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.

Theoretical Insights into the Reaction Mechanism of Direct Hydrogenation of Maleic Anhydride to Produce 1,4-Butanediol on the Cu–ZnO Surface

Theoretical Insights into the Reaction Mechanism of Direct Hydrogenation of Maleic Anhydride to Produce 1,4-Butanediol on the Cu–ZnO Surface

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.

Ni@C nanocatalysts for the highly efficient hydrogenation of maleic anhydride to γ-butyrolactone

Core-shell Ni@C catalysts with a uniform grain size distribution were synthesised via a simple hydrothermal method followed by pyrolysis carbonisation, and their catalytic performance for the liquid-phase hydrogenation of maleic anhydride (MA) was investigated herein. When the pyrolysis temperature was 350 °C, the resulting Ni@C catalyst (Ni@C-350) possessed abundant Ni/NiO heterostructures and a carbon surface layer. Among the analysed catalysts, Ni@C-350 demonstrated the lowest apparent activation energy for the hydrogenation of CC bonds (Ea = 34.3 KJ/mol) and CO bonds (Ea = 65.18 KJ/mol), yielding an MA conversion of 100 % and a γ-butyrolactone (GBL) selectivity of 99.89 % under mild reaction conditions (200 °C, 3 MPa hydrogen pressure, and 0.05 g catalyst). Furthermore, the Ni@C-350 catalyst exhibited high stability, with the yield of GBL above 95 % after five consecutive usage cycles. Ni@C-350 significantly outperformed other previously reported catalysts for the liquid-phase hydrogenation of MA.

Nickel–Potassium/Clay Catalyst for Hydrogenation of Maleic Anhydride in Low-Polarity System

Nickel–Potassium/Clay Catalyst for Hydrogenation of Maleic Anhydride in Low-Polarity System

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.

1T-phase MoS2 edge-anchored Pt1−S3 active site boosting selective hydrogenation of biomass-derived maleic anhydride

1T-phase MoS2 edge-anchored Pt1−S3 active site boosting selective hydrogenation of biomass-derived maleic anhydride

PtFeCoNiCu High-Entropy Alloy Catalyst for Aqueous-Phase Hydrogenation of Maleic Anhydride

High-entropy alloys (HEAs), as new heterogeneous catalytic materials, possess remarkable catalytic performance in numerous reactions. However, rational and controllable synthesis of these complex structures remains a challenge. In this work, bulk and carbon nanotube (CNT)-supported ultrasmall PtFeCoNiCu HEA nanoparticles with an average particle size of 1.58 nm are prepared by lithium naphthalenide-driven reduction under mild conditions. The supported PtFeCoNiCu/CNT catalyst exhibits high catalytic activity in the aqueous-phase hydrogenation of maleic anhydride to succinic acid with a selectivity of 98% at full conversion of maleic acid (the hydrolysis product of maleic anhydride), a low apparent activation energy (Ea = 49 kJ mol-1), and excellent stability. Moreover, a much higher mass-specific activity of Pt in the catalyst is displayed over PtFeCoNiCu/CNT (1515.4 mmolmaleicacid gPt-1 h-1) than that of 5 wt % Pt/CNT (388.0 mmolmaleicacid gPt-1 h-1). This work provides a strong support for HEAs as advanced heterogeneous catalysts and will be of great significance for promoting the research and application of HEAs in the field of selective hydrogenation.

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

Synthesis of Ni‐Al layered double hydroxide via coprecipitation: Formation mechanism, synthesis intensification, and catalytic application

AbstractHerein, the formation mechanism of Ni‐Al layered double hydroxide (NiAl‐LDH) synthesized by coprecipitation was explored. Moreover, NiAl‐LDH was prepared in a rotating packed bed (RPB) under different rotation speeds, which shows that increasing the rotation speed decreases the lateral size and thickness of NiAl‐LDH, since high rotation speed accelerates the nucleation of NiAl‐LDH. Additionally, the Ni/mixed metal oxides (MMO) catalysts derived from NiAl‐LDH were prepared for maleic anhydride (MA) hydrogenation. Result shows that Ni/MMO catalyst obtained from NiAl‐LDH prepared under a higher rotation speed exhibits higher MA conversion due to its larger surface area and smaller nickel particle size. The Ni/MMO catalyst obtained from NiAl‐LDH prepared under 500 rpm exhibits 100% MA conversion and 100% succinic anhydride selectivity under 30°C and 2 MPa within 1 h. This work provides fundamental insight to understand the formation of NiAl‐LDH. Moreover, RPB as an effective technique to synthesize NiAl‐LDH and Ni‐based catalysts was validated.

