Gas holdup in a two-phase vertical tubular reactor at high pressure

Gas holdup in a tubular reactor was measured at pressures from 5 to 14 MPa at 300°C using a differential pressure cell. The effects on gas holdup of gas density, liquid superficial velocity and gas superficial velocity were studied using vacuum tower bottoms from a Venezuelan feedstock with 95.1 wt% +524°C material. Hydrogen was used at superficial gas velocities from 0.7 to 2.0 cm/s. The feed density at 15°C (0.1 MPa), 300°C (5.57 MPa) and 400°C (13.9 MPa) was measured and showed a linear decrease with temperature. Increased gas density at a constant temperature of 300°C increased the gas holdup at all superficial gas velocities. An increase in the liquid flow rate from about 0.04 to 0.1 cm/s did not affect the gas holdup.     

Depolymerization of waste polybutylene terephthalate in hot compressed water in a fused silica capillary reactor and an autoclave reactor: Monomer phase behavior,stability, and mechanism

Depolymerization is a potentially viable means of recycling waste polymers, converting them back into monomers or other useful compounds. Terephthalic acid (TPA) and 1,4‐butanediol (1,4‐BD) are the depolymerization monomer products of polybutylene terephthalate. Their yields from depolymerization in hot compressed water (HCW) were previously found to be lower than reported theoretical values. Thus, the phase behavior, stability, and mechanism of monomers in HCW were investigated in a fused silica capillary reactor (FSCR) and a stainless steel autoclave reactor. Phase change observations showed that TPA was completely dissolved in water at 300°C, was relatively stable at 320 to 350°C, and that its recovery significantly decreased at temperatures above 350°C. The decomposition of TPA increased with increasing heating time. However, the recovery of 1,4‐BD decreased rapidly with increasing temperature or heating time. A mechanism for the stability of TPA and 1,4‐BD is proposed based on their depolymerization products. The products were quantified by Fourier transform‐infrared spectroscopy, high‐performance liquid chromatography, and gas chromatography coupled with mass spectrometry. The wall effect of the stainless steel autoclave promoted the decomposition of TPA and 1,4‐BD in HCW. POLYM. ENG. SCI., 57:544–549, 2017. © 2016 Society of Plastics Engineers     

Bio-oil from olive oil industry wastes: Pyrolysis of olive residue under different conditions

Olive residues were pyrolysed in a fixed bed reactor under different pyrolysis conditions to determine the role of final temperature, sweeping gas flow rate and steam velocity on the product yields and liquid product composition with a heating rate of 7 °C/min. Final temperature range studied was between 400 and 700 °C and the highest liquid product yield was obtained at 500 °C. Liquid product yield increased significantly under nitrogen and steam atmospheres. Liquid products obtained under the most suitable conditions were characterised by elemental analyses, FT-IR and ¹H-NMR. In addition, column chromatography was employed and the yields of the sub-fractions were calculated. Gas chromatography was achieved on n-pentane fractions. The results show that it is possible to obtain liquid products similar to petroleum from olive residue if the pyrolysis conditions are chosen accordingly.     

Bio-oil from olive oil industry wastes: Pyrolysis of olive residue under different conditions

Olive residues were pyrolysed in a fixed bed reactor under different pyrolysis conditions to determine the role of final temperature, sweeping gas flow rate and steam velocity on the product yields and liquid product composition with a heating rate of 7 °C/min. Final temperature range studied was between 400 and 700 °C and the highest liquid product yield was obtained at 500 °C. Liquid product yield increased significantly under nitrogen and steam atmospheres. Liquid products obtained under the most suitable conditions were characterised by elemental analyses, FT-IR and ¹H-NMR. In addition, column chromatography was employed and the yields of the sub-fractions were calculated. Gas chromatography was achieved on n-pentane fractions. The results show that it is possible to obtain liquid products similar to petroleum from olive residue if the pyrolysis conditions are chosen accordingly.     

Removal of Cyanides from Water by Air Oxidation in a Cocurrent Downflow Fixed Bed Reactor

A method for removal of cyanides from water is described. The method involves the air oxidation of cyanides in a fixed bed reactor with cocurrent downflow. Effects of parameters such as temperature, concentration, gas and liquid flow rates on the oxidation yield are studied. It was observed that the yield increases by increasing temperature and decreasing gas and liquid flow rates. Altering the concentration had no clear effect on the yield. A yield of 86 % was achieved at high temperature (60°C) while the maximum yield was 68 % at room temperature.     

