生物质热解过程中内在矿物质的作用
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摘要
本文借助水洗和酸洗预处理及纤维组成的定量分析等方法,以稻草和白松为研究对象,细致研究了生物质的固定床热解过程及内部矿物质对其热解产物分布、产物组成和纤维组成分解特性的影响。内容主要包括：
首先,考察稻草、水洗稻草和酸洗稻草的矿物质及有机组成差异发现,水洗可以洗去稻草内部大部分的碱金属(K和Na),酸洗可以基本完全除去碱金属和碱土金属(K、Na、Ca和Mg),水洗和酸洗均可造成稻草中大量的中性溶解物(NDS)的明显溶出,但对于半纤维素、纤维素和木质素几乎没有影响。对于三种稻草的热解产物产率和组成分析发现,矿物质金属和有机结构的共同影响下,洗涤后稻草热解产生较多的液体产物,较少的气体产物；固体焦炭的产率变化随温度有所不同。同时,研究发现稻草内部矿物质对NDS、半纤维素、纤维素和木质素的分解有一定的催化作用,而在275℃的低温下Ca对NDS和半纤维素的分解则有一定的阻碍作用。生物质炭的组成分析显示,炭并不是由单一基质组成的,即使在700℃热解产生的炭也包括一定量的NDS、“纤维素”和“木质素”。
其次,分析比较白松和稻草的热解焦炭组成,结果验证了稻草内部矿物质对半纤维素、“纤维素”以及“木质素”组分的催化作用。同时发现生物质热解过程中低温段焦炭的富集主要来自于NDS的分解；纤维素低温段热解后主要产生气体和焦油,对焦炭的贡献很小。
This paper focused on the pyrolysis process of biomass on the fixed-bed reactor and the effect of internal inorganic matters on the products distribution, products compositions as well as on the decomposition of each fiber constituent in biomass. Rice straw and pine wood (PW) were selected and analyzed by using water or acid washing method, fiber constituent analyses and so on. This paper included the following parts:
Firstly, there were evident differences in internal metals and organic matters between rice straw (RS), water-washed rice straw (WRS) and acid-washed rice straw (ARS). It was found that water removed most alkali metals (K and Na); whereas acid removed more alkali and alkali earth metals (K, Na, Ca and Mg). Either the water washing or the acid washing removed a portion of NDS but virtually unaffected the constituents of hemi cellulose, cellulose and lignin in RS. The differences in the product distribution and constituents between RS, WRS and ARS were influenced by both the internal mineral metals and the changed organic matter. Either WRS or ARS produced slightly more liquid product and less gaseous product than RS. The differences in the char yield between RS, WRS and ARS were changed with pyrolysis temperature. Meanwhile, it was revealed that the internal metals played a catalytic role in the promoted decomposition of each constituent of NDS, hemicellulose, cellulose and lignin in whole RS. However, calcium in RS and WRS appeared to prevent NDS and hemicellulose from decomposition at a lower temperature of 275℃. A conclusion also could be drawn that the char product was not a single carbon material. There existed NDS, "cellulose" and "lignin" in the chars.
Secondly, the fiber constituents of chars obtained from RS were quite different from those from PW, which successfully proved the important effect of internal metals on the decomposition of hemicellulose, "cellulose" and "lignin". This paper also proved that the char obtained at low temperature mainly came from the decomposition of NDS, other than cellulose.
