Formation of Dimethyl Carbonate on Nature Clay Supported Bimetallic Copper-Nickel Catalystsby Yingjie Zhou, Shuanjin Wang, Min Xiao, Dongmei Han, Yixin Lu, Yuezhong Meng

Journal of Cleaner Production


Carbon Formation and CO Methanation on Silica-Supported Nickel and Nickel–Copper Catalysts in CO + H2Mixtures

M.T. Tavares, I. Alstrup, C.A. Bernardo, J.R. Rostrup-Nielsen

Deactivation of supported nickel catalysts during the reforming of methane by carbon dioxide

H.M. Swaan, V.C.H. Kroll, G.A. Martin, C. Mirodatos

Nickel-supported metal-carbon nanocomposites: New catalysts of hydrogenation of phenylacetylene

A. V. Erokhin, E. S. Lokteva, E. V. Golubina, K. I. Maslakov, A. Ye. Yermakov, M. A. Uimin, V. V. Lunin

Prevention of Growth of Filamentary Carbon in Supported iron and Nickel Catalysts.

E.T.C. Vogt, A.J. van Dillen, J.W. Geus


ur gm rovi iona eliver erable products (Ozalp et al., 2010). The reduction of CO2 emission presents great economic and environmental interests (Van-Dal and Bouallou, 2013). The direct formation of dimethyl carbonate (DMC) from CO2 and methanol is one of the promising reactions for this purpose (Delledonne et al., 2001; Sakakura and Kohno, mates as well as a promising octane enhancer (Ono, 1997; Pacheco for the synthesis osgene-methanol onate with methNeverthless, these d corrosive gases otential explosion

Hence, the direct e most attractive hemistry and sus997; Leino et al., 2010). However, the activation of highly stable CO2 and the limitation of the reaction thermodynamic prohibits its widespread development. Up to now, many researchers have tried to shift the reaction equilibrium by pressurizing CO2, using effective dehydrating agents and developing effective catalysts (Choi et al., 2002;

Sakakura and Kohno, 2009).

The organometallic-catalyzed (Kizlink, 1993) formation of DMC from CO2 and methanol was first proposed. Thereafter, inorganometallic compounds have been employed as catalysts for this one* Corresponding authors. Tel./fax: þ86 20 84114113.

E-mail addresses: (S. Wang), mengyzh@mail.sysu.

Contents lists availab

Journal of Clean .e ls

Journal of Cleaner Production xxx (2014) (Y. Meng).is thought to be the primary aspect of cleaner production (Benhelal et al., 2013; Vet}one Mozner, 2013). Recent studies have attempted to explore several ways to reduce CO2 emission (Tonn et al., 2014), including readjusting industrial structures by the expansion of enterprises with low emission and low energy consumption, the exploration of new, efficient, and clean industrial energy, the capture and storage of CO2 for industry demand, and the alternation of CO2 to valuable chemicals. The last strategy involving both the consumption of greenhouse gas CO2 and the production of value-added chemicals (Aresta and Dibenedetto, 2007; Dong et al., 2009; He et al., 2009, 2006; Hunt et al., 2010) and Marshall, 1997; Tundo and Selva, 2002).

Historically, there are several reaction routes of DMC (Delledonne et al., 2001), including ph process, the transesterification of alkene carb anol, and oxidative carbonylation of methanol. synthesis methods involve using poisonous an such as phosgene, carbon monoxide, and bear p hazards in the case of methanol carbonylation.

DMC formation from CO2 and methanol is th alternate route from the viewpoint of green c tainable development (Aresta and Quaranta, 1green chemicals, sustainable materials and environmentally pref- ronment friendly intermediate for higher carbonates and carba-18 August 2014

Accepted 22 August 2014

Available online xxx


Dimethyl carbonate

Carbon dioxide

Halloysite nanotubes

Bimetallic catalyst 1. Introduction

Cleaner production designs and d 0959-6526/© 2014 Published by Elsevier Ltd.

Please cite this article in press as: Zhou, Y., e of Cleaner Production (2014), http://dx.doi.oHNTs (KHNTs) and the synthesized catalysts were characterized by thermogravimetric and differential thermalgravimetric analysis (TG-DTA), temperature programmed reduction (TPR), X-ray photoelectron spectrum (XPS), scanning electron microscope (SEM), transmission electron microscope (TEM), X-ray powder diffraction (XRD), and temperature programmed desorption (TPD) techniques. The catalyst activities were evaluated in a continuous fixed-bed tubular microreactor under 1.2 MPa at 130 C. The effects of the metal weight loadings on the catalytic performances and surface acidebase properties were studied. It was found that moderately acidebase balance on the catalysts surface were important for the

DMC yield. © 2014 Published by Elsevier Ltd. s strategic solutions for 2009). DMC is an important green chemical substitute for corrosive and toxic carbonylating and methylating agents, such as dimethyl sulfate and phosgene. It is also considered as an envi-Received in revised form 2Article history:

Received 26 April 2014

Halloysite nanotubes supported CueNi bimetallic catalysts were synthesized and applied to the direct formation of dimethyl carbonate (DMC) from methanol and CO . Halloystite nanotubes (HNTs), K treatedFormation of dimethyl carbonate on nat

CueNi catalysts

Yingjie Zhou a, Shuanjin Wang a, *, Min Xiao a, Don

Yuezhong Meng a, * a The Key Laboratory of Low-carbon Chemistry & Energy Conservation of Guangdong P

Technologies, Sun Yat-Sen University, Guangzhou 510275, PR China b Department of Chemistry & Medicinal Chemistry Program, Office of Life Sciences, Nat

Singapore a r t i c l e i n f o a b s t r a c t journal homepage: wwwt al., Formation of dimethyl ca rg/10.1016/j.jclepro.2014.08.0e clay supported bimetallic ei Han a, Yixin Lu b, nce / State Key Laboratory of Optoelectronic Materials and l University of Singapore, Singapore 117543, Republic of le at ScienceDirect er Production evier .com/locate/ jc leprorbonate on nature clay supported bimetallic CueNi catalysts, Journal 75 anerstep process, such asmetal (IV) tetra-alkoxide (Kizlink andPastucha, 1995), potassium carbonate (Fang and Fujimoto, 1996), zirconiabased catalysts (Ikeda et al., 2000; Tomishige et al., 2001, 1999), cerium-based catalysts (Aresta et al., 2010, 2008; Choi et al., 2002), heteropoly compounds (Allaoui and Aouissi, 2006), H3PO4eV2O5 (Wu et al., 2005), CueNi bimetallic (Bian et al., 2009a, 2009b;Wang et al., 2007; Wu et al., 2006) supported on different carriers. These traditional catalysts suffer fromtedious preparationprocess, and the

DMC yield is still not ideal due to the deactivation of catalysts by in situ produced water. In order to overcome these obstacles, the kinetic removal of water from the catalytic systems in the presence of dehydrates or additives such as CaCl2, 2,2-dimethoxy propabe (DMP), benzonitrile, butylene oxide, molecular sieves and etc. have beenwidely studied (Eta et al., 2011; Tomishige andKunimori, 2002;