Influence of Temperature on SO2 Removal Enhanced by Water Vapor Using a Corona‐Discharge Reactor

A reactor using d.c. corona discharge of negative polarity was applied to remove sulfur dioxide from an oxygen‐nitrogen mixture in the presence or absence of water vapor for temperatures ranging from room temperature to 350 °C. It was observed that increasing the reactor temperature caused a decrease in the removal efficiency. Mixing water vapor with the process gas resulted in an increase of the removal efficiency. The effect of the presence of water vapor on improving the removal efficiency was significant under low temperature conditions, while it was relatively moderate under high temperature conditions. In addition, the solid deposit formed inside the reactor at two temperatures, room temperature and 200 °C, was analyzed with both a differential scattering calorimeter and an X ray diffractometer. The analysis indicated that SO₂ was ultimately converted to solid sulfur in both the presence and absence of water vapor in the gas flow.     

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.     

One-dimensional heterogeneous model of a Fischer-Tropsch synthesis reactor with a fixed catalyst bed in the isothermal granules approximation

A one-dimensional heterogeneous model has been developed for a cat6alytic fixed-bed Fischer-Tropsch (FT) synthesis reactor in the isothermal granules approximation. The FT process has been simulated for a laboratory-scale reactor. The effects of the linear gas velocity and of the inner diameter of the reactor on the thermal stability of the process are considered. The size of the reactor is limited by the possibility of a “thermal explosion” occurring in the frontal layer of the catalyst. Raising the linear gas velocity enhances heat transfer, thereby reducing the overheating of the catalyst bed. The synthesis of solid hydrocarbons can be conducted in reactors no larger than 18 mm in diameter. According to calculations, the maximum temperature drop in a 3-, 4-, and 6-m-long reactor is 4.7, 4.2, and 3.6°C, respectively. The corresponding CO conversion is 35.0, 34.4, and 33.9%, respectively. For producing liquid hydrocarbons in a high-performance reactor, it is necessary to decrease its inner diameter to 12 mm. In this case, the maximum temperature drop at a reactor length of 3, 4, and 6 m is 9.6, 8.7, and 7.6°C, and the CO conversion is 78.0, 77.4, and 76.7%, respectively. The mathematical model devised here provides means to estimate the necessary design parameters of the reactor and the appropriate FT synthesis conditions for producing liquid or solid hydrocarbons.     

Surface temperature of decomposing construction materials studied by laser‐induced phosphorescence

Measurements of surface temperature and mass loss of decomposing construction materials during rapid pyrolysis are presented. Experiments have been performed with samples of low‐density fiberboard, medium‐density fiberboard, particleboard and poly(methyl methacrylate) in a single particle reactor at temperatures between 300° and 600°C. Ultraviolet laser light was used to excite micrometer‐sized thermographic phosphor particles that were deposited on the investigated materials, and the temperature was obtained from temporally resolved measurements of the laser‐induced emission. The wood‐based materials show a similar behavior, with small differences being attributed to differences in material properties. The surface temperature rapidly increases to about 400°C when a particle is introduced to the hot reactor. The initial phase is followed by rapid decomposition during which the surface temperature is 380°–540°C. The heating rate is slowed down during the rapid pyrolysis, and again increases as the remaining char is heated to the reactor temperature. The poly (methyl methacrylate), however, melts and at high temperatures can be characterized as a liquid with a boiling point of about 400°C. Thermographic phosphors are concluded to be suitable for high precision remote measurements of the surface temperature of decomposing construction materials, and possibilities for further studies and developments of the technique are discussed. Copyright © 2004 John Wiley & Sons, Ltd.     

