MPa H2 Research Articles

Reversible hydrogenation of AB2-type Zr–Mg–Ni–V based hydrogen storage alloys

The development of hydrogen energy is hindered by the lack of high-efficiency hydrogen storage materials. To explore new high-capacity hydrogen storage alloys, reversible hydrogen storage in AB2-type alloy is realized by using A or B-side elemental substitution. The substitution of small atomic-radius element Zr and Mg on A-side of YNi2 and partial substitution of large atomic-radius element V on B-side of YNi2 alloy was investigated in this study. The obtained ZrMgNi4, ZrMgNi3V, and ZrMgNi2V2 alloys remained single Laves phase structure at as-annealed, hydrogenated and dehydrogenated states, indicating that the hydrogen-induced amorphization and disproportionation was eliminated. From ZrMgNi4 to ZrMgNi2V2 with the increase of the degree of vanadium substitution, the reversible hydrogen storage capacity increased from 0.6 ​wt% (0.35H/M) to 1.8 ​wt% (1.0H/M), meanwhile the lattice stability gradually increased. The ZrMgNi2V2 alloy could absorb 1.8 ​wt% hydrogen in about 2 ​h ​at 300 ​K under 4 ​MPa H2 pressure and reversibly desorb the absorbed hydrogen in approximately 30 ​min ​at 473 ​K without complicated activation process. The prominent properties of ZrMgNi2V2 elucidate its high potential for hydrogen storage application.

Coupling of nanoconfinement with metallic catalysis in supported NaAlH4 for low-temperature hydrogen storage

Realizing of near room-temperature hydrogen storage in complex hydrides is the key challenge for its practical application. Here, we demonstrate a synergy strategy of confinement and metallic catalysis to enable NaAlH4 desorption close to 100 °C for the first time. As a platform for exerting the synergy effect, the Raney Ni with pore size of ~3 nm is prepared by alkali-etching and then the NaAlH4 is loaded into it via wet impregnation (denoted as NaAlH4/Raney Ni). The hydrogen desorption of NaAlH4/Raney Ni (1:4 in mass ratio) shows one step feature that starts at around 85 °C and completes at approximately 260 °C with an apparent activation energy of as low as ~20 kJ mol−1. Moreover, the dehydrogenated products of NaH + Al can readily regenerate back to NaAlH4 at 150 °C, 7 MPa H2 pressure. More importantly, the absorbed hydrogen can release again at temperature as low as 70 °C upon second dehydrogenation. These remarkable enhancements should be ascribed to both shorter diffusion routes by confining in nanoporous supports and more catalytic sites of metallic Ni, which provides an effective route to improve the hydrogen storage properties of complex hydrides by nanoporous metal supports.

A promoter effect on hydrodeoxygenation reactions of oleic acid by zeolite beta catalysts

In this study, various metal-modified zeolite beta-based catalysts such as La(10)zeo(90), Co(10)zeo(90), Fe(10)zeo(90), Mg(10)zeo(90), Mn(10)zeo(90) and Zn(10)zeo(90) were investigated in the hydrodeoxygenation (HDO) of oleic acid (OA) to produce renewable diesel. The La(10)zeo(90) catalyst showed a conversion of OA up to 99 % with 83 % C15 and C17 selectivity after the reaction at 350 °C for 2 h under 4 MPa H2 pressure. The superior activity of La(10)zeo(90) was attributed to the synergistic interaction between La-Si-Al, a sufficient amount of weak + medium acid sites and excellent textural properties (large pore diameter). Larger pore diameter of La(10)zeo(90) is highly desirable as it will generate greater diffusion of bulky molecules, thereby improving the accessibility of the reactant and hence excellent catalytic activity. The vacuum distillation was used to purify the crude liquid product (CLP), producing high-quality diesel fractions mainly comprising C14, C15, and C17 fractions.

