- Selective Hydrogenolysis of α-C-O Bond in Biomass-Derived 2-Furancarboxylic Acid to 5-Hydroxyvaleric Acid on Supported Pt Catalysts at Near-Ambient Temperature
-
Hydrogenolysis of the α-C-O bond in abundantly available biomass-based furfural and its derivatives provides a viable route for sustainable synthesis of valuable C5 compounds, particularly with two terminal oxygen-containing functional groups. However, efficient cleavage of this bond under mild conditions still remains a crucial challenge, primarily because of the competing cleavage of the α-C-O bond and hydrogenation of furan ring. Here, we report that supported Pt catalysts were extremely active for the selective α-C-O cleavage in 2-furancarboxylic acid (FCA) hydrogenolysis to synthesize 5-hydroxyvaleric acid (5-HVA), affording a high yield (～78%) on Pt/SiO2 with a Pt particle size of 4.2 nm at an unprecedentedly low temperature of 313 K. In this reaction, the turnover rate and 5-HVA selectivity sensitively depend on the size of the Pt nanoparticles and the underlying support, as a consequence of their effects on the exposed Pt surfaces. Combined reaction kinetic, infrared spectroscopic, and theoretical assessments reveal that while the exposed high-index Pt surfaces (containing higher fraction of step sites) facilitate the kinetically relevant addition of the first H atom to the unsaturated C atom in furan ring and thus the hydrogenolysis activity, the low-index surfaces (containing higher fraction of terrace sites), together with the electron-withdrawing effect of the carboxylic substituent in FCA, favorably stabilize the dangling C2 atom in the transition states of α-C-O cleavage and lower their activation barriers, leading to the observed high 5-HVA selectivity. Such pivotal roles of the intrinsic properties of metal surfaces and substituents in tuning the reaction pathways will provide a viable strategy for highly selective upgrading of furan derivatives and other biomass-based oxygenates.
- Sun, Qianhui,Wang, Shuai,Liu, Haichao
-
-
Read Online
- One-pot selective conversion of furfural into 1,5-pentanediol over a Pd-added Ir-ReOx/SiO2 bifunctional catalyst
-
One-pot selective conversion of furfural into 1,5-pentanediol (1,5-PeD) was carried out over Pd-added Ir-ReOx/SiO2 catalysts through two-step reaction temperatures. The Pd(0.66 wt%)-Ir-ReOx/SiO 2 catalyst showed the best performance in the production of 1,5-PeD from furfural. The maximum yield of 1,5-PeD was 71.4%. The furfural conversion and yield of 1,5-PeD was almost maintained during four repeated tests when the catalyst was calcined again. The characterization results from TPR, XRD, XANES, EXAFS and FT-IR of adsorbed CO indicated that Pd-Ir-ReOx/SiO 2 catalysts consisted of ReOx-modified Pd metal particles and ReOx-modified Ir metal particles. The lower-temperature reaction step was very crucial for the total hydrogenation of furfural into a tetrahydrofurfuryl alcohol intermediate, which was converted into 1,5-PeD by hydrogenolysis during the high temperature step over the ReOx- modified Ir metal particles.
- Liu, Sibao,Amada, Yasushi,Tamura, Masazumi,Nakagawa, Yoshinao,Tomishige, Keiichi
-
-
Read Online
- HOMOGENEOUS CATALYTIC HYDROGENATION OF FREE CARBOXYLIC ACIDS IN THE PRESENCE OF CLUSTER RUTHENIUM CARBONYL HYDRIDES
-
Saturated monocarboxylic acids up to C6, several bicarboxylic acids and some of the corresponding anhydrides are hydrogenated in the homogeneous phase with H4Ru4(CO)8(PBu3)4 as catalyst to give the corresponding alcohols (present among the reaction products as esters) or lactones at 100-200 deg C under a pressures of 100-200 atm of hydrogen.Anhydrides react at temperatures lower than those needed for acids.Esters are not reduced.Only δ-valerolactone is hydrogenated to 1,5-pentanediol.Ruthenium carbonyl carboxylates have been recovered at the end of the reaction andappear to be catalytically active intermediates.
- Bianchi, Mario,Menchi, Gloria,Francalanci, Franco,Piacenti, Franco,Matteoli, Ugo,et al.
-
-
Read Online
- One-pot biosynthesis of 1,6-hexanediol from cyclohexane by: De novo designed cascade biocatalysis
-
1,6-Hexanediol (HDO) is an important precursor in the polymer industry. The current industrial route to produce HDO involves energy intensive and hazardous multistage (four-pot-four-step) chemical reactions using cyclohexane (CH) as the starting material, which leads to serious environmental problems. Here, we report the development of a biocatalytic cascade process for the biotransformation of CH to HDO under mild conditions in a one-pot-one-step manner. This cascade biocatalysis operates by using a microbial consortium composed of three E. coli cell modules, each containing the necessary enzymes. The cell modules with assigned functions were engineered in parallel, followed by combination to construct E. coli consortia for use in biotransformations. The engineered E. coli consortia, which contained the corresponding cell modules, efficiently converted not only CH or cyclohexanol to HDO, but also other cycloalkanes or cycloalkanols to related dihydric alcohols. In conclusion, the newly developed biocatalytic process provides a promising alternative to the current industrial process for manufacturing HDO and related dihydric alcohols. This journal is
- Kang, Lixin,Li, Aitao,Li, Qian,Li, Renjie,Wang, Fei,Yu, Xiaojuan,Zhang, Zhongwei,Zhao, Jing
-
-
Read Online
- HYDROGENATION OF FURFURAL ON POLYMER-CONTAINING CATALYSTS
-
The catalytic hydrogenation of furfural with molecular hydrogen has been investigated under mild conditions in the presence of metal complex catalysts with a polymeric macroligand.It has been shown that the reaction proceeds according to a consecutive scheme with the formation of furfuryl and tetrahydrofurfuryl alcohols.The kinetics of furfural hydrogenation has been investigated and the order of the reaction established; the rate constants of the first and second stages have been determined.The influence of the solvent and of the metal-to-polymer ratio on the furfural conversion have been investigated.
- Karakhanov, E. A.,Neimerovets, E. B.,Pshezhetskii, V. S.,Dedov, A. G.
-
-
Read Online
- RING CLEAVAGE REARRANGEMENT OF CYCLOBUTYLMETHYLBORANES
-
Boranes derived from hydroboration of methylenecyclobutane with borane/THF, 9-borabicyclononane, and borane-methyl sulfide rearranged on heating in situ at 100-160 deg C to open chain structures.Products after oxidation were the unrearranged cyclobutylmethanol, and 4-penten-1-ol, 1,4-pentane-diol and 1,5-pentanediol.The unsaturated alcohol was the major product in reactions with a stoichiometric ratio of alkene to BH bonds, and the diols were formed with excess borane.With borane-methyl sulfide as hydroborating reagent, the rate of rearrangement at 100 deg C in triglyme was not significantly dependent upon the initial alkene/borane ratio (3/1 or 1.15/1) or the presence of excess methyl sulfide.However, an equivalent amount of pyridine prevented rearrangement.Rearrangement in THF using borane/THF also occurred at comparable rates in the presence and absence of excess borane.Little or no isomerization of the boron function into the cyclobutane ring was observed.Results are interpreted on the basis of a concerted four-center mechanism which requires a vacant boron orbital.
- Hill. E. Alexander,Nylen, Patricia A.,Fellinger, John H.
