- Enzyme-catalyzed asymmetric acylation and hydrolysis of cis-2,5-disubstituted tetrahydrofuran derivatives: Contribution to development of models for reactions catalyzed by porcine liver esterase and porcine pancreatic lipase
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Pig liver esterase, lipase from porcine pancreas, lipase from Pseudomonas sp. (lipase YS), and lipase from Candida cylindracea catalyzed hydrolyses of the cis-diacetate 1 and the trans-diacetate (±)-4 to give the cis-monoacetate 3 and the trans-monoacetate 6 in optically active forms, respectively. Lipase YS-catalyzed acylations of the cis-diol 2 and the trans-diol (±)-5 with an acylating agent in cyclohexane yielded (-)-3 and (-)-6, respectively. The group adjacent to the R stereogenic center preferentially reacted in lipase YS-catalyzed hydrolyses of 1 and (±)-4 and acylations of 2 and (±)-5, and the enantioselectivites are rationalized by our rule recently proposed for lipase YS.
- Naemura,Fukuda,Takahashi,Konishi,Hirose,Tobe
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- Catalytic Response and Stability of Nickel/Alumina for the Hydrogenation of 5-Hydroxymethylfurfural in Water
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The catalytic response of Ni on Al2O3 obtained from Ni-Al layered double hydroxides was studied for the liquid-phase hydrogenation of hydroxymethyl furfural to tetrahydrofuran-2,5-diyldimethanol (THFDM) in water. The successive calcination and reduction of the precursors caused the removal of interlayer hydroxyl and carbonate groups and the reduction of Ni2+ to Ni0. Four reduced mixed oxide catalysts were obtained, consisting of different amount of Ni metal contents (47-68 wt %) on an Al-rich amorphous component. The catalytic activity was linked to Ni content whereas selectivity was mainly affected by reaction temperature. THFDM was formed in a stepwise manner at low temperature (353 K) whereas 3-hydroxymethyl cyclopentanone was generated at higher temperature. Coke formation caused deactivation; however, the catalytic activity can be regenerated using heat treatment. The results establish Ni on Al2O3 as a promising catalyst for the production of THFDM in water.
- Perret, Noémie,Grigoropoulos, Alexios,Zanella, Marco,Manning, Troy D.,Claridge, John B.,Rosseinsky, Matthew J.
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- Catalytic selective hydrogenation and rearrangement of 5-hydroxymethylfurfural to 3-hydroxymethyl-cyclopentone over a bimetallic nickel-copper catalyst in water
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The selective hydrogenation and rearrangement of 5-hydroxymethylfurfural (5-HMF) to 3-hydroxymethyl-cyclopentone (HCPN) were studied over a MOF-derived bimetallic nickel-copper catalyst in water. The combination of nickel and copper dramatically improved the efficiency in both the selective hydrogenation of the carbonyl group of 5-HMF and the hydrogenative ring-rearrangement of the C5 ring, affording 70.3% yield for HCPN and 99.8% yield for the rearrangement products. Moreover, it was indicated that water acted as a solvent, reactant, and proton donor by dissociation at an elevated temperature, which supplied slightly acidic conditions and promoted the rearrangement reaction.
- Zhang, Shujing,Ma, Hong,Sun, Yuxia,Luo, Yang,Liu, Xin,Zhang, Meiyun,Gao, Jin,Xu, Jie
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- Selective hydrogenation of aromatic furfurals into aliphatic tetrahydrofurfural derivatives
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Tetrahydrofurfural (THFF) and 5-hydroxymethyltetrahydro-2-furaldehyde (5-HMTHFF) are important chemicals. Synthesis of THFF and 5-HMTHFF from the selective hydrogenation of furfural (FF) and 5-hydroxymethylfurfural (HMF) is highly desirable. However, it is a great challenge to hydrogenate furanyl rings while keeping CO intact. Herein, we found that Pd/LDH-MgAl-NO3 could efficiently catalyze the hydrogenation of FF to THFF and HMF to 5-HMTHFF in water. At near complete conversion of FF and HMF, the selectivities of THFF and 5-HMTHFF could reach 92.6% and 83.7%, respectively. A series of control experiments showed that both the LDH-MgAl-NO3 support and water solvent played an important role in the unusual performance of the catalytic system. The hydrogenation of the furanyl ring occurred on the surface of Pd. Water prohibited the hydrogenation of the CO group, and the special nature of LDH-MgAl-NO3 prevented hydrogenation of the CO group on the support by the hydrogen spillover. Thus, the furanyl ring was selectively hydrogenated, and high selectivity of the desired product was successfully achieved. As far as we know, efficient hydrogenation of FF to THFF or HMF to 5-HMTHFF has not been reported. This work opens the way to selectively hydrogenate the furanyl ring while keeping CO in the same molecule unchanged. This journal is
- Chen, Bingfeng,Han, Buxing,Li, Shaopeng,Liu, Huizhen,Shen, Xiaojun,Wang, Yanyan,Yang, Youdi
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- Combination of Pd/C and Amberlyst-15 in a single reactor for the acid/hydrogenating catalytic conversion of carbohydrates to 5-hydroxy-2,5- hexanedione
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Here we show that combination of Pd/C and Amberlyst-15 in a single reactor allowed fructose and inulin to be converted to 5-hydroxy-2-5-hexanedione, a valuable chemical platform, in a one-pot process. the Partner Organisations 2014.
- Liu, Fei,Audemar, Maite,De Oliveira Vigier, Karine,Clacens, Jean-Marc,De Campo, Floryan,Jerome, Francois
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- Palladium/carbon dioxide cooperative catalysis for the production of diketone derivatives from carbohydrates
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The one-pot production of industrially valuable diketone derivatives from carbohydrates is achieved through a bifunctional catalytic process. In particular, Pd/C-catalyzed hydrogenation of HMF in water and under CO 2 affords 1-hydroxypentane-2,5-dione with up to 77 % yield. The process is also eligible starting from fructose and inulin, affording 1-hydroxyhexane-2,5-dione with 36 % and 15 % yield, respectively. The key of the process is reversible in situ formation of carbonic acid, which is capable of assisting Pd/C during the hydrogenation reaction by promoting the dehydration of carbohydrates and the ring-opening of furanic intermediates. Interestingly, by changing the reaction medium from H2O to a H2O/THF mixture (1:9), it is possible to switch the selectivity of the reaction and to produce 2,5-hexanadione with 83 % yield. Within the framework of sustainable chemistry, reactions presented in this report show 100 % carbon economy, involve CO 2 to generate acidity, require water as a solvent, and are conducted under rather low hydrogen pressures (10 bar).
- Liu, Fei,Audemar, Ma?té,De Oliveira Vigier, Karine,Clacens, Jean-Marc,De Campo, Floryan,Jér?me, Fran?ois
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- Homogeneous catalysed hydrogenation of HMF
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In this report, hydroxymethylfurfural (HMF) is used as a bio-based feedstock for homogeneous metal-catalysed hydrogenation. Several ligand classes and metals are employed to reduce the aldehyde and aromatic ring of HMF. The previously unknown homogeneous catalysed hydrogenation of HMF to tetrahydrofuran-dimethanol (THFDM) was investigated using different catalyst systems. NHCs and phosphites give higher trans/cis ratios (between 1:1.25 and 1:3.95) of the product THFDM, but low conversions of only up to 17% accompanied by up to 92% yield of bis(hydroxymethyl)furan at 10 bar H2 and 120 °C. Conversely, di-phosphine ligated ruthenium catalysts in up to 87% yield lead to the highest overall conversion but only moderate trans/cis ratios of only 1:3.1-1:5.
- Cadu, Alban,Sekine, Kohei,Mormul, Jaroslaw,Ohlmann, Dominik M.,Schaub, Thomas,Hashmi, A. Stephen K.
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- Immobilized Ru clusters in nanosized mesoporous zirconium silica for the aqueous hydrogenation of furan derivatives at room temperature
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Ru lonesome tonight? Immobilized ruthenium clusters (50Ru atoms) in nanosized mesoporous zirconium silica were synthesized by using an impregnation method starting from an aqueous solution of RuCl3. The Ru cluster catalysts were thermally stable at 500°C and showed remarkable activity for the hydrogenation of furan derivatives in water at room temperature under 5bar hydrogen pressure.
