- Efficient alcoholysis of furfuryl alcohol to n-butyl levulinate catalyzed by 5-sulfosalicylic acid
-
It is urgent to study the utilization of biomass energy to solve the environmental problems caused by the excessive use of fossil fuels. In this study, a rapid and efficient route for the conversion of furfuryl alcohol (FA) into n-butyl levulinate (BL) has been catalyzed by 5-sulfosalicylic acid. The nearly complete conversion of FA and a considerable 99.7% selectivity of BL are obtained under the optimal conditions. Based on the experimental results, a possible mechanism for the alcoholysis of FA is proposed. The present study provided a promising way for alkyl levulinates synthesis over economical and environmentally benign catalysts.
- Zhao, Wenguang,Ding, Hui,Tian, Yi,Xu, Qiong,Liu, Xianxiang
-
p. 1339 - 1345
(2021/02/26)
-
- Utilization of renewable resources: Investigation on role of active sites in zeolite catalyst for transformation of furfuryl alcohol into alkyl levulinate
-
A bio-derived furfuryl alcohol transformation into various high-value chemicals is a growing field of interest among researchers. This study reports an exclusive investigation of the porosity and active sites responsible for the efficient alcoholysis of furfuryl alcohol to alkyl levulinate by the aid of zeolite catalyst. Alkyl levulinate is a promising platform chemical potentially used as a fuel additive and also for the production of chemicals. A detailed study using well-characterized HZSM-5 catalyst on the influence of acidity and post synthesis modification like desilication, dealumination, metal ion exchange and phosphate modification revealed the most desired type of acid sites required to catalyze this reaction. Among the HZSM-5 catalysts tested, HZSM-5 (SAR 95) showed the best performance of ≥ 99 % furfuryl alcohol conversion and 85 % butyl levulinate selectivity under optimum conditions. The catalyst exhibited good recyclability additionally addressing all the challenges reported in the previous literature fulfilling the green chemistry principles.
- Vaishnavi,Sujith,Kulal, Nagendra,Manjunathan, Pandian,Shanbhag, Ganapati V.
-
-
- Eco-Friendly Natural Clay: Montmorillonite Modified with Nickel or Ruthenium as an Effective Catalyst in Gamma-Valerolactone Synthesis
-
Ni/Ru metals supported on cheap and available support montmorillonite K10 were used for the selective hydrogenation of levulinic acid to γ-valerolactone. Different loadings of the metals were applied by the impregnation method, and detailed characterization was performed (UV–VIS, XRD, TPR, TPD, particle size distribution, SEM, XRF). Metals’ homogeneous distribution on the surface was confirmed. The selectivity to the desired product was almost independent on the used material. A detailed study of the influence of solvents on the studied reaction was also performed—protic alcohol-based solvents caused the formation of levulinic and valeric acid esters in the reaction mixture. The selectivity was influenced mainly by the alcohol structure (the highest selectivity obtained using isopropyl alcohol and sec-butanol). Mainly the solvent’s donor number (except ethanol) influenced the reaction rate. The prepared catalysts are promising, available, and cheap materials for the studied reaction. Solvent may significantly influence the yield of γ-valerolactone. Graphic Abstract: [Figure not available: see fulltext.].
- ?erveny, Libor,Trejbal, Ji?í,Vaňková, Michaela,Vrbková, Eva,Vysko?ilová, Eli?ka
-
-
- Esterification of levulinic acid over Sn(II) exchanged Keggin heteropolyacid salts: An efficient route to obtain bioaditives
-
In this paper, we describe a process to add value to the biomass derivatives (i.e., levulinic acid), converting it to bioadditives over solid Sn(II) exchanged Keggin heteropolyacid salts. These solid catalysts are an attractive alternative to the traditional soluble and corrosive Br?nsted acid catalysts. Among Sn(II) heteropoly salts, the Sn1.5PW12O40 was the most active and selective catalyst, achieving high conversions (ca. 90 %) and selectivity (90–97 %) for alkyl esters and angelica lactone, the main reaction products. The impacts of the main reaction parameters (i.e., catalyst load, temperature, and the molar ratio of alcohol to acid) were investigated. The use of renewable raw material, and an efficient and recyclable catalyst are the main positive features of this process. The Sn1.5PW12O40 catalyst was easily recovered and reused without loss activity.
