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.     

Coke Formation on Pt?CSn/Al2O3 Catalyst in Propane Dehydrogenation: Coke Characterization and Kinetic Study

The influences of gas compositions on the rates of coke formation over a Pt?CSn/Al₂O₃ catalyst are studied. The coke formed on the catalyst is characterized by thermal gravimetric analysis, IR spectroscopy, Raman spectroscopy and elemental analysis. Two kinds of coke are identified from the TPO profiles and assigned to the coke on the metal and the coke on the support, respectively. The coke formed on the metal is softer (containing more hydrogen) than that formed on the support. The rate of coke formation on the metal is weakly dependent on the propylene and hydrogen pressures but increasing with the propane pressure, while the rate of coke formation on the support is increasing with the propane and propylene pressures and decreasing with the hydrogen pressure. Based on the kinetic analysis, a mechanism for the coke formation on the Pt?CSn/Al₂O₃ catalyst is proposed, and the dimerization of adsorbed C₃H₆ is identified to be the kinetic relevant step for coke formation on the metal.     

Gas phase hydrogenation of ortho-chloronitrobenzene (O-CNB) to ortho-chloroaniline (O-CAN) over unpromoted and alkali metal promoted-alumina supported palladium catalysts

A series of alkali metals (Li, Na, K and Cs) promoted alumina-supported palladium catalysts were prepared by a wet impregnation method and characterized by X-ray diffraction (XRD) and CO chemisorption measurements. The samples were tested for the gas phase hydrogenation of ortho-chloronitrobenzene (O-CNB) to ortho-chloroaniline (O-CAN) in a fixed-bed micro reactor at 250 °C under normal atmospheric pressure. The promoted-Pd/Al₂O₃ catalysts show higher conversion for O-CNB and the hydrogenation activity of O-CNB per site decreases with the increasing ionic radius of the alkali metal promoter ions. However, the selectivity for O-CAN remains more or less the same in both unpromoted and promoted catalysts and also irrespective of the nature of the alkali metal promoter ions used for promotion of alumina support. Despite, similar activity and selectivity observed between Li- and Na-promoted Pd/Al₂O₃ catalysts, the Na-promoted showed higher resistance for coke formation than a Li-promoted catalyst. The increase in the intrinsic activity of palladium site on alkali promotion has been attributed to the increase in hydrogenation activity over promoted catalysts.     

Coke formation on hydrodesulphurization catalysts

The extent of coke formation was measured on a number of different hydrodesulphurization catalysts, primarily as a function of the catalyst chemical composition. Variations in the concentration of MoD₃ on the alumina, the type of catalyst promoter, the promoter/MoO₃ ratio, the presulphiding material and the reaction temperature were made. Increases in the reaction rate caused by either changes in the catalyst composition or by moderate changes in the reaction temperature were compared to the catalyst coke content. It was suggested that two types of coke were present on the catalyst, a reactive coke which is subsequently converted to reaction products and an unreactive coke which blocks catalytic sites.     

Hydrodesulphurization activity and coking propensity of carbon and alumina supported catalysts

Co—Mo, Fe and Mo catalysts were prepared on alumina and carbon supports. The reactivity of sulphided catalysts for thiophene hydrodesulphurization and the propensity for coke deposition of nonsulphided catalysts during propylene cracking and anthracene carbonization were measured. The hydrodesulphurization activity of Co—Mo and Fe catalysts increased in the order γ-Al₂O₃ < C-black composite < active carbon. For a given metal, considerable differences in activity were found both between the carbons and alumina and between the carbons themselves. Possible reasons for the different activities include the influence of the supports on metal dispersion and the presence of impurities in the carbons. For alumina supported catalysts there is a correspondence between hydrodesulphurization activity and coking propensity. On carbon supported catalysts, the rates of carbon deposition appear insensitive to the nature of the metal component(s) whereas hydrodesulphurization activity is not. Thus it is possible to enhance the latter without attendant increases in the susceptibility to coke-forming reactions. Increasing Mo loading from 0–12 wt% was found to substantially increase the rate of carbon deposition on alumina, whereas the effect on a carbon support was comparatively small. This behaviour appears to relate to the inherent support acidity and its modification on metal addition.     

