Kinetics of heptane reforming on Pt/L zeolite

The kinetics of heptane reforming over 0.64% Pt/KBaL have been measured over a wide range of conditions from 390 to 475 ° C, 0.05 to 1.00 atm heptane, and 0.2 to 25.0 atm hydrogen. Below about 6 atm H₂, the catalyst deactivates due to carbon fouling of the platinum particles. The reaction rate increases with hydrogen pressure under these conditions, presumably because this accelerates the rate of carbon hydrogenation off the metal surface. Above 6 atm H₂, no deactivation occurs. The activation energies and reaction orders in heptane and hydrogen at high H₂ pressure are: 39 kcal/mol, 0.7 and –1.9 for hydrogenolysis; 60 kcal/mol, 0.6 and –2.8 for isomerization; and 58 kcal/mol, 0.4 and –2.7 for dehydrocyclization. These kinetics are the same as those observed over platinum on nonacidic supports, and indicate that the reaction mechanism on Pt/KBaL is no different from that on monofunctional Pt catalysts.     

Proton‐poor, gallium‐ and indium‐loaded zeolite dehydrogenation catalysts

The catalytic (propane dehydrocyclization) and reduction behaviors of near 1:1 cation (Ga, In)/framework‐Al MFI zeolites were examined under conditions where the materials were initially either in fully protonated or zero−protonated states. Reductions at appropriate temperatures proceeded up to ∼100% exchange of protons for reduced univalent cations. Further aqueous exchange of alkali (K⁺>) or alkaline earth (Ba²⁺) cations increased the selectivity for dehydrogenation reactions at little or no sacrifice in overall activity. This revised version was published online in July 2006 with corrections to the Cover Date.     

Catalytic activity of Pt‐Re‐Pb/Al2O3 naphtha reforming catalysts

BACKGROUND: The main purpose of the naphtha reforming process is to obtain high octane naphtha, aromatic compounds and hydrogen. The catalysts are bifunctional in nature, having both acid and metal sites. The metal function is supplied by metal particles (Pt with other promoters like Re, Ge, Sn, etc.) deposited on the support. The influence of the addition of Pb to Pt‐Re/Al₂O₃ naphtha reforming catalysts was studied in this work. The catalysts were prepared by co‐impregnation and they were characterized by means of temperature programmed reduction, thermal programmed desorption of pyridine and several test reactions such as cyclohexane dehydrogenation, cyclopentane hydrogenolysis and n‐heptane reforming. RESULTS: It was found that Pb interacts strongly with the (Pt‐Re) active phase producing decay in the metal function activity. Hydrogenolysis is more affected than dehydrogenation. Part of the Pb is deposited over the support decreasing the acidity and the strength of the most acidic sites. CONCLUSION: The n‐heptane reforming reaction shows that Pb modifies the stability and selectivity of the Pt‐Re catalysts. Small Pb additions increase the stability and greatly improve the selectivity to C₇ isomers and aromatics while they decrease the formation of low value products such as methane and gases. Copyright © 2011 Society of Chemical Industry     

Proton-Ionizable Crown Compounds: Transport of Alkali and Alkaline Earth Cations Using Proton-Ionizable Triazolo Macrocycles

Abstract

The macrocycle-mediated flaxes of the alkali and alkaline earth metal cations have been determined in a H₂O-CH₂Cl₂-H₂O bulk liquid membrane system. Water-insoluble proton-ionizable macrocycles of the triazolo type were used. The proton-ionizable feature allows the coupling of cation transport to reverse H⁺ transport. This feature offers promise for the effective separation and/or concentration of alkali metal ions with the metal transport being driven by a pH gradient. A counter anion in the source phase is not co-transported. Transport of the alkali cations only occurred when the source phase pH was greater than the aqueous pK_a value for the carriers. Transport increased regularly with increasing source phase pH. Transport of alkaline earth cations from neutral pH source phases was minimal. The alkali cation selectivity order was K⁺ > Rb⁺ > Cs⁺ > Na⁺ > Li⁺ for the l8-crown-6 sized macrocycles, while little selectivity was observed with the 15-crown-5 sized macro-cycle.     

