Catalytic cracking of endothermic fuels in coated tube reactor

Suspensoid of HZSM-5 or HY zeolites mixed with a self-made ceramic-like binder was coated on the inner wall of a tubular reactor by gas-aided fluid displacement technology. The coated zeolites were characterized by means of X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR) and scanning electron microscopy (SEM). The coating thickness is 10–20 ?m and the particle size of the zeolites is in the range of 1–5 ?m. In the coated reactor, cracking of endothermic fuels including n-dodecane and aviation fuel RP-3 was carried out separately under supercritical conditions at 600°C and 625°C to investigate their heat sinks and conversion of catalytic reactions. For the reaction catalyzed by HY(25% mass fraction) coating, the heat sink capacity of n-dodecane are 815.7 and 901.9 kJ/kg higher than that of the bare tube at 600°C and at 625°C, respectively. Conversion of n-dodecane also increases from 42% to 60% at 600°C and from 66% to 80% at 625°C. The coated zeolite can significantly inhibit the carbon deposition during supercritical cracking reactions.     

Effect of the granulometric composition of microspherical catalyst on the product yield for the dehydrogenation of <Emphasis Type="Italic">iso</Emphasis>-butane

The effect of the granulometric composition of microspherical KDI alumina-chromia catalysts on variation of the height and density of a fluidized bed was analyzed during pilot industrial testing at the OAO Nizhnekamskneftekhim iso-butane dehydrogenation plant. It was ascertained that one of the factors determining the acceleration of the cracking reactions was a rise in temperature to 600–610°C in the upper part of the reactor at the level of grid no. 10 due to the reduction of the upper boundary of the fluidized bed as a result of carryover from the reactor-regenerator system of catalyst particles smaller than 20 microns. The formation of a stable fluidized bed on the upper grid of the reactor depends on the content of 20–40 μm particles within the circulating catalyst. In order to compensate for the carryover of the catalyst, it is recommended that the mixture of catalysts accumulated in the first and second electrofilter fields be loaded into the system as well. This load consists of ∼25 wt % of the fraction with particle sizes of 20–40 μm and is as good the initial KDI in terms of catalytic parameters, ensuring stabilization of the fluidized bed height at a level of 52%, lowering of the temperature at the tenth grid of the reactor to 568°C, reduction of the yield of cracking products to 4.0 wt %, a 3% increase in the average daily output of iso-butylene, and a 7% decrease in the consumption of iso-butane. Recovery of the irrevocable carryout of the catalyst from the system and the formation of a stable fluidized bed were achieved by alternating the additional loading of the catalysts from the first and second fields of the electrofilter and the initial KDI with optimized fraction composition at a 4: 1 ratio.     

Catalytic cracking of n-dodecane over HZSM-5 zeolite under supercritical conditions: Experiments and kinetics

The catalytic cracking of n-dodecane over HZSM-5 zeolite catalyst was investigated at 400–450 °C under supercritical and subcritical pressures (0.1–4.0 MPa). The results show that both the activity of the catalyst and its stabilization towards deactivation decrease with increasing pressure, and the catalyst maintains substantially higher activity when feed rate exceeds 4.00 ml/min under supercritical conditions. A first-order Langmuir kinetic model with a novel decay function is developed for the supercritical catalytic cracking of hydrocarbon incorporating supercritical extraction effect on catalyst stability, which is satisfactory to describe the kinetic behaviors of catalytic cracking of supercritical n-dodecane. According to the estimated reaction rate and adsorption constant of n-dodecane on HZSM-5 at different temperature, the activation energy of 125.4 kJ/mol and adsorption heat 109.5 kJ/mol were calculated. An index of CRSE is proposed to define contribution ratio of supercritical extraction to the activity of the HZSM-5 catalyst in the developed kinetics model, and it is found that the CRSE increases with increasing hydrocarbon feed rates and decreasing catalytic activities, and reaches maximum value when the coke formation rate equals to the coke removal rate by supercritical hydrocarbon.     