- Chen, Jiazhi,Lu, Fang,Zhang, Junjie,Yu, Weiqiang,Wang, Feng,Gao, Jin,Xu, Jie
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- Biomass into chemicals: One-pot production of furan-based diols from carbohydrates via tandem reactions
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In this work, the direct production of furan-based diols from carbohydrates and their upstream raw materials via one-pot tandem reactions in ionic liquid/water system is presented. In this novel reaction system, ionic liquid serves as an advantageous solvent for polysaccharide (cellulose, inulin, sucrose) hydrolysis and hexose dehydration reactions, and heterogeneous Pd, Pt, Ir, Ni, Ru-based catalysts catalyze HMF hydrogenation reaction under relatively mild condition (50 °C, 6 MPa H2) to afford moderate to high yield (34.0-89.3%) of furan-based diols, namely, 2,5-dihydroxymethylfuran (DHMF) and 2,5-dihydroxymethyltetrahydrofuran (DHMTF). Our results show that the metal species strongly affects the selectivity of the products, while the nature of the support influences the activity of the catalysts significantly. By selecting the proper metal species and the support, controllable production of DHMF or DHMTF was realized. Based on the intermediates identified and the conversion results, the proposed reaction pathway, including possible side reactions were presented. Taken together, our catalytic system featured with simple process, mild condition, high yield of diols and adjustable product selectivity. The direct conversion of the carbohydrates and the upstream materials drives our technology nearer to real application for cost-efficient production of chemicals from biomass.
- Cai, Haile,Li, Changzhi,Wang, Aiqin,Zhang, Tao
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- Highly efficient hydrogenative ring-rearrangement of furanic aldehydes to cyclopentanone compounds catalyzed by noble metals/MIL-MOFs
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Hydrogenative ring-rearrangement reaction of biomass-derived furanic aldehydes to cyclopentanone compounds catalyzed by metal/support bifunctional catalysts suffers a low selectivity of target product and serious carbon loss because of the Br?nsted acid catalysis. Herein, a series of pure Lewis acid sites MIL-MOFs (Fe-MIL-100, Fe-MIL-101 and Cr-MIL-101) with different crystal topology structures and metals are synthesized. Then the nanoparticles of Ru, Pt, Pd and Au are uniformly dispersed on the internal surface of the MOF support. The hydrogenation rate catalyzed by the noble metals/Fe-MIL-100 is three times faster than those obtained with Fe-MIL-101 and Cr-MIL-101-based catalysts due to the higher dispersion of nanoparticles on the former to make it more accessible to reactants. Meanwhile, both of the noble metals on Fe-MIL-100 and Fe-MIL-101 have a higher selectivity of cyclopentanone compounds than that on Cr-MIL-101, since the Fe ions in the MOF host with a higher oxophilicity will promote the adsorption and hydrolysis of the intermediate furanic alcohols (furfural alcohol or 2,5-bis(hydroxymethyl)furan). Furthermore, the noble metals/MIL-MOFs catalyst can maintain a good activity and stability after recycling for five runs. The current work will present an efficient catalytic reaction system for the hydrogenative ring-rearrangement of furfural and 5-hydroxymethyl furfural to synthesize cyclopentanone compounds.
- Li, Xiang,Deng, Qiang,Zhang, Likang,Wang, Jun,Wang, Rong,Zeng, Zheling,Deng, Shuguang
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- Ru/MnCo2O4 as a catalyst for tunable synthesis of 2,5-bis(hydroxymethyl)furan or 2,5-bis(hydroxymethyl)tetrahydrofuran from hydrogenation of 5-hydroxymethylfurfural
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Manganese and cobalt metals-based mixed oxide (MnCo2O4) spinels supported ruthenium (Ru) nanoparticles, Ru/MnCo2O4, is found to be an active catalyst to execute outstandingly the hydrogenation of 5-hydroxymethylfurfural (HMF) to produce two useful furan diols such as 2,5-bis(hydroxymethyl)furan (BHMF) and 2,5-bis(hydroxymethyl)tetrahydrofuran (BHMTHF) in highly selective fashion without any additive. It could found that Ru/MnCo2O4 was able to catalyze not only the oxidation but also the reduction of HMF due to the redox properties of the MnCo2O4. Moreover, the characterization details responsible for the high activity of this catalyst in the hydrogenation of HMF were investigated by several spectroscopic methods. In order to maximize the products yield and HMF conversion, the effect of reaction variables such as time, temperature, pressure, and various metal oxides supported Ru nanoparticles was also investigated. Furthermore, the reusability tests exhibited that Ru/MnCo2O4 catalyst could be reused at several consecutive cycles, retaining almost its original activity.
- Mishra, Dinesh Kumar,Lee, Hye Jin,Truong, Cong Chien,Kim, Jinsung,Suh, Young-Wong,Baek, Jayeon,Kim, Yong Jin
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- Conversion of HMF to methyl cyclopentenolone using Pd/Nb2O5 and Ca-Al catalysts: Via a two-step procedure
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The catalytic conversion of HMF to 2-hydroxy-3-methyl-2-cyclopenten-1-one (MCP), which is a valuable edible essence that has traditionally been obtained from adipic acid, was achieved with an isolated yield of 58%. This procedure comprised two steps: the hydrogenation of 5-hydroxymethylfurfural (HMF) to 1-hydroxy-2,5-hexanedione (HHD) in water on Pd/Nb2O5 catalysts and then the isomerization of HHD to MCP in the presence of a base. The Nb2O5 supports, which were acidic, were characterized by FTIR, XRD and NH3-TPD. The supported Pd/Nb2O5 catalysts, in which Pd was highly dispersed, were synthesized employing cyclohexene as a reductant and were characterized by XRD, TEM, ICP-AES, XPS, EDX and CO pulse chemisorption. The high conversion of HMF was attributed to the high dispersion of Pd, and the acidity of the supports led to high selectivity for HHD. The conversion of HHD to MCP was an intramolecular aldol condensation reaction, and the protonic solvent favored this reaction. Ca-Al was proved to be an effective solid base for the conversion of HHD to MCP in water.
- Duan, Ying,Zheng, Min,Li, Dongmi,Deng, Dongsheng,Ma, Lu-Fang,Yang, Yanliang
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- Preparation of 1-Hydroxy-2,5-hexanedione from HMF by the Combination of Commercial Pd/C and Acetic Acid
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The development of a simple and durable catalytic system for the production of chemicals from a high concentration of a substrate is important for biomass conversion. In this manuscript, 5-hydroxymethylfurfural (HMF) was converted to 1-hydroxy-2,5-hexanedione (HHD) using the combination of commercial Pd/C and acetic acid (AcOH) in water. The influence of temperature, H2 pressure, reaction time, catalyst amount and the concentration of AcOH and HMF on this transformation was investigated. A 68% yield of HHD was able to be obtained from HMF at a 13.6 wt% aqueous solution with a 98% conversion of HMF. The resinification of intermediates on the catalyst was characterized to be the main reason for the deactivation of Pd/C. The reusability of the used Pd/C was studied to find that most of the activity could be recovered by being washed in hot tetrahydrofuran.
- Duan, Ying,Yang, Dexi,Yang, Yanliang,Zhang, Chi,Zheng, Min
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- Highly selective ring rearrangement of 5-hydroxymethylfurfural to 3-hydroxymethylcyclopentanon catalyzed by non-noble Ni-Fe/Al2O3
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3-Hydroxymethylcyclopentanone (HCPN) has been regarded as a considerable intermediate for the synthesis of polymers, pesticides and fragrances, which is mainly produced from petrochemical refinery. In recent years, the preparation of HCPN from biomass has gradually attracted attention. HCPN can be obtained through the selective ring rearrangement of biomass-based 5-hydroxymethyl furfural (5-HMF). In this paper, the Ni-Fe/Al2O3 was fabricated and used as an efficient catalyst for the production of HCPN, giving a 5-HMF complete conversion with a high HCPN selectivity (86 %) at 160 °C under 4 MPa H2 for 4 h. The optimized Ni-Fe/Al2O3 showed excellent activity towards the production of HCPN compared with monometallic catalysts, suggesting that there was a synergistic effect in Ni-Fe alloy. The introduction of Fe into Ni/Al2O3 improved the H2 adsorption capacity and also changed the acidic/basic sites, which are beneficial for the formation of HCPN. Moreover, Ni-Fe/Al2O3 exhibited superb stability and could be successively used four times without obvious loss in catalytic activity.
- Li, Jiachen,Feng, Yunchao,Wang, Huiqiang,Tang, Xing,Sun, Yong,Zeng, Xianhai,Lin, Lu
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- Selective hydrogenation of biomass-based 5-hydroxymethylfurfural over catalyst of palladium immobilized on amine-functionalized metal-organic frameworks
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A catalyst of palladium [Pd/MIL-101(Al)-NH2] supported on amine-functionalized Metal-Organic Frameworks (MOFs) allows selective hydrogenation of biomass-based 5-hydroxymethylfurfural (HMF) to 2,5-dihydroxymethyl-tetrahydrofuran (DHMTHF) with 2,5-dihydroxymethylfuran (DHMF) as an observed "intermediate". The Pd/MIL-101(Al)-NH2 was prepared by using a direct anionic exchange approach and subsequent gentle reduction. The presence of free amine moieties in the frameworks of MIL-101(Al)-NH2 is suggested to play a key role on the formation of uniform and well-dispersed palladium nanoparticles on the support. The adsorption experiments reveal that the amine-functionalized MOF supports show preferential adsorption to hydrogenation intermediate DHMF than in the case of reactant HMF owing to an enhanced hydrophilic nature of DHMF as well as improved hydrogen bonding interactions between DHMF and the MOF support, which promotes a further hydrogenation of DHMF to DHMTHF upon the in situ formation of DHMF over Pd/MIL-101(Al)-NH2. Moreover, our results also indicate that the observed high selectivity toward DHMTHF form HMF is closely related to the cooperation between the metallic site and the free amine moiety on the MOF support. Under the optimal conditions, a maximum DHMTHF yield of 96% with a full conversion of HMF is obtained by using Pd/MIL-101(Al)-NH2 (Pd 3.0 wt %) catalyst at a low reaction temperature of 30 °C in aqueous medium. The research thus highlights new perspectives for aluminum-based and amine-functionalized MOF material for biomass transformation.
