Selective Hydrogenation Of Maleic Anhydride Research Articles

PtPdCoNiCu/TiO2 High-Entropy alloy catalyst for synthesis of γ-Butyrolactone by selective hydrogenation of maleic anhydride

The continuous flow selective hydrogenation of maleic anhydride (MA) to γ-butyrolactone (GBL) over highly efficient and long-term stable catalysts is a considerable promising strategy for both lab-scale as well as industrial application. In this work, a PtPdCoNiCu/TiO2 high-entropy alloy (HEA) catalyst is developed by the colloidal impregnation method, in which the HEA colloids are synthesized by lithium naphthalenide-driven reduction at mild conditions according to the redox potential of the various metals. The PtPdCoNiCu/TiO2 catalyst exhibits highly efficient in the hydrogenation of MA with 91 % selectivity to GBL at full conversion of MA under the weighted hourly space velocity of 1.14 h−1, 3 MPa H2, and 260 °C. Due to the present of oxygen vacancy in the TiO2 support and the hydrogen spillover, the PtPdCoNiCu/TiO2 HEA catalyst presents a low apparent activation energy (75 kJ mol−1), boosting the hydrogenolysis of C=O bonds for generating of GBL. The cocktail effect is presented in the PtPdCoNiCu/TiO2 catalyst, and its catalytic activity is much better than that of corresponding monometallic and bimetallic catalysts. It realizes the reduction and substitution of precious metal catalysts. In addition, the PtPdCoNiCu/TiO2 catalyst with sintering resistance and acid resistance shows excellent long-term stability within 132 h. This work is of great significance for understanding HEA catalysis at the atomic level and provides the possibility for developing low-cost and efficient precious metal industrial catalysts.

One-step synthesis of 1,4-butanediol from maleic anhydride by gas-phase selective hydrogenation over xRe/CuZnZr catalysts

Producing 1,4-butanediol with selective hydrogenation of maleic anhydride has significant financial benefits. This work reported a “green” one-step method for preparing 1,4-butanediol from maleic anhydride in a gas-phase fixed bed continuous flow reactor over an efficient 2Re/CuZnZr catalyst for the first time. In this paper, CuZnZr composite metal oxides were synthesized using the co-precipitation technique, followed by impregnation of Re to produce xRe/CuZnZr catalysts. The study aimed to investigate the effects of including Re on the catalyst's structure and performance. The results obtained from the characterization indicate that the presence of Re in the system restricts the growth of Cu0 grains. In addition, the inclusion of Re facilitated the utilization of ZnO as an effective spacer, reducing the size and quantity of Cu species agglomerates and enhancing active metal dispersion. This phenomenon may be attributed to being the primary factor responsible for the observed enhancement in the activity of the maleic anhydride hydrogenation reaction. Meanwhile, Re facilitated the transformation of γ-butyrolactone, an intermediate resulting from the hydrogenation of maleic anhydride into 1,4-butanediol. The 2Re/CuZnZr catalyst exhibited favorable catalytic activity under the conditions of 190 °C and 6 MPa, resulting in the complete conversion of maleic anhydride and a selectivity of 85 % towards 1,4-butanediol. The catalyst showed consistent catalytic performance throughout the 200 h. The finding about the impact of Re promoter on Cu-based catalysts has the potential to yield a highly efficient catalytic system for alcohol generation.

Acid-durable intermetallic CaNi2Si2 catalyst with electron-rich Ni sites for aqueous phase hydrogenation of unsaturated organic anhydrides/acids

