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Mesityl oxide is standardly used to produce methyl iso butyl ketone but it can be also used to produce other useful compounds. Three catalysts were used for the reaction of the mesityl oxide reduction. They were NiW, NiMo, and CoMo supported on phonolite modified by HCl (metals/Ph-HCl). The fresh catalysts were characterized by XRD, XRF, BET surface, Hg porosimetry, SEM, H2-TPR, NH3-TPD, CO2-TPD. The materials were directly used, previously reduced in H2 or sulfided for the mesityl oxide reduction under H2 atmosphere. The reaction was performed in an autoclave at T = 375 °C, p = 50 bar (H2), and TOS = 1.5 h. The products were analyzed by GC/MS, GC/FID-TCD, ATR. The main products were methyl isobutyl ketone, 2-methyl pentane, and 2-methyl-2-pentene. Sulfided metal catalysts were the most active in the methyl isobutyl ketone, where the NiWSx/Ph-HCl catalyst showed the highest activity. For the non-previously-activated and hydrogen activated catalysts the most active catalyst was the NiMo/Ph-HCl for the production of methyl isobutyl ketone. The catalyst CoMo/Ph-HCl activated in hydrogen was the most active for the production of 2-methyl pentane compared to the other two hydrogen-activated materials.

Using the results of an earlier study of the physicochemical properties of the reaction system of the process of producing mesityl oxide, an analysis of the statics of the combined variant of the organization of this process was carried out. It is shown that of practical interest are the modes of the process corresponding to the first specified separation. In this case, the limiting stationary states, characterized by the maximum acetone conversion, selectivity, and the yield of the target product — mesityl oxide, are distinguished. The possibility of practical implementation of the limiting stationary state of the reactive distillation process for producing mesityl oxide, which provides almost complete conversion of acetone with a yield of mesityl oxide approaching 100%, has been proved. The limit stationary state corresponds to the reaction-distillation process with the selection of a single product stream. For the mode of carrying out the combined process that corresponds to the selected limiting stationary state, a schematic flow chart for the production of the target product has been proposed. By means of computational research, it has been established that the most rational option for organizing a reaction hub is to use a single apparatus in it — the reaction-distillation column. In the Aspen Plus® software package, a process model was constructed that corresponded to the proposed technological scheme and through a computational experiment, its structural and parametric optimization was carried out. As a result, the static parameters of the technological system were established, as well as the characteristics of the apparatuses, allowing to obtain the required quality product in the reactiondistillation column. output, approaching 100%. It has been shown that when modeling a chemicaltechnological system, it is necessary to use different sets of parameters of the basic equation used to describe phase equilibrium. Thus, for calculating reactive distillation and distillation columns, the liquid – vapor phase equilibrium parameters for the mesityl oxide–water system should be used, and when calculating the Florentine vessel for this mixture, it is necessary to use the parameters corresponding to the liquid – liquid equilibrium. The use of a single set of parameters of the basic equation leads to significant errors and inadequate description of the process of producing mesityl oxide by condensation of acetone.

We report a systematic DRIFTS-MS study of surface acetone aldolization and self-deoxygenation reactions on ZrO2 and Zn1Zr10Oz, using temperature programmed surface reactions of both acetone reactant and possible intermediate compounds including diacetone alcohol, mesityl oxide, phorone, and isophorone. DRIFTS was used to monitor the evolution of surface species while MS was used to track corresponding gas phase products, in an attempt to identify the distinct reaction pathways observed on the two catalysts as well as the role zinc plays in the corresponding reaction pathways. It is found that aldol condensation (or aldolization) of acetone occurs readily at low temperature (298 K), forming mainly acetone dimers (i.e., diacetone alcohol, DAA/mesityl oxide, MSO) on both ZrO2 and Zn1Zr10Oz with the latter being more active. At elevated temperatures, secondary MSO reactions are diverted, mainly caused by the different Lewis basicity on the two catalysts. Over ZrO2, MSO reacts with activated acetone (acetone enolate) to form a surface 4,4-dimethyl-2,6-heptadione (phorone-C), which is further converted into a stable isophorone intermediate. At temperatures above 473 K, polymerization/oligomerization of isophorone along with basic hydroxyl promoted decomposition reactions occur, leading to the formation of heavier carbonaceous surface species and gas-phase side products (methane and CO2). The addition of zinc balances the surface acid-base properties on ZnxZryOz (i.e., Zn1Zr10Oz) via not only enhancing the surface Lewis basicity but passivating the strong acidity. This balance, especially the enhanced surface Lewis basicity largely promotes the α-H abstraction of MSO to form MSO enolate on the Zn1Zr10Oz, which thus favors the aldolization of MSO enolate and acetone, a reaction tends to form 2,6-dimethyl-2,5-heptadien-4-one (phorone-A). Phorone-A then readily decomposes to produce isobutene as a major product at temperature as low as 373 K. Note that, despite the facile formation of isobutene at low temperatures, a high temperature (673 K) is still necessary to release the strongly adsorbed formate/carbonate/acetate species via CO2 formation.

