Zeolite–supported nickel phyllosilicate catalyst for CO hydrogenolysis of cyclic ethers and polyols
Graphical abstract
Introduction
The dependence of the chemical industry on traditional oil feedstocks is of growing concern, especially when oil reserves are continually being depleted. Furthermore, the environmental hazards that the usage of oil poses have become a strong motivation for the development of environmentally friendlier, bio–renewable feedstock for the chemical industry [1]. Furanic compounds and their derivatives have been well established as a bio–renewable feedstock for the production of a wide range of high value–added chemicals [2]. As a well–known example, furfural can be obtained from acid–catalyzed dehydration of pentoses obtained from plant biomass [3,4]. Tetrahydrofurfuryl alcohol (THFA), which can be produced from the total hydrogenation of furfural over Ni–based catalysts [5,6], can then undergo ring opening to form 1,5–Pentanediol (15PDO) when the ring–opening is catalyzed by noble metals such as Rh or Ir modified by Mo or Re oxide [[7], [8], [9], [10]]. Similarly, 5–hydroxymethyl furfural (HMF) can undergo sequential hydrogenation and ring–opening to produce value–added 1,6–hexanediol (16HDO) [11]. These linear carbon chains with both terminal OH groups, known as α,ω–diols, are widely used as monomers for the production of polyesters and polyurethanes.
For such ring–opening reactions, catalysis by noble metals have been extensively studied. However, due to the rarity and price of such metals, it is desired to use non–noble metals as potential replacements for these catalysts. A pioneer work developed a multiple approach to synthesize 15PDO from THFA via a dehydration–hydration–hydrogenation pathway, with an overall yield of ca. 70% [12]. Very recently, this process has been modified by Dumesic et al. for the production of 15PDO from biomass–derived THFA over inexpensive catalysts, reaching a significantly higher overall yield of 90% [13]. The process consists of the following three steps: (1) dehydration of THFA to 3,4–2H–dihydropyran (DHP) over γ–Al2O3 in the vapor phase; (2) hydration of DHP to 2–hydroxytetrahydropyran (2–HTHP) without addition of any external catalyst in the liquid phase; and (3) ring–opening tautomerization of 2–HTHP to δ–hydroxyvaleraldehyde which can be subsequently hydrogenated into 15PDO over Ru catalysts. Similar multi–step approach was applied to ring–opening of tetrahydropyran–2–methanol (THPM) into 16HDO, resulting in a maximum 34% overall yield of 16HDO [14].
Our previous study [15] has demonstrated that Ni itself is capable of ring opening of THFA at the more sterically hindered secondary CO bond, yielding mostly 15PDO along with 1,2,5–pentanetriol (125PTO), which was identified for the first time in aqueous–phase hydrogenolysis of THFA at high temperatures. Furthermore, nickel supported on ZSM–5 is a promising candidate as an inexpensive catalyst with high chemoselectivity for both ring–opening and ring–closure, yielding tetrahydropyran (THP). THP has a wide range of applications as a solvent or as an intermediate in organic synthesis to produce glutaric acid, 1,5–dichloropentane, heptanediamine, and pimelic acid [16,17]. Additionally, it can undergo ring–opening/dehydration to produce pentadienes [18]. The key advantage of this route is the use of a relatively cheap non–noble metal such as Ni in the direct synthesis of THP from THFA. Therefore, it is important to further explore the factors affecting the performance of such Ni–based catalysts.
One of the most critical factors affecting catalyst activity is the catalyst preparation method [19,20]. nickel–zeolite catalysts are typically prepared by the relatively simple incipient wetness impregnation (IWI) method. However, catalysts prepared by impregnation methods typically suffer from relatively low metal dispersion and hence low catalytic activity [21]. To improve the dispersion and activity of the nickel–zeolite catalysts, the ion exchange and deposition–precipitation (D–P) method [[22], [23], [24], [25]] were studied and it was found that those methods are able to boost higher initial activity and recyclability after repeated runs as compared to impregnation, particularly when using organic solvents [23]. One key reason for this difference is the improved degree of dispersion of nickel on the support surface for the latter two methods as compared to the impregnation one. However, ion exchange method is limited to relatively low metal loading. Previous studies also reported the presence of different nickel species, including nickel hydroxide, nickel oxide, nickel phyllosilicate species, in zeolite–supported catalyst prepared by D–P method [[21], [22], [23],26]. Besides, our previous studies showed that the nickel catalysts prepared via phyllosilicate precursor could suppress sintering of nickel particles [27]. Hence, it is of great interest to unravel if this stabilizing effect of highly dispersed nickel using the D–P method leads to a good catalytic performance during ring–opening reactions in liquid (aqueous) phase.
