碱催化促进Ni-W/<i>β</i>分子筛催化剂氢解纤维素产1, 2-丙二醇的研究

杨龙; 孔玲; 石惠娴; 秦舒浩; 张唯; 顾敏燕; 沈峥; 张亚雷

碱催化促进Ni-W/β分子筛催化剂氢解纤维素产1, 2-丙二醇的研究

杨龙^{1, 2},
孔玲^{1, 2},
石惠娴¹,
秦舒浩³,
张唯^{1, 2},
顾敏燕²,
沈峥^{1, 2, ,},
张亚雷^{1, 2}

1.
同济大学国家设施农业工程技术研究中心, 上海 200092
2.
同济大学污染控制与资源化研究国家重点实验室, 上海 200092
3.
国家复合改性聚合物材料工程技术研究中心, 贵州贵阳 550014

基金项目:

国家自然科学基金 21376180

国家自然科学基金 21676205

国家自然科学基金 51625804

中央高校基础研究基金 2870219026

中央高校基础研究基金 2870219028

上海科委国际合作项目 14230710800

详细信息

通讯作者:
沈峥, Tel:021-65985811, E-mail:shenzheng@tongji.edu.cn

中图分类号: O643
计量
- 文章访问数: 75
- HTML全文浏览量: 27
- PDF下载量: 15
- 被引次数: 0
出版历程
- 收稿日期: 2016-07-27
- 修回日期: 2016-10-21
- 网络出版日期: 2021-01-23
- 刊出日期: 2017-01-10

Study on the synthesis of propylene glycol through cellulose hydrogenation using alkaline promoted Ni-W/β-zeolite catalysts

YANG Long^{1, 2},
KONG Ling^{1, 2},
SHI Hui-xian¹,
QIN Shu-hao³,
ZHANG Wei^{1, 2},
GU Min-yan²,
SHEN Zheng^{1, 2
, ,},
ZHANG Ya-lei^{1, 2}

1.
National Engineering Research Center of Protected Agriculture, Tongji University, Shanghai 200092, China
2.
State Key Laboratory of Pollution Control and Resource Reuse, Tongji University, Shanghai 200092, China
3.
The National Engineering Research Center for Compounding and Modification of Polymer Materials, Guiyang 550014, China

Funds:

the National Natural Science Foundation of China 21376180

the National Natural Science Foundation of China 21676205

the National Natural Science Foundation of China 51625804

the Fundamental Research Funds for the Central Universities 2870219026

the Fundamental Research Funds for the Central Universities 2870219028

the International Collaborative Project from Shanghai Science and Technology Commission 14230710800

摘要

摘要: 为提高纤维素催化氢解产醇类产物中1，2-丙二醇（1，2-PG）的收率，采用等体积浸渍法制备了以β分子筛为载体负载Ni和W的催化剂。结果表明，当7Ni-20W/β分子筛作为催化剂时，在240℃反应温度和6.0 MPa H₂的条件下反应30 min后，纤维素实现完全转化，1，2-PG和乙二醇（EG）产率分别达到19.3%和45.3%；不同于其他载体催化剂，β分子筛可以明显提高1，2-PG选择性。当不同碱催化剂加入到Ni-W/β分子筛催化剂反应体系后，可以进一步提高1，2-PG的选择性。尤其是当加入Ba（OH）₂后，1，2-丙二醇产率从19.3%提高了32.5%。为了探究碱催化剂在反应中的作用，以葡萄糖为底物进行了一系列的碱催化反应。结果表明，碱催化剂主要作用是有助于将葡萄糖异构化为果糖，从而促进纤维素转化为1，2-PG。催化剂在两次回收重复利用之后1，2-PG的收率只下降3.9%，乙二醇产率收率下降4.1%。
- Ni-W/β分子筛 /
- 纤维素 /
- 1, 2-丙二醇 /
- 碱催化剂 /
- 氢解
Abstract: A series of Ni-W/β zeolite catalysts were prepared via incipient impregnation method in order to improve the yield of 1, 2-propylene glycol (1, 2-PG) in the alcohol products of cellulose hydrogenation. Under the reaction conditions of 240℃ and 6.0 MPa H₂ for 30 min, the complete conversion of cellulose was obtained and the yields of 1, 2 propylene glycol and ethylene glycol (EG) were 19.3% and 45.3%, respectively. Different from other supports, the selectivity of 1, 2-PG was highly improved when β zeolite was used. The selectivity of 1, 2-PG was further improved after the addition of alkaline, and the yield of 1, 2-PG was up to 32.5% especially for Ba (OH)₂. The function of alkaline catalysts in the reaction was also discussed based on a series of reactions using glucose as the substrate, indicating that alkaline was favorable for the isomerization of glucose to fructose and thus promoted the conversion of cellulose into 1, 2-PG. After two cycles of reuse, the yield of 1, 2-PG and EG slightly decreased (3.9% and 4.1%, respectively).
- Ni-W/β zeolite /
- cellulose /
- 1, 2-propylene glycol /
- alkaline catalysts /
- hydrogenation

