Catalytic systems for the direct synthesis of dimethyl carbonate from carbon dioxide and methanol containing dehydrating agent, a review
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摘要: 碳酸二甲酯(DMC)是一种用途广泛的环境友好型绿色化学品,利用CO2和CH3OH直接合成DMC是近年来CO2清洁转化的一个研究重点。设计高效稳定的催化剂和反应工艺促进CO2的转化,是DMC直接合成法能否工业化的技术关键。本工作综述了CO2和CH3OH直接合成DMC催化体系的研究进展,介绍了不同类型催化剂的反应机理,主要包括离子液体催化剂、碱金属碳酸盐催化剂、过渡金属氧化物催化剂等,阐述了各种脱水剂的脱水原理和对反应的促进作用,对不同催化-脱水体系的优势及缺点进行分析。据此预测,开发高效稳定的催化剂和对水选择渗透性强的膜材料,构建和实施新型的脱水工艺,将是今后DMC直接合成的研究重点。Abstract: Dimethyl carbonate (DMC) is a widely used environment-friendly green chemical, and the direct synthesis of DMC from CO2 and CH3OH has become one of the research focuses on the clean conversion of CO2 in recent years. The design of efficient and stable catalysts and reaction processes to promote the conversion of CO2 is the key to realize the direct synthesis of DMC in industry. In this paper, the research progress of catalytic systems for the direct synthesis of DMC from CO2 and CH3OH is reviewed and the reaction mechanism of different types of catalysts is summarized, mainly including the ionic liquid catalyst, alkali metal carbonate catalyst, transition metal oxide catalyst, etc. The operation principle of various dehydrating agents and their promoting effect on the production of DMC are expounded, while the advantages and disadvantages of different catalytic-dehydration systems are analyzed. It is predicted that the development of efficient and stable catalysts and membrane materials with strong permeability to water as well as the construction and implementation of new dehydration processes will be the focus of future research on the direct synthesis of DMC from CO2 and CH3OH.
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Key words:
- carbon dioxide /
- methanol /
- dimethyl carbonate /
- catalysts /
- dehydrating agents
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图 7 (a) 催化活性与催化剂中等强度酸性位点数量关系,(b) 催化活性与催化剂中等强度碱性位点数量关系[39]
Figure 7 Relationship between the catalytic activity and the number of acidic sites in the catalyst (a) as well as the relationship between the catalytic activity and the number of basic sites in the catalyst (b) in the synthesis of DMC from CO2 and CH3OH[39] (with permission from Elsevier)
表 1 DMC合成方法
Table 1 Summary of DMC synthesis methods
Synthesis method Advantage Disadvantage Current status Phosgene method 1. The method is easy to operate. 2. The method has a high DMC yield and can generate considerable returns 1. Phosgene is highly toxic and is classified as a Class A deadly compound. 2. Phosgene and by-product HCl are demanding on the equipment The method has been phased out Indirect vapor phase methanol oxidative carbonylation 1. The reaction conditions are mild.
2. Product purity is higher than 99% and selectivity is higher than 96%1. This method uses an expensive Pd catalyst. 2. NO/O2 mixtures pose an explosion risk.
3. The intermediate product methyl nitrite is highly toxicThe method has been phased out Direct vapor phase methanol oxidative carbonylation 1. Raw materials are low cost and less toxic. 2. By-products (CO2 and H2O) are non-toxic and easy to handle. 3. High product quality 1. The methanol conversion rate is low, and the by-product water is easy to inactivate the catalyst. 2. The cost of this method is higher than that of liquid phase methanol oxidative carbonylation The method has been industrially applied Oxidative carbonylation of liquid phase methanol 1. High safety, simple process, no environmental pollution. 2. The product has high purity and selectivity of more than 98% 1. Cl− leakage can easily inactivate the catalyst and corrode the equipment. 2. Water can severely reduce catalyst lifetime. 3. There are serious safety risks in the reaction system The method has fewer industrial applications Transesterification method 1. The reaction conditions are mild, the process is simple, and the catalytic efficiency and product purity are high. 2. Ethylene glycol is a co-produced high value-added chemical product 1. This method uses high-cost propylene oxide and ethylene oxide . 2. Ethylene oxide is flammable and explosive, with geographical restrictions The method has been industrially applied Urea alcohol hydrolysis 1. Low cost of raw materials.
