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Synthesis of isosorbide from sorbitol in water over high-silica aluminosilicate zeolites
Accepted Manuscript Title: Synthesis of isosorbide from sorbitol in water over high-silica aluminosilicate zeolites Author: Ryoichi Otomo Toshiyuki Yokoi Takashi Tatsumi PII: DOI: Reference:
S0926-860X(15)30086-7 http://dx.doi.org/doi:10.1016/j.apcata.2015.07.034 APCATA 15484
To appear in:
Applied Catalysis A: General
Received date: Revised date: Accepted date:
21-5-2015 14-7-2015 22-7-2015
Please cite this article as: R. Otomo, T. Yokoi, T. Tatsumi, Synthesis of isosorbide from sorbitol in water over high-silica aluminosilicate zeolites, Applied Catalysis A, General (2015), http://dx.doi.org/10.1016/j.apcata.2015.07.034 This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
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Synthesis of isosorbide from sorbitol in water over high-silica
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aluminosilicate zeolites
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Ryoichi Otomo, Toshiyuki Yokoi,* and Takashi Tatsumi
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Chemical Resources Laboratory, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku,
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Yokohama 226-8503, Japan
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*Corresponding author: Toshiyuki Yokoi
Tel: +81-45-924-5265, Fax: +81-45-924-5282, E-mail: [email protected]
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Abstract:
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Dehydration of sorbitol to isosorbide in water was studied using various types of
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aluminosilicate zeolites as heterogeneous catalyst. Among the zeolite catalysts tested, the
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especially, beta zeolite with the Si/Al ratio of 75, designated as beta(75), gave an isosorbide yield as
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high as 80%. We have found that the three-dimensional large pore structure is favorable for
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enhancing the diffusion of sorbitol and the products. In addition, beta with a low Al content
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exhibited a higher catalytic activity than that with a high Al content, despite the small number of
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acid sites. The reason for this high catalytic activity is ascribed to hydrophobicity of the catalyst
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surface. Hydrothermal stability is another critical factor in determining the catalytic performance.
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The influence of reaction parameters such as temperature and the catalyst amount was investigated.
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The beta(75) proved to be reusable without loss of activity after calcination at 550 ºC.
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BEA-type aluminosilicate zeolite (beta) showed a remarkably high catalytic performance;
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KEYWORDS: Dehydration, Hydrophobicity, Isosorbide, Sorbitol, Zeolites 1 Page 1 of 28
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1. Introduction Sorbitol is a promising feedstock for utilization of biomass as useful chemicals and fuels
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[1-5] and ranked as one of the top 10 important targets from biomass [6-8]. Conventionally, sorbitol
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has been produced in industry through hydrogenation of glucose derived from starch [9-11]. In the
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past decade, however, a great deal of effort has been devoted to the production of sorbitol from
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cellulose through hydrolytic hydrogenation. The research advances have expanded the potential of
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sorbitol as bio-based feedstock and its production from cellulose has been achieved in high yields
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[12-24].
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Isosorbide (1,4:3,6-dianhydrosorbitol) is produced through double intramolecular
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dehydration of sorbitol (Scheme 1). Because of its high stability, two symmetrical OH groups and
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unique properties, isosorbide has many applications in wide industrial fields [25]. For example,
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isosorbide has been used in the pharmaceutical industry [7,26]. Another important application of
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isosorbide is to use as plastic monomer [27,28]. Poly-(ethylene-co-isosorbide) terephthalate is a
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bio-based alternative to polyethylene terephthalate (PET) and shows a higher glass transition
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temperature than PET [29]. Isosorbide also replaces bisphenol A in the production of polycarbonate
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and epoxy resins with high functionality [30,31].
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Dehydration of sorbitol to isosorbide has been investigated by many researchers and a
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variety of reaction conditions and acid catalysts have been explored. A typical homogeneous
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catalyst is sulfuric acid [32-36]. Huchette and Flèche reported that sorbitol was dehydrated to
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isosorbide in 77% yield by using sulfuric acid as catalyst in vacuo at 135 ºC [35]. Although this
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process achieved the high yield, it requires neutralization and decoloration of the dark-colored
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mixture. For industrial application, a heterogeneous reaction system has advantages in many points
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and various types of heterogeneous catalysts have been explored; for example, modified metal
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oxides [37-41], zeolites [42-46], metal phosphates [47-49], supported heteropoly acids [50],
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supported metals [51-53], and ion-exchange resin [54-59]. Xiao et al. reported that a mesoporous 2 Page 2 of 28
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polymer-based catalyst bearing SO3H groups efficiently promoted the dehydration of sorbitol in
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vacuo, achieving ca. 88% yield of isosorbide [60]. Very recently, Fukuoka et al. achieved 76% yield
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of isosorbide using a high-silica beta zeolite under neat conditions [46]. Numerous examples have been reported for the dehydration of sorbitol without any solvent
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or in organic solvents such as xylene [32,35,39,40,45,55-61]. Makkee et al. reported the production
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of isosorbide from cellulose in molten salt hydrate medium, achieving 95% yield [62,63]. Since
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sorbitol can be produced through the hydrolytic hydrogenation of cellulose, performing the
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dehydration reaction in water could simplify the process of isosorbide production [47,64-67].
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Although the high yields of isosorbide have been achieved under neat conditions, successful
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production of isosorbide by the dehydration in water with heterogeneous catalysts has not been
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reported. Recently, metal-loaded zeolites have been found to be excellent catalysts for the
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hydrolytic hydrogenation of cellulose to sorbitol in water [18,23,24], presenting the possibility that
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a one-pot production of isosorbide from cellulose might be accomplished if the dehydration of
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sorbitol can be performed in a high yield in water with a zeolite catalyst.
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Here, we report on the unique catalytic properties of aluminosilicate zeolites for the
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dehydration of sorbitol in water. Influences of the framework type and framework composition of
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the zeolites were extensively investigated. Among the zeolite catalysts tested, a high-silica Beta
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zeolite was found to be a promising catalyst for the dehydration of sorbitol in water.
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2. Experimental
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2.1. Materials
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The aluminosilicate zeolites used in this work were purchased from chemical companies or
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kindly given by Catalysis Society of Japan as follows: ZSM-5 (Si/Al = 13, Catalysis Society of
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Japan, JRC-Z5-25H), ZSM-5 (Si/Al = 40, Zeolyst, CBV8014), ZSM-5 (Si/Al = 140, Zeolyst,
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CBV28014), mordenite (Si/Al =10, Catalysis Society of Japan, JRC-Z-HM20(2)), mordenite (Si/Al
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= 45, Catalysis Society of Japan, JRC-Z-HM90), mordenite (Si/Al = 110, Tosoh, HSZ-690HOA), 3 Page 3 of 28
beta (Si/Al =13, Catalysis Society of Japan, JRC-Z-HB25), beta (Si/Al = 75, Catalysis Society of
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Japan, JRC-Z-HB150), beta (Si/Al = 150, Zeolyst, CP-811C-300), Y (Si/Al = 3, Catalysis Society
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of Japan, JRC-Z-HY5.6(2)), USY (Si/Al = 5, Tosoh, HSZ-350HUA), USY (Si/Al = 30, Zeolyst,
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CBV760), and USY (Si/Al = 55, Tosoh, HSZ-385HUA). All the catalysts were calcined at 550 ºC
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for 8 h prior to use. Zeolite samples are designated with their Si/Al ratios in the parentheses. Other
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chemicals were purchased and used without any further purification: D-sorbitol (Aldrich),
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1,4-anhydro-D-sorbitol (Tronto Research Chemicals), 1,5-anhydro-D-sorbitol (Wako pure
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chemical) and 2,5-anhydro-D-sorbitol (Tronto Research Chemicals) were used.
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2.2.