Mechanistic studies and kinetics of the desulfurization of 2-phenylcyclohexanethiol over sulfided Mo, Ni-Mo, and Co-Mo on γ-Al2O3

The desulfurization of 2-phenylcyclohexanethiol (2-PCHT) was studied over sulfided Mo/γ-Al2O3, Ni-Mo/γ-Al2O3, and Co-Mo/γ-Al2O3 catalysts under 5.0 MPa H2 or Ar at 240 °C. Under H2, the desulfurization of 2-PCHT proceeded mainly through the hydrogenolysis and β-elimination pathways. The former was faster than the latter over Mo/γ-Al2O3. Ni and Co accelerated the β-elimination pathway but hardly affected the hydrogenolysis pathway. The activity of Mo/γ-Al2O3 was enhanced by Ni, whereas Co did not show any promoting effect. Under Ar, the desulfurization of 2-PCHT occurred mainly through the β-elimination and dehydrogenation pathways. The β-elimination pathway was faster than the dehydrogenation pathway. Both pathways were enhanced by Ni and Co. Ni and Co promoted the dehydrogenation pathway mainly by promoting the dehydrogenation-ring closure reaction. The inhibiting effects of piperidine depended on the reaction and catalyst. Under Ar, Ni-Mo/γ-Al2O3 was more sensitive to piperidine inhibition.

H2 In Situ Inducing Strategy on Pt Surface Segregation Over Low Pt Doped PtNi5 Nanoalloy with Superhigh Alkaline HER Activity

AbstractSurface segregation constitutes an efficient approach to enhance the alkaline hydrogen evolution reaction (HER) activity of bimetallic PtxNiy nanoalloys. Herein, a new strategy is proposed by utilizing the small gas molecule of H2 as the structure directing agent (SDA) to in situ induce Pt surface segregations over a series of PtNi5‐n samples with extremely low Pt doping (Pt/Ni = 0.2). Impressively, the sample of PtNi5‐0.3 synthesized under 0.3 MPa H2 delivers an extremely low overpotential of 26.8 mV (−10 mA cm−2) and Tafel slope of 19.2 mV dec−1, which is superior to most of the previously reported PtxNiy electrocatalysts. This is substantially related to the strong H2 in situ inducing effect to generate Pt‐rich@Ni‐rich core‐shell nanostructure of PtNi5‐0.3 with an ultrahigh Pt surface content of 46%. The specific mechanistic effects of H2 during the PtNi5‐n synthesis process are well illustrated based on the combined experimental and theoretical studies. The density functional theory mechanism simulations further unravel that the evolved active site of PtNi5‐n can efficiently reduce the reaction Gibbs free energies; especially for the scenario of PtNi5‐0.3, the downward‐shifted d band center of the Pt active site significantly reduces the PtH bond strength, eventually resulting in the lowest absolute value of ΔGH.

Furfural hydrogenation to 2‐methylfuran over efficient sol‐gel copper‐cobalt/zirconia catalyst

Abstract2‐Methylfuran (MF) is a candidate to be a high‐quality fuel additive. For the first time, efficient Co‐Cu/ZrO2 catalysts were prepared by the sol‐gel method and herein used for MF synthesis from furfural. Although a 9.2% MF yield and no MF was obtained using Cu/ZrO2 and Co/ZrO2, respectively, a 77.5% MF yield was observed at 200°C, under 1.5 MPa initial H2 pressure for 4 hours using a Co‐Cu/ZrO2 catalyst. The Co amount was changed in the catalyst structure and the effect of the Co amount on furfural hydrogenation was investigated. The most effective catalyst was the Co‐Cu/ZrO2 catalyst, with 0.08 g/g (8 mass%) Cu and 0.118 g/g (11.8 mass%) Co. The activity tests of the catalysts were carried out for hydrogenation of furfural to MF by changing reaction parameters such as pressure, loading of catalyst, temperature, and time. A 94.1% MF yield was achieved in the presence of the Co‐Cu/ZrO2 catalyst with 0.08 g/g (8 mass%) Cu and 0.118 g/g (11.8 mass%) Co at 200°C for 6 hours under 1.5 MPa H2 pressure. The catalyst also showed good reusability properties after the fifth use. The catalysts were characterized by Brunauer‐Emmet‐Teller method, X‐ray diffraction, X‐ray photoelectron spectroscopy, and temperature programmed reduction techniques.

