Synthesis Of Methyl Isobutyl Ketone Research Articles

Process Development for Methyl Isobutyl Ketone Production Using the Low-Pressure One-Step Gas-Phase Selective Hydrogenation of Acetone

Methyl isobutyl ketone (MIBK) is a highly valuable product in the chemical industry. It is widely used as an extracting agent for heavy metals, antibiotics, and lubricating oils. Generally, MIBK can be produced by three-step and one-step liquid-phase methods. These methods are expensive and energy-demanding due to the high pressure and low conversion of acetone. A novel nano-Pd/nano-ZnCr2O4 catalyst was developed to produce MIBK with high conversion and selectivity of 77.3% and 72.1%, respectively, at 350 °C and ambient pressure, eliminating the need for high pressure in conventional MIBK processes. This study is the first that proposes a newly developed process of methyl isobutyl ketone (MIBK) production using the low-pressure one-step gas-phase selective hydrogenation of acetone. In this work, a novel process flow diagram has been developed for the production of MIBK using the developed nano-catalyst. The process was heat integrated, resulting in a 26% and a 19.5% reduction in the heating and cooling utilities, respectively, leading to a 12.6% reduction in the total energy demand. An economic analysis was performed to determine the economic feasibility of the developed process, which shows that the process is highly profitable, in which it reduced both the capital and operating costs of MIBK synthesis and showed a return on investment (ROI) of 29.6% with a payback period of 2.2 years. It was found that the ROI could be increased by 18% when the reactor temperature is increased to 350 °C. In addition, the economic sensitivity analysis showed that the process is highly sensitive to product prices and least sensitive to utility prices, which is due to the versatility of the process that requires only a low amount of energy.

Novel Pd/Al2O3–CeO2 Nanosheets for One-Pot Synthesis of Methyl Isobutyl Ketone from Acetone

Novel Pd/Al2O3–CeO2 Nanosheets for One-Pot Synthesis of Methyl Isobutyl Ketone from Acetone

Experimental study on the role of water and kinetic enhancement in the one-step synthesis of methyl isobutyl ketone via catalytic distillation

Two pilot scale experiments investigating the one-step synthesis of methyl isobutyl ketone (MIBK) from acetone and hydrogen were conducted via catalytic distillation (CD) utilizing a Pd/Nb2O5/SiO2 catalyst at a reaction temperature of 160 °C and system pressure of about 1.4 MPa. Moisture analysis of liquid samples extracted about the major axis of the CD column revealed that when the reactor was initially operated at 100% reflux as suggested in the patent of Lawson and Nkosi, water had accumulated in the top half of the reactor as evidenced by water concentrations of 9.4 and 21.0 wt% in the reactive and rectification sections respectively, resulting in the suppression of the DAA dehydration reaction and consequently a relatively low MIBK productivity. However, operation of the CD column at 83–97% reflux enabled the rapid in situ separation of water from the reactive section via the overhead distillate stream, which directly resulted in increases in the MIBK productivity and the hydrogen uptake efficiency by factors of about 20. This result demonstrates a unique advantage of CD technology, whereby a substantial kinetic enhancement may be realized from the selective in situ separation of a kinetically relevant inhibiting substrate from the reactant mixture. MIBK in excess of 50 wt% was observed in the reboiler product during this mode of operation, which is significant since state of the art processes for MIBK production typically yield less than 30 wt% MIBK in the reactor effluent. The reboiler product was found to be essentially moisture free, which is also significant since MIBK and water are known to produce azeotropic mixtures resulting in difficult and costly downstream separations. An experiment was conducted to study the effects of the hydrogen and reflux flow rates on the MIBK yield. The CD process for MIBK synthesis was found to be controlled by the rate of external mass transfer of hydrogen. The results indicate that the catalyst wetting efficiency affects the catalytic hydrogenation as evidenced by an increase in mesityl oxide conversion with decreasing reflux flow rate. This suggests the catalyst wetting efficiency is an important design criterion for this process.