Characterization of catalysts
Powder X-ray diffraction (XRD) patterns of the samples were collected on a Rigaku
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Ultima III diffractometer using a Cu Kα radiation (40 kV, 40 mA). Solid-state
Si MAS NMR
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spectra were measured on a JEOL ECA-400 spectrometer at a resonance frequency of 79.5 MHz by
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using a 6 mm sample rotor with a spinning rate of ~5.5 kHz. Nitrogen adsorption-desorption
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measurements were conducted by using a BEL-mini (BEL Japan) analyzer at -196 ºC and the BET
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surface area was calculated in the P/P0 region of 0 – 0.1. Vapor-phase water adsorption isotherms
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were obtained by using a BEL-max (BEL Japan) analyzer at 25 ºC. The number of acid sites shown
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in Table 1 was determined by temperature-programed desorption (TPD) of NH3 using BEL-CAT
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(BEL Japan) with a Q-MS detector. The TPD profiles are shown in Fig. S1 – S4. The amount of
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organic deposition on a catalyst recovered after a reaction run was calculated on the basis of weight
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loss in thermogravimetric analysis (TGA) by using a Rigaku ThermoPlus analyzer. The weight loss
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above 200 ºC was attributed to the combustion of the organic deposition.
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2.4. Catalytic tests
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Catalytic dehydration experiments were performed in a Teflon-lined stainless-steel
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autoclave (50 ml). In a typical reaction, 15 ml of reactant solution containing 7.5 mmol of sorbitol 4 Page 4 of 28
(0.5 mol/l, ~9 wt%) was poured into the autoclave and to the solution a desired amount of a zeolite
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was added. The reaction mixture was heated and magnetically stirred at approximately 800 rpm.
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Zero time was taken at the moment when the temperature of the reaction mixture reached a set point.
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At a set time, the reaction was quenched by cooling the autoclave in an ice bath. The reaction
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mixture was filtered prior to quantitative analysis to remove a solid catalyst. The recovered catalyst
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was thoroughly washed with water and dried at ambient temperature. The dried powder was
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characterized and in some cases used in a reuse test. Throughout the reuse test, a small amount of a
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solid catalyst was lost during the work-up. Therefore, the recycle runs were done in a smaller scale
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than the first run with the composition of the reaction mixture constant. Reaction results at different
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reaction times were performed in separate batches.
Sorbitol and water-soluble products were analyzed by an HPLC (Shimadzu, LC-20A) with
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an REZEX RCM-monosaccharide column (300 mm x 7.8 mm, Phenomenex) by an RI detector.
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Mixtures of anhydrosorbitol (AHSO) isomers are produced in the dehydration of sorbitol via
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elimination of a water molecule between hydroxyl groups at different positions and such isomers
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have very similar molecular structures. For example, 1,4-AHSO and 3.6-AHSO are epimeric and
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cannot be separated from each another. Therefore, the combined amount of 1,4- and 3,6-isomers
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was measured and expressed as 1,4-AHSO. Also produced were 1,5-AHSO and 2,5-AHSO, but the
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combined selectivity to these two isomers were always much lower than that to 1,4-AHSO. The
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total amount of these two isomers is expressed as “Other AHSO”. Galactitol and mannitol were also
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found in slight yields. A few unidentified products were detected in negligibly small peaks at similar
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retention times to 1,5-AHSO and 2,5-AHSO. These products in small yields and missing products
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that were not detected by the HPLC analysis were lumped together into “Others”.
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3. Results and discussion
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3.1. Influence of structural and compositional properties
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First, we evaluated catalytic performance of various types of zeolites in the dehydration of 5 Page 5 of 28
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sorbitol. Representative 12-membered ring zeolites (*BEA, FAU and MOR) and MFI-type zeolites
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with 10-membered rings were examined. Fig. 1 shows the conversion of sorbitol and the distribution of products in the reactions
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performed at 200 ºC for 2 h. In the absence of a catalyst, the conversion of sorbitol was 10% and
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1,4-AHSO was the sole product detected by the HPLC analysis. The reaction mixture was colored
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pale brown after the reaction, indicating the formation of polymeric species other than 1,4-AHSO,
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included in “Others”. The ratio of sorbitol molecules to Al atoms of the zeolite (Sor/Al ratio) was
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fixed at 50 by varying the amount of the catalyst. Fig. 1 indicates that the framework type has a
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significant influence on the catalytic performance. Among the high-silica zeolites, the sorbitol
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conversion was in the following order: *BEA, MOR, MFI, and FAU. Beta, which has a
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three-dimensional pore system, showed the better performance than mordenite with a
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two-dimensional system. The large pore openings and three-dimensional pore system would
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enhance the diffusion of sorbitol and cyclic products, leading to the high catalytic activity. The
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reason for the low activities of the FAU-type zeolites is discussed below. For all the catalysts, the
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main product was 1,4-AHSO, and a small amount of 1,5-AHSO and 2,5-AHSO were also detected.
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The combined selectivity to these two isomers was always below 5%. Formation of isosorbide was
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observed when the conversion of sorbitol was high, being consistent with the successive reaction
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mechanism for the production of isosorbide (Scheme 1).
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Notably, the framework composition is also an important factor for determining the
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catalytic performance. High-aluminum zeolites such as ZSM-5(13), mordenite(10) and Y(3)
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showed almost no activity, as observed in similar reaction results to the blank run. On the other
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hand, high-silica zeolites such as ZSM-5(40) and mordenite(110) showed perceptible catalytic
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activities, demonstrating that high-silica composition is favorable for the dehydration of sorbitol in
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water. High-silica large pore zeolites such as mordenite(110), beta(75) and beta(150) exhibited a
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high catalytic performance and especially beta(75) showed the best performance; at the sorbitol
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conversion of 87%, the selectivities to 1,4-AHSO and isosorbide reached 44 and 33%, respectively. 6 Page 6 of 28
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3.2. Importance of high-silica composition Generally, in conversion of hydrocarbons, high Al contents generally lead to enhanced
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formation of carbonaceous deposition and so high-aluminum zeolites quickly deactivate. As shown
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in Table 2, the carbonaceous deposition was similar in amount irrespective of the Al content for
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ZSM-5 catalysts (ca. 0.075 g/g-zeolite) and Y-type catalysts (ca. 0.11 g/g-zeolite). The deposition
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on mordenite(10) was smaller in amount than that on mordenite(110). These results indicates that
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the poor activities of high-aluminum zeolites was not due to the quick deactivation but to an
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intrinsic character.
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One of the reasons for the importance of high-silica composition can be attributed to
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hydrophobicity of a catalyst surface [68]. Recently, it was reported that under neat conditions,
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hydrophobic surface of the catalyst facilitated the desorption of water molecules formed by the
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dehydration; Xiao et al. have reported that for the polymer-based catalyst the hydrophobic surface
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can keep the water molecules away [60]. Fukuoka et al. have proposed that the water molecules are
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destabilized on the hydrophobic surface on the high-silica zeolite [46]. A much larger amount of
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water is present in our reaction system compared to that formed by the dehydration reaction.
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Moreover, the autogenous pressure during the reaction is ~1.5 MPa where adsorption and intrusion
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of water molecules occur [69,70]. Hence, it is expected that during the reaction, the intrazeolitic
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space could be filled with water molecules, which form clusters and/or larger structures through
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hydrogen bonds [71-73]. Even in such a situation, hydrophobicity is an important factor. Dang et al.
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conducted a computer simulation of the adsorption structure of water molecules on beta zeolites
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with different Al contents in the wide range of pressure and temperature [70]; the number of water
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molecules occluded in intrazeolitic space is increased along with the Al content at high temperature
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and high pressure and then the interaction between the zeolite and the water molecules becomes
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stronger. Moreover, as revealed by vapor-phase adsorption experiments, the clusters around
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Brønsted acid sites delocalize the positive charge through hydrogen bonding, which would lead to
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decreased acidity [72]. Based on these reports, we assume that intrazeolitic diffusion of sorbitol
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and/or kinetically relevant steps would be strongly interfered by water molecules on high-aluminum
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zeolites. However, hydrophobicity originating from the high-silica composition would reduce the
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unfavorable effects induced by water molecules, leading to a better catalytic performance. We compared vapor-phase water adsorption properties among beta zeolites (Fig. 2). The
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amount of water molecule adsorbed increased along with the Al content because Brønsted and
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Lewis acid sites on a zeolite strongly adsorb water molecules [73]. High-silica beta zeolites are
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generally prepared by the dealumination of high-aluminum beta zeolites and as a result, a large
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number of silanol groups, which could increase hydrophilicity, are formed; beta(150) had a larger
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number of silanol groups than beta(75) as revealed by a higher proportion of Q3 species in
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MAS NMR spectra (Fig. S5). Nevertheless, beta(150) showed a smaller adsorption capacity,
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demonstrating that the number of silanol groups does not significantly affect the water adsorption
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amount compared to the Al content [74]. Thus, we deduce that a high density of Al atoms mainly
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decreases hydrophobicity and catalytic activity per Al site.
