Dehydration of fructose to 5-hydroxymethylfurfural in sub-critical water over heterogeneous zirconium phosphate catalysts

Asghari, Feridoun Salak; Yoshida, Hiroyuki

doi:10.1016/j.carres.2006.06.025

Cited by 174 publications

(120 citation statements)

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“…The pyridine adsorption spectra of the heterogeneous catalysts obtained by FTIR spectroscopy is given in Figure 2 except for that of SO 4 (Figure 3). It reached 90% in less than 1 min, and complete conversion of fructose was achieved in 30 min.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…23 However, the monoclinic phases were found to favor the side products formation. 24,27 Selectivities obtained for SO 4 /AC and SO 4 /SiO 2 catalysts include the contribution from leached sulfur. Thus, the results cannot be related to their acidity only.…”

Section: Industrial and Engineering Chemistry Researchmentioning

confidence: 99%

“…20,22 In this study, various catalysts were prepared by sulfation of different supports. These catalysts were SO 4 2 . The precipitate was washed with deionized water until the pH of the solution became 7.…”

Section: ■ Introductionmentioning

confidence: 99%

“…The mixture was transferred into an autoclave and then kept in an oven at 180°C for 24 h. After the autoclave was cooled in an ice bath, the mixture was washed with hot distilled water at 80°C and dried at 100°C overnight. The obtained catalyst was labeled as SO 4 / AC.…”

Section: ■ Introductionmentioning

confidence: 99%

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Fructose Dehydration to 5-Hydroxymethylfurfural over Sulfated TiO₂–SiO₂, Ti-SBA-15, ZrO₂, SiO₂, and Activated Carbon Catalysts

Kılıç

2015

Ind. Eng. Chem. Res.

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Different sulfated catalysts including SO 4 /TiO 2 −SiO 2 , SO 4 /Ti-SBA-15, SO 4 /ZrO 2 , SO 4 /AC, and SO 4 /SiO 2 were tested in fructose dehydration to 5-hydroxymethylfurfural (HMF). Reactions were carried out in dimethyl sulfoxide (DMSO) at 110°C. Characterization results indicated that no sulfur leaching was observed from SO 4 /ZrO 2 , SO 4 /TiO 2 −SiO 2 , and SO 4 /Ti-SBA-15 catalysts in the reaction tests. The SO 4 /TiO 2 −SiO 2 catalyst had a high amount of strong acid sites and the highest amount of Bronsted sites. The highest selectivity to HMF at high conversion, that is, 89% selectivity at 77% fructose conversion was obtained over this catalyst. It preserved its activity after four times reuse. ■ INTRODUCTIONDiminishing fossil fuel reserves and CO 2 emission problems force people to find alternative and sustainable resources to produce valuable chemicals. Production of these chemicals from biomass is an environmentally friendly process compared to a petroleum based process. 5-Hydroxymethylfurfural (HMF) is one of the key intermediates in order to convert the biomass to valuable chemicals such as polymers, biofuels, and bulk chemicals. 1 The most effective way of producing HMF is by carbohydrate conversion, especially dehydration of fructose.Fructose dehydration reaction occurs on the acid sites of the catalyst. Acid concentration, type of acid sites, and acid strength of the catalyst affect the product distribution significantly. 2−4 It is reported that fructose conversion to intermediates takes place on the Lewis sites, whereas Bronsted sites are responsible for the HMF formation from these intermediates. 5 Various acid catalysts including homogeneous (ionic liquids, mineral and organic acids) and heterogeneous types have been investigated. Because of the product contamination and recovery problems, heterogeneous catalysts are generally preferred. Wide ranges of heterogeneous catalysts (e.g., resins, metal sulfates, metal phosphates, heteropolyacids, zeolites, niobic acid based catalysts) have been tested. 3,6−15 However, no satisfactory yields have been achieved yet. Some of the catalysts have low stabilities due to leaching and some of them are not selective and promote side product formation such as formic acid and levulinic acid. Therefore, there are still studies pursued to find a stable, active, selective, and cheap heterogeneous catalyst for fructose dehydration to HMF.Sulfur ions and sulfate groups create Bronsted and strong acid sites when loaded on a support, such as iron oxide, alumina, titania, and zirconia. They were very active in fructose dehydration. 7,17 However, they leached during the reaction in different solvents. Solvent type also affects HMF yield. Different types of solvents from environmentally benign alcohols and water to the high-boiling-point polar aprotic solvents (dimethyl sulfoxide (DMSO) and dimethylamide (DMA)) have been investigated. High yields of HMF have been achieved by using high-boiling-point solvents such as DMSO and DMA. 9 Zirconia is known as ...