Catalytic cracking and skeletal isomerization of n-hexenes on HY zeolite

The catalytic cracking and skeletal isomerization of n-hexenes on 80/100 mesh HY zeolite has been studied in the temperature range 350–405°C, and compared with results previously obtained on ZSM-5 zeolites. Species with less than three carbon atoms were not observed as primary cracking products, with traces of ethylene formed only as a secondary product. Although propylene and propane may be formed partially by monomolecular cracking of n-hexenes, the dominant cracking process is bimolecular. Dimerization, followed by disproportionation gives stable C₃, C₄ and C₅ species, in addition to C₉, C₈ and C₇ fragments. The probability of these larger fragments undergoing further cracking before desorption increases with temperature, but is significantly less than found on ZSM-5 zeolites. The main products of skeletal isomerization were monomethylpentenes, with those isomers which can originate from tertiary carbonium ions dominant. Dimethylbutenes were formed mainly as secondary products. The rate of the dimerization-cracking process in which two n-hexene species participate is ? six times slower than the reaction involving a monomethylpentene species and a linear hexene. The increase in the rate of the latter process with respect to the former is reduced on ZSM-5, and this can be attributed to the narrower pore size within this zeolite. In contrast to ZSM-5, there is significant formation of alicyclics, paraffins and aromatic species. The residual coke was found to be considerably poorer in hydrogen content than comparable material formed on ZSM-5.     

Catalytic cracking and skeletal isomerization of n-Hexene on ZSM-5 Zeolite

The catalytic cracking and skeletal isomerization of n-hexenes on 60/80 mesh ZSM-5 zeolite were studied in the temperature range 350–405°C. By applying the time-on-stream theory, the products of the reaction were identified as primary, secondary or both according to their optimum performance envelope (OPE) curves on product selectivity plots. The products of cracking were found to be almost exclusively mono-olefins and those in the range C₃-C₅ were found to be stable primary, or primary plus secondary products. No C₁ was found, and only traces of C₂ as ethylene. The observed product distributions can be explained by a dimerization-cracking mechanism with no product species having more than twelve carbon atoms. The probability of a fragment undergoing further cracking before desorption increased with temperature and the observed initial selectivities must be corrected to account for this process. Methylpentenes, formed as unstable primary products, were the main isomers produced by skeletal rearrangement, with those derived from more stable carbenium ions predominating. Paraffins, coke and aromatics were found in small amounts only.     

醋酸钾对轻石脑油裂解结焦的影响

为考察碱金属元素对裂解结焦的影响,以醋酸钾为结焦抑制剂,在850℃下对退役25Cr35Ni炉管试样内表面进行了结焦实验。利用扫描电子显微镜(SEM)、场发射扫描电镜(FE-SEM)、能量色散谱仪(EDS）、X射线衍射(XRD)和Raman光谱对退役25Cr35Ni炉管试样内表面和焦层进行了表征。结果表明,退役25Cr35Ni炉管内表面主要由Cr_1.3Fe_0.7O₃相似文献   

Tuning the Activity and Selectivity of CuCl2/γ-Al2O3 Ethene Oxychlorination Catalyst by Selective Promotion

CuCl₂/γ-Al₂O₃ catalysts with and without promoter metal chlorides (Cu5.0, K3.1Cu5.0, La10.9Cu5.0, Li0.5Cu5.0, Cs10.4Cu5.0, Mg1.9Cu5.0, Ce5.5La5.45Cu5.0, and K1.55La5.45Cu5.0) were studied for the ethene oxychlorination reaction in a fixed-bed reactor at 503 and 573 K, with C₂H₄:HCl:O₂:He = 1.0:1.1:0.38:14.4 (mole ratio), P(tot) = 1 atm and weight hourly space velocity (WHSV) = 1.5 g g^?1 h^?1 (based on ethene). It was found that all promoter metals enhanced the activity of the catalyst, as well as its selectivity towards the target product 1,2-dichloroethane (1,2-EDC). Co-promoted catalysts (K1.55La5.45Cu5.0 and Ce5.5La5.45Cu5.0) gave even higher activity and product selectivity than the single metal promoted catalysts. The activity of the CuCl₂/γ-Al₂O₃ catalyst, as well as the γ-Al₂O₃ support, both with and without metal chloride promoter(s), were further tested for 1,2-EDC conversion to byproducts in a fixed-bed reactor at 503 K, under a feed stream of 1,2-EDC:Ar = 1:11.5 (mole ratio), at P(tot) = 1 atm and WHSV = 1.5 g g^?1 h^?1 (based on 1,2-EDC). Prior to testing, the catalysts were pretreated in flowing ethene, HCl and/or O₂. It was observed that Lewis and Brønsted acid sites on the alumina surface were main reaction sites for conversion of 1,2-EDC to chlorinated byproducts: vinyl chloride monomer (VCM), 1,1-EDC, 1,2-dichloroethene (1,2-DCE) and ethyl chloride (EC) as well as dimerisation (butadiene) and aromatisation reactions (toluene), both with and without the presence of the Cu phase. The Cu phase was shown to contribute mainly to CO₂ and trichloroethane formation from 1,2-EDC via VCM. Co-promotion (K1.55La5.45Cu5.0) was found to enhance the activity of the Cu phase, and to mask acid sites on the alumina surface, thereby promoting ethene oxychlorination while at the same time hindering undesired conversion of the target product 1,2-EDC.     

