镧改性Cu/SiO<sub>2</sub>催化剂的乙酸甲酯高效加氢催化性能研究

张传明; 李伟杰; 康金灿; 林丽娜; 李昌鑫; 李林才; 邹昊宇; 朱红平

doi:10.1016/S1872-5813(23)60382-2

镧改性Cu/SiO₂催化剂的乙酸甲酯高效加氢催化性能研究

doi: 10.1016/S1872-5813(23)60382-2

厦门大学化学化工学院固体表面物理化学国家重点实验室醇醚酯化工清洁生产国家工程实验室, 福建厦门 361005

基金项目: 国家自然科学基金（21972112，22172123）和福建省高校产学合作项目（2021H6002）资助

详细信息

通讯作者:
E-mail: kangjc@xmu.edu.cn

hpzhu@xmu.edu.cn

中图分类号: O643.38
计量
- 文章访问数: 284
- HTML全文浏览量: 77
- PDF下载量: 97
- 被引次数: 0
出版历程
- 收稿日期: 2022-07-03
- 修回日期: 2022-08-04
- 录用日期: 2023-08-02
- 网络出版日期: 2023-09-18
- 刊出日期: 2024-02-02

Catalytic performance of La-modified Cu/SiO₂ in the hydrogenation of methyl acetate

State Key Laboratory of Physical Chemistry of Solid Surfaces, National Engineering Laboratory for Green Chemical Productions of Alcohols-Ethers-Esters, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China

Funds: The project was supported by National Natural Science Foundation of China (21972112, 22172123) and Productive and Researching Foundation of Fujian Province (2021H6002).

摘要

摘要: 采用蒸氨法制备了镧（La）改性的负载型铜硅（Cu/SiO₂）催化剂，并对其乙酸甲酯（MeOAc）气相加氢制乙醇（EtOH）的催化性能进行了研究。采用N₂吸附-脱附（N₂ adsorption-desorption）、X射线粉末衍射（XRD）、电感耦合等离子体发射光谱（ICP-OES）、氢气程序升温还原（H₂-TPR）、傅里叶红外光谱（FT-IR）、高分辨透射电镜（HRTEM）、光电子能谱（XPS）和原子发射光谱仪（AES）等手段对催化剂进行了的表征，发现La物种的加入产生了较多的层状硅酸铜，增强了Cu和La物种之间的相互作用。La物种的加入在结构方面提高了催化剂的比表面积，降低了铜物种的粒径，提高了铜物种的分散度；在电子还原调控方面提高了Cu⁺的含量，增强了催化剂吸附酰基和甲氧基的能力。与未改性的Cu/SiO₂催化剂相比，镧改性后Cu/SiO₂催化剂的乙酸甲酯加氢性能得到大幅提升；其中La掺杂量0.5%的Cu/SiO₂催化剂表现出最佳的催化性能，乙酸甲酯转化率达98.5%，乙醇的总收率为97.0%。
- 乙酸甲酯 /
- 加氢 /
- 乙醇 /
- Cu/SiO₂ /
- La改性
Abstract: A series of Cu/SiO₂ catalysts modified with lanthanum (La) (30Cu-nLa/SiO₂, n=0, 0.5, 1 and 2) were synthesized using the ethanol (EtOH)-assisted ammonia-evaporation method; their catalytic performance in the gas-phase hydrogenation of methyl acetate (MeOAc) to produce ethanol (EtOH) was investigated. The results indicate that the catalytic performance of Cu/SiO₂ can be greatly enhanced by La modification. In particular, the 30Cu-0.5La/SiO₂ catalyst exhibits excellent performance in the MeOAc hydrogenation; under 230 °C, 2 MPa H₂, an LHSV of 2 h⁻¹ and an H₂/MeOAc molar ratio of 20, the MeOAc conversion reaches 98.5%, with a total EtOH yield of 97.0%. The N₂-sorption, XRD, ICP-OES, H₂-TPR, FT-IR, TEM, XPS, and AES characterization results reveal that the introduced La metal has a strong interaction with Cu, which can promote the dispersion of the copper species on the SiO₂ support. Moreover, the content of Cu⁺ is increased significantly, which can enhance the electronic interaction with MeOAc via the acyl and methoxide groups and thus promote the hydrogenation of MeOAc to EtOH.
- methyl acetate /
- hydrogenation /
- ethanol /
- Cu/SiO₂ /
- La modification

HTML全文

FIG. 2922. FIG. 2922.

