Effect of mesoporous construction on catalytic performance of CuY methanol oxidative carbonylation

doi:10.11949/0438-1157.20201937

Abstract

Abstract:

H₄EDTA, H₂Na₂EDTA and NaOH aqueous solutions were used to modify the original NaY zeolite separately by acid-base modification and continuous acid-base modification, and the corresponding CuY catalyst was prepared by the liquid-phase ion exchange method. The N₂-physisorption, TEM, XRD, ²⁹Si NMR, ²⁷Al NMR, NH₃-TPD, Py-IR, ICP, XPS and CO-FTIR were used to characterize the structure of the support and catalyst. The effect of mesoporous construction in NaY zeolite on catalytic performance of CuY for oxidative carbonylation of methanol was investigated. The results indicated that partial framework Al of NaY zeolite were extracted after sole treatment by H₄EDTA, with the formation of extra-framework Si and Al species, and the obtained E-NaY did not form obvious mesoporous. Extra-framework and partial framework Al of E-NaY zeolite were removed after acid washing by H₂Na₂EDTA, and the obtained EW-NaY generated obvious mesoporous. The extracted Al species were reinserted back into the framework of zeolite accompanied with desilication during alkali treatment of E-NaY and EW-NaY by 0.2 mol/L NaOH, and abundant mesopores were formed in the obtained E0.2AT-NaY and EW0.2AT-NaY zeolite. Moreover, the utilization of exchanged sites for Cu⁺ accessible to reactants for EW0.2AT-NaY attained the maximum due to the highest mesopore volume (0.45 cm³/g) and abundant Al-defects structure. Nevertheless, the number of exchanged sites for Cu⁺ (66 μmol/g) accessible to reactants was significantly less than that of E0.2AT-NaY (176 μmol/g) due to higher dealumination degree of EW0.2AT-NaY than that of E0.2AT-NaY. Consequently, the number of Cu⁺ active sites and catalytic activity for EW0.2AT-CuY were just slightly lower than that for E0.2AT-CuY, and the catalytic activities for both were about 2.2 times as that of the pristine CuY catalyst.

Key words: zeolite, catalyst, mesopore, Cu⁺ active sites, oxidative carbonylation

摘要：

采用H₄EDTA、H₂Na₂EDTA和NaOH溶液对原始NaY分子筛分别进行单独酸碱改性和酸碱连续改性，并采用液相离子交换法制备相应的CuY催化剂。结合N₂物理吸附、TEM、XRD、²⁹Si NMR、²⁷Al NMR、NH₃-TPD、Py-IR、ICP、XPS和CO-FTIR等对载体和催化剂的结构进行表征，研究了NaY分子筛介孔构建对CuY催化甲醇氧化羰基化反应活性的影响。结果表明，NaY分子筛经H₄EDTA单独处理后，部分骨架铝被脱除形成非骨架硅铝物种，得到的E-NaY并未形成明显的介孔；E-NaY经H₂Na₂EDTA酸洗处理后，非骨架铝和部分骨架铝被脱除，得到的EW-NaY具有明显的介孔结构；而E-NaY和EW-NaY经0.2 mol/L NaOH碱处理后，分子筛发生脱硅，同时伴随着非骨架铝重新插回分子筛骨架，得到的E0.2AT-NaY和EW0.2AT-NaY具有丰富的介孔结构。其中，EW0.2AT-NaY的介孔孔容（0.45 cm³/g）最大，且有丰富的Al缺陷结构，能够与反应物接触的Cu⁺交换位利用率最高。然而，由于EW0.2AT-NaY脱铝程度明显高于E0.2AT-NaY，导致能够与反应物接触的Cu⁺交换位数量（66 μmol/g）明显小于E0.2AT-NaY（176 μmol/g），最终导致EW0.2AT-CuY催化剂中Cu⁺活性位数量及催化活性略低于E0.2AT-CuY，二者的催化活性约为原始CuY催化剂的2.2倍。

关键词: 分子筛, 催化剂, 介孔, Cu⁺活性位, 氧化羰基化

CLC Number:

TQ 028.8

Jiahao LIANG, Guoqiang ZHANG, Yuan GAO, Jiao YIN, Huayan ZHENG, Zhong LI. Effect of mesoporous construction on catalytic performance of CuY methanol oxidative carbonylation[J]. CIESC Journal, 2021, 72(9): 4685-4697.