The study of the aqueous-phase selective hydrogenation of maleic anhydride to succinic acid is important for expanding the coal chemical industry chain and promoting biomass conversion. The key lies in the development of highly efficient and stable non-noble metal catalysts. Herein, we report a novel intermetallic CaNi2Si2 catalyst with high activity and stability for the aqueous-phase selective hydrogenation of maleic anhydride. The results from the experiments and theoretical calculations demonstrated that the high catalytic performance was due to the synergy of the electron-rich Ni active sites, enhanced adsorption of C=C bonds, and favorable activation of H2. The yield of succinic acid can be 100% over the CaNi2Si2 catalyst at the contact time of 5.4 gcat/(mmolreactant·min−1) under 3 MPa and 120 °C in the continuous flow reactor. Furthermore, the special coordination environment and electronic structure of Ni in CaNi2Si2 inhibit the formation of carboxylates, thus enhancing the acid resistance in the reaction environment. The fine design and regulation of the structure of intermetallic silicides will be important references for the controllable optimization of maleic anhydride hydrogenation catalysts and provide new insights into the development of efficient and stable selective hydrogenation catalysts in harsh reaction environments.

Improved polyol synthesis of palladium nanorods: an efficient catalyst for the selective hydrogenation of maleic anhydride to succinic anhydride

Improved polyol synthesis of palladium nanorods: an efficient catalyst for the selective hydrogenation of maleic anhydride to succinic anhydride

Pd/BN catalysts for highly efficient hydrogenation of maleic anhydride to succinic anhydride

A 0.33 wt% Pd/BN catalyst has been proved highly active for the liquid-phase selective hydrogenation of maleic anhydride (MA) to succinic anhydride (SA) at room temperature and highly selective to SA within a wide temperature range, far beyond the Pd/Al2O3 and Pd/MgO catalysts. An SA productivity of 6000 KgSA KgPd−1 h−1 and a high TOF value of 9.0 s−1 can be achieved at room temperature on the Pd/BN, and the high SA selectivity over 99.7% can be retained at the reaction temperature up to 150 ºC. Detailed structural characterizations and reactant-adsorption/desorption tests have demonstrated that the support effect on MA hydrogenation is related not only to the adsorption configurations of MA on Pd, which exhibits the indirect effect of the support via the electronic interaction with Pd, but also to the direct adsorption of MA on the support itself. In particular, for our catalysts with the low Pd loading, the difference of metal centers is largely masked by the adsorption of the support itself. For the Pd/BN, the predominant MA adsorption on Pd through a di-σ mode, the weak MA adsorption with a small amount on BN, and a high H-spillover ability are responsible for its high activity and selectivity. Moreover, it has been also revealed that the catalyst prereduction temperature can change the catalytic performance of the Pd/BN through an integrated effect including the removal of residual chlorine on Pd and the growth of Pd particles.

Effect of surface acidity/basicity on the selective hydrogenation of maleic anhydride to succinic anhydride over supported nickel catalysts

The catalysts 60%Ni/Al2O3, 60%Ni/MgAlO and 60%Ni/MgO were prepared and used for the hydrogenation of maleic anhydride (MA) to succinic anhydride (SA). Characterization results showed that Ni particles were highly dispersed in the catalysts so that they possessed the high density of active Ni sites, and thus the high activities for the reaction. In particular, it was found that the surface acidity favored the conversion of MA on Ni, but was unfavorable for the selectivity to SA, while the surface basicity played the opposite role. The Ni/MgAlO exhibited the proper acidity and basicity and thus the excellent performance for the reaction.

Pd/C modified with Sn catalyst for liquid-phase selective hydrogenation of maleic anhydride to gamma-butyrolactone

Pd catalysts suffered from poor selectivity and stability for liquid-phase hydrogenation of maleic anhydride (MA) to gamma-butyrolactone (GBL). Thus, Pd/C catalysts modified with different Sn loadings were synthesized, and characterized by XRD, XPS, TEM and elemental mapping. The types of alloy phase and the amounts of the surface Pd-SnOx sites altered along with Sn/Pd mass ratios from 0–1.0 synthesized in the process of preparation. The maximum reaction rate was 0.57mol-GBL/(mol-Pdmin) and selectivity was 95.94% when the Sn/Pd mass ratio was 0.6. It might be attributed to the formation of Pd2Sn alloy and less amounts of Pd-SnOx sites.

