Gas-phase hydrodechlorination of pentachlorophenol over supported nickel catalysts

The gas-phase hydrodechlorination of pentachlorophenol (PCP) over nickel/silica and nickel/Y zeolite catalysts at 573 K has been studied. Each catalyst was 100% selective in cleaving the C–Cl bonds, leaving the hydroxyl substituent and benzene ring intact. The variation of catalytic activity and selectivity (in terms of partial and full dechlorination) with time-on-stream is illustrated and catalyst deactivation is addressed. Dechlorination efficiency is quantified in terms of dechlorination rate constants, phenol selectivity/yield and the ultimate partitioning of chlorine in the parent organic and product inorganic host. Increasing the nickel loading on silica was found to raise the overall level of dechlorination while the use of a zeolite support introduced spatial constraints that severely limited the extent of dechlorination. Product composition was largely determined by steric effects where resonance stabilisation had little effect. The reaction pathways, with associated pseudo-first-order rate constants, are also presented. This revised version was published online in November 2006 with corrections to the Cover Date.     

The catalytic hydrodechlorination of mono-, di- and trichlorobenzenes over supported nickel

The gas phase hydrodechlorination (HDC) of chlorobenzene (CB), chlorotoluene(s) (CT), 3-chlorophenol (3-CP), dichlorobenzene(s) (DCB) and trichlorobenzene(s) (TCB) over the temperature range 473 K≤T≤573 K has been studied using 1.5% and 6.1% (w/w) Ni/SiO₂ catalysts; the catalytic data have been obtained in the absence of any appreciable short-term deactivation. HDC of DCB and TCB generated the partially or the fully dechlorinated aromatic product + HCl and there was no significant cyclohexene or cyclohexane in the effluent stream. The conversion of mono-chloroarenes yielded the following reactivity sequence CB < 2-CT < 3-CT < 4-CT < 3-CP, i.e. the presence of an electron donating ring substituent enhances HDC and steric hindrance lowers reactivity. HDC kinetics have been adequately represented by a pseudo-first order approximation. Chlorine removal from DCB and TCB isomers proceeded through sequential and concerted routes, the relative importance of each dependent on the nature of the isomer and reaction conditions; apparent HDC activation energy increases in the order CB < DCB < TCB. The relationship between dechlorination selectivity and residence time/fractional conversion is addressed. The higher Ni loaded catalyst delivered consistently higher (specific) dechlorination rates and higher benzene yields from a polychlorinated feedstock. Catalytic HDC over Ni/SiO₂ is presented as a viable means of treating/detoxifying concentrated chlorinated gas streams and the best strategy for generating the parent benzene or a target partially dechlorinated product is discussed.     

Inhibition effects of organosulphur compounds on the hydrodechlorination of tetrachloroethylene over Pd/Al2O3 catalysts

The hydrodechlorination of tetrachloroethylene in presence of thiophene over a commercial Pd/Al₂O₃ catalyst was studied in a continuous packed-bed reactor at different temperatures (200–300 °C) and thiophene concentrations (0–5 wt.%). Results indicate that thiophene reversibly decreases tetrachloroethylene conversion and increases the selectivity for trichloroethylene formation. The kinetics of the hydrodechlorination of tetrachloroethylene in the presence of thiophene to form trichloroethylene and ethane can be represented by a Langmuir–Hinshelwood model.     

Gas phase hydrodechlorination of chlorinated aromatic compounds on nickel catalysts

Supported Ni/-Al₂O₃ catalysts were studied in the gas phase hydrodechlorination of substituted chlorobenzenes. The catalytic properties of the catalysts were shown to be determined by the metal nickel. A correlation between the rate of the gas phase hydrodechlorination of substituted chlorobenzene and donor-acceptor properties of substituents was established. The electron-donor substituents increase and the electron-acceptor ones decrease their reactivity. The correlation analysis of data treated via the Hammett equation shows that hydrodechlorination on Ni/-Al₂O₃ catalysts is a reaction of electrophilic type.     