Sintering‐induced aromatization during n‐heptane reforming on Pt/Al2O3 catalysts

A platinum/alumina catalyst was sintered in oxygen and hydrogen atmospheres using two metal loadings of the catalyst: 0.3% Pt and 0.6% Pt. After sintering, the aromatization selectivity was investigated with the reforming of n‐heptane as the model reaction at a temperature of 500 °C and a pressure of 391.8 kPa. The primary products of n‐heptane reforming on the fresh platinum catalysts were methane and toluene, with subsequent conversion of benzene from toluene demethylation. To induce sintering, the catalysts were treated with oxygen at a flow rate of 60 mL min^?1, pressure of 195.9 kPa and temperatures between 500 and 800 °C. The 0.3% Pt/Al₂O₃ catalyst exhibited enhanced aromatization selectivity at various sintering temperatures while the 0.6% Pt/Al₂O₃ catalyst was inherently hydrogenolytic. The fact that aromatization was absent on the 0.6% Pt/Al₂O₃ catalyst was attributed to the presence of surface structures with dimensionality between two and three as opposed to essentially 2‐D structures on the 0.3% Pt/Al₂O₃ catalyst surface. On the 0.3% Pt/Al₂O₃ catalyst, the reaction product ranged from only toluene at a 500 °C sintering temperature to predominantly cracked product at a sintering temperature of 650 °C and no reaction at 800 °C. For sintering at about 650 °C, subsequent conversion of n‐heptane was complete and dropped thereafter. The turnover number was observed to change from 0.07 to 2.26 s^?1 as the dispersion changed from 0.33 to 0.09. The Koros–Nowark (K–N) test was used to check for the presence of internal diffusional incursions and Boudart's criterion was used for structural sensitivity determination. The K–N test indicated the absence of diffusional resistances while n‐heptane reforming was found to be structure sensitive on the Pt/Al₂O₃ catalyst. Copyright © 2006 Society of Chemical Industry     

Reforming of C6 Hydrocarbons Over Model Pt Nanoparticle Catalysts

Size-controlled model Pt nanoparticle catalysts, synthesized by colloidal chemistry, were used to study the hydrogenative reforming of three C₆ hydrocarbons in mixtures with 5:1 excess of H₂: methylcyclopentane, n-hexane and 2-methylpentane. We found a strong particle size dependence on the distribution of different reaction products for the hydrogenolysis of methylcyclopentane. The reactions of 50?Torr methylcyclopentane in 250?Torr H₂ at 320 °C, using 1.5 and 3.0 nm Pt nanoparticles produced predominantly C₆ isomers, especially 2-methylpentane, whereas 5.2 and 11.3 nm Pt nanoparticles were more selective for the formation of benzene. For the hydrogenolysis of n-hexane and 2-methylpentane, strong particle size effects on the turnover rates were observed. Hexane and 2-methylpentane reacted up to an order of magnitude slower over 3.0 nm Pt than over the other particle sizes. At 360 °C the isomerization reactions were more selective than the other reaction pathways over 3.0?nm Pt, which also yielded relatively less benzene.     

Comparative study of aromatization selectivity during N‐heptane reforming on sintered Pt/Al2O3 and Pt‐Re/Al2O3 catalysts

BACKGROUND: The metal dispersed over a support can be present as small crystallites with sizes less than 5 nm. The smaller crystallites favour aromatization while larger crystallites favour cracking/hydrogenolysis. Sintering results in the agglomerization of smaller metal crystallites. Correlation of size with aromatization selectivity was investigated. RESULTS: The primary products of n‐heptane reforming on fresh Pt were methane, toluene, and benzene, while on fresh Pt‐Re, the only product was methane. Both catalysts exhibited enhanced aromatization selectivity at different oxygen sintering temperatures. The reaction products ranged from only toluene at 500 °C sintering temperature to methane at a sintering temperature of 650 °C with no reaction at 800 °C for the Pt/Al₂O₃ catalyst. On Pt‐Re/Al₂O₃ catalyst, methane was the sole product at a sintering temperature of 500 °C while only toluene was produced at a sintering temperature of 800 °C. CONCLUSION: This is the first time that sintering has been used to facilitate aromatization of supported Pt and Pt‐Re catalysts. A superior selectivity behaviour associated with bi‐metallic Pt catalysts is established. It was found that no reaction occurred on Pt catalyst after sintering at 800 °C whereas sintering Pt‐Re at 800 °C promoted aromatization solely to toluene. Copyright © 2008 Society of Chemical Industry     

