Chem. J. Chinese Universities ›› 2015, Vol. 36 ›› Issue (12): 2540.doi: 10.7503/cjcu20150285
• Physical Chemistry • Previous Articles Next Articles
WANG Yuchun1,2, ZHENG Huayan1, LIU Bin1, ZHANG Guoqiang1, LI Zhong1,*()
Received:
2015-04-13
Online:
2015-12-10
Published:
2015-10-12
Contact:
LI Zhong
E-mail:lizhong@tyut.edu.cn
Supported by:
CLC Number:
TrendMD:
WANG Yuchun, ZHENG Huayan, LIU Bin, ZHANG Guoqiang, LI Zhong. Chloride-free CuY Catalyst Prepared by Solid State Reaction for Oxidative Carbonylation of Methanol† — Effect of Solid State Reactive Temperature and Copper Loading[J]. Chem. J. Chinese Universities, 2015, 36(12): 2540.
Fig.1 XRD patterns of NH4Y and catalysts 10CuY with different temperature of solid state reaction(SSR) a. NH4Y; b. 10CuY170; c.10CuY200; d. 10CuY250;e. 10CuY280.
Fig.2 H2-TPR patterns and Gaussian fitting of low temperature peaks (A) a. Cu2+-Y(6.3); b. CuY(6.3); c. 6CuY250; d. CuY(10.6); e. 10CuY250.(B) a. 10CuY170; b. 10CuY200; c. 10CuY250; d. 10CuY280.
Catalyst | Mass fraction(%) | ||||
---|---|---|---|---|---|
Cu2+(Supercage) | Cu2+(Sodalite cage) | CuO | Cu+ | Cusum | |
10CuY170 | 2.99 | 0.84 | 2.36 | 3.30 | 9.49 |
10CuY200 | 3.30 | 1.39 | 1.31 | 3.39 | 9.39 |
10CuY250 | 3.38 | 1.40 | 0.98 | 3.76 | 9.52 |
10CuY280 | 2.78 | 0.91 | 2.68 | 3.04 | 9.41 |
Table 1 Cu species content of 10CuYT catalysts
Catalyst | Mass fraction(%) | ||||
---|---|---|---|---|---|
Cu2+(Supercage) | Cu2+(Sodalite cage) | CuO | Cu+ | Cusum | |
10CuY170 | 2.99 | 0.84 | 2.36 | 3.30 | 9.49 |
10CuY200 | 3.30 | 1.39 | 1.31 | 3.39 | 9.39 |
10CuY250 | 3.38 | 1.40 | 0.98 | 3.76 | 9.52 |
10CuY280 | 2.78 | 0.91 | 2.68 | 3.04 | 9.41 |
Fig.3 STYDMC and conversion(A) and selectivities of DMC, DME, DMM and MF(B) vs. SSR temperature Feed composition(volume fraction): 31.8%CH3OH, 62.5%CO, 5.7%O2; GHSV 3250 h-1.
Fig.4 XRD patterns of NH4Y and catalysts with different copper loadings a. NH4Y; b. 6CuY250; c. 8CuY250; d. 10CuY250; e. 12CuY250; f. 15CuY250; g. 20CuY250.