Thin film YSZ coatings on functionally graded freeze cast NiO/YSZ SOFC anode supports

Intermediate temperature (600–800 °C) solid oxide fuel cell (SOFC) technology is often limited by inadequate gas transport in electrodes, and high ion transport resistance electrolytes. In this study, large area filtered arc deposition (LAFAD) and hybrid filtered arc-assisted e-beam physical vapor deposition (FA-EBPVD) technologies, in combination with freeze-tape-casting, were used to fabricate SOFC anode/electrolyte bi-layers with functionally graded porous anode microstructures and thin film electrolytes favorable for both gas transport and low resistance. Traditionally-processed NiO/YSZ in addition to freeze-tape-cast NiO/YSZ anode substrates were fabricated and subsequently coated with thin film (<1–20 μm) YSZ via LAFAD and FA-EBPVD. LAFAD was found to be effective in applying thin (~1 μm) dense YSZ films on porous substrates at ~400 °C. FA-EBPVD produced relatively thick (~10–20 μm) dense YSZ coatings on porous substrates, with columnar morphology and nano-metrical grain size. A ~10 μm FA-EBPVD YSZ coating was observed to bridge NiO/YSZ surface pores of ~10 μm, which typically requires pre-filling prior to conventional thin film coating processes. Coated substrates exhibited negligible curvature, yielding flat anode/electrode bi-layers up to 2.5 cm in diameter. These results are presented with conderations for future SOFC development discussed.     

Formation of coke in thermal cracking of jet fuel under supercritical conditions

Continuous-flow reactor experiments were carried out to study coke formation from thermal cracking of home-made jet fuel RP-3 under supercritical conditions. The mechanism and precursor of coke forming were analyzed. The starting cracking temperature of RP-3 fuel was determined to be 471.8°C by differential scanning calorimetry (DSC). Temperature-programmed oxidation and scanning electron microscopy (SEM) characterizations of the stressed tubes showed that there are three different coke species including chemisorbed carbon, amorphous carbon and filamentous coke in the solid deposits. More than 90% of coke deposits are carried away by the supercritical fluid, which has strong capabilities of extraction for coke deposits and their precursors. There were 17.1 wt-% of iron and 11.1 wt-% of chromium found on the coke surface detected by energy dispersive spectroscopy (EDS) which suggests carburetionon alloy. RP-3 fuel and its cracking liquids were analyzed by GC-MS,which showed that the content of alkyl benzene and alkyl naphthalene increased evidently in cracking liquids. __________ Translated from Petrochemical Technology, 2006, 35(12): 1151–1155 [译自:石油化工]     

Catalytic reactions of n-hexenes on amorphous silica-alumina

Reactions of n-hexenes on 80/100 mesh amorphous silica-alumina have been studied in a plug flow reactor at 405°C, and compared with results previously obtained using HY and H-ZSM-5. The dominant primary reaction is skeletal isomerization while the initial selectivity for cracking is very low compared to that on the zeolite catalysts. The dimerization-cracking reaction, the major cracking process on the zeolites, was not a primary reaction on amorphous silica-alumina. This and the slowness of reactions leading to paraffins and dehydrogenated species is attributed to the small number of strongly acidic sites on the amorphous material.     

Transformation of propane,n-butane and n-hexane over H3PW12O40 and cesium salts. Comparison to sulfated zirconia and mordenite catalysts

Over H₃PW₁₂O₄₀ and its acidic cesium salts at 250°C, alkane transformations occur through the mechanisms previously proposed for sulfated zirconia and mordenite catalysts: propane is mainly transformed into butanes through a trimerization–isomerization–cracking process, n-butane into isobutane, propane and pentanes through a dimerization–isomerization–cracking process, n-hexane into methylpentanes and 2,3-dimethylbutane through a monomolecular mechanism. With all the samples, n-butane transformation is initially much faster than propane transformation, the difference in rate increasing significantly with the Cs content: from 25 times with H₃PW₁₂O₄₀ to 350 times with Cs_2.4H_0.6PW₁₂O₄₀. On the other hand, n-hexane transformation is 2.3 to 7 times faster than n-butane transformation. A decrease in acid strength and in acid site density with Cs introduction is proposed to explain the increase in the rate ratios. For all the reactions, sulfated zirconia pretreated at 600°C is 2–3 times more active than the heteropolycompounds. HMOR10 which is the most active catalyst for n-hexane transformation is the least active for n-butane and especially propane transformation. This very low activity of mordenite for these bimolecular processes can be related to particularities of its pore system: bimolecular reactions are strongly unfavoured in the narrow non-interconnected channels of this zeolite. This revised version was published online in August 2006 with corrections to the Cover Date.     