Selective synthesis of MIBK via acetone hydrogenation over Cu-Al mixed oxide catalysts

This work involves direct synthesis of methyl isobutyl ketone (MIBK) using a multifunctional catalyst via vapor phase hydrogenation of acetone at atmospheric pressure. Cu-Al mixed oxide catalysts were prepared from inexpensive precursors by co-precipitation of Cu and Al hydroxides with varying Cu:Al atomic ratio. The catalysts were characterized with N2 physisorption, FESEM (coupled with EDS), CO2/NH3-TPD, H2-TPR, FTIR and XRD. The evaluation of catalyst activity was performed in a continuous tubular reactor. The catalytic reactions were studied from variation of parameters such as temperature (200–300 °C), 0.5–1.25 H2/CH3COCH3 mole ratio and space-time (13.34–21.45 kg cat h/kmol acetone). The mixed oxide with Cu/Al atomic ratio of 0.25 showed highest selectivity (74%) for MIBK at 250 °C. Kinetics of the reaction was studied by varying space-velocity at different temperatures. Rate equations based on L-H-H-W model were validated with the kinetic data obtained at four temperatures. The activation energy was found to be 81 kJ/mol.

A Pd-NP/AC‐CATALYZED TRANSFER‐HYDROGENATION OF MESITYL OXIDE TO METHYL ISOBUTYL KETONE USING SODIUM FORMATE AS HYDROGEN DONOR

Methyl isobutyl ketone (MIBK) is an α,β-unsaturated carbonyl compound, which is often used as solvent and extractor for antibiotics in the pharmaceutical industry. One alternative to the synthesis of MIBK from mesityl oxide (MO) is through catalytic transfer hydrogenation (CTH) using various organic compounds as hydrogen donors in the presence of a catalyst. The purpose of this study was to synthesize MIBK from MO through the CTH reaction using sodium formate as the hydrogen donor and Pd nanoparticles deposited on the activated charcoal (Pd-NP/AC) as the catalyst. Based on the Gas Chromatography-Mass Spectrometry (GC-MS) analysis, the conversion value of MO was obtained in 97.3% and the yield of the MIBK formation was 10.5%. Meanwhile, the highest selectivity was obtained in 17% at 40° C. The results show that sodium formate can effectively be used to reduce MO into MIBK in the presence of Pd-NP/AC catalyst at 70° C for 5 hours.

An active and stable multifunctional catalyst with defective UiO-66 as a support for Pd over the continuous catalytic conversion of acetone and hydrogen.

The one-pot synthesis of methyl isobutyl ketone (MIBK) and methyl isobutyl methanol (MIBC) from acetone and hydrogen is a typical cascade reaction comprised of aldol condensation-dehydration-hydrogenation. Pd loss and aggregation during long term operation are typical problems in industrial application. In this paper, an active and stable catalyst was achieved with defective UiO-66 as a support for Pd, which was synthesized with the ratio 15 : 1 of ZrOCl2·8H2O to ZrCl4 as Zr-precursors. The resultant Pd catalyst remained active for at least 1000 h with a MIBK + MIBC selectivity of 84.87–93.09% and acetone conversion of 45.26–53.22% in a continuous trickle-bed reactor. Besides the increased Brønsted acid amount generated by the defect sites was favorable for the activity, the cavity confinement in the UiO-66 (R = 15 : 1) structure also efficiently prevented Pd loss and aggregation during the long term run. The contrast of the characterization of the fresh and used Pd/UiO-66 (R = 15 : 1) indicated that the deactivation of the catalyst was attributed to carbonaceous accumulation on the catalyst surface, which could be easily regenerated by calcination. This work supplied a new alternative for the design and utilization of industrial catalysts for MIBK and MIBC synthesis.

An efficient multifunctional catalyst for one-pot synthesis of methyl isobutyl ketone: Phosphor-doped h-BN with adjustable acid-base property as support

Developing multifunctional catalyst for cascade reactions such as one-pot synthesis of methyl isobutyl ketone (MIBK) from acetone and hydrogen is critical for practical applications. Here, we adjusted the acid-base property by doping phosphor into h-BN and used it as support for Pd. Experiments and characterizations indicated that the phosphor-doped h-BN could catalyze the aldol condensation and dehydration by modulating the ratio of BNH2, N2P=O and N3P-OH groups thereon. An acetone conversion of 58.24% and MIBK selectivity of 68.39% were achieved over Pd/BN(H)P-E-0.07, providing a new avenue for metal-free materials utilized in the cascade reactions.

