谢晶^1,2,3,舒歌平^2,3,高山松^2,3,王洪学^2,3,李剑宇¹,卢晗锋¹,陈银飞¹

• 1:浙江工业大学 化学工程学院，浙江 杭州 310014
• 2:中国神华煤制油化工有限公司上海研究院，上海 201108
• 3:煤直接液化国家重点工程实验室，上海 201108

摘要(Abstract)：

为了提高钼基催化剂的煤直接液化催化性能和工业应用的可能性，研究了含钼化合物粉体催化剂性质与煤直接催化性能的关系，制备出高稳定性的三氧化钼油浆催化剂和两种高活性的钼铁复合催化剂。结果表明，含钼化合物的催化活性主要与分散性和晶粒度相关，纳米级三氧化钼活性高，微米级含钼化合物活性低；通过高速剪切和分散剂的锚固作用，纳米三氧化钼粉体能更好地分散于溶剂油中并保持长时间稳定，催化活性也得到显著提高；浸渍法和共沉淀法制备的钼铁复合催化剂中的钼元素处于高度分散状态，钼铁复合催化剂在煤直接液化中展现出协同催化作用，相比Fe催化剂油产率提高了4.5%~5%。

关键词(KeyWords)： 煤直接液化;钼催化剂;粒度;分散性;油产率

Abstract:

Keywords:

基金项目(Foundation): 国家重点研发计划（2016YFB0600303）；国家能源集团科技创新（GJNY-19-21）。

作者(Author): 谢晶^1,2,3,舒歌平^2,3,高山松^2,3,王洪学^2,3,李剑宇¹,卢晗锋¹,陈银飞¹

DOI: 10.3969/j.issn.1003-9015.2020.05.012

参考文献(References)：

• [1] 舒歌平. 神华煤直接液化工艺开发历程及其意义[J]. 神华科技, 2009, 27(1):78-82. SHU G P. Development history and its significance of Shenhua coal liquefacion[J]. Shenhua Science and Technology, 2009, 7(1):78-82.
  [2] 刘振宇. 煤直接液化技术发展的化学脉络及化学工程挑战[J]. 化工进展, 2010, 2(2):193-197. LIU Z Y. Principal chemistry and chemical engineering challenges in direct coal liquefaction technology[J]. Chemical Industry and Engineering Progress, 2010, 2(2):193-197.
  [3] SHUI H F, CAI Z C, XU C. Recent advances in direct coal liquefaction[J]. Energies, 2010, 3(2):155-170.
  [4] 李军芳, 赵学社, 李文博, 等. 煤直接液化油航空煤油馏分的性质与组分分析[J]. 煤炭转化, 2013, 36(4):32-34 LI J F, ZHAO X S, LI W B, et al. Property of constituents analysis of coal direct liquefaction aviation kerosene distillate[J]. Coal Conversion, 2013, 36(4):32-34.
  [5] LI X, HU S, JIN L, et al. Role of iron-based catalyst and hydrogen transfer in direct coal liquefaction[J]. Energy & Fuels, 2008, 22(2):1126-1129.
  [6] DERBYSHIRE F. Role of catalysis in coal liquefaction research and development[J]. Energy & Fuels, 1989, 3(3):273-277.
  [7] 吴艳, 赵鹏, 毛学锋. 煤液化条件下铁系催化剂的相变[J]. 煤炭学报, 2018, 43(5):1448-1454. WU Y, ZHAO P, MAO X F. Phase transformation of iron-based catalyst at coal liquefaction[J]. Journal of China Coal Society, 2018, 43(5):1448-1454.
  [8] KANEKO T, TAZAWA K, KOYAMA T, et al. Transformation of iron catalyst to the active phase in coal liquefaction[J]. Energy & Fuels, 1998, 12:897-904.
  [9] ANDERSON R R, BOCKRATH B C. Effect of sulphur on coal liquefaction in the presence of dispersed iron or molybdenum catalysts[J]. Fuel, 1984, 63(3):329-333.
  [10] 李克健, 吴秀章, 舒歌平. 煤直接液化技术在中国的发展[J]. 洁净煤技术, 2014, 20(2):39-43. LI K J, WU X Z, SHU G P. Development of direct coal liquefaction technology in China[J]. Clean Coal Technology, 2014, 20(2):39-43.
  [11] 王村彦, 朱晓苏, 吴春来. 煤直接液化催化剂及其高分散化[J]. 煤炭转化. 1998, 21(2):14-16. WANG C Y, ZHU X S, WU C L. Catalyst for direct coal liquefaction and its high dispersing[J]. Coal Conversion, 1998, 21(2):14-16.
  [12] SUZUKI T. Development of highly dispersed coal liquefaction catalysts[J]. Energy & Fuels, 1994, 8(2):341-347.
  [13] HIRSCHON A S, JR R B W. Highly dispersed coal liquefaction catalysts[J]. Fuel, 1992, 71(9):1025-1031.
  [14] XIE J, LU H F, SHU G P, et al. The relationship between the microstructures and catalytic behaviors of iron-oxygen precursors during direct coal liquefaction[J]. Chinese Journal of Catalysis, 2018, 39(4):857-866.
  [15] MOCHIDA I, SAKANISHI K, SUZUKI N, et al. Progresses of coal liquefaction catalysts in Japan[J]. Catalysis Surveys from Japan, 1998, 2(1):17-30.
  [16] 谢晶, 卢晗锋, 陈银飞, 等. 助剂改性FeOOH及其煤直接液化催化活性[J]. 化工学报. 2016, 67(5):1892-1899. XIE J, LU H F, CHEN Y F, et al. Promoters modified feooh and their catalytic performances for direct coal liquefaction[J]. CIESC Journal, 2016, 67(5):1892-1899.
  [17] ZHAO J, FENG Z, HUGGINS F E, et al. Binary iron oxide catalysts for direct coal liquefaction[J]. Energy & Fuels, 1994, 8(1):38-43.
  [18] EKLUND P C, STENCEL J M, BI X X, et al. Ultrafine iron catalysts for coal dissolution[J]. Preprints of Papers-American Chemical Society, Division of Fuel Chemistry, 1991, 36(2):551-559.
  [19] LINEHAN J C, BEAN R M, MATSON D W, et al. New synthetic methods for the production of ultra-fine coal liquefaction catalysts[J]. Preprints of Papers-American Chemical Society, Division of Fuel Chemistry, 1992, 37(1):488-496.
  [20] 周晓东, 马凤云, 刘景梅, 等. 包覆型Fe基纳米催化剂制备及对低阶煤直接液化的影响[J]. 煤炭学报, 2018, 43(10):2895-2902. ZHOU X D, MA F Y, LIU J M, et al. Effect of coated Fe₂O₃ nanocatalysts on direct liquefaction of lower-rank coal[J]. Journal of China Coal Society, 2018, 43(10):2895-2902.
  [21] BURGESS C E, ARTOK L, SCHOBET H H. Effect of molybdenum sulfide catalyst on the mechanism of coal liquefaction[J]. Preprints of Papers-American Chemical Society, Division of Fuel Chemistry, 1991, 36(2):462-469.
  [22] INUKAI Y. Hydroliquefaction of illinois no.6 coal with petroleum atmospheric residue using oil-soluble molybdenum catalyst[J]. Fuel Process Technology, 1995, 43(2):157-167.
  [23] WARZINSKI R P, BOCKRATH B C. Molybdenum hexacarbonyl as a catalyst precursor for solvent-free direct coal liquefaction[J]. Energy & Fuels, 1996, 10(3):612-622.
  [24] HU H, BAI J, GUO S, et al. Coal liquefaction with in situ impregnated Fe₂(MoS₄)₃ bimetallic catalyst. Fuel, 2002, 81(11/12):1521-1524.
  [25] 艾军, 黄澎, 谷小会, 等. 钼系催化剂对神东煤直接液化的影响[J]. 洁净煤技术, 2011, 17(2):38-40. AI J, HUANG P, GU X H, et al. Effect of molybdenum catalysts on direct shendong coal liquefaction[J]. Clean Coal Technology, 2011, 17(2):38-40.
  [26] ZHAO J M, FENG Z, HUGGINS F E, et al. Role of molybdenum at the iron oxide surface[J]. Journal of Catalysis, 1994, 148(1):194-197.
  [27] 岳国, 蒋庆哲, 宋昭峥. 煤直接液化高分散性催化剂的研究进展[J]. 化工进展, 2008, 27(s1):223-228. YUE G, JIANG Q Z, SONG Z Z. Progress of highly dispersed catalysts for direct coal liquefaction[J]. Chemical Industry and Engineering Progress, 2008, 27(s1):223-228.