-
-
Read Online
- Promoting effect of Mo on the hydrogenolysis of tetrahydrofurfuryl alcohol to 1,5-pentanediol over Rh/SiO2
-
Addition of Mo to Rh/SiO2 promoted the hydrogenolysis of tetrahydrofurfuryl alcohol to 1,5-pentanediol drastically. Addition of Re and W to Rh/SiO2 was also effective, but the promoting effect of Mo was more remarkable in terms of ca
- Koso, Shuichi,Ueda, Naoyuki,Shinmi, Yasunori,Okumura, Kazu,Kizuka, Tokushi,Tomishige, Keiichi
-
-
Read Online
- One-pot selective conversion of C5-furan into 1,4-pentanediol over bulk Ni-Sn alloy catalysts in an ethanol/H2O solvent mixture
-
Inexpensive bulk Ni-Sn alloy-based catalysts demonstrated a unique catalytic property in the selective conversion of C5-furan compounds (e.g., furfuraldehyde (FFald), furfuryl alcohol (FFalc), and 2-methylfuran (2-MTF)) in an ethanol/H2O solvent mixture and selectively produced 1,4-pentanediol (1,4-PeD) in a one-pot reaction. The synergistic actions between the bulk Ni-Sn alloy catalyst, hydrogen gas, and the hydroxylated H2O or ethanol/H2O solvents are believed to play a prominent role in the catalytic reactions. Bulk Ni-Sn alloy catalysts that consisted of Ni3Sn or Ni3Sn2 alloy phases allowed an outstanding yield of 1,4-PeD up to 92% (from FFald), 67% (from FFalc), and 48% (from 2-MTF) in ethanol/H2O (1.5:2.0 volume ratio) at 433 K, 3.0 MPa H2 and 12 h. As the reaction temperature increased to 453 K, the yield of 1,4-PeD slightly decreased to 87% (from FFald), whereas it slightly increased to 71% (from FFalc). The bulk Ni-Sn alloy catalysts were reusable without any significant loss of selectivity.
- Rodiansono,Dewi Astuti, Maria,Hara, Takayoshi,Ichikuni, Nobuyuki,Shimazu, Shogo
-
-
Read Online
- Selective Activation of C-OH, C-O-C, or Ca? C in Furfuryl Alcohol by Engineered Pt Sites Supported on Layered Double Oxides
-
The selective activation of targeted bonds in biomass-derived furfural or furfuryl alcohol with complex chemical linkages (C-C/C-H/C-O, Ca? C/Ca? O, or C-O-H/C-O-C) is of great challenge for biomass upgrading, expecting well-defined catalyst and definite catalytically active sites. This work demonstrates an efficient targeted activation to C-OH, C-O-C, or Ca? C by engineering the structure of catalytic Pt sites, affording 2-methylfuran (2-MF), tetrahydrofurfuryl alcohol (THFA), or 1,2-pentanediol (1,2-PeD) as product in the hydroconversion of furfuryl alcohol. The catalytic Pt sites have been engineered as atomic Pt, coordination unsaturated Pt-Pt in atom-thick dispersion, or coordination unsaturated 3D Pt-Pt by tailoring the Pt dispersion (single atom, 2D cluster, or 3D cluster) on Mg and Al-containing layered double oxide (Mg(Al)O) support. The selective activation of C-OH, C-O-C, or Ca? C has been traced with the FT-IR spectra recorded surface reaction. On atomic Pt, C-O-H is easily activated, with the assistance of Mg(Al)O support, with O-terminal adsorption without affecting furan C-O and Ca? C. However, Ca? C in the furan ring is easier to be activated on coordination-unsaturated Pt-Pt in atom-thick dispersion, resulting in a step-by-step hydrogenation to generate THFA. On coordination-unsaturated 3D Pt-Pt, the hydrogenolysis of furan ring is favored, resulting in the cleavage of furan C-O to produce 1,2-PeD. Also, the Mg(Al)O supports derived from Mg and Al layered double hydroxides (LDHs) here also play a key role in promoting the selectivity to 1,2-PeD by providing basic sites.
- An, Zhe,He, Jing,Jiang, Yitao,Ma, Xiaodan,Shu, Xin,Song, Hongyan,Xiang, Xu,Zhang, Jian,Zhang, Zhijun,Zhao, Wenfang,Zheng, Lirong,Zhu, Yanru
-
-
Read Online
- Highly Efficient and Convenient Deprotection of Methoxymethyl Ethers and Esters Using Bismuth Triflate in an Aqueous Medium
-
A simple and efficient method has been developed for the hydrolysis of methoxymethyl (MOM) ethers and esters to the corresponding alcohols and acids employing a catalytic amount of bismuth triflate in an aqueous medium. The conversions occur at ambient temperature and the yields of the deprotected alcohols are very good. The reaction was highly selective in the presence of other protecting groups such as TBDMS, TBDPS, benzyl, and allyl ethers.
- Venkat Reddy,Jagadeeshwar Rao,Sampath Kumar,Madhusudana Rao
-
-
Read Online
- Comparative studies of the deprotection of various acid sensitive protecting groups with pyridinium p-toluenesulphonate
-
Selective deprotection of the various acid sensitive protecting groups c.g. ethoxyethyl (EE) I-butyl dimethylsiyl (TBDMS) and t-butoxycarbonyl (BOC) groups with the inexpensive reagent pyridinum p-toulenesulphonate (PPTS), under mild conditions is reported.
- Zaidi, Javid H.,Fauq, Abdul H.,Ahmed, Naseera
-
-
Read Online
- Pd/Lewis Acid Synergy in Macroporous Pd@Na-ZSM-5 for Enhancing Selective Conversion of Biomass
-
Pd nanometal particles encapsulated in macroporous Na-ZSM-5 with only Lewis acid sites have been successfully synthesized by a steam-thermal approach. The synergistic effect of Pd and Lewis acid sites have been investigated for significant enhancement of the catalytic selectivity towards furfural alcohol in furfural hydroconversion.
- Liu, Jia-Wen,Wu, Si-Ming,Wang, Li-Ying,Tian, Ge,Qin, Yuan,Wu, Jing-Xian,Zhao, Xiao-Fang,Zhang, Yan-Xiang,Chang, Gang-Gang,Wu, Lu,Zhang, Yue-Xing,Li, Zhao-Fei,Guo, Cheng-Yu,Janiak, Christoph,Lenaerts, Silvia,Yang, Xiao-Yu
-
-
Read Online
- Hydrogenolysis of tetrahydrofuran-2-carboxylic acid over tungsten-modified rhodium catalyst
-
Catalysts for reduction of tetrahydrofuran-2-carboxylic acid (THFCA), which can be synthesized from furfural via oxidation and hydrogenation, were explored among the combinations of noble metal and reducible metal oxide supported on SiO2. Rh-WOx/SiO2 catalysts showed activity in C-O hydrogenolysis at 2-position of THFCA (to δ-valerolactone and 5-hydroxyvaleric acid) and higher yield ratio of these C-O hydrogenolysis products to carboxylic acid hydrogenation products than other bimetallic catalysts. The activity of Rh-WOx/SiO2 catalysts was highest at W/Rh = 0.25 mol/mol. XRD, TPR, CO adsorption and XAFS characterizations showed that the Rh-WOx/SiO2 (W/Rh = 0.25) catalyst contained Rh metal particles with surface modification with isolated W2+ oxide species. The mechanism that hydride-like species formed on Rh atom attacks the C atom at the α-position (2-position) of adsorbed carboxylate on W atom is proposed based on the similar kinetics and similar catalyst structure to Rh-MOx/SiO2 (M = Re, Mo) which is known to be active in THFA hydrogenolysis to 1,5-pentanediol.
- Asano, Takehiro,Nakagawa, Yoshinao,Tamura, Masazumi,Tomishige, Keiichi
-
-
Read Online
- Direct catalytic conversion of furfural to 1,5-pentanediol by hydrogenolysis of the furan ring under mild conditions over Pt/Co 2AlO4 catalyst
-
A new strategy was developed for the direct conversion of furfural to 1,5-pentanediol by the hydrogenolysis of the furan ring under mild conditions based on Pt/Co2AlO4 catalyst. This is the first report of the direct catalytic conversion of furfural to 1,5-pentanediol with high yield. The Royal Society of Chemistry.
- Xu, Wenjie,Wang, Haifeng,Liu, Xiaohui,Ren, Jiawen,Wang, Yanqin,Lu, Guanzhong
-
-
Read Online
- Defining Pt-compressed CO2 synergy for selectivity control of furfural hydrogenation
-
The development of a sustainable methodology for catalytic transformation of biomass-derived compounds to value-added chemicals is highly challenging. Most of the transitions are dominated by the use of additives, complicated reaction steps and large volumes of organic solvents. Compared to traditional organic solvents, alternative reaction media, which could be an ideal candidate for a viable extension of biomass-related reactions are rarely explored. Here, we elucidate a selective and efficient transformation of a biomass-derived aldehyde (furfural) to the corresponding alcohol, promoted in compressed CO2 using a Pt/Al2O3 catalyst. Furfural contains a furan ring with CC and an aldehyde group, and is extremely reactive in a hydrogen atmosphere, resulting in several by-products and a threat to alcohol selectivity as well as catalyst life. The process described has a very high reaction rate (6000 h-1) with an excellent selectivity/yield (99%) of alcohol, without any organic solvents or metal additives. This strategy has several key features over existing methodologies, such as reduced waste, and facile product separation and purification (reduced energy consumption). Combining the throughput of experimental observation and molecular dynamics simulation, indeed the high diffusivity of compressed CO2 controls the mobility of the compound, and eventually maintains the activity of the catalyst. Results are also compared for different solvents and solvent-less conditions. In particular, combination of an effective Pt catalyst with compressed CO2 provides an encouraging alternative solution for upgradation of biomass related platform molecules.