- Da Silva, Márcio José,Chaves, Diego Morais,Teixeira, Milena Galdino,Oliveira Bruziquesi, Carlos Giovani
-
-
- Encapsulation of heteropolyacids within hollow microporous polymer nanospheres for sustainable esterification reaction
-
Herein, the Keggin structural phosphotungstic acid (HPW) has been successfully encapsulated within hollow microporous polymer nanospheres (H-MPNs) by a “ship-in-bottle” approach. The H-MPNs are formed by self-assembly induced by hyper-crosslinking of polylactide-b-polystyrene (PLA-b-PS). The obtained catalysts (HPW@H-MPNs) exhibit more sustainable availability than the previously reported HPW-supported catalysts in esterification reaction. This excellent sustainability can be attributed to the stable microporous channels in H-MPNs which are smaller than the molecular size of HPW, thereby effectively preventing the HPW from leaking out. Moreover, such catalysts also perform well in terms of catalytic activity and universality because of the combination of a hollow structure in the interior and permeable pore channels in the shells. This type of polymer carrier and general encapsulation method may provide a new strategy for developing more sustainable catalysts for various chemical reactions.
- He, Zhiwei,Huang, Kun,Song, Chunmei,Wang, Huaqing,Yu, Haitao,Zhang, Li
-
-
- Method for preparing alkyl levulinate by regulating water content
-
The invention discloses a method for preparing alkyl levulinate by regulating water content. The method comprises the following steps: at least mixing furfuryl alcohol, alkyl alcohol and an acidic catalyst to form a reaction system, carrying out a reaction under the conditions of continuous stirring and reflux condensation, regulating the content of water in the reaction system to enable a mol ratio of the furfuryl alcohol to the water to be 1: (0.1-5), and carrying out aftertreatment to obtain alkyl levulinate. The structural formula of the alkyl levulinate is as shown in the specification. In the structural formula, R is any one selected from the group consisting of -CH3, -C2H5, -C3H7, -C4H9 and -C5H11. Compared with the prior art, the method provided by the invention has the advantagesthat the alkyl levulinate is prepared by regulating the water content; process is simple and feasible; conditions are mild; cost is low; few byproducts are produced; maximum yield reaches 99.8%; and the problem of low yield of alkyl levulinate in conventional synthesis methods is solved.
- -
-
Paragraph 0054-0057
(2020/04/17)
-
- Carbon nanotube/PTFE as a hybrid platform for lipase B fromCandida antarcticain transformation of α-angelica lactone into alkyl levulinates
-
In this work an enzymatic method for the synthesis of alkyl levulinates from α-angelica lactone has been reported for the first time. Lipase B fromCandida antarcticawas immobilizedviainterfacial activation on the surface of a hybrid support, consisting of commercially available multi-walled carbon nanotubes (MWCNTs) and polytetrafluoroethylene (PTFE). Among the biocatalysts with various contents of PTFE in the support, the CALB/MWCNT-PTFE (0.10 wt%) biocatalyst with 22.5 wt% CALB loading was determined as the most active one in the model synthesis of then-butyl levulinate in toluene.n-Butyl levulinate was obtained quantitively after 120 min of the reaction under the selected reaction conditions (2-fold molar excess ofn-butanol, 0.150 g of biocatalyst per 1 mmol of α-angelica lactone, 20 °C). The yield ofn-butyl levulinate was found to be higher than that in the presence of accurate amounts of sulfuric acid or Novozyme-435. Additionally, the unique stability of the developed biocatalyst was demonstrated over 6 reaction cycles at 20 °C. The biocatalyst remained stable over 3 reaction cycles at 60 °C as well. The essence of the proposed approach lies in the possibility to overcome the equilibrium limitations occurring in the conventional Fisher esterification. The activity of the elaborated hybrid biocatalyst in the reactions non-specific for lipases is a clear proof of the versatility of the novel system.
- Boncel, Slawomir,Chrobok, Anna,Jurczyk, Sebastian,Kolanowska, Anna,Latos, Piotr,Szelwicka, Anna
-
p. 3255 - 3264
(2020/06/17)
-
- Preparation method of alkyl levulinate under mild conditions
-
The invention discloses a preparation method of alkyl levulinate under mild conditions. The preparation method comprises the following steps: uniformly mixing furfuryl alcohol, alkyl alcohol and a solid catalyst, carrying out a reaction under the conditions of continuous stirring and condensation reflux, and carrying out post-treatment to obtain alkyl levulinate, wherein the alkyl levulinate has astructural formula represented by a formula I, and R is selected from any one of -CH3, -C2H5, -C3H7 and -C4H9. Compared with the method in the prior art, the preparation method of the invention is simple and easy to implement, mild in condition and few in by-product, has the yield of alkyl levulinate of up to 99.8%, can directly obtain a pure product, and solves the problem of high temperature condition required for the high yield of alkyl levulinate in the existing synthesis method.
