Synthesis of ethylene and propylene on a SAPO-34 silica—alumina—phosphate catalyst

A process for the preparation of ethylene and propylene from methanol on a microporous silica—alumina—phosphate SAPO-34 catalyst is described. The influence of the temperature and the nature and concentration of the diluting agent on the catalyst activity, its selectivity with respect to C₂₌-C₄₌ olefins, and ability to be regenerated were studied. The SAPO-34 catalyst was shown to be highly effective in the selectivity of ethylene and propylene formation; the total yield of C₂₌-C₄₌ olefins at 350–450°C was 77–84% and methanol conversion was up to 96–99%. In the conversion of methanol under helium at 450°C, the yield of ethylene (∼36%) was higher than at 375°C (∼29%), while the yield of propylene (∼30%) was lower (∼38%). The use of water and helium vapors as a diluent increased the yield of ethylene to ∼36% at 375°C and to ∼50% at 450°C. In the conversion of methanol at 450°C in water vapors without helium, the yield of ethylene reached ∼44–49% and the yield of propylene was 24–29%. The C₃₌ to C₂₌ ratio in the process varied from ∼0.5 to 1.5. The high efficiency of the SAPO-34 catalyst is the consequence of the microporous structure of zeolite and the high content of acid centers of medium strength. In the course of methanol conversion, the catalyst was deactivated due to coking. After regeneration with air at 550°C, the catalyst activity was completely restored, while the crystal structure and the acid properties did not change. The activity of the catalyst in a cycle is prolonged if water vapors are used as a diluent and the catalyst is processed at a high temperature with vapors. The industrial processes for the production of ethylene and propylene from nonpetroleum materials are not used in Russia. The results of this study are comparable to the data obtained from the UOP/Norsk Hydro process on the SAPO-34 catalyst. The catalyst can be recommended for further trials on an FCC type pilot plant with a moving catalyst bed.     

Analysis of the deactivation of Claus alumina catalyst during its industrial exploitation

Change in the activity of AO-NKZ-2 (AO-MK-2) alumina catalyst in the Claus reaction and transformations of carbonyl sulfide during operation over four years in the Claus reactor at the Magnitogorsk Metallurgical Combine’s coke-oven gas purification shop were studied at an average temperature of 245–260°C and a volume velocity of ∼2000 h⁻¹. The rate constants of the Claus reactions and COS transformation were determined, and the changes in the active surface area of the catalyst were investigated. Fundamental discrepancies in the rate and deactivation mechanism of the Claus catalysts were revealed with respect to the reactions of the conversion of hydrogen sulfide and carbonyl sulfide.     

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.     

Thermal degradation behaviour of aromatic poly(ester–imide) investigated by pyrolysis–GC/MS

The thermal degradation behaviours of a novel aromatic poly(ester–imide) (PEI) derived from pyromellitic dianhydride and 2,7-bis(4-aminobenzoyloxy)naphthalene have been investigated by thermogravimetric analysis (TGA) and by pyrolysis–gas chromatography/mass spectrometry (pyrolysis–GC/MS). The weight of PEI fell slightly in the temperature range of 350–450 °C in the TGA analysis, but the major weight loss occurred at 520 °C. Evolve gas analysis (EGA) of the PEI showed maximum release of pyrolyzates at 550 °C. The chemical structure of the volatile products resulted from the PEI pyrolysis at different temperatures was identified by pyrolysis–GC/MS. The cleavage of the ester linkage within the polymer chain initiated at 350 °C, and bond scission in the partially hydrolyzed pyromellitimide unit occurred in the temperature range of 450–500 °C. The bonds within the pyromellitimide unit started to cleave at 550 °C. The extensive decomposition of the pyromellitimide segment within the polymer backbone occurred at 600 °C. The possible thermal degradation pathways of this PEI are proposed on the basis of the pyrolysis products.     