- Chatterjee, Maya,Chatterjee, Abhijit,Ishizaka, Takayuki,Kawanami, Hajime
-
-
Read Online
- Mechanism of the hydrogenolysis of ethers over silica-supported rhodium catalyst modified with rhenium oxide
-
The Rh-ReOx/SiO2 (Re/Rh = 0.5) exhibited high activity in the hydrogenolysis of ethers with an OH group. The CO bond neighboring CH2OH group was selectively dissociated: The hydrogenolysis of tetrahydro-5-methyl-2-furfuryl alcohol and 2-isopropoxyethannol gave 1,5-hexanediol and ethanol + isopropanol, respectively. This tendency suggests the regioselective CO dissociation mechanism via anion intermediate formed by the attack of hydride and the subsequent protonation of the anion.
- Koso, Shuichi,Nakagawa, Yoshinao,Tomishige, Keiichi
-
-
Read Online
- Synthesis of 1,5-Pentanediol by Hydrogenolysis of Furfuryl Alcohol over Ni–Y2O3 Composite Catalyst
-
The addition of Y2O3 into Ni formed a composite catalyst that selectively produced 1,5-pentanediol rather than 1,2-pentanediol in the hydrogenolysis of furfuryl alcohol at 2.0 MPa H2 and 423 K. Clearly, 1,5-pentanediol was produced over the Ni0–Y2O3 boundary. This report highlights the properties of Ni–Y2O3, catalytic performance, and reaction route in the synthesis of 1,5-pentanediol from furfuryl alcohol.
- Wijaya, Husni Wahyu,Kojima, Takashi,Hara, Takayoshi,Ichikuni, Nobuyuki,Shimazu, Shogo
-
-
Read Online
- Performance and characterization of rhenium-modified Rh-Ir alloy catalyst for one-pot conversion of furfural into 1,5-pentanediol
-
One-pot selective conversion of highly concentrated furfural to 1,5-pentanediol (1,5-PeD) was carried out over Rh-added Ir-ReO x/SiO2 catalysts through two-step reaction temperatures. Over the optimized catalyst, Rh(0.66 wt%)-Ir-ReOx/SiO2, the maximum yield of 1,5-PeD was 71.1% from highly concentrated furfural (50 wt%) and 78.2% from diluted furfural (10 wt%). These values were higher than those obtained with Ir-ReOx/SiO2 or Pd-Ir-ReO x/SiO2 catalysts. Rh-Ir-ReOx/SiO2 showed much higher activity in the hydrogenation of furfural to tetrahydrofurfuryl alcohol intermediate in the low temperature step than Ir-ReOx/SiO2, although the hydrogenation activity was lower than that of Pd-Ir-ReOx/SiO2. A long reaction time in the low temperature step is necessary to obtain a good 1,5-PeD yield over Rh-Ir-ReOx/SiO2 in two-step reaction of furfural. The hydrogenolysis activity of Rh-Ir-ReOx/SiO2 for tetrahydrofurfuryl alcohol to 1,5-PeD in the high temperature step was higher than that of Pd-Ir-ReOx/SiO2 and was comparable to that of Ir-ReOx/SiO2. The characterization results of TPR, XRD, XANES, EXAFS, STEM-EDX and FT-IR of adsorbed CO indicated that Rh-Ir-ReO x/SiO2 catalysts showed the structure of Ir-Rh alloy particles partially covered with ReOx species. The hydrogenation activity of Rh-Ir-ReOx/SiO2 for the furan ring was higher than those of the mixture of Rh-Ir/SiO2 and Ir-ReO x/SiO2 or the mixture of Rh-ReOx/SiO 2 and Ir-ReOx/SiO2. Both Ir-Rh alloy formation and ReOx modification of alloy particles are essential for the high hydrogenation activity.
- Liu, Sibao,Amada, Yasushi,Tamura, Masazumi,Nakagawa, Yoshinao,Tomishige, Keiichi
-
-
Read Online
- Hydrogenolysis of tetrahydrofurfuryl alcohol to 1,5-pentanediol over a nickel-yttrium oxide catalyst containing ruthenium
-
A Ni-Y2O3 catalyst containing ruthenium (Ru/Ni-Y2O3) was synthesized and applied to the hydrogenolysis of tetrahydrofurfuryl alcohol (THFA) to produce 1,5-pentanediol (1,5-PeD), which showed superior catalytic performance over that of the Ni-Y2O3 catalyst itself. The optimized ruthenium-containing catalyst, which was prepared by impregnation of 1.0 wt% ruthenium in Ni-Y2O3, showed high catalytic activity for producing 1,5-PeD, giving an 86.5% yield at 93.4% conversion of THFA under 2.0 MPa of H2 at 423K after 40 h. The formation of Ru-Ni0-Y2O3 boundaries was proposed to accelerate the C-O bond scission of the tetrahydrofuran ring to give 1,5-PeD.
- Wijaya, Husni Wahyu,Hara, Takayoshi,Ichikuni, Nobuyuki,Shimazu, Shogo
-
-
Read Online
- Selective reduction of aldehydes to alcohols using alumina with a catalytic amount of base under microwave irradiation
-
Aldehydes are selectively reduced to the corresponding alcohols in very good yields with alumina containing a catalytic amount of base under microwave irradiation at 300 W for 8-15 min.
- Pradhan, Prasun K.,Jaisankar, Parasuraman,Pal, Bikash,Dey, Sumit,Giri, Venkatachalam S.
-
-
Read Online
- Insights on the One-Pot Formation of 1,5-Pentanediol from Furfural with Co?Al Spinel-based Nanoparticles as an Alternative to Noble Metal Catalysts
-
CoAl-spinel nanoparticles prepared by liquid-feed flame spray pyrolysis (L?F FSP) and activated by reduction at different temperatures were used to investigate the hydrogenation process of furfural (FA) under mild conditions. Reduction of the spinel at 500 °C resulted in high FA conversion and selectivity to furfuryl alcohol (FFA, 81 % yield, in 1 hour). Reduction at higher temperatures (i. e., 700 and 850 °C) led to the direct formation of diols (i. e., 1,5-PeD and 1,2-PeD) from FA. The differences in activity are attributed to the formation of surface metallic cobalt nanoparticles upon reduction at high temperature. A maximum of 30 % 1,5-PeD was yielded after 8 hours of reaction under the optimized conditions of150 °C, 30 bar of H2 and with 40 mg of catalyst reduced at 700 °C. This is the first report on the direct catalytic conversion of furfural to1,5-pentanediol with a non-noble metal solid catalyst.
- Gavilà,L?hde,Jokiniemi,Constanti,Medina,del Río,Tichit,álvarez
-
-
Read Online
- Hydrogenation of furfural by noble metal-free nickel modified tungsten carbide catalysts
-
Nickel-tungsten carbide catalysts convert furfural to high value products in a liquid phase catalytic reaction. The product distribution depends on the solvent and the Ni-W-ratio of the catalyst. In isopropyl alcohol a combination of Ni and WxC enables the opening of the furan ring to yield 1,2-pentanediol. Nickel accelerates the tungsten oxide reduction in the tungsten carbide catalyst synthesis and facilitates the carbon insertion. Nickel modified tungsten carbide is a promising, noble metal-free catalyst system for the upgrading of furfural based renewable resources. Its preparation is facilitated compared to unmodified tungsten carbide catalysts.
