Thermo-catalytic decomposition of waste lubricating oil over carbon catalyst

The thermo-catalytic decomposition of waste lubricating oil over a carbon catalyst was investigated in an I.D. of 14.5mm and length of 640mm quartz tube reactor. The carbon catalysts were activated carbon and rubber grade carbon blacks. The decomposition products of waste lubricating oil were hydrogen, methane, and ethylene in a gas phase, carbon in a solid phase and naphthalene in a liquid phase occurring within the temperature ranges of 700 °C-850 °C. The thermo-catalytic decomposition showed higher hydrogen yield and lower methane yield than that of a non-catalytic decomposition. The carbon black catalyst showed higher hydrogen yield than the activated carbon catalyst and maintained constant catalytic activity for hydrogen production, while activated carbon catalyst showed a deactivation in catalytic activity for hydrogen production. As the operating temperature increased from 700 °C to 800 °C, the hydrogen yield increased and was particularly higher with carbon black catalyst than activated carbon. As a result, carbon black catalyst was found to be an effective catalyst for the decomposition of waste lubricating oil into valuable chemicals such as hydrogen and methane.     

Controlled degradation of polystyrene

For the purpose of efficient utilization of waste polystyrene, the recovery method of a styrene oligomer having a molecular weight of 1000–3000 was studied. Thermal and catalytic degradations were carried out. It was impossible to obtain a styrene oligomer with a molecular weight less than 5000 by thermal degradation in the temperature range of 300–500°C. Catalytic degradation in the presence of silica–alumina catalyst in the temperature range of 190–230°C made it possible to control the decrease in molecular weight and to obtain a styrene oligomer having a molecular weight of 500–3000. Simultaneously, the molecular structures of the reaction products from thermal and catalytic degradations were determined by NMR analysis.     

Thermolysis of polystyrene

Styrene was recovered from polystyrene (molecular weight of 138,000) by thermolysis in a nitrogen atmosphere at temperatures between 368 and 407°C. The results were independent of the initial weight of polystyrene, which was varied between 30 and 480 g. Up to 90% of the polystyrene was converted to liquid products. The liquid products had a styrene concentration as high as 90% and the styrene yield increased with temperature. Above 390°C, the residue left in the reactor (less than 30% of initial polystyrene charge) consisted mainly of styrene monomer, dimer, and trimer (MW of 190). The kinetics support a first-order reaction with regard to the rate of production of volatiles. The activation energy was estimated to be 166.5 kJ/mol. © 1995 John Wiley & Sons, Inc.     

Thermal dissociation of tetralin between 300 and 450 °C

Most studies of the hydrogenation of coal in hydrogen-donor solvents involve the reaction of hydrogen with coal slurried in tetralin, with or without catalysts. Reaction schemes proposed usually ignore the possibility of the contribution of products of the thermal breakdown of tetralin itself. In the work presented below tetralin was heated for various periods at temperatures between 300 and 450 °C without hydrogen or coal, and the products were analysed by capillary chromatography. The main products formed were naphthalene and the tetralin isomer 1-methyl indan. Tetralin did not disproportionate to naphthalene and decalin, although this has been suggested in the literature as a mechanism for the formation of the naphthalene usually observed. Naphthalene was produced, at temperatures as low as 350 to 400 °C, by dehydrogenation of the saturated ring. This ring also rearranged to give 1-methyl indan, and at higher temperatures broke open to yield alkyl benzenes. This cracking of the saturated ring was found to enhance the naphthalene formation.     

A study of thermal decomposition of alkanethiols in pressure reactor

The thermal decomposition of four alkanethiols was investigated in this paper. The test was processed in a pressure reactor at 200–400 °C. GC/MS and GC/SCD were used to detect the products of thermal decomposition. The result indicates that the alkane groups of alkanethiols have great influence on the thermal stability of alkanethiols. N-butylthiol, isobutylthiol and n-hexylthiol begin to pyrolyse at about 250 °C and more than 75% decomposes at 400 °C after being maintained for 4 h. However, tert-octylthiol can be broken down at lower temperature below 200 °C and almost 75% decomposes at 250 °C after 4 h. The main product of thermal decomposition is H₂S and a free radical reaction is used to explain the decomposition mechanism.     