梁家豪, 张国强, 高源, 尹娇, 郑华艳, 李忠. 介孔构建对CuY甲醇氧化羰基化反应活性的影响[J]. 化工学报, 2021, 72(9): 4685-4697.

Figures/Tables 17

Fig.1 N2-physisorption of NaY zeolites

Table 1 Textural properties and relative crystallinity of NaY zeolites

Sample	S_BET^①/ (m²/g)	S_micro^②/ (m²/g)	S_meso^②/ (m²/g)	V_total^③/ (cm³/g)	V_micro^②/ (cm³/g)	V_meso^④/ (cm³/g)	D_meso/ nm	Crystallinity^⑤/ %
NaY	775	758	17	0.38	0.31	0.07	1.91	100
E-NaY	620	595	25	0.36	0.27	0.09	1.93	24
EW-NaY	628	438	190	0.39	0.21	0.18	3.45	32
0.2AT-NaY	718	697	20	0.42	0.33	0.09	1.93	92
E0.2AT-NaY	720	627	93	0.53	0.29	0.24	3.59	67
EW0.2AT-NaY	670	465	205	0.66	0.21	0.45	3.59	52

Fig.2 TEM images of NaY zeolites

Fig.3 XRD patterns of NaY zeolites

Fig.4 29Si MAS NMR and 27Al MAS NMR spectra of NaY zeolites

Table 2 Relative content of various Si units and framwork ratio of Si/Al calculated from 29Si MAS NMR spectra

Sample	Relative content of various Si units/%						n (Si)/ n (Al)
Sample	Si(4Al)	Si(3Al)	Si(2Al)	Si(1Al)	Si(0Al)	Amorphous Si	n (Si)/ n (Al)
NaY	3.24	10.25	32.75	43.62	10.15	—	2.30
E-NaY	2.55	8.18	18.74	47.92	15.49	7.12	2.96
EW-NaY	1.95	5.33	18.24	53.14	12.06	5.98	3.17
0.2AT-NaY	5.05	14.44	35.14	37.49	7.88	—	2.33
E0.2AT-NaY	4.57	16.05	38.35	30.83	10.2	—	2.35
EW0.2AT-NaY	4.04	13.48	28.29	45.14	9.05	—	2.54

Fig.5 NH3-TPD profiles of HY zeolites

Table 3 Acidity of HY zeolites

Sample	Acidity/(mmol/g)^①	Acidity/(μmol/g)^②
Sample	Total	Br?nsted	Lewis
HY	2.429	96	71
E-HY	0.749	47	65
EW-HY	0.510	54	61
0.2AT-HY	1.946	191	103
E0.2AT-HY	1.864	176	124
EW0.2AT-HY	1.072	66	97

Fig.6 FTIR spectra of pyridine adsorption on HY zeolites

Fig.7 XRD patterns of CuY catalysts

Fig.8 Representative TEM and HRTEM images of CuY catalysts

Fig.9 Cu 2p3/2 XPS spectra of CuY catalysts

Table 4 Quantitative analysis of the Cu 2p3/2 XPS curve fitting of CuY catalysts

Catalyst	Peak area		(Cu⁺/Cu_sum)/%
Catalyst	Cu⁺	Cu²⁺	(Cu⁺/Cu_sum)/%
CuY	38508.2	14516.7	72.6
E-CuY	22944.8	7801.4	74.6
EW-CuY	27367.8	8287.9	76.7
0.2AT-CuY	36988.2	13005.5	73.9
E0.2AT-CuY	42272.8	9049.7	82.3
EW0.2AT-CuY	45612.5	8050.7	84.9

Table 5 Catalytic performance of CuY catalysts for oxidative carbonylation of methanol