Regulating the states of Ni species by controlling the silanols of MCM-41 support to promote the hydrogenation of maleic anhydride

Nickel (Ni) supported on MCM-41 zeolite as hydrogenation catalysts have been widely applied in various reactions, however, the synergism between Ni and the support remains obscure. To prepare more efficient catalysts and reveal the metal-support interaction, MCM-41 zeolite was modified with ammonium hexafluorosilicate (AHFS) before Ni loading. Results show that fluoride ions could selectively convert the vicinal silanols into isolated silanols on MCM-41 surface, which weakens the interactions between Ni precursors and the SiO2 supports. Over the modified MCM-41 zeolites, the attenuated interaction results in the agglomeration of NiO particles that is more easily to be reduced, rather than the formation of nickel phyllosilicate which is extraordinarily difficult towards reduction. The easily-reduced Ni particles provided more adsorption sites for CC bond instead of CO bond, and the adsorption strength was also regulated. Therefore, the AHFS modified catalyst demonstrated a notable enhancement in hydrogenation of maleic anhydride (MA) into succinic anhydride (SA), presenting 98.4 % MA conversion and 99.8 % SA selectivity at 90 °C under 3.0 MPa H2. Moreover, the optimum catalyst was recycled for 5 runs to analyze the deactivation mechanism, it was found out that the loss of activities stems from the leaching of large Ni particles. Overall, our work shed light on the metal-support interactions for Ni/MCM-41 catalyst, determining the vicinal hydroxyl groups were responsible for the state of Ni species, which is helpful for the rational design of other hydrogenation catalysts.

Synthesized Ni/MMO catalysts via ultrathin Ni-Al-LDH in a rotating packed bed for hydrogenation of maleic anhydride

• Ni-Al-LDH with thicknesses of 1–19 nm were synthesized to prepare Ni/MMO catalysts. • The features of Ni/MMO can be tuned by regulating the thicknesses of Ni-Al-LDH. • Ni/MMO catalysts obtained from Ni-Al-LDH exhibit irregular core–shell structure. • The highest hydrogenation rate for Ni/MMO is 9.45 (10 -3 ·mol MA ·g cat −1 ·min −1 , 80 °C, 2 MPa). • Maleic anhydride hydrogenation to succinic anhydride exhibits structure-sensitive. Fabricating highly active supported Ni-based catalysts is a fundamental challenge in the industry. Herein, the Ni-Al-LDH with controllable thicknesses from 1 to 19 nm were first synthesized to fabricate Ni/MMO catalysts (MMO: Mixed Metal Oxides) using coprecipitation in a rotating packed bed (RPB), followed by hydrothermal aging. It was found that despite the collapse of the sheet-like structure of the ultrathin Ni-Al-LDH during the thermal treatment, the Ni/MMO (designated as 2-NiAl) catalyst obtained from ultrathin Ni-Al-LDH nanosheets (2 nm) possesses the smallest Ni particle size, highest amount of acid sites and surface ratios of Ni/Al among the prepared catalysts. Thus, 2-NiAl demonstrates the optimal activity for the hydrogenation of maleic anhydride (MA), of which the hydrogenation rate is 9.45 (10 -3 ·mol MA ·g Ni -1 ·min −1 , 80 °C, 2 MPa) with ∼100% selectivity to succinic anhydride, higher than most of previous reported values. Moreover, the turnover frequencies as a function of Ni particle sizes demonstrate a linear correlation, indicating that MA hydrogenation is a structure-sensitive reaction. These results provide a new route to optimize the catalytic performance of Ni-based catalysts and a guidance for designing catalysts derived from LDH for hydrogenation reactions. Furthermore, the prepared 2-NiAl catalyst is a potential catalyst for hydrogenation of MA into SA in the industry.

