介孔构建对CuY甲醇氧化羰基化反应活性的影响

doi:10.11949/0438-1157.20201937

摘要/Abstract

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

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

中图分类号:

TQ 028.8

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.

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.

图/表 17

图1 NaY分子筛的N2物理吸附图

Fig.1 N2-physisorption of NaY zeolites

表1 NaY分子筛的织构性质

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

图2 NaY分子筛的TEM图

Fig.2 TEM images of NaY zeolites

图3 NaY分子筛的XRD谱图

Fig.3 XRD patterns of NaY zeolites

图4 NaY分子筛的Si和Al核磁谱图

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

表2 从29Si MAS NMR谱图计算得到的各种硅单元的相对含量和骨架硅铝比

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

图5 HY分子筛的NH3-TPD谱图

Fig.5 NH3-TPD profiles of HY zeolites

表3 HY分子筛的酸量

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

图6 HY分子筛的吡啶吸附红外谱图

Fig.6 FTIR spectra of pyridine adsorption on HY zeolites

图7 CuY催化剂的XRD谱图

Fig.7 XRD patterns of CuY catalysts

图8 CuY催化剂的TEM和HRTEM图

Fig.8 Representative TEM and HRTEM images of CuY catalysts

图9 CuY催化剂的Cu 2p3/2 XPS谱图

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

表4 CuY催化剂的Cu 2p3/2 XPS谱图拟合结果分析

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

表5 CuY催化剂在甲醇氧化羰基化中的催化性能指标

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

表5 CuY催化剂在甲醇氧化羰基化中的催化性能指标

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

图10 DMC的时空收率随时间的变化趋势

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

图11 CuY催化剂的CO吸附红外谱图

Fig.11 FTIR spectra of CO adsorption on CuY catalysts

图12 CuY催化剂的DMC时空收率与CO吸附峰面积的线性关系

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

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