Catalyst	w_Cu^①/%	CO-Cu⁺peak area^②	CO-Cu⁺ peak area/ Br?nsted^③	STY_DMC/(mg/(g·h))	X_CH $3$ _OH/%	Selectivity of products/%
Catalyst	w_Cu^①/%	CO-Cu⁺peak area^②	CO-Cu⁺ peak area/ Br?nsted^③	STY_DMC/(mg/(g·h))	X_CH $3$ _OH/%	DMC	DME	DMM	MF
CuY	5.4	2.6	0.027	75.3	2.8	49.1	3.7	39.4	7.8
E-CuY	5.8	3.9	0.082	101.7	3.2	59.4	1.3	27.2	12.1
EW-CuY	5.9	4.6	0.085	131.1	4.2	61.4	1.1	23.2	14.3
0.2AT-CuY	6.0	3.4	0.018	93.0	3.1	54.8	1.7	31.5	11.9
E0.2AT-CuY	5.8	6.8	0.039	172.7	5.7	65.3	1.0	28.1	6.2
EW0.2AT-CuY	5.0	5.9	0.089	166.2	5.3	65.2	1.1	27.1	6.5

Table 5 Catalytic performance of CuY catalysts for oxidative carbonylation of methanol

Catalyst	w_Cu^①/%	CO-Cu⁺peak area^②	CO-Cu⁺ peak area/ Br?nsted^③	STY_DMC/(mg/(g·h))	X_CH $3$ _OH/%	Selectivity of products/%
Catalyst	w_Cu^①/%	CO-Cu⁺peak area^②	CO-Cu⁺ peak area/ Br?nsted^③	STY_DMC/(mg/(g·h))	X_CH $3$ _OH/%	DMC	DME	DMM	MF
CuY	5.4	2.6	0.027	75.3	2.8	49.1	3.7	39.4	7.8
E-CuY	5.8	3.9	0.082	101.7	3.2	59.4	1.3	27.2	12.1
EW-CuY	5.9	4.6	0.085	131.1	4.2	61.4	1.1	23.2	14.3
0.2AT-CuY	6.0	3.4	0.018	93.0	3.1	54.8	1.7	31.5	11.9
E0.2AT-CuY	5.8	6.8	0.039	172.7	5.7	65.3	1.0	28.1	6.2
EW0.2AT-CuY	5.0	5.9	0.089	166.2	5.3	65.2	1.1	27.1	6.5