Dehydrogenation of Ethylbenzene to Styrene Using Commercial Ceramic Membranes as Reactors

Abstract

The catalytic dehydrogenation of ethylbenzene to styrene in a membrane reactor was studied at 600° to 640°C. The reactor selected in this study is a commercial alumina membrane tube with 40Å pore diameter packed with granular catalysts. One of the reaction products, hydrogen, was separated through the membrane. Therefore, the catalytic dehydrogenation was enhanced by reducing the hydrogen partial pressure in the reactor. The conversion of ethylbenzene increased ～15% compared to the conversion in the packed-bed reactor. The hydrothermal stability of membrane reactor after reactions was examined by nitrogen permeation test and SEM. It indicated that the pore diameter increased to 60 ～ 90Å and the microstructure of membrane remained intact.     

Preparation of epoxy hardeners from waste rigid polyurethane foam and their application

Aliphatic amines were used as decomposer to decompose waste rigid polyurethane and polyisocyanurate foams, and the obtained decomposed products were directly used as curing agent of epoxy resin. Effects of the decomposing condition including amine type, foam–decomposer ratio, and reaction temperature on the decomposition reaction and properties of the decomposed products were investigated. Using amines with low molecular weight could enhance decomposition reaction rate and total amine number and lessen viscosity of the obtained decomposed products. Viscosity of the decomposed products decreased with increase of reaction temperature, but increased with increment of foam–decomposer ratio. Shear strength of adhesives consisting of decomposed products and epoxy resin was measured, and their thermal properties were analyzed. The adhesives could be cured completely over 60°C and their shear strength enhances with adding coupling agent in the adhesive system. The adhesives have good thermal stability and show satisfactory shear strength with more than 15, 15, 7, and 3 MPa at 25, 60, 100, and 150°C, respectively. The results demonstrate that the obtained adhesive systems can be used as structural adhesive. © 1995 John Wiley & Sons, Inc.     

Thermal cracking of indan in deuterium at 8 MPa pressure

The thermal cracking of indan, at 500 and 515 °C in an atmosphere of pressurized deuterium of 8 MPa, produces several cracking products, each of which consists of a mixture of isotopically-substituted molecules with various numbers of deuterium atoms. The yield of the deuterated components increases with the reaction time; the products formed at reaction times close to zero contain no or only low levels of deuterium. The deuterium in the reaction products results from a stepwise hydrogen-deuterium exchange, which occurs preferentially at naphthenic carbon atoms. In the cracking reactions of indan, which proceed by α- and β-ring opening mechanisms, indan itself functions as a hydrogen donor substance which splits off the hydrogen atoms required in the initiation of the α-ring opening and which quenches radical intermediates by intermolecular hydrogen transfer. Radical quenching with deuterium gas is a much slower reaction and accounts for <25% of the primary products formed. Taken with conclusions from previous work, the present findings indicate that the thermal hydrocracking of indan might shift from the α- or β-ring opening mechanism with direct radical -H₂ interactions towards a H-donor mechanism where radical intermediates are quenched by H-transfer from indan. This shift would be caused by increasing the concentration of indan in the system.     

Study on Selective Dimerization of α-Methylstyrenes Promoted by Ionic Liquids

The catalytic systems composed of ionic liquids containing BF₄⁻ anion and HBF₄ showed high catalytic activity to produce 4-methyl-2,4-diphenyl-1-pentene (MDP-1) or 1,1,3-trimethyl-3-phenylindan (TPI) under different temperature conditions. Up to 90.8% selectivity to MDP-1 with a 98.7% conversion of α-methylstyrene was obtained at 60 °C in the presence of [HexMIm]BF₄–HBF₄, while exclusive TPI was yielded when the reaction temperature increased to 120 °C. Further studies showed that another ionic liquid, [BMIm]Cl · 2AlCl₃, could act as an excellent catalyst and solvent for the dimerization of α-methylstyrene to produce TPI. The dimerization of α-methylstyrene catalyzed by [HexMIm]BF₄–HBF₄ and [BMIm]Cl · 2AlCl₃ performed the same reaction mechanism and the proton was the active species.     