- Chen, Jinzhu,Liu, Ruliang,Guo, Yuanyuan,Chen, Limin,Gao, Hui
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- Selective conversion of 5-hydroxymethylfurfural to diketone derivatives over Beta zeolite-supported Pd catalysts in water
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Conversion of 5-hydroxymethylfurfural (HMF) in water to the linear diketone derivatives 1-hydroxyhexane-2,5-dione (HHD) and 2,5-hexanedione (HXD) was investigated over a series of Beta zeolite-supported transition metal catalysts (Co, Ni, Cu, Ru, Pd). Their catalytic performance was tested in a batch stirred reactor (T = 110 °C, PH2 = 20 bar) with Pd showing the highest activity and selectivity to HHD and HXD. The effects of Pd particle size, zeolite Si/Al ratio and reaction conditions (T = 80–155 °C, PH2 = 5–60 bar) were also investigated. The incorporation of Pd into Beta zeolite by the deposition-coprecipitation method produced the most efficient catalyst, affording complete HMF conversion (T = 110 °C, PH2 = 60 bar) predominantly to HHD (68% selectivity) and HXD (8% selectivity). The combination of a bifunctional acid/redox solid catalyst and water enhances the hydrolytic ring-opening and subsequent hydrogenation of the furan ring. Catalytic activity can be partially restored by a simple regeneration treatment. This work establishes a catalytic route to produce valuable diketone derivatives from renewable furanic platform sources in water.
- Ramos, Rubén,Grigoropoulos, Alexios,Griffiths, Ben L.,Katsoulidis, Alexandros P.,Zanella, Marco,Manning, Troy D.,Blanc, Frédéric,Claridge, John B.,Rosseinsky, Matthew J.
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- Selective hydrogenation of 5-hydroxymethylfurfural and its acetal with 1,3-propanediol to 2,5-bis(hydroxymethyl)furan using supported rhenium-promoted nickel catalysts in water
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The high reactivity of the formyl group of 5-hydroxymethylfurfural (5-HMF) is problematic, because it leads to undesired oligomerization reactions. This is usually countered by working in dilute non-aqueous solutions. Here, we present a novel approach to convert concentrated aqueous solutions of 5-HMF to 2,5-bishydroxymethylfuran (BHMF), which is a prospective monomer for polyesters and self-healing polymers. Our approach is based on the protection of the formyl group of 5-HMF using acetalization with 1,3-propanediol. Hydrogenation is carried out using an optimized bimetallic Ni-Re catalyst supported on TiO2 at a carefully controlled pH, resulting in balanced rates of deprotection and hydrogenation and high BHMF yield. Under optimized conditions at a benign temperature of 40 °C, hydrogenation of concentrated solutions (10-20 wt%) of protected 5-HMF in water gave 81-89% yields of BHMF without having to resort to platinum-group metals such as palladium or platinum.
- Wiesfeld, Jan J.,Kim, Minjune,Nakajima, Kiyotaka,Hensen, Emiel J. M.
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- Total hydrogenation of bio-derived furans over supported Ru subnanoclusters prepared via amino acid-assisted deposition
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Development of a highly efficient and robust catalyst with reduced usage of noble metals is extremely desirable for selective hydrogenations of furan-containing bio-based feedstocks, which represents an attractive and sustainable alternative to petrochemical resources. Herein, we describe a new type of well-dispersed Ru subnanoclusters (ca. 0.50 wt%) supported on commercial P25 TiO2 material obtained from a facile and effective amino acid-assisted deposition-precipitation strategy. The as-synthesized catalyst exhibits superior catalytic activity and selectivity for direct hydrogenation of industrially important furfural as well as a range of structurally diverse bio-based furanic compounds to their corresponding fully hydrogenated derivatives. An average turnover frequency (ATOF) value as high as 367 h-1 at 80 °C and 4 MPa H2 is obtained, which is the highest reported value. This catalyst also shows stable furfural total hydrogenation in 5 reaction cycles conducted at 80 °C (52 mmol-scale, turnover number up to 12?500). In terms of the kinetic and structural characterizations, the key performances of the ultrasmall Ru clusters are proposed to mainly originate from an enhanced number of unsaturated surface Ru atoms and change in local coordination environment. Our work highlights the importance of the subnanometric size of Ru clusters in the advancement of efficient and affordable approaches towards bio-based chemical production.
- Qian, Yang,Li, Ze-Jun,Du, Xian-Long,Zhang, Qi,Zhao, Yi,Liu, Yong-Mei,Cao, Yong
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- Direct synthesis of 1,6-hexanediol from HMF over a heterogeneous Pd/ZrP catalyst using formic acid as hydrogen source
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A new approach is developed for hydrogenolytic ring opening of biobased 5-hydroxymethylfurfural (HMF), dehydration product of hexoses, towards 1,6-hexanediol (HDO) under atmospheric pressure. The highest yield of HDO, 43 %, is achieved over reusable Pd/zirconium phosphate (ZrP) catalyst at 413 K in the presence of formic acid as hydrogen source. In comparison with various Bronsted and/or Lewis acidic supports, the specific Bronsted acidity on ZrP support effectively accelerated the cleavage of C-O bond in a furan ring.
- Tuteja, Jaya,Choudhary, Hemant,Nishimura, Shun,Ebitani, Kohki
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- Reductive conversion of 5-hydroxymethylfurfural to 1,2,6-hexanetriol in water solvent using supported Pt catalysts
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One-pot conversion of biomass derived 5-hydroxymethylfurfural (HMF) to 1,2,6-hexanetriol (1,2,6-HT) in water solvent was performed using Pt catalysts supported on various acid-base metal oxides. Pt catalysts supported on hydrotalcite, MgO, and CeO2 showed better yield of 1,2,6-HT and 2,5-bis(hydroxymethyl)-tetrahydrofuran (BHF), while ring-rearranged cyclopentanol derivatives were predominant products on the other Pt catalysts. The product distribution with time course on Pt/hydrotalcite revealed that HMF is at first hydrogenated to BHF, then the following parallel reactions proceed; ring-rearrangement to cyclopentanol derivatives, ring-hydrogenation to BHF, and hydrogenolysis to 1,2,6-HT. When pure hydrotalcite, MgO and CeO2 were physically mixed with Pt/SiO2, the selectivity to 1,2,6-HT was almost zero or less than 10 %. It was suggested that the formation of 1,2,6-HT proceeds at metal-support interface. The effect of metal-support interface was examined by means of IR spectra of adsorbed methanol. It was indicated that both basic property of supports and surface monodentate alkoxide formation are essential for the production of 1,2,6-HT. The maximum yield of 1,2,6-HT (42 %) was obtained using Co-promoted Pt/CeO2 catalysts pre-reduced at 200 °C.
- Kataoka, Hiroto,Kosuge, Daichi,Ogura, Keiji,Ohyama, Junya,Satsuma, Atsushi
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- Perovskite type oxide-supported Ni catalysts for the production of 2,5-dimethylfuran from biomass-derived 5-hydroxymethylfurfural
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The hydrogenolysis of C-O and CO in 5-hydroxymethylfurfural for the production of furan biofuel 2,5-dimethylfuran (DMF) is of great importance for biomass refining. However, development of non-noble metal-based catalysts which perform stably for this process is still challenging. Here, perovskite-supported Ni catalysts were used for the hydrogenolysis of 5-hydroxymethylfurfural at 230 °C, with 98.3% yield of DMF being obtained. The effects of reaction conditions such as temperature and pressure were investigated and discussed, and the catalyst could maintain good activity after being used at least 5 times. In order to further explore the reaction mechanism, dynamic experiments at different times were carried out and a possible reaction pathway was proposed. The development of efficient perovskite-supported Ni catalysts verified their great potential in biomass conversion.
