Cyclohexane Dehydrogenation Using an Economical Iron Catalyst: Influence of Alumino-Silicate Structure on the Catalytic Activity

The effect of mixing both local Egyptian hematitic ore and activated aluminosilicate material (bentonite clay) on the dehydrogenation activity of the former was studied.

Three mixtures were prepared in which bentonite percentages were 10, 20, and 40 wt%. Cyclohexane used as a model reactant for the catalytic dehydrogenation reaction carried out in catalytic flow system within reaction temperature ranged from 150 to 500°C in the presence of hydrogen stream (75 mL/min) and at constant space velocity 3.71 h^-1.

The results obtained indicated that in spite of the drop in the selectivity of the local material toward benzene formation by clay addition, a distinct increase in the benzene yield was observed. The maximum conversion attained ∼28.14% at reaction temperature 500°C using a mixture containing 20 wt% activated bentonite.     

LIQUEFACTION OF BEYPAZARI LIGNITE USING NiCl2-KCl-LiCl CATALYSTS. 1. DIFFERENCE IN SOLID AND MOLTEN SALT CATALYSIS

Liquefaction of Beypazan lignite in tetralin using NiCl₂-KCl-LiCl (14:36:50 molar percentages) as catalyst was investigated. Effects of the catalyst/lignite ratio and temperature were determined in experiments done at 275°C, 300°C and 360°C. Liquid products were separated into oils, asphaltenes and asphaltols by a solvent extraction method. Yield of liquefaction increased with temperature in all experiments, the highest yield was observed in experiments performed at the eutectic temperature of the catalyst mixture. The highest yields of oils were 20% and 30% with a catalyst/coal ratio of 0.5 at 275°C and 300°C, respectively. The activity of the catalyst increased in experiments in which the catalyst was molten. The yield of asphaltenes were not affected with increases in the catalyst/coal ratio in the experiments done at 275°C or 300°C in which the catalyst mixtures were in solid state. Asphaltene yields decreased from 25% to less than 5% with increasing values of catalyst/coal ratio and the asphaltol yields remained constant at 10% between catalyst/coal ratios of 0.25 and 1.00 and suddenly increased to 30% and 40% for catalyst/coal ratios of 1.50 and 2.00, respectively, at 360°C. The molecular weights of the oils decreased from 340 to a minimum value of 245 as the catalyst/coal ratio was increased from 0 to 1.00 in experiments done at 360°C where the catalyst was molten. As the catalyst/coal ratio was further increased from 1.00 to 2.00 the molecular weight increased to 310.It seemed that the N1Cl₂-KCl-LiCl catalyst mixture in all catalyst/coal ratios was more efficient in molten phase than it was used as a solid mixture.     

REFORMING OF N-OCTANE ON A Pt/Al2O3 CATALYST. II. KINETIC ANALYSIS OF HYDROGEN DEPENDENCE.

The conversion of n-octane on Pt/Al₂O₃ catalyst was found to pass through pronounced maxima with the variation of the partial pressure of hydrogen at temperatures between 420°C-460°C, P_N = 7·63 × 10^-3 atm and W/F = 0·11lg min cm_-3. The products of reaction were hydrocracked products, octane, ethylbenzene, o-.p-,m,-xylene and toluene. The order of appearance of the optimum PH for the various reactions were: Isooctane>Dehydrocyclized products>Hydrocracked products.

A sequence of elementary steps earlier postulated was found to predict the maximum in the n-octane P_H profiles for the three temperatures investigated. The rate determining steps for the two rate equations that were found suitable were conversion of adsorbed isooctane to adsorbed o-xylene and ethylbenzene.     

Oxidative Dehydrogenation of Methanol on Chromium Oxide/Montmorillonite K10 Catalysts

Methanol conversion was carried out on a mesoporous material—chromia/montmorillonite K10 (MK10)—in a pulse microcatalytic system. Methanol was converted to formaldehyde and ethylene by two different mechanisms. Methanol dehydrogenation increases by increasing reaction temperature (300-400°C) and as chromia loading decrease. On the other hand, the dehydration of methanol occurs at a higher temperature (400-500°C) and as chromia loading increase, 3-18% Cr. Redox and exposed nonredox Cr³⁺ are responsible for formaldehyde formation. There is a relationship between increased C₂H₄ production and the increase of Cr⁶⁺ phase according to the acidity of chromia catalysts 34 and 76 μL tert-Butylamine/g catalyst for 3% Cr and 18% Cr, respectively. Formaldehyde formation is diffusionally controlled at high temperatures (400-500°C) and kinetically controlled at a lower reaction temperature (300-400°C), while methanol dehydration to ethylene is surface reaction controlled at 400-500°C.     