Intrinsic kinetics of one-step dimethyl ether synthesis from hydrogen-rich synthesis gas over bi-functional catalyst

The reaction kinetics of the dimethyl ether synthesis from hydrogen-rich synthesis gas over bi-functional catalyst was investigated using an isothermal integral reactor at 220–260°C temperature, 3–7 MPa pressure, and 1,000–2,500 mL/g·h space velocity. The H₂/CO ratio of the synthetic gas was chosen between 3 : 1 and 6 : 1. The bi-functional catalyst was prepared by physically mixing commercial CuO/ZnO/Al₂O₃ and γ-alumina, which act as methanol synthesis catalyst and dehydration catalyst, respectively. The three reactions, including methanol synthesis from CO and CO₂ as well as methanol dehydration, were chosen as independent reactions. The Langmuir-Hinshelwood kinetic models for dimethyl ether synthesis were adopted. Kinetics parameters were obtained using the Levenberg-Marquardt mathematical method. The model was reliable according to statistical and residual error analyses. The effects of different process conditions on the reactor performance were also investigated.     

Alkaline peroxide generation using a novel perforated bipole trickle-bed electrochemical reactor

A novel perforated bipole trickle-bed electrochemical reactor is investigated for the electro-synthesis of alkaline peroxide. The process uses a relatively simple cell configuration in which a single electrolyte flows with oxygen gas in a flow-by graphite felt cathode, sandwiched between a micro-porous diaphragm and a perforated bipolar electrode plate. The graphite felt cathodes are 120 mm high by 25 mm wide and have a thickness of 3.2 mm. The reactor is operated at current densities in the range 1–5 kA m⁻², ca. 800 kPa (abs) pressure and temperature (In/Out) 20–45 °C with one and two-cells. The reactor shows good performance (current efficiency ∼78% at 2 kA m⁻² and a specific energy of 5 kWh per kg of peroxide generated) with peroxide concentrations from 0.02 to 0.15 M in 1 M NaOH.     

In situ time-resolved characterization of novel Cu–MoO2 catalysts during the water–gas shift reaction

A novel and active Cu–MoO₂ catalyst was synthesized by partial reduction of a precursor CuMoO₄ mixed-metal oxide with CO or H₂ at 200–250 °C. The phase transformations of Cu–MoO₂ during H₂ reduction and the water–gas shift reaction could be followed by in situ time resolved XRD techniques. During the reduction process the diffraction pattern of the CuMoO₄ collapsed and the copper metal lines were observed on an amorphous material background that was assigned to molybdenum oxides. During the first pass of water–gas shift (WGS) reaction, diffraction lines for Cu₆Mo₅O₁₈ and MoO₂ appeared around 350 °C and Cu₆Mo₅O₁₈ was further transformed to Cu/MoO₂ at higher temperature. During subsequent passes, significant WGS catalytic activity was observed with relatively stable plateaus in product formation around 350, 400 and 500 °C. The interfacial interactions between Cu clusters and MoO₂ increased the water–gas shift catalytic activities at 350 and 400 °C.     

Remote plasma enhanced metal organic chemical vapor deposition of TiN for diffusion barrier

TiN films were deposited with remote plasma metal organic chemical vapor deposition (MOCVD) from tetrakis-diethyl-amido-titanium (TDEAT) at substrate temperature of 250–500°C and plasma power of 20–80 W. The growth rate using N₂ plasma is slower than that with H₂ plasma and showed 9.33 kcal/mol of activation energy. In the range of 350–400°C., higher crystallinity and surface roughness were observed and resistivity was relatively low. As the temperature increased to 500°C., randomely oriented structure and smooth surface with higher resistivity were obtained. At low deposition temperature, carbon was incorporated as TiC phase, as the deposition temperature increases, carbon was found as hydrocarbon. At 40 W of plasma power, higher crystallinity and rough surface with lower resistivity were obtained and increasing the plasma power to 80 W leads to low crystallinity, smooth surface and higher resistivity. It may be due to the incorporation of hydrocarbon decomposed in the gas phase. Surface roughness was found to be related to the crystallinity of the film.     