- Bretzler, Patrick,Huber, Michael,K?hler, Klaus,Nickl, Simon
-
-
Read Online
- C?O Hydrogenolysis of Tetrahydrofurfuryl Alcohol to 1,5-Pentanediol Over Bi-functional Nickel-Tungsten Catalysts
-
In this study, we report a series of bimetallic Ni?WOx catalyst for the ring-opening of THFA into 15PDO. The structure-performance relationship of the catalysts was discussed based on extensive characterization using techniques such as BET, H2-TPR, NH3-TPD, Pyr-IR, IPA-TPD-MS, XRD, XPS and EXAFS/XANES. The acidity measurements show that higher W density leads to the higher amount of acid density, which could be assigned to the creation of Lewis acid sites mainly on the surface of the calcined catalysts. H2-TPR profiles of Ni?WOx catalysts show that there is a strong interaction between Ni and W species, enhancing the reducibility of WOx. XRD measurements of calcined Ni?WOx catalysts reveal that the dispersion of Ni particles is enhanced after addition of WOx species. After reduction, different peaks corresponding to metallic Ni and WO3?x are identified for 10Ni?WOx catalysts, as well as new peak assigned to Ni?W intermetallic phase on 10Ni?30WOx catalyst. The formation of Ni?W intermetallic phase was further proved using XPS and EXAFS studies. THFA hydrogenolysis was also conducted under aqueous-phase conditions over Ni?WOx catalysts, yielding up to 47 % selectivity to 15PDO, along with a highest combined C5 polyols (i. e., 15PDO and 125PTO) selectivity of approximately 64 %. However, the Ni?WOx catalytic system suffers from deactivation process due to the hydrothermal dissolution of the active phase. Further investigation reveals the better stability of metallic tungsten and Ni?W intermetallic phase (Ni4W) against leaching since their corresponding peaks in the XRD patterns of spent catalysts remains nearly unchanged. Finally, 1,4-dioxane as an organic solvent was employed in THFA hydrogenolysis reaction, resulting in different product distribution, with a THP yield of around 54 %. The catalyst crystalline structure is preserved because of very low Ni and W leaching when 1,4-dioxane is used as solvent.
- Soghrati, Elmira,Kok Poh, Chee,Du, Yonghua,Gao, Feng,Kawi, Sibudjing,Borgna, Armando
-
-
Read Online
- Method for preparing 1, 5-pentanediol or 1, 6-hexanediol from bio-based furan compound
-
The invention discloses a method for preparing 1, 5-pentanediol or 1, 6-hexanediol by utilizing a bio-based furan compound, which comprises the following steps of: reacting the bio-based furan compound serving as a raw material for 1-48 hours in a proper solvent under the conditions of pressure of 0.5-10 MPa and temperature of 20-200 DEG C in a reducing gas atmosphere under the action of a catalyst, separating the catalyst, and distilling out the solvent to obtain the target product 1,5-pentanediol or 1, 6-hexanediol. According to the method disclosed by the invention, efficient conversion of the bio-based furan compound is realized under relatively mild and environment-friendly conditions by utilizing chemically synthesized renewable resource bio-based furan, and the produced 1, 5-pentanediol or 1, 6-hexanediol is a polymer monomer, so that the application range of the bio-based furan compound is expanded, the comprehensive utilization of the straws is further promoted, and carbon neutralization is promoted.
- -
-
Paragraph 0006; 0017; 0019
(2021/06/26)
-
- Unravelling the one-pot conversion of biomass-derived furfural and levulinic acid to 1,4-pentanediol catalysed by supported RANEY Ni-Sn alloy catalysts
-
Bimetallic Ni-Sn alloys have been recognised as promising catalysts for the transformation of furanic compounds and their derivatives into valuable chemicals. Herein, we report the utilisation of a supported bimetallic RANEY nickel-tin alloy supported on aluminium hydroxide (RNi-Sn(x)/AlOH; x is Ni/Sn molar ratio) catalysts for the one-pot conversion of biomass-derived furfural and levulinic acid to 1,4-pentanediol (1,4-PeD). The as prepared RNi-Sn(1.4)/AlOH catalyst exhibited the highest yield of 1,4-PeD (78%). The reduction of RNi-Sn(x)/AlOH with H2 at 673-873 K for 1.5 h resulted in the formation of Ni-Sn alloy phases (e.g., Ni3Sn and Ni3Sn2) and caused the transformation of aluminium hydroxide (AlOH) to amorphous alumina (AA). The RNi-Sn(1.4)/AA 673 K/H2 catalyst contained a Ni3Sn2 alloy as the major phase, which exhibited the best yield of 1,4-PeD from furfural (87%) at 433 K, H2 3.0 MPa for 12 h and from levulinic acid (up to 90%) at 503 K, H2 4.0 MPa, for 12 h. Supported RANEY Ni-Sn(1.5)/AC and three types of supported Ni-Sn(1.5) alloy (e.g., Ni-Sn(1.5)/AC, Ni-Sn(1.5)/c-AlOH, and Ni-Sn(1.5)/γ-Al2O3) catalysts afforded high yields of 1,4-PeD (65-87%) both from furfural and levulinic acid under the optimised reaction conditions.
- Ansyah, Fathur Razi,Astuti, Maria Dewi,Hara, Takayoshi,Husain, Sadang,Mustikasari, Kamilia,Rodiansono,Shimazu, Shogo
-
p. 241 - 250
(2022/01/19)
-
- Hydrodeoxygenation of C4-C6 sugar alcohols to diols or mono-alcohols with the retention of the carbon chain over a silica-supported tungsten oxide-modified platinum catalyst
-
The hydrodeoxygenation of erythritol, xylitol, and sorbitol was investigated over a Pt-WOx/SiO2 (4 wt% Pt, W/Pt = 0.25, molar ratio) catalyst. 1,4-Butanediol can be selectively produced with 51% yield (carbon based) by erythritol hydrodeoxygenation at 413 K, based on the selectivity over this catalyst toward the regioselective removal of the C-O bond in the -O-C-CH2OH structure. Because the catalyst is also active in the hydrodeoxygenation of other polyols to some extent but much less active in that of mono-alcohols, at higher temperature (453 K), mono-alcohols can be produced from sugar alcohols. A good total yield (59%) of pentanols can be obtained from xylitol, which is mainly converted to C2 + C3 products in the literature hydrogenolysis systems. It can be applied to the hydrodeoxygenation of other sugar alcohols to mono-alcohols with high yields as well, such as erythritol to butanols (74%) and sorbitol to hexanols (59%) with very small amounts of C-C bond cleavage products. The active site is suggested to be the Pt-WOx interfacial site, which is supported by the reaction and characterization results (TEM and XAFS). WOx/SiO2 selectively catalyzed the dehydration of xylitol to 1,4-anhydroxylitol, whereas Pt-WOx/SiO2 promoted the transformation of xylitol to pentanols with 1,3,5-pentanetriol as the main intermediate. Pre-calcination of the reused catalyst at 573 K is important to prevent coke formation and to improve the reusability.
- Betchaku, Mii,Cao, Ji,Liu, Lujie,Nakagawa, Yoshinao,Tamura, Masazumi,Tomishige, Keiichi,Yabushita, Mizuho
-
supporting information
p. 5665 - 5679
(2021/08/16)
-
- Synthetic method of linear dihydric alcohol
-
The invention discloses a synthetic method of linear dihydric alcohol. The synthetic method comprises the following steps: (1) carrying out hydrosilylation reaction on alpha-olefin and siloxane to obtain alkyl siloxane; (2) carrying out hydroxymethylation reaction on alkyl siloxane, organic metal alkali and a hydrogen acceptor to obtain silyl alcohol; and (3) carrying out oxidation reaction on the silyl alcohol, fluorine-containing metal salt and peroxide to obtain the linear dihydric alcohol. The method has the advantages of mild process, easily available raw material sources, no need of post-treatment after the reaction is completed, capability of being directly used for the next reaction, simplification of the process flow, high conversion rate, high selectivity, low cost and suitability for large-scale production.
- -
-
Paragraph 0111-0112; 0115-0117
(2021/09/01)
-
- Hydroformylation reaction ligand, hydroformylation catalyst and diol preparation method
-
The invention discloses a hydroformylation reaction ligand, a hydroformylation catalyst and a diol preparation method According to the invention, the structural formula of the hydroformylation reaction ligand is shown in the specification, wherein R1 and R2 are mutually independent one of H, aryl or substituted aryl, thienyl, pyrrolyl, thiazolyl, imidazolyl and pyridyl; the ligand disclosed by the invention is high in catalytic activity and good in metal active center stability, by-products of aldehyde in a conventional hydroformylation reaction can be reduced, and linear diol with a high normal/isomer ratio can be obtained by a one-step method; and the method has the advantages of simple and convenient process, low cost and energy consumption, good production safety, high product quality and the like, and is particularly suitable for large-scale industrial production.