Active ruthenium catalysts prepared by Cacumen Platycladi leaf extract for selective hydrogenation of maleic anhydride

Ruthenium-based catalysts were prepared by a biogenic method via Cacumen Platycladi leaf extract and tested in the liquid phase hydrogenation of maleic anhydride to the corresponding succinic anhydride. The reaction conditions were optimized by varying the Ru loading, reaction temperature, hydrogen pressure, reaction time and organic solvents to achieve the superb catalytic performance. Reusability tests and comparison with commercial catalysts were also studied on the biosynthesized Ru-based catalysts. Furthermore, a variety of characterization techniques, such as TEM, HRTEM, EDS and XPS showed the effectively introduction of ruthenium nanoparticles into the carbon supports. The analyses of FTIR and TG confirmed that the plant extract served as both reducing and protecting agents..

Selective Hydrogenation of Maleic Anhydride to Succinic Anhydride Over Nickel-palladium Catalysts

Hydrogenation of maleic anhydride (MA) to succinic anhydride (SA) over Ni-Pd bimetallic catalysts prepared by impregnation method has been studied at different Pd contents, pressures and temperatures. Catalytic activity was greatly influenced by the Pd content, pressure and temperature. Use of 5wt%Ni-0.02wt%Pd/clay catalyst, the 100% conversion for MA and 100% selectivity for SA were obtained for MA hydrogenation at normal pressure. The catalysts were characterized by an array of techniques, including X-ray diffraction (XRD) and H2 temperature-programmed reduction (TPR). XRD and TPR studies showed that nickel was present as Ni2+ species on the support, and that there was no elemental nickel (Ni0) and Ni2O3 in the unreduced samples. XRD and TPR also showed that Pd was as amorphous existence on the catalysts.

Vapor-phase selective hydrogenation of maleic anhydride to succinic anhydride over Ni/TiO2 catalysts

A series of supported Ni/TiO2 catalysts were prepared by incipient wetness impregnation method under different calcination temperatures, and the as-prepared catalysts were characterized by X-ray diffraction (XRD), hydrogen temperature-programmed reduction (H2-TPR) and X-ray photoelectron spectroscopy (XPS). The catalytic properties of these Ni/TiO2 catalysts were investigated in the vapor phase hydrogenation of maleic anhydride (MA) to succinic anhydride (SA). The results showed that the catalytic activity and the selectivity of the Ni/TiO2 catalysts were strongly affected by the calcination temperature. The catalyst calcined at 1023K showed a relatively higher SA selectivity of 96% at high MA conversion (96%) under the tested conditions (493K and 0.2MPa). The improvement of SA selectivity could be mainly assigned to the presence of suitable metal–support interaction, which can play a role in catalytic property of active nickel species as electron promoter. Besides, the change of surface properties of TiO2 support with the increasing calcination temperatures, e.g., the decrease of Lewis acid sites, might also have some positive role in reducing the side-products like γ-butyrolacetone (GBL).

Selective hydrogenation of maleic anhydride over Pd/Al2O3 catalysts prepared via colloid deposition

Pd/Al2O3 catalysts were prepared via colloid deposition and the performance of the catalysts was examined in the selective hydrogenation of maleic anhydride to succinic anhydride. When the reaction was carried on in a batch system with 1,4-dioxane as the solvent (353 K and 1.0 MPa), high conversion of maleic anhydride (>98%) and high selectivity (>99%) for succinic anhydride were observed after 5 h. The as-prepared Pd/Al2O3 catalyst also showed excellent performance in solvent-free system and fixed-bed systems. The maleic anhydride (MA) conversion was greater than 98%, and high selectivity (>99%) for succinic anhydride was obtained after 1600 h in a fixed bed reacter. The results showed that the activity of the Pd/Al2O3 catalysts was excellent due to its high active surface area. Pd/Al2O3 catalysts were prepared via colloid deposition and the performance of the catalysts was examined in the selective hydrogenation of maleic anhydride (MA) to succinic anhydride (SA). The MA conversion was >98%, and selectivity for SA was >99%.