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The product selectivity was compared between beta(13) and beta(75) at around 40%
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conversion, finding similar product selectivities (Table S1). In addition, beta(75) and beta(150)
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showed similar product selectivities at around 85% conversion. These results indicated that the
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product selectivity was not significantly affected by the Al content.
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The catalytic performance was compared on the basis of the catalyst weight (Fig. S6).
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ZSM-5(40) and mordenite(45) showed the best performance among ZSM-5 and mordenite catalysts,
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respectively. Beta zeolites, on the whole, showed high catalytic activity and beta(75) showed the
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best performance. Beta(13) showed higher conversion than beta(150), although the activity per Al
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site was in the opposite order. Among each type of zeolites, the zeolites with the intermediate Si/Al
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ratio showed the best performance. This tendency demonstrates that catalytic activity based on the
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catalyst mass is determined by a balance between the number of acid sites and the degree of
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hydrophobicity. 8 Page 8 of 28
ZSM-5(13) showed a poor activity, while beta(13) with the same Al content showed the
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remarkable activity. The water adsorption properties were compared between these two zeolites,
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finding that at a low relative pressure, ZSM-5(13) showed a steep increment, which was larger than
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that for beta(13) in spite of the lower micropore volume (Figs 2 and S7). This behavior indicated
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that ZSM-5(13) more strongly interacted with water molecules than beta(13). It is consistent with
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the assumption that the activity of the catalyst with hydrophilic nature is strongly inhibited by water
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molecules.
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The numbers of Brønsted and Lewis acid sites on the beta zeolites were separately
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estimated by IR spectroscopy with pyridine as probe molecule (Table S2). High-silica beta zeolites
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such as beta(75) and beta(150), which had very small numbers of Lewis acid sites, showed a
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remarkably high catalytic activity, as shown in Fig. 1. These results demonstrate that the
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dehydration of sorbitol to isosorbide cannot be promoted by Lewis acids but can be by Brønsted
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acids [35]. Note that Beta zeolites, which generally have weak acid sites, showed the high catalytic
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activity compared to ZSM-5 and mordenite, which have strong acid sites [75,76]. These results
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suggested that weak acid sites can promote the dehydration of sorbitol. Thus, we considered that the
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catalytic activity was not determined by the strength of the acid sites.
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There is some literature on the efficient catalysis of high-silica aluminosilicate zeolites in
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water such as hydrolysis of ester and hydration of alkene [77-79]. These early reports mainly
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concerned the preferable adsorption of oleophilic molecules on hydrophobic surface of a zeolite.
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Recently, it was also proposed that hydrophobic property is advantageous for adsorption and
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catalytic reactions of highly water-soluble compounds [80,81]. The present study also suggests that
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hydrophobicity of an aluminosilicate zeolite is important for the reaction of highly water-soluble
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compounds over Brønsted acid sites in water solvent.
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3.3. Importance of hydrothermal stability According to Figs. 1 and S6, FAU-type zeolites showed the poor activities in the 9 Page 9 of 28
screening tests irrespective of the Si/Al ratio although they have the largest three-dimensional
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12-membered ring structure and the high-silica compositions. Fig. 3 shows XRD patterns of the
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FAU-type zeolites recovered after the catalytic reactions performed with the Sor/Al ratio of 50 at
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200 ºC for 2 h. For high-aluminum zeolites, Y(3) and USY(5), their framework structures were
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completely retained after the reactions. Note that the diffraction intensities of the peaks at 2θ ˂ 15 º
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were decreased for all the samples after the reactions; however, this decrease should have derived
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from organic compounds occluded in the micropores and did not correlate with the decrease of
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crystallinity. However, USY(30) recovered showed only a halo peak, and USY(55) showed
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weakened diffraction peaks superposed on a halo peak. The XRD analyses revealed that these two
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types of USY zeolites were hydrothermally unstable and their framework structures were collapsed
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during the reactions [82]. Silanol defect sites, which were formed by the acid treatment included in
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the preparation of USY zeolites, were preferentially hydrolyzed and the framework of high-silica
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USY zeolites (i.e. Si/Al = 15 – 50) was unstable under hydrothermal conditions [83]. The
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hydrothermal stability of other high-silica zeolites was also investigated. Fig. 4 shows XRD patterns
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of ZSM-5(40), mordenite(110) and beta(75) before and after the reactions. Obviously, the
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framework structures were totally retained after the reactions. In conclusion, the poor activities of
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the high-silica USY zeolites would be due to their poor hydrothermal stability under the reaction
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conditions studied.
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3.4. Influence of reaction conditions
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3.4.1. Reaction temperature
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The reaction conditions were optimized by using beta(75). First, the effect of the reaction
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temperature was investigated. The reaction rate of sorbitol strongly depended on the temperature;
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the conversion of sorbitol after 2 h was 43% at 180 ºC, while >99% conversion of sorbitol was
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achieved at 220 ºC (Fig. 5). The yield of isosorbide at prolonged reaction time was 81, 77 and 74%
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at 180, 200 and 220 ºC, respectively. The decrease in the maximum yield at the high temperature 10 Page 10 of 28
would be due to the side reactions of sorbitol and 1,4-AHSO to form missing products (carbon
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balance at 180, 200 and 220 ºC were ~92, 86 and 83%, respectively). The combined yield of other
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AHSO was almost the same (< 3%). The 81% yield of isosorbide was as high as the result (80%)
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reported by Hoelderich et al. [49] that has been the best for a heterogeneous reaction system to our
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knowledge. We can conclude that operation at a relatively low temperature is favorable for
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achieving a high yield of isosorbide, although it needs a long reaction time.
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3.4.2. Catalyst amount
To improve the productivity of isosorbide, the dehydration reactions were performed with
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the amount of beta(75) varied (Fig. 6). The catalyst amount was adjusted to the Sor/Al ratio of 25,
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50 and 100. Although the large amount of catalyst certainly led to an increase in the sorbitol
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conversion, the rate of the production of isosorbide was not so much increased and the carbon
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balance became worse, indicating the escalated formation of missing products. The maximum yield
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of isosorbide in the reaction runs with the Sor/Al raito of 25, 50 and 100 were 69, 78 and 80%,
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respectively. The carbonaceous deposition of organic matters on the catalyst could account for a
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part of the missing products. Fig. 7 shows the changes in the conversion of sorbitol, the yield of
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“Others” and the yield of the deposition as revealed by TGA along with the reaction time at the
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Sor/Al ratios of 25 and 50, where the yield of the deposition is expressed in percent by weight.
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Although the yield of “Others” includes the small amount of the detected products, a majority of
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“Others” would be the missing products (See experimental section). For the run performed at the
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ratio of 50, the yield of “Others” were rapidly increased to 16% during the first 1 h of the reaction
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and thereafter remained fairly constant. This behavior was similar to the evolution of the deposition
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on the catalyst, which was increased to 9 wt% during 1 h and thereafter remained at ca. 9-10 wt%.
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For the run at the ratio of 25, the yield of “Others” was high (ca. 26-29%) compared to the run at
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the ratio of 50. Organic deposition on the catalyst was also high (ca. 17-18 wt%). Obviously, the
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deposition on the catalysts accounted for a major part of the missing products. Thus operation with
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a small amount of a catalyst is favorable from the viewpoint of product selectivity as well as
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economics.
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3.5. Regeneration of catalyst The reusability of beta(75) was examined. Fig. 8a shows the conversion of sorbitol and the
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distribution of products during the recycle runs performed at the Sor/Al ratio of 50 at 200 ºC for 18
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h. The conversion of sorbitol was gradually decreased from 99 to 71% through the consecutive runs.
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The yield of isosorbide was drastically decreased from 78 to 17%. Note that the framework
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structure of the used catalyst was completely retained after four runs (Fig. S8). The amount of the
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organic deposition after the first run was 0.10 g/g-zeolite, which was gradually increased to 0.16
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g/g-zeolite after the fourth run. The deactivation would be caused by the deposition of carbonaceous
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matters on the catalyst. Therefore we performed another set of recycle runs by using the used
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catalyst calcined at 550 ºC after each run (Fig. 8b). The calcination efficiently regenerated the
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catalyst; the conversion of sorbitol was over 99% and the yield of isosorbide was kept constant at
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76 – 77% throughout the recycle runs. These results indicate that the deposition of carbonaceous
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matters on the catalyst is the main cause of the deactivation. There were no significant changes in
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the framework structure, Al content and acidic properties were between the fresh beta(75) and the
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spent one after the four recycling runs (Figs. S9 and S10, and Table S3). Thus, beta(75) can be used
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four times without a significant loss of activity.