首先,考察稻草、水洗稻草和酸洗稻草的矿物质及有机组成差异发现,水洗可以洗去稻草内部大部分的碱金属(K和Na),酸洗可以基本完全除去碱金属和碱土金属(K、Na、Ca和Mg),水洗和酸洗均可造成稻草中大量的中性溶解物(NDS)的明显溶出,但对于半纤维素、纤维素和木质素几乎没有影响。对于三种稻草的热解产物产率和组成分析发现,矿物质金属和有机结构的共同影响下,洗涤后稻草热解产生较多的液体产物,较少的气体产物；固体焦炭的产率变化随温度有所不同。同时,研究发现稻草内部矿物质对NDS、半纤维素、纤维素和木质素的分解有一定的催化作用,而在275℃的低温下Ca对NDS和半纤维素的分解则有一定的阻碍作用。生物质炭的组成分析显示,炭并不是由单一基质组成的,即使在700℃热解产生的炭也包括一定量的NDS、“纤维素”和“木质素”。
其次,分析比较白松和稻草的热解焦炭组成,结果验证了稻草内部矿物质对半纤维素、“纤维素”以及“木质素”组分的催化作用。同时发现生物质热解过程中低温段焦炭的富集主要来自于NDS的分解；纤维素低温段热解后主要产生气体和焦油,对焦炭的贡献很小。
This paper focused on the pyrolysis process of biomass on the fixed-bed reactor and the effect of internal inorganic matters on the products distribution, products compositions as well as on the decomposition of each fiber constituent in biomass. Rice straw and pine wood (PW) were selected and analyzed by using water or acid washing method, fiber constituent analyses and so on. This paper included the following parts:
Firstly, there were evident differences in internal metals and organic matters between rice straw (RS), water-washed rice straw (WRS) and acid-washed rice straw (ARS). It was found that water removed most alkali metals (K and Na); whereas acid removed more alkali and alkali earth metals (K, Na, Ca and Mg). Either the water washing or the acid washing removed a portion of NDS but virtually unaffected the constituents of hemi cellulose, cellulose and lignin in RS. The differences in the product distribution and constituents between RS, WRS and ARS were influenced by both the internal mineral metals and the changed organic matter. Either WRS or ARS produced slightly more liquid product and less gaseous product than RS. The differences in the char yield between RS, WRS and ARS were changed with pyrolysis temperature. Meanwhile, it was revealed that the internal metals played a catalytic role in the promoted decomposition of each constituent of NDS, hemicellulose, cellulose and lignin in whole RS. However, calcium in RS and WRS appeared to prevent NDS and hemicellulose from decomposition at a lower temperature of 275℃. A conclusion also could be drawn that the char product was not a single carbon material. There existed NDS, "cellulose" and "lignin" in the chars.
Secondly, the fiber constituents of chars obtained from RS were quite different from those from PW, which successfully proved the important effect of internal metals on the decomposition of hemicellulose, "cellulose" and "lignin". This paper also proved that the char obtained at low temperature mainly came from the decomposition of NDS, other than cellulose.
引文
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[2]Bridgwater AV. Production of high grade fuels and chemicals from catalytic pyrolysis of biomass [J]. Catalysis Today 1996; 29:285-295.
[3]Varhegyi G, Antal MJ, Jakab E, Szabo P. Kinetic modeling of biomass pyrolysis [J]. Journal of Analytical Applied Pyrolysis 1997; 42:73-87.
[4]Mansaray KG and Ghaly AE. Thermal degradation of rice husk in nitrogen atmosphere [J]. Bioresource Technology 1998; 65:13-20.
[5]Demirbas A, Arin G. An overview of biomass pyroysis [J]. Energy Sources 2002; 24: 471-482.
[6]Czernik S and Bridgwater AV. Overview of applications of biomass fast pyrolysis oil [J]. Energy & Fuels 2004; 18:590-598.
[7]Yaman S. Pyrolysis of biomass to produce fuels and chemical feedstocks [J]. Energy Conversion and Management 2004; 45:651-671.
[8]Worasuwannarak N, Sonobe T, Tanthapanichakoon W. Pyrolysis behaviors of rice straw, rice husk, and corncob by TG-MS technique [J]. Journal of Analytical Applied Pyrolysis 2007; 78:265-271.
[9]Bridgwater AV. Review of fast pyrolysis of biomass and product upgrading [J]. Biomass & Bioenergy 2011:1-27.
[10]杨海平,陈汉平,王贤华,辛芬,张世红,郑楚光.生物质热解研究的进展[J].煤气与热力2006；26：18-22.
[11]Wang ZY, Wang F, Cao JQ, Wang J. Pyrolysis of pine wood in a slowly heating fixed-bed reactor:comparison of using potassium carbonate and calcium hydroxide as catalysts [J]. Fuel processing technology 2009; 160:8-15.
[12]Patwardhan PR, Satrio JA, Brown RC, Shanks BH. Influence of inorganic salts on the primary pyrolysis products of cellulose [J]. Bioresource Technology 2010; 101: 4646-4655.
[13]Yang HP, Yan R, Chen HP, Zheng CG, Lee DH, Liang DT. Influence of mineral matter on pyrolysis of palm oil wastes [J]. Combustion and Flame 2006; 146:605-611.
[14]王震亚,曹建勤,鹿丹,王杰.碱金属催化剂对生物质裂解的影响[J].化学工程于生物化工年会2008；11.
[15]Sun Q, Yu S, Wang FC, Wang J. Decomposition and gasification of pyrolysis volatiles from pine wood through a bed of hot char [J]. Fuel 2010;90:1041-1048.
[16]孙青松,于桑,曹建勤,王杰.松木热解焦油的炭催化二次裂解特性[J].生物产业技术2009；87-92.