Fig.10 Variation of STYDMC with time on stream of the catalysts

Fig.11 FTIR spectra of CO adsorption on CuY catalysts

Fig.12 The relationship between the space time yield of DMC and CO-Cu+ peak area

References 40

1	Olsbye U, Svelle S, Bjørgen M, et al. Conversion of methanol to hydrocarbons: how zeolite cavity and pore size controls product selectivity[J]. Angewandte Chemie International Edition, 2012, 51(24): 5810-5831.
2	Dai W L, Yang L, Wang C M, et al. Effect of n-butanol cofeeding on the methanol to aromatics conversion over Ga-modified nano H-ZSM-5 and its mechanistic interpretation[J]. ACS Catalysis, 2018, 8(2): 1352-1362.
3	Saada R, AboElazayem O, Kellici S, et al. Greener synthesis of dimethyl carbonate using a novel tin-zirconia/graphene nanocomposite catalyst[J]. Applied Catalysis B: Environmental, 2018, 226: 451-462.
4	Tian P, Wei Y X, Ye M, et al. Methanol to olefins (MTO): from fundamentals to commercialization[J]. ACS Catalysis, 2015, 5(3): 1922-1938.
5	Aricò F, Tundo P. Dimethyl carbonate as a modern green reagent and solvent[J]. Russian Chemical Reviews, 2010, 79(6): 479-489.
6	Huang S Y, Yan B, Wang S P, et al. Recent advances in dialkyl carbonates synthesis and applications[J]. Chemical Society Reviews, 2015, 44(10): 3079-3116.
7	Nam J K, Choi M J, Cho D H, et al. The influence of support in the synthesis of dimethyl carbonate by Cu-based catalysts[J]. Journal of Molecular Catalysis A: Chemical, 2013, 370: 7-13.
8	Ding X S, Dong X M, Kuang D T, et al. Highly efficient catalyst PdCl₂-CuCl₂-KOAc/AC@Al₂O₃ for gas-phase oxidative carbonylation of methanol to dimethyl carbonate: preparation and reaction mechanism[J]. Chemical Engineering Journal, 2014, 240: 221-227.
9	Itoh H, Watanabe Y, Mori K J, et al. Synthesis of dimethyl carbonate by vapor phase oxidative carbonylation of methanol[J]. Green Chem., 2003, 5(5): 558-562.
10	Dang T T H, Bartoszek M, Schneider M, et al. Chloride-free Cu-modified SAPO-37 catalyst for the oxidative carbonylation of methanol in the gas phase[J]. Applied Catalysis B: Environmental, 2012, 121/122: 115-122.
11	Zhang Y H, Bell A T. The mechanism of dimethyl carbonate synthesis on Cu-exchanged zeolite Y[J]. Journal of Catalysis, 2008, 255(2): 153-161.
12	Zhang Y H, Briggs D N, de Smit E, et al. Effects of zeolite structure and composition on the synthesis of dimethyl carbonate by oxidative carbonylation of methanol on Cu-exchanged Y, ZSM-5, and mordenite[J]. Journal of Catalysis, 2007, 251(2): 443-452.
13	Wang H B, Zhang H, Hu J, et al. Metal-halide/ionic-liquid oxidative carbonylation of ethanol to synthesize diethyl carbonate with high activity and low corrosion[J]. ChemistrySelect, 2019, 4(45): 13265-13270.
14	Richter M, Fait M J G, Eckelt R, et al. Gas-phase carbonylation of methanol to dimethyl carbonate on chloride-free Cu-precipitated zeolite Y at normal pressure[J]. Journal of Catalysis, 2007, 245(1): 11-24.
15	李忠, 付廷俊, 郑华艳. CuY制备方法对其催化甲醇氧化羰基化活性中心的影响[J]. 无机化学学报, 2011, 27(8): 1483-1490.
	Li Z, Fu T J, Zheng H Y. Effect of preparation method on catalytic active center of CuY for oxidative carbonylation of methanol[J]. Chinese Journal of Inorganic Chemistry, 2011, 27(8): 1483-1490.
16	Engeldinger J, Domke C, Richter M, et al. Elucidating the role of Cu species in the oxidative carbonylation of methanol to dimethyl carbonate on CuY: an in situ spectroscopic and catalytic study[J]. Applied Catalysis A: General, 2010, 382(2): 303-311.
17	Drake I J, Zhang Y H, Briggs D, et al. The local environment of Cu⁺ in Cu-Y zeolite and its relationship to the synthesis of dimethyl carbonate[J]. The Journal of Physical Chemistry B, 2006, 110(24): 11654-11664.
18	Huang S Y, Chen P Z, Yan B, et al. Modification of Y zeolite with alkaline treatment: textural properties and catalytic activity for diethyl carbonate synthesis[J]. Industrial & Engineering Chemistry Research, 2013, 52(19): 6349-6356.
19	Beyerlein R A, Choi-Feng C, Hall J B, et al. Effect of steaming on the defect structure and acid catalysis of protonated zeolites[J]. Topics in Catalysis, 1997, 4(1/2): 27-42.
20	Zhang G Q, Liang J H, Yin J, et al. An efficient strategy to improve the catalytic activity of CuY for oxidative carbonylation of methanol: modification of NaY by H₄EDTA-NaOH sequential treatment[J]. Microporous and Mesoporous Materials, 2020, 307: 110500.
