Ni-W2C催化葡萄糖氢解制备低碳二元醇反应机理研究

doi:10.11949/j.issn.0438-1157.20181426

摘要/Abstract

摘要：

采用HPLC、LC-MS、GC-MS等分析手段对不同工艺条件下Ni/W₂C催化葡萄糖加氢转化的中间产物及终产物进行定性定量分析，研究了葡萄糖加氢转化过程的反应机制和历程。研究发现：葡萄糖加氢转化过程中同时平行发生了加氢、异构和逆向羟醛缩合（氢解）三类反应；葡萄糖发生加氢反应能够得到六元醇且其不会再进一步转化，发生逆向羟醛缩合反应主要生成乙二醇（C₂产物），发生异构反应则可生成果糖，其进行逆向羟醛缩合的产物则为1,2-丙二醇和甘油（C₃产物）；高浓度葡萄糖条件下，其异构产物果糖发生脱水反应生成的5-HMF浓度过高发生聚合，进而导致结焦。根据葡萄糖加氢转化的反应网络，提出了调控反应过程中C₂产物和C₃产物分布的策略，并通过增加催化剂用量来加快果糖脱水的竞争反应速率(加氢、氢解)，进而实现了高浓度（10%，质量分数）葡萄糖的加氢转化。此外，葡萄糖加氢转化过程中存在明显的浓度效应，反应物浓度越低，越有利于发生逆向羟醛缩合反应，反之则有利于发生加氢反应。

关键词: 生物质, Ni-W₂C催化剂, 加氢, 低碳二元醇, 反应机理

Abstract:

The HPLC and LC-MS, GC-MS and other analytical methods were used to qualitatively and quantitatively analyze the intermediates and final products of Ni/W₂C catalyzed glucose hydrotreating under different process conditions. Ni-W₂C was recently reported as a promising catalyst for the hydrogenolysis of cellulose or glucose to EG with the highest yield of 75%, yet this was achieved at the substrate concentration less than 1% because the concentrated substrate will lead to coking. This meant low productivity and high cost for commercial production, thus hinder this promising process from industry application. Therefore, insights into the reaction network to elucidate the coking mechanism and to optimize the process are needed. In this work, the mechanistic study on the glucose conversion, especially with the concentrated glucose substrate, over 2%Ni-30%W₂C/AC was systematically carried out. The reaction parameters including temperature, initial glucose concentration and H₂ pressure have been investigated and the results, in combination with the intermediate analysis by LC, LCMS and GCMS, showed that three parallel reaction pathways including retro-aldol reaction, isomerization and hydrogenation were involved in the reaction. C₂ product (EG) was originated from glucose hydrogenolysis while the C₃ products (1,2-PG and glycerol) were originated from fructose hydrogenolysis, and the dehydration of fructose led to 5-HMF and finally to coke in concentrated glucose conversion. Based on these understanding, the ratio of C₃ products to C₂, on the one hand, has been manipulated by tuning of isomerization of glucose into fructose with base additive and on the other hand, coking has been avoided by accelerating its competing reactions even at the glucose concentration of 10%（mass）. More interestingly, it was indicated that glucose of low concentration favors retro-aldol reaction while the one of high concentration tends to hydrogenate.

Key words: biomass, Ni-W₂C catalyst, hydrogenation, glycols, mechanism

中图分类号:

侯莲霞, 袁兆平, 乔鸿昌, 周静红, 周兴贵. Ni-W₂C催化葡萄糖氢解制备低碳二元醇反应机理研究[J]. 化工学报, 2019, 70(4): 1390-1400.

Lianxia HOU, Zhaoping YUAN, Hongchang QIAO, Jinghong ZHOU, Xinggui ZHOU. Mechanistic study on catalytic conversion of glucose into low carbon glycols over nickel promoted tungsten carbide catalyst[J]. CIESC Journal, 2019, 70(4): 1390-1400.

图/表 14

表1 不同温度下葡萄糖加氢转化的产物分布

Table 1 Product distributions of glucose conversion at different temperatures

T/K	Conversion/%	Yield/%
T/K	Conversion/%	Ery	Gly	EG	1,2-PG	Sor	Others
393	6.4	0	0	0	0	4.0	2.0
413	27.4	0.6	0.1	1.4	0	18.8	6.5
433	61.4	4.7	1.0	9.2	4.1	16.4	26.0
453	86.0	7.7	2.4	29.3	9.7	12.1	24.8
473	100.0	4.7	2.4	28.0	9.4	13.4	42.1
493	100.0	8.3	3.4	33.6	13.5	11.0	30.2

表2 不同初始浓度下葡萄糖加氢转化的产物分布

Table 2 Product distributions of glucose conversion at different initial concentrations

