甲醇体系电镀污泥衍生磁性多金属材料催化糠醛加氢转化

doi:10.11949/0438-1157.20220385

化工学报 ›› 2022, Vol. 73 ›› Issue (7): 2996-3006.DOI: 10.11949/0438-1157.20220385

• 催化、动力学与反应器 • 上一篇下一篇

甲醇体系电镀污泥衍生磁性多金属材料催化糠醛加氢转化

张军^1,^2,³(),胡升^1,⁴(),顾菁^1,^2,³,袁浩然^1,^2,³(),陈勇^1,^2,³

^1.中国科学院广州能源研究所，广东广州 510640
^2.中国科学院可再生能源重点实验室，广东广州 510640
^3.广东省新能源和可再生能源研究开发与应用重点实验室，广东广州 510640
^4.中国科学技术大学工程科学学院，安徽合肥 230026

收稿日期:2022-03-17 修回日期:2022-06-22 出版日期:2022-07-05 发布日期:2022-08-01
通讯作者: 袁浩然
作者简介:张军(1987—)，男，博士，副研究员，zhangjun@ms.giec.ac.cn|胡升(1995—)，男，硕士研究生，hs950515@mail.ustc.edu.cn
基金资助:
国家自然科学基金面上项目(51976222);能源清洁利用国家重点实验室开放基金课题项目(ZJU-CEU2020023)

Catalytic hydrogenation of furfural over magnetic polymetallic materials derived from electroplating sludge in methanol

Jun ZHANG^1,^2,³(),Sheng HU^1,⁴(),Jing GU^1,^2,³,Haoran YUAN^1,^2,³(),Yong CHEN^1,^2,³

^1.Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences (CAS), Guangzhou 510640, Guangdong, China
^2.CAS Key Laboratory of Renewable Energy, Guangzhou 510640, Guangdong, China
^3.Guangdong Provincial Key Laboratory of New and Renewable Energy Research and Development, Guangzhou 510640, Guangdong, China
^4.School of Engineering Science, University of Science and Technology of China, Hefei 230026, Anhui, China

Received:2022-03-17 Revised:2022-06-22 Online:2022-07-05 Published:2022-08-01
Contact: Haoran YUAN

摘要/Abstract

摘要：

以电镀行业废弃物电镀污泥为前体合成磁性多金属催化材料，考察其在甲醇供氢体系生物基糠醛加氢转化制备糠醇和2-甲基呋喃的催化性能。通过X射线衍射(XRD)、液氮吸脱附、NH₃程序升温脱附(NH₃-TPD)、扫描电镜(SEM)等手段对煅烧后电镀污泥进行表征，并研究了煅烧温度和各反应工艺条件对甲醇供氢体系糠醛转化的影响。结果表明，电镀污泥衍生磁性多金属材料均具有强酸性位点和部分介孔结构，以铜组分为主的催化活性中心在反应过程中部分被还原为零价，有助于促进甲醇重整产氢和糠醛加氢转化；以700℃煅烧的电镀污泥为催化剂，在240℃反应2 h以上，糠醛几乎完全转化，产物中糠醇和2-甲基呋喃最高收率(摩尔分数)分别为70.9%和31.9%，反应过程副产物以2-呋喃甲基甲醚和2-(二甲氧基甲基)呋喃为主。此外，基于甲醇重整产氢、铜镍组分原位还原以及糠醛加氢反应之间的耦合作用，推测出甲醇体系电镀污泥衍生磁性多金属材料催化糠醛加氢转化可能的反应机制。

关键词: 电镀污泥, 甲醇, 生物质, 糠醛, 加氢, 生物燃料

Abstract:

Magnetic multimetallic catalytic materials were synthesized by using electroplating sludge from electroplating industry as precursors, which were applied for the transfer hydrogenation of bio-based furfural using methanol as hydrogen donor. The calcined electroplating sludge was characterized by X-ray diffraction (XRD), liquid nitrogen adsorption and desorption, NH₃ temperature-programmed desorption (NH₃-TPD) and scanning electron microscopy (SEM). The effects of calcination temperature and reaction conditions on furfural conversion using methanol as hydrogen source were conducted. The results showed that the magnetic polymetallic materials had strong acid sites and partial mesoporous structure. Moreover, the copper component could be partially activated into Cu⁰ during the reaction, which benefited the hydrogen production from methanol reforming and followed furfural hydrogenation. Using electroplating sludge calcined at 700℃ as catalyst, furfural was almost completely transformed at 240℃ when prolonging reaction time over 2 h, in which the yields of furfuryl alcohol and 2-methylfuran reached up to 70.9% and 31.9% respectively. Noticeably, 2-furylmethyl methyl ether and 2-(dimethoxymethyl) furan were detected as the main by-products during the reaction. In addition, on the basis of the coupling effect among methanol reforming into H₂, in-situ reduction of copper/nickel components and furfural hydrogenation, the plausible reaction mechanism for furfural hydrogenation over magnetic polymetallic materials derived from electroplating sludge using methanol as hydrogen source and solvent was proposed.