Temperature and pH-sensitive chitosan hydrogels: DSC,rheological and swelling evidence of a volume phase transition

On heating, alkali chitin solutions undergo phase separation describing a characteristic “U-shaped” cloud point curve with a lower critical solution temperature (LCST) centered at ∼30 °C. The process is accompanied by gelation of the polymer-rich phase. A different strategy to induce alkali chitin phase separation/gelation is by applying vacuum to the solution at room temperature during aprox. 72 h. Once washed to neutrality, chitin gels had a degree of acetylation of ∼30–40% (i.e. they were converted into chitosan). On cooling, these gels exhibit an exothermic peak in micro-DSC and a depression in G^′′ and tan δ traces, evidencing a volume phase transition centered at ∼20 °C. This transition is observed only within a narrow range of pH ∼7.3–7.6. Variation in the mechanical response as a result of cyclic stepwise changes in temperature between 50 and 0 °C at pH values from 7.3–7.6, revealed that the G’ modulus of the gels increases on heating and decreases on cooling, a behavior that persists over at least four cycles of temperature change. Only marginal changes in G’ at pH 8.0 and not at all at pH 12.0 are observed. By contrast, the variation of G^′′ persists throughout the range of pH. This behavior is rationalized in terms of the existence of a fine balance between hydrophobic and hydrophilic interactions at varying temperature and pH, thus effectively controlling swelling and shrinking states of the gel network. The degree of swelling at pH 7.6 reaches a minimum at ∼22–25 °C.     

Promoted Fe/ZSM-5 catalysts prepared by sublimation: de-NOx activity and durability in H2O-rich streams

Fe/ZSM-5 catalysts with an Fe/Al ratio 1:0, were prepared by sublimation of FeCl3 into H/ZSM-5. They display high activity and durability for the selective catalytic reduction of NOx to N2, both in dry and wet gas flows. These catalysts have now been modified by exchanging a second cation into the zeolite. Mere neutralization of zeolite protons by Na⁺ lowers the selectivity for NOx reduction to N2, but the cations Ce₃ ⁺ and La₃ ⁺ act as true catalyst promoters. With isobutane as the reductant in a simulated vehicular emission gas, almost 90% of NOx is reduced to N2 at 350°C over the La-promoted catalyst. The presence of 10% H2O in the feed does not impair the catalyst performance at high temperature; in the temperature region below 350°C it even increases the N2 yield. The beneficial effect of La is due to its lowering of the catalyst activity for the undesired combustion of the hydrocarbon. No signs of zeolite destruction are evident after 100 h TOS in a wet gas flow at 350°C. Carbonaceous deposits causing a slight deactivation are easily removed in an O2/He flow at 500°C; this in situ regeneration fully restores the original activity. This revised version was published online in July 2006 with corrections to the Cover Date.     

The pyrolysis of waste mandarin residue using thermogravimetric analysis and a batch reactor

A study on the pyrolysis of waste mandarin residue, with the aim of producing bio-oil, is reported. To elucidate the thermodynamics and temperature-dependency of the pyrolysis reaction of waste mandarin residue, the activation energy was obtained by thermogravimetric analysis. Mass loss occurred within the temperature range 200–750 °C, and the average activation energy was calculated to be 205.5 kJ/mol. Pyrolysis experiments were performed using a batch reactor, under different conditions, by varying the carrier gas flow rate and temperature. When the carrier gas flow rate was increased from 15 to 30 and finally to 50ml/min, the oil yield slightly increased. Experiments performed within the temperature range 400–800 °C showed the highest oil yield (38.16 wt%) at 500 °C. The moisture content in the bio-oil increased from 35 to 45% as the temperature increased from 400 to 800 °C, which also resulted in reduction of the oxygenates content and increase in the phenolics and aromatics content, indicating that temperature is an important operating parameter influencing the yield and composition of bio-oil.     