We combine mid-infrared dual-comb spectroscopy with attenuated total reflectance measurements to provide in-situ monitoring of a chemical reaction. The mid-infrared dual-comb spectrometer measures quantitative absorption cross-sections of mesityl oxide and diacetone alcohol in the region of 3300–2700 cm−1 (3.0–3.7 μm). Based on these spectra, the system is then used to monitor the hydration of mesityl oxide to diacetone alcohol from which we extract reaction kinetics values. This work shows the potential of dual comb systems to measure and monitor reactions in the condensed phase.

In this study, we discuss the development of a static headspace gas chromatography method for the analysis of residual acetone as well as its enriched impurities including mesityl oxide and diacetone alcohol, in a spray dried dispersion. The major challenges include the instability of mesityl oxide and diacetone alcohol at high temperature and peak tailing of diacetone alcohol. It was found that the headspace oven temperature has to be controlled to 150°C or below to prevent degradation beyond an acceptable level (< 1%). The peak tailing of diacetone alcohol was attributed to the "Phase Soaking" effect due to excessive diluent, which may condense and temporarily modify the stationary phase. The peak shape of diacetone alcohol is dependent on the column loading capacity and the peak area of N-methyl pyrrolidone, the solvent that elutes after diacetone alcohol. The headspace oven temperature was set at 140°C, where the highest response ratio of diacetone alcohol/N-methyl pyrrolidone at 1.46 and thus the best sensitivity was obtained. The calculated quantitation limits were 1 ppm for acetone, 3 ppm for mesityl oxide and 31 ppm for diacetone alcohol. The method successfully passed validation criteria for specificity, linearity, accuracy, and precision.

Chrysotile-type Mg3Si2O5·(OH)4 nanotubes (MgSi-NTs) were obtained (by a hydrothermal method) using different SiO2 sources. Sources of silica, as raw material, were varied from sodium silicate (typical preparation) to colloidal silica of 12–22 nm colloid size. Around 13 g of MgSi-NTs were prepared by using 7.8 L Teflon-lined autoclave at 240 °C. In all synthesis attempts, XRD was used to identify chrysotile crystal phases, which were later confirmed by TEM, showing bundles of hollow cylindrical particles of MgSi-nanotubes from 60 to 218 nm length and internal diameters from 5 to 8 nm. Specific surface areas obtained by nitrogen adsorption of MgSi-NTs samples (annealed at 600 °C) were between 105 and 202 m2/g with average pore diameter from 7 to 32 nm, depending on silica precursor. Thermal stability of MgSi-NTs was examined by TGA-DTA, XRD and TEM. From TEM images, it was clear that nanotubes from colloidal silicas can hold up below 600 °C. Sodium silicate obtained nanotubes were less thermally stable (below 500 °C), though. The use of colloidal silica, instead of sodium silicate, upgraded specific surface area and pore volume values of resulting MgSi-NTs. Number of basic sites and properties were measured by CO2-TPD ranging between 66 and 89 μmol CO2/g cat, and their catalytic activity was assessed on aldol condensation of acetone reaction at 300–350 °C, where the main products obtained were mesityl oxide and isophorone, which are valuable products for fine-chemistry industry.

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.

Liquid–liquid equilibrium (LLE) data were measured for the ternary system of water + resorcinol + mesityl oxide under atmospheric pressure at temperatures of (298.2, 323.2, 333.2, 343.2 and 353.2) K. The reliability of the experimental data was verified by the Hand and Bachman equations. The distribution coefficient and selectivity were calculated from the experimental LLE data, which showed high efficiency of mesityl oxide extracting resorcinol from the aqueous solution. The NRTL and UNIQUAC models were employed to fit the measured experimental LLE data and yield corresponding binary interaction parameters.