Key words: electroplating sludge, methanol, biomass, furfural, hydrogenation, biofuel

中图分类号:

TQ 251

张军, 胡升, 顾菁, 袁浩然, 陈勇. 甲醇体系电镀污泥衍生磁性多金属材料催化糠醛加氢转化[J]. 化工学报, 2022, 73(7): 2996-3006.

Jun ZHANG, Sheng HU, Jing GU, Haoran YUAN, Yong CHEN. Catalytic hydrogenation of furfural over magnetic polymetallic materials derived from electroplating sludge in methanol[J]. CIESC Journal, 2022, 73(7): 2996-3006.

图/表 18

表1 电镀污泥主要元素成分

Table 1 Main elemental compositions of electroplating sludge

组成	质量分数/%
Fe	44.57
Cu	30.28
O	14.28
Ni	2.51
Sn	2.35
S	2.04
Si	1.04
Ca	0.96
其他	1.97

图1 煅烧后电镀污泥XRD谱图

Fig.1 XRD patterns of calcined electroplating sludge

图2 CES-T样品N2吸附-脱附等温线

Fig.2 N2 adsorption-desorption isotherms of as-prepared CES-T

表2 CES-T催化剂结构特性

Table 2 Structural properties of as-prepared CES-T

样品	比表面积/(m²/g)	平均孔径/nm	总孔容/(cm³/g)
CES-400	82.53	29.41	0.34
CES-550	48.13	30.20	0.21
CES-700	41.10	54.05	0.17
CES-850	10.14	3.41	0.02
CES-700R	25.47	3.86	0.10

图3 CES-T和CES-700R样品SEM图

Fig.3 SEM images of as-prepared CES-T and CES-700R

图4 CES-T催化剂NH3-TPD谱图

Fig.4 NH3-TPD profiles of as-prepared CES-T samples

表3 CES-T样品酸性位点分布

Table 3 Acid site distribution of as-prepared CES-T

样品	弱酸性/(μmol/g)	中等酸性/(μmol/g)	强酸性/(μmol/g)	总酸量/(μmol/g)
CES-400	1.8	2.4	8.1	12.3
CES-550	1.3	2.2	6.8	10.3
CES-700	—	—	24.6	24.6
CES-850	1.9	—	18.5	20.4

图5 催化剂回收前后的XPS谱图

Fig.5 XPS spectra of fresh and used CES-700

图6 CES-700催化甲醇重整气相色谱图(反应条件：甲醇12 ml，CES-700 30 mg，220℃, 2 h)

Fig.6 GC graph for methanol reforming over CES-700 (reaction conditions: methanol 12 ml, CES-700 30 mg, 220℃, 2 h)

表4 CES-700催化甲醇重整气相产物分布

Table 4 Gas phase product distribution from methanol reforming over CES-700

保留时间/min	组分	含量/%(体积分数)
1.001	H₂	11.41
1.807	CH₄	0.20
2.092	C₂H₆	0.0003
2.323	C₂H₄	0.0005
2.469	CO₂	0.74
6.702	CO	2.57

表5 CES-T对FFR转移加氢反应的催化活性

Table 5 Catalytic performance of CES-T on transfer hydrogenation of FFR

样品	FFR转化率/%	FA收率/%	MF收率/%
CES-400	58.4	3.7	0.8
CES-550	60.9	4.1	2.9
CES-700	96.8	40.4	5.9
CES-850	75.0	35.5	0.5

图7 反应温度对FFR加氢转化的影响(反应条件：FFR 0.6 mmol，甲醇12 ml，CES-700 30 mg，2 h)

Fig.7 Effect of reaction temperature on FFR hydrogenation (reaction conditions: FFR 0.6 ml, methanol 12 ml, CES-700 30 mg, 2 h)

图8 FFR加氢转化产物离子色谱图

Fig.8 The ion chromatogram of obtained products from FFR hydrogenation

图9 催化剂用量对FFR转移加氢的影响(反应条件：FFR 0.6 mmol，甲醇12 ml，240℃，2 h)

Fig.9 Effect of catalyst dosage on the transfer hydrogenation of FFR (reaction conditions: FFR 0.6 mmol, methanol 12 ml, 240℃, 2 h)

图10 反应时间对FFR转移加氢的影响(反应条件：FFR 0.6 mmol，甲醇12 ml，CES-700 20 mg，240℃)

Fig.10 Effect of reaction time on the transfer hydrogenation of FFR (reaction conditions: FFR 0.6 mmol, methanol 12 ml, CES-700 20 mg, 240℃)

图11 催化剂循环使用性能(反应条件：FFR 0.6 mmol，甲醇12 ml，CES-700 30 mg，240℃，2 h)

Fig.11 Catalyst recycling (reaction conditions: FFR 0.6 mmol, methanol 12 ml, CES-700 30 mg, 240℃, 2 h)

图12 使用后CES-700催化剂的热重特性图

Fig.12 Thermogravimetric characteristics of used CES-700

图13 甲醇供氢体系CES-T催化FFR加氢转化反应路径

Fig.13 Reaction path for FFR hydrogenation over CES-T using methanol as hydrogen donor

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甲醇体系电镀污泥衍生磁性多金属材料催化糠醛加氢转化

Catalytic hydrogenation of furfural over magnetic polymetallic materials derived from electroplating sludge in methanol

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