2. No CH3OH-H2O-DMC ternary azeotrope is generated during the reaction1. The reaction conditions are harsh, the single-pass conversion rate is low, and the reaction selectivity is poor. 2. It is necessary to solve the problems of environmental pollution, production safety, and catalyst inactivation The method urgently
needs to be developedCO2-CH3OH direct synthesis method 1. Raw materials are cheap, safe and accessible. 2. The reaction has high atomic utilization and few by-products 1. The reaction is limited by thermodynamic equilibrium. 2. The yield of this method is extremely low The method urgently needs to be developed 表 2 CO2和CH3OH合成DMC反应中化合物的热力学数据和比热容系数(298.15 K, 1.0 × 105 Pa)
Table 2 Thermodynamic data and specific heat capacity coefficients of various compounds in the synthesis of DMC from CO2 and CH3OH at 298.15 K and 1.0×105 Pa
Compound Thermodynamic data $\Delta { {}_{f}{}^{}{H}_{{\rm{m}}}^{\Theta } }^{}$ /(kJ∙mol−1) $\Delta {S}_{{\rm{m,B}}}^{\Theta }$ /(J∙mol−1∙K−1) AC BC /( × 10−2) DC ( × 10−4) CO2 −393.51 213.785 3.0050 0.6600 −0.0405 CH3OH −238.4 127.19 19.8589 −13.0668 3.3636 H2O −285.83 69.95 3.4700 0.1450 0.1405 DMC −608.74 235.8 19.0701 −6.3248 1.5830 表 3 离子液体催化剂上CO2和CH3OH合成DMC催化性能[21]
Table 3 Catalytic performance of various ionic liquids (ILs) for the synthesis of DMC from CO2 and CH3OH[21]
Ionic liquid A /mmol x /% s /% CH 1.63 0.6 95.2 CC − − − EmimOH 0.31 0.1 87.0 BmimOH trace − − KOH − − − EtmimOH 0.62 0.2 77.6 EtmimBr − − − CH/CaO 1.56 0.5 93.0 CH/CH3I 8.19 2.7 98.8 notes: A, amount of DMC produced; x, conversion of CH3OH; s, selectivity of DMC 表 4 [CnCmIm][HCO3]催化剂上CO2和CH3OH合成DMC催化性能[22]
Table 4 Catalytic performance of [CnCmIm][HCO3] catalysts for the synthesis of DMC from CO2 and CH3OH[22]
Entry Catalyst Base x /% s /% 1 [C1C4Im][HCO3] DBU 48 >99 2 [C1C4Im][HCO3] BABCO 24 82 3 [C1C4Im][HCO3] HTMP 36 >99 4 [C1C4Im][HCO3] Na2CO3 22 97 5 [C1C4Im][HCO3] NaHCO3 24 >99 6 [C1C4Im][HCO3] K2CO3 61 54 7 [C1C4Im][HCO3] KHCO3 24 >99 8 [C1C4Im][HCO3] Cs2CO3 45 >99 9a [C1C4Im][HCO3] Cs2CO3 26 >99 10b [C1C4Im][HCO3] Cs2CO3 37 >99 11c,d [C1C4Im][HCO3] Cs2CO3 74 97 12d [C1C4Im][HCO3] Cs2CO3 54 >99 13 [C1C4Im][HCO3] Cs2CO3 82 94 14 [C1C4Im][HCO3] None 14 >99 15 [C1C2Im][HCO3] Cs2CO3 36 >99 16 [C1C6Im][HCO3] Cs2CO3 47 >99 17 [C1C4Im][HCO3] Cs2CO3 16 >99 Reaction conditions: 5 mmol methanol, 5 mmol [CnCmIm][HCO3], 5 mmol base, 10 mL CH2Br2, 1.0×106 Pa CO2, 25 °C, reaction time of 24 h. DBU, 1,8-diazadicyclo[5.4.0]undecy-7-ene; BABCO, 1,4-diazadicyclo[2.2.2]octane; HTMP, 2,2,6,6-tetramethylpiperidine. (a) 0.25 mmol [CnCmIm][HCO3]; (b) 2.5 mmol [CnCmIm][HCO3]; (c) 20 mmol Cs2CO3; (d) reaction at 50 ℃ 表 5 碱金属碳酸盐催化剂上CO2和CH3OH合成DMC催化性能
Table 5 Catalytic performance of alkali metal carbonate catalysts for the synthesis of DMC from CO2 and CH3OH
Entry Catalyst t /℃ p / × 106 Pa x /% s /% References 1 K2CO3 70 8.0 4.1 81.8 [28] 2 KHCO3 70 8.0 2.0 74.1 [28] 3 Na2CO3 70 8.0 0.98 62.6 [28] 4 (NH4)2CO3 70 8.0 trace − [28] 5 Li2CO3 70 8.0 0.54 57.6 [28] 6 K2CO3 120 0.5 5.8 42.7 [29] 7 K2CO3 150 2.6 16.2 38.7 [30] notes: Entry 1–5: DMC was synthesized with the participation of CH3I and different alkali metal carbonates, reaction conditions: methanol 198 mmol, CH3I 24 mmol, catalyst 3 mmol, and reaction time of 4 h 表 6 过渡金属氧化物催化剂上CO2和CH3OH合成DMC的催化性能
