二甲醚羰基化丝光沸石成型催化剂黏结剂的研究

doi:10.11949/0438-1157.20200609

摘要/Abstract

摘要：

二甲醚（DME）羰基化制乙酸甲酯（MA），MA加氢合成乙醇工艺是一种新颖、绿色且经济的乙醇合成路线，催化剂成型对实现该工艺工业化具有重要意义。本论文选用拟薄水铝石及硅溶胶为黏结剂，对丝光沸石分子筛（MOR）进行挤条成型，制备了一系列不同黏结剂种类与含量的成型MOR催化剂。通过强度测试以及Weibull函数统计分析，探究了黏结剂对成型MOR的强度以及强度可靠性的影响；X射线衍射、N₂物理吸附、NH₃程序升温脱附、吡啶吸附原位红外等表征结合活性评价，探究了黏结剂对MOR的物理结构、酸性以及催化性能的作用。结果表明：黏结剂的引入不会影响MOR的晶体结构，且以拟薄水铝石为黏结剂时，催化剂力学性能及DME羰基化催化性能最佳。通过建立MA时空收率、TOF与微孔比表面积之间的定量关系，确定黏结剂不影响MOR内单位活性位点催化能力，产物时空收率与催化剂微孔比表面积呈线性正相关。

关键词: 分子筛, 合成气, 催化剂, 固定床, 挤条成型, 黏结剂

Abstract:

The carbonylation of dimethyl ether (DME) to produce methyl acetate (MA) and the hydrogenation of MA to ethanol is a novel, green and economical ethanol synthesis route. The formation of the catalyst is of great significance to the industrialization of this process. In this paper, pseudo-boehmite and silica sol are used as binders, and mordenite molecular sieve (MOR) is extruded to prepare a series of molded MOR catalysts with different binder types and contents. By using strength evaluation and Weibull distribution analysis, we investigated the mechanical stability and reliability of the extruded MOR. Afterwards, XRD, N₂-physisorption, NH₃-TPD and IR spectra of pyridine adsorption were employed to explore the influence of binder on textural properties, acidity and catalytic performance. The results showed that the crystal structure of MOR was maintained after addition of binder. When the pseudo-boehmite was used as a binder, the catalyst showed the best mechanical property and catalytic activity. By establishing the quantitative relationships among the yield, TOF and structure parameter, it is found that the space time yield of MA was linearly related to the specific surface area of micropores. Meanwhile, the almost constant TOF indicated that the binders did not affect the catalytic capacity of each activesites in MOR for carbonylation of dimethyl ether.

Key words: zeolite, syngas, catalyst, fixed-bed, extrusion, binder

中图分类号:

TQ203.2

黄守莹, 熊雄, 贺培, 王建豪, 李媖, 刘宏开, 吕静, 马新宾. 二甲醚羰基化丝光沸石成型催化剂黏结剂的研究[J]. 化工学报, 2020, 71(10): 4642-4651.

Shouying HUANG, Xiong XIONG, Pei HE, Jianhao WANG, Ying LI, Hongkai LIU, Jing LYU, Xinbin MA. Study on binder of extruded mordenite catalyst for dimethyl ether carbonylation[J]. CIESC Journal, 2020, 71(10): 4642-4651.

图/表 14

表1 催化剂配方及命名

Table 1 Formula and nomenclature for catalyst

MOR质量/g	黏结剂种类	黏结剂质量/g	去离子水质量/g	硝酸质量/g	命名
10	无	0	0	0	MOR-P
9	拟薄水铝石	1	6	0.125	10NI
8	拟薄水铝石	2	6	0.125	20NI
9	硅溶胶	1	6	0.125	10Si
8	硅溶胶	2	6	0.125	20Si
8	拟薄水铝石+硅溶胶	2	6	0.125	10NI10Si

图1 DME羰基化反应流程图

Fig.1 Schematics of the reaction system for DME carbonylation

图2 黏结剂对成型MOR催化剂强度的影响

Fig.2 Effect of binder on strength of extruded MOR

表2 成型MOR催化剂的强度数据统计

Table 2 Statistics of strength data for the extruded MOR

样品	F/(N/cm)	F₀/(N/cm)	m	F_10%
10NI	83 $±$ 24	93	2.80	35
20NI	177 $±$ 44	197	3.21	103
10Si	47 $±$ 15	52	2.84	22
20Si	105 $±$ 30	117	3.28	47
10NI10Si	142 $±$ 42	158	3.99	80