Structure and activity of unsupported NiWS2 catalysts for slurry phase hydrocracking of vacuum residue: XAFS studies

The catalytic activities of the dispersed NixW(1−x)S2 catalysts were investigated for hydrocracking (HCK) of vacuum residue (VR) at 693 K, 9.5 MPa H2 with the same amount of catalyst loading of 0.113 mmol as a metal basis. The catalysts were prepared in situ in the reaction using nickel acetylacetonate and tungsten hexacarbonyl as Ni and W precursors, respectively. Structural properties of the dispersed catalysts were characterized by extended X-ray absorption fine structure and transmission electron microscopy, which confirmed the formation of a well-dispersed NixW(1−x)S2 phase in the size range 8–10 nm. Moreover, it was demonstrated that the bimetallic metal sulfides of NixW(1−x)S2 feature promotional activity in the VR HCK, showing higher turnover frequency values and less coke formation in VR HCK than monometal sulfides.

The influence of pore structures and Lewis acid sites on selective hydrogenolysis of guaiacol to benzene over Ru/TS-1

Here, we report a Ru/TS-1 catalyst for selective hydrogenolysis of guaiacol to benzene in the aqueous phase at conditions of 240 °C and 0.2 MPa H2, achieving a benzene yield of 86% with a hydrogenolysis rate of 103.1 mmol g−1 h−1. It was found that Silicalite-1 (MFI type) with suitable pore sizes supported Ru nanoparticles (NPs) favored for hydrogenolysis of guaiacol, whereas de-aluminated Ru/HBEA, Ru/HY and Ru/MWW (without acidic sites) accelerated the parallel reactions of hydrogenation of aromatics. In addition, Ru NPs located at the orifice of Silicalite-1 was proved to be more electron-deficient and active than Ru NPs on the outer surface, as evidenced by CO-IR characterization and activity tests on Ru/Silicalite-1 (with and without templates). Moreover, Brønsted acid sites (BAS) on Ru/MFI highly promoted the hydrogenation rates of aromatics, while Lewis acid sites (LAS) on Ru/TS-1 and Ru/MFI led to a linear increase of guaiacol hydrogenolysis rate to benzene, probably due to the enhanced absorbance capability of guaiacol and phenol on the LAS of MFI. Thus, pore structure properties of MFI coupled with abundant LAS (TS-1) as well as Ru NPs on the orifice of pores of TS-1 construct a promising catalyst for achieving efficient aromatic hydrocarbons from selective hydrogenolysis of lignin.

Ruthenium Nanoparticles Intercalated in Montmorillonite (nano-Ru@MMT) Is Highly Efficient Catalyst for the Selective Hydrogenation of 2-Furaldehyde in Benign Aqueous Medium

Chemoselective hydrogenation of 2-furaldehyde to furfuryl alcohol using green solvents is an important research area to get eco-friendly fuels and fine chemicals. Herein, we report ruthenium nanoparticles (~1.8 nm) intercalated in montmorillonite as an efficient catalytic system, which can selectively hydrogenate 2-furaldehyde in a benign aqueous medium. The complete conversion was observed at 40 °C with 1 MPa H2, the selectivity of furfuryl alcohol being >99%, and turnover number 1165. After a catalytic run, the montmorillonite-supported ruthenium nanoparticles can be recycled and reused without losing their activity and selectivity.