Mesityl oxide is an important product of organic synthesis, which is used in the manufacture of pharmaceuticals and as a solvent. The demand for mesityl oxide is growing, which determines the need for further improvement of its production. The disadvantages of the traditional methods of obtaining mesityl oxide are low values of reagent conversion and selectivity. To eliminate them, it is proposed to obtain mesityl oxide in a combined reaction-rectification process. The combination of chemical transformation and separation of the resulting reaction mixture by means of rectification in one apparatus allows for a continuous withdrawal of the formed products from the reaction zone, which increases the rate of the target reaction, conversion and selectivity. In accordance with the modern strategy for the development of chemical-technological processes, the collection and processing of physical and chemical information on the properties of the components and mixtures contained in the reaction system was performed. Based on the experimental data, the parameters of the phase equilibrium model are determined, and its adequacy is estimated. The phase equilibrium model was used to construct a distillation diagram, to verify its consistency, and to conduct computational studies of the reaction-rectification process. The thermochemical parameters of the target reactions are calculated, the equilibrium constants are determined, and their temperature dependence is established. On the basis of the analysis of the literature data, a kinetic model of the process is proposed, and the conditions favorable for the course of the desired chemical transformation are determined with the use of this model. The obtained data are necessary for carrying out the analysis of the statics, constructing the basic technological scheme and calculating its static parameters.

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 C O bond cleavage of DAA efficiently.

Liquid–liquid equilibrium (LLE) data for the ternary system of (2-pentanone + catechol + water) and (mesityl oxide + catechol + water) was measured under atmospheric pressure at T = (298.2, 318.2 and 333.2) K. The distribution coefficients and separation factors were employed to assess the efficiency of extracting catechol from water. The nonrandom two liquid and universal quasichemical models were applied to correlate the LLE data, and the corresponding binary interaction parameters were obtained. The topological analysis of LLE correlation was used to confirm that the parameters satisfy the Gibbs stability criteria.

This paper presents investigation on the synthesis of 2,2,4-trimethyl-1,2-H-dihydroquinoline (TMQ) as a result of the reaction of aniline and both acetone and mesityl oxide in the presence of selected sulfonic acid silica catalysts. Condensation of aniline with acetone is very complex process with the formation of significant number of side products, both desirable and undesirable considering the final product (TMQ). In acidic conditions and elevated reaction temperature the reactivity of main raw materials (aniline, acetone) is significantly high, what causes the formation of many side by-products lowering the selectivity of this reaction. In this paper the reaction of aniline with acetone in the presence of heterogeneous acidic silica catalysts were investigated in more detail and discussed. The results were confirmed by GC/MS analysis, that the presence of TMQ isomers and other by-products significantly affected the formation of final product. The formation of previously not described structural isomer of TMQ has been also demonstrated.

Accurate liquid–liquid equilibria (LLE) data are of momentous significance for the design, simulation, as well as optimization of the extractive process. To assemble the essential data for the operation of extracting cyclohexanol from the aqueous solution, LLE data for {water + cyclohexanol + toluene}, {water + cyclohexanol + mesityl oxide}, and {water + cyclohexanol + p-xylene} ternary systems were experimentally measured at 303.15 and 323.15 K under 101.3 kPa. The separating power of the extractants was assessed via the distribution coefficient and selectivity. The Othmer–Tobias and Bachman equations were applied to confirm the experimental data coherence. The data obtained from experiments were correlated via the nonrandom two liquid (NRTL) and universal quasi-chemical (UNIQUAC) models, and the regression result was better since the RMSD values were all less than 0.2%. However, the UNIQUAC model was preferable since the RMSD was smaller. In addition, the relevant binary interaction parameters were also...

The phenols recovery process is a significant part of treating coal chemical wastewater with highly concentrated phenols and ammonia. Solvent extraction is an important unit for phenol recovery section. The accurate measurement of liquid–liquid equilibrium (LLE) data is essential for realizing partitioning. In this paper, the LLE data for the ternary system water + 2-, 3-, 4-methylphenol +3,3-dimethyl-2-butanone (also known as methyl tert-butyl ketone, MTBK) were studied at the temperatures of 333.2 K and 353.2 K under 101.3 kPa. The extraction performance of MTBK was estimated by partition coefficients and separation factors. The extraction efficiencies of MTBK were compared with those of MIBK, mesityl oxide, and those results of MTBK at five different temperatures from 298.2 K to 353.2 K were also contrasted with each other. In addition, the nonrandom two-liquid (NRTL) and universal quasi chemical (UNIQUAC) models were applied to fit the measured LLE data. The results indicate that the calculated data b...