下载: 全尺寸图片幻灯片

图 1 不同La掺杂量催化剂的沉淀前驱体FT-IR谱图

Figure 1 FT-IR spectra of the pre-calcined 30Cu- nLa/SiO₂ samples ( n=0, 0.5, 1, and 2)

下载: 全尺寸图片幻灯片

图 2 不同La掺杂量催化剂的N₂吸附-脱附等温线（a）和孔径分布（b）

Figure 2 N₂ adsorption-desorption isotherms (a) and pore distribution curves (b) of the 30Cu-nLa/SiO₂ catalysts with different La loadings

下载: 全尺寸图片幻灯片

图 3 不同La掺杂量的催化剂的XRD谱图

Figure 3 XRD patterns of the calcined (a) and reduced (b) 30Cu-nLa/SiO₂ catalysts with different La loadings

下载: 全尺寸图片幻灯片

图 4 不同La掺杂量催化剂的H₂-TPR谱图

Figure 4 H₂-TPR profiles of the 30Cu-nLa/SiO₂ catalysts with different La loadings

下载: 全尺寸图片幻灯片

图 5 不同La掺杂量的催化剂H₂还原后的Cu 2p（a）和La 3d（b） XPS谱图

Figure 5 Cu 2p (a) and La 3d (b) XPS spectra of the reduced 30Cu-nLa/SiO₂ catalysts with different La loadings

下载: 全尺寸图片幻灯片

图 6 不同La掺杂量的催化剂还原后的Cu LMM XAES谱图

Figure 6 Cu LMM XAES spectra of the reduced 30Cu-nLa/SiO₂ catalysts with different La loadings

下载: 全尺寸图片幻灯片

图 7 不同La掺杂量的还原后催化剂的TEM照片和粒径统计分布

Figure 7 TEM images of the reduced 30Cu- nLa/SiO₂ catalysts with different La loadings ((a) 30Cu/SiO₂, (b) 30Cu-0.5La/SiO₂, (c) 30Cu-1La/SiO₂, and (d) 30Cu-2La/SiO₂, where the insets display the particle size distribution) and (e) HRTEM image of 30Cu-0.5La/SiO₂

下载: 全尺寸图片幻灯片

表 1 30Cu-nLa/SiO₂、30Cu/SiO₂、2La/SiO₂、SiO₂催化乙酸甲酯加氢反应制乙醇的性能

Table 1 Catalytic reaction test results for the hydrogenation of MeOAc to EtOH

Catalyst	MeOAc conversion/ %	EtOH selectivity/ %	EtOAc selectivity/ %	EtOH yield/ %
30Cu/SiO₂	85.6	77.3	22.7	66.2
30Cu-0.5La/SiO₂	98.5	98.5	1.5	97.0
30Cu-1La/SiO₂	94.8	92.6	7.4	87.8
30Cu-2La/SiO₂	81.5	73.4	26.6	59.8
2La/SiO₂	1.40	68.7	31.3	1.0
SiO₂	0.10	−	−	−
Reaction conditions: 230 ℃, 2 MPa, LHSV=2 h⁻¹, and H₂/MeOAc=20.