Aqueous-phase hydrodechlorination of model chlorinated organic compounds over Ru/C catalyst

Effluents from the pharmaceutical and dye industries contain chlorinated organic pollutants. The effective treatment of such effluents constitutes a challenging task. In this work, 4-chlororesorcinol (PCRE) and 4-chloro-2-aminophenol (PCAP) were selected as model chloro-organic compounds. Catalytic hydrodechlorination (HDC) of PCRE and PCAP in the aqueous phase was investigated in a slurry reactor using commercial carbon supported ruthenium catalyst. HDC reactions of PCRE and PCAP were studied over the ranges in temperature, 313–353?K, H₂ partial pressure, 0.69–2.76?MPa, and catalyst loading, 0.2–1.2?kg/m³. The performance of Ru/C catalyst for hydrodechlorination and ring saturation was promising. The kinetic data were modeled using Langmuir–Hinshelwood–Hougen–Watson kinetics. The HDC reaction of PCRE and PCAP using Ru/C catalyst proceeds via a dual-site mechanism, wherein atomic H₂ reacts with the adsorbed organic substrate. The activation energy for the hydrodechlorination reactions of PCRE and PCAP was 41.6 and 49.4?kJ/mol, respectively.     

In situ production of nickel/graphitic carbon nanofiber composites and application in catalytic hydrodechlorination

The action of Ni/SiO₂ in the gas phase hydrodechlorination (at 573 K) of chlorobenzene, 1,3-dichlorobenzene and 1,3,5-trichlorobenzene is compared with that of a Ni/SiO₂ + C composite. The latter was prepared in situ by the decomposition of chlorobenzene at 873 K to generate graphitic carbon nanofibers bearing Ni particles at the fiber tips. The Ni/SiO₂ and Ni/SiO₂ + C (with varying C content) catalysts have been characterized by TEM, SEM, XRD and H₂ chemisorption. While the Ni/SiO₂ + C system delivered a lower initial fractional dechlorination, the composite outperformed the starting Ni/SiO₂ in terms of long-term activity, an effect that is linked to the structural characteristics.     

Effect of support modification on the chlorobenzene hydrodechlorination activity on Pt/Al2O3 catalysts

Al₂O₃ was modified with TiO₂ and ZrO₂ using organometallic precursors and is used in the preparation of supported platinum catalysts. The catalysts have been characterised by nitrogen adsorption, hydrogen chemisorption and X-ray diffraction and were tested for their activity in the hydrodechlorination of chlorobenzene. The investigations show that support modification controls the catalyst deactivation remarkably and the catalysts were found to be highly active and selective. This revised version was published online in July 2006 with corrections to the Cover Date.     

Reductibility of silica supported nickel oxide

The reduction of nickel/silica catalysts was studied in parallel by temperature programmed reduction (TPR) and X-ray diffraction (XRD) methods. The calcined materials contain nickel in the form of nickel oxide and nickel hydrosilicates and a part of the oxide particles is covered with the hydrosilicate species. This oxide is reduced in the same way as unsupported nickel oxide in the absence of water, and in a similar way to nickel hydrosilicates in the presence of water.     

Gas phase catalytic hydrodechlorination of chlorophenols using a supported nickel catalyst

The gas phase hydrodechlorination of single component and mixtures of o-, m- and p-chlorophenol was studied over the temperature range 423 K≤T≤573 K using a 1.5% (w/w) Ni/SiO₂ catalyst. The variation of catalyst activity with time-on-stream for each isomer is illustrated and the role of reaction temperature and thermodynamic limitations are addressed. The catalyst exhibits both short term and irreversible long term deactivation which is accounted for in terms of competitive adsorption and electronic effects. The hydrogen treatment of both phenol and chlorobenzene under the same reaction conditions are also considered for comparative purposes. The presence of the hydroxyl function enhances the rate of hydrodechlorination via an inductive effect. The relationship between rate and isomer structure is discussed on the basis of reactant adsorption where steric hindrance, in the case of the ortho-form, appreciably restricts dechlorination to such an extent that o-chlorophenol remains unreacted in equimolar o-/p- and o-/m-chlorophenol mixtures. Catalytic hydrodechlorination is viewed as a non-destructive low energy methodology for handling concentrated chlorine gas streams and relationships that describe the dependence of dechlorination rate on chlorine concentration are provided and can be used to evaluate the productive lifetime of the catalyst.     