Development and improvement of industrial technologies based on the principle of combining reaction and mass exchange processes is an urgent task. This is due to their advantage over the traditional sequential way of performing the chemical transformation and separation of the resulting reaction mixture. In reaction-rectification processes, the conversion of the process, the rate of reaction and selectivity may be increased due to continuous withdrawal of the formed products from the reaction zone. In addition, capital and energy costs in such processes are significantly reduced due to the reduction or even complete absence of external recycling in them. The modern method of developing reaction-rectifying processes is the analysis of statics, which allows isolating the limiting stationary states corresponding to the maximum yield of the target product. An essential disadvantage limiting the possibility of using this method for solving practical problems is the consideration of a single chemical reaction in its framework. At the same time, when passing to real processes, as a rule, this restriction is violated. The article offers a number of original approaches designed in the form of an algorithm that allows the analysis of statics to be extended to reaction-rectification processes with an unlimited number of components forming the reaction mixture and an unlimited number of chemical reactions taking place between them. On the basis of this algorithm, a ChIM program was developed in the SciLab environment, which makes it possible to single out sets of limiting stationary states of a combined process characterized by maximum reagent conversion values, selectivity and yield of the target product. The procedure for using the ChIM program is illustrated by the example of the industrial process for obtaining mesityl oxide from acetone. Calculations conducted using the software package Aspen Plus proved the possibility of practical implementation of limiting stationary state providing the maximum yield of mesityl oxide, which was predicted by using of ChIM.

Efficient production of diacetone alcohol (DAA), mesityl oxide (MO) and isophorone (IP) is important for the high value utilization of acetone. For this, a novel process is proposed for the aldol condensation of acetone by refluxing on CaC2, whereby 95% of total selectivity of (DAA, MO and IP) and 85% of acetone conversion are achieved simultaneously under mild conditions (56 °C, 100 kPa). This result is superior to the previously reported ones, which may be ascribed to the extremely high catalytic capacity of CaC2 for the aldol condensation and instant separation of the target products from the catalyst to suppress the unwanted successive condensations. Moreover, the target products may be adjusted by operation conditions. Lower temperature and higher reflux rate favour the production of DAA and MO; MO and IP are favoured otherwise. The present process integrates several functions into one unit, i.e. the basic catalysis of calcium carbide, aldol condensation of acetone, instant distillation separation of the condensates, and the hydrolysis of CaC2 to C2H2, which makes it feasible to coproduce C2H2 and high value derivatives of acetone simultaneously.

Bis(trimethylsilyl) hypophosphite reacts with unsaturated ketones (methyl vinyl ketone and mesityl oxide) to give, depending on the reaction conditions, 1: 1 or 1: 2 adducts after hydrolysis. It was found that the intramolecular cyclization of the 1: 2 reaction product with mesityl oxide, trimethylsilyl bis(2-methyl-4- oxopentan-2-yl)phosphinate, yields, after hydrolysis, a phosphorinane with exocyclic carbonyl and hydroxyl groups.

In order to separate and purify cyclohexanone from water, in 101.3 kPa, the liquid-liquid equilibrium (LLE) data of water (1) + cyclohexanone (2) + ethyl acetate (3) at 298.2, 303.2, and 313.2 K were measured. The extraction ability of ethyl acetate was evaluated by distribution coefficient (D) and selectivity factor (S). It was found that the extraction effect was higher at 313.2 K, and the selectivity was better at 298.2 K. At the same time, through comparison with the literature, it is found that mesityl oxide can selectively extract cyclohexanone from water better than ethyl acetate. The NRTL and UNIQUAC models were successfully associated with the LLE data with the root mean square deviation (RMSD) was not greater than 0.27%. Finally, it was verified that the regression parameters of the thermodynamic model have good consistency by GUI-MATLAB tools.

To separate and purify cyclohexanone from water, in 101.3 kPa, 298.2, 303.2 and 313.2 K, the liquid–liquid equilibrium (LLE) data of the ternary mixture of water + cyclohexanone (CYC) + mesityl oxide were presented. The distribution coefficient (D) and separation factor (S) appraised the utility of extracting cyclohexanone from water. The NRTL and UNIQUAC models successfully correlated the experimental data with RMSD less than 0.29%. The GUI-MATLAB tool was used to verify the good reliability of the regression parameters.