重整反应苛刻度低原因分析及处理措施

针对金陵石化I重整装置2016年2月出现的脱庚烷塔底物料中非芳含量上升、抽提原料中非芳含量上升、反应总温降下降以及单位产氢量下降等反应苛刻度低的问题进行详细分析,总结出可能引起反应苛刻度低的四个方面条件:I重整进出物料换热器内漏、原料性质、操作条件及催化剂性质,并分别对四个方面的条件进行详细的数据对比分析,最后得出本次I重整装置反应苛刻的低的主要原因为增加了S含量高达(4~6)×10-6的II加氢裂化装置重石掺炼量,致使重整催化剂出现轻微的S中毒,加快了催化剂积碳速率,且因I重整装置扩容改造后未增加催化剂再生能力,再生能力不足直接导致待生催化剂中C含量高达6.66%,从而使重整催化剂金属活性降低,直接降低了催化剂烷烃脱氢环化性能,使I重整反应苛刻度下降,脱庚烷塔底C8+物料及抽提进料中非芳含量明显升高。     

Influence of Indium Content on the Properties of Pt–Re/Al2O3 Naphtha Reforming Catalysts

The influence of indium on the properties of Pt–Re/Al₂O₃ catalysts used in naphtha reforming is studied. The addition of indium to the Pt–Re/Al₂O₃ catalyst produces a big decrease of acidity. It also produces an inhibition of the metal function, i.e., dehydrogenation and hydrogenolysis activity. The reaction of n-C₅ isomerization shows that indium addition decreases the total activity of the Pt–Re catalyst but increases the selectivity to the i-C₅ isomers. The selectivity to low cost light gases (C₁–C₃) is particularly decreased. The reaction of n-C₇ reforming showed that addition of indium increases the stability of the catalyst and the selectivity to aromatics, and decreases the production of light gases.     

Factors influencing the formation of 2-hydroxy-6-naphthoic acid from carboxylation of naphthol

The synthesis of 2-hydroxy-6-naphthoic acid (2,6-HNA) from carboxylation of alkali-naphthoxide was studied with varying alkali cation types and reaction conditions such as reactant concentration, reaction time, temperature, and pressure. The product selectivity was strongly affected by the types of alkali cation, reaction time, and temperature, while the product yield was governed by reaction pressure. The maximum HNA yield, 28.6%, was achieved with 2,6-HNA selectivity of 81.6% at 6 atm of CO₂, 543 K, and 6 h of reaction. The addition of K₂CO₃ led to further increase in the productivity of 2,6-HNA via suppression of the decarboxylation of HNA.     

Mixed reforming of heptane to syngas in the Ba0.5Sr0.5Co0.8Fe0.2O3 membrane reactor

Fuel cells are recognized as the most promising new power generation technology, but hydrogen supply is still a problem. In our previous work, we have developed a LiLaNiO/γ-Al₂O₃ catalyst, which is excellent not only for partial oxidation of hydrocarbons, but also for steam reforming and autothermal reforming. However, the reaction needs pure oxygen or air as oxidant. We have developed a dense oxygen permeable membrane Ba_0.5Sr_0.5Co_0.8Fe_0.2O₃ which has an oxygen permeation flux around 11.5 ml/cm² min at reaction conditions. Therefore, this work is to combine the oxygen permeable membrane with the catalyst LiLaNiO/γ-Al₂O₃ in a membrane reactor for hydrogen production by mixed reforming of heptane. Under optimized reaction conditions, a heptane conversion of 100%, a CO selectivity of 91–93% and a H₂ selectivity of 95–97% have been achieved.     