- Chen, Meng-Yuan,Chen, Chu-Bai,Zada, Bakht,Fu, Yao
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- Metal-free photocatalytic aerobic oxidation of biomass-based furfural derivatives to prepare γ-butyrolactone
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Efficient catalytic oxidative C-C bond cleavage with dioxygen is useful and challenging to prepare oxygenated fine chemicals from biomass. Herein, we report a catalytic strategy for the preparation of γ-butyrolactone (GBL) by photocatalytic oxidation of tetrahydrofurfuryl alcohol (THFA), tetrahydrofurfuric acid (THFCA), or other furfural derivatives at room temperature under visible-light irradiation. Metal-free mesoporous graphitic carbon nitride was used as the photocatalyst and O2was used as the oxidant. The effects of various semiconductor catalysts, light sources with different wavelengths, and the reaction time on the photocatalytic oxidation of THFA to GBL were separately investigated. Furthermore, the reaction mechanism was investigated through serious control experiments and the reaction pathway was investigated through density functional theory (DFT) calculations.
- Zhu, Rui,Zhou, Gongyu,Teng, Jia-Nan,Liang, Wanying,Li, Xinglong,Fu, Yao
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- Kinetics of Catalytic Hydrogenation of 5-Hydroxymethylfurfural to 2,5-bis-Hydroxymethylfuran in Aqueous Solution over Ru/C
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5-Hydroxymethylfurfural (5-HMF) is a cellulosic product of the hydrolysis of biomass, and it is widely considered for the production of several interesting chemicals and derivatives. In the present work, catalytic hydrogenation of 5-hydroxymethylfurfural to 2,5-bis-hydroxymethylfuran was investigated using 5% Ru/C in the aqueous phase. Kinetic data were experimentally obtained over a wide range of temperatures (313-343 K), H2 partial pressure (0.69-2.07 MPa), initial HMF concentration (19.8-59.5 mM), and catalyst loading (0.3-0.7 kg/m3) in a three-phase slurry reactor. Disappearance of initial 5-HMF concentrations was modeled using the power law and Langmuir-Hinshelwood-Hougen-Watson models. A model based on the competitive adsorption of molecular H2 and HMF was proposed. It is presumed that surface reaction between nondissociatively chemisorbed H2 and 5-HMF was rate determining. This model provided the best fit for the kinetic data. From the Arrhenius equation, the activation energy for the surface reaction was found to be 104.9 kJ/mol.
- Jain, Anandkumar B.,Vaidya, Prakash D.
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- Total hydrogenation of furan derivatives over silica-supported Ni-Pd alloy catalyst
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The Ni-Pd bimetallic catalysts supported on silica were prepared by co-impregnation method. The catalyst with Ni/Pd = 7 showed the best catalytic performance for the hydrogenation of 5-hydroxymethyl-2-furaldehyde (HMF). The catalyst was more active than commercial Raney Ni and more selective than Pd/C. The yield of 2,5-bis(hydroxymethyl)tetrahydrofuran reached 96%. Hydrogenation of other furanic compounds, cyclohexanone, phenol, and alkenols also proceeded. Characterizations by TEM and XRD revealed that Ni-Pd alloy particles were formed on Ni-Pd/SiO2 (Ni/Pd = 7).
- Nakagawa, Yoshinao,Tomishige, Keiichi
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- Synthesis of 1,6-hexanediol from HMF over double-layered catalysts of Pd/SiO2 + Ir-ReOx/SiO2 in a fixed-bed reactor
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1,6-Hexanediol (1,6-HDO) was effectively prepared from 5-hydroxymethylfurfural (HMF) over double-layered catalysts of Pd/SiO2 + Ir-ReOx/SiO2 in a fixed-bed reactor. Under optimal reaction conditions (373 K, 7.0 MPa H2, in solvent mixtures of 40% water and 60% tetrahydrofuran (THF)), 57.8% yield of 1,6-HDO was obtained. The double-layered catalysts loaded in double-layered beds showed much superior performance compared to that of a single catalyst of Pd-Ir-ReOx/SiO2, even when the same amount of active components were used in the catalysts. The reaction solvent significantly affected product distributions, giving a volcano-shape plot for the 1,6-HDO yield as a function of the ratio of water to THF. Br?nsted acidic sites were generated on the catalyst in the presence of water which played determining roles in 1,6-HDO formation. A high pressure of H2 contributed to 1,6-HDO formation by depressing the over-hydrogenolysis of reaction intermediates and products to form hexane and hexanol. The reaction route was proposed for HMF conversion to 1,6-HDO on the basis of conditional experiments.
- Xiao, Bin,Zheng, Mingyuan,Li, Xinsheng,Pang, Jifeng,Sun, Ruiyan,Wang, Hua,Pang, Xiaoli,Wang, Aiqin,Wang, Xiaodong,Zhang, Tao
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- Insight into the hydrogenation of pure and crude HMF to furan diols using Ru/C as catalyst
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5-hydroxymethylfurfural (HMF) is one of the most important renewable platform-chemicals, a very valuable precursor for the synthesis of bio-fuels and bio-products. In this work, the hydrogenation of HMF to two furan diols, 2,5-bis(hydroxymethyl)furan (BHMF) and 2,5-bis(hydroxymethyl)tetrahydrofuran (BHMTHF), both promising renewable monomers, was investigated. Three commercial catalysts, Ru/C, Pd/C and Pt/C, were tested in the hydrogenation of aqueous HMF solutions (2–3 wt%), using a metal loading of 1 wt% respect to HMF content. By appropriate tuning of the process conditions, either BHMF or BHMTHF were obtained in good yields, and Ru/C resulted the best catalyst for this purpose, allowing us to obtain BHMF or BHMTHF yields up to 93.0 and 95.3 mol%, respectively. This catalyst was also tested for in the hydrogenation of a crude HMF-rich hydrolyzate, obtained by one-pot the dehydration of fructose. The influence of each component of this hydrolyzate on the hydrogenation efficiency was investigated, including unconverted fructose, rehydration acids and humins, in order to improve the yields towards each furan diol. Moreover, ICP-OES and TEM analysis showed that the catalyst was not subjected to important leaching and sintering phenomena, as further confirmed by catalyst recycling study.
- Fulignati, Sara,Antonetti, Claudia,Licursi, Domenico,Pieraccioni, Matteo,Wilbers, Erwin,Heeres, Hero Jan,Raspolli Galletti, Anna Maria
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Read Online
- Selective conversion of 5-hydroxymethylfurfural to cyclopentanone derivatives over Cu-Al2O3 and Co-Al2O3 catalysts in water
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The production of cyclopentanone derivatives from 5-hydroxymethylfurfural (HMF) using non-noble metal based catalysts is reported for the first time. Five different mixed oxides containing Ni, Cu, Co, Zn and Mg phases on an Al-rich amorphous support were prepared and characterised (XRD, ICP, SEM, TEM, H2-TPR, NH3/CO2-TPD and N2 sorption). The synthesised materials resulted in well-dispersed high metal loadings in a mesoporous network, exhibiting acid/base properties. The catalytic performance was tested in a batch stirred reactor under H2 pressure (20-50 bar) in the range T = 140-180 °C. The Cu-Al2O3 and the Co-Al2O3 catalysts showed a highly selective production of 3-hydroxymethylcyclopentanone (HCPN, 86%) and 3-hydroxymethylcyclopentanol (HCPL, 94%), respectively. A plausible reaction mechanism is proposed, clarifying the role of the reduced metal phases and the acid/basic sites on the main conversion pathways. Both Cu-Al2O3 and Co-Al2O3 catalysts showed a loss of activity after the first run, which can be reversed by a regeneration treatment. The results establish an efficient catalytic route for the production of the diol HCPL (reported for the first time) and the ketone HCPN from bio-derived HMF over 3d transition metals based catalysts in an environmental friendly medium such as water.
- Ramos, Rubén,Grigoropoulos, Alexios,Perret, Noémie,Zanella, Marco,Katsoulidis, Alexandros P.,Manning, Troy D.,Claridge, John B.,Rosseinsky, Matthew J.
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Read Online
- Efficient synthesis of 2,5-dihydroxymethylfuran and 2,5-dimethylfuran from 5-hydroxymethylfurfural using mineral-derived Cu catalysts as versatile catalysts
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Selective conversion of 5-hydroxymethylfurfural (HMF) can produce sustainable fuels and chemicals. Herein, Cu-ZnO catalysts derived from minerals (malachite, rosasite and aurichalcite) were employed for selective hydrogenation of HMF for the first time. High yields of 2,5-dihydroxymethylfuran (~99.1%) and 2,5-dimethylfuran (~91.8%) were obtained tunably over the catalyst with a Cu/Zn molar ratio of 2, due to the well-dispersed metal sites tailored by mineral precursors, well-controlled surface sites and optimized reaction conditions. The relationship between catalytic performance and catalyst properties was elucidated by characterization based on the composition and the structural and surface properties, and catalytic tests. The catalyst can also be extended to selective hydrogenation of other bio-derived molecules (furfural and 5-methylfurfural) to target products. The construction of mineral-derived Cu-ZnO catalysts and the revelation of the structure-performance relationship can be applied to further rational design and functionalization of non-noble Cu catalysts for selective conversion of bio-derived compounds.
