Synthesis of Diphenyl Carbonate from Phenol and Carbon Dioxide in the Presence of Carbon Tetrachloride and Zinc Chloride

Diphenyl carbonate (DPC) was synthesized from phenol and dense phase CO₂ in the presence of CCl₄ and K₂CO₃ using different catalysts of ZnCl₂, ZnBr₂, Lewis acid ionic liquids including 1-butyl-3-methylimidazolium chloride (BMIMCl) and bromide (BMIMBr). It was found that K₂CO₃ was not required, ZnCl₂ and ZnBr₂ were similar in the catalytic performance, and the use of BMIMCl and BMIMBr was not effective for the production of DPC. For the reactions with ZnCl₂ in CCl₄, the effects of such reaction variables as temperature, CO₂ pressure, the amount of ZnCl₂, and the volume of CCl₄ were studied in detail. It was shown that the pressure was less influential while a larger amount of ZnCl₂, a smaller volume of CCl₄, and a low temperature of around 100°C were beneficial for the synthesis of DPC. On the basis of the results obtained, possible reaction mechanisms were discussed.     

Pyrolysis of pine wood in a slowly heating fixed-bed reactor: Potassium carbonate versus calcium hydroxide as a catalyst

Catalytic pyrolysis of pine wood was carried out in a fixed-bed reactor heated slowly from room temperature to 700 °C under a stream of purging argon to examine the effects of the physically mixed K₂CO₃ or Ca(OH)₂ on the pyrolysis behaviors. K₂CO₃ demonstrated a stronger catalysis for decomposition of hemicellulose, cellulose and lignin constituents, leading to the reduced yield of liquid product in conjunction with the increased yields of gaseous and char products because of the promoted secondary reactions of liquid product. With the addition of 17.7 wt.% of K₂CO₃, none of saccharides, aldehydes and alcohols was formed and the formation of acids, furans and guaiacols was substantially reduced, whereas the yields of alkanes and phenols were increased. Potassium led to an increase in the cumulative yields of H₂, CO₂ and CO at 700 °C. Ca(OH)₂ somewhat promoted the decomposition of cellulose and lignin constituents, and the effect of Ca(OH)₂ on the yields of liquid and char was opposite to that of K₂CO₃. With the addition of 22.2 wt.% Ca(OH)₂, some groups of liquid product such as acids and aldehydes disappeared completely and the yields of saccharides, furans and guaiacols were somewhat reduced, while the yield of alcohols was remarkably increased in contrast to the result of K₂CO₃. The addition of Ca(OH)₂ did not significantly change the total yield of gaseous product at 700 °C but enhanced the yield of H₂.     

Catalytic activity, stability and structure of multi-walled carbon nanotubes in the wet air oxidation of phenol

Multi-walled carbon nanotubes (MWCNTs), with no supported metal, were used as catalysts in the wet air oxidation of phenol. The MWCNTs were chemically modified using HCl or HNO₃-H₂SO₄. They were characterized by BET, SEM, TEM, FT-IR and Raman spectroscopy. The functionalized MWCNTs exhibited both high activity and good stability in the wet air oxidation of phenol. At 160 °C and 2.0 MPa with an initial phenol concentration of 1000 mg/L, 100% phenol conversion and 76% total organic carbon abatement could be achieved after 120 min reaction. Upon reaction, the short chain carboxylic acids mainly maleic/fumaric, malonic, oxalic, formic and acetic acid were produced. Surface functional groups (-COOH) were shown to play a key role in the high activity of the functionalized MWCNTs. A mechanism for the CWAO of phenol was proposed.     

Guava (Psidium guajava L.) seed oil obtained with a homemade supercritical fluid extraction system using supercritical CO2 and co-solvent

In this work we designed and built a homemade supercritical fluid extraction (HM-SFE) system, in which pure CO₂ and CO₂ with co-solvents were used. The HM-SFE was made by means of thermal dilatation-contraction (TDC). This HM-SFE system was used for obtaining guava (Psidium guajava L.) seed oil, using supercritical CO₂ adding ethanol as co-solvent (CO₂ SC/EtOH), extractions were performed at 313 K and different pressures (10, 20 and 30 MPa), each one in four stages of 30 min, the extract with higher yield was subjected to transesterification and high-resolution gas chromatography (HRGC) analysis. The highest extraction yield was obtained at 30 MPa (17.30% w/w), this yield was higher than one observed in a previous work using SC-CO₂, and near to the one obtained by Soxhlet extraction (20.2% w/w). HRGC enabled the identification of components of the derivatized extract as methyl esters of palmitic, oleic, linoleic, and stearic fatty acids. The results obtained with HM-SFE system was compared with a commercial SFE system, obtained very similar results. In this work was possible to construct a low cost and simple manner HM-SFE system which was employed for obtaining guava seed oil, using CO₂ SC/EtOH.     

