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

Abstract

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

CLC Number:

TQ203.2

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.

Figures/Tables 14

Table 1

Fig.1

Fig.2

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

Table 2

Fig. 3

Fig.4

Fig.5

Table 3

Fig.6

Table 4

Fig.7

Table 5

Table 6

Fig.8

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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

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

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

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

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

Study on binder of extruded mordenite catalyst for dimethyl ether carbonylation

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