NaOH处理ZSM-5催化香茅草残渣甲醇气氛中热解实验研究

doi:10.3969/j.issn.0253-2417.2020.05.007

摘要/Abstract

摘要：

采用NaOH处理的分子筛ZSM-5为载体，制备了镍铝层状双金属氧化物/分子筛复合催化剂（NiAl-LDO/ZSM-5），将其用于香茅草残渣在甲醇气氛中的热解实验研究。催化剂表征结果表明：经过NaOH处理后，ZSM-5的骨架有不同程度破坏，且破坏程度随NaOH浓度增加而增大；催化剂的比表面积在负载NiAl-LDO后降低，但随着NaOH浓度的升高逐渐增大；同时，催化剂的酸量随NaOH浓度的升高都明显增加。催化热解实验结果表明：未经NaOH处理的NiAl-LDO/ZSM-5催化热解的生物油收率为13.4%，与ZSM-5催化相比生物油中苯类物质由34.06%上升至43.15%，同时，萘类物质从63.31%下降至23.15%；经NaOH处理后生物油收率基本不变，但随着NaOH处理溶液浓度增大，热解生物油中芳香烃由16.35%增加至50.19%，非芳香含氧物质由35.35%逐渐下降至17.38%。

关键词: 催化热解, 复合金属氧化物, 分子筛, NaOH处理, 香茅草残渣

Abstract:

The pyrolysis of distilled residue of lemongrass, which is a traditional Chinese medicine residue, can not only solve the problem of solid waste, but also obtain high-value chemicals, thus achieve the purpose of resource utilization. In this study, Ni-Al layered double oxide/zeolite composite catalyst (NiAl-LDO/ZSM-5) was prepared by using NaOH-treated ZSM-5 as the support, and used in the pyrolysis of lemongrass residue under methanol atmosphere. The catalyst characterization results showed that the ZSM-5 framework was damaged by NaOH treatment, and the degree of damage increased with the increase of the concentration of NaOH solution. After loading NiAl-LDO, the specific surface area of catalyst decreased, but with the increase of NaOH concentration, the specific surface area of catalyst increased gradually as well as the weak acidic sites and the strong acidic sites. The catalytic pyrolysis results showed that the yield of bio-oil obtained by NiAl-LDO/ZSM-5 without NaOH treatment was 13.4%. As NiAl-LDO covered the strong acid sites of ZSM-5, the content of benzenes in the bio-oil increased from 34.06% to 43.15%, and the content of naphthalenes decreased from 63.31% to 23.15%. After the NaOH treatment of ZSM-5 support, the yield of bio-oil was almost unchanged. However, with the increase of the concentration of NaOH solution, the content of aromatic hydrocarbons in the pyrolysis bio-oil increased from 16.35% to 50.19%, and the content of oxygen-containing compounds decreased gradually from 35.35% to 17.38%.

Key words: catalytic pyrolysis, composite metal oxides, zeolites, NaOH treatment, lemongrass residue

中图分类号:

TQ35
TQ032

杨红美,徐威,高李璟,肖国民. NaOH处理ZSM-5催化香茅草残渣甲醇气氛中热解实验研究[J]. 林产化学与工业, 2020, 40(5): 50-56.

Hongmei YANG,Wei XU,Lijing GAO,Guomin XIAO. Pyrolysis of Lemongrass Residue Catalyzed by NaOH Treated ZSM-5 Under Methanol Atmosphere[J]. Chemistry and Industry of Forest Products, 2020, 40(5): 50-56.

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编号 No.	催化剂 catalysts	NaOH/ (mol·L^-1)	比表面积/(m²·g^-1) specific surface area	总孔体积/(mL·g^-1) total pore volume	平均孔径/nm average pore diameter
1	ZSM-5		313	0.25	3.14
2	NiAl-LDO/ZSM-5		304	0.33	4.30
3	NiAl-LDO/ZSM-5(0.1)	0.1	304	0.34	4.49
4	NiAl-LDO/ZSM-5(0.2)	0.2	322	0.32	4.01
5	NiAl-LDO/ZSM-5(0.3)	0.3	328	0.37	4.48
6	NiAl-LDO/ZSM-5(0.4)	0.4	341	0.43	5.08

催化剂 catalysts	弱酸weak acid		强酸strong acid		总酸量/(mmol·g^-1) total acid amount
催化剂 catalysts	酸量/(mmol·g^-1) amounts	温度^*/℃ temp.	酸量/(mmol·g^-1) amounts	温度^*/℃ temp.	总酸量/(mmol·g^-1) total acid amount
NiAl-LDO/ZSM-5	1.11	231.24	0.31	439.72	1.42
NiAl-LDO/ZSM-5(0.1)	1.20	225.52	0.28	417.50	1.48
NiAl-LDO/ZSM-5(0.2)	1.35	218.05	0.32	403.28	1.67
NiAl-LDO/ZSM-5(0.3)	1.38	220.35	0.33	401.88	1.71
NiAl-LDO/ZSM-5(0.4)	1.25	225.08	0.36	400.69	1.61

催化剂 catalysts	液相liquid		固相 solid	气相 gas
催化剂 catalysts	水相产物 aqueous product	生物油 bio-oil	固相 solid	气相 gas
无none	39.4	11.4	30.7	18.5
ZSM-5	40.2	13.5	29.7	16.6
NiAl-LDO/ZSM-5	41.1	13.4	29.4	16.1

组分 components		不同催化剂下的GC含量GC contents with different catalysts/%
组分 components		无none	No.1	No.2
脂肪烃 aliphatic hydrocarbons	烷烃类alkanes	—	—	—
脂肪烃 aliphatic hydrocarbons	烯烃类olefines	1.60	—	—
芳香烃 aromatic hydrocarbons	苯类benzenes	—	34.06	43.15
	萘类naphthalenes	4.27	63.31	23.15
	茚类indenes	—	0.80	0.53
	菲类phenanthrenes	—	0.30	—
芳香含氧物质 aromatic oxygenous compounds	不含甲氧基苯酚phenols without methoxy	—	—	0.49
	含甲氧基苯酚phenols with methoxy	10.39	—	12.57
	苯并吡喃酮类benzopyranones	13.15	—	—
非芳香含氧物质 non-aromatic oxygenous compounds	醇类alcohols	22.43	—	2.49
	酸类acids	39.62	1.53	15.92
	酮类ketones	3.20	—	0.42
	酯类esters	5.33	—	1.28

NaOH浓度/(mol·L^-1) NaOH concentration	液相liquid		固相 solid	气相 gas
NaOH浓度/(mol·L^-1) NaOH concentration	水相产物 aqueous product	生物油 bio-oil	固相 solid	气相 gas
0.1	42.5	13.8	27.2	16.5
0.2	43.1	14.3	27.3	15.3
0.3	42.5	12.3	28.4	16.8
0.4	42.0	11.1	29.1	17.3