Liquid-phase synthesis of methyl isobutyl ketone over bifunctional heterogeneous catalysts comprising cross-linked perfluorinated sulfonic acid Aquivion polymers and supported Pd nanoparticles

The solvent-free hydrogenation reaction of acetone over bifunctional heterogeneous catalysts, comprising cross-linked perfluorosulfonic acid (PFSA) resins and supported Pd nanoparticles, was investigated in the liquid phase under batch conditions. A systematic study was performed by analyzing separately the effect of the main reaction parameters on the reaction outputs. Acetone conversion, selectivity and productivity to methyl isobutyl ketone (MIBK) were measured as a function of the reaction temperature, the amount of catalyst, the Pd loading, the H2 pressure, the reaction time and the cross-linkage of the polymeric support. Reproducible trends were observed that could be explained in terms of properties of the catalyst, conversion path and kinetics. Best compromise results between selectivity (92 %) and productivity (37.0 mmolMIBK gcat−1 h-1) at 19.7 % acetone conversion were obtained for the 0.26Pd@X-link-08-PW79 catalyst, based on 0.8 % cross-linked PFSA support and 0.26 % wt Pd content.

Enhanced stability of Pd/SPS catalyst over the one-pot liquid-phase synthesis of methyl isobutyl ketone by adding GO

The low thermal-conductivity and poor thermal stability of resin limit the service life of commercial Pd/sulfonated polystyrene (SPS) catalyst for the industrial synthesis of methyl isobutyl ketone from acetone and H2. In this paper, a novel catalyst Pd/S(PS-GO) was fabricated via in situ microemulsion polymerization, followed by sulfonating and Pd loading. Both the long-term catalytic performance of Pd/S(PS-GO) and Pd/SPS catalysts were tested in a trickle-bed reactor. Results showed that Pd/S(PS-GO) catalyst exhibited obvious enhanced stability than Pd/SPS catalyst at 150 ℃ for 1000 h run. The characterizations of FT-IR, TGA, XPS, TEM and UV–vis revealed that the addition of GO significantly improved the thermal-conductivity and thermal stability of PS through noncovalent π–π stacking and covalent link between PS and GO sheets. As a consequence, the loss of –SO3H groups from resin matrix was efficiently depressed and led to the obvious enhanced stability of Pd/S(PS-GO) catalyst.

Higher Acetone Conversion Obtained Over a TiO2–Pd Bifunctional Catalyst for Liquid-Phase Synthesis of Methyl Isobutyl Ketone: The Role of Al2O3 Support

We reported a bifunctional catalyst TiO2/Al2O3 and Pd/Cor for one-pot liquid-phase synthesis of MIBK from acetone in this paper. The characterizations of FT-IR, Raman spectra, TEM, XPS, CO2-TPD, NH3-TPD, Py-IR and TGA spectra revealed that the TiO2/Al2O3 could possess more acid sites and especially Lewis acid sites due to the coexistence of TiO2 and Al2O3. So a higher acetone conversion 35–45% at 150 °C and 2.0 MPa pressure was achieved than ever reported for MIBK liquid-phase synthesis. In addition, the catalyst could keep active for at least 90 h on stream at 80–90% MIBK selectivity. The phenomenon of carbonaceous accumulation on TiO2/Al2O leaded to the deactivation of catalyst. Because of the coexistence of TiO2 and Al2O3. TiO2/Al2O3 could have more acid sites and especially Lewis acid sites. For liquid-phase synthesis of methyl isobutyl ketone, bifunctional catalyst TiO2/Al2O3&Pd/Cor showed higher acetone conversion.

