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

doi:10.11949/0438-1157.20220385

Abstract

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

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

CLC Number:

TQ 251

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.

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.

Figures/Tables 18

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

Fig.1 XRD patterns of calcined electroplating sludge

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

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

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

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

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

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

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

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

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

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

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

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

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℃)

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

Fig.12 Thermogravimetric characteristics of used CES-700

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

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