下载: 导出CSV

表 2 不同La掺杂量的催化剂的组织结构特征

Table 2 Textural properties of the 30Cu-nLa/SiO₂ catalysts with different La loadings

Catalyst	Cu loading w/%	La loading w/%	S_BET/(m²·g⁻¹)	d_pore/(cm³·g⁻¹)	v_pore/(cm³·g⁻¹)	d_Cu-XRD/nm	d_Cu-TEM/nm
30Cu/SiO₂	29.6	0.0	295.3	6.0	0.44	5.4	5.4
30Cu-0.5La/SiO₂	29.0	0.47	350.4	4.9	0.43	4.8	4.5
30Cu-1La/SiO₂	27.9	1.01	336.2	5.4	0.45	5.7	5.5
30Cu-2La/SiO₂	28.9	1.91	323.7	5.9	0.49	6.2	5.8
Note: Cu and Cu loadings were measured by ICP-OES; Specific surface area (S_BET), averaged pore diameter (d_pore), and averaged pore volume (v_pore) are determined by N₂ sorption; d_Cu-XRD and d_Cu-TEM for the Cu particle sizes are obtained from XRD using the Debye-Scherrer formula and TEM measurement, respectively.

下载: 导出CSV

表 3 不同La掺杂量的催化剂还原后的XPS和Cu LMM XAES反卷积结果

Table 3 Summary of the Cu XPS and Cu-LMM results

Catalyst	Binding energy/eV		Kinetic energy/eV		x_Cu⁺/%
Catalyst	Cu 2p_1/2	Cu 2p_3/2	Cu⁺	Cu⁰	x_Cu⁺/%
30Cu	952.3	932.2	914.0	918.0	38.2
30Cu-0.5La	952.1	932.5	914.0	918.0	49.4
30Cu-1La	952.3	932.6	914.0	918.0	46.7
30Cu-2La	952.8	933.0	914.0	918.0	44.8

下载: 导出CSV

参考文献(36)

