Dehydrocyclization of Alkanes Over Zeolite-Supported Metal Catalysts: Monofunctional or Bifunctional Route

The direct catalytic conversion of alkanes into aromatics has found potentially important industrial applications. Initially only alkanes with 6 and more carbon atoms in the chain were concerned. Supported platinum catalysts were found active for the aromatization of alkanes; the drawbacks of these catalysts were their deactivation with time on stream and the existence of simultaneous parallel reactions. Much discussion has been published on the aromatization of C₆₊ alkanes. A bifunctional mechanism which involves both the metal and the acid sites of the support and a monofunctional mechanism involving only the metallic sites operate over, respectively, Pt supported on acidic support and Pt supported on nonacidic support. In the present review the mechanisms proposed for the aromatization of alkanes are described. Over monofunctional Pt catalysts two possible mechanisms prevail: 1,6 ring closure on the Pt surface involving primary and secondary C-H bond rupture, followed by dehydrogenation of the cycloalkanes into aromatics (1,5 ring closure to a lesser extent also contributes to aromatic production); or dehydrogenation of the alkanes into olefins, dienes, and trienes followed by thermal ring closure. Zeolites were found most suitable as support for preparing catalysts more active and more selective in the alkane aromatization. In addition catalysts based on noble metals supported on zeolite appeared more resistant against deactivation by coke. In this review the aromatization of hexane, heptane, and octane over Pt-zeolite catalysts is discussed in detail. Comparisons between different zeolite structures and different dehydrogenation sites are given. In particular a critical analysis of the results and interpretation concerning Pt-KL catalysts strongly suggests that the exceptional high selectivity towards aromatization of n-hexane exhibited by Pt-KL could not be explained by only the nest or constraint effect exerted by the channel dimension and morphology, not by only the terminal cracking properties, not by only the partial electron transfer from the zeolite support to the Pt particles, and not by only the Pt particle size. Zeolite structure also affects the aromatic product distribution, in particular when the alkane contains more than 7 carbon atoms. It is shown how Pt on medium-pore zeolites such as In-ZSM-5, silicalites will favor the aromatization of C₈ alkane isomers into ethylbenzene-styrene with respect to other C₈ aromatics. Aromatization of light alkanes, C₂-C₅, requires the increase of the hydrocarbon chain length up to 6 carbon atoms and higher, followed by cyclization reaction. Recently new processes to convert C₂-C₅ alkanes into aromatics have been disclosed, M2-forming from Mobil, Cyclar from BP-UOP, and Aroforming from IFP-Saluted. In general these processes use bifunctional catalysts possessing a dehydrogenating and an acid function. The catalysts consist of a metal ion or metal oxide supported on a microporous acid solid. In this review we analyze the results concerning mainly platinum supported on pentasil-type zeolite. It is shown that althoug Pt has better dehydrogenating properties as compared with gallium and zinc, the efficiency of catalysts based on Pt-ZSM-5 for light alkane aromatization is less because undersirable reactions such as hydrogenolysis and ethene (olefins) hydrogenation occur on the platinum surface, resulting in the production of unreactive alkanes, CH₂, C₂H₆. These drawbacks could be partially suppressed by alloying Pt and by increasing the reaction temperature.     

ZSM-5 supported iron catalysts for Fischer-Tropsch production of light olefin

Fischer-Tropsch Synthesis (FTS) for olefin production from syngas was studied on Fe-Cu-K catalysts supported on ZSM-5 with three different Si/Al ratios. The catalysts were prepared by slurry-impregnation method of metallic components, and were characterized by BET surface area, XRD, hydrogen TPR and ammonia TPD. Fe-Cu-K/ZSM-5 catalyst with a low Si/Al ratio (25) is found to be superior to the other catalysts in terms of better C₂-C₄ selectivity in the FTS products and higher olefin/(olefin + paraffin) ratio in C₂-C₄ because of the facile formation of iron carbide during FTS reaction and also due to a larger number of weak acidic sites that are present in these catalysts.     

Fischer-Tropsch-Synthese. Neuere Untersuchungen und Entwicklungen

Fischer-Tropsch synthesis – Recent studies and Developments . This article surveys some results of recent research and new lines of development in Fischer-Tropsch synthesis. Most interest is focussed on variants synthesis showing high selectivity of C₂-C₄ alkenes or C₅-C₂₀ 1-alkenes or Diesel oil. In the last decade catalysts of improved alkene selectivity have been developed. Also the dependence of selectivity on process parameters such as pressure of hydrogen and carbon monoxide and temperature has been investigated in order to find appropriate conditions of operation for a synthesis of high selectivity. Some preliminary process designs are discussed.     