Besides preparation methods, another important factor in catalyst activity and effectiveness is the accessibility to the active sites and the ability of reactants/products to diffuse in/out the pores to reach the active sites. Since the structure of the support directly affects the diffusivity of reactants and products in and out of the pores, the structure of the zeolite may also affect the yield and selectivity of the reaction. The structure also affects the shape selectivity of the catalyst [28], which means that the structure may improve selectivity towards given products. Indeed, the effect of the zeolite structure has already been reported in previous studies using bare zeolites [29] and zeolite–supported Ni catalysts [30,31].
In order to get a better understanding of the physicochemical properties of zeolites on ring–opening reactions, this paper aims to understand the effect of catalyst preparation method (D–P) and zeolite structure of zeolite–supported Ni catalysts on performance and recyclability. To achieve this, various zeolites, including small pore zeolites (SAPO–34), medium pore zeolites (Ferrierite, ZSM–5, and ZSM–11), and large pore zeolites (Mordenite and BETA) were investigated for the hydrogenolysis of cyclic ethers and polyols derived from furanic compounds.
Section snippets
Catalyst preparation
The ammonium form of Ferrierite (FER), ZSM–5, Mordenite (MOR) and BETA zeolites with SiO2/Al2O3 ratios of 20, 30, 20, and 25, respectively, were obtained from Zeolyst and used as catalyst support. Nickel (II) Nitrate hexahydrate (98%, Alfa Aesar), Urea (ACS, 99.0–100.5% from Alfa Aesar) were used for catalyst preparation. THFA (99 wt%, Sigma Aldrich), THPM (98%, TCI), 1,2,5–pentanetriol (97%, TCI), 1,5–pentanediol (97%, Sigma Aldrich), 1,2,6–hexanetriol (96 wt%, Sigma Aldrich), and
Characterization results
The physicochemical properties for the parent zeolites and Ni–zeolite catalysts are summarized in Table S2 (Supplementary Material) and Table 2, respectively. The Ni loading of the catalysts was fixed at about 10 wt%. The nickel loadings determined by XRF range from 9.2 wt% to 10.3 wt%, being the differences attributed to the differences in catalyst supports and preparation methods. The variation of the solution pH during D–P of Ni (II) species on ZSM–5 is shown in Fig. S1 (Supplementary
Formation of Ni phyllosilicate precursors during D–P process
As presented in the result section, various characterization techniques were employed to elucidate the nature of active sites on the surface of prepared Ni–zeolite catalytic systems. Compared to the bare zeolites, all Ni–zeolites catalysts present larger external surface areas, total pore volumes, and mesoporous volumes, but smaller values of BET surface area, microporous surface area and pore volume. This is ascribed to the fact that the deposited Ni species partially block the micropores of
Conclusions
The physicochemical and structural properties of different zeolites, including small pore (SAPO–34), medium pore (Ferrierite, ZSM–5, and ZSM–11), and large pore zeolites (Mordenite and BETA), were investigated in C–O hydrogenolysis of cyclic ethers (THFA and THPM) and polyols using Ni catalysts. nickel–zeolite catalysts were synthesized via deposition–precipitation (D–P) method and analyzed with a wide range of characterization techniques. The characterization results show the existence of
Acknowledgements
The authors gratefully thank the Singapore Agency for Science, Technology and Research (A*STAR), National University of Singapore, and NEA (ETRP 1501 103) for their generous financial supports. The help of Dr. Liu Dapeng with synthesizing ZSM–11 and SAPO–34 zeolites is also greatly acknowledged. One of us (E.S.) is grateful to A*STAR for the Singapore International Graduate Award (SINGA) scholarship.
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