Effect of Na2CO3 on hexagonal boron nitride prepared from urea and boric acid

Formation of hexagonal boron nitride (hBN) from a precursor obtained by the reaction of urea and boric acid was studied in nitrogen, ammonia and argon atmospheres in 700-1200 °C temperature range. Effect of sodium carbonate (Na₂CO₃) addition on this process was investigated. Reaction products were subjected to X-ray diffraction, particle size distribution, gravimetric and Fourier transformed infrared spectroscopy analyses. Particle size and crystallite thickness of the formed hBN were seen to increase from about 60 nm and 5 nm at 700 °C to 230 nm and 19 nm at 1200 °C, respectively in NH₃ atmosphere with Na₂CO₃ addition. Highest conversion of boron in the precursor into hBN was achieved as 73.6% when Na₂CO₃ added precursor was reacted at 1200 °C in NH₃. hBN powder with high yield and relatively large particle size was obtained at low temperature such as 1200 °C with Na₂CO₃ addition. Role of Na₂CO₃ addition was suggested to be formation of a sodium borate melt from which hBN crystallized via the reaction of borate and nitrogen ions in the melt. Obtained hBN has the potential for utilization as a clean starting material for synthesis of B or N containing compounds.     

Copolymerization of carbon dioxide and propylene oxide with neodymium trichloroacetate-based coordination catalyst

The copolymerizations of carbon dioxide (CO₂) and propylene oxide (PO) were performed using new ternary rare-earth catalyst. It was found that the rare-earth coordination catalyst consisting of Nd(CCl₃COO)₃, ZnEt₂ and glycerine was very effective for the copolymerization of PO with CO₂. The effects of the relative molar ratio and addition order of the catalyst components, copolymerization reaction time, and operating pressure as well as temperature on the copolymerization were systematically investigated. At an appropriate combination of all variables, the yield could be as high as 6875 g/mol Nd per hour at 90 °C in a 8 h reaction period.     

Study of phenol removal using fluidized-bed Fenton process

In this paper, the removal of phenol from simulated wastewater was studied using gas–liquid fluidized bed with the Fenton reagent. The factors that affect the removal rate of phenol were investigated, including the initial concentrations of hydrogen peroxide [H₂O₂] and [Fe²⁺], the molar ratio of [Fe²⁺]/[H₂O₂], pH value, temperatures, reaction time, and the ventilation volume. It was found that the optimal operating conditions existed as: [H₂O₂] = 12 mmol/L, [H₂O₂]/[Fe²⁺] = 4:1, pH = 4, T = 60 °C, reaction time of 30 min, and a ventilation volume of 0.12 m³/h. Under these conditions, the phenol removal rate of about 96% was obtained.     

Direct synthesis of diphenyl carbonate by mediated electrocarbonylation of phenol at Pd-supported activated carbon anode

Mediated electrocarbonylation of phenol to diphenyl carbonate (DPC) at a PdCl₂-supported activated carbon anode in 1 atm CO at 298 K was studied. A dry CH₂Cl₂ or CH₃CN solvent and a galvanostatic electrolysis of 1 mA were necessary for formation of DPC, while the addition of a base and a supporting electrolyte was also essential. A combination of triethylamine (Et₃N) and tetrabutylammonium perchlorate (Bu₄NClO₄) was suitable in various combinations. The addition of 2 equiv. of Et₃N to the electrolyte (C₆H₅OH/Bu₄NClO₄/CH₂Cl₂) at 1-h intervals was more efficient in the formation of DPC than a single initial addition of the same amount of Et₃N. The yield of DPC was 130% based on Pd and its current efficiency (CE) was 42% for 6 h. The CE of the CO₂ formation was only 3%. Sodium phenoxide (PhONa) showed dual functionality as a base and supporting electrolyte. When the mediated electrocarbonylation was conducted in a C₆H₅OH/PhONa/CH₃CN electrolyte, DPC was produced in 172% yield and 40% CE for 6 h. The CE of the CO₂ formation was 10%. DPC formed continuously after a single initial addition of 4 equiv. of PhONa. Li or K phenoxide also worked as promoters for the mediated electrocarbonylation of phenol to DPC.     