Extraction of bitumen with sub- and supercritical water

The sub- and supercritical water extractions of Athabasca oil sand bitumens were studied using a micro reactor. The experiments were carried out in the temperature range of 360–380 °C, pressure 15–30 MPa and water density 0.07–0.65 g/cm³ for 0–2 hrs. The extraction conversion of bitumens increased with solvent power and temperature. A maximum conversion of 24% was obtained after 90 min extraction at the supercritical condition. Hydrogen and carbon mono-oxide were not detected in sub-critical region but in the supercritical region. The supercritical condition was favorable to the hydrogen formation for bitumen extraction. The extraction products were upgraded relative to the original bitumens due to direct hydrolysis of low-energy linkage and H₂ formed by water gas shift reaction in supercritical condition. 18% of initial sulfur in bitumen can be removed at maximum conversion condition. The asphaltene contents of the residue were significantly higher than that of original bitumen due to preferential extraction of aromatic compounds in supercritical condition.     

Conversion of oils to monoglycerides by glycerolysis in supercritical carbon dioxide media

Glycerolysis of soybean oil was conducted in a supercritical carbon dioxide (SC-CO₂) atmosphere to produce monoglycerides (MG) in a stirred autoclave at 150–250°C, over a pressure range of 20.7–62.1 MPa, at glycerol/oil molar ratios between 15–25, and water concentrations of 0–8% (wt% of glycerol). MG, di-, triglyceride, and free fatty acid (FFA) composition of the reaction mixture as a function of time was analyzed by supercritical fluid chromatography. Glycerolysis did not occur at 150°C but proceeded to a limited extent at 200°C within 4 h reaction time; however, it did proceed rapidly at 250°C. At 250°C, MG formation decreased significantly (P<0.05) with pressure and increased with glycerol/oil ratio and water concentration. A maximum MG content of 49.2% was achieved at 250°C, 20.7 MPa, a glycerol/oil ratio of 25 and 4% water after 4 h. These conditions also resulted in the formation of 14% FFA. Conversions of other oils (peanut, corn, canola, and cottonseed) were also attempted. Soybean and cottonseed oil yielded the highest and lowest conversion to MG, respectively. Conducting this industrially important reaction in SC-CO₂ atmosphere offered numerous advantages, compared to conventional alkalicatalyzed glycerolysis, including elimination of the alkali catalyst, production of a lighter color and less odor, and ease of separation of the CO₂ from the reaction products.     

Vapor phase isopropylation of quinoline over modified HY zeolites

The vapor phase isopropylation of quinoline was carried out over HY and modified HY zeolites in a fixed‐bed reactor at atmospheric pressure. The yield of 2‐isopropylquinoline was higher over modified zeolites, especially over doubly‐promoted LaKHY zeolite. The maximum yield of 2‐isopropylquinoline obtained was 48.8 wt% with 82.9% selectivity. The reaction favors on moderate Lewis acidic sites. This revised version was published online in July 2006 with corrections to the Cover Date.     

CO2 gasification of Thai coal chars: Kinetics and reactivity studies

Two sized fractions (<75 μm and 150–250 μm) of Ban Pu lignite A and Lampang subbituminous B coals were pyrolyzed in a drop tube fixed bed reactor under nitrogen atmosphere at 500–900 °C. Gasification of coal chars with excess carbon dioxide was then performed at 900–1,100 °C. The result was analyzed in terms of reactivity index, reaction rate and activation energy. It was found that chars at lower pyrolysis temperature had highest carbon conversion, and for chars of the same sized fraction and at the same pyrolysis temperature, reactivity indices increased with gasification temperature. The lower rank Ban Pu lignite A had higher R _s values than higher rank Lampang subbituminous B coals. Smaller chars from both coals had higher R _s values, due to the higher ash content. At present, it can be concluded that, within the gasification temperature range studied, gasification rates of chars obtained at various pyrolysis temperatures showed a linear correlation with temperature. However, additional experiment is needed to verify the correlation.     

Preparation of micro particles of functional pigments by gas-saturated solution process using supercritical carbon dioxide and polyethylene glycol

Particle design is presently a major development of supercritical fluids applications, mainly in the paint, cosmetic, pharmaceutical, and specialty chemical industries. The particles from the gas-saturated solutions (PGSS) process were used to micronize the functional compounds, fucoxanthin and astaxanthin. Fucoxanthin was extracted from brown seaweed using supercritical carbon dioxide (SC-CO₂) at 20 MPa and 45 °C. The particle formation of functional pigments with biodegradable polymer, polyethelene glycol (PEG) was performed by PGSS using SC-CO₂ in a thermostatted stirred vessel. Different temperatures (40 and 50 °C) and pressures (10–30MPa) were applied to optimize the conditions for the formation of functional pigment particles. Two nozzles of different diameter (250 and 300 μm) were used for PGSS and the reaction time was 1 hr. The average diameter of the particles obtained by PGSS at different conditions was about 0.78–1.42 μm.     