Solvent effects in the hydrodechlorination of 2,4‐dichlorophenol over Pd/Al2O3

Solvent effects in the liquid phase (0.1 MPa; 303 K) hydrodechlorination (HDC) of 2,4‐dichlorophenol have been established over Pd/Al₂O₃. In the absence of secondary reactions, catalyst deactivation, and transport limitations, a stepwise HDC yields 2‐chlorophenol and phenol, where product selectivity was insensitive to the nature of the solvent. In contrast, the initial HDC rates exhibited a marked dependence on the reaction medium and increased in the order: benzene < THF < n‐hexane < cyclohexane < alcohols < water. Higher rates result from the concomitant effect of an increase in the dielectric constant (ε) and a decrease in the molar volume ( $\overline {\nu}$ ) of the solvent, where the major (ca. 80%) contribution is due to ε. We attribute this response to the increased solvent capacity to stabilize the arenium intermediate at higher/lower ε/$\overline {\nu}$ , an effect that extends to reaction in water + organic combinations. We provide, for the first time, a reliable quantification of solvent effects that can be potentially applied to other catalytic hydrogenolysis systems. © 2009 American Institute of Chemical Engineers AIChE J, 2010     

Liquid phase hydrodechlorination of chlorophenols over Pd/C and Pd/Al2O3: a consideration of HCl/catalyst interactions and solution pH effects

The liquid phase hydrodechlorination (HDC) of 2-chlorophenol (2-CP) and 2,4-dichlorophenol (2,4-DCP) has been studied over 1% (w/w) Pd/C and Pd/Al₂O₃ under conditions of minimal mass transport constraints. The HDC of 2,4-DCP generated HCl and 2-CP as the only intermediate partially dechlorinated product which reacts further to yield phenol; cyclohexanone was formed over Pd/Al₂O₃, but not over Pd/C, prior to complete dechlorination. Pd/Al₂O₃ is characterized (on the basis of TEM analysis) by a narrow distribution of smaller Pd particles to give a surface area weighted mean particle DIAMETER = 2.4 nm that is appreciably lower than the value of 13.2 nm established for Pd/C, where the latter is characterized by a broader distribution of larger (spherical) particles. The addition of NaOH served to increase fractional dechlorination by suppressing HDC inhibition due to the HCl that is generated. Reuse of the catalysts revealed an appreciable deactivation of Pd/C and a limited loss of activity in the case of Pd/Al₂O₃. Deactivation of Pd/C can be linked to a decrease (up to ca. 60%) in the initial BET surface area allied to appreciable leaching (up to ca. 40%) of the starting Pd content through the corrosive action of HCl and, while the average Pd diameter is essentially unaffected, there is evidence of a preferred leaching of larger Pd particles. The stronger metal/support interactions prevalent in Pd/Al₂O₃ results in limited Pd leaching and comparable initial HDC activities during catalyst reuse with/without NaOH addition. Inclusion of HCl in the reaction mixture (pH 5–1.5) resulted in a marked decline in the initial HDC rate associated with Pd/Al₂O₃ and a lesser drop in HDC activity for Pd/C. The difference in response to bulk solution pH variations are discussed in terms of the nature of the reactive species in solution and the amphoteric behavior of the Pd supports.     

磷钨酸／硅胶催化剂催化合成环己酮1，2-丙二醇缩酮

以溶胶-凝胶法制备的磷钨酸／硅胶为催化剂、通过环己酮和1，2-丙二醇反应合成了环己酮1，2-丙二醇缩酮，探讨磷钨酸／硅胶对缩酮反应的催化活性，较系统地研究了酮醇量比、催化剂用量、反应时间、带水剂用量对产品收率的影响。实验表明：磷钨酸／硅胶是合成环己酮1-2-丙二醇缩酮的良好催化剂，在门（酮）：门（醇）=1：1．5、催化剂用量为反应物料总质量的0．5％、环己烷为带水剂、反应时间45min的优化条件下，环己酮1，2-丙二醇缩酮的收率可达79．8％．     