The effects of catalysts on the carbothermic reduction of zinc sulfide in the presence of calcium oxide

The effects of the type and the amount of various catalysts on the rate of the carbothermic reduction of zinc sulfide in the presence of calcium oxide were studied using thermogravimetric analysis system (TGA). Experimental results revealed that the order of the effects of the catalysts is Li₂CO₃ ≈ Na₂CO₃ ≈ Na₂SO₄ > Li₂SO₄ > K₂CO₃ > K₂SO₄. It was also observed that with more Li₂CO₃ the reaction is faster, when the amount of Li₂CO₃ was less than 2.0 wt.%.     

Effect of gas pressure on the phase behaviour of organometallic compounds

The knowledge of the phase behaviour of organometallic compounds in supercritical CO₂ is the key factor for determining the feasibility of homogeneous catalysis in supercritical fluid reaction. In the present study, the solid-liquid-gas equilibrium line for the system CO₂/Cu(thd)₂, CO₂/Pt(COD)Me₂ and He/Pt(COD)Me₂ was determined from 0.1 MPa to 25 MPa. In addition, experimental solubility data of Cu(thd)₂ in CO₂ at 333 K and pressures ranging from 10 MPa to 17 MPa as well as of Pt(COD)Me₂ in CO2 at 313 K, 333 K and 353 K and pressures ranging from 12 MPa to 32 MPa are presented. The solubility data are correlated using the linear relationship between the logarithm of the solubility and the logarithm of the reduced density of pure CO₂ proposed by Kumar and Johnston as well as an extension of the theory of dilute solution proposed by Mendez-Santiago and Teja. Both approaches gave reasonable results in the correlation of the experimental solubility data.     

Coal devolatilization and char conversion under suspension fired conditions in O2/N2 and O2/CO2 atmospheres

The aim of the present investigation is to examine differences between O₂/N₂ and O₂/CO₂ atmospheres during devolatilization and char conversion of a bituminous coal at conditions covering temperatures between 1173 K and 1673 K and inlet oxygen concentrations between 5 and 28 vol.%. The experiments have been carried out in an electrically heated entrained flow reactor that is designed to simulate the conditions in a suspension fired boiler. Coal devolatilized in N₂ and CO₂ atmospheres provided similar results regarding char morphology, char N₂-BET surface area and volatile yield. This strongly indicates that a shift from air to oxy-fuel combustion does not influence the devolatilization process significantly. Char combustion experiments yielded similar char conversion profiles when N₂ was replaced with CO₂ under conditions where combustion was primarily controlled by chemical kinetics. When char was burned at 1573 K and 1673 K a faster conversion was found in N₂ suggesting that the lower molecular diffusion coefficient of O₂ in CO₂ lowers the char conversion rate when external mass transfer influences combustion. The reaction of char with CO₂ was not observed to have an influence on char conversion rates at the applied experimental conditions.     

Transesterification of soybean oil to biodiesel using CaO as a solid base catalyst

In this study, transesterification of soybean oil to biodiesel using CaO as a solid base catalyst was studied. The reaction mechanism was proposed and the separate effects of the molar ratio of methanol to oil, reaction temperature, mass ratio of catalyst to oil and water content were investigated. The experimental results showed that a 12:1 molar ratio of methanol to oil, addition of 8% CaO catalyst, 65 °C reaction temperature and 2.03% water content in methanol gave the best results, and the biodiesel yield exceeded 95% at 3 h. The catalyst lifetime was longer than that of calcined K₂CO₃/γ-Al₂O₃ and KF/γ-Al₂O₃ catalysts. CaO maintained sustained activity even after being repeatedly used for 20 cycles and the biodiesel yield at 1.5 h was not affected much in the repeated experiments.     