Production of hydrocarbons by pyrolysis of methyl esters from rapeseed oil

The pyrolysis of a mixture of methyl esters from rapeseed oil has been studied in a tubular reactor between 550 and 850°C and in dilution with nitrogen. A specific device for the condensation of cracking effluents was used for the fractionated recovery of liquid and gaseous effluents, which were analyzed on-line by an infrared analyzer and by gas chromatography. The cracking products in the liquid effluent were identified by gas chromatography/mass spectrometry coupling. The effects of temperature on the cracking reaction were studied for a constant residence time of 320 ms and a constant dilution rate of 13 moles of nitrogen/mole of feedstock. The principal products observed were linear 1-olefins,n-paraffins, and unsaturated methyl esters. The gas fraction also contained CO, CO₂, and H₂. The middle-chain olefins (C₁₀–C₁₄ cut) and short-chain unsaturated esters, produced with a high added value, had an optimum yield at a cracking temperature of 700°C.     

Oligomerization of α-octene catalyzed by zeolites

The oligomerization of octene-1 was studied in the presence of zeolites of different structural types (e.g., Y, Beta, ZSM-12, and ZSM-5). It was shown that at 150–200°C, wide-pore zeolite catalysts Y, Beta, and ZSM-12 exhibit high catalytic activity in the reaction. The conversion of catalyzed octene can be as high as 96%, and the yield of oligomers is 88–100 wt %. Zeolite ZSM-5 at 150–180°C has low activity and mainly catalyzes the isomerization of octene-1. As the temperature rises to 250°C, low molecular weight oligomers resulting from the cracking process are the main products of this reaction. The activity and selectivity of zeolite catalysts in the oligomerization of octene-1 are conditioned by their acidic properties and structural characteristics, as well as by the reaction conditions. It was revealed that the main oligomerization products are octene dimers having an alkylnaphthene structure and containing unsaturated hydrocarbons with tri- and tetra-substituted double bonds in amounts of 2.2–3.2%. The properties of the octene oligomers synthesized in the presence of zeolite Beta are similar to the characteristics of hydrogenated poly-α-olefins, the oligomerization of which was performed on AlCl₃ complexes.     

Ring-opening polymerization of γ-glycidoxypropyltrimethoxysilane catalyzed by multi-metal cyanide catalyst

Ring-opening polymerizations of γ-glycidoxypropyltrimethoxysilane (GPTMS) were carried out by using multi-metal cyanide (MMC) catalyst and the synthesized homopolymer was a comb-shaped polymer with regular structure. The structure of the polymer obtained (P-GPTMS) was characterized by FTIR, ¹H-NMR, and ²⁹Si-NMR spectroscopy, and the molecular weight and its distribution were analyzed by size-exclusion chromatography with multi-angle laser light scattering (SEC-MALLS). The thermal behavior of P-GPTMS was investigated by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). P-GPTMS with high molecular weight (M _n = 18,000–80,000) and narrow molecular weight distribution (1.10–1.35) were synthesized when the dosage of MMC catalyst was 0.1% and polymerization temperature was 130 °C. The molecular weight of the product could be adjusted by controlling the polymerization time. The T _g of P-GPTMS is in the range of −34 to −30 °C. On the basis of the TGA data, the decomposition rate of P-GPTMS reached its peak at 374.14 °C and the entire decomposition stopped at 600 °C.     

Synthesis and characterization of thioether-containing polyimides with high refractive indices

Colorless and transparent polymers with high refractive indices and high temperature resistance have aroused great interest in the industrial community. Here, a series of polyimides (PIs) were prepared from a newly synthesized thioether-containing dianhydride, 1,4-bis(3,4-dicarboxy-phenylenesulfanyl)-benzene dianhydride, and various diamines by a two-step polycondensation reaction. Some flexible and tough films were obtained by casting solutions of them in poly(amic acid) (PAA). The tensile strengths and elongations at break of these PI films were greater than 58 MPa and 10%, respectively. All of them were thermally stable up to 500 °C in both air and nitrogen. Their glass transition temperatures were in the range from 204.5 to 265.8 °C. PI films with a thickness of 10–20 μm showed good optical transparency in the visible light region. Their cutoff wavelengths were lower than 400 nm and their transmittance was higher than 80% at 460 nm. The thioether linkages in the PIs endowed them with high average refractive indices (n _AV) of 1.68–1.74 and low birefringence values (Δn) of 0.0085–0.0120.     