Effects of penta-coordinated Al3+ sites and Ni defective sites on Ni/Al2O3 for CO methanation

Engineering sophisticated structure of Al₂O₃ and controlling the structure of counterpart metal active sites remain challenges to achieve a high catalytic-performance in heterogeneous catalysis. Herein, we present a confinement strategy to stabilize homogeneous Ni by penta-coordinated Al³⁺ anchoring sites in Al₂O₃. This approach is involved in using a metal–organic framework as host to load Ni²⁺ ions, by the aim of producing a confined Ni/Al₂O₃ catalyst after a standard calcination. Metal–support interaction between Ni and Al₂O₃ was tailored to be medium to avoid the formation of inactive NiAl₂O₄, which favors the generation of more available Ni active sites accessible to the reactants. The resultant Ni/Al₂O₃ exhibited superior catalytic performance in comparison with the control Ni/Al₂O₃ in CO methanation owing to the presence of defective sites on sufficient Ni⁰ surface. Furthermore, the presence of oxygen vacancies on Al₂O₃ and hydrogen spillover contributed toward excellent coke resistance properties in the reaction.     

Deactivation and coke formation on palladium and platinum catalysts in vegetable oil hydrogenation

Deactivation of palladium and platinum catalysts due to coke formation was studied during hydrogenation of methyl esters of sunflower oil. The supported metal catalysts were prepared by impregnating γ-alumina with either palladium or platinum salts, and by impregnating α-alumina with palladium salt. The catalysts were reused for several batch experiments. The Pd/γ-Al₂O₃ catalyst lost more than 50% of its initial activity after four batch experiments, while the other catalysts did not deactivate. Samples of used catalysts were cleaned from remaining oil by repeated extractions with methanol, and the amount of coke formed on the catalysts was studied by temperature-programmed oxidation. The deactivation of the catalyst is a function of both the metal and the support. The amount of coke increased on the Pd/γ-Al₂O₃ catalyst with repeated use, but the amount of coke remained approximately constant for the Pt/γ-Al₂O₃ catalyst. Virtually no coke was detected on the Pd/α-Al₂O₃ catalyst. The formation of coke on Pd/α-Al₂O₃ may be slower than on the Pd/γ-Al₂O₃ owing to the carrier’s smaller surface area and less acidic character. The absence of deactivation for the Pt/γ-Al₂O₃ catalyst may be explained by slower formation of coke precursors on platinum compared to palladium.     

Potassium and nickel doped β-Mo2C catalysts for mixed alcohols synthesis via syngas

Potassium and nickel doped β-Mo₂C catalysts were prepared and their performances of CO hydrogenation were investigated. The main products over β-Mo₂C catalyst were hydrocarbons, and only few alcohols were obtained. The potassium promoter resulted in remarkable selectivity shift from hydrocarbons to alcohols over β-Mo₂C. Moreover, it was found that the potassium promoter enhanced the ability of chain propagation of β-Mo₂C catalyst and resulted in a higher selectivity to C₂₊OH. When doped by potassium and nickel, β-Mo₂C catalyst showed high activity and selectivity for mixed alcohols synthesis, the Ni promoter further enhanced the whole chain propagation to produce alcohols especially for the step of C₁OH–C₂OH. From the XPS analysis, it had been proved that the formation of higher alcohols might be attributable to the presence of Mo^IV species, whereas the formation of hydrocarbons was closely associated with the presence of Mo^II species on the surface of the catalysts.     