Electrochemically reduced titanocene dichloride as a catalyst of reductive dehalogenation of organic halides

We have studied a reaction between the reduced form of titanocene dichloride (Cp₂TiCl₂) and a group of organic halides: benzyl derivatives (4-XC₆H₄CH₂Cl, X = H, NO₂, CH₃; 4-XC₆H₄CH₂Br, X = H, NO₂, PhC(O); 4-XC₆H₄CH₂SCN, X = H, NO₂) as well as three aryl halides (4-NO₂C₆H₄Hal, Hal = Cl, Br; 4-CH₃O-C₆H₄Cl). It has been shown that the electrochemical reduction of Cp₂TiCl₂ in the presence of these benzyl halides leads to a catalytic cycle resulting in the reductive dehalogenation of these organic substrates to yield mostly corresponding toluene derivatives as the main product. No dehalogenation has been observed for aryl derivatives. Based on electrochemical data and digital simulation, possible schemes of the catalytic process have been outlined. For non-substituted benzyl halides halogen atom abstraction is a key step. For the reaction of nitrobenzyl halides the complexation of Ti(III) species with the nitro group takes place, with the electron transfer from Ti(III) to this group (owing to its highest coefficient in LUMO of the nitro benzyl halide) followed by an intramolecular dissociative electron redistribution in the course of the heterolytic CHal bond cleavage.The results for reduced titanocene dichloride centers immobilized inside a polymer film showed that the catalytic reductive dehalogenation of the p-nitrobenzyl chloride does occur but with a low efficiency because of the partial deactivation of the film due to the blocking of the electron charge transport between the electrode and catalytic centers.     

Kinetics of phenol mineralization by Fenton-like oxidation

The kinetics of hydrogen peroxide decomposition and the mineralization rate of phenol in homogeneous aqueous solution (pH < 3) via Fenton-like reaction were studied. Results were correlated with the generation of hydroxyl radicals as well as with iron speciation. Batch experiments were carried out in de-ionized water in a completely mixed batch reactor under a wide range of experimental conditions (3500 ≤ [H₂O₂] ≤ 8250 mg/L; 100 mg/L ≤ [Fe] ≤ 2350 mg/L; 2.5 ≤ [H₂O₂]/[Fe] ≤ 83; 0 mg/L ≤ [TOC] ≤ 1000 mg/L). Results demonstrated that the rate of hydrogen peroxide decomposition, phenol mineralization and ferrous ions formation depended on both the initial concentration of the phenol and on the weight ratio between hydrogen peroxide and iron. A linear correlation was found between the mineralization rate of phenol and the decomposition rate of hydrogen peroxide indicated that 10 g of hydrogen peroxide was required to mineralize 1 g of phenol.     

Kinetics of absorption of carbon dioxide into aqueous solution of 2-(1-piperazinyl)-ethylamine

The absorption of CO₂ into aqueous solution of 2-(1-piperazinyl)-ethylamine (PZEA) were studied at 303, 313, and 323 K within the amine concentration range of 0.083-1.226 kmol m⁻³ using a wetted wall column absorber. The experimental results were used to interpret the kinetics of the reaction of CO₂ with PZEA within the amine concentration range of 0.150-1.226 kmol m⁻³ for the above mentioned temperature range. Based on the pseudo-first-order condition for the CO₂ absorption, the overall second order reaction rate constants were determined from the kinetic measurements. The reaction order was found to be in between 0.99 and 1.03 with respect to amine for the later mentioned concentration range. The kinetic rate parameters were calculated and presented at each experimental condition. The second-order rate constants k₂, were obtained as 31867.6, 56354.2, and 100946 m³ kmol^-1 s^-1 at 303, 313, and 323 K, respectively, with activation energy of 47.3 kJ mol⁻¹. This new amine in the field of acid gas removal can be used as an activator by mixing with other alkanolamine solvents due to its very high rate of reaction with CO₂.     

The performances of higher alcohol synthesis over nickel modified K2CO3/MoS2 catalyst

Ni modified K₂CO₃/MoS₂ catalyst was prepared and the performance of higher alcohol synthesis catalyst was investigated under the conditions: T = 280–340 °C, H₂/CO (molar radio) = 2.0, GHSV = 3000 h^− 1, and P = 10.0 MPa. Compared with conventional K₂CO₃/MoS₂ catalyst, Ni/K₂CO₃/MoS₂ catalyst showed higher activity and higher selectivity to C₂⁺OH. The optimum temperature range was 320–340 °C and the maximum space-time yield (STY) of alcohol 0.30 g/ml h was obtained at 320 °C. The selectivity to hydrocarbons over Ni/K₂CO₃/MoS₂ was higher, however, it was close to that of K₂CO₃/MoS₂ catalyst as the temperature increased. The results indicated that nickel was an efficient promoter to improve the activity and selectivity of K₂CO₃/MoS₂ catalyst.     