Heat transfer in a high temperature fluidized bed

The heat transfer characteristics between the bed and immersed tube in a high temperature fluidized bed (7.5 cm I.D.×70 cm H) were investigated with sand and iron ore particles. The heat transfer coefficients were measured at operating temperatures of 200–600°C and gas velocities of 1–10 U_mf. The bed emissivity measured by the radiation probe was found to be 0.8–0.9. The experimentally obtained radiative heat transfer coefficient was in the range of 30–80 W/m²K for the operating temperature of 400–800°C and the contribution of radiation to total heat transfer was about 13% and 18% for the operating temperatures of 400°C and 600°C, respectively.     

Tensile strength and morphological investigation of SiC-coated carbon fibers

SiC-coated film onto carbon fibers as a barrier of oxidation resistance and reaction between carbon fibers and metals was investigated. The chemical vapor deposition of silicon carbide onto carbon fibers was performed at various temperatures ranging from 700 to 1000°C using triisopropylsilane vapor carried by hydrogen gas. The strength of the SiC-coated carbon fibers was decreased due to deterioration of fibers and chemical attack of hydrogen on the surface of carbon fibers during the coating process. The oxidation and the thermal resistance of the SiC-coated carbon fibers compared to the uncoated carbon fibers were improved at temperature range of 600–800°C and 1000–1200°C, respectively. Morphological change by air oxidation at temperature range of 500–800‡C was also investigated for the SiC-coated and the uncoated carbon fibers, respectively. The SiC-coated film between carbon fiber and aluminum was sufficient as a barrier of reaction on carbon fiber reinforced aluminum at temperature of above 1000°C.     

Single step direct coating of 3-way catalysts on cordierite monolith by solution combustion method: High catalytic activity of Ce 0.98Pd0.02O2-δ

A new process of coating of active exhaust catalyst over γ-Al₂O₃ coated cordierite honeycomb is reported here. The process consists of (a) growing γ-Al₂O₃ on cordierite by solution combustion of Al(NO₃)3 and oxylyldihydrazide (ODH) at 600 °C and active catalyst phase Ce_0.98Pd_0.02O_2-δ on γ-Al₂O₃ coated cordierite again by combustion of ceric ammonium nitrate and ODH with 1.2 × 10⁻³ M PdCl₂ solution at 500 °C. Weight of active catalyst can be varied from 0.02 to 2 wt% which is sufficient but can be loaded even up to 12 wt% by repeating dip dry combustion. Adhesion of catalyst to cordierite surface is via oxide growth which is very strong. About 100% conversion of CO is achieved below 80 °C at a space velocity of 880 h⁻¹. At much higher space velocity of 21,000 h⁻¹, 100% conversion is obtained below 245 °C. Activation energy for CO oxidation is 8.4 kcal/mol. At a space velocity of 880 h⁻¹ 100% NO conversion is attained below 185 °C and 100% conversion of ‘HC’ C₂H₂ below 220 °C. At same space velocity 3-way catalytic performance over Ce_0.98Pd_0.02O_2-δ coated monolith shows 100% conversion of all the pollutants below 220 °C with 15% of excess oxygen. In this method, handling of nano material – powder is avoided.     

Catalytic synthesis of triazine compounds using a flexible technology

Based on laboratory pilot studies, we have developed a flow sheet for the catalytic synthesis of triazine compounds from carbamide using a flexible technology and a catalyst for this process. The main process parameters are as follows: a carbamide melt is fed into the reactor under a pressure of 0.8 MPa at 140–160°C; the volume rate of feeding the circulating gas into the reactor is 500–750 h⁻¹, its temperature is 350–500°C, and the melt-to-gas mass ratio is 1: (7–9). The temperature of synthesis in the reactor is 350–450°C; the pressure in the reactor is 0.1–0.2 MPa. The sublimation temperature is 180–200°C. The conversion of carbamide is ∼98%. The content of the target component in the product is ∼98.8%. Depending on the composition of the circulating gas, it is possible to obtain products of melamine, cyanuric acid, or melamine cyanurate. A catalyst in the form of promoted active aluminum oxide with an inner surface of 300 to 400 m²/g and a technique for its preparation have been developed.