Table 6 Catalytic performance of transition metal oxide catalysts for the synthesis of DMC from CO2 and CH3OH
Catalyst t /℃ p / × 106 Pa x /% s /% Ref. H3PO4/V2O5 140 1.0 1.80 92.1 [31] ZrO2 170 5.0 0.34 100 [32] CeO2 130 1.2 0.25 100 [34] Ga2O3/Ce0.6Zr0.4O2 170 6.0 0.50 100 [36] Ce0.5Zr0.5O2 140 7.5 4.93 100 [37] Ce0.5Zr0.5O2 120 15.0 0.77 100 [38] Fe0.3Zr0.7Oy 110 5.0 0.66 100 [39] CeO2 120 15.0 0.66 100 [40] CeO2 140 6.5 0.51 100 [41] Ti0.04Ce0.96O2 120 0.8 5.38 83.1 [42] Ti0.10Ce0.90O2/Hcc 140 2.4 24.3 79.0 [46] Ce0.90Mg0.10O2/Hcc 140 2.4 25.42 79.8 [47] Zn0.10Ce0.90O2/Hcc 160 2.4 20.5 82.3 [48] Bi0.12Ce0.88Oδ/Hcc 140 2.4 20.8 83.5 [49] notes: Hcc means honeycomb cordierite 表 7 MO/ Ce0.6Zr0.4O2催化剂上DMC生成量、比表面积、酸度、碱度[36]
Table 7 Amount of DMC generated, related to the surface area, acidity and basicity of the MO/Ce0.6Zr0.4O2 catalyst for the synthesis of DMC from CO2 and CH3OH[36]
Catalyst DMC amount
/(mmol·g−1)Surface area
/(m2·g−1)aAcidity
/(mol·g−1)bBasicity
/(mol·g−1)cCe0.6Zr0.4O2 0.75 53.8 85.7 17.0 Ga2O3/Ce0.6Zr0.4O2 2.4 50.0 226.3 121.8 La2O3/Ce0.6Zr0.4O2 2.1 52.2 210.4 110.8 Ni2O3/Ce0.6Zr0.4O2 1.85 42.8 188.6 94.2 Fe2O3/Ce0.6Zr0.4O2 1.83 48.1 180.1 88.0 Y2O3/Ce0.6Zr0.4O2 1.8 45.8 164.5 84.6 Co3O4/Ce0.6Zr0.4O2 1.7 43.4 146.5 78.3 Al2O3/Ce0.6Zr0.4O2 1.5 41.9 132.6 68.2 notes: a: the surface area was calculated by the BET (Brunauer-Emmett-Teller) equation, b: acidity was determined by NH3-TPD measurement, c: the basicity the CO2-TPD measurement 表 8 基于Eley-Rideal和Langmuir-Hinshelwood的反应机制[33,37]
Table 8 Reaction mechanisms for the synthesis of DMC from CO2 and CH3OH, based on the Eley-Rideal and Langmuir-Hinshelwood mechanisms[33,37]
Elementary
reactionEley-Rideal mechanism Langmuir-Hinshelwood mechanism S1 MeOH + * ↔ MeOH* CO2 + * ↔ CO2* S2 MeOH* + CO2 ↔ MC* MeOH + * ↔ MeOH* S3 MC* + MeOH* ↔ DMC + H2O + * 2MeOH* + CO2* ↔ DMC* + H2O* + * S4 DMC* ↔ DMC + * S5 H2O* ↔ H2O + * Controlling step S2 S3 or S1 Apparent rate law R = k[CO2][MeOH][*] R = k[CO2][MeOH]2[*]
or R = k[CO2][*]3*: Active sites; MC: methyl carbonate 表 9 Cu-Ni合金催化剂上CO2和CH3OH合成DMC催化性能
Table 9 Catalytic performance of the Cu-Ni alloy for the synthesis of DMC from CO2 and CH3OH
Catalyst t /℃ p / × 106 Pa x /% s /% Ref. Cu-Ni/VSO 140 0.9 2.4 87.2 [49] Cu-Ni/MWCNT 120 1.2 4.44 91 [50] Cu-Ni/HNTs 130 1.2 7.85 89 [53] Cu-Ni/GO 105 1.2 9.0 88.0 [54] Cu-Ni/MS 120 1.1 5.0 86.0 [55] Cu-Ni/VAC 110 1.2 7.76 89.9 [56] Cu-Ni/VSiO 140 1.2 4.2 93.1 [57] MWCNT: multi-walled carbon nanotubes; HNTs: halloysite nanotubes; GO: graphite oxide; VAC: vanadium doped with activated carbon 表 10 杂多酸催化剂上CO2和CH3OH合成DMC催化性能
Table 10 Performance of the heteropolyacid catalysts for the synthesis of DMC from CO2 and CH3OH
表 11 不同催化-脱水体系中CO2和CH3OH合成DMC性能
Table 11 Performance of various catalytic-dehydration systems for the synthesis of DMC from CO2 and CH3OH
Catalysts-dehydrants agent t /℃ p / × 106 Pa x /% s /% Ref. CeO2-2–CP 120 20 95 99 [71] CeO2-2–CP 120 5.0 97 99 [72] CeO2-2–CP 120 3.0 88 100 [77] Ce0.5Zr0.5O2-TMM 100 12.0 10.4 100 [78] NiL2-DCC 80 1.0 61 100 [80] Cu-Ni/diatomite-3A MS 120 1.2 6.5 91.2 [82] Bu2SnO- CaC2 180 15.0 11.3 100 [83] KCl-DBC 140 1.5 40 100 [84] CuCeO2-MTCL 140 5.0 14 80 [85] MS: molecular sieves -
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