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4. Conclusions
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We studied the dehydration of sorbitol to isosorbide in water using various types of zeolite
23
catalysts and successfully found that catalytic performance of a zeolite is determined by its
24
framework structure, composition (i.e., Al content) and hydrothermal stability. Beta showed the
25
high catalytic performance because the large pore openings and multi-dimensional pore systems
26
enhanced the diffusion of sorbitol and products. As the Si/Al ratio of a zeolite increased, its catalytic 12 Page 12 of 28
activity per Al site was increased. We assume that high-aluminum zeolites strongly interacted with a
2
large number of water molecules during the reaction and that such an interaction unfavorably
3
affects the transportation and/or kinetic steps. Catalytic activity based on the catalyst mass is
4
determined by a balance between the number of acid sites and the degree of hydrophobicity.
5
High-silica USY zeolites were hydrothermally unstable under the reaction conditions and showed
6
the poor activities. On the other hand, high-silica ZSM-5, mordenite, and beta zeolites showed no
7
structural changes after the reactions.
cr
ip t
1
The operation at a relatively low temperature is favorable for suppressing side-reactions of
9
sorbitol. A small amount of catalyst compared to sorbitol is also favorable for decreasing the
10
amount of carbonaceous deposition on the catalyst, which is a major part of missing products as
11
well as the cause of catalyst deactivation.
an
us
8
The yield of isosorbide reached 80% by using beta zeolite with the Si/Al ratio of 75.
13
Furthermore, this catalyst can be regenerated by simple calcination and the catalytic performance
14
remained constant during four consecutive runs.
d
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12
Ac ce pt e
15 16
Acknowledgements
17
We thank Dr. Tohru Setoyama (Mitsubishi Chemical Group, Science and Technology Research
18
Center) for helpful discussion. This work was partly supported by the research project
19
"Technological development of process from manufacturing chemicals derived from non-edible
20
plant resources" organized by New Energy and Industrial Technology Development Organization
21
(NEDO), Japan.
22 23
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754–768.
ip t
6
cr
7 8
us
9
Dehydration of sorbitol in water over various zeolite catalysts was studied.
11
Beta zeolite with a high-silica composition showed high catalytic performance. Hydrophobic catalyst surface contributed to the high catalytic performance. Hydrothermal stability of a zeolite is important for the reaction in water. A catalyst deactivated by organic deposition was regenerated by calcination.
an
10 12 13
M
14 15
d
16 17
Ac ce pt e
Table 1 Structural and acid properties of zeolite catalysts. BET surface area
Acid amount
2
(m /g)
(mmol/g)
13
389
0.90
40
463
0.32
140
409
0.08
10
524
0.97
mordenite(45)
45
580
0.27
mordenite(110)
110
502
0.17
13
547
0.55
75
678
0.21
150
583
0.08
28
545
0.78
USY(5)
5.4
890
0.80
USY(30)
30
946
0.27
USY(55)
55
805
0.07
Sample
ZSM-5(13) ZSM-5(40) ZSM-5(140)
mordenite(10)
beta(13) beta(75)
Structure
3D, 10 × 10 × 10
2D, 12 × 8
3D, 12 × 12 × 12
beta(150) Y(3)
3D, 12 × 12 × 12
Si/Al ratio
18 18 Page 18 of 28
1 2
Table 2 Organic deposition on zeolite catalysts after the reaction.
a
Organic deposition Sample
ZSM-5(40)
0.072
mordenite(10)
0.022
mordenite(110)
0.084
beta(13)
0.14
beta(75)
0.11
Y(3)
0.11
USY(55)
0.11
a
cr
0.076
d
M
an
us
Reaction conditions: Sor/Al ratio equal to 50; sorbitol, 7.5 mmol; water, 15 ml; Temperature, 200 ºC; Time, 2 h.
Ac ce pt e
3
ZSM-5(13)
ip t
(g/g-zeolite)
19 Page 19 of 28
us
cr
ip t
1
2 3
an
a
d
M
Reaction conditions: Sor/Al ratio equal to 50; sorbitol 7.5 mmol; water 15ml; Temperature, 200 ºC; Time, 2 h.
Ac ce pt e
4
a
Fig. 1 Dehydration of sorbitol over various types of zeolites performed at Sor/Al ratio of 50.
20 Page 20 of 28
cr
ip t
1
2
d
M
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Fig. 2 Vapor-phase H2O adsorption isotherms of beta zeolites measured at 25 ºC.
Ac ce pt e
3
21 Page 21 of 28
a
Fig. 3 XRD patterns of FAU-type zeolites before and after the reaction. (a) fresh Y(3), (b) used Y(3), (c) fresh USY(5), (d) used USY(5),
4
M
Reaction conditions: Sor/Al ratio equal to 50; sorbitol, 7.5 mmol; water, 15 ml; Temperature, 200 ºC; Time, 2 h.
d
5
(e) fresh USY(30), (f) used USY(30), (g) fresh USY(55), and (h) used USY (55). a
Ac ce pt e
2 3
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us
cr
ip t
1
22 Page 22 of 28
us
cr
ip t
1
2 a
4
used mordenite(110), (e) fresh beta(75), (f) used beta(75). a
M
Reaction conditions: Sor/Al ratio equal to 50; sorbitol, 7.5 mmol; water, 15 ml; Temperature, 200 ºC; Time, 2 h.
d
5
an
Fig. 4 XRD patterns of zeolites before and after the reaction. (a) fresh ZSM-5(40), (b) used ZSM-5(40), (c) fresh mordenite(110), (d)
Ac ce pt e
3
23 Page 23 of 28
cr
ip t
1
d
M
an
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2
Ac ce pt e
3
4 5 6
Fig. 5 Temperature dependence of (a) conversion of sorbitol, (b) yield of 1,4-AHSO, and (c) yield of isosorbide. (circle) 180 ºC, (triangle)
7
200 ºC, (square) 220 ºC.
8 9
a
a
Reaction conditions: catalyst, beta(75); Sor/Al ratio equal to 50; sorbitol, 7.5 mmol; water, 15 ml; Temperature, 180 – 220 ºC; Time, 0.25 – 60 h.
24 Page 24 of 28
cr
ip t
1
d
M
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2
Ac ce pt e
3
4 5
Fig. 6 Dehydration of sorbitol with different amounts of beta(75). (a) conversion of sorbitol, (b) yield of 1,4-AHSO, and (c) yield of
6
isosorbide.
7 8
a
a
Reaction conditions: Sor/Al ratio equal to (circle) 100, (triangle) 50, (square) 25; sorbitol, 7.5 mmol; water, 15 ml; Temperature, 200 ºC; Time, 0.25 – 48 h.
25 Page 25 of 28
cr
ip t
1
d
M
an
us
2
Ac ce pt e
3 4
Fig. 7 The time course change of (circle) sorbitol conversion, (square) yield of “Others” and (triangle) organic deposition on beta(75) in
5
the reaction runs with Sor/Al ratio equal to (a) 50 and (b) 25.
6
a
a
Reaction conditions: Sor/Al ratio equal to 25 and 50; sorbitol, 7.5 mmol; water, 15 ml; Temperature, 200 ºC.
26 Page 26 of 28
us
a
a
M
an
Reaction conditions: Sor/Al ratio equal to 50; sorbitol 7.5 mmol; water 15ml; Temperature, 200 ºC; Time, 18 h.
d
4
Fig. 8 Recycling use of beta(75) catalyst (a) without calcination and (b) with calcination at 550 ºC after each run.
