CIESC Journal ›› 2020, Vol. 71 ›› Issue (10): 4642-4651.doi: 10.11949/0438-1157.20200609

• Catalysis, kinetics and reactors • Previous Articles     Next Articles

Study on binder of extruded mordenite catalyst for dimethyl ether carbonylation

Shouying HUANG(),Xiong XIONG,Pei HE,Jianhao WANG,Ying LI,Hongkai LIU,Jing LYU,Xinbin MA()   

  1. Key Laboratory for Green Chemical Technology of Ministry of Education, Collaborative Innovation Center of Chemical Science and Engineering, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China
  • Received:2020-05-18 Revised:2020-07-15 Online:2020-10-05 Published:2020-07-30
  • Contact: Xinbin MA E-mail:huangsy@tju.edu.cn;xbma@tju.edu.cn

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

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
10000MOR-P
9拟薄水铝石160.12510NI
8拟薄水铝石260.12520NI
9硅溶胶160.12510Si
8硅溶胶260.12520Si
8拟薄水铝石+硅溶胶260.12510NI10Si

Fig.1

Schematics of the reaction system for DME carbonylation"

Fig.2

Effect of binder on strength of extruded MOR"

Table 2

Statistics of strength data for the extruded MOR"

样品F/(N/cm)F0/(N/cm)mF10%
10NI83±24932.8035
20NI177±441973.21103
10Si47±15522.8422
20Si105±301173.2847
10NI10Si142±421583.9980

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)"

Fig.4

XRD patterns of the parent and extruded MOR"

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)"

Table 3

Textural properties of parent and extruded MOR"

样品

SBET/

(m2/g)

Smicro/

(m2/g)

Smeso/

(m2/g)

Vmicro/

(cm3/g)

Vmeso/(cm3/g)Dmeso/nm
MOR-P462431310.1590.1098.1
10NI449399500.1450.1265.6
20NI449385740.1410.1365.7
10Si435365700.1320.1324.2
20Si398299990.1090.1544.4
10NI10Si435338970.1160.1595.0
NI2832830.2966.0
Si3313310.4114.1

Fig.6

NH3-TPD profiles of the parent and extruded MOR catalyst"

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-P209.7255331.1262535.11110
10NI213.4233380.4288537.31007
20NI214.0234378.2317538.1950
10Si211.5217340.2215530.2903
20Si212.0180341.2176531.2739
10NI10Si213.0247350.6227533.4864

Fig.7

Pyridine-IR spectra of the parent and extruded MOR"

Table 5

The amounts of acid for parent and extruded MOR"

样品Btotal/(μmol/g)B12-MR/(μmol/g)L12-MR/(μmol/g)B8-MR/(μmol/g)B8-MR/B12-MR
MOR-P1110351477592.2
10NI1007307737002.3
20NI950292916582.3
10Si903294456092.1
20Si739241414982.1
10NI10Si864279635852.1

Table 6

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

样品Smicro/ (m2/g)B8-MR/ (μmol/g)STY(MA)/ (g/(kg·h))TOF/h-1
MOR-P4317595049.1
10NI3997004699.0
20NI3856584379.0
10Si3656094149.1
20Si2994983409.1
10NI10Si3385853959.1

Fig.8

Relationship between Smicro, STY(MA)and TOF"

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