Pd Nanoparticles Encapsulated in Mesoporous HZSM-5 Zeolite for Selective One-Step Conversion of Acetone to Methyl Isobutyl Ketone

Here we report a bifunctional catalyst comprised of Pd nanoparticles encapsulated in a solid acid mesoporous HZSM-5 zeolite for one-step synthesis of methyl isobutyl ketone (MIBK) from acetone at 150 °C and atmospheric pressure. The Pd nanoparticles are encapsulated in conventional HZSM-5 and mesoporous HZSM-5, prepared using a carbon template procedure. The nanoparticles are encapsulated using in situ encapsulation during the zeolite synthesis and post impregnation to investigate the effect of preparation procedure, zeolite confinement and distribution of nanoparticles. Additionally, the influence of Si to Al ratio of HZSM-5 zeolite and hence the effect of acidity was also analyzed. The prepared materials are characterized with various techniques including SEM, TEM, XRF, nitrogen physisorption and XRD among others. Of different materials, palladium nanoparticles encapsulated inside mesoporous zeolite via in situ encapsulation (Pd@MesoHZSM-5) were found to be the most active and highly selective (> 99%) for the formation of MIBK with a conversion of 37%. Moreover, the mesoporous zeolite structure increased the mass transfer and thereby enabling acetone to diffuse easily to the active sites excluding the formation of by-products.

Stability Investigation of a Supported TiO2–Pd Bifunctional Catalyst over the One-Pot Liquid-Phase Synthesis of Methyl Isobutyl Ketone from Acetone and H2

The one-pot liquid-phase synthesis of methyl isobutyl ketone (MIBK) from acetone and H2 is a significant process in the fine-chemicals industry. In this paper, we fabricated a series of TiO2–SiO2/SiO2(F)&Pd/Cor bifunctional catalysts and optimized the ratio of TiO2 to SiO2 to be 1. The catalyst with the optimal mole ratio of TiO2 to SiO2 was further investigated in a long-term operation in a trickle-bed reactor, which delivered a stable MIBK selectivity of 83–93% at 26–36% acetone conversion for 300 h. The characterizations of Fourier transform infrared spectra, Raman spectra, thermogravimetric analysis, X-ray diffraction, X-ray photoelectron spectroscopy, temperature-programmed desorption of CO2 and NH3, and pyrolysis infrared spectra reveal that the active sites of acetone condensation and dehydrogenation could be attributed to the Ti–O–Si bonds. Deactivation of the catalyst resulted from a decrease of the active sites because of the aggregation of TiO2 and carbonaceous accumulation on the catalyst surface.

The mechanism and kinetics of methyl isobutyl ketone synthesis from acetone over ion-exchanged hydroxyapatite

The synthesis of methyl isobutyl ketone (MIBK) can be carried out by the condensation of acetone in the presence of hydrogen over a supported metal catalyst. Previous studies have shown that hydroxyapatite is an excellent catalyst for condensation reactions. The present investigation was undertaken in order to elucidate the reaction mechanism and site requirements for acetone coupling to MIBK over a physical mixture of hydroxyapatite and Pd/SiO2. The reaction is found to proceed by consecutive aldol addition to form diacetone alcohol (DAA), dehydration of DAA to mesityl oxide (MO), and hydrogenation of MO to MIBK. The products formed by feeding DAA and MO reveal that aldol addition of acetone is rapid and reversible, and that the subsequent dehydration of DAA is rate-limiting. Pyridine and CO2 titration show that aldol dehydration occurs over basic sites via an E1cB mechanism. A series of cation-substituted hydroxyapatite samples were prepared by ion-exchange to further investigate the role of acid-base strength on catalyst performance. Characterization of these samples by PXRD, BET, ICP-OES, XPS, CO2-TPD, and Raman spectroscopy demonstrated that the exchange procedure used does not affect the bulk properties of hydroxyapatite. DFT calculations reveal that in addition to affecting the Lewis acidity/basicity of the support, the size of the cation plays a significant role in the chemistry: cations that are too large (Ba2+) or too small (Mg2+) adversely affect reaction rates due to excessive stabilization of intermediate species. Strontium-exchanged hydroxyapatite was found to be the most active catalyst because it promoted α-hydrogen abstraction and CO bond cleavage of DAA efficiently.

