Highly efficient catalyst PdCl2–CuCl2–KOAc/AC@Al2O3 for gas-phase oxidative carbonylation of methanol to dimethyl carbonate: Preparation and reaction mechanism

Ding, Xiaoshu; Dong, Xiangmo; Kuang, Dongting; Wang, Shufang; Zhao, Xinqiang; Wang, Yanji

doi:10.1016/j.cej.2013.11.079

Cited by 44 publications

(11 citation statements)

References 30 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The supported catalysts based on the inorganic carriers can act as the more stable alternatives of the organic ligands if the similar coordination surrounding can be provided. The metal oxides (e.g., MgO, Al 2 O 3 ,, ) and zeolites ,, are often used as the carriers to prepare the supported palladium catalytic systems for this reaction. However, the Pd(II) centers on the surface of these metal oxide carriers are largely unsaturated (Figure a), implying the instability of this supported catalytic system.…”

Section: Resultsmentioning

confidence: 99%

“…Dimethyl carbonate (DMC) is an important oxygenate needed for polycarbonate production, , lithium batteries, − fuel oil additives. − as well as replacing the toxic chemicals (e.g., dimethyl sulfate, phosgene) in the reactions. − Industrially, over 90% of the DMC production adopts a transesterification route, in which the raw materials of propylene oxide first react with CO 2 to form cyclic carbonate intermediate, and then the transesterification process occurs between the cyclic carbonate intermediate and methanol to generate DMC. However, propylene oxide is derived from petroleum via a chlorohydrination process, which leads to a high cost of production as well as a serious pollution issue …”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Synthesis of High-Performance and High-Stability Pd(II)/NaY Catalyst for CO Direct Selective Conversion to Dimethyl Carbonate by Rational Design

Tan

Chen

et al. 2019

ACS Catal.

View full text Add to dashboard Cite

Direct selective catalytic conversion of CO to C 2+ oxygenates with high performance and high stability is challenging. Generating dimethyl carbonate (DMC), a high added-value oxygenate, by CO direct catalytic conversion with Pdbased catalyst is of particular interest as an economic and environmentally friendly potential alternative of the traditional transesterification route. Pd(II)-based catalysts were often used in this route to selectively generate DMC. However, Pd(II) easily reduces to Pd(0) in the presence of CO, which leads to the byproduct of dimethyl oxalate (DMO). A high-performance and high-stability catalytic system selective toward DMC is thus hard to achieve. We herein reveal, by density functional theory calculations, that the mononuclear-isolated nature of Pd(II) centers is critical for the selectivity toward DMC while the aggregation of Pd(0) centers leads to the selective generation of DMO. Inspired by this picture, heterogeneous catalyst with mononuclear-isolated Pd(II) centers anchored on Y-type silico-alumina zeolite was produced experimentally using an ultrasonic-assisted ammonia evaporation approach. This catalyst demonstrates a high selectivity (>99.5%) to target DMC over 100 h, a stability beyond any other reported results. Characterization of the catalyst structure as well as the reaction intermediates and kinetics further verified the computational mechanism. Current work provides a high-performance catalytic system to selectively produce DMC with high-stability through rational design and controlled synthesis, and sheds the light on how to synthesize high-performance and long-lived catalysts for the future industrialization of this process route.

show abstract

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Synthesis of High-Performance and High-Stability Pd(II)/NaY Catalyst for CO Direct Selective Conversion to Dimethyl Carbonate by Rational Design

Tan

Chen

et al. 2019

ACS Catal.

View full text Add to dashboard Cite

show abstract

“…More recently, Ding et al [32] proposed a novel catalyst to improve the selectivity (98 % selectivity of DMC to CH 3 OH, 70 % selectivity of DMC to CO) and catalytic stability: PdCl 2 -CuCl 2 -KOAc/AC-AL 2 O 3 ; furthermore, a gas-phase reaction mechanism was proposed. Meng et al [33] also studied a bimetallic Wacker-type catalyst for the oxy-carbonylation of methanol: CuCl 2 -PdCl 2 .…”