HTML全文

图 1 不锈钢反应釜结构示意图

Figure 1 Structure of stainless steel reaction kettle

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图 2 不同载体催化剂对催化反应的影响

Figure 2 Effect of catalysts with different

supports on the reactionPG: 1, 2-propylene glycol; EG: ethylene glycol; S: sorbitol; M: mannitol reaction conditions: 30 min, 6 MPa H₂, 518 K, 40 mL H₂O, 0.5 g cellulose, 0.15 g catalyst

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图 3 不同Ni/W质量比对纤维素催化氢解的影响

Figure 3 Effect of weight ratio of Ni/W on cellulose hydrogenolysis

PG: 1, 2-propylene glycol; EG: ethylene glycol; S: sorbitol; M: mannitol reaction conditions: 30 min, 6 MPa H₂, 518 K, 40 mL H₂O, 0.5 g cellulose, 0.15 g catalyst

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图 4 不同比例Ni-W催化剂的XRD谱图

Figure 4 XRD patterns of the catalysts with different weight ratios of Ni/W

a: 1Ni-20W/β; b: 3Ni-20W/β; c: 7Ni-20W/β; d: 15Ni-20W/β; e: 7Ni-15W/β; f: 7Ni-25W/β

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图 5 碱催化剂种类及用量对纤维素催化氢解的影响

Figure 5 Effect of base catalyst type and amount on hydrogenolysis of cellulose

PG: 1, 2-propylene glycol; EG: ethylene glycol; S: sorbitol; M: mannitol reaction conditions: 30 min, 6 MPa H₂, 518 K, 40 mL H₂O, 0.5 g cellulose, 0.15 g catalyst

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图 6 催化剂回收利用次数对纤维素催化降解的影响

Figure 6 Effect of catalyst recycle on cellulose hydrogenolysis

PG: 1, 2-propylene glycol; EG: ethylene glycol; S: sorbitol; M: mannitol reaction conditions: 30 min, 6 MPa H₂, 518 K, 40 mL H₂O, 0.5 g cellulose, 0.15 g catalyst

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表 1 催化剂的孔结构

Table 1 Pore structure of the catalyst

Catalyst	BET surface area A/(m²·g^-1)	Pore volume v/(cm³·g^-1)	Pore size d/nm
1Ni-20W/β	368	0.11	11.1
3Ni-20W/β	357	0.09	9.5
5Ni-20W/β	342	0.08	8.4
7Ni-20W/β	329	0.07	7.8
9Ni-20W/β	313	0.06	7.2
15Ni-20W/β	287	0.06	6.9
7Ni-5W/β	371	0.10	10.1
7Ni-15W/β	348	0.07	7.5
7Ni-25W/β	277	0.05	6.7

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表 2 碱催化剂种类和用量对葡萄糖异构化为果糖的影响

Table 2 Effect of type and amount of base catalyst on glucose isomerization

Catalyst	Conversion x/%	Yield w/%
Catalyst	Conversion x/%	mannose	fructose
No base	6	trace	4
5 mmol/L NaOH	33	6	26
10 mmol/L NaOH	41	5	28
15 mmol/L NaOH	47	4	27
5 mmol/L Ca (OH)₂	41	6	29
10 mmol/L Ca (OH)₂	44	5	28
15 mmol/L Ca (OH)₂	50	3	27
5 mmol/L Ba (OH)₂	36	6	26
10 mmol/L Ba (OH)₂	42	5	27
15 mmol/L Ba (OH)₂	45	4	24
reaction conditions: 30 min，6 MPa H₂，518 K，40 mL H₂O，0.5 g glucose，0.15 g catalyst

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