表2 成型MOR催化剂的强度数据统计

Table 2 Statistics of strength data for the extruded MOR

样品	F/(N/cm)	F₀/(N/cm)	m	F_10%
10NI	83 $±$ 24	93	2.80	35
20NI	177 $±$ 44	197	3.21	103
10Si	47 $±$ 15	52	2.84	22
20Si	105 $±$ 30	117	3.28	47
10NI10Si	142 $±$ 42	158	3.99	80

图3 不同成型催化剂及未成型分子筛DME羰基化催化性能（反应条件：温度200℃，总压1.5 MPa, 混合气比例DME∶CO∶Ar=1∶47∶2，空速6000 h-1）

Fig. 3 Catalytic performance of parent and extruded catalyst in DME carbonylation (Reaction conditions: T=200℃, p=1.5 MPa, DME∶CO∶Ar=1∶47∶2, GHSV=6000 h-1)

图4 未成型分子筛及成型催化剂的XRD谱图

Fig.4 XRD patterns of the parent and extruded MOR

图5 成型催化剂与未成型MOR的N2吸脱附等温线（除10NI10Si样品，其余吸脱附等温线依次向上平移100 cm3/g）

Fig.5 Nitrogen adsorption-desorption isotherms of the parent and extruded MOR (except for 10NI10Si, the isotherms for other samples are shifted 100 cm3/g upward respect to each other)

表3 成型催化剂与未成型MOR催化剂的物理结构性质

Table 3 Textural properties of parent and extruded MOR

样品	S_BET/ (m²/g)	S_micro/ (m²/g)	S_meso/ (m²/g)	V_micro/ (cm³/g)	V_meso/(cm³/g)	D_meso/nm
MOR-P	462	431	31	0.159	0.109	8.1
10NI	449	399	50	0.145	0.126	5.6
20NI	449	385	74	0.141	0.136	5.7
10Si	435	365	70	0.132	0.132	4.2
20Si	398	299	99	0.109	0.154	4.4
10NI10Si	435	338	97	0.116	0.159	5.0
NI^①	283	—	283	—	0.296	6.0
Si^②	331	—	331	—	0.411	4.1

图6 成型催化剂及未成型MOR催化剂NH3-TPD表征

Fig.6 NH3-TPD profiles of the parent and extruded MOR catalyst

表4 NH3-TPD测试及分峰结果

Table 4 The de-convolution results of NH3-TPD profiles

样品	弱酸峰/℃	酸含量/(μmol/g)	中强酸峰/℃	酸含量/(μmol/g)	强酸峰/℃	酸含量/(μmol/g)
MOR-P	209.7	255	331.1	262	535.1	1110
10NI	213.4	233	380.4	288	537.3	1007
20NI	214.0	234	378.2	317	538.1	950
10Si	211.5	217	340.2	215	530.2	903
20Si	212.0	180	341.2	176	531.2	739
10NI10Si	213.0	247	350.6	227	533.4	864

图7 未成型分子筛及成型催化剂吡啶红外光谱图

Fig.7 Pyridine-IR spectra of the parent and extruded MOR

表5 成型催化剂及未成型MOR酸量

Table 5 The amounts of acid for parent and extruded MOR

样品	B_total/(μmol/g)	B_12-MR/(μmol/g)	L_12-MR/(μmol/g)	B_8-MR/(μmol/g)	B_8-MR/B_12-MR
MOR-P	1110	351	47	759	2.2
10NI	1007	307	73	700	2.3
20NI	950	292	91	658	2.3
10Si	903	294	45	609	2.1
20Si	739	241	41	498	2.1
10NI10Si	864	279	63	585	2.1

表6 成型催化剂及未成型分子筛微孔比表面、8元环Br?nsted酸量及催化性能汇总

Table 6 The specific surface area (Smicro), B8-MR and catalytic performance of the parent and extruded MOR

样品	S_micro/ (m²/g)	B_8-MR/ (μmol/g)	STY(MA)/ (g/(kg·h))	TOF/h^-1
MOR-P	431	759	504	9.1
10NI	399	700	469	9.0
20NI	385	658	437	9.0
10Si	365	609	414	9.1
20Si	299	498	340	9.1
10NI10Si	338	585	395	9.1

图8 MA时空收率及TOF与微孔比表面积之间的关系

Fig.8 Relationship between Smicro, STY(MA)and TOF

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