEN Y Y,YAN W P,WANG S J.Experimental investigation on N migration of biomass pyrolysis[J].Boiler Technology,2010,41(5):75-78.
[9]GIRODS P,ROGAUME Y,DUFOUR A,et al.Low-temperature pyrolysis of wood waste containing urea–formaldehyde resin[J].Renewable Energy,2008,33(4):648-654.
[10]苟进胜,常建民,任学勇.生物质热解过程中氮元素迁移规律研究进展[J].科技导报,2012,30(14):70-74.GOU J S,CHANG J M,REN X Y.A review on the release characterization of nitrogen speicies during biomass pyrolysis[J].Science&Technology Review,2012,30(14):70-74.
[11]张军.微波热解污水污泥过程中氮转化途径及调控策略[D].哈尔滨:哈尔滨工业大学,2013.ZHANG J.Nitrogen conversation and control of nitrogen compounds during microwave pyrolysis of sewage sludge[D].Harbin:Harbin Institute of Technology,2013.
[12]LIU H,ZHANG Q,HU H,et al.Catalytic role of conditioner Ca O in nitrogen transformation during sewage sludge pyrolysis[J].Proceedings of the Combustion Institute,2014,35(3):2759-2766.
[13]孙来芝,张晓东,陈雷,等.Ca O作用下生物质三组分快速热解实验研究[C]//第二届能源转化化学与技术研讨会.太原:2015.SUN L Z,ZHANG X D,CHEN L,et al.Study on rapid pyrolysis of three components of biomass under the action of Ca O[C]//Second Symposium on Energy Conversion Chemistry and Technology.Shanxi,Taiyuan,2015.
[14]HAYHURST A N,LAWRENCE A D.The effect of solid Ca O on the production of NOx,and N2O in fluidized bed combustors:studies using pyridine as a prototypical nitrogenous fuel[J].Combustion&Flame,1996,105(4):511-527.
[15]夏海岸,黄彩燕,肖媛媛,等.磷酸铁催化热解纤维素制备左旋葡萄糖酮[J].广东化工,2013,40(18):15-16.XIA H A,HUANG C Y,XIAO Y Y,et al.Catalytic pyrolysis of cellulose into levoglucosenone using Fe PO4 as catalyst[J].Guangdong Chemical Industry,2013,40(18):15-16.
[16]柏继松.生物质燃烧过程氮和硫的迁移、转化特性研究[D].杭州:浙江大学,2012.BAI J S.Nitrogen and sulfur conversion mechanism during biomass combustion[D].Hangzhou:Zhejiang University,2012.
[17]LI C Z,LI L T.Formation of NOx and SOx precursors during the pyrolysis of coal and biomass.PartⅢ.Further discussion on the formation of HCN and NH3 during pyrolysis[J].Fuel,2000,79(15):1899-1906.
[18]郝菊芳,郭吉兆,谢复炜,等.不同裂解条件对天冬酰胺主要裂解产物的影响[J].分析测试学报,2013,32(5):519-526.HAO J F,GUO J Z,XIE F W,et al.Influences of pyrolysis conditions on the major pyrolytic products of asparagine[J].Journal of Instrumental Analysis,2013,32(5):519-526.
[19]沈洪浩,金晶,林郁郁,等.Ca O对大豆蛋白热解特性及NH3等含氮化合物释放的影响[J].化工进展,2016,35(7):2263-2267.SHEN H H,JIN J,LIN Y Y,et al.Influence of Ca O on soybean protein pyrolysis characteristics and NH3 and other nitrogenous compounds release[J].Chemical Industry and Engineering Progress,2016,35(7):2263-2267.
[20]任强强,赵长遂,梁财,等.麦秆热解过程中氮迁移特性的试验研究[J].中国电机工程学报,2008,28(23):99-104.REN Q Q,ZHAO C S,LIANG C,et al.Experimental research on formation behavior of fuel-nitrogen during wheat straw pyrolysis[J].Proceedings of the CSEE,2008,28(23):99-104.