Selective steam reforming of aromatic hydrocarbons: IV. Steam conversion and hydroconversion of selected monoalkyl- and dialkyl-benzenes on Rh catalysts

Steam conversion and hydroconversion of a series of monoalkylbenzenes (C₆H₅R, R = C₂H₅, n-C₃H₇, i-C₃H₇, tert-C₄H₉) and of dialkylbenzenes (o- and p-xylenes) are studied at 713 K and atmospheric pressure on supported rhodium catalysts ($\text{Rh}\text{Al}{}_2\text{O}{}_3$, $\text{Rh}\text{SiO}{}_2$ and $\text{Rh}\text{TiO}{}_2$), and compared to the toluene steam dealkylation previously studied on the same catalysts. Three types of reaction, namely dealkylation (CC rupture on the side chain), dehydrogenation (on the side chain), and degradation (i.e., ring opening) account for virtually the whole product spectrum. Isomerization, transalkylation, and dehydrocyclization reactions may, in general, be discounted. In the presence of steam, the main initial product of monoalkylbenzene dealkylation is invariably benzene, but the splitting of the CC bonds in the middle or end of the side chain always increases with conversion. As a rule, the specific activities (per metal site) in dealkylation decrease with the degree of substitution in the alkyl group (primary > secondary > tertiary > quaternary carbon). On the other hand, the specific activities in ring opening remain constant for all the hydrocarbons and even for the benzene. In the presence of hydrogen, multiple CC bond splittings are invariably observed and benzene is no longer, in general, the principal initial product. The activities in ring opening are equally constant, but at a lower level than in steam conversion. These results are in overall agreement with the model of the dual active sites: sites I appear operative for dealkylation and dehydrogenation, whereas ring opening takes place at sites II with a high probability, independent of the alkyl group size. Possible adsorbed species on each type of site are described. An attempt is made to rationalize the effects of assorted selectivity-determining factors (metal particle size, support effects, selective poisons such as S and CO) in terms of electronic or geometric effects.     

CO hydrogenation over Co/SiO2: catalytic tests and surface analysis of adsorbed hydrocarbons

We have studied the CO hydrogenation over a Co/SiO₂ catalyst under mild reaction conditions (up to 4.4 bar total pressure, H₂/CO = 2,T = 483K) and performed a post-reaction analysis of the chemical surface composition by means of secondary ion mass spectrometry (SIMS) and temperature-programmed reaction (TPR) in hydrogen gas. A hydrocarbon chain growth probability α = 0.78 was found in the catalytic studies. The SIMS analysis revealed the existence of individually adsorbed C_xH_y species up to C₈H_y, in accordance with end-on bonding to the catalyst surface. These species were removed from the catalyst surface in the subsequent H₂-TPR experiment. Significant methane desorption occurred at temperatures (⩾500 K) well above those of the longer-chain hydrocarbons indicating either an increasing hydrogenolysis activity of Co metal during H₂-TPR or the presence of a more tightly bound “carbidic” adsorbate under FT conditions. This revised version was published online in July 2006 with corrections to the Cover Date.     

Influence of Reaction Parameters on the Hydrogenolysis of Hydroxymatairesinol Over Carbon Nanofibre Supported Palladium Catalysts

The density functional theory (DFT/B3LYP) calculations were applied to investigate the interaction of a Pt₆ particle with the ZSM-5 zeolite framework. The electronic structure of the metal particle is strongly affected by the interaction with basic framework oxygens and acid sites of the zeolite support. Adsorption on basic sites (E_ads = 6 kcal/mol) favors the formation of the electron enriched metal cluster. Interaction of the platinum cluster with the acid site characterized by stabilization energy of 47 kcal/mol results in oxidation of the metal particle and suppression of Brønsted acidity of the support. The hypothesis is put forward that the oxidized platinum particle can function as an active site for the alkane isomerisation on platinum supported high silica zeolites.     