Hydrodeoxygenation of fatty acid methyl esters and simultaneous products isomerization over bimetallic Ni‐Co / SAPO ‐11 catalysts

Bimetallic Ni-Co/SAPO-11 catalysts were prepared and investigated for hydrodeoxygenation (HDO) of fatty acid methyl esters (FAMEs) and sequential isomerization of the products in a continuous fixed-bed reactor. The physicochemical properties of the catalysts were characterized by means of N2 adsorption-desorption, temperature-programmed reduction of H2, temperature-programmed desorption of NH3, infrared spectra of adsorbed pyridine, and thermogravimetry. The conversion of FAMEs and selectivity of C15-18 are enhanced over the bimetallic Ni-Co/SAPO-11 catalysts compared with that of the corresponding monometallic counterparts, which is attributed to the modification effect by Co species. The balance between metal Ni and Co and the acidity of the support plays an important role in the catalytic performance. The Ni-Co/SAPO-11 catalysts with composition of 3% Ni and 6% Co exhibit optimal catalytic performance, specifically the conversion of FAMEs, selectivity of C15-18, and isomerization ratio of C15-18, respectively, reaching 100.0%, 93.0%, and 36.1% at 400°C and 1.5 Mpa H2.

Functional group hydrogenation of cinnamaldehyde to hydrocinnamyl alcohol over nickel-ruthenium containing hydrotalcite

Functional group hydrogenation of α-β unsaturated aldehydes to fine chemicals is a potential process in organic synthesis. In this study, we demonstrate the complete functional group hydrogenation of cinnamaldehyde (CAL) to hydrocinnamyl alcohol (HCOL) over magnesium aluminium hydrotalcite (MAHT) having bimetallic nickel/ruthenium (1.3% Ni and 0.74% Ru) species (MANR–HT). The catalyst shows complete conversion of CAL with 97.5% selectivity of HCOL at 150 °C and 1 MPa H2 pressure. The synergic effect of bimetallic Ni/Ru and basicity of the HT material facilitated the high catalytic activity of MANR–HT in the CAL hydrogenation. The catalyst also demonstrated comparable activity even after several runs.

Liquid fuel synthesis via CO2 hydrogenation by coupling homogeneous and heterogeneous catalysis

Summary Synthesis of liquid fuel (C5+ hydrocarbons) via CO2 hydrogenation generally involves cascade catalysis of reverse water gas shift (RWGS) and Fischer-Tropsch synthesis (FTS) reactions over heterogeneous catalysts. Because of thermodynamic limitations of the cascade reactions, the reported heterogeneous catalysts usually suffer from high temperature (above 300°C) and low selectivity. Here, we report the liquid fuel production from CO2 hydrogenation by coupling homogeneous RuCl3 and heterogeneous Ru0 catalysts, which proceeded at the lowest temperature reported so far (180°C) and reached the highest C5+ selectivity to date (71.1%). The TOF of the CO2 hydrogenation reached 9.5 h−1, which is comparable with that of the reported Ru0 catalyzed FTS reaction using syngas. Detailed study indicates that synergy of homogeneous and heterogeneous catalysis is the key for the outstanding performance.

ВПЛИВ Fe ТА Y НА ВОДЕНЬСОРБЦІЙНІ ВЛАСТИВОСТІ, ТЕРМІЧНУ СТІЙКІСТЬ ТА КІНЕТИКУ ДЕСОРБЦІЇ ВОДНЮ З ГІДРИДНОЇ ФАЗИ MgH2 МЕХАНІЧНОГО СПЛАВУ Mg + 10%ваг.Fe + 5% ваг.Y