Liquid–liquid equilibria provide basic data and guidance regarding the design, simulation, and development of an appropriate solvent extraction process. In the current work, the data for the liquid–liquid equilibrium (LLE) of water + cyclohexanone + isophorone and water + cyclohexanone + mesityl oxide systems have been measured at temperatures of 308.15–328.15 K and pressure of 101.3 kPa. The empirical Bachman and Hand equations were utilized to confirm the consistency of experimentally determined LLE data. Meanwhile, the solute distribution ratio and separation parameter were obtained from the experimental equilibrium data to evaluate the extraction properties of the selected solvents. Additionally, a mathematical regression of experimental tie-line compositions for all of the investigated ternary mixtures was performed by means of the nonrandom two-liquid and universal quasi-chemical activity coefficient models to acquire corresponding optimized binary interaction parameters. The correlation results wer...

The extractant has a great influence on the performance and economy of the Phenols Recovery processes for treating coal-gasification wastewater. Meanwhile, computer-aided screening techniques have been applied to discern candidate solvents from the molecular perspective. In this paper, mesityl oxide, as a novel extractant, is found with high phenols removal efficiency through quantum chemical calculations. To confirm that, the removal performance with three different solvents (diisopropyl ether (DIPE), methyl isobutyl ketone (MIBK) and mesityl oxide) are investigated and compared via multi-stage counter-current extraction experiments. The experimental results identified that the performance using mesityl oxide as solvent is better than that using DIPE and MIBK. The total phenols concentration can be reduced from more than 5000 mg/L to less than 250 mg/L. Then, Phenols Recovery process using mesityl oxide as solvent is developed and conceptual designed. In view of the better performance and lower cost, mesityl oxide is a very promising extractant for the removal of phenols.

In this work, liquid-liquid equilibrium (LLE) data for the water + propionic acid or butyric acid + mesityl oxide ternary systems were measured at (298.2 and 323.2) K under atmospheric pressure. The reliability of the experimental tie-line data was verified by the Othmer-Tobias and Hand equations. The distribution coefficient and selectivity, calculated from the LLE data, showed high efficiency for mesityl oxide extracting propionic or butyric acid from the aqueous solution. A comprehensive comparison with various other extractants not only confirmed the high extraction efficiency of mesityl oxide, but also revealed some general guide lines for further screening extractants for carboxylic acids. The experimental data were successfully correlated by both UNIQUAC and NRTL models, yielding binary interaction parameters for relevant process simulations.

A stepwise isopropylation reaction of acetone is developed for preparation of methyl isobutyl ketone (MIBK) through acetone condensation and a recoverable Pt/C-catalyzed transfer hydrogenation of mesityl oxide (MO) with isopropanol (IPA). Almost quantitative MO conversion (up to 99.9%) and excellent MIBK selectivity (up to 99.3%) could be achieved by the method. Since IPA can be obtained from propane, a cheap petrochemical product, the by-product acetone (AT) generated in the reduction of MO could be easily recovered and reused in the preparation of MO, and the Pt/C catalyst could be recycled and reused, this H2- and waste-free reaction may be a green and practical method for preparation of the useful fine chemical MIBK.

In this work, liquid-liquid equilibrium (LLE) data for the ternary systems, mesityl oxide + o-, m-, p-cresol + water, were determined at 333.2 K and 353.2 K under 101 kPa. The high distribution coefficient and selectivity calculated by the experimental tie-line data indicate excellent efficiency for mesityl oxide extracting cresols from aqueous solutions. The NRTL and UNIQUAC models were used to correlate the experimental LLE data, with root mean square deviations (RMSDs) below 2.1% and 1.5%, respectively. The COSMO-SAC model was also employed to calculate the LLE data, which agreed with the experimental results quite well.