Ac ce pt e
2 3
cr
ip t
1
27 Page 27 of 28
Scheme 1 Reaction pathways of sorbitol in the presence of zeolite catalysts.
us
2 3
cr
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1
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28 Page 28 of 28
S0926-860X(15)30086-7 http://dx.doi.org/doi:10.1016/j.apcata.2015.07.034 APCATA 15484
To appear in:
Applied Catalysis A: General
Received date: Revised date: Accepted date:
21-5-2015 14-7-2015 22-7-2015
Please cite this article as: R. Otomo, T. Yokoi, T. Tatsumi, Synthesis of isosorbide from sorbitol in water over high-silica aluminosilicate zeolites, Applied Catalysis A, General (2015), http://dx.doi.org/10.1016/j.apcata.2015.07.034 This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
1
Synthesis of isosorbide from sorbitol in water over high-silica
2
aluminosilicate zeolites
3
Ryoichi Otomo, Toshiyuki Yokoi,* and Takashi Tatsumi
4
ip t
5
Chemical Resources Laboratory, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku,
7
Yokohama 226-8503, Japan
10
*Corresponding author: Toshiyuki Yokoi
Tel: +81-45-924-5265, Fax: +81-45-924-5282, E-mail: [email protected]
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9
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Abstract:
M
11 12
cr
6
Dehydration of sorbitol to isosorbide in water was studied using various types of
14
aluminosilicate zeolites as heterogeneous catalyst. Among the zeolite catalysts tested, the
15
*
16
especially, beta zeolite with the Si/Al ratio of 75, designated as beta(75), gave an isosorbide yield as
17
high as 80%. We have found that the three-dimensional large pore structure is favorable for
18
enhancing the diffusion of sorbitol and the products. In addition, beta with a low Al content
19
exhibited a higher catalytic activity than that with a high Al content, despite the small number of
20
acid sites. The reason for this high catalytic activity is ascribed to hydrophobicity of the catalyst
21
surface. Hydrothermal stability is another critical factor in determining the catalytic performance.
22
The influence of reaction parameters such as temperature and the catalyst amount was investigated.
23
The beta(75) proved to be reusable without loss of activity after calcination at 550 ºC.
Ac ce pt e
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BEA-type aluminosilicate zeolite (beta) showed a remarkably high catalytic performance;
24 25
KEYWORDS: Dehydration, Hydrophobicity, Isosorbide, Sorbitol, Zeolites 1 Page 1 of 28
1 2
1. Introduction Sorbitol is a promising feedstock for utilization of biomass as useful chemicals and fuels
4
[1-5] and ranked as one of the top 10 important targets from biomass [6-8]. Conventionally, sorbitol
5
has been produced in industry through hydrogenation of glucose derived from starch [9-11]. In the
6
past decade, however, a great deal of effort has been devoted to the production of sorbitol from
7
cellulose through hydrolytic hydrogenation. The research advances have expanded the potential of
8
sorbitol as bio-based feedstock and its production from cellulose has been achieved in high yields
9
[12-24].
us
cr
ip t
3
Isosorbide (1,4:3,6-dianhydrosorbitol) is produced through double intramolecular
11
dehydration of sorbitol (Scheme 1). Because of its high stability, two symmetrical OH groups and
12
unique properties, isosorbide has many applications in wide industrial fields [25]. For example,
13
isosorbide has been used in the pharmaceutical industry [7,26]. Another important application of
14
isosorbide is to use as plastic monomer [27,28]. Poly-(ethylene-co-isosorbide) terephthalate is a
15
bio-based alternative to polyethylene terephthalate (PET) and shows a higher glass transition
16
temperature than PET [29]. Isosorbide also replaces bisphenol A in the production of polycarbonate
17
and epoxy resins with high functionality [30,31].
Ac ce pt e
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M
an
10
18
Dehydration of sorbitol to isosorbide has been investigated by many researchers and a
19
variety of reaction conditions and acid catalysts have been explored. A typical homogeneous
20
catalyst is sulfuric acid [32-36]. Huchette and Flèche reported that sorbitol was dehydrated to
21
isosorbide in 77% yield by using sulfuric acid as catalyst in vacuo at 135 ºC [35]. Although this
22
process achieved the high yield, it requires neutralization and decoloration of the dark-colored
23
mixture. For industrial application, a heterogeneous reaction system has advantages in many points
24
and various types of heterogeneous catalysts have been explored; for example, modified metal
25
oxides [37-41], zeolites [42-46], metal phosphates [47-49], supported heteropoly acids [50],
26
supported metals [51-53], and ion-exchange resin [54-59]. Xiao et al. reported that a mesoporous 2 Page 2 of 28
1
polymer-based catalyst bearing SO3H groups efficiently promoted the dehydration of sorbitol in
2
vacuo, achieving ca. 88% yield of isosorbide [60]. Very recently, Fukuoka et al. achieved 76% yield
3
of isosorbide using a high-silica beta zeolite under neat conditions [46]. Numerous examples have been reported for the dehydration of sorbitol without any solvent
5
or in organic solvents such as xylene [32,35,39,40,45,55-61]. Makkee et al. reported the production
6
of isosorbide from cellulose in molten salt hydrate medium, achieving 95% yield [62,63]. Since
7
sorbitol can be produced through the hydrolytic hydrogenation of cellulose, performing the
8
dehydration reaction in water could simplify the process of isosorbide production [47,64-67].
9
Although the high yields of isosorbide have been achieved under neat conditions, successful
10
production of isosorbide by the dehydration in water with heterogeneous catalysts has not been
11
reported. Recently, metal-loaded zeolites have been found to be excellent catalysts for the
12
hydrolytic hydrogenation of cellulose to sorbitol in water [18,23,24], presenting the possibility that
13
a one-pot production of isosorbide from cellulose might be accomplished if the dehydration of
14
sorbitol can be performed in a high yield in water with a zeolite catalyst.
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Here, we report on the unique catalytic properties of aluminosilicate zeolites for the
16
dehydration of sorbitol in water. Influences of the framework type and framework composition of
17
the zeolites were extensively investigated. Among the zeolite catalysts tested, a high-silica Beta
18
zeolite was found to be a promising catalyst for the dehydration of sorbitol in water.
19
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20
2. Experimental
21
2.1. Materials
22
The aluminosilicate zeolites used in this work were purchased from chemical companies or
23
kindly given by Catalysis Society of Japan as follows: ZSM-5 (Si/Al = 13, Catalysis Society of
24
Japan, JRC-Z5-25H), ZSM-5 (Si/Al = 40, Zeolyst, CBV8014), ZSM-5 (Si/Al = 140, Zeolyst,
25
CBV28014), mordenite (Si/Al =10, Catalysis Society of Japan, JRC-Z-HM20(2)), mordenite (Si/Al
26
= 45, Catalysis Society of Japan, JRC-Z-HM90), mordenite (Si/Al = 110, Tosoh, HSZ-690HOA), 3 Page 3 of 28
beta (Si/Al =13, Catalysis Society of Japan, JRC-Z-HB25), beta (Si/Al = 75, Catalysis Society of
2
Japan, JRC-Z-HB150), beta (Si/Al = 150, Zeolyst, CP-811C-300), Y (Si/Al = 3, Catalysis Society
3
of Japan, JRC-Z-HY5.6(2)), USY (Si/Al = 5, Tosoh, HSZ-350HUA), USY (Si/Al = 30, Zeolyst,
4
CBV760), and USY (Si/Al = 55, Tosoh, HSZ-385HUA). All the catalysts were calcined at 550 ºC
5
for 8 h prior to use. Zeolite samples are designated with their Si/Al ratios in the parentheses. Other
6
chemicals were purchased and used without any further purification: D-sorbitol (Aldrich),
7
1,4-anhydro-D-sorbitol (Tronto Research Chemicals), 1,5-anhydro-D-sorbitol (Wako pure
8
chemical) and 2,5-anhydro-D-sorbitol (Tronto Research Chemicals) were used.
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11
2.2.
Characterization of catalysts
Powder X-ray diffraction (XRD) patterns of the samples were collected on a Rigaku
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29
Ultima III diffractometer using a Cu Kα radiation (40 kV, 40 mA). Solid-state
Si MAS NMR
13
spectra were measured on a JEOL ECA-400 spectrometer at a resonance frequency of 79.5 MHz by
14
using a 6 mm sample rotor with a spinning rate of ~5.5 kHz. Nitrogen adsorption-desorption
15
measurements were conducted by using a BEL-mini (BEL Japan) analyzer at -196 ºC and the BET
16
surface area was calculated in the P/P0 region of 0 – 0.1. Vapor-phase water adsorption isotherms
17
were obtained by using a BEL-max (BEL Japan) analyzer at 25 ºC. The number of acid sites shown
18
in Table 1 was determined by temperature-programed desorption (TPD) of NH3 using BEL-CAT
19
(BEL Japan) with a Q-MS detector. The TPD profiles are shown in Fig. S1 – S4. The amount of
20
organic deposition on a catalyst recovered after a reaction run was calculated on the basis of weight
21
loss in thermogravimetric analysis (TGA) by using a Rigaku ThermoPlus analyzer. The weight loss
22
above 200 ºC was attributed to the combustion of the organic deposition.