Pyrolysis of used sunflower oil in the presence of sodium carbonate by using fractionating pyrolysis reactor

Pyrolysis of used sunflower oil was carried out in a reactor equipped with a fractionating packed column (in three different lengths of 180, 360 and 540 mm) at 400 and 420°C in the presence of sodium carbonate (1, 5, 10 and 20% based on oil weight) as a catalyst. The use of packed column increased the residence times of the primer pyrolysis products in the reactor and packed column by the fractionating of the products which caused the additional catalytic and thermal reactions in the reaction system and increased the content of liquid hydrocarbons in gasoline boiling range. The conversion of oil was high (42–83 wt.%) and the product distribution was depended strongly on the reaction temperature, packed column length and catalyst content. The pyrolysis products consisted of gas and liquid hydrocarbons, carboxylic acids, CO, CO₂, H₂ and water. Increase in the column length increased the amount of gas and coke–residual oil and decreased the amount of liquid hydrocarbon and acid phase. Also, increase of sodium carbonate content and the temperature increased the formation of liquid hydrocarbon and gas products and decreased the formation of aqueous phase, acid phase and coke–residual oil. The major hydrocarbons of the liquid hydrocarbon phase were C₅–C₁₁ hydrocarbons. The highest C₅–C₁₁ yields (36.4%) was obtained by using 10% Na₂CO₃ and a packed column of 180 mm at 420°C. The gas products included mostly C₁–C₃ hydrocarbons.     

Study on characterization of pyrolysis and hydrolysis products of poly(vinyl chloride) waste

Poly(vinyl chloride) PVC pyrolysis and hydrolysis are conducted in a fixed bed reactor and in an autoclave, respectively, under different operating conditions such as the temperature and time. The product distribution is studied. For the PVC pyrolysis process, the main gas product is HCl (55% at 340°C), there is 9% hydrocarbon gas (C₁–C₅), the liquid product fraction is about 5% (at 340°C), and the solid residue fraction is about 31% (at 340°C). For the hydrolysis process, the main gas product is HCl (55.8% at 240°C) and the solid residue is about 49.6% (at 240°C). The pyrolysis liquid product is analyzed by using gas chromatography with magic‐angle spinning. Aromatic hydrocarbons are the main class (90%), of which the major part is benzene (33%). The residue produced through pyrolysis and hydrolysis is investigated by high‐resolution solid‐state ¹³C‐NMR. These details revealed by the high‐field NMR spectra provide importmant information about the chemical changes in the PVC pyrolysis and hydrolysis process. The mechanism of PVC hydrolysis dechlorination is also discussed. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3252–3259, 2003     

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.     

Study of stability of high‐temperature polyimides using TG/MS technique

The oxidative stability of the carbon fiber‐reinforced composite of polyimide was examined, in real time, using the evolved gas analysis techniques. Off‐gas degradation products suggested the onset temperature for chain scissions to be fairly low at about 190–220°C. Based on the off‐gas products present and the trend of their release, the composite degradation mechanism appeared to be similar between 190 and 371°C, thereby marking 371°C to be the highest accelerated aging temperature for its long‐term lifetime prediction. Beyond 371°C, different degradation mechanisms would apply. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1219–1227, 2002     

Competition between hydrotreating and polymerization reactions during pyrolysis oil hydrodeoxygenation

Hydrodeoxygenation (HDO) of pyrolysis oil is an upgrading step that allows further coprocessing of the oil product in (laboratory‐scale) standard refinery units to produce advanced biofuels. During HDO, desired hydrotreating reactions are in competition with polymerization reactions that can lead to unwanted product properties. To suppress this polymerization, a low‐temperature HDO step, referred to as stabilization, is typically used. Small batch autoclaves have been used to study at near isothermal conditions the competition between hydrotreating and polymerization reactions. Although fast polymerization reactions take place above 200°C, hydrogen consumption was already observed for temperatures as low as 80°C. Hydrogen consumption increased with temperature and reaction time; however, when the end temperature exceeded 250°C, hydrogen consumption achieved a plateau. This was thought to be caused by the occurrence of fast polymerization reactions and the refractivity of the products to further hydrotreating reactions. The effect of the gas–liquid mass transfer was evaluated by using different stirring speeds. The results of these experiments (carried out at 300°C) showed that in the first 5 min of HDO, gas–liquid mass transfer appears to be limiting the overall rate of hydrotreating reactions, leading to undesired polymerization reactions and product deterioration. Afterward, intraparticle mass transfer/kinetics seems to be governing the hydrogen consumption rate. Estimations on the degree of utilization (effectiveness factor) for industrially sized catalysts show that this is expected to be much lower than 1, at least, in the early stage of HDO (first 30 min). Catalyst particle size should, thus, be carefully considered when designing industrial processes not only to minimize reactor volume but also to improve the ratio of hydrotreating to polymerization reactions. © 2011 American Institute of Chemical Engineers AIChE J, 2011     

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.     