DIRECT HYDROGENATION OF A SPANISH LOW RANK COAL. THE EFFECT OF PROCESS VARIABLES

The effect of operating conditions on the liquefaction behaviour of a Spanish lignite was studied using a 250 ml stirred autoclave, and the following operating conditions (except otherwise specified): 400 °C, 1 hour, 3.5 MPa initial (cold) H₂ pressure, 400 rpm and 40 g/10 g tetralin/coal charge. The liquefaction products were fractionated into oils, asphaltenes, preasphaltenes and solid residue using pentane, toluene and THF as extractive solvents

The influence of temperature was explored in the 300-475 °C range, observing little further improvement in liquefaction yields over 400 °C, and retrogressive reactions over 450 °C. The effect of time was studied from 0 to 180 minutes and was concluded that 1 hour is an appropriate period for liquefying a black lignite, since there is little further conversion for longer times. The influence of pressure and gas type was studied using 0, 3.5 and 7.0 MPa initial (cold) pressure of H₂ and of N₂, and the effect of stirring using 0 and 400 rpm. Little influence of these variables was observed, which is attributed to the strong H-donor solvent, high solvent/coal ratio and long reaction time used.     

Kinetic Modeling of Hydrocarbon Conversion to Asphaltenes in Sulphur-treated Asphalts

A study was made of the kinetics of the conversion of the hydrocarbon constituents of residual asphalts to asphaltenes at temperatures of 210-250°C. The reactions occurring led to the manifold increases in the composition of asphaltenes. Kinetic rate parameters were determined at different temperatures and the temperature effect was correlated by Arrhenius dependency. The reaction order was found to vary with temperature, increasing from 1.60 and yielding a maximum order of 4.2 at 250°C, thus confirming other results obtained in the literature. An activation energy of 266.0 kJ/mol was also recorded which is quite lower than 373 kJ/mol reported for the noncatalytic reaction. The overall effect of the catalyst employed was the reduction of the temperature at which maximum asphaltene yield could be obtained.     

EFFECTS OF HYDROTREATING COKER LIGHT GAS OIL ON FUEL QUALITY

Coker light gas oil (LGO) derived from Athabasca bitumen was hydrotreated in a fixed bed reactor using two commercial NiO-MoO₃/Al₂0₃ catalysts. The effect of temperature on product quality was investigated in a pilot plant between 330 and 390 °C at 12.4 MPa, space velocity of 0.5 Ir1 and 700 liter of hydrogen per liter of coker LGO (L/L). The product quality was monitored by ^I3C NMR spectroscopy, elemental analysis, density and distillation techniques.

The data showed that coker LGO can be hydrotreated using nickel-molybdenum catalysts at 350 °C, 0.5 h¹, 12.4 MPa and 700 L/L to meet the diesel product specifications, namely, 0.5 wt % sulfur, 20% aromatics and cetane index of 40. The cetane index improvement and aromatic saturation, which are affected by thermodynamic equilibrium at temperature higher than 370 °C, could reach 29 and 86% respectively. The cetane improvement was attributed to aromatic saturation and hydrocracking with hydrogen consumption ranging from 215-340 L/L. The Ketjenfine KF-840 catalyst was found slightly better performance than Procatalyse HR-348 catalyst.     

SOLID STATE 13C NMR STUDY OF THERMALLY UPGRADED LOW RANK COALS

The results of solid-state ¹³C NMR study aimed at evaluating the chemical changes and extent of upgrading achieved in the thermal treatment of two western Canadian low rank coals are discussed. The coals were thermally treated at varying temperatures (200 - 500°C) using different process media (nitrogen, steam and products of combustion)

Apparent aromaticity of the two coals was increased after the thermal treatment and increased with treatment temperature. Significant chemical changes, such as loss of the protonated aromatic carbons, quaternary carbons in alkylated rings and aliphatic ethers, were observed at 400°C and above. Condensation and polymerization of the chemical components were also evident. The effect of process medium was found to depend on the coal feed and the treatment temperature.     