Fabrication of Pd-based metal-acid-alkali multifunctional catalysts for one-pot synthesis of MIBK

The one-pot synthesis of methyl isobutyl ketone (MIBK) from acetone using multifunctional catalysts is an important sustainable organic synthesis method with high atom and energy efficiency. Herein. we report a series of Pd supported on mixed metal oxide (MMO) catalysts with controllable acidic/basic/metallic sites on the surface. We study the relationship between the nature, synergy, and proximity of active sites and the catalytic performance of the multifunctional catalyst in the tandem reaction, in detail. In the existence of Lewis acid and base sites, the catalysts with medium-strength acidic/basic sites show preferred activity and/or MIBK selectivity. For multifunctional catalysts, the catalytic properties are more than just a collection of active sites, and the Pd/Mg3Al-MMO catalyst possessing 0.1% Pd loading and ~0.4 acid/base molar ratio exhibits the optimal 42.1% acetone conversion and 37.2% MIBK yield, which is among the best reported so far for this tandem reaction under similar conditions. Moreover, the proximity test indicates that the intimate distance between acidic/basic/metallic sites can greatly shorten the diffusion time of the intermediate species from each active site, leading to an enhancement in the catalytic performance.

Supported TiO2–Pd bifunctional catalysts for the one-pot synthesis of methyl isobutyl ketone from acetone: modulation of the acid and base property of loaded TiO2 by support

In this work, we prepared a series of supported TiO2–Pd bifunctional catalysts for one-pot synthesis of methyl isobutyl ketone (MIBK) from acetone. The effects of supports including SiO2 with different pore structure, Al2O3 calcined at varied temperature, and F-modification on the catalytic performance were investigated. The results showed that microporous SiO2 was not beneficial to the dispersion of TiO2 inspite its high specific surface area. The calcination of Al2O3 had little effect on the acid and base property of TiO2 loaded thereon. F-modification of support was proved to be an effective way to modulate the acid and base property of TiO2 loaded thereon. As for the catalytic performance, TiO2 loaded on the F-modified mesoporous SiO2 showed the performance 60.9% MIBK yield, with acetone conversion of 77.2% and MIBK selectivity of 78.9%, higher than those ever reported. The excellent performance could be attributed to the enhanced electronic transfer between TiO2 and SiO2 after F modification which greatly affected the acid and base property of loaded TiO2. Taking the advantages of facile synthesis and high performance, the as-reported TiO2/SiO2(B-F)&Pd/Cor catalyst could be a promising alternative for one-pot synthesis of MIBK from acetone.

Cascade engineered synthesis of ethyl benzyl acetoacetate and methyl isobutyl ketone (MIBK) on novel multifunctional catalyst

A novel trifunctional catalyst with basic, acidic and metal sites was synthesized by nanocolloidal method and used in industrially important reactions. in the laboratory. The synthesized catalyst consisted of palladium and hydrotalcite supported on transition metal modified hexagonal mesoporous silica (HMS) and was characterized in virgin and reused states using a number of techniques such as elemental analysis, FTIR, NH3− TPD, CO2− TPD, H2− TPR, XRD and BET surface area. The activity of particular catalytic site was engineered so that a desired reaction pathway was followed in spite of possibility of multiple series and parallel or complex reactions. One pot cascade engineered synthesis of ethyl benzyl acetoacetate from benzaldehyde and ethyl acetoacetate was studied in solvent free condition in a batch reactor. The effects of various parameters on the rates of reaction were analysed to establish instantaneous selectivity. Reaction mechanism and kinetic modelling was studied to validate the experimental results. The reaction follows Langmuir-Hinshelwood-Hougen-Watson mechanism involving weak adsorption of reactants and products. The apparent activation energy was found to be 13kcal/mol and intrinsic kinetic constant 33cm6mol−1gcat−1s−1. This study was further extended to synthesis of methyl isobutyl ketone (MIBK) from acetone in solvent free condition. Similar experimental and theoretical analysis was done for MIBK synthesis for which the activation energy and intrinsic kinetic constant were found to be 12kcal/mol and 4cm6mol−1gcat−1s−1, respectively.