[17]Gilbert P, Ryu C, Sharifi V, Swithenbank J. Tar reduction in pyrolysis vapours from biomass over a hot char bed [J]. Bioresource Technology 2009; 100:6045-6051.
[18]于飞,岳宝华,汪学广,耿淑华,鲁雄刚,丁伟中Ni/Ce-ZeO2/γ-Al2O3催化剂上高温焦炉煤气中焦油组分的常压加氢裂解[J].催化学报2009；30：690-696.
[19]Miyazawa T, Kimura T, Nishikawa J, Kado S, Kunimori K, Tomushige K. Catalytic performance of supported Ni catalysts in partial oxidation and steam reforming of tar derived from the pyrolysis of wood biomass [J]. Catalysis Today 2006; 115:254-262.
[20]Liao C, Wu C, Yan Y, Huang H. Chemical elemental characteristics of biomass fuels in China [J]. Biomass Bioenergy 2004; 27:119-130.
[21]马隆龙,吴创之,孙立.生物质气化技术及应用[M].北京：化学工业出版社,2003.
[22]程备久等.生物质能学[M].北京：化学工业出版社,2008.
[23]Mok WS, Antal MJ, Szabo P, Varhegyi G, Zelei B. Formation of charcoal from biomass in a sealed reactor[J]. Industrial & Engineering Chemistry Research 1992; 31: 1162-1166.
[24]刘世锋,王述洋,白雪双.生物质闪速热解技术及生物油的应用.林业劳动安全2006：19：29-33.
[25]袁振宏,吴创之,马隆龙等.生物质能利用原理与技术[M].北京：化学工业出版社,2005.
[26]翟秀静,刘奎仁,韩庆.新能源技术[M].北京：化学工业出版社,2005.
[27]Orio A, J Corello J, Narvaez I. Proceedings of conference on developments on thermochemical biomass conversion [J]. Blackie academic& Profession:1996.
[28]谭洪,王树荣,骆仲泱等.金属盐对生物质热解特性影响实验研究[J].工程热物理学报,2005；26：742-744.
[29]Jensen A, Dam-Johansen K, Wojtowicz MA, Serio MA. TG-FTIR study of the influence of potassium chloride on wheat straw pyrolysis [J]. Energy Fuels 1998; 12: 929-938.
[30]Nowakowski DJ, Jones JM, Brydson RMD, Ross AB. Potassium catalysis in the pyrolysis behavior of short rotation willow coppice[J]. Fuel 2007; 86:2389-2402.
[31]Kleen M, Gellerstedt G. Influence of inorganic species on the formation of polysaccharide and lignin degradation products in the analytical pyrolysis of pulps [J]. Journal of Analytical Applied Pyrolysis 1995; 35:15-41.
[32]Raveendran K, Ganesh A, Khilar KC. Influence of mineral matter on biomass pyrolysis characteristics [J]. Fuel 1995; 74:1812-1822.
[33]王贤华,陈汉平,王静,辛芬.无机矿物质盐对生物质热解特性的影响[J].燃料化学学报2008；36：679-683.
[34]Hosoya T, Kawamoto H, Saka S. Influence of inorganic matter on wood pyrolysis at gasification temperature [J]. Journal of Wood Science 2007; 53:351-357.
[35]Vamvuka D, Troulinos S, Kastanaki E. The effect of mineral matter on the physical and chemical activation of low rank coal and biomass materials [J]. Fuel 2006; 85: 1763-1771.
[36]Hwang B, Obst JR. Basic studies on the pyrolysis of lignin compounds. International Conference on Forest Products 2003:1165-1170.
[37]Sharma RK, Wooten JB, Baliga VL, Lin XH, Chan WG, Hajaligol MR. Characterization of chars from pyrolysis of lignin [J]. Fuel 2004; 83:1469-1482.
[38]Fahmi R, Bridgwater AV, Donnison I, Yates N, Jones JM. The effect of lignin and inorganic species in biomass on pyrolysis oil yields, quality and stability [J]. Fuel 2008; 87:1230-1240.
[39]Yang HP, Yan R, Chen HP, Lee AH, Zheng CG. Characteristics of hemicellulose, cellulose and lignin pyrolysis [J]. Fuel 2007; 86:1781-1788.
[40]陈永辉,蔡海燕.纤维素和木质素含量对稻草、锯木热解及燃烧特性的影响[J].新能源与技术2008：38-42.
[41]Yang HP, Yan R, Chen HP, Zheng CG, Lee DH, Liang DT. In-depth investigation of biomass pyrolysis based on three major components:hemicellulose, cellulose and lignin [J]. Energy& Fuels 2006; 20:388-393.
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