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2.4. Catalytic tests
25
Catalytic dehydration experiments were performed in a Teflon-lined stainless-steel
26
autoclave (50 ml). In a typical reaction, 15 ml of reactant solution containing 7.5 mmol of sorbitol 4 Page 4 of 28
(0.5 mol/l, ~9 wt%) was poured into the autoclave and to the solution a desired amount of a zeolite
2
was added. The reaction mixture was heated and magnetically stirred at approximately 800 rpm.
3
Zero time was taken at the moment when the temperature of the reaction mixture reached a set point.
4
At a set time, the reaction was quenched by cooling the autoclave in an ice bath. The reaction
5
mixture was filtered prior to quantitative analysis to remove a solid catalyst. The recovered catalyst
6
was thoroughly washed with water and dried at ambient temperature. The dried powder was
7
characterized and in some cases used in a reuse test. Throughout the reuse test, a small amount of a
8
solid catalyst was lost during the work-up. Therefore, the recycle runs were done in a smaller scale
9
than the first run with the composition of the reaction mixture constant. Reaction results at different
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reaction times were performed in separate batches.
Sorbitol and water-soluble products were analyzed by an HPLC (Shimadzu, LC-20A) with
12
an REZEX RCM-monosaccharide column (300 mm x 7.8 mm, Phenomenex) by an RI detector.
13
Mixtures of anhydrosorbitol (AHSO) isomers are produced in the dehydration of sorbitol via
14
elimination of a water molecule between hydroxyl groups at different positions and such isomers
15
have very similar molecular structures. For example, 1,4-AHSO and 3.6-AHSO are epimeric and
16
cannot be separated from each another. Therefore, the combined amount of 1,4- and 3,6-isomers
17
was measured and expressed as 1,4-AHSO. Also produced were 1,5-AHSO and 2,5-AHSO, but the
18
combined selectivity to these two isomers were always much lower than that to 1,4-AHSO. The
19
total amount of these two isomers is expressed as “Other AHSO”. Galactitol and mannitol were also
20
found in slight yields. A few unidentified products were detected in negligibly small peaks at similar
21
retention times to 1,5-AHSO and 2,5-AHSO. These products in small yields and missing products
22
that were not detected by the HPLC analysis were lumped together into “Others”.
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3. Results and discussion
25
3.1. Influence of structural and compositional properties
26
First, we evaluated catalytic performance of various types of zeolites in the dehydration of 5 Page 5 of 28
1
sorbitol. Representative 12-membered ring zeolites (*BEA, FAU and MOR) and MFI-type zeolites
2
with 10-membered rings were examined. Fig. 1 shows the conversion of sorbitol and the distribution of products in the reactions
4
performed at 200 ºC for 2 h. In the absence of a catalyst, the conversion of sorbitol was 10% and
5
1,4-AHSO was the sole product detected by the HPLC analysis. The reaction mixture was colored
6
pale brown after the reaction, indicating the formation of polymeric species other than 1,4-AHSO,
7
included in “Others”. The ratio of sorbitol molecules to Al atoms of the zeolite (Sor/Al ratio) was
8
fixed at 50 by varying the amount of the catalyst. Fig. 1 indicates that the framework type has a
9
significant influence on the catalytic performance. Among the high-silica zeolites, the sorbitol
10
conversion was in the following order: *BEA, MOR, MFI, and FAU. Beta, which has a
11
three-dimensional pore system, showed the better performance than mordenite with a
12
two-dimensional system. The large pore openings and three-dimensional pore system would
13
enhance the diffusion of sorbitol and cyclic products, leading to the high catalytic activity. The
14
reason for the low activities of the FAU-type zeolites is discussed below. For all the catalysts, the
15
main product was 1,4-AHSO, and a small amount of 1,5-AHSO and 2,5-AHSO were also detected.
16
The combined selectivity to these two isomers was always below 5%. Formation of isosorbide was
17
observed when the conversion of sorbitol was high, being consistent with the successive reaction
18
mechanism for the production of isosorbide (Scheme 1).
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19
Notably, the framework composition is also an important factor for determining the
20
catalytic performance. High-aluminum zeolites such as ZSM-5(13), mordenite(10) and Y(3)
21
showed almost no activity, as observed in similar reaction results to the blank run. On the other
22
hand, high-silica zeolites such as ZSM-5(40) and mordenite(110) showed perceptible catalytic
23
activities, demonstrating that high-silica composition is favorable for the dehydration of sorbitol in
24
water. High-silica large pore zeolites such as mordenite(110), beta(75) and beta(150) exhibited a
25
high catalytic performance and especially beta(75) showed the best performance; at the sorbitol
26
conversion of 87%, the selectivities to 1,4-AHSO and isosorbide reached 44 and 33%, respectively. 6 Page 6 of 28
1 2
3.2. Importance of high-silica composition Generally, in conversion of hydrocarbons, high Al contents generally lead to enhanced
4
formation of carbonaceous deposition and so high-aluminum zeolites quickly deactivate. As shown
5
in Table 2, the carbonaceous deposition was similar in amount irrespective of the Al content for
6
ZSM-5 catalysts (ca. 0.075 g/g-zeolite) and Y-type catalysts (ca. 0.11 g/g-zeolite). The deposition
7
on mordenite(10) was smaller in amount than that on mordenite(110). These results indicates that
8
the poor activities of high-aluminum zeolites was not due to the quick deactivation but to an
9
intrinsic character.
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One of the reasons for the importance of high-silica composition can be attributed to
11
hydrophobicity of a catalyst surface [68]. Recently, it was reported that under neat conditions,
12
hydrophobic surface of the catalyst facilitated the desorption of water molecules formed by the
13
dehydration; Xiao et al. have reported that for the polymer-based catalyst the hydrophobic surface
14
can keep the water molecules away [60]. Fukuoka et al. have proposed that the water molecules are
15
destabilized on the hydrophobic surface on the high-silica zeolite [46]. A much larger amount of
16
water is present in our reaction system compared to that formed by the dehydration reaction.
17
Moreover, the autogenous pressure during the reaction is ~1.5 MPa where adsorption and intrusion
18
of water molecules occur [69,70]. Hence, it is expected that during the reaction, the intrazeolitic
19
space could be filled with water molecules, which form clusters and/or larger structures through
20
hydrogen bonds [71-73]. Even in such a situation, hydrophobicity is an important factor. Dang et al.
21
conducted a computer simulation of the adsorption structure of water molecules on beta zeolites
22
with different Al contents in the wide range of pressure and temperature [70]; the number of water
23
molecules occluded in intrazeolitic space is increased along with the Al content at high temperature
24
and high pressure and then the interaction between the zeolite and the water molecules becomes
25
stronger. Moreover, as revealed by vapor-phase adsorption experiments, the clusters around
26
Brønsted acid sites delocalize the positive charge through hydrogen bonding, which would lead to
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7 Page 7 of 28
1
decreased acidity [72]. Based on these reports, we assume that intrazeolitic diffusion of sorbitol
2
and/or kinetically relevant steps would be strongly interfered by water molecules on high-aluminum
3
zeolites. However, hydrophobicity originating from the high-silica composition would reduce the
4
unfavorable effects induced by water molecules, leading to a better catalytic performance. We compared vapor-phase water adsorption properties among beta zeolites (Fig. 2). The
6
amount of water molecule adsorbed increased along with the Al content because Brønsted and
7
Lewis acid sites on a zeolite strongly adsorb water molecules [73]. High-silica beta zeolites are
8
generally prepared by the dealumination of high-aluminum beta zeolites and as a result, a large
9
number of silanol groups, which could increase hydrophilicity, are formed; beta(150) had a larger
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10
number of silanol groups than beta(75) as revealed by a higher proportion of Q3 species in
29
11
MAS NMR spectra (Fig. S5). Nevertheless, beta(150) showed a smaller adsorption capacity,
12
demonstrating that the number of silanol groups does not significantly affect the water adsorption
13
amount compared to the Al content [74]. Thus, we deduce that a high density of Al atoms mainly
14
decreases hydrophobicity and catalytic activity per Al site.