Catalyst | SBET/(m2·g-1) | Smicro/(m2·g-1) | Smeso/(m2·g-1) | Vmicro/(cm3·g-1) | Vmeso/(cm3·g-1) |
---|---|---|---|---|---|
NH4Y | 791.9 | 746.4 | 45.5 | 0.36 | 0.10 |
6CuY250 | 737.5 | 690.9 | 46.7 | 0.34 | 0.13 |
8CuY250 | 718.0 | 668.4 | 49.6 | 0.33 | 0.18 |
10CuY250 | 705.0 | 656.3 | 48.9 | 0.32 | 0.12 |
12CuY250 | 560.3 | 514.2 | 46.1 | 0.26 | 0.12 |
15CuY250 | 549.6 | 507.9 | 41.7 | 0.25 | 0.12 |
20CuY250 | 530.1 | 481.9 | 48.2 | 0.24 | 0.12 |
Table 2 Specific surface area and pore volume of catalysts with different Cu loadings*
Catalyst | SBET/(m2·g-1) | Smicro/(m2·g-1) | Smeso/(m2·g-1) | Vmicro/(cm3·g-1) | Vmeso/(cm3·g-1) |
---|---|---|---|---|---|
NH4Y | 791.9 | 746.4 | 45.5 | 0.36 | 0.10 |
6CuY250 | 737.5 | 690.9 | 46.7 | 0.34 | 0.13 |
8CuY250 | 718.0 | 668.4 | 49.6 | 0.33 | 0.18 |
10CuY250 | 705.0 | 656.3 | 48.9 | 0.32 | 0.12 |
12CuY250 | 560.3 | 514.2 | 46.1 | 0.26 | 0.12 |
15CuY250 | 549.6 | 507.9 | 41.7 | 0.25 | 0.12 |
20CuY250 | 530.1 | 481.9 | 48.2 | 0.24 | 0.12 |
Fig.7 Hydrogen TPR profiles for the catalysts with different copper loadings a. 6CuY250; b. 8CuY250; c. 10CuY250; d. 12CuY250;e. 15CuY250; f. 20CuY250.
Fig.9 Influence on catalysis of copper loading STYDMC and XCH3OH vs. copper loading(A), selectivities of DMC, DME, DMM and MF vs. copper loading(B) and time-on-stream performance of xCuY250 catalysts(C) Feed composition(volume fraction): 31.8% CH3OH, 62.5% CO, 5.7% O2; GHSV 3250 h-1.
Catalyst | Preparation method | Mass fraction of Cu loading(%) | STYDMC /(mg·g-1·h-1) | SDMC(%) | |
---|---|---|---|---|---|
6CuY250 | SSR | 6.1 | 11.3a | 33.9 | 0.6 |
8CuY250 | SSR | 8.0 | 50.5a | 58.7 | 1.5 |
10CuY250 | SSR | 9.5 | 192.7a | 67.6 | 5.1 |
12CuY250 | SSR | 11.3 | 267.3a | 69.2 | 6.9 |
15CuY250 | SSR | 13.9 | 211.7a | 69.6 | 5.4 |
20CuY250 | SSR | 16.1 | 204.5a | 72.1 | 5.0 |
CuHY-3[ | IEIM | 11.9 | 200.5b | 51.7 | 13.0 |
CuCl2/HY[ | SSIE | 12.2 | 97.3b | 74.6 | 4.4 |
Cu2(OH)3Cl/AC[ | DP | 18.7 | 139.1b | 67.3 | 6.9 |
12Cu- | DP | 12.0 | 152.1c | 56.3 | 8.4 |
Table 3 Catalytic activities of CuY catalysts in the oxidative carbonylation of methanol
Catalyst | Preparation method | Mass fraction of Cu loading(%) | STYDMC /(mg·g-1·h-1) | SDMC(%) | |
---|---|---|---|---|---|
6CuY250 | SSR | 6.1 | 11.3a | 33.9 | 0.6 |
8CuY250 | SSR | 8.0 | 50.5a | 58.7 | 1.5 |
10CuY250 | SSR | 9.5 | 192.7a | 67.6 | 5.1 |
12CuY250 | SSR | 11.3 | 267.3a | 69.2 | 6.9 |
15CuY250 | SSR | 13.9 | 211.7a | 69.6 | 5.4 |
20CuY250 | SSR | 16.1 | 204.5a | 72.1 | 5.0 |
CuHY-3[ | IEIM | 11.9 | 200.5b | 51.7 | 13.0 |
CuCl2/HY[ | SSIE | 12.2 | 97.3b | 74.6 | 4.4 |
Cu2(OH)3Cl/AC[ | DP | 18.7 | 139.1b | 67.3 | 6.9 |
12Cu- | DP | 12.0 | 152.1c | 56.3 | 8.4 |
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