- -
-
Paragraph 0051-0052
(2020/04/01)
-
- Catalytic conversions of isocyanate to urea and glucose to levulinate esters over mesoporous α-Ti(HPO4)2·H2O in green media
-
We have described a facile solvothermal synthesis of a sheet-like α-Ti(HPO4)2·H2O nanomaterial. The material comprises 10.7 nm nanoparticles along with ordered mesopores throughout its hexagonal building blocks. The material possesses a bandgap of 3.86 eV and works as an efficient catalyst for the selective synthesis of ureas from a broad range of isocyanates in the presence of H2O at room temperature with a high product yield (up to 93%) and a TOF value up to 15.25 h-1. The α-Ti(HPO4)2·H2O nanomaterial also catalytically converts glucose to levulinic acid (LA) and subsequently LA to alkyl levulinates in the presence of different alcohols with a high product yield (up to 98%) and a TOF value up to 43.00 h-1. Furthermore, all the reactions are performed under green and facile catalytic conditions without using any hazardous solvent. The α-Ti(HPO4)2·H2O catalyst material was also found to be reusable for manifold cycles for all the reactions, keeping its catalytic efficiency along with its structural and morphological characteristics unaffected, supporting its industrial relevance.
- Hazra Chowdhury, Arpita,Hazra Chowdhury, Ipsita,Biswas, Surajit,Chakrabortty, Pekham,Islam, Sk. Manirul
-
p. 16452 - 16460
(2020/10/14)
-
- Inexpensive and tuneable protic ionic liquids based on sulfuric acid for the biphasic synthesis of alkyl levulinates
-
Alkyl levulinates are bio-derived chemicals, increasingly popular for their uses as solvents, additives and intermediates. However, efficient and recyclable catalysts for their synthesis are still the subject of intensive research. In this study, a wide range of alkyl levulinates was synthesized under mild conditions (room temperature, atmospheric pressure), using inexpensive and efficient Br?nsted acidic ionic liquids (ILs) based on sulfuric acid and off-the-shelf bases. Acidity of the ILs was closely related to their activity. The ILs could be easy separated and recycled, without significant changes in conversion or selectivity over 10 cycles (yields ca. 90–95%). Under optimized conditions, a 99% yield of pentyl levulinate (model reaction) was achieved. The method was demonstrated to be efficient in the synthesis of levulinates of C1-C16 linear, branched and cyclic alcohols. This innovative, green route to alkyl levulinates fits well within the sustainable development strategy.
- Chrobok, Anna,Gillner, Danuta,Matuszek, Karolina,Przypis, Marta,Swad?ba-Kwa?ny, Ma?gorzata
-
-
- A New Sulfonic Acid-Functionalized Organic Polymer Catalyst for the Synthesis of Biomass-Derived Alkyl Levulinates
-
Abstract: Alkyl levulinates are important biobased chemicals with great fuel-blending properties and good reactivity. In this work, a new functionalized nitrogen-containing organic polymer bearing sulfonic acid groups (PDVTA-SO3H) was successfully prepared and studied for the esterification of levulinic acid with alcohols to produce alkyl levulinates. The results showed that this sulfonic acid-functionalized organic polymer possessed high catalytic activity, and the yield of n-butyl levulinate reached 97.4% under the mild conditions. PDVTA-SO3H exhibited strong acidic sites and high stability, and would be well expected to be a potential candidate better than some commercial sulfonic solid catalysts for alkyl levulinates production. The catalyst had been reused without any treatment for five times and the results proved its potential for industrial applications. Graphic Abstract: A new sulfonic acid-functionalized organic polymer showed high activity in the conversion of biomass derived levulinic acid into alkyl levulinates.[Figure not available: see fulltext.]
- Tian, Yi,Zhang, Ruoqi,Zhao, Wenguang,Wen, Sha,Xiang, Yanping,Liu, Xianxiang
-
p. 3553 - 3560
(2020/05/22)
-
- Catalytic conversion of furfuryl alcohol or levulinic acid into alkyl levulinates using a sulfonic acid-functionalized hafnium-based MOF
-
Biomass conversion using reusable solid acid catalysts are highly desirable to comply with the principles of green chemistry. Here, we report a sulfonic acid-functionalized hafnium-based metal-organic framework (MOF), UiO-66(Hf)-SO3H, as an efficientsolid acidcatalyst for the alcoholysis of furfuryl alcohol (FA) andesterification of levulinic acid (LA) affording alkyl levulinates (ALs). Among the as prepared UiO-66 based MOFs(UiO-66(Hf), UiO-66(Hf)-NH2, UiO-66(Hf)-SO3H and UiO-66(Zr)-SO3H), UiO-66(Hf)-SO3H holds highest Br?nsted acidity and therefore exhibits excellent catalytic activity towards production of ALs. The highest Br?nsted acidity in UiO-66(Hf)-SO3His the result of the covalently bound sulfonic acid groups present inorganic linkers along with the ligated hydroxyl groups (Hf-μ3-OH) to the Hf metal clusters.