- -
-
Paragraph 0069; 0075-0076
(2021/06/22)
-
- Hydrosilylation of Esters Catalyzed by Bisphosphine Manganese(I) Complex: Selective Transformation of Esters to Alcohols
-
Selective and efficient hydrosilylations of esters to alcohols by a well-defined manganese(I) complex with a commercially available bisphosphine ligand are described. These reactions are easy alternatives for stoichiometric hydride reduction or hydrogenation, and employing cheap, abundant, and nonprecious metal is attractive. The hydrosilylations were performed at 100 °C under solvent-free conditions with low catalyst loading. A large variety of aromatic, aliphatic, and cyclic esters bearing different functional groups were selectively converted into the corresponding alcohols in good yields.
- Bagh, Bidraha,Behera, Rakesh R.,Ghosh, Rahul,Khamari, Subrat,Panda, Surajit
-
supporting information
p. 3642 - 3648
(2020/04/20)
-
- Effective synthesis of 5-amino-1-pentanol by reductive amination of biomass-derived 2-hydroxytetrahydropyran over supported Ni catalysts
-
A highly efficient and green process was developed for the synthesis of useful 5-amino-1-pentanol (5-AP) from biomass-derived dihydropyran by coupling the in situ generation of 5-hydroxypentanal (5-HP, via the ring-opening tautomerization of 2-hydroxytetrahydropyran (2-HTHP)) and its reductive amination over supported Ni catalysts. The catalytic performances of the supported Ni catalysts on different oxides including SiO2, TiO2, ZrO2, γ-Al2O3, and MgO as well as several commercial hydrogenation catalysts were investigated. The Ni/ZrO2 catalyst presented the highest 5-AP yield. The characterization results of the oxide-supported Ni catalysts showed that the Ni/ZrO2 catalyst possessed high reducibility and a high surface acid density, which lead to the enhanced activity and selectivity of the catalyst. The effect of reaction parameters on the catalytic performance of the Ni/ZrO2 catalyst was studied, and a high 5-AP yield of 90.8% was achieved in the reductive amination of 2-HTHP aqueous solution under mild conditions of 80 °C and 2 MPa H2. The stability of the Ni/ZrO2 catalyst was studied using a continuous flow reactor, and only a slight decrease in the 5-AP yield was observed after a 90-h time-on-stream. Additionally, the reaction pathways for the reductive amination of 2-HTHP to synthesize 5-AP were proposed.
- Li, Xuemei,Tian, Junying,Liu, Hailong,Tang, Congkui,Xia, Chungu,Chen, Jing,Huang, Zhiwei
-
p. 631 - 641
(2020/01/28)
-
- Preparation method of cis-atracurium besylate
-
The invention belongs to the field of medicinal chemistry and chemical synthesis, and particularly relates to a preparation method and application of atracurium. The invention provides a synthetic method of high-purity cis-atracurium besylate. The invention also provides a preparation method of the raw material high-purity refined 1,5-pentanediol for synthesizing the high-purity atracurium. The synthesis method of cis-atracurium besylate provided by the invention has the advantages of simple method, high yield, high raw material conversion rate and high product purity, and has been used for industrial production.
- -
-
Paragraph 0045-0049
(2020/12/29)
-
- METHOD FOR PRODUCING ALCOHOL
-
PROBLEM TO BE SOLVED: To provide a method for producing selectively alcohol from carboxylic acid under mild conditions. SOLUTION: In the presence of a catalyst with M1 and M2 as metal species supported on a support, a substrate is reduced to produce a corresponding alcohol. (M1 is Rh, Pt, Ru, Ir, or Pd; M2 is Sn, V, Mo, W, or Re; the support is ZrO2, hydroxyapatite, Nb2O5, fluoroapatite, or hydrotalcite; the substrate is the formula 1a, 1b, or 1c). SELECTED DRAWING: None COPYRIGHT: (C)2020,JPO&INPIT
- -
-
Paragraph 0101-0110
(2020/11/26)
-
- Manganese catalyzed selective hydrogenation of cyclic imides to diols and amines
-
Herein we report the selective hydrogenation of cyclic imides to diols and amines, homogeneously catalyzed for the first time by a complex of an earth-abundant metal, a manganese pincer complex. A plausible catalytic cycle is proposed based on informative mechanistic experiments.
- Das, Uttam Kumar,Janes, Trevor,Kumar, Amit,Milstein, David
-
supporting information
p. 3079 - 3082
(2020/06/19)
-
- PROCESS OF PREPARATION OF 1,2-PENTANEDIOL FROM FURFURAL
-
The present invention relates to hydrogenolysis process for preparation of 1,2-pentanediol from furfural. In particular, the present invention provides a conversion of 1,2-pentanediol from furfural in presence of methanol and using a catalyst based on Rhodium on porous Manganese dioxide octahedral molecular sieve in a single step carried out at temperature range between 130 °C to 170 °C. The advantages of present invention is that it avoids formation of Intermediate-2 and directly give product 1,2-pentanediol with good selectivity over 1,5-pentanediol.
- -
-
Page/Page column 10-13
(2020/08/22)
-
- Ruthenium complexes with N-functionalized secondary amino ligands: a new class of catalysts toward efficient hydrogenation of esters
-
A series of ruthenium complexes (o-PPh2C6H4NHR)2RuCl2 (R = Me, 3; Et, 4; CH2Ph, 5) and (o-PPh2C6H4NH2)[(CH2NHR)2]RuCl2 (R = Me, 7; Et, 8; iPr, 9) modulated with mono-N-functionalized secondary amino ligands were synthesized and demonstrated as efficient catalysts in the hydrogenation of esters into alcohols. The catalytic performances of these new complexes are much better than their corresponding primary amino ligand-constituted complexes (o-PPh2C6H4NH2)2RuCl2 (2) and (o-PPh2C6H4NH2)[(CH2NH2)2]RuCl2 (6). The significant improvement is attributed to the increased electron density of the secondary amino ligand in comparison with that of the primary amino ligand.
- Fang, Xiaolong,Li, Bin,Zheng, Jianwei,Wang, Xiaoping,Zhu, Hongping,Yuan, Youzhu
-
supporting information
p. 2290 - 2294
(2019/02/19)
-
- General and Phosphine-Free Cobalt-Catalyzed Hydrogenation of Esters to Alcohols
-
Catalytic hydrogenation of esters is essential for the sustainable production of alcohols in organic synthesis and chemical industry. Herein, we describe the first non-noble metal catalytic system that enables an efficient hydrogenation of non-activated esters to alcohols in the absence of phosphine ligands (with a maximum turnover number of 2391). The general applicability of this protocol was demonstrated by the high-yielding hydrogenation of 39 ester substrates including aromatic/aliphatic esters, lactones, polyesters and various pharmaceutical molecules.
- Shao, Zhihui,Zhong, Rui,Ferraccioli, Raffaella,Li, Yibiao,Liu, Qiang
-
supporting information
p. 1125 - 1130
(2019/10/22)
-
- Hydro-Oxygenation of Furfural in the Presence of Ruthenium Catalysts Based on Al-HMS Mesoporous Support
-
Ru-containing catalyst based on an Al-HMS mesoporous aluminosilicate was synthesized. The mesoporous support and the catalyst on its basis were characterized by the methods of low-temperature desorption/adsorption of nitrogen, temperature-programmed desorption of ammonia, transmission electron microscopy, X-ray photoelectron microscopy, and energy-dispersive X-ray fluorescence analysis. The synthesized catalyst was investigated in the hydrodeoxygenation of the model compound of bio-oil, furfural, in the presence of H2O. The reaction was carried out at initial hydrogen pressures of 1–7 MPa at 200°C–300°C temperature range. The results revealed that the synthesized catalyst displayed a high activity in the hydrotransformation of furfural. The conversion was 100% in 1 hr at a 5 MPa hydrogen pressure and 200°C.