Comparison of Titania Particles Between Oxidation of Titanium Tetrachloride and Thermal Decomposition of Titanium Tetraisopropoxide

Thermal decomposition of TTIP was compared with oxidation of TiCl 4 in morphology and primary particle size of produced TiO 2 particles in a tubular reactor 2.7 cm in diameter and 54 cm in length under equal rate constants. The reactor temperature was varied from 850 to 1000°C for TiCl 4 oxidation and from 492 to 579°C for TTIP decomposition. The lower and upper limits of decomposition temperature for TTIP were determined so that the rate constants become equal, at corresponding limits, between TiCl 4 oxidation and TTIP decomposition. In order to maintain constant concentration with variation of reactor temperature, the flow rate of dilution gas was adjusted to compensate for the volume change of gas with temperature. The precursor concentration at the reaction condition was in the range of 1.09 2 10 m 6 to 1.09 2 10 m 5 mol/L, and the residence time of 3.1 to 10.8 s was based on the reactor set temperature. Particles from TTIP were spherical, while those from TiCl 4 were polyhedral. A considerable fraction of the precursor admitted to the reactor was consumed on the tube wall by surface reaction to form a zone coated with TiO 2 . The loss of precursor to the wall was greater with TiCl 4 oxidation. The particle size was, however, larger by 20% with TiCl 4 oxidation. By replacing the straight reaction tube with a concentric tube, the loss could be reduced, thereby increasing the amount of TiCl 4 available for particle formation significantly; the particle size was similar, however. With the straight tube a mixture of TiCl 4 and oxygen entered the reactor and the reaction occurred over the gradual increase from 650°C to a reactor set temperature of 900°C. With the concentric tube, the reactants had been preheated separately and then brought into contact right at the set temperature. The difference in the history of temperature for reaction may have brought about a difference in nucleation rate and consequently yielded particles of similar size. By analyses of BET surface area, X-ray diffraction patterns, and thermogravimetric data, TiO 2 particles from both routes were nearly nonporous, showed anatase peaks in majority, and contained no appreciable volatiles.     

Hydrogen production by catalytic decomposition of methane over carbon catalysts in a fluidized bed

A fluidized bed reactor made of quartz tube with an I.D. of 0.055 m and a height of 1.0 m was employed for the thermocatalytic decomposition of methane to produce CO₂ — free hydrogen. The fluidized bed was used for continuous withdrawal of the carbon products from the reactor. Two kinds of carbon catalysts — activated carbon and carbon black — were employed in order to compare their catalytic activities for the decomposition of methane in the fluidized bed. The thermocatalytic decomposition of methane was carried out in a temperature range of 800–925°C, using a methane gas velocity of 1.0–3.0 U _mf and an operating pressure of 1.0 atm. Distinctive difference was observed in the catalytic activities of two carbon catalysts. The activated carbon catalyst exhibited higher initial activity which decreased significantly with time. However, the carbon black catalyst exhibited somewhat lower initial activity compared to the activated carbon catalyst, but its activity quickly reached a quasi-steady state and was sustained over time. Surfaces of the carbon catalysts before and after the reaction were observed by SEM. The effect of various operating parameters such as the reaction temperature and the gas velocity on the reaction rate was investigated.     

Pyrolysis–molecular weight chromatography–vapor-phase infrared spectrophotometry: An on-line system for analysis of polymers. III. Thermal decomposition of polysulfones and polystyrene

The thermal decomposition of poly(butene-1 sulfone), poly(pentene-1 sulfone), poly(hexene-1 sulfone), poly(styrene sulfone), and polystyrene was investigated in helium at a heating rate of 20°C/min using an experimental system which consists of a programmable pyrolyzer, a thermal conductivity detector, a mass chromatograph, and a vapor-phase infrared spectrophotometer. Poly(butene-1 sulfone), poly(penetene-1 sulfone), and poly(hexene-1 sulfone) displayed two-step decomposition; the primary products of decomposition at both steps were the comonomers (olefin and SO₂). For poly(styrene sulfone), in addition to styrene and SO₂, products with molecular weights corresponding to dimers of styrene were observed. Decomposition of this polymer was compared with that of polystyrene, which formed mostly monomer.     