Preparation and properties of organosoluble polyimide/silica hybrid materials by sol–gel process

Organosoluble polyimide/silica hybrid materials were prepared using the sol–gel process. The organosoluble polyimide was based on pyromellitic anhydride (PMDA) and 4,4′‐diamino‐3,3′‐dimethyldiphenylmethane (MMDA). The silica particle size in the hybrid is increased from 100–200 nm for the hybrid containing 5 wt % silica to 1–2 µm for the hybrid containing 20 wt % silica. The strength and the toughness of the hybrids are improved simultaneously when the silica content is below 10 wt %. As the silica content is increased, the glass transition temperature (T_g) of the hybrids is increased slightly. The thermal stability of the hybrids is improved obviously and their coefficients of thermal expansion are reduced. The hybrids are soluble in strong polar aprotic organic solvents when the silica content is below 5 wt %. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2977–2984, 1999     

The effect of cationic surfactant and some organic/inorganic additives on the morphology of mesostructured silica templated by pluronics

Tri-block copolymers (poly(ethylene oxide)–poly(propylene oxide)–poly(ethylene oxide), represented as EO_xPO_yEO_x), pluronics (F127 = EO₁₀₆PO₇₀EO₁₀₆, P65 = EO₂₀PO₃₀EO₂₀, P85 = EO₂₇PO₃₉EO₂₇, P103 = EO₁₇PO₅₅EO₁₇, and P123 = EO₂₀PO₇₀EO₂₀) and cationic surfactants (cethyltrimethylammonium bromide (CTAB)), two surfactant systems, form complex micelles that self-assemble into mesostructured particles with distinct morphology depending on the pluronic type, the concentration of the cationic surfactant and the organic–inorganic ingredients in a siliceous reaction media under acidic conditions. The CTAB–P65 and CTAB–P85 systems form spheres, CTAB–P103 and CTAB–P123 systems form wormlike particles, and CTAB–F127 system form single crystals of mesostructured silica particles under very similar conditions. However addition of various salts (such as KCl and NaNO₃) into a CTAB–P103 or CTAB–P123 solution system and cyclohexane and KCl into a CTAB–P85 solution system produces the mesostructured silica spheres and wormlike particles, respectively. By controlling the hydrophilic–hydrophobic character of the pluronics, core–corona interface, by means of additives, such as small organic molecules or salts, one could obtain the desired morphology that is dictated by the shape of the micelles of the pluronic–cationic surfactant complex. The effects of the additives and the formation mechanism of those morphologies have been discussed using spectroscopy (FT-IR and Raman), diffraction (XRD) and microscopy (POM and SEM) data.     

Kinetics of oxidative cracking of n‐hexane to olefins over VOx/Ce‐Al2O3 under gas phase oxygen‐free environment

The kinetics of oxidative cracking of n‐hexane to olefins using lattice oxygen of VO_x/Ce‐Al₂O₃ is investigated. The TPR/TPO analysis shows a consistent reducibility (79%) of VO_x/Ce‐Al₂O₃ in repeated redox cycles. The total acidity of the sample is found to be 0.54 mmol/g with 22% are strong acid sites that favors olefin selectivity. The oxidative cracking of n‐hexane in a fluidized CREC Riser simulator gives approximately 60% olefin selectivity at 30% n‐hexane conversion. A kinetic model is developed considering (1) cracking, (2) oxidative dehydrogenation (ODH), and (3) catalyst deactivations. The proposed cracking mechanism considers adsorption, C–H and C–C bond fission and desorption as elementary steps and implemented by pseudo steady state hypothesis. A Langmuir‐Hinshelwood mechanism is found to represent the ODH reactions. The developed model fits the experimental data with favorable statistical indicators. The estimated specific reaction rate constants are also found to be consistent with the product selectivity data. © 2016 American Institute of Chemical Engineers AIChE J, 63: 130–138, 2017     

Dechlorination kinetics of monochlorobiphenyls by Fe/Pd: Effects of solvent, temperature, and PCB concentration