21	Jiao W Q, Fu W H, Liang X M, et al. Preparation of hierarchically structured Y zeolite with low Si/Al ratio and its applications in acetalization reactions[J]. RSC Adv., 2014, 4(102): 58596-58607.
22	Sing K S W. Reporting physisorption data for gas/solid systems with special reference to the determination of surface area and porosity (Recommendations 1984)[J]. Pure and Applied Chemistry, 1985, 57(4): 603-619.
23	Verboekend D, Vilé G, Pérez-Ramírez J. Hierarchical Y and USY zeolites designed by post-synthetic strategies[J]. Advanced Functional Materials, 2012, 22(5): 916-928.
24	Nakrani D, Belani M, Bajaj H C, et al. Concentrated colloidal solution system for preparation of uniform zeolite-Y nanocrystals and their gas adsorption properties[J]. Microporous and Mesoporous Materials, 2017, 241: 274-284.
25	Bortolatto L B, Boca Santa R A A, Moreira J C, et al. Synthesis and characterization of Y zeolites from alternative silicon and aluminium sources[J]. Microporous and Mesoporous Materials, 2017, 248: 214-221.
26	Li C, Guo L L, Liu P, et al. Defects in AHFS-dealuminated Y zeolite: a crucial factor for mesopores formation in the following base treatment procedure[J]. Microporous and Mesoporous Materials, 2018, 255: 242-252.
27	Liu X S, Klinowski J, Thomas J M. Hydrothermal isomorphous insertion of aluminium into the framework of zeolite Y: a convenient method of modifying the siting of Al and Si in faujastic catalysts[J]. Journal of the Chemical Society, Chemical Communications, 1986 (8): 582.
28	Qin Z X, Shen B J, Yu Z W, et al. A defect-based strategy for the preparation of mesoporous zeolite Y for high-performance catalytic cracking[J]. Journal of Catalysis, 2013, 298: 102-111.
29	Pál-Borbély G, Beyer H K. Isomorphous solid-state substitution of Si for framework Al in Y zeolite using crystalline (NH₄)2[SiF₆] as reactant[J]. Phys. Chem. Chem. Phys., 2003, 5(10): 2145-2153.
30	Li W L, Zheng J Y, Luo Y B, et al. Hierarchical zeolite Y with full crystallinity: formation mechanism and catalytic cracking performance[J]. Energy & Fuels, 2017, 31(4): 3804-3811.
31	Gola A, Rebours B, Milazzo E, et al. Effect of leaching agent in the dealumination of stabilized Y zeolites[J]. Microporous and Mesoporous Materials, 2000, 40(1/2/3): 73-83.
32	Jin D F, Hou Z Y, Zhang L W, et al. Selective synthesis of para-para’-dimethyldiphenylmethane over H-beta zeolite[J]. Catalysis Today, 2008, 131(1/2/3/4): 378-384.
33	Zhou H X, Wang S P, Wang B W, et al. Oxycarbonylation of methanol over modified CuY: enhanced activity by improving accessibility of active sites[J]. Chinese Chemical Letters, 2019, 30(3): 775-778.
34	Huang S Y, Wang Y, Wang Z Z, et al. Cu-doped zeolites for catalytic oxidative carbonylation: the role of Brønsted acids[J]. Applied Catalysis A: General, 2012, 417/418: 236-242.
35	Engeldinger J, Richter M, Bentrup U. Mechanistic investigations on dimethyl carbonate formation by oxidative carbonylation of methanol over a CuY zeolite: an operandoSSITKA/DRIFTS/MS study[J]. Physical Chemistry Chemical Physics, 2012, 14(7): 2183-2191.
36	Wang Y C, Zheng H Y, Li Z. Effect of NH4+ exchange on CuY catalyst for oxidative carbonylation of methanol[J]. Chinese Journal of Catalysis, 2016, 37(8): 1403-1412.
37	王玉春, 郑华艳, 刘斌, 等. 固相反应制备无氯CuY催化剂及其催化氧化羰基化: 固相反应温度和铜负载量的影响[J]. 高等学校化学学报, 2015, 36(12): 2540-2549.
	Wang Y C, Zheng H Y, Liu B, et al. Chloride-free CuY catalyst prepared by solid state reaction for oxidative carbonylation of methanol—effect of solid state reactive temperature and copper loading[J]. Chemical Journal of Chinese Universities, 2015, 36(12): 2540-2549.
38	Wang Y C, Zheng H Y, Li Z, et al. Investigation of the interaction between Cu(acac)₂ and NH₄Y in the preparation of chlorine-free CuY catalysts for the oxidative carbonylation of methanol to a fuel additive[J]. RSC Advances, 2015, 5(124): 102323-102331.
39	尹娇, 张国强, 阎立飞, 等. 反应过程中Cu物种演变对其催化甲醇氧化羰基化反应活性的影响[J]. 高等学校化学学报, 2019, 40(7): 1510-1519.
	Yin J, Zhang G Q, Yan L F, et al. Influence of structure evolution of CuY catalyst during the reaction process on its catalytic performance for oxidative carbonylation of methanol[J]. Chemical Journal of Chinese Universities, 2019, 40(7): 1510-1519.
40	Qin Z X, Shen W, Zhou S G, et al. Defect-assisted mesopore formation during Y zeolite dealumination: the types of defect matter[J]. Microporous and Mesoporous Materials, 2020, 303: 110248.

