Fe-Ce/SiO2 solid base catalyst for preparing dimethyl carbonate

doi:10.11949/0438-1157.20191152

Abstract

Abstract:

A tetravalent supported iron catalyst is prepared by chemical reduction and oxidized to a Fe³⁺ basic active center by air. The activity and selectivity of the catalyst in the transesterification of propylene carbonate with methanol to prepare dimethyl carbonate were evaluated. The prepared catalysts were characterized by N₂ adsorption-desorption, TEM, XRD, XPS and CO₂-TPD. Compared with Fe or Ce single metal catalyst, the basic amount of Fe-Ce/SiO₂ catalyst is greatly improved, and the interaction between Fe and Ce formed a stable amorphous structure. Propylene carbonate conversion of 88% and dimethyl ester selectivity of 92% were reached under the reaction conditions of alcohol ester molar ratio of 15∶1, reaction temperature of 140℃, catalyst dosage of 0.5% of the total mass of the reactants, and Ce/Fe atomic ratio of 2∶1. The activity of the catalyst remained unchanged after 10 cycles of use.

Key words: solid base, catalyst, propylene carbonate, transesterification, dimethyl carbonate, reactivity, stability

摘要：

采用化学还原法制备亚价负载铁催化剂，通过空气氧化为Fe³⁺碱性活性中心。考察了该催化剂在碳酸丙烯酯与甲醇酯交换制备碳酸二甲酯反应中的活性和选择性。采用N₂吸附-脱附、TEM、XRD、XPS和CO₂-TPD等对所制备的催化剂进行了表征。结果表明：催化剂的表面结构与碱性是影响其活性的重要因素。相对于Fe或Ce单金属催化剂，Fe-Ce/SiO₂催化剂的碱量大幅度提升，且Fe与Ce通过相互作用形成了稳定的非晶态结构。在醇酯比为15∶1、反应温度为140℃、催化剂用量为反应物总质量的0.5%、 Ce/Fe原子比为2∶1的反应条件下，碳酸丙烯酯转化率为88%，碳酸二甲酯的选择性为92%。催化剂在循环使用10次之后，其活性保持不变。

关键词: 固体碱, 催化剂, 碳酸丙烯酯, 酯交换, 碳酸二甲酯, 活性, 稳定性

CLC Number:

O 643.36

Chenliang WU, Xiaoqing LI, Chao ZHANG, Hefeng ZHANG, Xinhuan YAN. Fe-Ce/SiO₂solid base catalyst for preparing dimethyl carbonate[J]. CIESC Journal, 2020, 71(1): 297-305.

吴辰亮, 李小青, 张超, 张荷丰, 严新焕. Fe-Ce/SiO₂固体碱催化剂用于制备碳酸二甲酯[J]. 化工学报, 2020, 71(1): 297-305.

Figures/Tables 14

Fig.1 TEM images of catalysts

Fig.2 EDX-mapping images of catalyst

Table 1 Textural properties of different catalysts

催化剂	S_BET^① /(m²·g^-1)	D^② /(nm)	V^③ /(cm³·g^-1)
SiO₂	193.7	14.84	1.37
10Ce/SiO₂	162.9	7.35	1.12
2.5Fe-10Ce/SiO₂	172.4	7.18	1.15
5Fe-10Ce/SiO₂	171.8	8.06	1.09
7.5Fe-10Ce/SiO₂	199.6	7.97	1.15
10Fe-10Ce/SiO₂	224.5	8.56	1.04

Fig.3 XRD patterns of catalystsa—5Fe/SiO2; b—10Ce/SiO2; c—2.5Fe+10Ce/SiO2; d—5Fe+10Ce/SiO2;e—7.5Fe+10Ce/SiO2; f—10Fe+10Ce/SiO2

Fig.4 Ce 3d XPS spectra of catalystsa—5Fe/SiO2; b—10Ce/SiO2; c—2.5Fe+10Ce/SiO2; d—5Fe+10Ce/SiO2;e—7.5Fe+10Ce/SiO2

Fig.5 Fe 2p XPS spectra of catalystsa—5Fe/SiO2; c—2.5Fe+10Ce/SiO2; d—5Fe+10Ce/SiO2;e—7.5Fe+10Ce/SiO2; f—10Fe+10Ce/SiO2

Fig.6 CO2-TPD patterns of catalysta—5Fe/SiO2; b—10Ce/SiO2; c—2.5Fe+10Ce/SiO2; d—5Fe+10Ce/SiO2;e—7.5Fe+10Ce/SiO2; f—10Fe+10Ce/SiO2

Table 2 Absorbed CO2 of catalysts

催化剂	CO₂吸附量/(mmol/g)			总CO₂吸附量/(mmol/g)
催化剂	弱(<200℃)	中等(200~450℃)		总CO₂吸附量/(mmol/g)
5Fe/SiO₂	0.04	0.71	0.75
10Ce/SiO₂	0.76	0.78	1.54
2.5Fe-10Ce/SiO₂	0.90	0.93	1.83
5Fe-10Ce/SiO₂	0.97	0.90	1.87
7.5Fe-10Ce/SiO₂	0.91	0.94	1.85
10Fe-10Ce/SiO₂	0.96	0.95	1.91