Section: Dmc -Conventional Processesmentioning

confidence: 99%

Review for the Direct Synthesis of Dimethyl Carbonate

et al. 2014

View full text Add to dashboard Cite

This review summarizes the state-of-the-art for direct synthesis of dimethyl carbonate (DMC) from carbon dioxide and methanol. In addition, conventional and alternative processes are also discussed in order to understand the advantages and disadvantages of the direct synthesis of DMC. Furthermore, the major applications of DMC are described: solvent, fuels additive, and building block for organic synthesis. The major drawbacks of the direct synthesis of DMC are the low yield and reaction rate, mostly induced by the highly stable carbon dioxide molecules. The development of novel catalyst and strategies to enhance the DMC yield -such as dehydrating agents that remove the water from the reacting mixture -are pointed out as the key solution for this route. Therefore, the main catalysts (homogeneous and heterogeneous catalysts) used so far are presented, together with the respective operating conditions and catalyst performance. The use of different dehydrating agents to increase the DMC yield is also discussed.

show abstract

“…Dimethyl carbonate (DMC) is a green, oxygen-rich (up to 53.3% oxygen content), and nonpolluting fuel. 11 Its special structure contains an oxygen atom between carbon−carbon bonds and less carbon (39.9%). Moreover, DMC is in full contact with oxygen during combustion, which reduces the possibility of an incomplete combustion and formation of CO 2 .…”

Section: Introductionmentioning

confidence: 99%

“…Dimethyl carbonate (DMC) is a green, oxygen-rich (up to 53.3% oxygen content), and nonpolluting fuel . Its special structure contains an oxygen atom between carbon–carbon bonds and less carbon (39.9%).…”

Section: Introductionmentioning

confidence: 99%

Effects of EGR Dilution on Combustion and Emission Performance of a Compression Ignition Engine Fueled with Dimethyl Carbonate and 2-Ethylhexyl Nitrate Additive

et al. 2019

View full text Add to dashboard Cite

The combination dimethyl carbonate (DMC)/diesel-blended fuels and the exhaust gas recirculation (EGR) can decrease nitrogen oxide (NO X ) and soot emissions simultaneously emitted from the compression ignition engine. Nevertheless, the low cetane number of DMC/diesel mixtures at low loads results in a delayed combustion phase. The combustion phase has a significant influence on the engine emissions and combustion performance. Therefore, 2-ethylhexyl nitrate (EHN) must be added as cetane improver to fuel blends to ensure that the DMC/diesel mixtures have suitable combustion performance. In this paper, a four-cylinder diesel engine was used to investigate combustion and emissions performance. The five test fuels included diesel (D100) and a mixture of 20% DMC with 80% diesel (DMC20). In addition, EHN was added to DMC20 at ratios of 0.5%, 1%, and 2%. The results showed that the DMC20 increased the maximum heat release rate (MHRR), ignition delay (ID), and maximum pressure rise rate (MPRR) and reduced the soot emissions, nucleation, and accumulation mode particles. However, the brake-specific fuel consumption (BSFC) increased, and the brake thermal efficiency (BTE) decreased. Furthermore, when using the EGR, the NO X emission significantly decreased. When adding EHN to DMC20, the ID was shortened, the combustion phase advanced, and the MPRR decreased. The BTE first decreased and then increased with increasing EHN proportion. In general, use of the EGR coupled with DMC and EHN simultaneously decreased the NO X −soot emissions, and use of 0.5% and 1% EHN in combination with 20−30% EGR led to better engine emissions and combustion performance.

show abstract

Highly efficient catalyst PdCl2–CuCl2–KOAc/AC@Al2O3 for gas-phase oxidative carbonylation of methanol to dimethyl carbonate: Preparation and reaction mechanism

Cited by 44 publications

References 30 publications

Synthesis of High-Performance and High-Stability Pd(II)/NaY Catalyst for CO Direct Selective Conversion to Dimethyl Carbonate by Rational Design

Synthesis of High-Performance and High-Stability Pd(II)/NaY Catalyst for CO Direct Selective Conversion to Dimethyl Carbonate by Rational Design

Review for the Direct Synthesis of Dimethyl Carbonate

Effects of EGR Dilution on Combustion and Emission Performance of a Compression Ignition Engine Fueled with Dimethyl Carbonate and 2-Ethylhexyl Nitrate Additive

Contact Info

Product

Resources

About