- Zhu, Yifeng,Kong, Xiao,Zheng, Hongyan,Ding, Guoqiang,Zhu, Yulei,Li, Yong-Wang
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Read Online
- Process condition-based tuneable selective catalysis of hydroxymethylfurfural (HMF) hydrogenation reactions to aromatic, saturated cyclic and linear poly-functional alcohols over Ni-Ce/Al2O3
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The related immense versatility of a ceria-promoted transition metal catalyst, utilized for the hydrogenation of 5-hydroxymethylfurfural (HMF), is demonstrated in this research study. We reveal a strategy to achieve considerable selective yields of three important high-value HMF-derived compounds by simply modifying the analysed reaction conditions and/or water-containing process medium.
- Grilc, M.,Likozar, B.,Pomeroy, Brett
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supporting information
p. 7996 - 8002
(2021/11/01)
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- Formic Acid-Assisted Selective Hydrogenolysis of 5-Hydroxymethylfurfural to 2,5-Dimethylfuran over Bifunctional Pd Nanoparticles Supported on N-Doped Mesoporous Carbon
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Biomass-derived 5-hydroxymethylfurfural (HMF) is regarded as one of the most promising platform chemicals to produce 2,5-dimethylfuran (DMF) as a potential liquid transportation fuel. Pd nanoparticles supported on N-containing and N-free mesoporous carbon materials were prepared, characterized, and applied in the hydrogenolysis of HMF to DMF under mild reaction conditions. Quantitative conversion of HMF to DMF was achieved in the presence of formic acid (FA) and H2 over Pd/NMC within 2 h. The reaction mechanism, especially the multiple roles of FA, was explored through a detailed comparative study by varying hydrogen source, additive, and substrate as well as by applying in situ ATR-IR spectroscopy. The major role of FA is to shift the dominant reaction pathway from the hydrogenation of the aldehyde group to the hydrogenolysis of the hydroxymethyl group via the protonation by FA at the C-OH group, lowering the activation barrier of the C?O bond cleavage and thus significantly enhancing the reaction rate. XPS results and DFT calculations revealed that Pd2+ species interacting with pyridine-like N atoms significantly enhance the selective hydrogenolysis of the C?OH bond in the presence of FA due to their high ability for the activation of FA and the stabilization of H?.
- Hu, Bin,Warczinski, Lisa,Li, Xiaoyu,Lu, Mohong,Bitzer, Johannes,Heidelmann, Markus,Eckhard, Till,Fu, Qi,Schulwitz, Jonas,Merko, Mariia,Li, Mingshi,Kleist, Wolfgang,H?ttig, Christof,Muhler, Martin,Peng, Baoxiang
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supporting information
p. 6807 - 6815
(2021/02/01)
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- Preparation method 2 and 5 - tetrahydrofuran dimethanol
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The preparation method of 2-5 - tetrahydrofuran dimethanol (THFDM) comprises the following steps: mixing a solvent containing 5 - hydroxymethylfurfural raw material with a catalyst, and reacting in an atmosphere containing hydrogen to obtain the 2 and 5 - tetrahydrofuran dimethanol. The purity of 5 - hydroxymethyl furfural raw material is 90 - 99%. The catalyst comprises a carrier and an active component. The active component is loaded on the carrier. The active component includes a noble metal element. The carrier comprises a carbon material. The method is simple in synthesis process, and has a great application prospect in the field of a plurality of fields, especially degradable materials.
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Paragraph 0072-0106
(2021/11/19)
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- Selective aqueous-phase hydrogenation of furfural to cyclopentanol over Ni-based catalysts prepared from Ni-MOF composite
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Metal-organic frameworks (MOFs) as an emerging class of porous materials exhibit some unique advantages, including controllable composition, a large surface area, high porosity, and so on. In this work, the spherical NiMo bimetal catalysts supported on porous carbon matrix were prepared using a simple wet impregnation method and studied for selective hydrogenation of furfural (FFA). Three different catalysts were investigated including Ni/C-Mo-BTC, Ni/C-Mo-DHTA and Ni/C-Mo-PTA. Of the catalysts studied the Ni/C-Mo-BTC catalyst could achieve the highest selectivity of CPL (up to 90%) under moderate reaction conditions (140 °C, 2 MPa, 2 h) in aqueous medium. In addition, other Ni-based catalysts (Ni/C-Fe, Ni/C-Zn, Ni/C-Cu, Ni/C-Ce) were also investigated to achieve yields of 20–70% under the same reaction conditions. The influence of temperature, H2 pressure, time and solvent were investigated for the best performing catalyst. Based on the optimal reaction condition, various of furfural derivatives could also be effectively transferred to produce corresponding products. The detailed physicochemical characterization was carried out by means of XRD, SEM, TEM, XPS, NH3-TPD and Raman analysis. In the end, the optimal Ni/C-Mo0.4 catalyst could be recycled magnetically and efficiently applied in the next run for five consecutive recycling tests in the FFA hydrogenation to CPL. The results suggested Ni/C-Mo0.4 catalyst occurred to increasingly favor the formation of Ni-Mo alloys and suggested a metallic active site in FFA hydrogenation with the addition of element Mo. Mechanism study indicated that water was a key factor contributing to the formation of different desired products, which was responsible for the arrangement of furan compound.
- Chen, Changzhou,Jiang, Jianchun,Li, Jing,Ren, Jurong,Wu, Dichao,Xia, Haihong,Zhou, Minghao
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- Highly Controllable Hydrogenative Ring Rearrangement and Complete Hydrogenation Of Biobased Furfurals over Pd/La2B2O7 (B=Ti, Zr, Ce)
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Developing a highly selective catalyst to upgrade furfurals (5-hydroxymethyl furfural and furfural) to cyclopentanones (3-hydroxymethyl cyclopentanone and cyclopentanone) and tetrahydrofuran alcohols (2,5-bishydroxymethyl tetrahydrofuran and tetrahydrofuran alcohol) is highly significant for biobased fine chemical synthesis. Here, a series of La2B2O7 (B=Ti, Zr, Ce) metal oxides, featuring the same chemical formula but different topological structures are fabricated. After Pd loading, the Lewis acidity and metal-support interaction are well governed by the support type, which further affects the hydrogenation and acid-catalyzed ability. A greater than 82 % yield of cyclopentanones is obtained via a hydrogenative ring rearrangement route over Pd/La2Ti2O7. However, Pd/La2Ce2O7 shows high catalytic efficiency for tetrahydrofuran alcohols with an approximately 80 % yield via a complete hydrogenation route. Additionally, the catalyst exhibits outstanding recycling performance and structural stability. This study presents an interesting design strategy for the selective preparation of cyclopentanones and tetrahydrofuran alcohols through the regulation of the adsorption mechanism.
- Tong, Zhikun,Gao, Rui,Li, Xiang,Guo, Lingyun,Wang, Jun,Zeng, Zheling,Deng, Qiang,Deng, Shuguang
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p. 4549 - 4556
(2021/09/09)
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- Preparation method of 2, 5-tetrahydrofuran dimethanol
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The invention provides a preparation method of 2, 5-tetrahydrofurandimethanol, which at least comprises the following steps: contacting a raw material containing 2, 5-furandimethanol with a catalyst,and reacting in a hydrogen-containing atmosphere to obtain 2, 5-tetrahydrofurandimethanol; wherein the catalyst comprises a carrier and an active component, the active component is loaded on the carrier; wherein the active component comprises active metal elements; wherein the active metal elements comprise at least one of palladium, platinum, ruthenium, nickel and rhodium; and the carrier comprising carbon material. The method for preparing the 2, 5-tetrahydrofuran dimethanol is high in activity and high in selectivity, and the reaction raw material 2,5-tetrahydrofuran dimethanol can also beprepared from 5-hydroxymethylfurfural which is a renewable source.
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Paragraph 0055-0131
(2020/06/20)
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- Self-tuned properties of CuZnO catalysts for hydroxymethylfurfural hydrodeoxygenation towards dimethylfuran production
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5-Hydroxymethylfurfural (HMF) is a very valuable platform molecule obtained from biomass. It can be catalytically transformed to many industrially relevant products of both oxidation and reduction reactions. In this work, we showed that robust CuZnO can be an efficient, self-tuned catalyst for 2,5-dimethylfuran (DMF) (biofuel additive) synthesis. We showed that CuZnO catalysts can be further activated in the reaction environment and this process depends strongly on the initial catalyst properties and therefore on the catalyst preparation method. Smaller copper particles are more active but more prone to carbon deposit formation. Based on activity tests and extensive characterization, we have concluded that both Cun+ and Cu0 sites are necessary for high HMF conversion. While these two sites favor high conversion and high 2,5-bishydroxymethylfuran (BHMF) yield, the in situ formation of Lewis acid sites is proposed to be necessary for achieving a high DMF yield.