Ефективний і безпечний спосіб зберігання водню - це його хімічне зв'язування в металогідридах. Незважаючи на те, що вчені приділяють велику увагу гідриду магнію, він ще не знайшов широке застосування в якості акумулятора водню для автомобільної промисловості через високу температуру (300 °C при 0,1 МПа H2) і повільну кінетику дисоціації. У даній роботі досліджена можливість зниження температури, поліпшення кінетики розкладу стехіометричного гідриду MgH2 за рахунок його комплексного легування Fe і Y з застосуванням методу реактивного механохімічного сплавлення (РМС). Були синтезовані механічні сплави Mg + 10% ваг. Fe + 5% ваг. Y (МС1) і Mg + 10% ваг. Fe (МС2) і досліджено їх фазовий склад, мікроструктуру, водородосорбційні властивості, термічну стабільність і кінетику десорбції водню з використанням методів рентгенівської дифракції (XRD), скануючої електронної мікроскопії (SEM) і термодесорбційної спектроскопії (TDS). Для оцінки впливу комплексного легування на температуру розкладу і термостабільність фази MgH2 отримані ізобари десорбції водню при першому нагріванні після синтезу РМС зразків механічних сплавів і після подальшого їх циклічного гідрування з газової фази. Всі ізобари отримані при тиску водню в реакторі 0,1 МПа і швидкості нагріву зразка 30/ хв. і використані для визначення як температури початку десорбції водню (Тпоч.) з гідридної фази MgH2 МС, так і температури Тмакс., що відповідає максимальній швидкості виділення водню. Кінетичні криві десорбції водню з механічних сплавів-композитів отримані при постійному тиску водню 0,1 МПа в реакторі і температурах 310 і 330 °С і були використані для визначення як часу виділення половини кількості водню (τ1/2), так і загальної кількості виходу водню (τп) з МС. Встановлено, що додавання Fe і Y до магнію призводить до значного поліпшення кінетики десорбції водню з гидридної фази MgH2, про що свідчить значне зменшення (в 15 і 6 разів) часу виділення з неї половини і всього водню при 330 0С. Розроблені матеріали можуть знайти практичне використання в стаціонарних умовах їх застосування.Бібл. 48, табл.2, рис. 9.

Hydrogenolysis of lignin to produce aromatic monomers over Fe[sbnd]Pd bimetallic catalyst supported on HZSM-5

Highly dispersed FePd bimetallic catalyst supported on HZSM-5 (Fe-Pd/HZSM-5) was prepared by impregnation method for the hydrogenolysis of lignin. The correlation between the textural properties of the catalyst and its catalytic activity to lignin hydrogenolysis were investigated. The presence of Fe facilitates the dispersion of Pd, and the particle size decreases from 6.1 nm for 3.0 wt% Pd/HZSM-5 (Pd-3.0) to 2.5 nm for 9.0 wt% Fe-1.0 wt% Pd/HZSM-5 (FP-1.0). Fe is mainly existed in the oxidized state which means that electrons in Pd tend to transfer to FeOx, facilitating the activation of H2 to form active H atoms. Due to the geometric and electronic synergistic effects, FP-1.0 bimetallic catalyst exhibits a good catalytic activity to lignin hydrogenolysis, contributing to as higher as 98.17% of lignin conversion and 27.92% of aromatic monomers yield under the optimal reaction conditions of 1 MPa H2 at 320 o C for 120 min in ethanol-water solvent. FP-1.0 bimetallic catalyst with low cost and highly catalytic activity may be a potentially useful catalyst for selective hydrogenolysis of lignin.

Hydrocracking of Polyethylene to Jet Fuel Range Hydrocarbons over Bifunctional Catalysts Containing Pt- and Al-Modified MCM-48

A low-density polyethylene was hydrocracked to liquid hydrocarbons in autoclave reactors over catalysts containing Pt- and Al-modified MCM-48. Two kinds of Al-modified MCM-48 were synthesized for the reaction: Al-MCM-48 was synthesized using a sol–gel method by mixing Al(iso-OC3H7)3 with Si(OC2H5)4 and surfactant in a basic aqueous solution before hydrothermal synthesis, and Al/MCM-48 was synthesized using a post-modification method by grafting Al3+ ions on the surface of calcined Al/MCM-48. X-ray diffraction (XRD) patterns indicated that both Al-MCM-48 and Al/MCM-48 had a cubic mesoporous structure. The Brunauer–Emmett–Teller (BET) surface areas of Al-MCM-48 and Al/MCM-48 were larger than 1000 m2/g. 27Al Magic Angle Spinning-NMR (MAS NMR) indicated that Al3+ in Al-MCM-48 was located inside the framework of mesoporous silica, but Al3+ in Al/MCM-48 was located outside the framework of mesoporous silica. The results of ammonia temperature-programmed desorption (NH3-TPD) showed that the acidic strength of various samples was in the order of H-Y > Al/MCM-48 > Al-MCM-48 > MCM-48. After 4 MPa H2 was charged in the autoclave at room temperature, 1 wt % Pt/Al/MCM-48 catalyst showed a high yield of C9−C15 jet fuel range hydrocarbons of 85.9% in the hydrocracking of polyethylene at 573 K for 4 h. Compared with the reaction results of Pt/Al/MCM-48, the yield of light hydrocarbons (C1−C8) increased over Pt/H-Y, and the yield of heavy hydrocarbons (C16−C21) increased over Pt/Al-MCM-48 in the hydrocracking of polyethylene. The yield of C9−C15 jet fuel range hydrocarbons over the used catalyst did not decrease compared to the fresh catalyst in the hydrocracking of polyethylene to jet fuel range hydrocarbons over Pt/Al/MCM-48.