Dehydrochlorination of Intermediates in the Production of Vinyl Chloride over Lanthanum Oxide-Based Catalysts

Lanthanum oxide-based catalysts are active in the elimination of HCl from C₂H₅Cl, 1,2-C₂H₄Cl₂ and 1,1,2-C₂H₃Cl₃ leading to the formation of their respective chlorinated ethenes. An oxygen-rich catalytic surface may form CO, CO₂ and C₂HCl as side products, whereas with chlorine-rich catalytic surfaces a stable product distribution is achieved with 100% selectivity towards the formation of ethenes, such as the valuable C₂H₃Cl intermediate.     

Direct partial oxidation of methane over ZSM-5 catalyst: effects of additives

Previously, it was reported that the direct partial oxidation (DPO) of CH₄ with O₂ over HZSM-5 catalysts produces C₅₊ hydrocarbon liquids when the feed contains a propane or propene additive. This work studies additive effects on C₅₊ production in this system by processing a CH₄/C₃H₈ feed with subsequent removal of the C₃ additive and by processing natural gas feed. Results show C₅₊ production is maintained at constant yields for HZSM-5 catalysts having different zeolitic Al contents after removal of the C₃ additive. Mechanistic implications are discussed. Natural gas DPO consistently produced C₅₊ liquids due to the presence of C₂₊ components in the feed. While C₅₊ yields from natural gas DPO are higher than those observed for CH₄/C₃ feeds, increasing feed O₂ concentration, and thus conversion, deleteriously affected C₅₊ selectivity.     

Cyclic alkanes as geochemical markers in coal liquefaction products

Branched-chain/cyclic alkanes have been obtained, by solvent extraction and molecular-sieve adsorption, from a UK low-temperature (Rexco) coal tar, a USA fluidized-bed pyrolysis (FMC COED) coal tar, and a novel supercritical-gas-extract of a Turkish (Elbistan) lignite. Mass spectrometry (with gas chromatography and field-desorption) established the presence of mono-, di (including sesquiterpanes), tri-, tetra- (steranes only), and pentacyclic (triterpanes only) alkanes, including several steranes and triterpanes not previously reported as coal-tar constituents. The potential of cyclic alkanes as geochemical markers, even for commercial coal products subjected to appreciable heat treatment, is demonstrated by the identification of C₁₂, C₁₃, C₁₅ and C₁₆ dicyclics (including isoprenoid alkanes), C₁₇-C₂₆ tricyclics, and C₂₇ and C₂₉ hopane-type pentacyclics (triterpanes) in FMC, and of C₁₆-C₃₈ monocyclics, C₃₄-C₃₆ dicyclics, C₂₂-C₃₆ tricyclics, C₂₇-C₃₀ tetracyclics (steranes), and C₂₇, C₂₉, C₃₀, C₃₁, C₃₂, and C₃₃ hopane-type pentacyclics (triterpanes) in Rexco tar. Tetra- and pentacyclic alkanes were also preserved in the lignite extract.     

On the influence of the acid-base character of catalysts on the oxidative dehydrogenation of alkanes

Vanadium oxides supported on metal oxide, i.e. Al₂O₃, MgO and Mg-Al mixed oxide, and V-containing microporous materials (VAPO-5 and MgVAPO-5) have been tested in the oxidative dehydrogenation of C₂-C₄ alkanes. In all cases, tetrahedral vanadium species (isolated and/or associated) were mainly observed from⁵¹V-NMR and diffuse reflectance spectroscopies. The reducibility of V⁵⁺-species, determined from the onset-reduction temperature, decreases as follows: VO_x/AL > VAPO-5 > MgVAPO-5 =VO_x/MG > VO_x/MG + AL. The acid character of catalysts, determined from the FTIR spectra of pyridine adsorbed, decreases as: MgVAPO-5 > VO_x/AL > VAPO-5 > VO_x/MG + AL > VO_x/MG. A similar trend between V-reducibility of the catalyst and its catalytic activity for the alkane conversion was observed. However, the selectivity to olefins depends on the acid-base character of catalyst and the alkane fed. In the ODH ofn-butane, the higher the acid character of the catalyst the lower the selectivity to C₄-olefins, while in the ODH of ethane an opposite trend between the catalyst acidity and the selectivity to ethene was observed.On leave from the Department of Industrial Chemistry and Materials, V. le Risorgimento 4, 40136 Bologna, Italy.     

