多级孔HZSM-5分子筛催化快速热解生物质制芳烃

doi:10.11949/0438-1157.20200091

摘要/Abstract

摘要：

采用酸和/或碱处理法制备了一系列多级孔HZSM-5分子筛，采用XRD、N₂吸附、XRF、TEM、²⁷Al MAS NMR和NH₃-TPD等表征手段对其孔道结构和酸性进行表征。表征结果表明，采用碱处理方法，可获得孔径集中于3~6 nm的介孔结构，通过改变酸、碱处理次序，可调变酸中心数量和强酸/总酸中心比例。在Py-GC/MS装置上，以纤维素和水稻秸秆为原料，研究多级孔分子筛结构对催化快速热解（CFP）制芳烃反应的影响。反应评价结果表明，同商品级HZSM-5相比，采用先碱后酸处理获得的多级孔HZSM-5分子筛（HZ-OH/H），可将纤维素CFP芳烃碳产率由32.3%提高至43.6%，可将水稻秸秆CFP芳烃碳产率由23.0%提高至30.8%。多级孔HZ-OH/H分子筛的孔道结构和酸中心分布特征，对开发应用于生物质制芳烃的高效工业催化剂具有借鉴意义。

关键词: 多级孔HZSM-5, 催化, 热解, 生物质, 芳烃, 纤维素, 秸秆, 沸石

Abstract:

A series of HZSM-5 molecular sieves with hierarchical porosity were prepared by acid and/or alkali treatments, and their pore structure and acidity were characterized by XRD, N₂ adsorption, XRF, TEM, ²⁷Al MAS NMR and NH₃-TPD. The characterization results show that the alkali treatment method used in this paper can generate the mesoporous structure with a pore size concentrated at 3—6 nm. By changing the order of acid and alkali treatment, the number of acid centers and the ratio of strong acid to total acid center can be adjusted. In addition, the catalytic performance of the hierarchical porosity catalysts were studied for the catalytic fast pyrolysis (CFP) of cellulose and rice straw to aromatics on the Py-GC/MS. Compared with the commercial HZSM-5, the catalysts (HZ-OH/H) obtained by alkali first and then acid treatment can increase the aromatics carbon yield of cellulose CFP from 32.3 % to 43.6%, and same for rice straw from 23.0% to 30.8%. The pore structure and acid center distribution characteristics of the multi-stage HZ-OH/H molecular sieve have reference significance for the development of high-efficiency industrial catalysts applied to biomass to produce aromatics.

Key words: hierarchical HZSM-5, catalysis, pyrolysis, biomass, aromatics, cellulose, rice straw, zeolite

中图分类号:

TQ 032.4

马会霞,周峰,武光,傅杰,乔凯. 多级孔HZSM-5分子筛催化快速热解生物质制芳烃[J]. 化工学报, 2020, 71(11): 5200-5207.

Huixia MA,Feng ZHOU,Guang WU,Jie FU,Kai QIAO. Catalytic fast pyrolysis of biomass to aromatics over hierarchical HZSM-5[J]. CIESC Journal, 2020, 71(11): 5200-5207.

图/表 9

图1 酸和/或碱处理法制备多级孔HZSM-5分子筛的XRD谱图

Fig.1 XRD patterns of hierarchical HZSM-5 prepared by acid and/or alkali treatment

图2 酸和/或碱处理法制备多级孔HZSM-5分子筛的氮气吸附图

Fig.2 N2-adsorption of hierarchical HZSM-5 prepared by acid and/or alkali treatments

表1 多级孔HZSM-5分子筛的硅铝比、比表面积和孔容

Table 1 Si/Al ratio, specific surface area and pore volume of the hierarchical HZSM-5 molecular sieve

编号	Si/Al^①	比表面积/(m²/g)			孔容/(cm³/g)
编号	Si/Al^①	BET^②	微孔^③	外比表面^③	总孔容^④	微孔^⑤	介孔^⑤
HZ	38.6	277.2	222.5	54.7	0.15	0.09	0.06
HZ-H	41.6	302.9	236.2	66.7	0.18	0.11	0.07
HZ-OH	34.7	376.6	201.6	175.0	0.24	0.09	0.15
HZ-H/OH	39.6	408.9	253.2	155.7	0.22	0.10	0.12
HZ-OH/H	37.8	332.7	246.3	86.4	0.20	0.10	0.10

图3 酸碱处理法制备多级孔HZSM-5分子筛的TEM图片

Fig.3 TEM images of hierarchical HZSM-5 prepared by acid and/or alkali treatments

图4 酸碱处理法制备多级孔HZSM-5分子筛的27Al核磁谱图

Fig.4 27Al MAS NMR spectra of hierarchical HZSM-5 prepared by acid and/or alkali treatments

图5 酸和/或碱处理法制备多级孔HZSM-5分子筛的NH3-TPD谱图

Fig.5 NH3-TPD spectra of hierarchical HZSM-5 prepared by acid and/or alkali treatments

表2 酸和/或碱处理法制备多级孔HZSM-5分子筛的NH3-TPD数据及酸量

Table 2 NH3-TPD data and acid amount for hierarchical HZSM-5 prepared by acid and/or alkali treatment

编号	脱附峰/℃		酸量/(mmol/g)
编号	LT- peak	HT- peak	总酸量	弱酸	强酸	强酸/总酸
HZ	198	395	1.19	0.48	0.71	0.59
HZ-H	189	394	0.80	0.29	0.51	0.63
HZ-OH	194	396	1.23	0.50	0.73	0.59
HZ-H/OH	189	390	0.97	0.38	0.59	0.60
HZ-OH/H	183	396	1.11	0.54	0.57	0.50

图6 多级孔HZSM-5分子筛催化纤维素CFP制芳烃产物产率分布

Fig.6 Aromatics yield distribution of cellulose CFP catalyzed by hierarchical HZSM-5 molecular sieve

表3 水稻秸秆CFP产物产率分布

Table 3 Yield distribution for rice straw CFP products

编号	CFP产物产率/%
编号	芳烃	CO+CO₂	烯烃	焦炭
HZ	23.0	22.4	7.6	47.0
HZ-OH/H	30.8	27.8	7.1	34.3

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