- Roldugina,Shayakhmetov,Maksimov,Karakhanov
-
p. 1306 - 1315
(2019/11/03)
-
- Base-Free Iron Catalyzed Transfer Hydrogenation of Esters Using EtOH as Hydrogen Source
-
Herein, we report on the use of the iron pincer complex Iron-MACHO-BH, in the base-free transfer hydrogenation of esters with EtOH as a hydrogen source. More than 20 substrates including aromatic and aliphatic esters and lactones were reduced affording the desired primary alcohols and diols with moderate to excellent isolated yields. It is also possible to reduce polyesters to the diols with this method, enabling a novel way of plastic recycling. Reduction of the renewable substrate methyl levulinate proceeds to form 1,4-pentanediol directly. The yields are largely governed by the equilibrium between the alcohol and the ethyl ester.
- Farrar-Tobar, Ronald A.,Wozniak, Bartosz,Savini, Arianna,Hinze, Sandra,Tin, Sergey,de Vries, Johannes G.
-
supporting information
p. 1129 - 1133
(2019/01/04)
-
- A Dinuclear Dysprosium Complex as an Air-Stable and Recyclable Catalyst: Applications in the Deacetylation of Carbohydrate, Aliphatic, and Aromatic Molecules
-
Two dinuclear DyIII complexes, [Dy2(hmb)2(OTf)2(H2O)4]?HOTf?2 THF (A?HOTf?2 THF) and [Dy2(hmi)3(H2O)2]?2 HOTf (B?2 HOTf), have been synthesized by the reaction of Dy(OTf)3 and the Schiff-base ligands H2hmb (N′-(2-hydroxy-3-methoxybenzylidene)benzohydrazide) or H2hmi ((2-hydroxy-3-methoxyphenyl)methylene isonicotinohydrazine). Disarmed glycosyl trichloroacetimidates can be activated by complex A in the synthesis of 1,2-trans-glycosides with primary and secondary acceptors. This method offers an efficient route to selectively deacetylated monosaccharides and disaccharides in high yields and a green catalyst that can be easily recycled and reused.
- Chiu, Ting-Yu,Chin, Wei,Guo, Jiun-Rung,Liang, Chien-Fu,Lin, Po-Heng
-
supporting information
p. 627 - 633
(2019/02/09)
-
- Metal complex and preparation method and application thereof
-
The invention discloses a post-transition metal bisphosphine diamine complex catalyst which is good in substrate applicability, and capable of efficiently catalyzing a hydrogenation alcohol productionreaction of various carbonyl derivatives such as esters, amides and carbonates different in structure. Central metal coordination of the metal complex catalyst has two diaminodiphosphine ligands o-PPh2C6H4NR1R2 and Ph2PCH2CH2NR3R4 (or o-PPh2C6H4CH2NR3R4, Ph2P(CH2) 3NR3R4) different in structure, and the metal complex can be obtained through a simple two-step synthesis method. The catalysts show the advantages of the two ligands in the catalytic hydrogenation process, and the defects of a complex catalyst formed by a single ligand in the aspect of applicability of substrates can be effectivelyovercome.
- -
-
Paragraph 0034; 0049; 0052
(2019/06/07)
-
- Metal complex catalyst as well as preparation method and application thereof (by machine translation)
-
The invention provides a phosphine amine, diamine ligand transition metal complex catalyst containing a secondary amine functional group and a preparation method and application, and relates to a carbonyl derivative molecular hydrogenation alcohol metal complex catalyst capable of efficiently catalyzing ester, aldehyde, ketone and the like under the condition of lower additive usage. O-PPh coordinated with catalyst metal center2 C6 H4 NHR1 Ligands and o-PPh2 C6 H4 NHR2 Ligands or o-PPh2 C6 H4 NHR1 Ligands and R2 HNNCH2 CH2 NHR3 Ligands, which can be prepared by a simple two-step synthesis method. In the process of participating in the catalytic hydrogenation reaction, only a small amount of auxiliary "base" is needed to obtain excellent catalytic hydrogenation performance, and the defect. (by machine translation)
- -
-
Paragraph 0038; 0077
(2019/07/29)
-
- Production of 1,5-pentanediol via upgrading of tetrahydrofurfuryl alcohol
-
A method of making 1,5-pentanediol from tetrahydrofurfural alcohol. The method includes the steps of dehydrating tetrahydrofurfural alcohol (THFA) to dihydropyran (DHP); hydrating at least a portion of the DHP to 2-hydroxy-tetrahydropyran (2-HY-THP) in the presence of a solid acid catalyst; and hydrogenating at least a portion of the 2-HY-THP to 1,5-pentanediol. The method can be conducted entirely in the absence of noble metal catalysts.
- -
-
-
- CATALYST AND PROCESS FOR THE PRODUCTION OF 1,5-PENTANEDIOL
-
The present invention relates generally to select rhodium-rhenium (Rh-Re) or iridium-rhenium (Ir-Re) catalysts and their use in processes for the catalytic hydrogenolysis of tetrahydrofurfuryl alcohol (THFA) to 1,5-pentanediol.
- -
-
Paragraph 0091-0093
(2019/01/05)
-
- Preparation method of alcohol compound
-
The invention discloses a preparation method of an alcohol compound. The preparation method is characterized by carrying out ring opening under combined action of an esterifying agent, lewis acid anda hydrogenation catalyst by taking a furan derivative as a raw material, thus obtaining an ester intermediate; further saponifying, thus obtaining the alcohol compound. According to the preparation method disclosed by the invention, the product selectivity is high, byproducts are few, the yield is high, the purity is good, product separation is convenient, and the technology is simple.
- -
-
Paragraph 0050; 0054; 0056; 0062; 0064; 0065; 0066; 0068
(2018/09/20)
-
- Selective hydrogenolysis of furfuryl alcohol to 1,5- and 1,2-pentanediol over Cu-LaCoO3 catalysts with balanced Cu0-CoO sites
-
Selective hydrogenolysis of biomass-derived furfuryl alcohol (FFA) to 1,5- and 1,2-pentanediol (PeD) was conducted over Cu-LaCoO3 catalysts with different Cu loadings; the catalysts were derived from perovskite structures prepared by a one-step citrate complexing method. The catalytic performances of the Cu-LaCoO3 catalysts were found to depend on the Cu loading and pretreatment conditions. The catalyst with 10 wt% Cu loading exhibited the best catalytic performance after prereduction in 5%H2-95%N2, achieving a high FFA conversion of 100% and selectivity of 55.5% for 1,5-pentanediol (40.3%) and 1,2-pentanediol (15.2%) at 413 K and 6 MPa H2. This catalyst could be reused four times without a loss of FFA conversion but it resulted in a slight decrease in pentanediol selectivity. Correlation between the structural changes in the catalysts at different states and the simultaneous variation in the catalytic performance revealed that cooperative catalysis between Cu0 and CoO promoted the hydrogenolysis of FFA to PeDs, especially to 1,5-PeD, while Co0 promoted the hydrogenation of FFA to tetrahydrofurfuryl alcohol (THFA). Therefore, it is suggested that a synergetic effect between balanced Cu0 and CoO sites plays a critical role in achieving a high yield of PeDs with a high 1,5-/1,2-pentanediol selectivity ratio during FFA hydrogenolysis.
- Gao, Fangfang,Liu, Hailong,Hu, Xun,Chen, Jing,Huang, Zhiwei,Xia, Chungu
-
p. 1711 - 1723
(2018/08/21)
-
- Selective Hydrogenation of Cyclic Imides to Diols and Amines and Its Application in the Development of a Liquid Organic Hydrogen Carrier
-
Direct hydrogenation of a broad variety of cyclic imides to diols and amines using a ruthenium catalyst is reported here. We have applied this strategy toward the development of a new liquid organic hydrogen carrier system based on the hydrogenation of bis-cyclic imide that is formed by the dehydrogenative coupling of 1,4-butanediol and ethylenediamine using a new ruthenium catalyst. The rechargeable system has a maximum gravimetric hydrogen storage capacity of 6.66 wt%.