- Brzezińska, Magdalena,Keller, Nicolas,Ruppert, Agnieszka M.
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p. 658 - 670
(2020/02/27)
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- CATALYTIC PRODUCTION OF 1,2,5,6-HEXANETETROL FROM LEVOGLUCOSENONE
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A method of making of 1,2,5,6-hexanetetrol ("tetrol"). The method includes the steps of contacting a reaction solution containing water as well as levoglucosenone, dihydrolevoglucosenone, and/or levoglucosanol, with a catalyst ontaining metal and acid functionalities, at temperature of from about 100 °C to about 175 °C, and a hydrogen partial pressure of from about 1 bar to about 50 bar (about 0.1 MPa to about 5 MPa), and for a time wherein at least a portion of the reactant is converted into 1,2,5,6-hexanetetrol.
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Paragraph 10; 12
(2019/11/12)
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- Preparation of nickel (oxide) nanoparticles confined in the secondary pore network of mesoporous scaffolds using melt infiltration
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Effective encapsulation strategies are highly sought-after in heterogeneous catalysis for preparing highly active and stable metal (oxide) nanocatalysts. Herein, we report an optimized Melt Infiltration (MI) procedure to confine nickel(oxide) nanoparticles (NPs) into hierarchical microporous-mesoporous scaffolds. Three SBA-15 silicas were synthesized in order to obtain different degrees of interconnectivity between the main mesopores. The impact of the SBA-15 pore characteristics, i.e., this interconnectivity, also named secondary intra-wall porosity (IWP), on the final nickel (oxide) NPs size and localization has been specifically investigated. Using MI, which consisted in the diffusion of the precursor in the liquid state inside the porosity of the support in the presence of the native surfactant occluding the pores, a selective localization of the NiO NPs inside the IWP was obtained, without large NPs plugging the main mesopores if IWP pores connecting the main mesopores do exist. When IWP – selective localization – occurs for the NPs, they show a size directly depending on the IWP dimensions. The obtained materials were tested, after reduction, in the hydrogenation reactions of cinnamaldehyde and 5-hydroxymethylfurfural. The catalytic results underline the positive effect of IWP - confinement of NPs to obtain and maintain an elevated dispersion of the metallic Ni active phase and to reach a high catalytic activity in hydrogenation under mild reaction conditions.
- Chen,Ciotonea,Ungureanu,Dumitriu,Catrinescu,Wojcieszak,Dumeignil,Royer
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- Interface synergy between IrOx and H-ZSM-5 in selective C–O hydrogenolysis of glycerol toward 1,3-propanediol
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Site-selective deoxygenation of hydroxyl groups represents essential processes to access valuable functionalized bio-based compounds with industrial potential. One of the challenging tasks in this context is to convert biodiesel-derived glycerol in the presence of abundant water directly to 1,3-propanediol (1,3-PDO), a key component of the emerging polymer industry. Herein, a monometallic iridium supported on H-ZSM-5 in the absence of Re oxophilic metal oxides was prepared via grinding-assisted impregnation procedures and attempted as an effective and recyclable catalyst for the aqueous-phase selective hydrogenolysis of glycerol toward 1,3-PDO in the absence of acid additives. The results revealed the necessity to control the Ir domain dispersions, Ir0/Ir3+ ratio and the amounts of overall acid/Br?nsted acid sites. Activity depended linearly on the amount of overall and Br?nsted acid sites, and 1,3-PDO selectivity increased in the presence of Ir-induced Br?nsted acid sites, denoted as Ir-O(H)-H-ZSM-5. We speculate that Ir-O(H)-H-ZSM-5 are generated by the interfacial synergistic interaction between IrOx and H-ZSM-5 through hydrogen spillover and reverse hydrogen spillover according to the reported literatures. The reaction mechanism to elucidate the role of Ir-O(H)-H-ZSM-5 sites in glycerol hydrogenolysis was also postulated based on extensive characterization and catalytic reaction results.
- Wan, Xiaoyue,Zhang, Qi,Zhu, Mingming,Zhao, Yi,Liu, Yongmei,Zhou, Chunmei,Yang, Yanhui,Cao, Yong
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p. 339 - 350
(2019/07/03)
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- Toward an Integrated Conversion of 5-Hydroxymethylfurfural and Ethylene for the Production of Renewable p-Xylene
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The use of biomass as a solution to satisfy the pressing needs for a fully sustainable biocommodity industry has been explored for a long time. However, limited success has been obtained. In this study, a highly effective two-stage procedure for the direct preparation of para-xylene (PX) from 5-hydroxymethylfurfural (HMF) and formic acid in one pot is described; these chemicals are two of the major bio-based feedstocks that offer the potential to address urgent needs for the green, sustainable production of drop-in chemical entities. The use of a robust, efficient heterogeneous catalyst, namely, bimetallic Pd-decorated Au clusters anchored on tetragonal-phase zirconia, is crucial to the success of this strategy. This multifunctional catalytic system can not only facilitate a low-energy-barrier H2-free pathway for the rapid, nearly exclusive formation of 2,5-dimethylfuran (DMF) from HMF but also enable the subsequent ultraselective production of PX by the dehydrative aromatization of the resultant DMF with ethylene. With increasing pressure around the world to move toward a bio-based economy, it is essential that industrially important commodity chemicals can be readily accessed from biomass resources. Para-xylene (PX) synthesis is one such target that is being actively pursued through the development of several biorefinery schemes based on integrated biomass processing. Significant progress has recently been achieved either in the selective synthesis of biorenewable PX from Diels-Alder-like coupling of ethylene with 2,5-dimethylfuran (DMF) or making DMF from 5-hydroxymethylfurfural (HMF) using hydrogen as the terminal reductant. However, a green and direct conversion of HMF, an essential feedstock source for future biorefinery schemes, into PX has yet to be developed. We have established an integrated process that directly converts HMF to PX in a highly compact and hydrogen-independent manner, thereby providing a new perspective on the potential of advanced biorefinery technologies. Cao and colleagues describe an alternative strategy for producing para-xylene through a more sustainable method than the current bio-based approaches. The strategy relies on an integrated conversion of 5-hydroxymethylfurfural with formic acid and ethylene, made possible by the use of a single multifunctional catalyst based on bimetallic Pd-decorated Au deposited on tetragonal-phase zirconia. The proposed process is particularly appealing because it is fully fossil independent, implying a viable and greener biorefinery scheme.
- Tao, Lei,Yan, Tian-Hao,Li, Wenqin,Zhao, Yi,Zhang, Qi,Liu, Yong-Mei,Wright, Mark M.,Li, Zhen-Hua,He, He-Yong,Cao, Yong
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supporting information
p. 2212 - 2227
(2018/10/02)
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- PRODUCTION METHOD OF ALCOHOL
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PROBLEM TO BE SOLVED: To provide a production method of alcohol, which can obtain alcohol that is a target at a high yield while suppressing a side reaction and has long term operation stability when producing alcohol from a biomass raw material. SOLUTION: When producing alcohol from a biomass raw material, a method in which alcohol is produced via an acetal intermediate having a furan skeleton is provided. Alcohol is produced by producing an acetal intermediate and by undergoing a step of hydrogenating this with hydrogen gas. SELECTED DRAWING: Figure 1 COPYRIGHT: (C)2018,JPOandINPIT
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Paragraph 0143
(2018/05/26)
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- Application of apatite substance in catalytic hydrogenation and tetrahydrofurfuryl alcohol preparation method
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The invention discloses application of an apatite substance in catalytic hydrogenation and a tetrahydrofurfuryl alcohol preparation method. The method can be used for an alcohol or alkane solvent system, furfural is completely hydrogenated in the hydrogen atmosphere of 0.1-6 MPa at the temperature of 0-200 DEG C under the effects of Pd-HAP prepared from hydroxyapatite and palladium metal by adopting an ion exchange method and other catalysts to generate the tetrahydrofurfuryl alcohol, and the method is provided for efficient utilization of biomass raw materials. The used catalysts can be used for high-conversion-rate and high-yield preparation of tetrahydrofurfuryl alcohol in the alcohol or alkane solvent system, and the conversion rate of the furfural and the yield of the furfural can be up to 100%. The tetrahydrofurfuryl alcohol preparation method is simple, reaction devices are simple, the operation is simple and convenient, a product and the catalysts are easy to separate, the catalysts are cheap and easy to obtain, and the catalysts have good hydrothermal stability and recycling performance, are suitable for industrial production and have a very broad application prospect.
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Paragraph 0099-0101; 0103; 0104
(2017/08/29)
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- POROUS SHAPED METAL-CARBON PRODUCTS
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The present invention provides a porous metal-containing carbon-based material that is stable at high temperatures under aqueous conditions. The porous metal-containing carbon-based materials are particularly useful in catalytic applications. Also provided, are methods for making and using porous shaped metal-carbon products prepared from these materials.