Table 3 Catalytic performance test results

催化剂	Ce/Fe比例	PC转化率/%	DMC选择性/%
5Fe/SiO₂	—	78	77
10Ce/SiO₂	—	69	75
2.5Fe-10Ce/SiO₂	4:1	83	84
5Fe-10Ce/SiO₂	2:1	88	92
7.5Fe-10Ce/SiO₂	4:3	81	84
10Fe-10Ce/SiO₂	1:1	79	77

Fig.7 Effect of reaction temperature on transesterification of propylene carbonate with methanol

Fig.8 Effect of methanol/PC molar ratio on transesterification of propylene carbonate with methanol

Fig.9 Effect of catalyst dosage on transesterification of propylene carbonate with methanol

Fig.10 Stability of 5Fe-10Ce/SiO2 catalyst

Fig.11 XRD patterns of recycled catalyst

References 34

1	Keller N, Rebmann G, Keller V. Catalysts, mechanisms and industrial processes for the dimethylcarbonate synthesis[J]. Journal of Molecular Catalysis A: Chemical, 2010, 317(1/2): 1-18.
2	Ono Y. Catalysis in the production and reactions of dimethyl carbonate, an environmentally benign building block[J]. Applied Catalysis A General, 1997, 155(2): 133-136.
3	Delledonne D, Rivetti F, Romano U. Developments in the production and application of dimethylcarbonate[J]. Applied Catalysis A General, 2001, 221(1/2): 241-251.
4	Lu P F, Wang H J, Hu K K. Synthesis of glycerol carbonate from glycerol and dimethyl carbonate over the extruded CaO-based catalyst[J]. Chemical Engineering Journal, 2013, 228: 147-154.
5	Alvarez M G, Segarra A M, Contreras S, et al. Enhanced use of renewable resources: transesterification of glycerol catalyzed by hydrotalcite-like compounds[J]. Chemical Engineering Journal, 2010, 161(3): 340-345.
6	Li Z H, Cheng B W, Su K M, et al. The synthesis of diphenyl carbonate from dimethyl carbonate and phenol over mesoporous MoO₃/SiMCM-41[J]. Journal of Molecular Catalysis A: Chemical, 2008, 289(1/2): 100-105.
7	常雁红, 王化军. 酯交换法合成碳酸二甲酯研究进展[J]. 化工进展, 2007, 26(5): 642-646.
	Chang Y H, Wang H J. Process in synthesis of dimethyl carbonate via transesterification[J]. Chemical Industry and Engineering Progress, 2007, 26(5): 642-646.
8	赵峰, 刘绍英, 李建国, 等. 酯交换合成碳酸二甲酯催化剂研究进展[J]. 工业催化, 2006, 14(11): 6-11.
	Zhao F, Liu S Y, Li J G, et al. Latest researches in synthesis of dimethyl carbonate over transesterification catalysts[J]. Industrial Catalysis, 2006, 14(11): 6-11.
9	Lee H J, Park S Y, Song I K, et al. Direct synthesis of dimethyl carbonate from methanol and carbon dioxide over Ga₂O₃/Ce_0.6Zr_0.4O₂ catalysts: effect of acidity and basicity of the catalysts[J]. Catalysis Letters, 2011, 141(4): 531-537.
10	Zhao W B, Peng W C, Wang D F, et al. Zinc oxide as the precursor of homogeneous catalyst for synthesis of dialkyl carbonate from urea and alcohols[J]. Catalysis Communications, 2009, 10(5): 655-658.
11	黄振东, 王睿, 于美青. KOH/ZrO₂催化剂制备生物柴油工艺[J]. 化工学报, 2016, 67: 176-183.
	Huang Z D, Wang R, Yu M Q. New technique of biodiesel preparation catalyzed by KOH/ZrO₂[J]. CIESC Journal, 2016, 67: 176-183.
12	商辉, 丁禹, 张文慧. 微波法制备生物柴油研究进展[J]. 化工学报, 2019, 70: 15-22.
	Shang H, Ding Y, Zhang W H. Research progress of microwave assisted biodiesel production[J]. CIESC Journal, 2019, 70: 15-22.
13	Liao Y, Li F, Pu Y, et al. Solid base catalysts derived from Ca-Al-X(X=F^-, Cl^- and Br^-)layered double hydroxides for methanolysis of propylene carbonate[J]. RSC Advances, 2018, 8(2): 785-791.
14	Liao Y H, Li F, Dai X. Dimethyl carbonate synthesis over solid base catalysts from Ca-Al layered double hydroxides[J]. Chemical Papers, 2018, 72(8): 1963-1971.
15	Axel P, Wolfgang H, Karsten M. Dimethyl carbonate via transesterification of propylene carbonate with methanol over ion exchange resins[J]. Applied Catalysis B Environmental, 2012, 125: 486-491.
16	Kumar P, Srivastava V C, Mishra I M. Synthesis of dimethyl carbonate by transesterification reaction using ceria-zinc oxide catalysts prepared with different chelating agents[J]. Applied Clay Science, 2017, 150: 275-281.