Mo2C/MoO2-ZrO2催化剂上正己烷异构化

以十六烷基三甲基溴化铵（CTAB）和聚乙二醇20 000（PEG20 000）为模板剂,采用共沉淀法制备前躯体MoO3/ZrO2,然后使用程序升温法,以正己烷为碳源,制备了Mo2C/MoO2-ZrO2催化剂。XRD和BET分析结果显示,催化剂具有明显的β-Mo2C特征峰和适宜的孔径孔体积。以正己烷为原料,在连续流动的固定床反应装置上,通过改变温度、压力、体积空速以及氢烃体积比等参数,考察了该催化剂的异构化性能。结果表明,Mo2C/MoO2-ZrO2上的正己烷异构化优化反应反应温度380 ℃、反应压力2.5 MPa、体积空速1.0 h-1、氢烃体积比400:1,在此条件下的正己烷转化率达到67.5%,异构化选择性和异构化收率分别为82.5%和55.7%。     

EFFECT OF PREHYDROGENATION ON HYDROCONVERSION OF MAYA RESIDUUM, PART I: PROCESS CHARACTERIZATION

Maya 650°F residuum was mildly prehydrogenated over a standard, commercially available, hydrodesulfurization catalyst. The product was then distilled to yield hydrogenated Maya 650°F residuum. This prehydrogenated residuum, and the untreated Maya 650°F residuum were separately hydroprocessed further at different process severities. The resulting products were then examined by elemental analyses to determine the effects of die prehydrogenation step on overall conversion and product quality.

The primary effect of the prehydrogenation step was to increase the overall conversions for sulfur, MCR, nitrogen, and asphaltenes. As a result, the hydro-conversion products derived from the prehydrogenation were substantially better quality than the corresponding direct hydroconversion products. The prehydrogenation step also lowered the severity required for equivalent residuum hydroconversion upgrading.     

PYROLYSIS OF SUNNYSIDE (UTAH) TAR SAND: CHARACTERIZATION OF VOLATILE COMPOUND EVOLUTION

Sunnyside (Utah) tar sand was subjected to programmed temperature pyrolysis and the volatile products were detected by tandem on-line mass spectrometry (MS/MS) in real time analyses. A heating rate of 4°C/min from room temperature to 900°C was employed.

Evolution of hydrogen, light hydrocarbons, nitrogen-, sulfur-, and oxygen-containing compounds was monitored by MS or MS/MS detection. Evolution of volatile organic compounds occurred in two regimes: 1) low temperature (maximum evolution at 150 to 175°C), corresponding to entrained organics, and 2) high temperature (maximum evolution at 440 to 460°C), corresponding to cracking of large organic components. Alkanes and alkenes of two carbons and higher had temperatures of maximum evolution at approximately 440°C, and methane at approximately 474°C. Aromatic hydrocarbons had temperatures of maximum evolution slightly higher, at approximately 450° C. Some nitrogen-, sulfur-, and oxygen-'ccntaining compounds were also detected in the volatile products.

Comparing the Sunnyside pyrolysis to the pyrolysis of other domestic tar sands indicated the following for hydrocarbon evolution: 1) the evolution of entrained organics relative to the total evolution was much less for Sunnyside tar sand, 2) the temperatures of maximum evolution of hydrocarbons due t o cracking reactions were slightly lower, and 3) the temperatures of maximum evolution for benzene and toluene are slightly higher than observed for other tar sands.

In general, the noncondensible gases, H₂, CO, and CO₂, exhibited evolution associated with hydrocarbon cracking reactions, and high temperature evolution associated with mineral decomposition, the water-gas shift reaction, and gasification reactions. Pyrolysis yields were dominated by the evolution of carbon oxides and water. The CO₂ primarily appeared t o cane from the decomposition of carbonate minerals. Compared t o other domestic tar sands, the gas evolution reflected more mineral decomposition character for Sunnyside tar sand.     

IN-SITU ACTIVATION OF METHANOL SYNTHESIS CATALYST IN A THREE-PHASE SLURRY REACTOR

In the liquid phase methanol synthesis process, syngas reacts in the presence.of fine catalyst particles slurried in the oil phase, in a three phase slurry reactor system. A method for activating high concentration ( ≤25 wt. %) of the CuO-ZnO-Al₂O₃ catalyst in the catalyst-oil slurry has been successfully developed. This catalyst activation process can be of crucial significance in the research and development of the methanol synthesis process in a liquid entrained reactor.

The reducing gas contains 2% hydrogen in nitrogen mixture and this activation procedure is carried out at a pressure of 125 psi. The catalyst-oil slurry is subjected to a controlled temperature ramping from 110° to 250° C. The catalyst has beemshown to be effectively reduced after following this activation procedure, that is valid especially for high catalyst loadings in slurry. Since the reduction is carried out in the process liquid medium and inside the reactor system, the catalyst-oil slurry after the treatment is ready for the synthesis of methanol.     