Role of chlorine in improving selectivity in the oxidative coupling of methane to ethylene

Samarium, magnesium and manganese oxide and alkali-promoted oxide catalysts have been prepared and tested for the oxidative coupling of methane. The results show that alkali-promoted oxides inhibit total oxidation and have a higher selectivity for the formation of C₂ products than the undoped metal oxides. These catalysts have been promoted by injecting pulses of gaseous chlorinated compounds (dichloromethane and chloroform) during the reaction. It has been found that these chlorinated compounds markedly increase the selectivity for the formation of C₂ products for all the MnO₂-based catalysts and for lithium-doped MgO and Sm₂O₃ catalysts. The effect is greatest in MnO₂-based catalysts. When dichloromethane is added to a pure, unpromoted MnO₂ catalyst the selectivity for the formation of carbon dioxide decreases from 82.6% to 4.1% and the selectivity for the formation of C₂H₄ increases from virtually zero to 56.3%. The highest C₂ selectivity observed after promotion of pure MnO₂ by dichloromethane is about 93%. Promotion of these pure oxide catalysts by gaseous chlorinated compounds provides an alternative to alkali promotion as a method of inhibiting total oxidation and of increasing ethylene production.     

Conversion of light paraffins for preparing small olefins over ZSM-5 zeolites

The conversion of C₃-C₉ paraffins to small olefins over ZSM-5 zeolite is investigated. The small olefins are primary products and are usually converted into other more stable secondary products such as aromatics on the ZSM-5 zeolites. Thermally treated HZSM-5, K/HZSM-5 and Ba/HZSM-5 catalysts were developed and favourable oxidative conditions were introduced for the conversion process to maximize selective conversion of light paraffins to small olefins at the relatively low temperature of 873 K. The role of K and Ba is to minimize bimolecular hydrogen transfer reactions and enhance the dehydrogenation activity of the catalysts. Meanwhile, the oxygen in the gas phase is effective to improve the olefin selectivity and yield. C₂-C₄ olefin selectivities of 70.4 and 66.8% have been obtained for propane andn-hexane feed-stocks, respectively, at a temperature of 873 K.     

Selective partial oxidation of light paraffins with hydrogen peroxide on thin-layer supported Nafion-H catalysts

Thin-layer carbon supported Nafion-H catalysts were found to be active and highly selective (S>98%) for the partial oxidation of C₁-C₃ alkanes, in a three phase catalytic membrane reactor (3PCMR), under mild conditions and in the presence of H₂O₂. The influences of the catalyst teflon loading and H₂O₂ concentration on the reaction rate have been evaluated. A reaction pathway, based on the electrophilic hydroxylation of the C-H bond of alkanes with protonated hydrogen peroxide (H₃O ₂ ⁺ ), is discussed.     

Determination of the Specific Heat of the Normal Alkanes C<Subscript>7</Subscript>-C<Subscript>11</Subscript>

Using precise experimental data on the specific heat at constant pressure C _p of the normal alkanes C₇-C₁₁ over a wide parameter range, the C _p values are determined on the liquid and vapor branches of the boundary curve from the normal boiling point to 0.98T _c. In the coordinates C _p-P _s-T _s, orthogonal projections of the reduced phase diagram of these hydrocarbons are constructed and analyzed. Existing generalized expressions for C _p of the liquid and gas phases of the normal alkanes C₅-C₁₁ on the boundary curve as a function of temperature are evaluated, and new expressions for C _p are proposed.__________Translated from Teoreticheskie Osnovy Khimicheskoi Tekhnologii, Vol. 39, No. 4, 2005, pp. 476–480.Original Russian Text Copyright © 2005 by Kuznetsov, Gorbachev.     