- Gupta, Shyam Sunder R.,Kantam, Mannepalli Lakshmi
-
-
- Catalytic Transfer Hydrogenation of Biomass-Derived Ethyl Levulinate into Gamma-Valerolactone Over Graphene Oxide-Supported Zirconia Catalysts
-
Abstract: The transformation of biomass-derived intermediates into value-added chemicals and liquid fuels is of great importance in sustainable chemistry. In this study, graphene oxide supported ZrO2 (ZrO2/GO) was found to be an active heterogeneous catalyst for the transfer hydrogenation of ethyl levulinate to γ-valerolactone (GVL) with iso-propanol as the hydrogen donor. Several important reaction parameters such as the hydrogen donor, the reaction temperature and the catalyst loading were studied in detail with the aim to get a high yield of GVL. It was found that the structure of alcohols had a great effect towards the activity of the ZrO2/GO catalyst and the selectivity of GVL. Iso-propanol was the best hydrogen donor for the transfer hydrogenation of ethyl levulinate to GVL. The highest GVL yield reached 91.7% with an ethyl levulinate conversion of 96.2% under optimal reaction conditions. More importantly, the ZrO2/GO catalyst demonstrated a high stability without the loss of its catalytic activity during the recycling experiments, which should be due to the strong interaction between GO and ZrO2. Graphical Abstract: The graphene oxide supported ZrO2 (ZrO2/GO) catalyst showed high activity for the transfer hydrogenation of ethyl levulinate to GVL with a high yield up to 91.7%.[Figure not available: see fulltext.].
- Lai, Jinhua,Zhou, Shuolin,Liu, Xianxiang,Yang, Yongjun,Lei, Jing,Xu, Qiong,Yin, Dulin
-
p. 2749 - 2757
(2019/09/03)
-
- Esterification and ketalization of levulinic acid with desilicated zeolite β and pseudo-homogeneous model for reaction kinetics
-
To maximize the production of esters (E), keto (K) and keto-ester (KE) by esterification and ketalization of levulinic acid (LA) has been reacted using diols such as 1,2-propane diol (PDOL),1,2-ethane diol (EDOL), and 1,2,3-propane triol or glycerol (TRIOL) with desilicated Hβ. This work aims to assess the conversion and selectivity for the production of esters using conventional and microwave-irradiated (MWI) reactors. Catalysts characterizations were performed using NH3-temperature programme desorption, Brunauer, Emmett and Teller surface area (BET), Barrett, Joyner, and Halenda (BJH), scanning electron microscope, transmission electron microscope, and dynamic light scattering. Operating parameters such as reaction temperature (170–180°C), reaction time (20–80?min), feed composition (LA:PDOL/EDOL/TRIOL, 1:8/10/12), and microwave energy (300–500 watt) have been systematically investigated. Note that 99–100% conversion was achieved with the product selectivity of E (40%), K (30%), and KE (30%) with1,2-EDOL; E (56%), K (2%), and KE (17%) with 1,2-PDOL; E (69%), K(0%), and KE (22%) with TRIOL using D-Hβ as a solid catalyst in an MWI reactor. Reaction paths and kinetics were studied using pseudo-homogeneous (PH) model.
- Umrigar, Vaishali,Chakraborty, Mousumi,Parikh, Parimal
-
p. 299 - 308
(2019/02/01)
-
- Continuous Synthesis of Fuel Additives Alkyl Levulinates via Alcoholysis of Furfuryl Alcohol over Silica Supported Metal Oxides
-
Abstract: Aiming at synthesizing alkyl levulinates via alcoholysis of furfuryl alcohol in continuous mode for the first time an attempt is made using cheapest and eco-friendly solid acid catalysts. Different silica supported solid acid catalysts containing the oxides of aluminium, tungsten, zirconium and titanium have been prepared. The nature, number and strength of surface acidic sites were evaluated by DRIFT spectroscopy with pyridine adsorption and NH3-TPD and also structural and textural features of the catalysts have been investigated by XRD and BET surface area techniques. Al2O3/SiO2 catalyst exhibited better activity with 100% conversion of furfuryl alcohol and 92.8% selectivity of methyl levulinate, which may be due to more number of surface acidic sites with large number of weak Lewis acidic sites. The catalytic activity of these solid acid catalysts is as follows: Al2O3/SiO2 > ZrO2/SiO2 > WO3/SiO2 > TiO2/SiO2. This is well correlated with the number of surface acidic sites. The stable catalytic activity during the 10?h time-on-stream study confirmed the sturdiness of Al2O3/SiO2 catalyst and also it is active for the selective formation of ethyl, n-propyl, n-butyl levulinates.