Pore structure alteration of porous carbon by catalytic coke deposition

The feasibility of preparing Carbon Molecular Sieve (CMS) by tailoring pore structure of activated carbon under catalytic cracking of benzene has been examined. In this method, benzene vapour was cracked over metal-impregnated activated carbon particles at 523–773 K. Among the metal catalysts tested, only cobalt exhibited significant cracking activity toward benzene. In this range of temperature coke was originated on the metal surface only, therefore an excessive coke deposition as indicated in non-catalytic process was not observed. The amount of coke and the site of deposition in the pore network were determined to some extent by the metal loading as well as the rate of benzene cracking. Raman spectra indicated that the coke produced was less amorphous than those produced in non-catalytic processes. Only a small loss in micropore volume and surface area was observed after the coke deposition process. The CMS produced was tested for its adsorption characteristics of carbon dioxide and methane. The improvement in the CO₂/CH₄ kinetic selectivity was observed.     

Methanol to olefins conversion over metal containing MFI-type zeolites

A series of metal containing MFI-type zeolites were synthesized by the rapid crystallization method with in two hours. Al(III), Cr(III), Cu (II), and Fe(III) metal ions were incorporated in the structure. Pure siliceous (Al free) MFI structured zeolite was also prepared by the same procedure as used for the metallosilicate synthesis. Si/M ratio of the synthesis gel was 100 for metallosilicates aiming for high-silica zeolites. The products have been characterized by elemental analysis, specific surface area determination, scanning electron microscopy with EDX analysis, electron spin resonance, and thermal analysis. Catalytic property of the zeolites was measured for methanol to olefin conversion reaction. The results of XRD measurement showed the only crystalline phase present was that of MFI-type zeolite. E.s.r spectroscopy has been used to study the isomorphic substitution of the metal ions incorporated in the structure. The results show that Fe(III) and Cu (II) were mainly incorporated while, Cr(III) was observed to be present in non-framework sites. The amount of template occluded into the structure was determined by thermal analysis and found to be the same for metallosilicates and highly crystalline aluminum free zeolite. The results of catalytic activity showed that about 85% selectivity (based on gaseous hydrocarbon) for C₂⁼–C₄⁼ olefin was achieved in the case of iron containing synthesized high-silica zeolite as compared with 58% in the case of Al-containing zeolite catalyst.     

Selective catalytic reduction of nitrogen oxides with hydrocarbons over Zn–Al–Ga complex oxides

Selective reduction of NO with hydrocarbons was studied using metal oxide catalysts having a spinel structure. A Zn–Al–Ga complex oxide was found to be very active and selective for the catalytic reduction of NO with both C₃H₆ and CH₄. It was revealed that the role of oxygen at the initial stage of the reaction strongly depends on the reductants; oxygen is mainly used for NO oxidation to NO₂ in the reduction with CH₄, whereas it is used both for NO oxidation to NO₂ and oxidation of C₃H₆ to an active intermediate in the reduction with C₃H₆. This revised version was published online in July 2006 with corrections to the Cover Date.     

Studies of jasmine wax: I. Physical properties and chemical composition

Jasmine wax was fractionated using thin layer chromatography. Six fractions were isolated, purified and identified using combined gas liquid chromatography and mass spectrometry. Infrared spectra were adopted for the chemical structure confirmation of each fraction. The fractions were 49.44% hydrocarbons, 15.73% esters, 3.49% aldehydes and ketones, 7.91% primary fatty alcohols, 8.31% free fatty acids and 8.99% was considered origin. The hydrocarbon fraction was found to consist mainly of saturated chains with C₂₉, C₃₁ and C₂₇ the most predominant. The aldehyde fraction was characterized by straight chains with even numbers of carbon atoms ranging between C₁₀ and C₂₈, whereas the ketone fraction was found to contain a longer chain structure, i.e., C₃₆. However, the C = O was found to be at the C₈ and C₁₁ positions. Free primary alcohols were found to occur in short chains, indicating their existence in the liquid phase, whereas the free fatty acids were found in long chains and were more likely in the solid phase.     

Aldol condensation of acetaldehyde to form high molecular weight compounds on TiO2

Temperature-programmed desorption, hydrogenation, and oxidation are used to show that acetaldehyde undergoes continued aldol condensation beyond crotonaldehyde formation on Degussa P-25 titania to form hexan-2,4-diene-al and higher molecular weight compounds containing conjugated C=C bonds. Aromatic compounds also form, and at higher temperatures coke forms. Degussa P-25 TiO₂ has more sites that catalyze chain propagation reactions beyond formation of C₄ species than do pure anatase or rutile surfaces. These reactions may be responsible for deactivation observed during photocatalytic oxidation of acetaldehyde at elevated temperatures. This revised version was published online in August 2006 with corrections to the Cover Date.