Thermal and catalytic pyrolysis of a synthetic mixture representative of packaging plastics residue

A synthetic mixture of real waste packaging plastics representative of the residue from a material recovery facility (plasmix) was submitted to thermal and catalytic pyrolysis. Preliminary thermogravimetry experiments coupled with Fourier transform infrared spectroscopy were performed to evaluate the effects of the catalysts on the polymers’ degradation temperatures and to determine the main compounds produced during pyrolysis. The thermal and catalytic experiments were conducted at 370°C, 450°C and 650°C using a bench scale reactor. The oil, gas, and char yields were analyzed and the compositions of the reaction products were compared. The primary aim of this study was to understand the effects of zeolitic hydrogen ultra stable zeolite Y (HUSY) and hydrogen zeolite socony mobil-5 (HZSM5) catalysts with high silica content on the pyrolysis process and the products’ quality. Thermogravimetry showed that HUSY significantly reduces the degradation temperature of all the polymers—particularly the polyolefines. HZSM5 had a significant effect on the degradation of polyethylene due to its smaller pore size. Mass balance showed that oil is always the main product of pyrolysis, regardless of the process conditions. However, all pyrolysis runs performed at 370°C were incomplete. The use of either zeolites resulted in a decrease in the heavy oil fraction and the prevention of wax formation. HUSY has the best performance in terms of the total monoaromatic yield (29 wt-% at 450°C), while HZSM5 promoted the production of gases (41 wt-% at 650°C). Plasmix is a potential input material for pyrolysis that is positively affected by the presence of the two tested zeolites. A more effective separation of polyethylene terephthalate during the selection process could lead to higher quality pyrolysis products.     

Pyrolysis of model compounds of the flame retardant poly(N-dimethylphosphonomethyl acrylamide)

An investigation of the thermal decomposition of N-dimethylphosphonomethyl amides has shown that the major volatile products for decomposition above 300°C are methanol, the methyl ester of the carboxylic acid, the nitrile, the carboxylic acid, the N-methyl amide, and the N,N-dimethyl amide. Also, benzoic acid was the only volatile product detected in the decomposition of α-benzamidomethylphosphonic acid. A mass balance for the decomposition of N-dimethylphosphonomethyl benzamide at 420°C showed methanol and methyl benzoate to be the major volatile products. Methanol and benzonitrile formation increased with an increase in temperature at a faster rate than the other volatile products. The reaction of amides and phosphonates was further studied using sealed tubes in a furnace. Reaction of N-methylbenzamide with dimethyl methylphosphonate at 307°C in a sealed tube produced methyl benzoate and N,N-dimethylbenzamide. N,N-dimethylbenzamide and dimethylmethylphosphonate were also shown to produce methyl benzoate at 310°C. After a 5-min period more methyl benzoate was produced in the N,N-dimethylbenzamide reaction than in the N-methylbenzamide reaction. Also, addition of ethanol to the N,N-dimethylbenzamide/dimethyl methylphosphonate reaction resulted in less ethyl benzoate methyl benzoate after heating at 310°C.     

Supported Gold Nanoparticles Catalysts for Solvent-free Selective Oxidation of Benzylic Compounds into Ketones at 1 atm O2

Supported gold nanoparticles catalyst (Au/TiO₂) was investigated for the oxidation of benzylic compounds into corresponding ketones without any organic solvent at 1 atm O₂ under mild reaction conditions (≤100 °C). For instance, indan was oxidized with conversion of 46% and 1-indanone selectivity of 90% at 90 °C for 24 h. Effect of various reaction parameters viz., temperature, time, and effect of a range of supports was studied for the oxidation of indan. The conversion of indan and selectivity of 1-indanone over recycled catalyst remains almost same.     