17	Xu J, Long K Z, Wu F. Efficient synthesis of dimethyl carbonate via transesterification of ethylene carbonate over a new mesoporous ceria catalyst[J]. Applied Catalysis A General, 2014, 484: 1-7.
18	Saada R, AboElazayem O, Kellici S, et al. Greener synthesis of dimethyl carbonate using a novel tin-zirconia/graphene nanocomposite catalysts[J]. Applied Catalysis B Environmental, 2018, 226: 451-462.
19	Kumar P, Srivastava V C, Mishra I M. Dimethyl carbonate synthesis from propylene carbonate with methanol using Cu-Zn-Al catalyst[J]. Energy & Fuels, 2015, 29(4): 2664-2675.
20	Nivangune N T, Ranade V V, Kelkar A A. MgFeCe ternary layered double hydroxide as highly efficient and recyclable heterogeneous base catalyst for synthesis of dimethyl carbonate by transesterification[J]. Catalysis Letters, 2017, 147: 2558-2569.
21	Zeng H Y, Xu S, Liao M C, et al. Activation of reconstructed Mg/Al hydrotalcites in the transesterification of microalgae oil[J]. Applied Clay Science, 2014, 91/92: 16-24.
22	Zhang L, Wu Y S, Bian X F, et al. Short-range and medium-range order in liquid and amorphous Al₉₀Fe₅Ce₅ alloys[J]. Journal of Non-Crystalline Solids, 2000, 262: 169-176.
23	Chang L H, Sasirekha N, Chen Y W, et al. Preferential oxidation of CO in H₂ stream over Au/MnO₂-CeO₂ catalysts[J]. Industrial & Engineering Chemistry Research, 2006, 45(14): 4927-4935.
24	Zou Z Q, Meng M, Guo L H, et al. Synthesis and characterization of CuO/Ce_1-_xTi_xO₂ catalysts used for low-temperature CO oxidation[J]. Journal of Hazardous Materials, 2009, 163(2/3): 835-842.
25	Zhan S H, Zhang H, Zhang Y, et al. Efficient NH₃-SCR removal of NO_x with highly ordered mesoporous WO₃(χ)-CeO₂ at low temperatures[J]. Applied Catalysis B Environmental, 2017, 203: 199-209.
26	Yamashita T, Hayes P. Analysis of XPS spectra of Fe²⁺ and Fe³⁺ ions in oxide materials[J]. Applied Surface Science, 2008, 254(8): 2441-2449.
27	Lee S Y, Kim D H, Choi S C, et al. Porous multi-walled carbon nanotubes by using catalytic oxidation via transition metal oxide[J]. Microporous and Mesoporous Materials, 2014, 194: 46-51.
28	Sánchez G, Dlugogorski B Z, Kennedy E M, et al. Zeolite-supported iron catalysts for allyl alcohol synthesis from glycerol[J]. Applied Catalysis A General, 2016, 509: 130-142.
29	Gong J, Yao K, Liu J, et al. Striking influence of Fe₂O₃ on the “catalytic carbonization” of chlorinated poly(vinyl chloride) into carbon microspheres with high performance in the photo-degradation of Congo red[J]. Journal of Materials Chemistry A, 2013, 1(17): 5247-5255.
30	Hong W J, Iwamoto S J, Inoue M. Direct decomposition of NO on Ba catalysts supported on Ce-Fe mixed oxides[J]. Catalysis Letters, 2010, 135: 190-196.
31	Kumar P, Srivastava V C, Mishra I M. Synthesis and characterization of Ce-La oxides for the formation of dimethyl carbonate by transesterification of propylene carbonate[J]. Catalysis Communication, 2015, 60: 27-31.
32	Liao Y H, Li F, Dai X, et al. Solid base catalysts derived from Ca-M-Al(M=Mg, La, Ce, Y)layered double hydroxides for dimethyl carbonate synthesis by transesterification of methanol with propylene carbonate[J]. Chinese Journal of Catalysis, 2017, 38: 1860-1869.
33	Song Z W, Subramaniam B, Chaudhari R V. Kinetic study of CaO-catalyzed transesterification of cyclic carbonates with methanol[J]. Industrail & Engineering Chemistry Research, 2018, 57(44): 14977-14987.
34	Song Z W, Jin X, Hu Y F, et al. Intriguing catalyst(CaO) pretreatment effects and mechanistic insights during propylene carbonate transesterification with methanol[J]. ACS Sustainable Chemistry & Engineering, 2017, 5(6): 4718-4729.

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Fe-Ce/SiO₂solid base catalyst for preparing dimethyl carbonate

Fe-Ce/SiO₂固体碱催化剂用于制备碳酸二甲酯

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