- Chada, Raji Reddy,Koppadi, Kumara Swamy,Enumula, Siva Sankar,Kondeboina, Murali,Kamaraju, Seetha Rama Rao,Burri, David Raju
-
p. 1731 - 1738
(2018/04/05)
-
- Porous iron-phosphonate nanomaterial as an efficient catalyst for the CO2 fixation at atmospheric pressure and esterification of biomass-derived levulinic acid
-
Chemical fixation of CO2 and synthesis of biofuels through convenient reaction pathways are very demanding in the context of sustainable and eco-friendly catalysis. Herein, we report the synthesis of iron-phosphonate nanoparticles HPFP-1(NP) through the simple chemical reaction between hexamethylenediamine-N,N,N′,N′-tetrakis-(methylphosphonic acid) and FeCl3 under hydrothermal conditions. The material has been characterized by transmission electron microscopy (TEM), powder X-ray diffraction (PXRD), N2 adsorption/desorption studies and FE-SEM. This porous material showed high catalytic activity for the synthesis of organic carbonates from a wide range of epoxides at room temperature in the presence of CO2 at atmospheric pressure. This nanocatalyst also exhibited excellent catalytic activity for the conversion of levulinic acid into alkyl levulinates. The HPFP-1(NP) catalyst showed high recycling efficiency in these catalytic reactions.
- Ghosh, Swarbhanu,Bhanja, Piyali,Salam, Noor,Khatun, Resmin,Bhaumik, Asim,Islam, Sk. Manirul
-
p. 253 - 262
(2017/09/30)
-
- Clean synthesis of alkyl levulinates from levulinic acid over one pot synthesized WO3-SBA-16 catalyst
-
The present work highlights the application of solid acid catalyst to produce alkyl levulinate from levulinic acid in continuous mode under vapor phase conditions. In this context, tungsten oxide incorporated SBA-16 catalysts were prepared by one pot direct synthesis method and evaluated for the titled reaction. Under optimized reaction conditions, 3 wt% WO3-SBA-16 catalyst delivered complete conversion of levulinic acid with 95% selectivity towards ethyl levulinate. The synthesized catalysts were characterized to know the physico-chemical features by various techniques, namely, X-ray diffraction, N2 physisorption, temperature programmed reduction of hydrogen (H2-TPR), temperature programmed desorption of ammonia (NH3-TPD), DR-UV–vis spectroscopy, Fourier transform infrared (FTIR) spectroscopy, transmission electron microscopy (TEM) and scanning electron microscopy (SEM). The characterization results suggest that, the superior catalytic activity can be ascribed due to the enhanced acidity of SBA-16 obtained through incorporation of tungsten oxide and easy of accessibility for the dispersed active sites through uniform pore channels. The constant catalytic activity in 10 h time on study shows the sturdiness of the catalyst and the spent catalyst can be regenerated several times. Moreover, various alkyl levulinates (methyl, n-propyl, and n-butyl) were synthesized with more than 90% selectivity over this catalyst.
- Enumula, Siva Sankar,Gurram, Venkata Ramesh Babu,Chada, Raji Reddy,Burri, David Raju,Kamaraju, Seetha Rama Rao
-
-
- Heteropoly acid supported on silicalite–1 possesing intracrystalline nanovoids prepared using biomass – an efficient and recyclable catalyst for esterification of levulinic acid
-
Researchers prepared silicalite-1 containing intracrystalline nanovoids under hydrothermal synthesis conditions by adding corn stem pith powder into the zeolite synthesis gel. The nanovoids found to increase the external surface area of the zeolite and, when HPA was supported, it was loaded onto these nanovoids which improved dispersion of HPA and accesssiblity of acid sites. X-ray photoelectron spectroscopy and 31 31P- MAS NMR indicated interfacial bond formation between the silicalite-1 surface and HPA which would facilitate dispersion.
- Manikandan,Cheralathan
-
p. 237 - 247
(2017/09/19)
-
- Catalytic Conversion of Carbohydrates to Levulinate Ester over Heteropolyanion-Based Ionic Liquids
-
An efficient one-pot approach for the production of levulinate ester from renewable carbohydrates is demonstrated over heteropolyanion-based ionic liquid (IL-POM) catalysts with alcohols as the promoters and solvents. The relationships between the structure, acidic strength, and solubility of the IL-POM in methanol and the catalytic performance were studied intensively. A cellulose conversion of 100 % could be achieved with a 71.4 % yield of methyl levulinate over the catalyst [PyPS]3PW12O40 [PyPS=1-(3-sulfopropyl)pyridinium] at 150 °C for 5 h. This high efficiency is ascribed to the reasonably high activity of the ionic liquid (IL) catalyst and reaction coupling with rapid in situ esterification of the generated levulinic acid with the alcohol promoter, which allows the insolubility of cellulose encountered in biomass conversion to be overcome. Furthermore, the present process exhibits high feedstock adaptability for typical carbohydrates and handy catalyst recovery by a simple self-separation procedure through temperature control.