Well-known, yet undefined, changes in the conditions and activity of palladized zerovalent iron (Fe/Pd) over an extended period of time hindered a careful study of dechlorination kinetics in long-term experiments. A short-term experimental method was, therefore, developed to study the effects of temperature and solvent on the dechlorination of monochlorobiphenyls (MCBs), 2-chlorobiphenyl (2-ClBP), in particular by Fe/Pd. The experiments started with specified initial conditions and lasted only for 10 min. The average value (k) of the first-order rate constant for the dechlorination of 2-ClBP was 0.13 ± 0.03 L m⁻² h⁻¹, not significantly different from the average values for 3-chlorobiphenyl and 4-chlorobiphenyl. The apparent activation energy was 20 ± 4 kJ mol⁻¹ and 17 ± 7 kJ mol⁻¹, in a temperature range between 4 °C and 60 °C, for the dechlorination of 2-ClBP using two batches of Fe/Pd catalyst. The k values decreased significantly in mixtures with a methanol concentration higher than 10%. The values of the rate constant were slightly influenced by the initial concentrations in the experiments at a low temperature and in a solution with a high methanol concentration. The concentration dependence was described with a Langmuir equation, based on the Langmuir–Hinshelwood mechanism that includes an adsorption step of a single species preceding a rate-determining catalytic reaction.     

Catalytic combustion of chlorobenzene over MnOx–CeO2 mixed oxide catalysts

A series of MnOx–CeO₂ mixed oxide catalysts with different compositions prepared by sol–gel method were tested for the catalytic combustion of chlorobenzene (CB), as a model of volatile organic compounds of chlorinated aromatics. MnOx–CeO₂ catalysts with different ratios of Mn/Ce + Mn were found to possess high catalytic activity in the catalytic combustion of CB, and MnOx(0.86)–CeO₂ was identified as the most active catalyst, on which the temperature of complete combustion of CB was 254 °C. Effects of systematic variation of reaction conditions, including space velocity and inlet CB concentration on the catalytic combustion of CB were investigated. Additionally, the stability and deactivation of MnOx–CeO₂ catalysts were studied by various characterization methods and other assistant experiments. MnOx–CeO₂ catalysts with high Mn/Ce + Mn ratios present a stable high activity, which is related to their high ability to remove the adsorbed Cl species and a large amount of active surface oxygen.     

The effect of water on the reduction of nickel/alumina catalysts

The crucial role of water in the reduction of calcined nickel/alumina catalysts is demonstrated. A fraction of nickel oxide in the catalysts is reduced as NiO powder in the absence of water vapour, and as a nickel aluminate in the presence of water. A much higher dispersion of nickel is attained when the reduction is carried out at low concentration of water vapour.     

Adsorption and degradation of the cationic dyes over Co doped amorphous mesoporous titania–silica catalyst under UV and visible light irradiation

Cobalt doped amorphous mesoporous titania–silica with Ti/Si mass ratio of 0.8 (Co–TiO₂–SiO₂) was synthesized and used for the photodegradation of six cationic dyes (gentian violet, methyl violet, methylene blue, fuchsin basic, safranine T, and Rhdamine B) under UV and visible light illumination. The catalyst was characterized by a combination of various physicochemical techniques, such as N₂ physisorption, diffuse reflectance UV–vis, X-ray diffraction, and FT-IR.Co–TiO₂–SiO₂ exhibited activity under UV light and had better activity under visible light when compared with that of Degussa P25 TiO₂. The activity of Co–TiO₂–SiO₂ was also compared with that of Co-MCM-41, Co doped mesoporous titania with a crystalline framework (Co–MTiO₂) and titania-loaded Co doped MCM-41 (TiO₂/Co-MCM-41) for the degradation of gentian violet under visible light irradiation. It was also found that the degradation rates of Co–TiO₂–SiO₂ for gentian violet, methyl violet, methylene blue, fuchsin basic and safranine T were greater in alkaline media than in acid and neutral media, while it did not exhibit any significant activity for the photodegradation of Rhdamine B in alkaline media or in acid media under visible light irradiation.