Isoparaffin production by aqueous phase processing of sorbitol over the Ni/HZSM-5 catalysts: Effect of the calcination temperature of the catalyst

Ni/HZSM-5 catalysts calcined at different temperatures were used in the isoparaffin production by aqueous phase processing of sorbitol and characterized by N₂ physical adsorption, temperature-programmed reduction (H₂-TPR), temperature-programmed desorption of ammonia (NH₃-TPD) and Raman techniques. The effect of calcination temperature of the catalysts on the catalytic performance for the reaction was investigated. The activity test results indicated that the maximal i-C₆H₁₄ selectivity of 45.4% and the total i-C₆H₁₄ and i-C₅H₁₂ yield of 32.3% were obtained over the catalyst calcined at 500 °C, which exhibited the optimum surface area and pore structure with 100% of the reducibility of Ni species on the surface of HZSM-5. In addition, the amount and the strength distribution of acidic surface sites of the catalyst decreased with the increase of calcination temperature at 500 °C above. All these factors result in an increase in the formation of isoparaffin.     

High efficient mesoporous HZSM-5 nanocatalyst development through desilication with mixed alkaline solution for methanol to olefin reaction

Methanol to olefin (MTO) process is a non-oil route for the light olefins production. We report the mesoporous and high siliceous HZSM-5 nanocatalyst development through the new desilication process including the mixed alkaline solution. The properties of nanocatalysts were characterized using TGA/DTA, XRD, ICP, FE-SEM, BET, FT-IR, and NH₃-TPD techniques. FE-SEM images represent the spherical morphology of parent nanocatalyst including smooth surface. The XRD analysis confirms that applied desilication does not change the typical MFI-type structure of ZSM-5 nanocatalysts. The BET and NH₃-TPD results show that mixed alkaline solution including 40 wt% TPAOH results in the best adjustment of textural (299.7 m²/g) and acidity (strong/weak ratio of 0.21) properties, respectively. The PHZ-NaTP0.4 nanocatalyst represents the highest methanol conversion (99.2%), propylene selectivity (48.3%), C₃ ⁼/C₂ ⁼ molar ratio (7.4) as well as lowest selectivity to C₁–C₄ alkanes (4.6%) for long time on stream (170 h). The low selectivity of light alkanes (C₁–C₄) and high total light olefins (ca. 75%) confirm the stable performance of nanocatalyst. Consequently, the developed PHZ-NaTP0.4 nanocatalyst is a high efficient MTO catalyst and can be candidate for commercial scale up.     

Methods of increasing the stability of the catalytic effect of MFI type zeolites and the total service life of catalysts based on them

Increasing the operational stability of MFI-type zeolite catalysts is topical for the creation of highly efficient catalysts for the conversion of methanol or C₂-C₄ hydrocarbon gases into aromatic hydrocarbons, i.e., important industrial processes. This study proposes three new approaches to increasing the stability of zeolite catalysts: selective dealumination on the outer surface of MFI zeolite crystals, structurally selective ion exchange on the outer surface of crystals, and the application of an isothermal (multitube) reactor. The effect of selective dealumination and structurally selective ion exchange conditions on the SiO₂/Al₂O₃ molar ratio in the zeolite on the interregeneration period duration in the conversion of methanol into hydrocarbons has been studied. It has been established that the selective dealumination of the outer surface increased the interregeneration period duration by 3–5 times. Structurally selective ion exchange on the outer surface of zeolite crystals allows us to increase the interregeneration period duration by 2–4 times and to decrease the regeneration temperature and duration due to the change of the properties of deposited coke. The application of a multitube reactor facilitates the procedure of regeneration in comparison with an adiabatic reactor due to the formation of less condensed coke depositions.     

Hydrogen transfer and activation of propane and methane on ZSM5-based catalysts

Hydrogen exchange between undeuterated and perdeuterated light alkanes (CD₄-C₃H₈, C₃D₈-C₃H₈) occurs on H-ZSM5 and on Ga- and Zn-exchanged H-ZSM5 at 773 K. Alkane conversion to aromatics occurs much more slowly because it is limited by rate of disposal of H-atoms formed in C-H scission steps and not by C-H bond activation. Kinetic coupling of these C-H activation steps with hydrogen transfer to acceptor sites (Ga ⁿ⁺, Zn ^m+) and ultimately to stoichiometric hydrogen acceptors (H⁺, CO₂,O₂, CO) often increases alkane activation rates and the selectivity to unsaturated products. Reactions of¹³ CH₄/C₃H₈ mixtures at 773 K lead only to unlabelled alkane, alkene, and aromatic products, even though exchange between CD₄ and C₃H₈ occurs at these reaction conditions. This suggests that the non-oxidative conversion of CH₄ to higher hydrocarbons on solid acids is limited by elementary steps that occur after the initial activation of C-H bonds.     