- Song, Changhua,Liu, Sijie,Peng, Xinwen,Long, Jinxing,Lou, Wenyong,Li, Xuehui
-
p. 3307 - 3316
(2016/12/16)
-
- Efficient conversion of furfuryl alcohol to ethyl levulinate with sulfonic acid-functionalized MIL-101(Cr)
-
Catalytic ethanolysis of furfuryl alcohol (FA) to ethyl levulinate (EL) with MIL-101(Cr)-SO3H, prepared by simple one-pot hydrothermal treatment, is presented for the first time. The as-prepared catalyst with high surface area, hydrothermal and chemical stability, good dispersion, and feasible accessibility of -SO3H Br?nsted acid sites was found to show superior performance to other sulfonic acid-functionalized solid catalysts. Besides the special textural properties, the obtained good catalytic activity of 79.2% EL yield and 100% FA conversion were also dependent on the density and strength of the Br?nsted acid and the reaction parameters. A slight loss of catalytic activity after five consecutive recycles and the hot filtration experiment confirmed the good stability of MIL-101(Cr)-SO3H. Two coexisting reaction paths for the ethanolysis of FA to EL catalyzed by MIL-101(Cr)-SO3H were proposed, wherein 2-ethoxymethylfuran (2-EMF) was observed to be the dominant intermediate.
- Liu, Xiao-Fang,Li, Hu,Zhang, Heng,Pan, Hu,Huang, Shan,Yang, Kai-Li,Yang, Song
-
p. 90232 - 90238
(2016/10/09)
-
- A solid acid catalysis process for high-yield preparation levulic ester (by machine translation)
-
The invention discloses a solid acid catalysis process for high-yield preparation levulic ester, belonging to the field of organic synthesis. The invention will be 1 parts by weight of a sugar, 10-100 parts by weight alcohol, 0.01-0.2 parts by weight of acid and B 0.1-1 parts by weight of a L acid mix, 130-190 °C reaction under the temperature 1-20h, aminolevulinic acid methyl ester solution obtained; the L acid as tin-containing molecular sieve, B acid as SBA-15-SO 3 H, Carbon-SO 3 H or Amberlyst-15 a in. Raw material carbohydrate is cheap and easy to obtain, for the acid L, B acid can be repeated using a catalytic effect to be reduced is not obvious, the one-step process for preparing the laevulinic acid ester compound, can be widely applied to food additive, essence, chemical reaction intermediates and gasoline, diesel fuel additive and other industries. (by machine translation)
- -
-
Paragraph 0043; 0044
(2017/02/24)
-
- A fructose-based biomass catalytic conversion systems furan derivatives
-
A method for preparing furan derivatives by catalytic conversion of fructose-based biomass is characterized by: taking biomass such as fructose, cane sugar, inulin and the like as raw materials, taking low-boiling-point alcohols comprising aliphatic alcohols or alicyclic alcohols all with six or less than six carbon atoms as a solvent, and under the effect of a catalyst, performing reactions comprising hydrolysis, dehydration, etherfication and the like for coupling so as to obtain furan derivatives such as 5-alkoxymethyl furfural, levulinate esters, 5-hydroxymethylfurfural and the like. The method has the advantages of high raw material utilization rate, high in-situ coupling efficiency in the dehydration and etherfication reactions, and easily separated and purified system.
- -
-
Paragraph 0020
(2017/02/09)
-
- Highly efficient metal salt catalyst for the esterification of biomass derived levulinic acid under microwave irradiation
-
The esterification of levulinic acid (LA) to alkyl levulinates has been investigated in the presence of various metal salt catalysts under microwave irradiation. The reaction obtained 99.4% yield of methyl levulinate (ML) in the presence of Al2(SO4)3 catalyst in methanol solution under microwave conditions. The optimized reaction conditions were 110 °C and 10 minutes with a 20 mol% catalyst loading. Alcohols with longer carbon chains showed lower reactivities in the microwave electromagnetic field due to their poorer abilities to absorb and transmit microwave energy. Moreover, microwave irradiation provided a significantly higher reaction rate compared to conventional oil bath heating. LA aqueous solution was also converted to ML with high yields. The Al2(SO4)3 catalyst was successfully applied to the esterification of other biomass derived organic acids to their corresponding esters in high yields. Finally, the catalyst was recycled 5 times without much decrease in activity.
- Huang, Yao-Bing,Yang, Tao,Cai, Bo,Chang, Xin,Pan, Hui
-
p. 2106 - 2111
(2016/01/20)
-
- Indium(III) triflate promoted synthesis of alkyl levulinates from furyl alcohols and furyl aldehydes
-
A facile protocol for the alcoholysis of furfuryl alcohol into levulinate esters has been developed employing low catalyst loadings of indium(III) triflate. This method provides a rapid and efficient route for the synthesis of these useful materials. The alcoholysis reactions of 5-hydroxymethylfurfural (HMF), furfural and furfural dimethylacetal were also investigated under these reaction conditions.
- Kean, Jacqueline R.,Graham, Andrew E.
