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

李伟杰; 张传明; 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和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: 32
- HTML全文浏览量: 23
- PDF下载量: 11
- 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

Study on highly efficient hydrogenation of methyl acetate over the lanthanum metal-modified Cu/SiO₂ catalyst

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 and 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，并研究了其催化乙酸甲酯（MeOAc）气相加氢制乙醇（EtOH）的性能。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）等表征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，在相同反应条件下，La掺杂量0.5%的Cu/SiO₂催化剂表现出最佳的催化性能，获得了98.5%乙酸甲酯转化率和98.5%乙醇选择性，乙醇的总收率达97.0%。
- 乙酸甲酯 /
- 加氢 /
- 乙醇 /
- Cu/SiO₂ /
- La改性
Abstract: The lanthanum (La)-modified Cu/SiO₂ catalysts were synthesized by ammonia-evaporation method and applied in the gas-phase hydrogenation of methyl acetate (MeOAc) to produce ethanol (EtOH). These catalysts were characterized by means of the N₂ adsorption–desorption, XRD, ICP-OES, H₂-TPR, FT-IR, HRTEM, XPS, and AES techniques and so on in detail. Introduction of the La metal results in a strong interplay between the Cu and La, leading to generation of the copper phyllosilicate in a more amount. This increases the specific surface area of the catalyst of which the particle size of the copper metal is thus reduced. Addition of the La also makes the copper species more dispersed over the SiO₂ support. Especially, the Cu⁺ contents are increased, as then enhances an electronic absorption of the substrate MeOAc by the acyl and methoxide groups. Compared with the unmodified Cu/SiO₂ catalyst, the La-mixed (0.5%) Cu/SiO₂ catalyst showed the excellent catalytic property. The conversion of MeOAc by 98.5% was achieved along with the ethanol selectivity of 98.5%. A total yield of 97.0% for ethanol was therefore produced.
- methyl acetate /
- hydrogenation /
- ethanol /
- Cu/SiO₂ /
- La modification

HTML全文

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 profiles of the catalyst precursors with different La loadings

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 Tests of the catalysts with different La loadings by N₂ adsorption-desorption isotherm (a) and pore distribution curves (b)

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 profiles of catalysts with different La loadings upon treatment by calcination (a) and reduction (b)

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 The H₂-TPR curves of the 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 The Cu 2p (a) and La 3d (b) XPS spectra of the H₂-reduced 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 The Cu LMM XAES spectra of the reduced 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 The TEM images and the particle size distribution images of the reduced catalysts with different La loadings: (a) 30Cu/SiO₂, (b) 30Cu-0.5La/SiO₂, (c) 30Cu-1La/SiO₂, and (d) 30Cu-2La/SiO₂ (The insets are the particle size distribution for the reduced catalysts); (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结果

Table 1 Catalytic result for hydrogenation of MeOAc to EtOH by using 30Cu-nLa/SiO₂ 30Cu/SiO₂, 2La/SiO₂, and SiO₂

Catalyst	t_MeOAc/%	s_EtOH/%	乙酸乙酯选择性/%	w_EtOH/%
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	−	−	−
Conditions: t = 230 ℃, p = 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 Structural properties of the catalysts with different La loadings

catalyst	w_Cu/%	w_La/%	S_BET^b/(m²·g⁻¹)	d_pore^c/(cm³·g⁻¹)	v_pore^d/(cm³·g⁻¹)	d_Cu^e/nm	d_Cu^f/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: ^a: Tested by ICP-OES, ^b: Specific surface area, ^c: Averaged pore diameter, ^d: Averaged pore volume at p/p₀ = 0.995, ^e: Calculated from the Debye-Scheerer formula, ^f: Obtained through the TEM measurement.

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 Deconvolution results of XPS and Cu LMM XAES of the reduced catalysts with different La loadings

catalyst	XPS binding energy/eV		XAES kinetic energy/eV		x_Cu⁺/%
	Cu 2p_1/2	Cu 2p_3/2	Cu⁺	Cu⁰
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 Zhi-lian, TAI Zhi-jun, 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,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. 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. 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. ACS Catal. , 2015, 5(7): 4439-4448.
[8]	ZHANG X, WILSON K, LEE A. Heterogeneously catalyzed hydrothermal processing of C₅–C₆ sugars. 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. Chem. Soc. Rev. , 2012, 41(24): 8075-8098.
[10]	BRANDS D S, POELS E K, BLIEK A. Ester hydrogenolysis over promoted Cu/SiO₂ catalysts. Appl. Catal. A, 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. 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. 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. 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. 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. Appl. Catal. A, 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. Appl. Catal. A, 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. 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. 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 Zhu-xia, QIAN Zhi-gang, ZHAO Xiu-ge, 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. 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. 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 Wen-long, ZHAO Yu-jun, WANG Sheng-ping, 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 and Applied Chemistry,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 Shu-zhi, XU Pei-qiang, LI Rui-da. 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. 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. Appl. Catal. A, 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. Appl. Catal. A, 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. 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. 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. 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. 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. 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. 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