- Kumar, Amit,Janes, Trevor,Espinosa-Jalapa, Noel Angel,Milstein, David
-
supporting information
p. 7453 - 7457
(2018/06/08)
-
- PHENANTHROLINE BASED PINCER COMPLEXES USEFUL AS CATALYSTS FOR THE PREPARATION OF METHANOL FROM CARBONDIOXIDE
-
The present invention relates to a novel phenonthroline based pincer complexes and process for preparation thereof. The present invention also provides a one pot process for the conversion of carbon dioxide to methanol in the presence of a molecularly defined pincer-type single-site Ru-catalyst and secondary amine. Further the present invention provides the use of phenonthroline based pincer complexes for the esterification of alcohols and hydrogenation of esters under mild conditions.
- -
-
Paragraph 0134
(2018/04/02)
-
- Synergetic Catalysis of Bimetallic CuCo Nanocomposites for Selective Hydrogenation of Bioderived Esters
-
Bimetallic catalysts based on nonprecious transition metals have attracted increasing attention because of their unique synergistic effects in catalytic reactions, but the understanding of the nature of synergistic effects and their roles in a specific hydrogenation reaction remains lacking. Herein, a series of bimetallic CuxCoy/Al2O3 (x/y = 5:1, 2:1, 1:1, 1:2, 1:5) nanocomposite catalysts were fabricated via the successive calcination and reductive activation process of layered double hydroxide precursors. Their catalytic performance in the selective hydrogenation of bioderived ethyl levulinate to 1,4-pentanediol (1,4-PeD) depended sensitively on the chemical composition of bimetallic CuCo catalysts. The optimal bimetallic Cu2Co1/Al2O3 catalyst exhibited markedly improved catalytic activity and selectivity compared to monometallic Cu/Al2O3, as confirmed by its lower apparent activation energy barrier of 65.1 kJ mol-1 of the rate-determining step and its high selectivity of 93% to 1,4-PeD. Detailed characterization analyses and intrinsic catalytic studies revealed that the presence of CoOx species in the bimetallic CuxCoy/Al2O3 catalysts enhanced the metallic Cu dispersion and H2 activation ability. More importantly, the strong electronic interaction at the interface of Cu and adjacent CoOx species modified the chemical states of Cu species to create proper surface Cu0/Cu+ distributions and, particularly, provided synergic catalysis sites of Cu and electron-deficient CoOx species, which was primarily responsible for the excellent catalytic performance of bimetallic CuCo catalysts. The bimetallic CuCo catalysts exhibited good stability in both batch and fixed-bed continuous flow reactions. Furthermore, present CuCo nanocomposite catalyst could be applied to the highly selective hydrogenation of other carboxylic esters and lactones to synthesize valuable C4, C5, and C6 diols.
- Wu, Jun,Gao, Guang,Sun, Peng,Long, Xiangdong,Li, Fuwei
-
p. 7890 - 7901
(2017/11/10)
-
- PRODUCTION OF 1,5-PENTANEDIOL VIA UPGRADING OF TETRAHYDROFUFURYL ALCOHOL
-
A method of making 1,5-pentanediol from tetrahydrofurfural alcohol. The method includes the steps of dehydrating tetrahydrofurfural alcohol (THFA) to dihydropyran (DHP); hydrating at least a portion of the DHP to 2-hydroxy-tetrahydropyran (2-HY-THP) in the absence of homogeneous acid; and hydrogenating at least a portion of the 2-HY-THP to 1,5-pentanediol. The method can be conducted entirely in the absence of noble metal catalysts.
- -
-
Paragraph 0074; 0075; 0076; 0077
(2017/09/05)
-
- 1, 2 - pentanediol manufacturing method
-
PROBLEM TO BE SOLVED: To provide a method for selectively obtaining 1,2-pentane diol in a high yield from furfural, obtained by mainly using non-edible parts of biomass as raw material.SOLUTION: A method for producing 1,2-pentane diol is characterized by obtaining 1,2-pentane diol by subjecting furfural to hydrogenolysis in the presence of a catalyst, obtained by supporting zero-valent platinum on hydrotalcite, and hydrogen. The hydrogenolysis reaction is preferably carried out in the presence of an alcoholic solvent and/or an ether-based solvent.
- -
-
Paragraph 0044; 0045
(2017/08/02)
-
- CATALYTIC HYDROGENATION PROCESS FOR THE SYNTHESIS OF TERMINAL DIOLS FROM TERMINAL DIALKYL ALIPHATIC ESTERS
-
A phosphorus ligand-free, mild, efficient and complete catalytic hydrogenation process is for the sustainable production of terminal diols from renewable terminal dialkyl esters with improved yield. Soluble, phosphorus ligand free Ru (II)-pincer type complexes can be used as catalysts in the hydrogenation process.
- -
-
Paragraph 0067; 0068; 0069
(2018/01/09)
-
- Coordination Chemistry of an Unsymmetrical Naphthyridine-Based Tetradentate Ligand toward Various Transition-Metal Ions
-
An unsymmetrical ligand, 2-(2-pyridinyl)-7-(pyrazol-1-yl)-1,8-naphthyridine (L5) was prepared for the construction of a series of dinuclear complexes. Treatment of L5with [Ru2(μ-OAc)4Cl] followed by anion metathesis afforded [(L5)(μ-OAc)3Ru2](PF6) (3). Reaction of L5with 2 equiv. of Ni(OAc)2provided [Ni4(L5)2(μ-OH)4(CF3COO)2](CF3COO)2(5). Reaction of [Re2(CO)8(CH3CN)2] with L5in a refluxing chlorobenzene solution gave a mixture of dirhenium (6) and monorhenium (7) complexes. The monocobalt complex 8 was obtained from complexation of L5with CoCl2. These new complexes were characterized by elemental analysis and spectroscopic techniques. The structures of complexes 3, 5 and 8 were further confirmed by X-ray crystallography. Nickel complex 5 was evaluated as a catalyst for reduction reactions involving the conversion of ester functionalities into their corresponding alcohols.
- Tsai, Bing-Chen,Liu, Yi-Hung,Peng, Shie-Ming,Liu, Shiuh-Tzung
-
p. 2783 - 2790
(2016/07/11)
-
- Method of producing hydroxyacid
-
PROBLEM TO BE SOLVED: To provide a hydrogenolysis catalyst applicable for industrial production, which affords a hydroxy compound from an ether compound having a hydroxymethyl group at a high reaction rate with a good yield and high selectivity.SOLUTION: There is provided a process for producing a hydroxy compound, comprising hydrogenolysis of an ether compound containing a hydroxymethyl group in the presence of an amine compound, the hydrogenolysis being carried out under presence of a hydrogen source using a catalyst obtained by mixing at least one metal compound selected from the group consisting of (A) metal compounds containing any of metals of Group 3 to Group 11 of the Periodic Table, (B) metal oxides containing a metal of either Group 5, Group 6 or Group 7 of the Periodic Table, and (C) high-valence metal compounds containing any of metals of Group 8 or Group 11 of the Periodic Table, followed by a reduction treatment of the obtained mixture.
