MOR负载的自还原型双功能催化剂用于催化纤维素氢解制乙二醇的研究

肖竹钱; 沙如意; 计建炳; 毛建卫

MOR负载的自还原型双功能催化剂用于催化纤维素氢解制乙二醇的研究

肖竹钱^{1, 2, 3, 4},
沙如意^{1, 2, 3, ,},
计建炳⁴,
毛建卫^{1, 2, 3}

1.
浙江科技学院生物与化学工程学院, 浙江杭州 310023
2.
浙江省农产品化学与生物加工技术重点实验室, 浙江杭州 310023
3.
浙江省农业生物资源生化制造协同创新中心, 浙江杭州 310023
4.
浙江工业大学化学工程学院, 浙江杭州 310014

基金项目:

浙江省教育厅科研项目 Y20112088

浙江省科技计划项目 2011R09028-10

详细信息

中图分类号: TQ352
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- 被引次数: 0
出版历程
- 收稿日期: 2016-06-06
- 修回日期: 2016-07-10
- 网络出版日期: 2021-01-23
- 刊出日期: 2016-10-10

Mordenite supported Ni-W self-reducing bifunctional catalyst for cellulose hydrogenolysis into ethylene glycol

XIAO Zhu-qian^{1, 2, 3, 4},
SHA Ru-yi^{1, 2, 3
, ,},
JI Jian-bing⁴,
MAO Jian-wei^{1, 2, 3}

1.
School of Biological and Chemical Engineering, Zhejiang University of Science & Technology, Hangzhou 310023, China
2.
Zhejiang Provincial Key Laboratory of Chemical and Biological Processing Technology of Farm Products, Hangzhou 310023, China
3.
Collaborative Innovation Center of Agricultural Biological Resources Biochemical Manufacturing of Zhejiang Province, Hangzhou 310023, China
4.
College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310014, China

More Information

Corresponding author: Tel: 0571-85070390, E-mail: zjhzxzq@yeah.net

摘要

摘要: 以丝光沸石分子筛（MOR）为载体，以高温生物碳源分解产物H₂或CO为还原剂，采用等体积浸渍法制备自还原型双功能催化剂Ni-W/MOR，不经过还原过程直接将其应用于纤维素水相氢解制备低碳乙二醇的研究。考察了催化剂的煅烧温度、活性金属含量配比对纤维素转化率和目标产物收率的影响。结果表明，催化剂的煅烧温度在773 K为宜；XRD表征结果说明，催化剂中活性金属结晶度和晶体的种类与催化剂的配比有关；TEM照片可直观地说明，采用上述方法制备的催化剂中活性金属在载体上具有较好的分散性，粒径均小于20 nm。当Ni、W含量分别为10%和15%，煅烧温度为773 K，反应条件为513 K、5.0 MPa、2 h时低碳多元醇总收率为56.92%，其中，乙二醇收率为52.30%。
- 丝光沸石分子筛 /
- 自还原型催化剂 /
- 糖醇 /
- 氢解 /
- 乙二醇
Abstract: Based on the reducing gases (H₂ and CO) generated from biomass-based carbon at high clacination temperature, self-reducing bifunctional catalyst Ni-W/MOR was prepared by incipient impregnation. This series of catalysts were directly applied to cellulose hydrogenolysis to low carbon polyols in aqueous solution, omitting the catalysts reduction step. The effects of catalysts temperature of the catalyst and weight ratio of active components on conversion of cellulose and yield of target products were investigated. The optimal calcination temperature was 773 K through experimental results. XRD analysis showed that the crystallinity and species of metallic alloys were related to different weight ratios of nickel and tungsten. It was intuitively observed that the active metals showed good dispersion on the surface of MOR through TEM characterization, with particles sizes less than 20 nm. The total yield of low carbon polyols was up to 56.92%, including 52.30% of EG under the reaction condition of 5.0 MPa of H₂ for 2 h reaction time and the calcination temperature of catalysts was 773 K.
- mordenite /
- self-reducing catalysts /
- sugar polyols /
- hydrogenolysis /
- ethylene glycol

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图 1 等体积浸渍法制备自还原型催化剂过程示意图

Figure 1 Incipient-wetness impregnation method for preparing self-reducing catalysts

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图 2 MOR负载的不同催化剂的BET分析

Figure 2 BET analysis of self-reducing catalysts

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图 3 自还原型催化剂的热分析

Figure 3 Thermal analysis of self-reducing catalysts

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图 4 不同活性组分配比的自还原型催化剂的XRD谱图

Figure 4 XRD patterns of self-reducing catalysts with different Ni/W weight ratios