-
p. 175 - 179
(2015/02/19)
-
- Heterogeneous acidic TiO2 nanoparticles for efficient conversion of biomass derived carbohydrates
-
Selective conversion of biomass derived carbohydrates into fine chemicals is of great significance for the replacement of petroleum feedstocks and the reduction of environmental impacts. Levulinic acid, 5-hydroxymethyl furfural (HMF) and their derivatives are recognized as important precursor candidates in a variety of different areas. In this study, the synthesis, characterization, and catalytic activity of acidic TiO2 nanoparticles in the conversion of biomass derived carbohydrates were explored. This catalyst was found to be highly effective for selective conversion to value-added products. The nanoparticles exhibited superior activity and selectivity towards methyl levulinate from fructose in comparison to current commercial catalysts. The conversion of fructose to methyl levulinate was achieved with 80% yield and high selectivity (up to 80%). Additionally, conversions of disaccharides and polysaccharides were studied. Further, the production of versatile valuable products such as levulinic esters, HMF, and HMF-derived ethers was demonstrated using the TiO2 nano-sized catalysts in different solvent systems.
- Kuo, Chung-Hao,Poyraz, Altug S.,Jin, Lei,Meng, Yongtao,Pahalagedara, Lakshitha,Chen, Sheng-Yu,Kriz, David A.,Guild, Curtis,Gudz, Anton,Suib, Steven L.
-
p. 785 - 791
(2014/02/14)
-
- Efficient production of 5-hydroxymethylfurfural and alkyl levulinate from biomass carbohydrate using ionic liquid-based polyoxometalate salts
-
Direct conversion of fructose into 5-hydroxymethylfurfural (HMF) and alkyl levulinate is achieved by making use of ionic liquid-based polyoxometalate salts (IL-POMs) as solid acid catalysts. Among these solid acids, phosphotungstic acid-derived IL-POM shows the highest catalytic performance in both the HMF and ethyl levulinate (EL) formation. A study for optimizing the reaction conditions such as the reaction time and the temperature has been performed. High HMF and EL yields of up to 99% and 82%, respectively, are obtained from fructose under the investigated conditions. Moreover, the generality of the catalyst is further demonstrated by processing representative di- and polysaccharides such as sucrose and inulin with good yields to HMF (76% from inulin and 48% from sucrose) and EL (67% from inulin and 45% from sucrose), again under mild conditions, thereby eliminating the separate hydrolysis step before the dehydration reaction. The catalyst recycling experiment indicates that the adsorption and accumulation of oligomeric products on the catalyst surface results in a partial deactivation of catalyst. The mechanism research reveals that a major pathway for EL formation involves a fructose-to-HMF transformation followed by HMF etherification and rehydration of HMF-ether to give EL. The research highlights an efficient, environment-friendly and recyclable solid acid for biomass valorization.
- Chen, Jinzhu,Zhao, Guoying,Chen, Limin
-
p. 4194 - 4202
(2014/01/06)
-
- CONVERSION OF CARBOHYDRATES TO LEVULINIC ACID ESTERS
-
The present invention relates to the field of converting carbohydrates into levulinic acid, a platform chemical for many chemical end products. More specifically the invention relates to a method for converting carbohydrates such as mono-, di- or polysaccharides, obtained from for example biomass production into a suitable levulinic acid ester in the presence of a zeolite or zeotype catalyst and a suitable alcohol, and the ester may be further converted into levulinic acid if desired.
- -
-
Page/Page column 18; 20; 21; 22; 23
(2014/02/16)
-
- Efficient and selective alcoholysis of furfuryl alcohol to alkyl levulinates catalyzed by double SO3H-functionalized ionic liquids
-
The production of alkyl levulinates from furfuryl alcohol (FAL) in alcohol media was investigated at moderate temperature in the presence of Bronsted acidic ionic liquids. The reaction was examined and optimized under batch conditions, where it was found that furfuryl alcohol was rapidly and almost quantitatively converted into intermediate products including 2-alkoxymethylfuran and 4,5,5-trialkoxypentan-2-one, and high alkyl levulinates yield of 95% can be achieved after reaching a steady state in 2 h. An advantage of this catalyst system is that undesired dialkyl ether (DEE) formed by a side reaction of the dehydration of alcohol is negligible. The Hammett method was used to determine the acidities of these ionic liquids, which indicated that the acidity and the molecular structure have strong effects on the catalytic activity of ionic liquids. Based on the experimental results, a possible mechanism for the alcoholysis of FAL is proposed.
- Wang, Guofeng,Zhang, Zhanquan,Song, Linhua
-
p. 1436 - 1443
(2014/03/21)
-
- Graphene oxide: An efficient acid catalyst for alcoholysis and esterification reactions
-
Evidence is presented for graphene oxide (GO), prepared by modified Hummers method, as a highly active, selective and reusable solid-acid catalyst for the production of alkyl levulinates via alcoholysis or esterification. 95.5% yield of ethyl levulinate was achieved by GO in furfuryl alcohol alcoholysis. Moreover, the surface SO3H groups were identified as the primary active sites, while the surface carboxyl groups worked synergistically to adsorb furfuryl alcohol.