Low supported nickel-cobalt catalyst for hydrogenation of maleic anhydride

In order to prepare supported catalysts with low-metal loading, a series of NiCo/Clay catalysts were prepared and used in the hydrogenation of maleic anhydride. The hydrogenation reaction was carried out in a fixed-bed for 8 h with reaction pressure = 1 MPa, reaction temperature = 180 °C, molar ratio of H2: maleic anhydride = 50, WHSV = 2 h−1. Ni4Co1/Clay (loaded 3 wt%Ni and 0.75 wt%Co) can maintain no obvious catalyst deactivation within 8 h. The overall conversion of maleic anhydride is not less than 95 %, and the selectivity of succinic anhydride is up to 100 %. N2 adsorption–desorption characterization, X-ray diffraction, temperature-programmed reduction, temperature-programmed desorption, X-ray photoelectron spectroscopy and transmission electron microscopy were performed to verify the changes in catalyst morphology, active species, reduction performance and hydrogenation activity after adding Co as a promoter. With the addition of Co additive, the distribution of active sites on the carrier is more uniform, the grain size of active metal becomes smaller and the reduction temperature decreases. The addition of Co not only increased the active center of the catalyst but also effectively avoided the catalyst's deactivation.

Tuning Particle Sizes and Active Sites of Ni/CeO2 Catalysts and Their Influence on Maleic Anhydride Hydrogenation.

Supported metal catalysts are widely used in industrial processes, and the particle size of the active metal plays a key role in determining the catalytic activity. Herein, CeO2-supported Ni catalysts with different Ni loading and particle size were prepared by the impregnation method, and the hydrogenation performance of maleic anhydride (MA) over the Ni/CeO2 catalysts was investigated deeply. It was found that changes in Ni loading causes changes in metal particle size and active sites, which significantly affected the conversion and selectivity of MAH reaction. The conversion of MA reached the maximum at about 17.5 Ni loading compared with other contents of Ni loading because of its proper particle size and active sites. In addition, the effects of Ni grain size, surface oxygen vacancy, and Ni–CeO2 interaction on MAH were investigated in detail, and the possible mechanism for MAH over Ni/CeO2 catalysts was deduced. This work greatly deepens the fundamental understanding of Ni loading and size regimes over Ni/CeO2 catalysts for the hydrogenation of MA and provides a theoretical and experimental basis for the preparation of high-activity catalysts for MAH.

Catalytic hydrogenation of maleic anhydride to γ-butyrolactone over a high-performance hierarchical Ni-Zr-MFI catalyst

High-performance MFI zeolite supported nickel catalysts were prepared by the ammonia evaporation method for maleic anhydride (MA) conversion to γ-butyrolactone (GBL). According to comprehensive characterizations, the Ni catalysts possessed petal-like morphology and hierarchical structures with meso and micro pores. Nickel species were highly dispersed on the silica support and generated abundant Lewis acid sites (LAS), which effectively activated carbonyl groups in the reactant and accounted for the high activity in MA hydrogenation. Zr species hydrothermally introduced into the catalyst increased the number of LAS and decreased the apparent activation energy for the reaction. The highest GBL yield reached 95.6% over 40Ni-2Zr-MFI with the assistance of 3A zeolite to in-situ remove water byproduct. The catalyst showed reasonably good stability in five-cycle operation thanks to the strong interaction between Ni and support. The reaction route for MA hydrogenation was investigated, in which succinic anhydride (SA-A) served as the major reaction intermediate for GBL formation.

Crystal-Plane and Shape Influences of Nanoscale CeO2 on the Activity of Ni/CeO2 Catalysts for Maleic Anhydride Hydrogenation.

Through use of the hydrothermal technique, various shaped CeO2 supports, such as nanocubes (CeO2-C), nanorods (CeO2-R), and nanoparticles (CeO2-P), were synthesized and employed for supporting Ni species as catalysts for a maleic anhydride hydrogenation (MAH) reaction. The achievements of this characterization illustrate that Ni atoms are capable of being incorporated into crystal lattices and can occupy the vacant sites on the CeO2 surface, which leads to an enhancement of oxygen vacancies. The results of the MAH reaction show that the morphology and shape of CeO2 play an important role in the catalytic performance of the MAH reaction. The catalyst for the rod-like CeO2-R obtains a higher catalytic activity than the other two catalysts. It can be concluded that the higher catalytic performances of rod-like CeO2-R sample should be attributed to the higher dispersion of Ni particles, stronger support-metal interaction, more oxygen vacancies, and the lattice oxygen mobility. The research on the performances of morphology-dependent Ni/CeO2 catalysts as well as the relative reaction strategy of MAH will be remarkably advantageous for developing novel catalysts for MA hydrogenation.