IDENTIFICATION OF NITROGEN COMPOUNDS AND THEIR EVOLUTIONDURINGAGEING NABSENCE ANDPRESENCE OF ADDITIVES EFFICIENCYOFHYDROTREATMENT

As established by several previous works, nitrogen compounds play a prominent role in the evolution of middle distillates containing cracked components, particularly regarding sediment formation and color evolution.

In a first part, this paper describes and compares stability properties of fuel blends using both an accelerated ageing method at 120°C (248°F ) and long term storage methods at 43°C(110°F) -ASTM 0 4625 - and at ambient temperature. Effectiveness of stabilizing additives is also evaluated. In mixtures containing LCOs, insoluble products are formed progressively during ageings, more or less rapidly according to the chemical constitution of the mixtures.

Then, it reports the complete identification of nitrogen compounds using gas chromatography equipped with a selective nitrogen detector and mass spectrometry showing that in light cycle oils, alkyl indoles and carbazoles are the main families.

Evolution of these compounds was followed kinetically during ageings in absence and presence of additives and alkyl indoles appeared as the moat evolutionary.

It appeared that some additives avoided evolutions of alkyl indoles without preventing sediment formation and color evolution. Oxidation mechanism involving nitrogen compounds should not be the only one to explain the storage evolutions of middle distillates.

Hydrotreatment converts all the alkyl indoles of LCO and prevents coloration end deposits in the storage of the mixtures of steaight-run distillates and LCOs.     

LIQUEFACTION OF ELB�STAN AND YATAĞAN LIGNITES I N CARBON MONOXIDE/HYDROGEN GAS MIXTURES

Thc effects of experimental parameters on the liquefaction yields of Elbistan and Yatagan lignites vcre investigated by using different solvents, guses and catalysts.

In hydroliquefaction of Elbistan lignite with anthracene and creosote oils, higher oil yields were obtained with anthracene oil. Based on this result, anthracene oil was chosen as solvent for further work done with Elbistan lignite. First the effect of moisture in lignite samples vas observed with synthesis gas as medium gas: then, the effect of carbon monoxide/ hydrogen ratio in liquefaction gas mixture was determined using moist lignite samples. The highest oil yield was obtained with moist lignite sample in 3CO/IH₂gas mixture and it was 57.3 % (daf).

The hydroliquefaction oil yields of Yatagan lignite obtained with creosote oil were higher than those obtained in anthracene ail. On Further work done with Yatagan lignite, creosote oil was chosen as solvent. First, the effects of CoMo and red mud catalysts, then in catalyzed medium, the effects of moisture in lignite samples and at last, using moist lignite samples and red mud catalyst. the effects o f carbon monaxide/hydrogen in synthesis gas medium and also, the increase in the oil yield a s an effect of catalyst presence, increased further: the 3CO/lH, ratio in gas medium was suitable for obtaining higher oil yields; and also for obtaining high oil yields, 440°c could be taken a s the most suitable temperature value and the pressure should be increased a s much as technical and economical conditions permit.     

THE EFFECT OF MATTALOPORHYRINS ON ASPHALT OXIDATION. II. THE EFFECT OF VANADYL CHELATES FOUND IN PETROLEUM

Four selected asphalts were blended with zero to five wt. percent of fractions rich in vamady cheltes prepared from two crude oils. The mixture was -coated in a teflon -support, and the whole was heated in an oven at. 113±2°C for 24 hours. The mixture then was analyzed for increases ketone, acid and anhydride functions.

in general, functions rich in vanady ponphyrims tended to promote asphalt oxidation, particularly as measured by increase in kentones. Corelation of vanadyl ponphyrim concentration with asphalt oxidation is observed to the direct only if asphalts are mixed with varying amounts of the same fraction derived from the same crude Possible reasons for this phenomenon are discussed in terms of oxidation susceptibility of aspha1ts, the importance of molecular associations, and the relative catalytic activities of metallaporphyrins and other metal chelates     

DEVOLATILIZATION STUDIES ON A BITUMINOUS COAL UNDER VARIOUS GAS ENVIRONMENTS

Devolatilization of a bituminous coal was studied in the temperature range 3 50°C to 550°C and at two pressures: 30 psig and 375 psig. Three separate particle sizes were investigated: (-2, +l),(-4, +3) and (-9, +6) mm. The runs, lasting up to 30 minutes, were carried out under two different types of flowing gas environments: a synthetic gas mixture of composition similar to that entering the devolatilization zone from the gasification zone below in a fixed bed gasifier, and containing 3% steam by volume; and, a helium-steam mixture, also containing 3% steam by volume.