The steel industry is currently a major water pollution source, releasing high quantities of chemicals. One of the pollutants is phenol, known for its toxicity even when it is present in low concentrations. Liquid-liquid extraction employing various aromatics and cycloalkanes (i.e., benzene, toluene, cyclohexane, ethylbenzene) and ketones (i.e., methyl isobutyl ketone, cyclohexanone and mesityl oxide) as solvents, is studied in the present paper. A comparison among the seven solvents is performed based on process modelling simulation tools and Life Cycle Assessment (LCA). The simulations of the seven cases under study are conducted at the same wastewater flowrate of 100 tons/h, with a phenol content of 0.2 wt.% and compared using various parameters (i.e., quantity of solvent, steam and power used, quantity of solvent present in the output phenol streams). The simulation results show that the lowest quantity of solvent is registered in the phenol removal which uses cyclohexanone as solvent (e.g., 34,212.40 kg/h), followed by the case which uses mesityl oxide for the liquid-liquid extraction (e.g., 34,759.80 kg/h) and by the case involving cyclohexanone (e.g., 37,490.60 kg/h). The lowest steam consumption is registered also in the case of cyclohexanone usage (e.g., 47.56 GJ/h) while the lowest power consumption corresponds to mesityl oxide usage (e.g., 11.20 MJ/h). The simulation results are then used to perform an environmental analysis, quantified in terms of environmental key performance indicators, embedding several solvents production methods as well as various fuels. Our life cycle assessment leads to the conclusions that the most environmentally friendly design is phenol removal using cyclohexanone as a solvent, whose provision comes from cyclohexane, which in turn is produced from benzene in conjunction with steam production from natural gas. For instance, the lowest global warming potential indicator score is about 342 kg CO2 equivalents per kg of phenol, while the same indicator for the worst solvent, i.e., toluene produced using reforming technology and steam being produced using hard coal as fuel, is almost double (e.g., 341.94 kg CO2 equivalents per kg of phenol vs. 575.30 CO2 equivalents per kg of phenol). Lower values for other impact indicators are also obtained in the phenol removal using cyclohexanone as a solvent with steam being generated form natural gas (e.g., acidification potential indicator is 0.42 kg SO2 equivalents per kg of phenol, eutrophication potential is 4.21 × 10−2 kg PO43- equivalents per kg phenol, ozone depletion potential is 1.13 × 10-9 kg R11 equivalents per kg phenol).

Acetone adsorption and catalytic interactions with a MgO nanoparticle surface was studied using in-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) at room temperature. Acetone showed adsorption bands at 2965, 1717, 1597, 1422, 1415, 1367, 1238, 1229, and 1204 cm−1. The MgO was found to be a good catalyst for the activation of the aldol condensation reaction of acetone to form di-acetonealcohol (DAA). The OH group role on the MgO surface was found to be a suppression agent to the further dehydration of DAA to mesityl oxide. This is probably because the OH group blocks the active sites on the MgO surfaces that adsorbed the water formed from the dehydration of DAA. This conclusion was confirmed by identifying the basic site concentrations on MgO surface using DRIFTS and TPD studies of CO2 adsorption/desorption on MgO nanoparticles surface. The high-strength basic sites which are required to dehydrate DDA to mesityl oxide was found to represent only 17.5 % of the total basic site concentration, while the low-strength basic sites resulted from hydroxyl surface group represent 22.5 %. On the other hand, the acetone interaction with the MgO surfaces produced several components such as formaldehyde, acetate, ethoxide, as well as other carbonate species such as bicarbonate, bidentate carbonate, and monodentate carbonate. The results of the present investigation supply important essential insights into catalytic reactions resulted from acetone adsorption on MgO nanoparticle surfaces.

To provide essential data for the separation of diethoxymethane and system water using mesityl oxide as the extractant, in this paper, the liquid-liquid equilibrium data of the ternary system of ‘mesityl oxide + diethoxymethane + water’ was measured at 303.2 K, 313.2 K and 323 K under normal pressure. The experimental results showed that partition coefficient and separation factor were both larger than 1, indicating that diethoxymethane and water could be well separated with mesityl oxide. The linear correlation coefficient of Bachman and Hand equation was larger than 0.99, indicating that our experimental data has good reliability. At the same time, the binary interaction parameters of the model were obtained by correlating the experimental data with the NRTL and UNIQUAC models. The relative root mean square error (RMSD) of the experimental value and the calculation formula was less than 0.79%, indicating that both the NRTL and UNIQUAC models can be well associated with experimental data.

Amino acid and primary amine/amide co-catalyzed acetone condensation was investigated. It was found that l-proline had overwhelming catalytic activity over other amino acids as well as the analogues with similar structures. Surprisingly, thiourea, a very cheap and stable chemical, was found to be the favorable co-catalyst. Co-catalyzed by the recyclable l-proline and thiourea, condensation of acetone led to the useful products mesityl oxide (MO), diacetone alcohol (DAA) and isophorone (IP) in the excellent 96.3% total selectivity.