Selective Hydrogenation of Maleic Anhydride to Succinic Anhydride in Liquid Phase over Ni-Cu/Al<SUB>2</SUB>O<SUB>3</SUB> Catalyst

A series of Ni-Cu/Al2O3 catalyst samples were prepared by the wetness impregnation method and characterized by N2 physisorption, H2 temperature-programmed reduction, H2 temperature-programmed desorption, X-ray diffraction, and CO temperature-programmed surface reaction. Their catalytic performance in the liquid phase hydrogenation of maleic anhydride was investigated. The results indicated that the particle size of nickel crystallites was reduced, and the nickel species was well dispersed. Then, the C=C hydrogenation activity was significantly improved when the catalyst was promoted by Cu. However, due to the interaction between Ni and Cu, the C=O hydrogenation was retarded. The combination of the above two factors led to high selectivity for succinic anhydride over 15%Ni-7%Cu/Al2O3 catalyst. The conversion of maleic anhydride and selectivity for succinic anhydride reached 100% under the reaction conditions of 5 MPa hydrogen pressure and 210 oC for 40 min.

Selective hydrogenation of maleic anhydride to succinic anhydride catalyzed by metallic nickel catalysts

Maleic anhydride was selectively hydrogenated to succinic anhydride over metallic nickel catalysts, such as Raney Ni and Ni nanoparticles, in liquid phase at reaction temperature lower than 130°C. When the Raney Ni catalyst in solvents with different polarities catalyzed the hydrogenation of maleic anhydride to succinic anhydride, the solvent with high polarity favored the hydrogenation of maleic anhydride to succinic anhydride as compared to that with low polarity. When the hydrogenation reaction was catalyzed by Raney Ni catalyst at 100°C and H2 pressure of 2.5MPa for 360min in acetic anhydride, the conversion of maleic anhydride and the selectivity of succinic anhydride were 99.6% and 100%, respectively. In solvent-free reaction system, γ-butyrolactone as a byproduct with the maximum selectivity of 14.8% was produced at 130°C. All of the Ni nanoparticles with average diameters ranging from 8 to 313nm showed higher catalytic activity than Raney Ni in liquid phase hydrogenation of maleic anhydride to succinic anhydride. When the Ni nanoparticles with an average diameter of 8nm were used as the catalysts in the liquid phase hydrogenation at 80°C and 2MPa of H2 for 150min and the weight ratio of catalyst to maleic anhydride was 1:100, the conversion of maleic anhydride and the selectivity of succinic anhydride were 99.8% and 100%, respectively. The small particle size and the polycrystalline structure of Ni nanoparticles played important roles in the liquid phase selective hydrogenation of maleic anhydride to succinic anhydride.

Gas phase hydrogenation of maleic anhydride at low pressure over silica-supported cobalt and nickel catalysts

The gas-phase hydrogenation of maleic anhydride over Ni/SiO2 and Co/SiO2 catalysts, prepared by the incipient wetness impregnation method, was studied. The catalytic tests were carried out at 1bar pressure, between 170 and 220°C and W/FMA0 in the range 5–25ghmol−1. In this work, the product distribution was different to those obtained at high pressures, previously reported in the open literature. Both Ni/SiO2 and Co/SiO2 catalysts were active for the selective hydrogenation of maleic anhydride (MA) into succinic anhydride (SA). Subsequently, SA was converted to γ-butyrolactone (GBL) and propionic acid (PA). Neither tetrahydrofurane nor butanediol were detected at the reactor outlet. GBL/PA ratio was strongly depending on the metallic catalyst and temperature. At 170°C, Ni/SiO2 was more selective to GBL than Co/SiO2. Besides, with Ni/SiO2, GBL formation rate diminished during the experiment while PA production showed a small increase. Instead, over Co/SiO2, both the PA and GBL formation rate decayed with time on stream. At 220°C, Co/SiO2 showed a higher initial selectivity to GBL than Ni/SiO2. However, the GBL formation rate diminished more rapidly with Co/SiO2 than with Ni/SiO2. Thus, both catalysts gave similar selectivity to GBL after 3h reaction at 220°C. The observed catalyst deactivation was attributed to carbonaceous species of different nature deposited on the metallic phase during reaction. The amount and type of these species depends on both metal catalysts and reaction conditions. Selectivity and stability of Ni/SiO2 and Co/SiO2 catalysts is explained on the basis of their hydrogenolytic activity.

