Low rank coal mild liquefaction coupled with carbonization and its products
-
摘要: 基于低阶煤温和液化-炭化耦合工艺, 主要研究了390-450 ℃液化温度条件下的产物分布特征, 分析了所得液相产物和半焦的性质。结果表明, 有机液相产率达23.44%-33.26%(干燥无灰基煤为基准), 半焦产率达49.56%-68.72%(干燥无灰基煤为基准); 所得液相产物水含量为1.30%-2.49%, 不含固体颗粒, 有机液相产物的正己烷可溶物含量达98.95%以上; 所得半焦碳含量高达87.87%-93.45%(干燥无灰基), 部分半焦产物具有强黏结性的特点, 并且黏结性与其沥青质含量相关。Abstract: The distribution of products was preliminarily studied based on a process of low rank coal mild liquefaction at 390-450 ℃ coupled with carbonization. The characteristics of liquid product and semi-coke were analyzed. The results showed that the organic liquid product yield is 23.44%-33.26% (daf, coal) and the semi-coke yield is 49.56%-68.72% (daf, coal). The water content of liquid product is 1.30%-2.49%. The n-hexane soluble content of organic liquid product is higher than 98.95% with no solid particles in liquid product. The carbon content of semi-coke obtained is 87.87%-93.45% (daf), some semi-cokes have the characteristics of strong caking property. There is a close correlation between caking property and asphaltene content of semi-coke.
-
图 2 液化温度390-450 ℃条件下液化-炭化产物的产率及液化产生气相产物组分
Figure 2 Yield of products (a) and gas composition (b) of liquefaction and carbonization at the liquefaction temperatures of 390-450 ℃
■: semi-cokes; ●: organic liquid products; ▲: gaseous products from liquefaction; ◆: gaseous products from carbonization; ▼: water; ▽: CH4; □: C2-4; ○: CO2; △: CO
表 1 原煤的工业分析和元素分析
Table 1 Proximate and ultimate analysis of raw coal
Proximate analysis w/% Ultimate analysis w/% H/C
(atomic ratio)Mad Ad Vdaf Cdaf Hdaf Ndaf St, d Oa 1.59 5.63 36.81 84.34 5.17 1.04 0.38 9.07 0.74 a:by difference 表 2 液化温度390-450 ℃条件下所得半焦的工业分析与元素分析
Table 2 Proximate and ultimate analysis of semi-cokes obtained at the liquefaction temperatures of 390-450 ℃
Temperature
t/℃Proximate analysis w/% Ultimate analysis w/% H/C
(atomic ratio)Mad Ad Vdaf Cdaf Hdaf Ndaf St, d Oa 390 0.35 9.39 29.02 87.87 5.16 0.95 0.71 5.31 0.70 410 0.29 10.73 27.71 89.85 5.12 0.91 0.79 3.33 0.68 430 0.27 12.52 25.43 91.81 4.95 0.90 0.88 1.46 0.65 450 0.23 13.42 19.91 93.45 4.04 0.79 0.98 0.74 0.52 a:by difference -
[1] 王建国, 赵晓红.低阶煤清洁高效梯级利用关键技术与示范[J].中国科学院院刊, 2012, 27(3): 382-388. http://www.cnki.com.cn/Article/CJFDTOTAL-KYYX201203019.htmWANG Jian-guo, ZHAO Xiao-hong. Demonstration of key technologies for clean and efficient utilization of low-rank coal[J]. Bull Chin Acad Sci, 2012, 27(3): 382-388. http://www.cnki.com.cn/Article/CJFDTOTAL-KYYX201203019.htm [2] LIU Z, SHI S, LI Y. Coal liquefaction technologies-development in China and challenges in chemical reaction engineering[J]. Chem Eng Sci, 2010, 65(1): 12-17. doi: 10.1016/j.ces.2009.05.014 [3] 郝玉良, 杨建丽, 李允梅, 刘沐鑫, 杨勇.低阶煤温和液化特征分析[J].燃料化学学报, 2012, 40(10): 1153-1160. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract18037.shtmlHAO Yu-liang, YANG Jian-li, LI Yun-mei, LIU Mu-xin, YANG Yong. Study on mild liquefaction of lower rank coal[J]. J Fuel Chem Technol, 2012, 40(10): 1153-1160. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract18037.shtml [4] RIZKIANA J, GUAN G, WIDAYATNO W B, HAO X, WANG Z, ZHANG Z, ABUDULA A. Oil production from mild pyrolysis of low-rank coal in molten salts media[J]. Appl Energy, 2015, 154: 944-950. doi: 10.1016/j.apenergy.2015.05.092 [5] 尚建选, 马宝岐, 张秋民, 沈和平.低阶煤分质转化多联产技术[M].北京:煤炭工业出版社, 2013.SHANG Jian-xuan, MA Bao-qi, ZHANG Qiu-ping, SHEN He-ping. Low Rank Coal Grading Conversion Poly-Generation Technology[M]. Beijing: China Coal Industry Publishing House, 2013. [6] HIRANO K. Outline of NEDOL coal liquefaction process development (pilot plant program)[J]. Fuel Process Technol, 2000, 62(2): 109-118. https://www.researchgate.net/publication/257210953_Outline_of_NEDOL_coal_liquefaction_process_development_pilot_plant_program [7] MIURA K, MAE K, SAKURADA K, HASHIMOTO K. Flash pyrolysis of coal following thermal pretreatment at low temperature[J]. Energy Fuels, 1992, 6: 16-21. doi: 10.1021/ef00031a003 [8] 朱豫飞.煤直接液化与残渣热解联合加工技术[J].煤炭学报, 2013, 38(8): 1454-1458. http://www.cnki.com.cn/Article/CJFDTOTAL-MTXB201308027.htmZHU Yu-fei. Integrated process of direct coal liquefaction and its residue pyrolysis[J]. J China Coal Soc, 2013, 38(8): 1454-1458. http://www.cnki.com.cn/Article/CJFDTOTAL-MTXB201308027.htm [9] CYPRES R, LI B. Effect of pretreatment by various gases on hydropyrolysis of a Belgian coal[J]. Fuel Process Technol, 1988, 20(1/3): 337-347. [10] 吴幼青, 吴诗勇, 高晋生, 李良.一种煤温和液化的工艺方法:中国, ZL201310539685.2[P]. 2014-02-05.WU You-qing, WU Shi-yong, GAO Jin-sheng, LI Liang. A mild coal liquefaction process: CN, 201310539685.2[P]. 2014-02-05. [11] 吴春来.煤炭直接液化[M].北京:化学工业出版社, 2010.WU Chun-lai. Direct Coal Liquefaction[M]. Beijing: Chemistry Industry Press, 2010. [12] 李刚, 凌开成.煤高温快速液化影响因素的研究[J].燃料化学学报, 2009, 37(6): 648-653. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract17506.shtmlLI Gang, LING Kai-cheng. Influencing factors on quick coal liquefaction at high temperature[J]. J Fuel Chem Technol, 2009, 37(6): 648-653. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract17506.shtml [13] WASAKA S, IBARAGI S, HASHIMOTO T, TSUKUI Y, KATSUYAMA T, SHIDONG S. Study on coal liquefaction characteristics of Chinese coals[J]. Fuel, 2002, 81: 1551-1557. doi: 10.1016/S0016-2361(02)00087-X [14] FINSETH D H, CILLO D L, SPRECHER R F, RETCOFSKY H L, LETT R G. Changes in hydrogen utilization with temperature during direct coal liquefaction[J]. Fuel, 1985, 64(12): 1718-1722. doi: 10.1016/0016-2361(85)90399-0 [15] 朱银惠, 郝临山.煤化学[M]. 2版.北京:化学工业出版社, 2011.ZHU Yin-hui, HAO Lin-shan. Coal Chemistry[M]. 2nd ed. Beijing: Chemical Industry Press, 2011. [16] 晏善成, 郑明东, 严文福.配煤技术的发展[J].山东冶金, 2006, 28(5): 31-32. http://www.cnki.com.cn/Article/CJFDTOTAL-SDYJ200605014.htmYAN Shan-cheng, ZHENG Ming-dong, YAN Wen-fu. The development of coal blending technology[J]. Shandong Metall, 2006, 28(5): 31-32. http://www.cnki.com.cn/Article/CJFDTOTAL-SDYJ200605014.htm [17] FLATMAN-FAIRS D P, HARRISON G. Suitability of UK bituminous and Spanish lignitous coals, and their blends for two stage liquefaction[J]. Fuel, 1999, 78(14): 1711-1717. doi: 10.1016/S0016-2361(99)00119-2