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The product selectivity was compared between beta(13) and beta(75) at around 40%
16
conversion, finding similar product selectivities (Table S1). In addition, beta(75) and beta(150)
17
showed similar product selectivities at around 85% conversion. These results indicated that the
18
product selectivity was not significantly affected by the Al content.
Ac ce pt e
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19
The catalytic performance was compared on the basis of the catalyst weight (Fig. S6).
20
ZSM-5(40) and mordenite(45) showed the best performance among ZSM-5 and mordenite catalysts,
21
respectively. Beta zeolites, on the whole, showed high catalytic activity and beta(75) showed the
22
best performance. Beta(13) showed higher conversion than beta(150), although the activity per Al
23
site was in the opposite order. Among each type of zeolites, the zeolites with the intermediate Si/Al
24
ratio showed the best performance. This tendency demonstrates that catalytic activity based on the
25
catalyst mass is determined by a balance between the number of acid sites and the degree of
26
hydrophobicity. 8 Page 8 of 28
ZSM-5(13) showed a poor activity, while beta(13) with the same Al content showed the
2
remarkable activity. The water adsorption properties were compared between these two zeolites,
3
finding that at a low relative pressure, ZSM-5(13) showed a steep increment, which was larger than
4
that for beta(13) in spite of the lower micropore volume (Figs 2 and S7). This behavior indicated
5
that ZSM-5(13) more strongly interacted with water molecules than beta(13). It is consistent with
6
the assumption that the activity of the catalyst with hydrophilic nature is strongly inhibited by water
7
molecules.
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The numbers of Brønsted and Lewis acid sites on the beta zeolites were separately
9
estimated by IR spectroscopy with pyridine as probe molecule (Table S2). High-silica beta zeolites
10
such as beta(75) and beta(150), which had very small numbers of Lewis acid sites, showed a
11
remarkably high catalytic activity, as shown in Fig. 1. These results demonstrate that the
12
dehydration of sorbitol to isosorbide cannot be promoted by Lewis acids but can be by Brønsted
13
acids [35]. Note that Beta zeolites, which generally have weak acid sites, showed the high catalytic
14
activity compared to ZSM-5 and mordenite, which have strong acid sites [75,76]. These results
15
suggested that weak acid sites can promote the dehydration of sorbitol. Thus, we considered that the
16
catalytic activity was not determined by the strength of the acid sites.
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17
There is some literature on the efficient catalysis of high-silica aluminosilicate zeolites in
18
water such as hydrolysis of ester and hydration of alkene [77-79]. These early reports mainly
19
concerned the preferable adsorption of oleophilic molecules on hydrophobic surface of a zeolite.
20
Recently, it was also proposed that hydrophobic property is advantageous for adsorption and
21
catalytic reactions of highly water-soluble compounds [80,81]. The present study also suggests that
22
hydrophobicity of an aluminosilicate zeolite is important for the reaction of highly water-soluble
23
compounds over Brønsted acid sites in water solvent.
24 25 26
3.3. Importance of hydrothermal stability According to Figs. 1 and S6, FAU-type zeolites showed the poor activities in the 9 Page 9 of 28
screening tests irrespective of the Si/Al ratio although they have the largest three-dimensional
2
12-membered ring structure and the high-silica compositions. Fig. 3 shows XRD patterns of the
3
FAU-type zeolites recovered after the catalytic reactions performed with the Sor/Al ratio of 50 at
4
200 ºC for 2 h. For high-aluminum zeolites, Y(3) and USY(5), their framework structures were
5
completely retained after the reactions. Note that the diffraction intensities of the peaks at 2θ ˂ 15 º
6
were decreased for all the samples after the reactions; however, this decrease should have derived
7
from organic compounds occluded in the micropores and did not correlate with the decrease of
8
crystallinity. However, USY(30) recovered showed only a halo peak, and USY(55) showed
9
weakened diffraction peaks superposed on a halo peak. The XRD analyses revealed that these two
10
types of USY zeolites were hydrothermally unstable and their framework structures were collapsed
11
during the reactions [82]. Silanol defect sites, which were formed by the acid treatment included in
12
the preparation of USY zeolites, were preferentially hydrolyzed and the framework of high-silica
13
USY zeolites (i.e. Si/Al = 15 – 50) was unstable under hydrothermal conditions [83]. The
14
hydrothermal stability of other high-silica zeolites was also investigated. Fig. 4 shows XRD patterns
15
of ZSM-5(40), mordenite(110) and beta(75) before and after the reactions. Obviously, the
16
framework structures were totally retained after the reactions. In conclusion, the poor activities of
17
the high-silica USY zeolites would be due to their poor hydrothermal stability under the reaction
18
conditions studied.
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3.4. Influence of reaction conditions
21
3.4.1. Reaction temperature
22
The reaction conditions were optimized by using beta(75). First, the effect of the reaction
23
temperature was investigated. The reaction rate of sorbitol strongly depended on the temperature;
24
the conversion of sorbitol after 2 h was 43% at 180 ºC, while >99% conversion of sorbitol was
25
achieved at 220 ºC (Fig. 5). The yield of isosorbide at prolonged reaction time was 81, 77 and 74%
26
at 180, 200 and 220 ºC, respectively. The decrease in the maximum yield at the high temperature 10 Page 10 of 28
would be due to the side reactions of sorbitol and 1,4-AHSO to form missing products (carbon
2
balance at 180, 200 and 220 ºC were ~92, 86 and 83%, respectively). The combined yield of other
3
AHSO was almost the same (< 3%). The 81% yield of isosorbide was as high as the result (80%)
4
reported by Hoelderich et al. [49] that has been the best for a heterogeneous reaction system to our
5
knowledge. We can conclude that operation at a relatively low temperature is favorable for
6
achieving a high yield of isosorbide, although it needs a long reaction time.
8
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3.4.2. Catalyst amount
To improve the productivity of isosorbide, the dehydration reactions were performed with
10
the amount of beta(75) varied (Fig. 6). The catalyst amount was adjusted to the Sor/Al ratio of 25,
11
50 and 100. Although the large amount of catalyst certainly led to an increase in the sorbitol
12
conversion, the rate of the production of isosorbide was not so much increased and the carbon
13
balance became worse, indicating the escalated formation of missing products. The maximum yield
14
of isosorbide in the reaction runs with the Sor/Al raito of 25, 50 and 100 were 69, 78 and 80%,
15
respectively. The carbonaceous deposition of organic matters on the catalyst could account for a
16
part of the missing products. Fig. 7 shows the changes in the conversion of sorbitol, the yield of
17
“Others” and the yield of the deposition as revealed by TGA along with the reaction time at the
18
Sor/Al ratios of 25 and 50, where the yield of the deposition is expressed in percent by weight.
19
Although the yield of “Others” includes the small amount of the detected products, a majority of
20
“Others” would be the missing products (See experimental section). For the run performed at the
21
ratio of 50, the yield of “Others” were rapidly increased to 16% during the first 1 h of the reaction
22
and thereafter remained fairly constant. This behavior was similar to the evolution of the deposition
23
on the catalyst, which was increased to 9 wt% during 1 h and thereafter remained at ca. 9-10 wt%.
24
For the run at the ratio of 25, the yield of “Others” was high (ca. 26-29%) compared to the run at
25
the ratio of 50. Organic deposition on the catalyst was also high (ca. 17-18 wt%). Obviously, the
26
deposition on the catalysts accounted for a major part of the missing products. Thus operation with
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1
a small amount of a catalyst is favorable from the viewpoint of product selectivity as well as
2
economics.
3 4
3.5. Regeneration of catalyst The reusability of beta(75) was examined. Fig. 8a shows the conversion of sorbitol and the
6
distribution of products during the recycle runs performed at the Sor/Al ratio of 50 at 200 ºC for 18
7
h. The conversion of sorbitol was gradually decreased from 99 to 71% through the consecutive runs.