Direct synthesis of formic acid by partial oxidation of methane on H-ZSM-5 solid acid catalyst

The direct synthesis of formic acid by partial oxidation of methane was studied using hydrogen peroxide (H₂O₂) as oxidant with keeping reaction temperature of 373 K and a pressure of 2.6 MPa. High yield (13.0%) and selectivity (66.8%) of formic acid (HCOOH) an important oxygenated compound in chemical industry were achieved using protonated pentasil-type zeolite (H-ZSM-5) as a solid acid catalyst. Tryphenylphosphene(Ph₃P) was used as a promoter in reaction system. A fairly large amount of CO₂ was also observed as deep oxidation product.     

Effect of chemisorbed carbon monoxide on Pt/C electrode on the mechanism of the hydrogen oxidation reaction

The influence of poisoning of Pt catalyst by CO on the kinetics and mechanism of H₂ oxidation reaction (HOR) at Pt/C electrode in 0.5 mol dm⁻³ HClO₄, saturated with H₂ containing 100 ppm CO, was examined with rotating disc electrode (RDE) at 22 °C. Commercial carbon black, Vulcan XC-72 was used as support, while Pt/C catalyst was prepared by modified polyol synthesis method in an ethylene glycol (EG) solution. The kinetically controlled current (I_k) for the HOR at Pt/C decreases significantly at CO coverage (Θ_CO) > 0.6. For Θ_CO < 0.6 the HOR takes place through Tafel-Volmer mechanism with Tafel reaction as rate-determining step at the low CO coverage, while Volmer step controls the overall reaction rate at the medium CO coverage. When CO coverage is higher then 0.6, Heyrovsky-Volmer mechanism is operative for the HOR with Heyrovsky as the rate-determining step (rds).     

Continuous production of fatty acid methyl esters from corn oil in a supercritical carbon dioxide bioreactor

Continuous production of fatty acid methyl esters (FAMEs) from corn oil was studied in a supercritical carbon dioxide (SC-CO₂) bioreactor using immobilized lipase (Novozym 435) as catalyst. Response surface methodology (RSM) based on central composite rotatable design (CCRD) was employed to investigate and optimize the reaction conditions: pressure (11-35 MPa), temperature (35-63 °C), substrate mole ratio (methanol:corn oil 1-9) and CO₂ flow rate (0.4-3.6 L/min, measured at ambient conditions). Increasing the substrate mole ratio increased the FAME content, whereas increasing pressure decreased the FAME content. Higher conversions were obtained at higher and lower temperatures and CO₂ flow rates compared to moderate temperatures and CO₂ flow rates. The optimal reaction conditions generated from the predictive model for the maximum FAME content were 19.4 MPa, 62.9 °C, 7.03 substrate mole ratio and 0.72 L/min CO₂ flow rate. The optimum predicted FAME content was 98.9% compared to an actual value of 93.3 ± 1.1% (w/w). The SC-CO₂ bioreactor packed with immobilized lipase shows great potential for biodiesel production.     

Kinetics of absorption of carbon dioxide into aqueous solutions of 2-amino-2-hydroxymethyl-1,3-propanediol

In this work the kinetics of the reaction between CO₂ and a sterically hindered alkanolamine, 2-amino-2-hydroxymethyl-1,3-propanediol (AHPD) were determined at temperatures of 303.15, 313.15 and 323.15 K in a wetted wall column contactor. The AHPD concentration in the aqueous solutions was varied in the range 0.5-2.4 kmol m⁻³. The ratio of the diffusivity and Henry's law constant for CO₂ in solutions was estimated by applying the N₂O analogy and the Higbie penetration theory, using the physical absorption data of CO₂ and N₂O in water and of N₂O in amine solutions. Based on the pseudo-first-order for the absorption of CO₂, the overall pseudo-first-order rate constants were determined from the kinetics measurements. By considering the zwitterion mechanism for the reaction of CO₂ with AHPD, the zwitterion deprotonation and second-order rate constants were calculated. The second-order rate constant, k₂, was found to be 285, 524, and 1067 m³ kmol⁻¹ s⁻¹ at 303.15, 313.15, and 323.15 K, respectively.