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图 5 10%Ni-15%W/MOR透射电镜照片

Figure 5 TEM images of 10%Ni-15%W/MOR self-reducing catalyst

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图 6 不同Ni/W质量比对反应性能的影响

Figure 6 Effect of Ni/W mass ratios on yields of products

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表 1 Ni-W/MOR催化剂的比表面积和孔结构

Table 1 BET results of Ni-W/MOR

Catalyst	BET specific surface area A/(m²·g^-1)	Pore volume v/(cm³·g^-1)	Average pore diameter d/nm
10%Ni-15%W/MOR-773 K	61.450	0.108	3.823
10%Ni-15%W/MOR-873 K	50.360	0.103	3.821
10%Ni-15%W/MOR-973 K	41.476	0.110	3.821
25%Ni-20%W/MOR-773 K	27.082	0.237	4.125

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表 2 煅烧温度对催化剂Ni-W/MOR活性的影响

Table 2 Effect of calcination temperature on catalytic activity of Ni-W/MOR^a

Entry	Catalyst	Yield w/%						Conv. x/%
Entry	Catalyst	EG^b	1, 2-PG	Gly	Ery	Sor	Glu	Conv. x/%
1	10%Ni-15%W/MOR-673 K	17.91	4.15	0.37	-	1.03	4.98	82
2	10%Ni-15%W/MOR-773 K	52.30	4.31	0.31	-	2.38	9.68	100
3	10%Ni-15%W/MOR-873 K	48.89	4.62	0.33	0.76	3.02	7.89	100
4	10%Ni-15%W/MOR-973 K	44.83	4.99	0.38	1.62	6.36	9.02	100
5	10%Ni-15%W/MOR-1073 K	21.65	1.32	4.82	-	2.53	5.14	95
^a: reaction condition: feedstock: cellulose 0.5 g, water 55 mL; catalyst: 0.2 g; temperature: 513 K; H₂ pressure: 5.0 MPa; reaction time: 2 h； ^b: EG: ethylene glycol; 1, 2-PG: 1, 2-propylene glycol; Gly: glycerol; Ery: erythritol; Sor: sorbitol; Glu: glucose

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表 3 Ni/W质量比对催化剂Ni-W/MOR活性的影响

Table 3 Effect of Ni/W mass ratio on catalytic activity of Ni-W/MOR^a

Entry	Catalyst	Ni/W (mass ratio)	Yield w/%						Conv. x/%
Entry	Catalyst	Ni/W (mass ratio)	EG	1, 2-PG	Gly	Ery	Sor	Glu	Conv. x/%
1	5%Ni-5%W/MOR-773 K	1:1^b	10.71	4.06	0.56	-	1.44	4.4	90
2	10%Ni-5%W/MOR-773 K	2:1	20.38	3.95	0.32	-	1.89	4.99	96
3	15%Ni-5%W/MOR-773 K	3:1	27.71	5.34	0.42	1.02	1.32	1.41	93
4	10%Ni-10%W/MOR-773 K	2:2	26.63	7.08	0.90	0.55	2.95	4.36	91
5	10%Ni-15%W/MOR-773 K	2:3	52.30	4.31	0.31	-	2.38	9.68	100
6	15%Ni-20%W/MOR-773 K	3:4	27.15	2.96	3.38	1.60	2.96	3.95	98
7	25%Ni-20%W/MOR-773 K	5:4	37.44	4.05	2.70	2.27	4.34	2.25	94
8	25%Ni-25%W/MOR-773 K	5:5	30.96	3.77	2.97	3.70	2.67	4.05	100
9	blank/MOR-773 K	-	0.23	-	0.12	-	2.16	4.90	33
10	10%Ni-15%W/MOR-773 K^c	2:3	trace	trace	-	-	3.04	3.80	62
11	10%Ni-15%W/MC^d	2:3	36.35	2.60	-	0.90	1.12	2.37	85
^a: reaction condition: feedstock: cellulose 0.5 g, water 55 mL; catalyst: 0.2 g; temperature: 513 K; H₂ pressure: 5.0 MPa; reaction time: 2 h; ^b: Ni/W mass ratio 1:1 represents the loading of Ni and W are 5% and 5% resperctively; ^c: with no sucrose; ^d: mesoporous carbon

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