In this work, liquid–liquid equilibria (LLE) data for the ternary system {mesityl oxide (1) + phenol (2) + water (3)} were measured at 298.15, 313.15, and 323.15 K under atmospheric pressure. The experimental LLE data were proven to be highly reliable by the Othmer–Tobias and Hand equations. The distribution coefficient and selectivity were calculated from the LLE data, which indicated mesityl oxide extracted phenol with a rather high efficiency. The NRTL and UNIQUAC models were employed to correlate the LLE data, yielding binary interaction parameters for simulating relevant extraction processes. The experimental LLE data were correlated successfully by both models.

A polymer resin-supported proline catalyst was developed. The material might serve as an eco-friendly recoverable organocatalyst with industrial application potential. Its catalytic activity in acetone condensation was tested. Catalyst prepared under optimized conditions showed good performances, giving mesityl oxide (MO), diacetone alcohol (DAA) and isophorone (IP) in up to 87.7 % total selectivity, while the catalyst could be recovered with less than 5 % mass lost and could be reused for at least seven times without deactivation. Being able to convert market-excess acetone into useful bulk fine chemicals, the catalyst is of significant industrial value.

Catalyst acidity is among the crucial parameters affecting the direction and degree of acid-catalyzed reactions. The Hammett acidity functions (H0) of binary mixtures of triflic acid (TfOH) and ionic liquids (ILs), namely, [BMim][HSO4], [BMim][TfO], and [BMim][TFA], were measured by the 13C NMR method using mesityl oxide as a probe. The results show that the H0 values of the mixtures can be effectively controlled by tailoring the structure of the IL or tuning the amount of IL added to the system. The −H0 values of the binary mixtures decrease with increasing amount of IL. Mixtures of [BMim][HSO4]/TfOH and [BMim][TfO]/TfOH show minimal changes in acidity (−H0 > 13.00) when the IL mole fraction is less than 0.05, a sharp decline in acidity (−H0 = 13.00 → 8.00) at an IL mole fraction of 0.05 to 0.20, and a relatively stable acidity (−H0 = 8.00 → 5.40) at an IL mole fraction of 0.20 to 0.50. These mixtures share nearly the same H0 value when the IL mole fraction is less than 0.20. The addition of [BMim][TFA] ...

The reaction of neat 3-chloroaniline with neat SCN–P(O)(OPh)2 leads to a new N-phosphorylated thiourea, 3-ClC6H4NHC(S)NHP(O)(OPh)2 (1). The same reaction in non-dried CH2Cl2 or C6H6 leads to the salt-like compounds [3-ClC6H4NH3]+[NCS]− (2) and [3-ClC6H4NH3]+[P(O)2(OPh)2]−·0.5C6H6 (3·0.5C6H6), respectively, while using non-dried acetone yields 1-(3-chlorophenyl)-4,4,6-trimethyl-3,4-dihydropyrimidine-2(1H)-thione (4). Dissolution of 1 in non-dried CH2Cl2, C6H6 or Me2CO leads to the direct formation of 2, 3·0.5C6H6 and 4, respectively. It was established that thione 4 is most likely formed through the thiourea 1-assisted aldol condensation of acetone leading to mesityl oxide. In turn the latter ketone interacts with 1 followed by its hydrolysis leading to 4. Compounds 1–4 have been characterized by NMR spectroscopy and elemental analysis and their molecular structures were elucidated by X-ray diffraction. Hirshfeld surface analysis showed that the structures of both 1 and 4 are mainly characterized by H⋯H, H⋯C, H⋯Cl and H⋯S contacts as well as by H⋯O in the structure of 1. The enrichment ratio, derived as the decomposition of the crystal contact surface between pairs of interacting chemical species, for 1 was found, as expected for the polar contacts, which are generally hydrogen bonds, to be significantly larger than unity for the contacts of the type H⋯O and H⋯S. A much larger than unity value was found for the enrichment ratio of the C⋯C contacts in the structure of 1, which is due to extensive π⋯π stacking in the crystal packing. The enrichment ratio for 4 was found to be larger than unity for the contacts of the type H⋯C and, but with a lesser degree, H⋯Cl and H⋯S.