[1]	ZHOU W, KANG J, CHENG K, et al. Direct conversion of syngas into methyl acetate, ethanol, and ethylene by relay catalysis via the intermediate dimethyl ether[J]. Angew Chem, Int Ed,2018,57(37):12012−12016. doi: 10.1002/anie.201807113
[2]	王辉, 吴志连, 邰志军, 等. 合成气经二甲醚羰基化及乙酸甲酯加氢制无水乙醇的研究进展[J]. 化工进展,2019,38(10):4497−4503. doi: 10.16085/j.issn.1000-6613.2019-0161 WANG Hui, WU Zhilian, TAI Zhijun, et al. Advances in synthesis of anhydrous ethanol from syngas via carbonylation of dimethyl ether and hydrogenation of methyl acetate[J]. Chem Ind Eng Prog,2019,38(10):4497−4503. doi: 10.16085/j.issn.1000-6613.2019-0161
[3]	WEHNER P, GUSTAFSON B. Catalytic hydrogenation of esters over Pd/ZnO[J]. J Catal,1992,135(2):420−426. doi: 10.1016/0021-9517(92)90043-H
[4]	WANG L, NIU X, CHEN J. SiO₂ supported Ni-In intermetallic compounds: Efficient for selective hydrogenation of fatty acid methyl esters to fatty alcohols[J]. Appl Catal B: Environ,2020,278:119293. doi: 10.1016/j.apcatb.2020.119293
[5]	WANG Y, LIAO J, ZHANG J, et al. Hydrogenation of methyl acetate to ethanol by Cu/ZnO catalyst encapsulated in SBA-15[J]. AIChE J,2017,63(7):2839−2849.
[6]	KUMMER R, TAGLIBER V, SCHNEIDER H-W. Continuous production of ethanol and plural stage distillation of the same, US4454358[P]. 1984-06-12.
[7]	VANDENBERG R, PARMERTIER T E, ELKJÆR C F, et al. Support functionalization to retard Ostwald ripening in copper methanol synthesis catalysts[J]. ACS Catal,2015,5(7):4439−4448.
[8]	ZHANG X, WILSON K, LEE A. Heterogeneously catalyzed hydrothermal processing of C₅–C₆ sugars[J]. Chem Rev,2016,116(19):12328−12368.
[9]	ALONSO D M, WERRSREIN S G, DUMESIC J A. Bimetallic catalysts for upgrading of biomass to fuels and chemicals[J]. Chem Soc Rev,2012,41(24):8075−8098.
[10]	BRANDS D S, POELS E K, BLIEK A. Ester hydrogenolysis over promoted Cu/SiO₂ catalysts[J]. Appl Catal A: Gen,1999,184(2):279−289.
[11]	ZHANG Y, YE C, GUO C, et al. In₂O₃-modified Cu/SiO₂ as an active and stable catalyst for the hydrogenation of methyl acetate to ethanol[J]. Chin J Catal,2018,39(1):99−108.
[12]	YE C L, GUO C L, ZHANG J L. Highly active and stable CeO₂-SiO₂ supported Cu catalysts for the hydrogenation of methyl acetate to ethanol[J]. Fuel Process Technol,2016,143:219−224.
[13]	REN Z, YOUNIS M N, ZHAO H, et al. Silver modified Cu/SiO₂ catalyst for the hydrogenation of methyl acetate to ethanol[J]. Chin J Chem Eng,2020,28(6):1612−1622.
[14]	LI F, LU C S, LI X N. The effect of the amount of ammonia on the Cu⁰/Cu⁺ ratio of Cu/SiO₂ catalyst for the hydrogenation of dimethyl oxalate to ethylene glycol[J]. Chin Chem Lett,2014,25(11):1461−1465.
[15]	YIN A, GUO X, DAI W L, et al. Highly active and selective copper-containing HMS catalyst in the hydrogenation of dimethyl oxalate to ethylene glycol[J]. Appl Catal A: Gen,2008,349(1/2):91−99.
[16]	ZHAO Y, ZHANG Y, WANG Y, et al. Structure evolution of mesoporous silica supported copper catalyst for dimethyl oxalate hydrogenation[J]. Appl Catal A: Gen,2017,539:59−69.
[17]	HUANG Z, CUI F, XUE J, et al. Synthesis and structural characterization of silica dispersed copper nanomaterials with unusual thermal stability prepared by precipitation-gel method[J]. J Phys Chem C,2010,114(39):16104−16113.
[18]	VANDERGTIFT C J G, ELBERSE P A, MULDER A, et al. Preparation of silica-supported copper-catalysts by means of deposition precipitation[J]. Appl Catal,1990,59(2):275−289.
[19]	李竹霞, 钱志刚, 赵秀阁, 等. 草酸二甲酯加氢Cu/SiO₂催化剂前体的研究[J]. 华东理工大学学报(自然科学版),2004,30(6):613−617. doi: 10.3969/j.issn.1006-3080.2004.06.001 LI Zhuxia, QIAN Zhigang, ZHAO Xiuge, et al. Research on the precursor of catalyst Cu/SiO₂ for hydrogenation of dimethyl oxalate[J]. J East China Univ Sci Technol, Nat Sci Ed,2004,30(6):613−617. doi: 10.3969/j.issn.1006-3080.2004.06.001