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.

Highly dispersed and confined Ni/MMO catalyst synthesized in a rotating packed bed for hydrogenation of maleic anhydride

AbstractCatalytic hydrogenation of maleic anhydride (MA) into succinic anhydride (SA) is one of the most important transformations in synthetic organic chemistry. Herein, we firstly synthesized well‐dispersed nickel particles confined by mixed metal oxides (Ni/MMO) derived from in situ transformation of Ni‐Al hydrotalcite in a rotating packed bed (RPB) to catalyze this process. A series of Ni/MMO catalysts (63 wt%–89 wt% Ni) were effectively fabricated and the structure–activity relationship was established. Results showed that a Ni/MMO catalyst (82 wt% Ni) with substantial surface defect sites and the highest Ni surface area among the prepared Ni/MMO catalysts, demonstrates the highest activity with ~100% MA conversion and ~100% selectivity to SA under 25°C within 77 min. This is, to our knowledge, the highest conversion and selectivity under room temperature to date. Moreover, the Ni/MMO catalyst prepared by RPB has higher specific surface area and Ni surface area, therefore possessing a higher hydrogenation rate compared to that by stirred tank reactor (1.69 vs. 1.36, 10−3·molMA/gcat/min). These results will provide an attractive option of the catalysts for MA hydrogenation, and a novel strategy for synthesizing nickel catalyst derived from Ni‐Al hydrotalcite.

Identification of potential technologies for 1,4‐Butanediol production using prospecting methodology

Abstract1,4‐Butanediol (1,4‐BDO) is a four‐carbon diol used for industrial applications such as organic solvents, and the production of adhesives, fibers and polyurethanes. 1,4‐BDO currently is produced through several petrochemical routes: hydrogenation of maleic anhydride, isomerization of propylene oxide, acetoxylation of butadiene, and the reaction between formaldehyde and acetylene. The current trends in 1,4‐BDO production involve the utilization of renewable sources such as biomass. In this context, the present study aimed to identify promising technologies of 1,4‐BDO production through prospecting methodology based on the analyses of patents and scientific article, describing the most relevant aspects of those emerging technologies. An increasing amount of 1,4‐BDO production focused on biotechnological routes has been reported, with the US heavily involved in the development of new technologies. This study tracked three promising technologies which have potential for application in a biorefinery context because those processes involve (i) production of 1,4‐BDO from sugars, classified herein as the biotechnological route; (ii) production of intermediates from sugar fermentation followed by catalytic conversion into 1,4‐BDO, classified herein as the hybrid route, and (iii) furan/furfural conversion into 1,4‐BDO. © 2020 Society of Chemical Industry

Optimization of anaerobic fermentation of Actinobacillus succinogenes for increase the succinic acid production

Succinic acid is a four-carbon dicarboxylic acid used as a building-block in the synthesis of valuable commodities and specialty chemicals. Succinic acid is produced petrochemically by hydrogenation of maleic anhydride and a “greener” alternative route is microbial fermentation. In this study, a 25−1 fractional factorial design (FFD) and a subsequent central composite rotatable design (CCRD) were used to investigate the influence of process parameters on succinic acid and biomass concentration during fermentation by Actinobacillus succinogenes. The independent factors were glucose concentration (19.29–42.45 g/L), yeast extract concentration (5–11 g/L), temperature (33–41 °C), pH (6–8), and agitation speed (100–300 rpm). Results showed that the main factors that influenced the succinic acid production were pH, yeast extract concentration and temperature. According to the CCRD results, the optimum conditions for succinic acid production were 37–41 °C, 13 g/L yeast extract concentration and pH 7. The maximum succinic acid concentration obtained was 17.5 g/L.