粘合剂和钡对Pt/L催化剂性能的影响

L分子筛芳构化催化剂与传统的双功能重整催化剂相比,链烷烃芳构化活性和选择性高得多。粘合剂影响L分子筛催化剂的强度、芳构化活性和选择性。Pt/K BaL催化剂比Pt/KL催化剂的芳构化活性和选择性高。钡含量影响Pt/K BaL催化剂的芳构化活性和选择性。微反结果表明,自制的Pt/KL和Pt/K BaL催化剂比文献报导的载铂L分子筛催化剂的芳构化活性和选择性高,100mL装置评价结果也证明两种自制催化剂具有很高的芳构化活性和选择性。     

Hydrogen production from oxidative steam reforming of ethanol in a palladium-silver alloy composite membrane reactor

In this investigation, we studied the oxidative steam reforming reaction of ethanol in a Pd-Ag/PSS membrane reactor for the production of high purity hydrogen. Palladium and silver were deposited on porous stainless steel (PSS) tube via the sequential electroless plating procedure with an overall film thickness of 20 μm and Pd/Ag weight ratio of 78/22. An ethanol-water mixture (n_water/n_ethanol = 1 or 3) and oxygen (n_oxygen/n_ethanol = 0.2, 0.7 or 1.0) were fed concurrently into the membrane reactor packed with Zn-Cu commercial catalyst (MDC-3). The reaction temperatures were set at 593-723 K and the pressures at 3-10 atm. The hydrogen flux in the permeation side increased proportionately with increasing pressure; however, it reduced slightly when increasing oxygen input. This is probably due to the fast oxidation reaction that consumes hydrogen before the onset of the steam reforming reaction. The effect of oxygen plays a vital role on the ethanol oxidation steam reforming reaction, especially for a Pd-Ag membrane reactor in which a higher flux of hydrogen is required. The selectivity of CO₂ increased with increasing flow rate of oxygen, while the selectivity of CO remained almost the same.     

Effects of small MoO3 additions on the properties of nickel catalysts for the steam reforming of hydrocarbons: II. Ni---Mo/Al2O3 catalysts in reforming, hydrogenolysis and cracking of n-butane

Addition of molybdenum to nickel catalysts has a favourable effect on their properties in the steam reforming of hydrocarbons. Some attempts were made to explain the mechanism of promoter action by determining the properties of such catalysts in hydrogenolysis and cracking reactions. With small amounts of promoter (≤0.5 wt.%) advantageneous changes in selectivity of steam reforming and disadvantageneous changes in n-butane hydrogenolysis were observed. The promoter does not affect practically the catalyst properties in n-butane cracking. The effect of molybdenum was compared with that of potassium promoter applied in the industry.     

Effect of Ba and rare earths cations on the properties and dehydrocyclization activity of Pt/K‐LTL catalysts

Several Pt/L‐zeolite catalysts were prepared by the impregnation method from L‐zeolite samples previously exchanged with Ba²⁺, La³⁺, Pr³⁺, Nd³⁺ and Sm³⁺. Lanthanides (Ln³⁺) increase the overall dispersion of platinum, measured by H₂–O₂ titration. TPR and CO/FTIR measurements indicate that these ions modify the distribution of Pt in the zeolite lattice, increasing the fraction of metal on the external surface. Additionally, both CO/FTIR and competitive hydrogenation of toluene–benzene mixtures indicate that, in the presence of Ln³⁺, the electron density of the platinum decreases in comparison with Pt/KL‐zeolite. On the other hand, Ba²⁺ does not substantially modify neither the distribution nor the electronic state of Pt. The reactivity measurements in the hydroconversion of n‐heptane show that Pt/BaKL and Pt/KL exhibit similar catalytic behaviour with a high dehydrocyclization activity. However, the exchange of K⁺ by Ln³⁺ increases the production of heptane isomers, while selectivities to aromatic and terminal hydrogenolysis products significantly decrease. This revised version was published online in July 2006 with corrections to the Cover Date.     

Effect of pressure on three catalytic partial oxidation reactions at millisecond contact times

The effects of pressure on reactant conversion and product selectivities in three catalytic oxidation systems have been examined at pressures between 1 and > 5 atm. Reaction was sustained autothermally near adiabatic operating conditions at temperatures of 1000°C with residence times over the noble metal catalysts between 10^–4 and 10^–2 s. The three systems investigated were (1) HCN synthesis over Pt-10% Rh gauze catalysts, (2) methane oxidation to synthesis gas (CO and H₂) over rhodium-coated monoliths, and (3) ethane conversion to ethylene over platinum-coated monoliths. We find that selectivities in all three reactions do not change dramatically with approximately a five-fold increase in pressure. This strongly suggests that free radical homogeneous chain reactions are not significant in these processes and that they can be operated reliably above atmospheric pressure. For the synthesis of HCN over Pt-10% Rh gauzes, the selectivity to HCN can be maintained above 0.75 at pressures up to 5.5 atm. Selectivities to synthesis gas (CO and H₂) from a methane-air mixture over a Rh-coated foam monolith at pressures up to 5.5 atm were maintained above 0.90. Over a Pt-coated foam monolith, the selectivity to ethylene from ethane-air and ethane-O₂ mixtures was independent of pressure up to 6.5 atm and conversion rose slightly although it was necessary to maintain constant velocity and residence time over the catalyst to avoid carbon formation.This research was supported by DOE under Grant No. DE-FG02-88ER13878.     