- -
-
Paragraph 0071-0081; 0083-0085; 0087-0089; 0090; 0091
(2019/05/28)
-
- METHOD FOR CONTINUOUSLY PRODUCING ORGANIC COMPOUND BY HYDROGENATION RING-OPENING REACTION OF CYCLIC ETHER
-
PROBLEM TO BE SOLVED: To provide a method for producing an objective organic compound by a hydrogenation ring-opening reaction of cyclic ether efficiently and continuously over a long period of time. SOLUTION: The method for continuously producing the organic compound comprises a step of performing the hydrogenation ring-opening reaction of cyclic ether in the presence of a hydrogenation catalyst by using an irrigated packed bed reactor. A porous substance is disposed in the irrigated packed bed reactor in addition to the hydrogenation catalyst. SELECTED DRAWING: None COPYRIGHT: (C)2016,JPOandINPIT
- -
-
Paragraph 0035; 0039
(2017/07/01)
-
- Preparing a chain carbonate to produce the process system and method (by machine translation)
-
The present invention provides a preparation chain carbonate and method for co-production of dihydric alcohol, the epoxide as the starting material, including: S1 : the dilution and after preheating with epoxides CO 2 reaction crude generating cyclic carbonates; S2 : the step S1 is part of the cyclic carbonic acid ester thick return to step S1 in order to dilute and preheating step S1 to be in the reaction of the epoxide, the remaining cyclic carbonate crude to carry on the refining and purifying; S3 : after the refining and purifying of the cyclic carbonate with fatty alcohol ester exchange reaction to obtain a chain carbonate and dihydric alcohol, refining and purifying is obtained separately. The invention also provides a preparation chain carbonate and dihydric alcohol process system. The present invention provides a method of synthesizing the continuity of the process system and is strong, the production is stable and reliable, the reaction time is short, the safety is good, high product yield, purity is good, the economic benefits are obvious, can further expand the scale industrial production of chain carbonic acid ester. (by machine translation)
- -
-
Paragraph 0051; 0052
(2017/04/03)
-
- Hydrogenation of dicarboxylic acids to diols over Re-Pd catalysts
-
A Re-Pd/SiO2 (Re/Pd = 8) catalyst was applied to hydrogenation of dicarboxylic acids (succinic acid, glutaric acid and adipic acid) to diols. In the hydrogenation of dicarboxylic acids, ex situ liquid-phase (in only 1,4-dioxane solvent) reduced Re-Pd/SiO2 showed much higher activity than in situ liquid-phase (in the mixture of dicarboxylic acid and 1,4-dioxane) and gas-phase reduced ones, in which the in situ liquid-phase reduced catalyst has been reported to show good activity in the hydrogenation of monocarboxylic acids. High diol yields (71-89%) were achieved in the hydrogenation of dicarboxylic acids on the ex situ liquid-phase reduced catalyst at 413 K. Lactones and hydroxycarboxylic acids were first formed as intermediates in the reaction of C4-C5 and ≥C6 dicarboxylic acids, respectively. Characterization using XRD, XPS and XAS indicates that ex situ liquid-phase reduced catalysts with high activity contains comparable amounts of Re0 and Ren+ species, both of which have been reported to be necessary for good performance. The amount of Ren+ species on the in situ liquid-phase reduced catalysts is much larger than that of surface Re0 species. This result suggests that the presence of dicarboxylic acids suppresses the reduction of Re species to Re0 on the calcined catalysts while that of monocarboxylic acids does not, which leads to the low activity in the hydrogenation of dicarboxylic acids on in situ liquid-phase reduced catalysts.
- Takeda, Yasuyuki,Tamura, Masazumi,Nakagawa, Yoshinao,Okumura, Kazu,Tomishige, Keiichi
-
p. 5668 - 5683
(2016/07/21)
-
- Selective hydrogenolysis of biomass-derived furfuryl alcohol into 1,2- and 1,5-pentanediol over highly dispersed Cu-Al2O3 catalysts
-
Cu nanoparticles supported on a variety of oxide supports, including SiO2, TiO2, ZrO2, Al2O3, MgO and ZnO, were investigated for the hydrogenolysis of biomass-derived furfuryl alcohol to 1,2-pentanediol and 1,5-pentanediol. A Cu-Al2O3 catalyst with 10 wt% Cu loading prepared by a co-precipitation method exhibited the best performance in terms of producing pentanediols compared with the other materials. This catalyst generated an 85.8% conversion and a 70.3% combined selectivity for the target pentanediols at 413 K and 8 MPa H2 over an 8-h reaction. The catalyst could also be recycled over repeated reaction trials without any significant decrease in productivity. Characterizations with X-ray diffraction, NH3/CO2-temperature programmed desorption, N2 adsorption, transmission electron microscopy and N2O chemisorption demonstrated that intimate and effective interactions between Cu particles and the acidic Al2O3 support in this material greatly enhanced its activity and selectivity. The promotion of the hydrogenolysis reaction was found to be especially sensitive to the Cu particle size, and the catalyst with Cu particles 1.9 to 2.4 nm in size showed the highest turnover frequency during the synthesis of pentanediols.
- Liu, Hailong,Huang, Zhiwei,Kang, Haixiao,Xia, Chungu,Chen, Jing
-
p. 700 - 710
(2016/05/19)
-
- METHOD FOR PRODUCING DIOL COMPOUND
-
PROBLEM TO BE SOLVED: To provide a catalyst which enables a diol compound to be highly selectively produced from a cyclic ester compound at high reaction rate and with high yield and which is applicable to industrial production and a method for producing the catalyst, and to provided a method for producing a diol compound, which enables the diol compound to be highly selectively produced at high reaction rate and with high yield by using the catalyst and which is applicable to industrial production. SOLUTION: The method for producing a diol compound is provided in which a cyclic ester compound is contacted with a catalyst in the presence of a hydrogen source. The catalyst is obtained by mixing: (A) at least two kinds of metallic compounds selected from a group consisting of rhodium, iridium, platinum, ruthenium, tantalum, rhenium, palladium, lanthanum, cerium, samarium, ytterbium, lutetium, zirconium, hafnium, niobium, molybdenum, tungsten, cobalt, nickel, copper and gold; and (B1) metal oxide or (B2) a metal carbonyl compound containing metals the Group 5, Group 6 or Group 7 in the periodic table and reducing the resultant mixture. COPYRIGHT: (C)2015,JPOandINPIT
- -
-
Paragraph 0065; 0069-0071; 0097-0098
(2018/11/03)
-
- Method of producing
-
PROBLEM TO BE SOLVED: To provide a method for producing a diol compound such as 1,5-pentanediol and 1,6-hexanediol, which is useful as a polymer raw material such as polyester and polycarbonate, a resin additive, a raw material for an intermediate of medical, agricultural or pharmaceutical chemicals, various solvents and the like, by using an industrially inexpensive raw material through an easy process with high selectivity.SOLUTION: A reaction catalyst is provided, comprising a first metal compound containing iridium and a second metal compound containing at least one kind of metal selected from the group consisting of rhenium, molybdenum and vanadium. The method for producing a diol compound comprises allowing hydrogen to react with a cyclic ether compound containing a hydroxyl methyl group expressed by general formula (1) in the presence of the above reaction catalyst. In general formula (1), R represents a hydrogen atom or a 1-5C hydrocarbon group; and Z represents a substituent having a methylene (-CH-) group.
- -
-
Paragraph 0080; 0083; 0084; 0085; 0088; 0089; 0090; 0091
(2016/10/10)
-
- METHOD FOR PRODUCING POLYOL COMPOUND
-
PROBLEM TO BE SOLVED: To provide a method for producing a polyol compound, in which method a catalyst, that can allow the polyol compound to be produced from a furan compound having a hydroxymethyl group or a formyl group at a high reaction rate, in high yield and with high selectivity and can be applied to industrial production, is used so that the polyol compound can be produced at the high reaction rate, in high yield and with high selectivity and which method can also be applied to industrial production. SOLUTION: The method for producing the polyol compound comprises the steps of: mixing a metal compound (A) containing at least one of metals belonging to group 3 to group 11 in the periodical table, a compound (B) containing at least one selected from the group consisting of oxidized ruthenium compounds (B1) and high-valent compounds (B2) each containing at least one of metals belonging to group 8 to group 11 in the periodical table, and a metal oxide (C) containing a metal of group 5, group 6 or group 7 in the periodic table; reducing an obtained mixture to obtain the catalyst for hydrocracking; bringing the furan compound into contact with the obtained catalyst for hydrocracking in the presence of a hydrogen source under a basic condition to obtain the polyol compound. COPYRIGHT: (C)2015,JPO&INPIT
- -
-
Paragraph 0065-0067; 0073
(2016/12/16)
-
- Due to the reduction of alcohol ether bond by hydrogenation synthesis (by machine translation)
-
PROBLEM TO BE SOLVED: To provide a synthetic method for alcohols by the reduction of an ether bond by a hydrogenation reaction. SOLUTION: There is provided a method of manufacturing alcohol by the reduction reaction of an ether compound by using, as a reaction medium, carbon dioxide having a pressure of normal pressure (0.1 MPa) or more and 20 MPa or less and a temperature of 32°C or more and 200°C or less and containing 0 mol% or more and 1,000 mol% or less of water with respect to the amount of carbon dioxide, using, as a catalyst, a solid catalyst containing mesoporous silica carrying nanoparticles composed of at least one of palladium and rhodium as a carrier, and using, as a reducing agent, hydrogen whose pressure is 0.1 MPa or more and 10 MPa or less. There is provided a new technology/new product relating to alcohol synthesis by the reduction of an ether bond for directly synthesizing an alcohol by cleaving the ether bond, which is difficult in a conventional manner, by a reduction reaction by hydrogen. COPYRIGHT: (C)2013,JPO&INPIT
- -
-
Paragraph 0023-0025
(2016/12/22)
-