The gas evolution rates from devolatilization show a peak at 5-10 minutes from the start of a run and then gradually taper off to zero as the run progresses. The concentration of methane in the off-gas stream is observed to be higher in the helium runs. There, however, is no significant effect of gas environment on the molecular weights of the tar, which show a maximum in the range 300-500. The tar yields, however, are higher for the helium runs; in all cases, the tar yields peak at 4 °C. The gas yield, however, is higher for the reactive gas environment. The total volatiles yield appears independent of particle size; however, it seems to increase with pressure, over the temperature range studied.     

EFFECT OF PREHYDROGENATION ON HYDROCONVERSION OF MAYA RESIDUUM, PART II: HYDROGEN INCORPORATION

Maya 650° F residuum (Maya AR) was prehydrogenated over a standard hydroprocessing catalyst. The 650°F residuum of this product lpar;HMaya ARrpar; and Maya AR were then separately hydroprocessed further at selected conditions. The products were examined by elemental, ¹H, and ¹³C NMR analyses to determine the how hydrogen was incorporated during processing.

For all processing steps, hydrogen was incorporated in capping fragments formed during cracking reactions, as well as in hydrogenation reactions, heteroatom removal, and hydrocarbon gas formation, but the distribution of the hydrogen was dependent upon the type and severity of the process: For the direct hydroconversion of Maya AR, 25 to 30% of the total hydrogen was incorporated for heteroatom removal and hydrocarbon gas formation. The remaining hydrogen was incorporated in hydrogenation and cracking reactions.

For the two-step hydroconversion process, 30 to 40% of the total hydrogen was incorporated for heteroatom removal and hydrocarbon gas formation. The remaining was primarily incorporated in hydrogenation reactions. Some was incorporated into cracking reactions in the moderate severity case, but almost none was seen in the low severity case.

The hydrogen incorporation during each specific processing step is discussed, along with an evaluation of the prehydrogenation step a residuum conversion process option. These results will be also compared to previously reported hydrogen incorporation measurements on other feeds and processing methods.     

REFORMING OF N-OCTANE ON A Pt/Al2O 3 CATALYST. 1. PRODUCT DISTRIBUTION AND KINETIC ANALYSIS.

The conversion of n-octane on Pt/Al₂O₃ catalyst to hydrocracked products, isooctane, ethylbenzene, o-,p-,m-xylene and toluene was investigated in hydrogen in a Berty CSTR at three different partial pressures of n-octane, 101·325 KPa total pressure, temperatures between 400°C-460°C and W/F values up to 0·33gmincm^-3. The hydrocracked products were the most predominant. Of the other products, isooctane was present in the highest yield. A sequence of elementary steps based on the suggested reaction network of Ako and Susu (1986) was found to predict the experimental conversion-W/F data with the conversion of adsorbed isooctane to adsorbed o-xylene as the rate determining step. The activation energies for the forward and backward reactions of this step were determined to be 21·2 and 14·3 Kcal/gmol, respectively.     

A MATHEMATICAL MODEL FOR MILD HYDROCRACKING:KINETICS AND PRODUCT YIELDS FROM A CRUDE OIL BLEND IN LIGHT GAS OIL OVER HYDROTREATING CATALYST.

Mild hydrocracking of 30% crude oil (Indian Crude oil.North Gujarat base)solution in light gas oil is carried out over a commercial hydrotreating catalyst at a temperature range of 300-450°c and pressure of 6. 8-20.OMpa in laboratory reactor. About 30 to 60% of the long residue (365° c+ cut) in the solution is converted to light distillates.

A mathematical model has been developed to predict the yields of products.     

SIMULATED DISTILLATION BY TRERMO GRAVIMETRIC MEASUREMENTS APPLIED TO THERMAL CRACKING AND THERMAL HYDROCRACKING

A suitable correlation can be made to represent the simulated distillation of heavy oils starting from thennoaravimetric measurements. This method is applicable to hydrocarbons having an initial boiling point equal or greater than 200°C.

The simulated thermogravimetric distillation fit was obtained from experiments with the standard compounds obtained from ASTM D-2887-83 (Boiling range distribution of petroleum fractions by gas chromatography). This method is simple, fast and without problems when applied to heavy feedstocks

The data were used in the determination of average boiling temperatures of products from thermal cracking and thermal hydrocracking. It was also possible to quantify coke yields

Average relative molecular masses of products from the above processes correlated well with the average boiling point temperatures. It indicates that, with respect to the hydrocarbon types, thermal cracking is not selective in comparison with thermal hydrocracking

The equation applied to find the average boiling temperature is following: T = (1/al) (Ttg-a2). T is the boiling temperature, al and a2 are the correction factors, Ttg is the thermogravimetric temperature.