Catalytic hydrogenation of carbon monoxide over silica-supported Ir-Mo-Rh catalyst

We present here some results on Ir-Mo-Rh metallic catalysts for the synthesis of C₂-C₄ alcohols from syngas. It was found that Ir-Mo-Rh supported on silica containing small amounts of Rh exhibited much higher activity for CO hydrogenation than Ir-Mo bimetallic catalyst. The selectivity to various alcohols did not change very much upon the addition of Rh. The activity was greatly affected by the impregnation procedure of the metals in the catalyst preparation.     

Steric effects of alkyl dibenzothiophenes: The root cause of frustrating efficacy of heterogeneous desulfurization for real diesel

High-carbon alkyl dibenzothiophenes (DBTs) in real diesel are difficult to remove. Their steric effect has been studied and identified as the controlling factor in heterogeneous catalytic oxidation desulfurization (ODS) process. Mixed alkyl DBTs (C₂-DBT, C₂-C₂-DBT, C₃-DBT, and C₃-C₃-DBT) were synthesized via DBT's Friedel–Crafts alkylation, and their reactivity is DBT > C₂-DBT > C₂-C₂-DBT > C₃-DBT > C₃-C₃-DBT. C₃-DBT, C₂-C₂-DBT, and C₃-C₃-DBT can be hardly removed by any of three efficient heterogeneous ODS processes, but are removed efficiently in a homogeneous ODS process of HAc-HPW-H₂O₂, which contrasts the great importance of their steric effects in heterogeneous catalytic process. Thus, the frustrating efficacy of various ODS processes for real diesel is likely originated from the unidentified high-carbon alkyl DBTs and their least reactivity in heterogeneous catalytic systems. And, the steric hindrance is diminished greatly in a homogeneous catalytic process. The results are instructive for the development of new catalysts and catalytic ODS processes for real diesel.     

Development of technologies for producing high-octane ethers

To produce alkyl(C₁-C₂)-tert-alkyl(C₄-C₇) ethers, different process designs are necessary depending on the raw materials and production rate. New production processes using catalytic distillation and cocurrent reactors are described and compared with conventional processes. The justification of the choice of efficient flow diagrams, reactors, and new methods for recovering C₁-C₂ alcohols from hydrocarbon product streams is given.     

Slurry-phase CO2 hydrogenation to hydrocarbons over a precipitated Fe-Cu-Al/K catalyst: Investigation of reaction conditions

The hydrogenation of CO₂ to hydrocarbons over a precipitated Fe-Cu-Al/K catalyst was studied in a slurry reactor for the first time. Reducibility of the catalyst and effect of reaction variables (temperature, pressure and H₂/CO₂ ratio of the feed gas) on the catalytic reaction performance were investigated. The reaction results indicated that the Fe-Cu-Al/K catalyst showed a good CO₂ hydrogenation performance at a relatively low temperature (533 K). With the increase of reaction temperature CO₂ conversion and olefin to paraffin (O/P) ratio in C₂-C₄ hydrocarbons as well as the selectivity to C₂-C₄ fraction increased, while CO and CH₄ selectivity showed a reverse trend. With the increase in reaction pressure, CO₂ conversion and the selectivity to hydrocarbons increased, while the CO selectivity and O/P ratio of C₂-C₄ hydrocarbons decreased. The investigation of H2/CO₂ ratio revealed that CO₂ conversion and CH₄ selectivity increased while CO selectivity and O/P ratio of C₂-C₄ decreased with increasing H₂/CO₂ ratio.     

Experimental study of the tail end selective hydrogenation of steam cracking C2-C3 mixture

Diolefins and alkynes in C₂-C₃ olefins streams can be selectively hydrogenated to produce high-purity mono-olefins for downstream polyolefin production. The aim of this paper is on the experimental study of the tail end selective hydrogenation of a stream cracking C₂-C₃ cut, over two different palladium/alumina catalysts. A series of integral reactor type experiments were performed and the integral method was used for the kinetic analysis. The minimization of the objective function was made by the Marquardt algorithm for multiple response and the continuity equation set integrated by fourth order Runge-Kutta technique. The comparison between experimental and observed values of the acetylene, ethylene, ethane, MAPD, propylene and propane molar fraction in the hydrocarbon mixture, which were used for the minimization, confirm the suitability of the fit.