Degradation of polystyrene in supercritical n-Hexane

Degradation of polystyrene was carried out in supercritical n-hexane under reaction temperature ranging from 330 °C to 390 °C, pressure ranging from 30 bar to 70 bar and reaction duration of 90 min. The conversion of polystyrene increased with rising temperature and pressure. The degradation performance was influenced by the temperature rather than applied pressure. Polystyrene rapidly degraded in 30 min after reaching a prescribed temperature ranging from 350 °C to 390 °C. At a prescribed temperature of 390 °C, the degree of degradation was higher than 90%. The degradation reaction was examined experimentally at a relatively low temperature of 330 °C. The degradation of polystyrene by using supercritical n-hexane has been found to be more effective compared to general pyrolysis (thermal degradation). Among the selectivity of liquid products, that of a single aromatic ring group like styrene at 390 °C increased up to 65% in 90 min. It was found from the analysis by a gel permeation Chromatograph (GPC), that high molecular-weight compounds decreased but oligomers increased with rising temperature.     

Untersuchungen über den Thermischen Zerfall von n-Dodecylcyclopentan in der Gasphase

Investigations on the Thermal Decomposition of n-Dodecylcyclopentane in the Gas Phase In the thermal decomposition of n-dodecylcyclopentane at 670 and 750°C in a laboratory tubular reactor mixtures of hydrogen and 57 and 113 hydrocarbons respectively are formed. The mixtures have been analyzed and identified by capillary gas chromatography and by mass spectrometry. The distribution of the reaction products is used for mechanistic discussions.     

废旧聚苯乙烯塑料裂解制备苯乙烯的方法研究

对聚苯乙烯塑料(PS)催化裂解制备苯乙烯的方法进行研究, 对聚苯乙烯热裂解的机理进行了分析, 考察了不同催化条件对聚苯乙烯裂解产物的影响.     

Thermal and catalytic upgrading of a biomass‐derived oil in a dual reaction system

The thermal and catalytic upgrsding of bio‐oil to liquid fuels was studied at atmospheric pressure in a dual reactor system over HZSM‐5, silica‐alumina and a mixed catalyst containing HZSM‐5 and silica‐alumina. This bio‐oil was produced by the rapid thermal processing of the maple wood. In this work, the intent was to improve the catalyst life. Therefore, the first reactor containing no catalyst facilitated thermal cracking of blo‐oil whereas the second reactor containing the desired catalyst upgraded the thermally cracked products. The effects of process variables such as reaction temperature (350°C to 410°C), space velocity (1.8 to 7.2 h^?1) and catalyst type on the amounts and quality of organic liquid product (OLP) were investigated, In the case of HZSM‐5 catalyst, the yield of OLP was maximum at 27.2 wt% whereas the selectivity for aromatic hydrocarbons was maximum at 83 wt%. The selectivities towards aromatics and aliphatic hydrocarbons were highest for mixed and silica‐alumina catalysts, respectively. In all catalyst cases, maximum OLP was produced at an optimum reaction temperature of 370°C in both reactors, and at higher space velocity. The gaseous product consisted of CO and CO₂, and C₁‐C₆ hydrocarbons, which amounted to about 20 to 30 wt% of bio‐oil. The catalysts were deactivated due to coking and were regenerated to achieve their original activity.     

Thermal Decomposition of Polymer Mixtures Containing Poly(vinyl chloride)

Thermal decomposition of a series of 1 : 1 mixtures of typical polymer waste materials [polyethylene (PE), poly(propylene) (PP), polystyrene (PS), polyacrylonitrile (PAN), polyisoprene, poly(methyl methacrylate) (PMMA), polyamide‐6 (PA‐6), polyamide‐12 (PA‐12), polyamide‐6,6 (PA‐6,6), and poly(1,4‐phenylene terephthalamide) (Kevlar)] with poly(vinyl chloride) (PVC) was examined using thermal analysis and analytical pyrolysis techniques. It was found that the presence of polyamides and PAN promotes the dehydrochlorination of PVC, but PVC has no effect on the main decomposition temperature of polyamides. The hydrogen chloride evolution from PVC is not altered when other vinyl polymers or polyolefins are present. The thermal degradation of PAN is retarded significantly, whereas that of the other vinyl polymers is shifted to a slightly higher temperature in the presence of PVC. Among the pyrolysis products of PAN‐PVC mixture methyl chloride was found in comparable amount to the other gaseous products at 500°C pyrolysis temperature.