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Paragraph 0228
(2017/05/17)
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- METHOD FOR PRODUCING COMPOSITIONS OF FURAN GLYCIDYL ETHERS, COMPOSITIONS PRODUCED AND USES OF SAME
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A method for producing a composition of glycidyl ethers synthesised from furan derivatives (furan glycidyl ethers), partly characterized by azeotropic distillation performed under reduced pressure and without the addition of a catalyst. Such products are used to produce epoxy resins, with the aim of forming a three-dimensional macromolecular network. With the compositions of the invention the cross-linking density of the network is increased, allowing the production of a material which is more resistant, both chemically and mechanically, and has a higher glass transition temperature (Tg) than the same materials produced with compositions of furan glycidyl ethers synthesized at atmospheric pressure according to prior art.
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Paragraph 0053
(2017/05/19)
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- Direct conversion of carbohydrates to diol by the combination of niobic acid and a hydrophobic ruthenium catalyst
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Tetrahydro-2,5-furandimethanol (THFDM) was obtained directly from a wide variety of carbohydrates by the combination of niobic acid and a hydrophobic ruthenium catalyst. Fructose, glucose, and polysaccharides consisting of fructose or glucose could be converted to THFDM in one-step. The selectivity to THFDM was kept around 60% while the glucose conversion varied from 9% to 49%. The as-synthesized niobic acid was characterized by TEM, N2 adsorption/desorption, XRD, NH3-TPD and FT-IR spectra of adsorpted pyridine. The niobic acid was proved to have medium and strong acid sites with a high Br?nsted/Lewis ratio, which played a great role for keeping high THFDM selectivity using glucose as a substrate.
- Duan, Ying,Zhang, Jun,Li, Dongmi,Deng, Dongsheng,Ma, Lu-Fang,Yang, Yanliang
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p. 26487 - 26493
(2017/07/07)
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- A fructose-based biomass preparation furan-based diol
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The invention relates to a method for preparing furyl glycol from fructose and fructosyl biomass, and specifically relates to a method for converting fructose and fructosyl biomass into 2,5-dihydroxy methyl tetrahydrofuran or 2,5- dihydroxy methyl furan through continuous dehydration and hydrogenation reaction in the presence of a catalyst under a proper temperature and pressure based on a mixed solvent ion liquid/water as a reaction medium. The method disclosed by the invention takes the biomass rich in fructose as the material to prepare a target product through a one-pot process, is coupled with multi-step reaction, simple in reaction step, cheap and reproducible in material, convenient to operate, and high in product yield; the invention provides a novel method for directly preparing chemicals from biomass.
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Paragraph 0028-0029
(2017/06/19)
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- SYNTHESIS OF R-GLUCOSIDES, SUGAR ALCOHOLS, REDUCED SUGAR ALCOHOLS, AND FURAN DERIVATIVES OF REDUCED SUGAR ALCOHOLS
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Disclosed herein are methods for synthesizing 1,2,5,6-hexanetetrol (HTO), 1,6 hexanediol (HDO) and other reduced polyols from C5 and C6 sugar alcohols or R glycosides. The methods include contacting the sugar alcohol or R-glycoside with a copper catalyst, most desirably a Raney copper catalyst with hydrogen for a time, temperature and pressure sufficient to form reduced polyols having 2 to 3 fewer hydoxy groups than the starting material. When the starting compound is a C6 sugar alcohol such as sorbitol or R-glycoside of a C6 sugar such as methyl glucoside, the predominant product is HTO. The same catalyst can be used to further reduce the HTO to HDO.
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- Selective hydrodeoxygenation of 5-hydroxymethylfurfural to 2,5-dimethylfuran on Ru-MoOx/C catalysts
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Selective hydrogenation of 5-hydroxymethylfurfural (HMF) has potential application in high quality biofuels. Herein, the catalytic hydrodeoxygenation (HDO) of HMF to 2,5-dimethylfuran (DMF) was investigated using bi-functional Ru-MoOx/C catalyst prepared by initial wetness impregnation. The high dispersion and electronic transfer between Ru and MoOx were demonstrated by a series of characterization techniques. During this HDO process, the synergy effect between metallic Ru and acidic MoOx species in the Ru-MoOx/C catalyst plays an essential role in obtaining maximized target product DMF (79.4%) via effective aldehyde group hydrogenation by Ru followed by dehydration over MoOx. This work also elucidated that DMF production proceeded through two distinct pathways: the 2,5-hydroxymethyl furan intermediate was preferable by the aldehyde group hydrogenation of HMF over the Ru-MoOx/C catalyst. Over MoOx/C catalyst, comparatively, 5-methyl furfural was the key intermediate by direct hydrogenolysis of the hydroxyl group in HMF. This kind of catalyst is stable for the first two runs by maintaining the target product yield. After the third run, the catalyst showed deactivation gradually but could be almost completely recovered after regeneration by H2 reduction.
- Yang, Yue,Liu, Qiying,Li, Dan,Tan, Jin,Zhang, Qi,Wang, Chenguang,Ma, Longlong
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p. 16311 - 16318
(2017/03/24)
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- Towards sustainable hydrogenation of 5-(hydroxymethyl)furfural: A two-stage continuous process in aqueous media over RANEY catalysts
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The hydrogenation of 5-(hydroxymethyl)furfural (HMF) to 2,5-bis(hydroxymethyl)tetrahydrofuran (DHMTHF) in aqueous media under relatively mild reaction conditions has been investigated over heterogeneous RANEY Cu and Ni catalysts using a continuous-flow hydrogenation reactor. These RANEY catalysts were selected following a screening of several catalysts including precious metals supported on carbon for the hydrogenation of HMF. A single-stage versus a two-stage process for the hydrogenation of HMF into DHMTHF, i.e. via 2,5-dihydroxymethylfuran (DHMF) has been evaluated. The best result with an average selectivity of 98% for DHMTHF was obtained using a two-stage process; RANEY Cu was used as a catalyst for the highly selective hydrogenation of HMF to DHMF (92 mol%) in the first stage and this product was used without further purification for in a second-stage selective hydrogenation of DHMF into DHMTHF using RANEY Ni as a catalyst. The influence of the HMF concentration in the feeding solution (1-3 wt%), flow rate (0.05-0.25 mL min-1) and total pressure (20-90 bar) were investigated for the first-stage hydrogenation of HMF into DHMF over RANEY Cu. HMF was found to exert an inhibiting effect on the conversion due to strong adsorption. The RANEY Ni catalyst used in the second stage gradually deactivated. A procedure for in situ regeneration of the partially deactivated RANEY Ni catalyst using acetic acid washing was investigated with limited success.
- Lima, Sérgio,Chadwick, David,Hellgardt, Klaus
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p. 31404 - 31407
(2017/07/10)
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- TYK2 INHIBITORS AND USES THEREOF
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The present invention provides compounds, compositions thereof, and methods of using the same for the inhibition of TYK2, and the treatment of TYK2-mediated disorders.
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Paragraph 00854-00855
(2017/03/21)
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- Tetrahydrofuran compound
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The present invention is a method for producing a tetrahydrofuran compound represented by general formula (2), the method comprising a reaction step for bringing a furan compound represented by general formula (1) into contact with a palladium catalyst in the presence of a hydrogen source. (In formula (1), R is a formyl group or hydroxymethyl group, R1a is a hydrogen atom, C1-5 alkyl group, formyl group, or hydroxymethyl group, R2 and R3 are each independently a hydrogen atom or C1-5 alkyl group, and R1a and R2 or R2 and R3 may bond together to form a ring.) (In formula (2), R1b is a hydrogen atom, C1-5 alkyl group or hydroxymethyl group, R2 and R3 are the same as defined above, and R1b and R2 or R2 and R3 can bond together to form a ring.)
