新型镍基镁渣催化重整松木热解挥发分焦油析出特性研究

doi:10.11949/0438-1157.20190269

摘要/Abstract

摘要：

采用过量浸渍法制备了镍基镁渣催化剂，并在小型气流床气化炉上开展了松木热解挥发分的催化重整研究。评估了煅烧/催化温度、镍含量和水碳比对焦油组分的影响，同时在不同煅烧/催化温度下与Ni/γ-Al₂O₃催化剂进行了裂解焦油性能的对比。采用比表面积测试（BET）、X射线衍射（XRD）、扫描电镜（SEM）和透射电镜（TEM）对催化剂进行了表征。结果表明，当镍含量为3%，煅烧/催化温度为800℃，水碳比为0.5时，镍基镁渣催化剂表现出最优异的催化裂解焦油能力：大幅度降低了重质多环芳烃的相对含量，并且焦油转化率达到95.69%，同时焦油露点温度降至40.2℃。XRD结果表明，Ni、Fe、Ca、Mg相互作用可以形成多种活性中心，进而协同提高催化剂活性。

关键词: 生物质, 热解, 焦油, 催化作用, 镍, 镁渣

Abstract:

The nickel-based magnesium slag catalyst was prepared by excess impregnation method, and the catalytic reforming of pine pyrolysis volatiles was carried out on a small entrained flow gasifier. The effects of calcination/catalytic temperature, Ni content and steam to carbon (S/C) ratio on the catalytic performance were investigated. Moreover, the tar creaking capability of Ni/MS catalyst and Ni/γ-Al₂O₃catalyst were explored under different calcination/catalytic temperatures. The catalysts were characterized by BET, XRD, SEM and TEM. The results indicated that the best tar conversion (95.69%) and the significant reduction in the relative content of heavy PAHs as well as the tar dew point of 40.2℃ were obtained over Ni/MS catalyst under the conditions of Ni content 3%, calcination/catalytic temperature 800℃, S/C = 0.5. Results from XRD showed that the interactions of Ni, Fe, Ca, and Mg formed multiple active centers to display synergistic catalytic effects, thereby jointly promoting catalyst activity.

Key words: biomass, pyrolysis, tar, catalysis, nickel, magnesium slag

中图分类号:

TK 6

刘阳, 刘捷成, 俞海淼, 陈德珍. 新型镍基镁渣催化重整松木热解挥发分焦油析出特性研究[J]. 化工学报, 2019, 70(8): 2991-2999.

Yang LIU, Jiecheng LIU, Haimiao YU, Dezhen CHEN. Characteristics of tar formation during catalytic reforming of pyrolysis volatile from pine saw dust over novel Ni-based magnesium slag catalyst[J]. CIESC Journal, 2019, 70(8): 2991-2999.

图/表 12

表1 松木锯屑的工业分析与元素分析

Table 1 Component analysis of pine sawdust

生物质原料	工业分析（质量分数）/%				元素分析（质量分数）/%					Q _LHV/(MJ/kg)
生物质原料	V_ad	A_ad	FC_ad	M_ad	C_ad	H_ad	N_ad	O_ad	S_ad	Q _LHV/(MJ/kg)
松木锯屑	76.16	0.26	14.07	9.51	46.42	4.38	0.30	38.97	0.16	17.91

表2 镁渣的元素组成（质量分数）

Table 2 Main chemical composition of magnesium

Ca	Fe	Mg	Si	Al	Mn	Ti	S
43.62	4.27	3.77	11.28	0.59	0.56	0.34	0.02

图1 两段式反应系统

Fig.1 Schematic diagram of experimental system

图2 煅烧/催化温度对焦油组分和焦油转化率的影响（镍含量为3%，水碳比为0）

Fig.2 Effect of calcination/catalytic temperature on tar composition and tar conversion (Ni content 3%, S/C = 0)

表3 不同煅烧/催化温度下的多环芳烃组成及焦油露点温度

Table 3 Effect of temperature on PAH composition categorized by molecular weight and tar dew point

催化剂	轻质多环芳烃(area)/%	重质多环芳烃(area)/%	焦油露点温度 ^① /℃
空白-700	29.88	2.03	110.1
空白-800	29.08	1.88	98.2
空白-900	28.41	2.66	111.1
3Ni/γ-Al₂O₃-700	27.14	2.22	109.2
3Ni/γ-Al₂O₃-800	12.26	0.29	51.3
3Ni/γ-Al₂O₃-900	53.76	3.02	85.1
3Ni/MS-700	25.63	0.92	78.4
3Ni/MS-800	10.58	0.12	42.4
3Ni/MS-900	52.53	1.32	72.6

图3 镍含量对焦油组分和焦油转化率的影响（煅烧/催化温度为800℃，水碳比为0）

Fig.3 Effect of Ni content on tar composition and tar conversion (calcination/catalytic temperature 800℃, S/C = 0)

表4 不同镍含量下的多环芳烃组成及焦油露点温度

Table 4 Effect of Ni content on PAH composition categorized by molecular weight and tar dew point

催化剂	轻质多环芳烃(area)/%	重质多环芳烃(area)/%	焦油露点温度 ^① /℃
1Ni/MS-800	7.33	0.52	57.0
2Ni/MS-800	7.88	0.32	50.3
3Ni/MS-800	10.58	0.12	42.4
4Ni/MS-800	8.87	0.22	47.2
5Ni/MS-800	8.18	0.36	52.0

图4 水碳比对焦油组分及焦油露点温度的影响（镍含量为3%，煅烧/催化温度为800℃）

Fig.4 Effect of S/C on tar composition and tar conversion (Ni content 3%, calcination/catalytic temperature 800℃)

表5 原料和煅烧后催化剂的理化性质

Table 5 Physicochemical properties of raw materials and freshly calcined catalysts

催化剂	比表面积/ (m²/g)	孔容^①/(cm³/g)	平均孔径^②/nm
γ-Al₂O₃	98.24	/	/
3Ni/γ-Al₂O₃-800	69.92	0.38	16.21
MS	0.90	/	/
3Ni/MS-700	11.31	0.09	25.98
3Ni/MS-800	4.36	0.03	20.53
3Ni/MS-900	2.74	0.02	22.52

图5 反应前后及不同煅烧温度下镍基镁渣催化剂的XRD谱图

Fig.5 XRD patterns of catalysts

图6 反应前和反应后的镍基镁渣催化剂的扫描电镜图

Fig.6 SEM images of fresh and used catalysts 3Ni/MS-800

图7 反应前的3Ni/MS-800催化剂的透射电镜图及粒径分布

Fig.7 TEM image and particle size distribution of freshly calcined 3Ni/MS-800 catalyst

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