Rapid pyrolysis and hydropyrolysis of Canadian coals

A range of Canadian coals were subjected to variable heating-rate conditions in a variety of atmospheres. Heating rate was found to have little effect on total weight loss of the coal, but a dramatic effect on the actual composition of products. High heating rates substantially increased the yield of light hydrocarbons. Operation in ≈100 KPa (1 atm) H₂ at high heating rate resulted in 5% conversion to light hydrocarbon gas and liquid products. Operation in ≈10 MPa (100 atm) H₂ at a heating rate of 600 Ks^?1 gave 10% coal conversion to light liquid products (benzene, xylene, toluene).     

Influence of alkali metal doping on selectivity behaviour of platinum catalysts for hydrogenation of 2-butyne-1,4-diol

Hydrogenation of 2-butyne-1,4-diol to 2-butene-1,4-diol (B₂D) and butane-1,4-diol (B₁D) using Pt catalysts doped with alkali metals was studied. These catalysts showed higher selectivity to the olefinic diol (B₂D) compared to that with monometallic platinum catalyst. Among various alkali metals, Cs-doped catalyst showed highest selectivity (>99%) to B₂D. The selectivity to B₂D increased (up to 99.9%) with increase in the concentration of Cs from 0.25% to 1%. The increase in the basic strength of alkali doped catalysts measured by CO₂-TPD, would be responsible for the increase in electron density of Pt hence, faster desorption and higher selectivity to the intermediate olefinic diol (B₂D). The reaction parameters, such as temperature, H₂ pressure and substrate concentration have strong influence on the catalyst activity but almost no effect on the selectivity to B₂D.     

Study of the performance of Mo2C for iso-octane steam reforming

In the present work, the performance of commercial molybdenum carbide (Mo₂C) for isooctane steam reforming has been investigated in order to determine the effects of major operating parameters (temperature, space velocity, and steam to carbon ratio) on the catalytic activity. While the results obtained indicate an onset reforming temperature of 850 °C, high concentrations of H₂ in the reforming environment were found to reduce the onset temperature to 750 °C. The catalytic activity at 850 °C was sufficient to produce hydrogen yields greater than 90% and carbon conversions close to 100%, with a low selectivity to CH₄ and CO₂. In addition, and consistent with thermodynamic predictions, a steam to carbon ratio of 1 appeared to optimize the reforming rates. Finally, based on experimental observations, a reaction mechanism was formulated and used to interpret the results obtained during catalytic activity measurements. This mechanism involves continuous oxidation and reduction of Mo metal, which can provide activity and stability to the catalyst when occurring at similar rates.     

Reforming of C6 hydrocarbons on a PtAl2O3 catalyst

Isomerization, dehydrocyclization and hydrocracking of C₆ hydrocarbons on a commercial reforming PtAl₂O₃ catalyst were studied in a tubular reactor. The temperature was varied from 420 to 500°C, the pressure from 1.6 to 16 bar, the molar H₂/hydrocarbon inlet ratios from 1.5 to 20. Reaction rate equations of the Hougen—Watson type, corresponding to a bifunctional mechanism, were found to describe the experimental data. Parameter estimates for the reforming reactions were obtained by application of a generalized least square criterion to the calculated and observed production rates of the gas phase components. Electrobalance experiments showed that both the reforming reaction rates and the coking rate decrease exponentially with coke content. Multiplying the reaction rates with one common exponential deactivation function allowed the prediction of the observed conversions by one single set of kinetic parameters. The coking rate equation was derived by fitting the final coke content profiles obtained in the tubular reactor. The main contribution to coke formation was attributed to Me-cyclopentadienes.