Catalytic hydrocracking of a Mexican heavy oil on a MoS2/al2o3catalyst: II. Study of the transformation of isolated aromatics fraction obtained from SARA analysis

Catalytic hydrocracking of isolated aromatics fraction from a heavy crude oil was studied on a slurry batch reactor at isothermal conditions using 8.27 MPa H2 pressure, different temperatures (380 °C, 390 °C, and 400 °C), different reaction times (1.0 h, 2.5 h, and 4.0 h) and employing a sulfided Mo/γ-Al2O3 catalyst. The ASTM D2007 method had been applied to a Mexican heavy oil to obtain the aromatics fraction. Feedstock and products (gas and liquid) were analyzed by GC-MSD and GC-FID. Additionally, the liquid phase was analyzed by the ASTM D7169 method. A kinetic model was proposed to establish the effect of the processing the heavy cuts (gasoil, atmospheric residue, and vacuum residue) to light distillate cuts production (gas, naphtha and, kerosene). It was determined that the feedstock is composed of aromatics (mono, di, tri, or tetra-cycle) with alkyl tails, oxygenated aromatics, nitrogen aromatics, and sulfur aromatics. The catalytic hydrocracking products were saturate compounds and lower molecular weight aromatics; no coke was detected. The produced gas was composed by saturated compounds. The fitted kinetic parameters and the chromatographic analyses indicate that aromatics in feedstock were transformed following primary reactions in series. The main producers of naphtha were aromatics in kerosene and atmospheric residue, the reactions were dealkylation or hydrogenation; this after the opening of aromatic rings in the high molecular aromatics. The gas producers were substituted aromatics in the kerosene cut that is kept at the liquid phase during reaction, also, at high temperatures the hydrotreatment reactions of aromatic compounds in gasoil produces gas.

One-pot conversion of levulinic acid into gamma-valerolactone over a stable Ru tungstosphosphoric acid catalyst

In this paper ruthenium exchanged tungstophosphoric acid (TPA) catalysts with different ruthenium loading (RuxTPA (x = 1,2,3)) were studied for conversion of levulinic acid (LA) into gamma-valerolactone (GVL) (a potential fuel/fuel additive). Studies were also conducted on a Ru/C catalyst as Ru/C catalysts have recently been reported to have significant promise for this reaction. Under the conditions used (130 °C, 1.0 MPa H2, 2 h in 1,4 dioxane solvent) one of the prepared catalysts achieved excellent conversion and selectivity to GVL. This catalyst also compared favorably to Ru/C catalysts that have been previously studied in terms of rate of production of GVL per gram Ru. Characterization studies showed that Ru metal surface area and extent of Lewis and Brønsted acidity were characteristics that had a significant influence on the conversion and selectivity of the RuxTPA catalysts studied. The best performing Ru3TPA catalyst was found to be highly recyclable with only a slight decrease in selectivity of GVL (from 100% to 98.3%) being observed after five cycles of testing.