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Section: ■ Results and Discussionmentioning

confidence: 99%

Section: Industrial and Engineering Chemistry Researchmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

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Fructose Dehydration to 5-Hydroxymethylfurfural over Sulfated TiO₂–SiO₂, Ti-SBA-15, ZrO₂, SiO₂, and Activated Carbon Catalysts

Kılıç

2015

Ind. Eng. Chem. Res.

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“…indicated that a direct glucose dehydration pathway should also be considered 8. Lewis acid metal chlorides in ionic liquids or metal oxides in water can convert glucose to HMF in good yields 9, 10, 11. The use of the CrCl 2 /1‐ethyl‐3‐methylimidazolium chloride system under relatively mild conditions showed the promise of Lewis acids in ionic liquid solvents 9.…”

Section: Introductionmentioning

confidence: 99%

Dehydration of Glucose to 5‐Hydroxymethylfurfural Using Nb‐doped Tungstite

Yue

Pidko

et al. 2016

ChemSusChem

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Dehydration of glucose to 5‐hydroxymethylfurfural (HMF) remains a significant problem in the context of the valorization of lignocellulosic biomass. Hydrolysis of WCl6 and NbCl5 leads to precipitation of Nb‐containing tungstite (WO3⋅H2O) at low Nb content and mixtures of tungstite and niobic acid at higher Nb content. Tungstite is a promising catalyst for the dehydration of glucose to HMF. Compared with Nb2O5, fewer by‐products are formed because of the low Brønsted acidity of the (mixed) oxides. In water, an optimum yield of HMF was obtained for Nb–W oxides with low Nb content owing to balanced Lewis and Brønsted acidity. In THF/water, the strong Lewis acidity and weak Brønsted acidity caused the reaction to proceed through isomerization to fructose and dehydration of fructose to a partially dehydrated intermediate, which was identified by LC‐ESI‐MS. The addition of HCl to the reaction mixture resulted in rapid dehydration of this intermediate to HMF. The HMF yield obtained in this way was approximately 56 % for all tungstite catalysts. Density functional theory calculations show that the Lewis acid centers on the tungstite surface can isomerize glucose into fructose. Substitution of W by Nb lowers the overall activation barrier for glucose isomerization by stabilizing the deprotonated glucose adsorbate.

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Monomers and Macromonomers from Renewable Resources

Gandini¹

2010

Biocatalysis in Polymer Chemistry

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Dehydration of fructose to 5-hydroxymethylfurfural in sub-critical water over heterogeneous zirconium phosphate catalysts

Cited by 174 publications

References 41 publications

Fructose Dehydration to 5-Hydroxymethylfurfural over Sulfated TiO₂–SiO₂, Ti-SBA-15, ZrO₂, SiO₂, and Activated Carbon Catalysts

Fructose Dehydration to 5-Hydroxymethylfurfural over Sulfated TiO₂–SiO₂, Ti-SBA-15, ZrO₂, SiO₂, and Activated Carbon Catalysts

Dehydration of Glucose to 5‐Hydroxymethylfurfural Using Nb‐doped Tungstite

Monomers and Macromonomers from Renewable Resources

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Dehydration of fructose to 5-hydroxymethylfurfural in sub-critical water over heterogeneous zirconium phosphate catalysts

Cited by 174 publications

References 41 publications

Fructose Dehydration to 5-Hydroxymethylfurfural over Sulfated TiO2–SiO2, Ti-SBA-15, ZrO2, SiO2, and Activated Carbon Catalysts

Fructose Dehydration to 5-Hydroxymethylfurfural over Sulfated TiO2–SiO2, Ti-SBA-15, ZrO2, SiO2, and Activated Carbon Catalysts

Dehydration of Glucose to 5‐Hydroxymethylfurfural Using Nb‐doped Tungstite

Monomers and Macromonomers from Renewable Resources

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Fructose Dehydration to 5-Hydroxymethylfurfural over Sulfated TiO₂–SiO₂, Ti-SBA-15, ZrO₂, SiO₂, and Activated Carbon Catalysts

Fructose Dehydration to 5-Hydroxymethylfurfural over Sulfated TiO₂–SiO₂, Ti-SBA-15, ZrO₂, SiO₂, and Activated Carbon Catalysts