8
The yield of isosorbide was drastically decreased from 78 to 17%. Note that the framework
9
structure of the used catalyst was completely retained after four runs (Fig. S8). The amount of the
10
organic deposition after the first run was 0.10 g/g-zeolite, which was gradually increased to 0.16
11
g/g-zeolite after the fourth run. The deactivation would be caused by the deposition of carbonaceous
12
matters on the catalyst. Therefore we performed another set of recycle runs by using the used
13
catalyst calcined at 550 ºC after each run (Fig. 8b). The calcination efficiently regenerated the
14
catalyst; the conversion of sorbitol was over 99% and the yield of isosorbide was kept constant at
15
76 – 77% throughout the recycle runs. These results indicate that the deposition of carbonaceous
16
matters on the catalyst is the main cause of the deactivation. There were no significant changes in
17
the framework structure, Al content and acidic properties were between the fresh beta(75) and the
18
spent one after the four recycling runs (Figs. S9 and S10, and Table S3). Thus, beta(75) can be used
19
four times without a significant loss of activity.
21
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4. Conclusions
22
We studied the dehydration of sorbitol to isosorbide in water using various types of zeolite
23
catalysts and successfully found that catalytic performance of a zeolite is determined by its
24
framework structure, composition (i.e., Al content) and hydrothermal stability. Beta showed the
25
high catalytic performance because the large pore openings and multi-dimensional pore systems
26
enhanced the diffusion of sorbitol and products. As the Si/Al ratio of a zeolite increased, its catalytic 12 Page 12 of 28
activity per Al site was increased. We assume that high-aluminum zeolites strongly interacted with a
2
large number of water molecules during the reaction and that such an interaction unfavorably
3
affects the transportation and/or kinetic steps. Catalytic activity based on the catalyst mass is
4
determined by a balance between the number of acid sites and the degree of hydrophobicity.
5
High-silica USY zeolites were hydrothermally unstable under the reaction conditions and showed
6
the poor activities. On the other hand, high-silica ZSM-5, mordenite, and beta zeolites showed no
7
structural changes after the reactions.
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The operation at a relatively low temperature is favorable for suppressing side-reactions of
9
sorbitol. A small amount of catalyst compared to sorbitol is also favorable for decreasing the
10
amount of carbonaceous deposition on the catalyst, which is a major part of missing products as
11
well as the cause of catalyst deactivation.
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The yield of isosorbide reached 80% by using beta zeolite with the Si/Al ratio of 75.
13
Furthermore, this catalyst can be regenerated by simple calcination and the catalytic performance
14
remained constant during four consecutive runs.
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Acknowledgements
17
We thank Dr. Tohru Setoyama (Mitsubishi Chemical Group, Science and Technology Research
18
Center) for helpful discussion. This work was partly supported by the research project
19
"Technological development of process from manufacturing chemicals derived from non-edible
20
plant resources" organized by New Energy and Industrial Technology Development Organization
21
(NEDO), Japan.
22 23
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ip t
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ip t
6
cr
7 8
us
9
Dehydration of sorbitol in water over various zeolite catalysts was studied.
11
Beta zeolite with a high-silica composition showed high catalytic performance. Hydrophobic catalyst surface contributed to the high catalytic performance. Hydrothermal stability of a zeolite is important for the reaction in water. A catalyst deactivated by organic deposition was regenerated by calcination.
an
10 12 13
M
14 15
d
16 17
Ac ce pt e
Table 1 Structural and acid properties of zeolite catalysts. BET surface area
Acid amount
2
(m /g)
(mmol/g)
13
389
0.90
40
463
0.32
140
409
0.08
10
524
0.97
mordenite(45)
45
580
0.27
mordenite(110)
110
502
0.17
13
547
0.55
75
678
0.21
150
583
0.08
28
545
0.78
USY(5)
5.4
890
0.80
USY(30)
30
946
0.27
USY(55)
55
805
0.07
Sample
ZSM-5(13) ZSM-5(40) ZSM-5(140)
mordenite(10)
beta(13) beta(75)
Structure
3D, 10 × 10 × 10
2D, 12 × 8
3D, 12 × 12 × 12
beta(150) Y(3)
3D, 12 × 12 × 12
Si/Al ratio
18 18 Page 18 of 28
1 2
Table 2 Organic deposition on zeolite catalysts after the reaction.
a
Organic deposition Sample
ZSM-5(40)
0.072
mordenite(10)
0.022
mordenite(110)
0.084
beta(13)
0.14
beta(75)
0.11
Y(3)
0.11
USY(55)
0.11
a
cr
0.076
d
M
an
us
Reaction conditions: Sor/Al ratio equal to 50; sorbitol, 7.5 mmol; water, 15 ml; Temperature, 200 ºC; Time, 2 h.
Ac ce pt e
3
ZSM-5(13)
ip t
(g/g-zeolite)
19 Page 19 of 28
us
cr
ip t
1
2 3
an
a
d
M
Reaction conditions: Sor/Al ratio equal to 50; sorbitol 7.5 mmol; water 15ml; Temperature, 200 ºC; Time, 2 h.
Ac ce pt e
4
a
Fig. 1 Dehydration of sorbitol over various types of zeolites performed at Sor/Al ratio of 50.
20 Page 20 of 28
cr
ip t
1
2
d
M
an
us
Fig. 2 Vapor-phase H2O adsorption isotherms of beta zeolites measured at 25 ºC.
Ac ce pt e
3
21 Page 21 of 28
a
Fig. 3 XRD patterns of FAU-type zeolites before and after the reaction. (a) fresh Y(3), (b) used Y(3), (c) fresh USY(5), (d) used USY(5),
4
M
Reaction conditions: Sor/Al ratio equal to 50; sorbitol, 7.5 mmol; water, 15 ml; Temperature, 200 ºC; Time, 2 h.
d
5
(e) fresh USY(30), (f) used USY(30), (g) fresh USY(55), and (h) used USY (55). a
Ac ce pt e
2 3
an
us
cr
ip t
1
22 Page 22 of 28
us
cr
ip t
1
2 a
4
used mordenite(110), (e) fresh beta(75), (f) used beta(75). a
M
Reaction conditions: Sor/Al ratio equal to 50; sorbitol, 7.5 mmol; water, 15 ml; Temperature, 200 ºC; Time, 2 h.
d
5
an
Fig. 4 XRD patterns of zeolites before and after the reaction. (a) fresh ZSM-5(40), (b) used ZSM-5(40), (c) fresh mordenite(110), (d)
Ac ce pt e
3
23 Page 23 of 28
cr
ip t
1
d
M
an
us
2
Ac ce pt e
3
4 5 6
Fig. 5 Temperature dependence of (a) conversion of sorbitol, (b) yield of 1,4-AHSO, and (c) yield of isosorbide. (circle) 180 ºC, (triangle)
7
200 ºC, (square) 220 ºC.
8 9
a
a
Reaction conditions: catalyst, beta(75); Sor/Al ratio equal to 50; sorbitol, 7.5 mmol; water, 15 ml; Temperature, 180 – 220 ºC; Time, 0.25 – 60 h.
24 Page 24 of 28
cr
ip t
1
d
M
an
us
2
Ac ce pt e
3
4 5
Fig. 6 Dehydration of sorbitol with different amounts of beta(75). (a) conversion of sorbitol, (b) yield of 1,4-AHSO, and (c) yield of
6
isosorbide.
7 8
a
a
Reaction conditions: Sor/Al ratio equal to (circle) 100, (triangle) 50, (square) 25; sorbitol, 7.5 mmol; water, 15 ml; Temperature, 200 ºC; Time, 0.25 – 48 h.
25 Page 25 of 28
cr
ip t
1
d
M
an
us
2
Ac ce pt e
3 4
Fig. 7 The time course change of (circle) sorbitol conversion, (square) yield of “Others” and (triangle) organic deposition on beta(75) in
5
the reaction runs with Sor/Al ratio equal to (a) 50 and (b) 25.
6
a
a
Reaction conditions: Sor/Al ratio equal to 25 and 50; sorbitol, 7.5 mmol; water, 15 ml; Temperature, 200 ºC.
26 Page 26 of 28
us
a
a
M
an
Reaction conditions: Sor/Al ratio equal to 50; sorbitol 7.5 mmol; water 15ml; Temperature, 200 ºC; Time, 18 h.
d
4
Fig. 8 Recycling use of beta(75) catalyst (a) without calcination and (b) with calcination at 550 ºC after each run.
Ac ce pt e
2 3
cr
ip t
1
27 Page 27 of 28
Scheme 1 Reaction pathways of sorbitol in the presence of zeolite catalysts.
us
2 3
cr
ip t
1
Ac ce pt e
d
M
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4
28 Page 28 of 28