Exhaustive catalytic hydrodechlorination

To develop technology for the utilization of waste from vinyl chloride production by the method of catalytic hydrodechlorination, the main aspects of kinetics are studied, which makes it possible to describe the process of exhaustive catalytic hydrodechlorination on a Pd/γ-Al₂O₃ catalyst. Conditions are determined that provide stable work of the catalyst and the complete extraction of chlorine from waste: excess hydrogen of ∼270°C and a contact time of 10–15 s. The process does not require high pressure. The rate of chlorinated hydrocarbon consumption in the process of hydrodechlorination of the main components of waste (1,2-dichloroethane, 1,1,2-trichloroethane, and tetrachloroethylene) is measured at 200–270°C. Mathematical equations for simulations of the hydrodechlorination reactor unit are obtained. The results can be used to develop an experimental pilot plant.     

Catalytic reduction of nitric oxide by methane over CaO catalyst

The selective catalytic reduction of nitric oxide by methane was studied over CaO catalyst in a bubbling fluidized bed in the temperature range of 800–900 °C, in which NO cannot be reduced by CH₄ without CaO catalyst. The nitric oxide conversion was found to depend on oxygen and CH₄ feed concentration, and also on temperature. In addition, the presence of water vapors in the flue gas enhanced the NO reduction admirably well in the absence of O₂. But water vapor has an inhibiting effect on the reaction while O₂ is present in the flue gas. The addition of CO₂ poisoned the CaO catalyst and exhibited a detrimental effect on NO conversion at the working temperature range, 800–900 °C. However, with a temperature rise to 900 °C the CO₂ poisoning effect on NO reduction was weakened. The mechanism was studied and discussed according to the references in the paper. This work was presented at the 6 ^th Korea-China Workshop on Clean Energy Technology held at Busan, Korea, July 4–7, 2006.     

Effects of Reaction Variables on Fischer–Tropsch Synthesis with Co-Precipitated K/FeCuAlO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> Catalysts

Abstract  

The effects of reduction temperature and reaction temperature, pressure and space velocity on iron-based K/FeCuAlO _x Fischer–Tropsch catalysts prepared by co-precipitation were investigated. The catalyst reduced at 150 °C deactivated quickly due to an abundance of unreduced iron species. With increasing reduction temperature, the iron oxide’s phase transformed from hematite (α-Fe₂O₃) to magnetite (Fe₃O₄) and finally to metallic iron (α-Fe). The induction period to reach steady-state catalytic activity was reduced at increased reduction temperatures due to in situ reduction by syngas during reaction. CO conversion increased with increasing reaction temperature, and selectivity to C₅+ decreased with increasing reaction pressure and space velocity. At reaction temperatures up to of 300 °C, CO₂ formation by the water–gas shift reaction was linearly correlated with the extent of CO conversion, and CO₂ formation was slightly suppressed at ≥350 °C by a reverse water–gas shift reaction.     

Polymerization of propylene with Ziegler–Natta catalyst: optimization of operating conditions by response surface methodology (RSM)

Optimization of operational conditions for the polymerization of propylene with Ziegler–Natta catalyst was carried out via RSM. Response surface methodology (RSM) based on a three-level, four-variable Box–Behnken design was used to evaluate the interactive effects of reaction conditions such as reaction temperature (60–80 °C), monomer pressure (5–8 bar), hydrogen volume (130–170 mL), and cocatalyst to catalyst ratio (Al/Ti, 340–500) on the catalyst activity and melt flow rate (MFR). The optimum reaction conditions derived via RSM were: temperature 70 °C, pressure 8 bar, hydrogen volume 151 mL, and cocatalyst to catalyst ratio 390. The experimental catalyst activity and MFR were 8 g polypropylene/mg catalyst and 10.9 g/10 min, respectively, under optimum conditions. Optimum values were determined from process cost point of view and offered better operational conditions.     