Sulfonated graphene oxide supported Pd bifunctional catalyst for one-pot synthesis of methyl isobutyl ketone from acetone with high conversion and selectivity

Sulfonated graphene oxide supported Pd bifunctional catalyst for one-pot synthesis of methyl isobutyl ketone from acetone with high conversion and selectivity

Ru–C–ZnO Composite Catalysts for the Synthesis of Methyl Isobutyl Ketone via Single Step Gas Phase Acetone Self-Condensation

Ruthenium/activated charcoal (Ru-C) was modified by a solid-solid interaction method with synthe- sized nano-zinc oxide (n-ZnO). Three different ratios of Ru-C:n-ZnO (1:2, 1:1 and 3:2) were used to prepare Ru- C-ZnO composite catalysts. These were used in the gas- phase, one-step self-condensation of acetone to methyl isobutyl ketone (MIBK). The composite catalyst (1:1 ratio) contained 2.5 wt% Ru showed superior conversion of acetone and selectivity for MIBK. Furthermore, this cata- lyst showed good consistency for MIBK formation for 100 h without any deactivation. Characterization of the catalysts revealed that balanced hydrogenation and acid- base functional character is crucial to obtain high catalytic performance.

Progress in One-Pot Synthesis of Methyl Isobutyl Ketone Using Multifunctional Layered Based Catalysts

Methyl isobutyl ketone (MIBK) is one of the most widely produced and used aliphatic ketones worldwide. The one-step MIBK process with no intermediate separation steps using multifunctional catalysts is an important development towards greener organic synthesis and generates tremendous interest among the researcher across the globe. The single step process is facile and more economically viable and has provided opportunity to develop new and improved catalyst systems capable of operating under mild conditions. A widely variety of catalytic systems have been used in one-step process during last three to four decades. The progress in one-pot synthesis of MIBK using different multifunctional catalysts with special reference to layered based catalysts was critically reviewed in this article.

Characterization and performance of the bifunctional platinum-loaded calcium-hydroxyapatite in the one-step synthesis of methyl isobutyl ketone

Calcium-hydroxyapatite catalysts loaded with different amounts of platinum Pt(x)/CaHAp were synthesized and characterized by N2-adsorption, X-ray diffraction, transmission electron microscopy, Fourier transform infrared, ultraviolet–vis–NIR spectroscopy and temperature programmed reduction. It was found that the loaded platinum was mainly exchanged and dispersed on the apatite surface, forming particles with an average size of 2nm. The exchanged platinum, as shown by XRD, did not affect the apatite structure or its crystallinity. The specific surface area of the bare CaHAp as well as the mean pore diameter, diminished by increasing the Pt loading, probably because the pores were partially blocked. The Pt(x)/CaHAp samples calcined at 500°C contained, beside the exchanged platinum, Pt and PtO. H2-TPR results showed that the platinum occupied on the apatite at least two different sites.The acid–base and redox properties of the catalysts were studied using, as the probe reaction, butan-2-ol conversion. The impregnation of CaHAp with Pt decreased its natural basic properties and enhanced markedly the dehydrogenation of butan-2-ol into methyl ethyl ketone (MEK). In the presence of air, the production of MEK increased abruptly with the temperature. The reaction started at 30°C, passed through a maximum (90% of conversion) at 60°C and then it decreased rapidly. This important activity at low temperatures was attributed to Pt and Pt2+ species associated with the basic Ca2+–O2− groups of the apatite.The synthesized bifunctional catalysts were also investigated in the acetone conversion, in one step, into methyl isobutyl ketone (MIBK). The optimal performance was achieved with the sample loaded with 0.5wt.% Pt. It displayed at 150°C and stationary state a MIBK yield of 23% with a selectivity of 74%. Moreover, all the Pt(x)/CaHAp catalysts showed an acceptable stability over time on stream with no production of heavy compounds.