[1]	Yitong LI, Hang GUO, Hao CHEN, Fang YE. Study on operating conditions of proton exchange membrane fuel cells with non-uniform catalyst distributions [J]. CIESC Journal, 2023, 74(9): 3831-3840.
[2]	Xuejin YANG, Jintao YANG, Ping NING, Fang WANG, Xiaoshuang SONG, Lijuan JIA, Jiayu FENG. Research progress in dry purification technology of highly toxic gas PH₃ [J]. CIESC Journal, 2023, 74(9): 3742-3755.
[3]	Jie CHEN, Yongsheng LIN, Kai XIAO, Chen YANG, Ting QIU. Study on catalytic synthesis of sec-butanol by tunable choline-based basic ionic liquids [J]. CIESC Journal, 2023, 74(9): 3716-3730.
[4]	Feifei YANG, Shixi ZHAO, Wei ZHOU, Zhonghai NI. Sn doped In₂O₃ catalyst for selective hydrogenation of CO₂ to methanol [J]. CIESC Journal, 2023, 74(8): 3366-3374.
[5]	Kaixuan LI, Wei TAN, Manyu ZHANG, Zhihao XU, Xuyu WANG, Hongbing JI. Design of cobalt-nitrogen-carbon/activated carbon rich in zero valent cobalt active site and application of catalytic oxidation of formaldehyde [J]. CIESC Journal, 2023, 74(8): 3342-3352.
[6]	Xin YANG, Xiao PENG, Kairu XUE, Mengwei SU, Yan WU. Preparation of molecularly imprinted-TiO₂ and its properties of photoelectrocatalytic degradation of solubilized PHE [J]. CIESC Journal, 2023, 74(8): 3564-3571.
[7]	Yajie YU, Jingru LI, Shufeng ZHOU, Qingbiao LI, Guowu ZHAN. Construction of nanomaterial and integrated catalyst based on biological template: a review [J]. CIESC Journal, 2023, 74(7): 2735-2752.
[8]	Yuming TU, Gaoyan SHAO, Jianjie CHEN, Feng LIU, Shichao TIAN, Zhiyong ZHOU, Zhongqi REN. Advances in the design, synthesis and application of calcium-based catalysts [J]. CIESC Journal, 2023, 74(7): 2717-2734.
[9]	Qiyu ZHANG, Lijun GAO, Yuhang SU, Xiaobo MA, Yicheng WANG, Yating ZHANG, Chao HU. Recent advances in carbon-based catalysts for electrochemical reduction of carbon dioxide [J]. CIESC Journal, 2023, 74(7): 2753-2772.
[10]	Pan LI, Junyang MA, Zhihao CHEN, Li WANG, Yun GUO. Effect of the morphology of Ru/α-MnO₂ on NH₃-SCO performance [J]. CIESC Journal, 2023, 74(7): 2908-2918.
[11]	Tan ZHANG, Guang LIU, Jinping LI, Yuhan SUN. Performance regulation strategies of Ru-based nitrogen reduction electrocatalysts [J]. CIESC Journal, 2023, 74(6): 2264-2280.
[12]	Kuikui HAN, Xianglong TAN, Jinzhi LI, Ting YANG, Chun ZHANG, Yongfen ZHANG, Hongquan LIU, Zhongwei YU, Xuehong GU. Four-channel hollow fiber MFI zeolite membrane for the separation of xylene isomers [J]. CIESC Journal, 2023, 74(6): 2468-2476.
[13]	Chen WANG, Xiufeng SHI, Xianfeng WU, Fangjia WEI, Haohong ZHANG, Yin CHE, Xu WU. Preparation of Mn₃O₄ catalyst by redox method and study on its catalytic oxidation performance and mechanism of toluene [J]. CIESC Journal, 2023, 74(6): 2447-2457.
[14]	Yong LI, Jiaqi GAO, Chao DU, Yali ZHAO, Boqiong LI, Qianqian SHEN, Husheng JIA, Jinbo XUE. Construction of Ni@C@TiO₂ core-shell dual-heterojunctions for advanced photo-thermal catalytic hydrogen generation [J]. CIESC Journal, 2023, 74(6): 2458-2467.
[15]	Jipeng ZHOU, Wenjun HE, Tao LI. Reaction engineering calculation of deactivation kinetics for ethylene catalytic oxidation over irregular-shaped catalysts [J]. CIESC Journal, 2023, 74(6): 2416-2426.