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Paragraph 0064; 0065; 0066
(2017/08/30)
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- METHOD FOR PRODUCING TETRAHYDROFURAN COMPOUND
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PROBLEM TO BE SOLVED: To provide a method for efficiently producing a tetrahydrofuran compound having a hydroxymethyl group by suppressing the hydrogenolysis of a hydroxymethyl group in a step of obtaining a tetrahydrofuran compound by reducing a furan compound. SOLUTION: There is obtained a corresponding tetrahydrofuran compound by reducing a furan compound represented by the following general formula (1) by bringing into contact with a palladium catalyst in a hydrogen atmosphere in the coexistence of a base. (wherein, Ra represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a formyl group or a hydroxymethyl group; Rb represents a formyl group or a hydroxymethyl group; R1 and R2 each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a hydroxyl group; and R1 and R2 may be bonded together to form a ring.) SELECTED DRAWING: None COPYRIGHT: (C)2016,JPOandINPIT
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Paragraph 0098; 0101
(2017/01/17)
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- Efficient hydrogenolysis of 5-hydroxymethylfurfural to 2,5-dimethylfuran over a cobalt and copper bimetallic catalyst on N-graphene-modified Al2O3
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2,5-Dimethylfuran (DMF) is an important candidate for liquid fuels and can be produced from biomass derived 5-hydroxymethylfurfural (HMF). Efficient transformation of HMF to DMF has not been achieved over a non-noble catalyst under milder conditions. Herein, we developed a copper and cobalt bimetallic nanoparticle catalyst supported on N-graphene-modified Al2O3 (CuCo/NGr/α-Al2O3). It was found that CuCo/NGr/α-Al2O3 could catalyze the conversion of HMF to DMF effectively and the yield of DMF could reach 99%. The catalyst was completely not active for the hydrogenation of the C=C bond in furan and thus no 2,5-bis(hydroxymethyl)tetrahydrofuran (DHTHF) and 2,5-dimethyltetrahydrofuran (DMTHF) were detected.
- Guo, Weiwei,Liu, Hangyu,Zhang, Suqi,Han, Hongling,Liu, Huizhen,Jiang, Tao,Han, Buxing,Wu, Tianbin
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p. 6222 - 6228
(2016/12/03)
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- Simultaneous hydrogenation and acid-catalyzed conversion of the biomass-derived furans in solvents with distinct polarities
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Furfural and 5-hydroxymethylfurfural (HMF), the two typical biomass-derived furans, can be converted into biofuels and value-added chemicals via hydrogenation or acid catalysis or both. The potential competition between the hydrogenation and the catalyzed-conversion of HMF and furfural has been investigated with Pd/C and Amberlyst 70 as the catalysts at 170°C in various solvents. In water, the hydrogenation of HMF or the derivatives of HMF could take place, but the acid-catalyzed conversion of HMF to the diketones (2,5-hexanedione) was the dominant reaction pathway. On the contrary, with ethanol as the solvent, the full hydrogenation of HMF to 2,5-tetrahydrofurandimethanol was the dominant route, and the acid-catalyzed routes became insignificant. The efficiency for hydrogenation of HMF was much higher in ethanol than in water. As for furfural, its hydrogenation proceeded more efficiently in the polar solvents (i.e. ethanol, diethyl ether) than in non-polar solvents (i.e. toluene): a polar solvent tended to favor the hydrogenation of the furan ring in furfural over that of the carbonyl group in the same furfural.
- Hu, Xun,Kadarwati, Sri,Song, Yao,Li, Chun-Zhu
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p. 4647 - 4656
(2016/01/29)
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- Tetrahydrofuran compound, as well as hydrogenation catalyst and method of manufacturing same
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PROBLEM TO BE SOLVED: To provide a method for producing a tetrahydrofuran compound from a furan compound at high reaction rate in high yield and in highly selective manner even under low temperature.SOLUTION: There is provided a method for producing a tetrahydrofuran compound, the method comprising a step of bringing a furan compound having a specific substituent into contact with hydrogen to obtain a tetrahydrofuran compound represented by general formula (2) in the presence of a catalyst obtained by mixing a palladium compound with a metallic compound having at least one metal element belonging to groups V to IX on the periodic table as constituent elements and subjecting to reduction treatment. In the formula (2), Rrepresents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or hydroxymethyl group, and Rand Reach independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
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Paragraph 0086; 0095
(2017/05/06)
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- METHOD FOR REDUCING HYDROXYMETHYLFURFURAL (HMF)
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The invention relates to the conversion of renewable biomass resources into valuable compounds. More specifically, it relates to the selective valorisation of 5-(hydroxymethyl)furfural into useful chemicals and fuels. Provided is a method of reducing hydroxymethylfurfural (HMF), comprising the steps of: - providing a starting material comprising HMF in a solvent into a reactor; - providing H2 into the reactor; and - contacting the starting material with a catalyst, wherein said catalyst is copper-zinc alloy in a nanoparticulate form.
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Page/Page column 25; 26; 27
(2016/04/09)
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- Chiral Pool/Henry/Enzymatic routes to acetogenin synthons
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Enantio specific and enantioselective approaches to the natural (16 R,19R)- and the unnatural (16S,19S)- THF core of the bioactive acetogenin annonacin are described which utilizes both a chiral pool synthesis and enzymatic transformations. In the antipodal (2S,5S) THF series derived from D-(+)-glucosamine, the semi-protected THF aldehyde synthon allows for two-directional synthetic elaboration through a Henry reaction with a lipid-like nitroalkane. The resulting nitroalcohol having the unnatural (2S,5S)-THF core was oxidized to the corresponding a-nitroketone using a modified Collins oxidation. The intermediate a-nitroketone has potential for the preparation of the C15-C32 core and analogues through subsequent removal of the nitro group and reduction of the carbonyl.
- Qayed, Wesam S.,Luzzio, Frederick A.
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p. 622 - 630
(2015/11/09)
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- Pd/C-catalyzed reactions of HMF: Decarbonylation, hydrogenation, and hydrogenolysis
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The diverse reactivity of 5-hydroxymethylfural (HMF) in Pd/C-catalyzed reactions is described with emphasis on the role of additives that affect selectivity. Three broad reactions are examined: decarbonylation, hydrogenation, and hydrogenolysis. Especially striking are the multiple roles of formic acid in hydrogenolysis/hydrogenation and in suppressing decarbonylation, as illustrated by the conversion of HMF to DMF. Hydrogenation of the furan ring is suppressed by CO2 and carboxylic acids. These results emphasize the utility of Pd/C as a convenient catalyst for upgradation of cellulosic biomass.
- Mitra, Joyee,Zhou, Xiaoyuan,Rauchfuss, Thomas
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supporting information
p. 307 - 313
(2018/04/16)
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- Ni Nanoparticles Inlaid Nickel Phyllosilicate as a Metal-Acid Bifunctional Catalyst for Low-Temperature Hydrogenolysis Reactions
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Hydrogenolysis of carbon-oxygen bonds is a versatile synthetic method, of which hydrogenolysis of bioderived 5-hydroxymethylfurfural (HMF) to furanic fuels is especially attractive. However, low-temperature hydrogenolysis (in particular over non-noble catalysts) is challenging. Herein, nickel nanoparticles (NPs) inlaid nickel phyllosilicate (NiSi-PS) are presented for efficient hydrogenolysis of HMF to yield furanic fuels at 130-150 °C, being much superior with impregnated Ni/SiO2 catalysts prepared from the same starting materials. NiSi-PS also shows a 2-fold HMF conversion intrinsic rate and 3-fold hydrogenolysis rate compared with the impregnated Ni/SiO2. The superior performance originated from the synergy of highly dispersed nickel NPs and substantially formed acid sites due to coordinatively unsaturated Ni (II) sites located at the remnant nickel phyllosilicate structure, as revealed by detailed characterizations. The model reactions over the other reference catalysts further highlighted the metal-acid synergy for hydrogenolysis reactions. NiSi-PS can also efficiently catalyze low-temperature hydrogenolysis of bioderived furfural and 5-methylfurfural, demonstrating a great potential for other hydrogenolysis reactions.
- Kong, Xiao,Zhu, Yifeng,Zheng, Hongyan,Li, Xianqing,Zhu, Yulei,Li, Yong-Wang
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p. 5914 - 5920
(2015/10/12)
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- Tailored one-pot production of furan-based fuels from fructose in an ionic liquid biphasic solvent system
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The one-pot catalytic transformation of biomass to useful products is desirable for saving cost and time. The integration of the various reaction steps need to address the presence of incompatible reaction conditions and numerous side reactions. We report a novel process for the one-pot production of furan-based fuels, 2,5-dimethylfuran (DMF) and 2,5-dihmethyltetrahydrofuran (DMTF), from fructose by optimizing the synergic effect of an ionic liquid promoted Ru/C catalyst and the solvent effect. The dehydration of fructose and subsequent in situ hydrodeoxygenation of HMF to DMF and DMTF on Ru/C were enhanced by the use of an ionic liquid and a biphasic [BMIm]Cl/THF solvent. Elemental analysis, X-ray Photoelectron Spectroscopy, Raman spectroscopy and H2-temperature programmed reduction-mass spectroscopy characterization showed that the ionic liquid modified the electronic density of the Ru species to favor HMF in situ hydrodeoxygenation. Moreover, THF served as a reaction-extraction solvent that extracted DMF and DMTF from the reaction layer to avoid further side reactions. A rational design that gave enhancement of the catalytic performance and product protection provides a promising strategy for the one-pot conversion of biomass to desired fuels.
- Li, Changzhi,Cai, Haile,Zhang, Bo,Li, Weizhen,Pei, Guangxian,Dai, Tao,Wang, Aiqin,Zhang, Tao
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p. 1638 - 1646
(2015/09/15)
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