The process for catalytic incineration of waste gas on IC-12-S102 platinum glass fiber catalyst

The process for catalytic afterburning of volatile organic compounds (VOCs) in waste industrial gases was developed on the basis of a new platinum glass fiber catalyst (GFC) IC-12-S102 with low platinum content (∼0.02 wt %). The catalyst was shown to be more effective than the known industrial afterburning catalysts. The way of glass fiber catalyst loading to a reactor in the form of vertical spiral cartridges, structured with wire mesh of bulk weaving is described. The successful application of the IC-12-S102 catalyst was confirmed by its operation at OAO Nizhnekamskneftekhim in the process of waste gases afterburning in an industrial reactor with cleaned gases capacity up to 15000 m³/h. During the reactor operation in harsh conditions (low oxygen content, high content of water vapor), the degree of gas cleaning was 99.5–99.9% and the residual VOC content in the purified gases was no higher than 10–15 mg/m³. For more than 15 months of catalyst operation, the degree of gas purification was not reduced; thus, overall lifetime of the IC-12-S102 catalyst may be substantially longer than the life of well-known industrial afterburning catalysts.     

Heterophase combustion of silane near the first ignition limit

Heterophase combustion of silane near the first ignition limit was studied. It was found that the reaction of chain initiation on quartz in the zone of hydrogen and silane combustion manifested itself as positive feedback, which was enhanced during exposure of the reactor walls to the products of the low-pressure flame. It was shown that, in a silane-oxygen flame at a temperature of 350–500°C the quartz surface was activated as a catalyst of heterogeneous chain initiation much more strongly than it was in a hydrogen flame. It was shown that the previously found increase in the concentration of atomic hydrogen during oxidation of silane in oxygen below the first limit was related to the formation of new lattice structures saturated with crystal lattice defects, whose number on the wall increases continuously during condensation of the final reaction products, together with adsorption silicon-containing radicals.     

Silicon carbide refractory castables

Optimum formulations for castables intended for different service conditions are proposed. Silicon carbide castables containing ultradisperse particles of cement, silica fume, and electrofused corundum are developed. The castables do not weaken on heating and display superior operational properties: the compressive strength is 40–80 MPa at sintering temperature 400°C and 50–85 MPa at 1300°C, the strain onset temperature under a load of 0.2 MPa is 1700–1510°C; thermal stability (1300°C — water) is better than 45 heating/cooling cycles (1300°C — water); no change in linear and volume dimensions was observed on heating. The newly-developed castables can find application in various sectors of industry, in particular, as the refractory material for the lining of Whiting furnaces and porcelain kilns. __________ Translated from Novye Ogneupory, No. 12, pp. 36–39, December, 2005.     

High‐Pressure High‐Temperature Transparent Fixed‐Bed Reactor for Operando Gas‐Liquid Reaction Follow‐up

A 3‐MPa, 350 °C fixed‐bed reactor was designed to follow‐up gas‐liquid‐solid reactions on a millimetric size heterogeneous catalyst with Raman spectroscopy. The transparent reactor is a quartz cylinder enclosed in a Joule effect heated stainless‐steel tube. A methodology to determine how to focus the microscope for liquid and solid phase characterization is presented. The setup was validated by performing diesel hydrodesulfurization on a CoMo/alumina extrudate catalyst with a conversion very close to expected values along with the acquisition of Raman spectra of the solid catalyst showing an evolution of the catalyst phase during sulfidation.     

Cycloaddition of carbon dioxide to butyl glycidyl ether using imidazolium salt ionic liquid as a catalyst

The catalytic performance of imidazolium salt ionic liquids in the cycloaddition of carbon dioxide to butyl glycidyl ether (BGE) was investigated. The catalytic activity was tested with different imidazolium salt ionic liquids at 60–140 °C under 0.62–2.17 MPa of CO₂ pressure. The imidazolium salt ionic liquid with the cation of bulkier alkyl chain length and with more nucleophilic anion showed higher conversion of BGE. High carbon dioxide pressure and high reaction temperature up to 140 °C was favorable for the high reactivity of the catalyst. The presence of zinc bromide co-catalyst enhanced the reactivity of the imidazolium salt ionic liquid. Kinetic studies with a semi-batch reactor revealed that the reaction could be considered as first order with respect to the concentration of BGE, and the activation energy was estimated as 22.6 and 22.8 kJ/mol for 1-ethyl-3-methylimidazolium chloride (EMImCl) and 1-butyl-3-methylimidazolium chloride (BMImCl), respectively.