- Zhu, Shanhui,Chen, Chengmeng,Xue, Yanfeng,Wu, Jianbing,Wang, Jianguo,Fan, Weibin
-
p. 3080 - 3083
(2015/02/02)
-
- Conversion of fructose into 5-hydroxymethylfurfural and alkyl levulinates catalyzed by sulfonic acid-functionalized carbon materials
-
A series of sulfonic acid-functionalized carbon materials (C-SO 3H), including poly(p-styrenesulfonic acid)-grafted carbon nanotubes (CNT-PSSA), poly(p-styrenesulfonic acid)-grafted carbon nanofibers (CNF-PSSA), benzenesulfonic acid-grafted CMK-5 (CMK-5-BSA), and benzenesulfonic acid-grafted carbon nanotubes (CNT-BSA), have been studied for fructose dehydration to 5-hydroxymethylfurfural (HMF) and fructose alcoholysis to alkyl levulinate. A study for optimizing the reaction conditions such as the catalyst loading, the reaction time, and the temperature has been performed. Under the optimal conditions, high HMF and ethyl levulinate yields of up to 89% and 86%, respectively, are obtained. The catalytic activities of C-SO3H for the conversions of fructose into both HMF and ethyl levulinate follow the order of their acid strength. The relationship between the catalytic activity and acid density of C-SO3H shows a linear correspondence in the fructose dehydration to HMF. The facile separation, ease of recovery, and high thermal stability make the developed C-SO3H efficient and environment-friendly catalytic materials for transforming biomass carbohydrate into fine chemicals.
- Liu, Ruliang,Chen, Jinzhu,Huang, Xing,Chen, Limin,Ma, Longlong,Li, Xinjun
-
supporting information
p. 2895 - 2903
(2013/10/08)
-
- Efficient conversion of furfuryl alcohol into alkyl levulinates catalyzed by an organic-inorganic hybrid solid acid catalyst
-
A clean, facile, and environment-friendly catalytic method has been developed for the conversion of furfuryl alcohol into alkyl levulinates making use of the novel solid catalyst methylimidazolebutylsulfate phosphotungstate ([MIMBS]3PW12O40). The solid catalyst is an organic-inorganic hybrid material, which consists of an organic cation and an inorganic anion. A study for optimizing the reaction conditions such as the reaction time, the temperature and the catalyst loading has been performed. Under optimal conditions, a high n-butyl levulinate yield of up to 93 % is obtained. Furthermore, the kinetics of the reaction pathways and the mechanism for the alcoholysis of furfuryl alcohol are discussed. This method is environmentally benign and economical for the conversion of biomass-based derivatives into fine chemicals. Size zero waste: A clean, facile, and environment-friendly catalytic method has been developed for the conversion of furfuryl alcohol into alkyl levulinates, making use of the novel solid catalyst methylimidazolebutylsulfate phosphotungstate ([MIMBS]3PW 12O40). Under the optimal conditions, a high n-butyl levulinate yield of up to 93 % was obtained, with easy work-up procedures and minimal waste generation.
- Zhang, Zehui,Dong, Kun,Zhao, Zongbao
-
experimental part
p. 112 - 118
(2012/01/06)
-
- METHOD FOR THE PREPARATION OF ALKYL LEVULINATES
-
A process for the conversion of furfuryl alcohol into levulinate esters in a single step reaction comprising addition of the product levulinate ester to the reaction mixture of an alkanol and furfuryl alcohol in the presence of a strong protic acid catalyst, wherein high yield of the levulinate ester is accompanied by low amounts of tarry residue that do not precipitate or solidify in the reaction mixture.
- -
-
Page/Page column 26-27
(2010/09/18)
-
- Furfuryl alcohol in synthesis of levulinic acid esters and difurylmethane with Fe and Rh complexes
-
The possibility of synthesis of levulinic acid esters by the reaction of furfuryl alcohol with aliphatic alcohols in the system CCl4-Fe(acac) 3 was studied.
- Khusnutdinov,Baiguzina,Smirnov,Mukminov,Dzhemilev
-
p. 1687 - 1690
(2008/03/27)
-
- Transformations of levoglucosenone at the anhydroglucoside bond
-
The results are given of transformations of levoglucosenone at the anhydroglucoside bond in the presence of a catalyst of the acid type in an aqueous medium, in TFAA, and in lower aliphatic alcohols. Possibilities are shown of obtaining hydroxymethylfurfural and levulinic acid or their derivatives from levoglucosenone in high yields. Possible mechanisms of the reactions taking place are discussed on the basis of kinetic studies and investigations on the composition of the intermediate compounds.
- Efremov
-
p. 582 - 589
(2007/10/03)
-