Glucose concentration/%(mass)	Conversion/%	Yield/%						Coking
Glucose concentration/%(mass)	Conversion/%	Ery	Gly	EG	1,2-PG	Sor	Others	Coking
0.5	100	7.4	3.0	52.2	15.8	5.9	15.7	no
2	100	8.3	3.4	33.6	13.5	11.0	30.2	no
5	100	trace	trace	trace	trace	trace	trace	yes
6.6	100	trace	trace	trace	trace	trace	trace	yes
10	100	trace	trace	trace	trace	trace	trace	yes

表3 不同总压（氢气）下葡萄糖加氢转化的产物分布

Table 3 Product distributions of glucose conversion at different reaction pressures

Reaction pressure/MPa	Conversion/%	Yield/%
Reaction pressure/MPa	Conversion/%	Ery	Gly	EG	1,2-PG	Sor	Others
2	100	trace	trace	trace	trace	trace	100
5	100	1.9	0.5	6.5	3.2	22.3	65.5
7	100	6.7	2.7	31.9	8.2	16.4	34.1
10	100	8.3	3.4	33.6	13.5	11.0	30.2

图1 不同时间下葡萄糖加氢转化的产物浓度

Fig.1 Product concentration (mass fraction) of glucose conversion at different times

图2 不同反应时间下葡萄糖加氢转化产物的液相色谱图

Fig.2 HPLC profile for intermediate products of glucose conversion

表4 计时0 min时葡萄糖加氢转化产物GC-MS分析结果

Table 4 Analysis results of extracted sample by GC-MS

出峰时间/min	CAS号	名称
3.479	116-09-6	羟基丙酮
3.978	107-21-1	乙二醇
4.769	57-55-6	1,2-丙二醇
7.495	97-99-4	四氢糠醇

表5 葡萄糖加氢转化中间产物及终产物的分类

Table 5 Product mixture category

产物分类	具体产物
C₆	甘露糖，果糖，山梨醇，甘露醇
C₄	赤藓糖醇，苏糖醇
C₃	甘油，1,2-丙二醇，羟基丙酮
C₂	乙二醇

图3 葡萄糖转化为山梨醇和甘露醇的反应路径

Fig.3 Proposed pathways for conversion of glucose to sorbitol and mannitol

图4 葡萄糖和甘露糖转化为乙二醇、赤藓糖醇和苏糖醇的反应路径

Fig.4 Proposed pathways for conversion of glucose and mannose to ethylene glycol, erythritol and threitol

图5 果糖转化为甘油和1,2-丙二醇的反应路径

Fig.5 Proposed pathways for conversion of fructose to glycerol and 1,2-propanediol

图6 葡萄糖加氢转化的反应网络简图

Fig.6 Simplified reaction networks of 2%Ni-30%W2C/AC catalyzed glucose conversion

表6 碱催化剂用量对葡萄糖加氢转化的影响

Table 6 Effect of base catalyst amount on glucose conversion

Base amount	Conversion/%	Yield/%
Base amount	Conversion/%	Ery	Gly	EG	1,2-PG	Sor	C₃	Others
0	100	5.7	2.7	30.1	10.8	15.6	13.5	34.4
6%Ba(OH)₂	100	1.1	13.2	7.1	28.5	14.4	41.7	35.7
10%Ba(OH)₂	100	1.5	14.4	5.1	30.0	8.7	44.4	40.3
15%Ba(OH)₂	100	1.1	8.2	3.2	25.2	13.2	33.4	50.2

表7 催化剂用量对10%葡萄糖加氢转化的影响

Table 7 Effect of catalyst amount on 10% glucose conversion

Catalyst amount/g	Yield /%						Coking
Catalyst amount/g	Ery	Gly	EG	1,2-PG	Sor	Others	Coking
0.5^①	trace	trace	trace	trace	trace	100	yes
0.5	trace	trace	trace	trace	trace	100	yes
1.0	4.8	3.2	18.6	4.9	22.1	43.4	no
1.5	6.1	4.1	17.1	4.6	38.5	26.2	no
2.0	5.6	3.8	7.7	2.8	67.1	10.2	no
3.0	6.4	3.7	9.6	3.0	66.7	8.9	no

表8 足量催化剂下初始浓度对葡萄糖加氢转化的影响

Table 8 Effect of initial glucose concentration on glucose conversion

Catalyst amount/g	Glucose concentration/%(mass)	(Glucose amount/ catalyst amount)/ (g/g)	Yield/%
Catalyst amount/g	Glucose concentration/%(mass)	(Glucose amount/ catalyst amount)/ (g/g)	Ery	Gly	EG	1,2-PG	Sor	Others
0.5	0.5	3.3/1	7.4	3.0	52.2	15.8	5.9	15.7
2.0	2	3.3/1	9.4	2.9	39.9	12.9	21.2	13.7
3.03^①	10	3.3/1	5.7	3.7	9.6	2.9	66.7	11.4

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Ni-W₂C催化葡萄糖氢解制备低碳二元醇反应机理研究

Mechanistic study on catalytic conversion of glucose into low carbon glycols over nickel promoted tungsten carbide catalyst

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