Selective Hydrogenation of Maleic Anhydride to Tetrahydrofuran over Cu−Zn−M (M = Al, Ti, Zr) Catalysts Using Ethanol As a Solvent

A series of Cu−Zn−M (M = Al, Ti, Zr) catalysts were prepared by coprecipitation method and characterized by X-ray diffraction, X-ray photoelectron spectroscopy, and N2 adsorption. The catalytic act...

Selective hydrogenation of maleic anhydride to γ-butyrolactone and tetrahydrofuran by Cu–Zn–Zr catalyst in the presence of ethanol

A series of Cu–Zn–Zr catalysts were prepared by a coprecipitation method and characterized by X-ray diffraction, X-ray photoelectron spectroscopy, temperature programmed reduction, and N 2 adsorption. The catalytic activity of the Cu–Zn–Zr catalyst in the hydrogenation of maleic anhydride using ethanol as a solvent was studied at 220–280 °C and 1 MPa. Maleic anhydride was mainly hydrogenated to γ-butyrolactone and tetrahydrofuran while ethanol dehydrogenated to ethyl acetate. After reduction, CuO species present in the calcined Cu–Zn–Zr catalysts were converted to metallic copper (Cu 0). The presence of ZrO 2 favored the deep hydrogenation of γ-butyrolactone to tetrahydrofuran while the presence of ZnO was beneficial to the formation of the intermediate product γ-butyrolactone. The molar ratios of the hydrogen produced in ethanol dehydrogenation to the hydrogen consumed in maleic anhydride hydrogenation increased with the increase of the reaction temperature.

Selective hydrogenation of maleic anhydride to γ-butyrolactone in supercritical carbon dioxide

Abstract The reaction rates of the hydrogenation of maleic anhydride (MAH) and succinic anhydride (SAH) were significantly accelerated and the selectivity to γ-butyrolactone (GBL) was enhanced largely when the reaction mixture was pressurized by a non-reactant of CO2. Above 99% selectivity to GBL was achieved in 14 MPa CO2, the superior selectivity in scCO2 was attributed to that MAH and/or SAH could be extracted to CO2 phase and separated from H2O, the hydrolysis were thus minimized and so the selectivity to GBL was improved.

Gas-phase hydrogenation of maleic anhydride to butyric acid over Cu/TiO 2/γ-Al 2O 3 catalyst promoted by Pd

The promoter effect of palladium on the Cu/TiO 2/γ-Al 2O 3 catalyst was investigated for the gas-phase selective hydrogenation of maleic anhydride to butyric acid at atmospheric pressure. The results show that Pd is added rarely into the Cu/TiO 2/γ-Al 2O 3 catalyst for the hydrogenation of maleic anhydride, the higher selectivity to butyric acid can be obtained. In the absence of Pd (or Cu) in the Cu–Pd/TiO 2/γ-Al 2O 3 catalyst, the selectivity to butyric acid (BA) is nearly zero. Using the Cu–Pd/TiO 2/γ-Al 2O 3 (Pd/Cu=3/100 (atom)) catalyst, 56.2% selectivity to BA and 100% conversion of maleic anhydride were obtained at 280 °C.

ChemInform Abstract: Selective Hydrogenation of Maleic Anhydride to γ‐Butyrolactone over Pd/Al2O3 Catalyst Using Supercritical CO2 as Solvent.

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Selective hydrogenation of maleic anhydride to gamma-butyrolactone over Pd/Al2O3 catalyst using supercritical CO2 as solvent.

A selective hydrogenation of maleic anhydride to either gamma-butyrolactone or succinic anhydride over simple Pd/Al2O3 catalyst under supercritical CO2 medium is described for the first time which has considerable promise for both lab-scale as well as industrial selective hydrogenations of low vapor pressure compounds without employing environmentally harmful organic solvents.