Modeling the Hydrogen Effect on the Constitutive Response of a Low Carbon Steel in Cyclic Loading

Abstract Hydrogen-accelerated fatigue crack growth is a most severe manifestation of hydrogen embrittlement. A mechanistic and predictive model is still lacking partly due to the lack of a descriptive constitutive model of the hydrogen/material interaction at the macroscale under cyclic loading. Such a model could be used to assess the nature of the stress and strain fields in the neighborhood of a crack, a development that could potentially lead to the association of these fields with proper macroscopic parameters. Toward this goal, a constitutive model for cyclic response should be capable of capturing hardening or softening under cyclic straining or ratcheting under stress-controlled testing. In this work, we attempt a constitutive description by using data from uniaxial strain-controlled cyclic loading and stress-controlled ratcheting tests with a low carbon steel, Japanese Industrial Standard (JIS) SM490YB, conducted in air and 1 MPa H2 gas environment at room temperature. We explore the Chaboche constitutive model which is a nonlinear kinematic hardening model that was developed as an extension to the Frederick and Armstrong model, and propose an approach to calibrate the parameters involved. From the combined experimental data and the calibrated Chaboche model, we may conclude that hydrogen decreases the yield stress and the amount of cyclic hardening. On the other hand, hydrogen increases ratcheting, the rate of cyclic hardening, and promotes stronger recovery.

Catalytic Hydroprocessing of White Pine Pyrolysis Bio-Oil over Cobalt-Molybdenum Carbide in a Continuous Packed-Bed Reactor

Catalytic hydroprocessing of white pine pyrolysis bio-oil over cobalt-molybdenum (CoMo) carbide supported on biochar was carried out in a continuous fixed-bed reactor at a temperature between 350 and 425 °C, hydrogen pressure between 7 and 12.5 MPa, and liquid hourly space velocity (LHSV) of 0.1–1.0 h−1 with a hydrogen flow rate of 500 mL/min. The results showed that the CoMo carbide catalyst can effectively improve the yield and qualities of hydrotreated bio-oil. Under the preferred reaction conditions of 400–425 °C, 10 MPa H2, and LHSV 0.3 h−1, the yield, the carbon content, the carbon recovery ratio, and the higher heating value of the upgraded bio-oil reached 24.2–25.7% of the feed, 86.5–87.4%, 48.1–52.1%, and 41.8–43.9 MJ/kg, respectively. The oxygen content, total acid number, and moisture of the hydrotreated bio-oil decreased to 0.1–1.6 wt%, aromatics > olefins > paraffins > naphthenes.

Hydrogenation of furfural to furfuryl alcohol over efficient sol-gel nickel-copper/zirconia catalyst

Furfuryl alcohol (FA), a valuable compound from furfural (FF) was synthesized by efficient Ni-Cu/ZrO2 catalysts. The catalysts with varying Ni and Cu loading were developed by sol-gel method and characterized by Brunauer-Emmet-Teller (BET) method, X-ray diffraction, Temperature Programmed Reduction (TPR), X-ray photoelectron spectroscopy techniques. Cu/ZrO2 and Ni/ZrO2 catalysts were also tested to compare the effect of the Ni-Cu/ZrO2 catalyst. Both Ni and Cu showed the synergistic effect on FA formation. The Ni-Cu/ZrO2 catalyst was used for hydrogenation of FF by changing pressure, catalyst loading, temperature and time. A 93% FA yield was achieved over the 7Ni-Cu/ZrO2 catalyst with 0.07 g Ni and 0.1 g Cu/1 g ZrO2 at 200 °C for 4 h under 1.5 MPa H2 pressure. The sol-gel Ni-Cu/ZrO2 catalyst without the use of expensive noble metals is effective on the hydrogenation of FF to FA relatively in mildly reaction pressure. The Ni-Cu/ZrO2 catalyst was used for hydrogenation of FF by changing pressure, catalyst loading, temperature and time. A 93% FA yield was achieved over the 7Ni-Cu/ZrO2 catalyst with 0.07 g Ni and 0.1 g Cu/1 g ZrO2 at 200 °C for 4 h under 1.5 MPa H2 pressure. The sol-gel Ni-Cu/ZrO2 catalyst without the use of expensive noble metals is effective on the hydrogenation of FF to FA relatively in mildly reaction pressure.