杂质对Ru/AC催化秸秆水解液加氢反应的抑制作用

doi:10.11949/0438-1157.20190703

摘要/Abstract

摘要：

采用Ru/AC催化主要成分为葡萄糖、木糖的秸秆水解液加氢，探究了水解液中各杂质对加氢反应性能的影响，通过N₂物理吸附、CO化学吸附、热重分析、场发射扫描电镜、热解气质联用等分析手段对反应后失活催化剂进行了系统表征。结果表明：水解液中可能存在的木质素、纤维素酶、无机盐、呋喃类衍生物、有机弱酸、芳香族化合物等杂质中，木质素和纤维素酶对加氢反应具有很强抑制作用，其余杂质仅在溶液中总杂质含量较高时才表现出明显的抑制作用；木质素和纤维素酶阻碍加氢反应的主要原因是其能够附着于催化剂上，堵塞催化剂孔道，并覆盖活性位，导致催化剂失活。

关键词: 秸秆水解液, Ru/AC催化剂, 加氢, 杂质, 失活

Abstract:

Ru/AC was used to catalyze the hydrogenation of corm stover with main components of glucose and xylose. The effect of various impurities in the hydrolysate on the catalytic performance was also investigated. The physiochemical properties of deactivated catalysts were extensively characterized by the techniques of N₂physisorption, CO chemisorption, thermogravimetric analysis, field emission scanning electron microscope and pyrolysis-gas chromatography/mass spectrometry. Results demonstrated that lignin and cellulose, among the impurities existed in the hydrolysate, significantly inhibited the hydrogenation while the other impurities such as inorganic salts, furan derivatives, organic acids and aromatic compounds showed obvious inhibitory effect only when high content impurities existed in solution. In addition, the deactivation of Ru/AC catalysts was mainly caused by the deposited impurities such as lignin and cellulase on the catalyst surface, which blocked channels in catalyst particles and covered the active sites, thus resulting in catalyst deactivation.

Key words: hydrolysate, Ru/AC catalyst, hydrogenation, impurities, deactivation

中图分类号:

TQ 35

侯莲霞, 任鑫, 周静红, 周兴贵. 杂质对Ru/AC催化秸秆水解液加氢反应的抑制作用[J]. 化工学报, 2020, 71(2): 633-641.

Lianxia HOU, Xin REN, Jinghong ZHOU, Xinggui ZHOU. Inhibition effect of impurities on hydrogenation of corn stover hydrolysate[J]. CIESC Journal, 2020, 71(2): 633-641.

图/表 8

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反应物	杂质	转化率/%
反应物	杂质	葡萄糖	木糖
秸秆水解液	—	0	0
混合糖液	—	100	100
混合糖液	表2中杂质1~16单独添加	100	100
混合糖液	木质素	73.2	75.2
混合糖液	纤维素酶	54.3	95.5
混合糖液	木质素+纤维素酶	28.1	68.8
混合糖液	表2中杂质1~16共同添加	18.4	58.0
混合糖液	表2中杂质1~18共同添加	0	0

反应物	杂质	转化率/%
反应物	杂质	葡萄糖	木糖
秸秆水解液	—	0	0
混合糖液	—	100	100
混合糖液	表2中杂质1~16单独添加	100	100
混合糖液	木质素	73.2	75.2
混合糖液	纤维素酶	54.3	95.5
混合糖液	木质素+纤维素酶	28.1	68.8
混合糖液	表2中杂质1~16共同添加	18.4	58.0
混合糖液	表2中杂质1~18共同添加	0	0

序号	杂质种类	添加量/%（质量）	序号	杂质种类	添加量/%（质量）
1	糠醛	0.3	10	苯甲酸	0.1
2	5-HMF	0.3	11	4-甲基苯甲酸	0.1
3	乙酸	0.2	12	4-羟基苯甲酸	0.1
4	乙酰丙酸	0.2	13	4-羟甲基苯甲酸	0.1
5	乳酸	0.2	14	4-羧基苯甲醛	0.1
6	CaSO₄	0.2	15	对羟基苯甲醛	0.1
7	间苯二酚	0.1	16	对苯二甲酸	0.1
8	香草酸	0.1	17	木质素	0.79
9	香草醛	0.1	18	纤维素酶	<0.2

序号	杂质种类	添加量/%（质量）	序号	杂质种类	添加量/%（质量）
1	糠醛	0.3	10	苯甲酸	0.1
2	5-HMF	0.3	11	4-甲基苯甲酸	0.1
3	乙酸	0.2	12	4-羟基苯甲酸	0.1
4	乙酰丙酸	0.2	13	4-羟甲基苯甲酸	0.1
5	乳酸	0.2	14	4-羧基苯甲醛	0.1
6	CaSO₄	0.2	15	对羟基苯甲醛	0.1
7	间苯二酚	0.1	16	对苯二甲酸	0.1
8	香草酸	0.1	17	木质素	0.79
9	香草醛	0.1	18	纤维素酶	<0.2

组别	反应物	催化剂	转化率/%
组别	反应物	催化剂	葡萄糖	木糖
1	混合糖液	新鲜Ru/AC	100	100
	混合糖液	Ru/AC₁^①	100	100
	混合糖液	Ru/AC₄^②	100	100
2	混合糖液+纤维素酶	新鲜Ru/AC	54.3	95.5
2	混合糖液	c-Ru/AC₁^③	53.6	94.2
3	混合糖液+木质素	新鲜Ru/AC	73.2	75.2
3	混合糖液	l-Ru/AC₁^④	72.2	74.3
4	混合糖液+纤维素酶+木质素	新鲜Ru/AC	28.1	68.8
4	混合糖液	cl-Ru/AC₁^⑤	27.4	69.4
5	秸秆水解液	新鲜Ru/AC	0	0
5	混合糖液	h-Ru/AC₁^⑥	21.1	17.8