[20]	TOUPANCE T, KERMAREC M, LOUIS C. Metal particle size in silica-supported copper catalysts. Influence of the conditions of preparation and of thermal pretreatments[J]. J Phys Chem B,2000,104(5):965−972.
[21]	VANDERGTIFT C J G, WIELERS A F H, JOGHI B P J, et al. Effect of the reduction treatment on the structure and reactivity of silica-supported copper particles[J]. J Catal,1991,131(1):178−189.
[22]	杨文龙, 赵玉军, 王胜平, 等. 铜硅催化剂中层状硅酸铜的形成过程[J]. 化学工业与工程,2016,33(1):1−5. doi: 10.13353/j.issn.1004.9533.20141120 YANG Wenlong, ZHAO Yujun, WANG Shengping, et al. Formation of copper phyllosilicate in silica supported copper catalyst[J]. Chem Ind Eng,2016,33(1):1−5. doi: 10.13353/j.issn.1004.9533.20141120
[23]	SING K S W. Reporting physisorption data for gas solid systems - with special reference to the determination of surface-area and porosity[J]. Pure Appl Chem,1982,54(11):2201−2218. doi: 10.1351/pac198254112201
[24]	刘淑芝, 徐培强, 李瑞达. 助剂La对Ni/γ-Al₂O₃催化剂加氢性能的影响[J]. 青岛科技大学学报(自然科学版),2016,37(4):388−391. LIU Shuzhi, XU Peiqiang, LI Ruida. Effect of La on Ni/γ-Al₂O₃ Catalyst in Benzene Hydrogenation[J]. J Qingdao Univ Sci Technol, Nat Sci Ed,2016,37(4):388−391.
[25]	LEI H, HOU Z, XIE J. Hydrogenation of CO₂ to CH₃OH over CuO/ZnO/Al₂O₃ catalysts prepared via a solvent-free routine[J]. Fuel,2016,164:191−198.
[26]	WANG Z L, LIU Q S, YU J F, et al. Surface structure and catalytic behavior of silica-supported copper catalysts prepared by impregnation and sol-gel methods[J]. Appl Catal A: Gen,2003,239(1/2):87−94.
[27]	MARCHI A J, FIERRO J L G, SANTAMARIA J, et al. Dehydrogenation of isopropylic alcohol on a Cu/SiO₂ catalyst: A study of the activity evolution and reactivation of the catalyst[J]. Appl Catal A: Gen,1996,142(2):375−386.
[28]	ZHENG X, LIN H, ZHENG J, et al. Lanthanum oxide-modified Cu/SiO₂ as a high-performance catalyst for chemoselective hydrogenation of dimethyl oxalate to ethylene glycol[J]. ACS Catal,2013,3(12):2738−2749.
[29]	GONG J, YUE H, ZHAO Y, et al. Synthesis of ethanol via syngas on Cu/SiO₂ catalysts with balanced Cu⁰-Cu⁺ sites[J]. J Am Chem Soc,2012,134(34):13922−13925.
[30]	HUANG J J, DING T, MA K, et al. Modification of Cu/SiO₂ catalysts by La₂O₃ to quantitatively tune Cu⁺-Cu⁰ dual sites with improved catalytic activities and stabilities for dimethyl ether steam reforming[J]. ChemCatChem,2018,10(17):3862−3871.
[31]	ZHU Y, KONG X, CAO D B, et al. The rise of calcination temperature enhances the performance of Cu catalysts: Contributions of support[J]. ACS Catal,2014,4(10):3675−3681.
[32]	XI Y, WANG Y, YAO D, et al. Impact of the oxygen vacancies on copper electronic state and activity of Cu-based catalysts in the hydrogenation of methyl acetate to ethanol[J]. ChemCatChem,2019,11(11):2607−2614.
[33]	AI P, TAN M, YAMANE N, et al. Synergistic effect of a boron-doped carbon-nanotube-supported Cu catalyst for selective hydrogenation of dimethyl oxalate to ethanol[J]. Chem Eur J,2017,23(34):8252−8261.
[34]	GONG X, WANG M, FANG H, et al. Copper nanoparticles socketed in situ into copper phyllosilicate nanotubes with enhanced performance for chemoselective hydrogenation of esters[J]. Chem Commun,2017,53(51):6933−6936. doi: 10.1039/C7CC02093G
[35]	YUE H, ZHAO Y, ZHAO S, et al. A copper-phyllosilicate core-sheath nanoreactor for carbon-oxygen hydrogenolysis reactions[J]. Nat Commun,2013,4(1):2339. doi: 10.1038/ncomms3339
[36]	WANG Z Q, XU Z N, PENG S Y, et al. High-performance and long-lived Cu/SiO₂ nanocatalyst for CO₂ hydrogenation[J]. ACS Catal,2015,5(7):4255−4259. doi: 10.1021/acscatal.5b00682