Production of H2 and medium Btu gas via pyrolysis of lignins in a fixed-bed reactor

Lignins are generally used as a low-grade fuel in the pulp and paper industry. In this work, pyrolysis of Alcell and Kraft lignins obtained from Alcell process and Westvaco, respectively, was carried out in a fixed-bed reactor to produce hydrogen and gas with medium heating value. The effects of carrier gas (helium) flow rate (13.4–33 ml/min/g of lignin), heating rate (5–15°C/min) and temperature (350–800°C) on the lignin conversion, product composition, and gas yield have been studied. The gaseous products mainly consisted of H₂, CO, CO₂, CH₄ and C₂₊. The carrier gas flow rate did not have any significant effect on the conversion. However, at 800°C and at a constant heating rate of 15°C/min with increase in carrier gas flow rate from 13.4 to 33 ml/min/g of lignin, the volume of product gas decreased from 820 to 736 ml/g for Kraft and from 820 to 762 ml/g for Alcell lignin and the production of hydrogen increased from 43 to 66 mol% for Kraft lignin and from 31 to 46 mol% for Alcell lignin. At a lower carrier gas flow rate of 13.4 ml/min/g of lignin, the gas had a maximum heating value of 437 Btu/scf. At this flow rate and at 800°C, with increase in heating rate from 5 to 15°C/min both lignin conversion and hydrogen production increased from 56 to 65 wt.% and 24 to 31 mol%, respectively, for Alcell lignin. With decrease in temperature from 800°C to 350°C, the conversion of Alcell and Kraft lignins were decreased from 65 to 28 wt.% and from 57 to 25 wt.%, respectively. Also, with decrease in temperature, production of hydrogen was decreased. Maximum heating value of gas (491 Btu/scf) was obtained at 450°C for Alcell lignin.     

Degradation of solvolysis lignin using Lewis acid catalysts

Alcell‐derived lignin was depolymerized in a batch reactor using the Lewis acid catalysts NiCl₂ and FeCl₃. The objective was to investigate the use of Lewis acids in the production of useful liquid products directly from solvolysis lignin. The effects of reaction temperature, time and catalyst were studied on the conversion of this lignin to gas, solid and liquid products. Also, selected monomeric compounds in the ether solubles were monitored in terms of the variation in their yields with different reaction conditions. The highest conversions, 30% and 26% from Ni and Fe, respectively, were both attained at the reaction conditions of 305°C and 1 h reaction time. The Ni produced a somewhat higher yield of ether solubles, reflecting its slightly higher performance. Under the reaction conditions studied, both catalysts apparently favour condensation reactions leading to the formation of insoluble reactor residue from solvolysis lignin. Low quantities of monomeric compounds were produced, with phenols dominating over ketones and aldehydes for both catalysts.     

The physicochemical origins of the seveso accident—I: Initial heatup

A large scale experimental simulation of the “preheating” transient in the Seveso reactor was achieved. A liquid surface temperature rise of 31°C was measured within a relatively short time period following the discontinuation of agitation. Subsurface spatial temperature distribution transients were also obtained. Analytical interpretations of these data confirm our previous proposal that molecular conduction controls the growth of the hot liquid stratum. The complete experimental transient, including wall and liquid temperatures was also adequately predicted by a simple conduction-radiation model.The simple conduction-radiation model was applied also to the reactor utilizing the prototypic values of geometry, heat loss coefficients, and initial temperatures. With an emissivity value of ? = 0.25, believed appropriate for the aged reactor surface, a liquid heatup by 33°C, to a maximum preheating temperature of 193°C, was predicted. Sensitivity studies on wall emissivity indicate that this preheat temperature was in the neighborhood of 200°C.     

An Investigation of the Performance of a Boron/Potassium‐Nitrate Based Pyrotechnic Igniter

The performance of a boron/potassium‐nitrate based pyrotechnic igniter, used as an initiator in airbag gas generators, was investigated at different initial temperatures. Igniter firings were conducted in a small vented combustion chamber in order to measure the instantaneous chamber pressures. A theoretical model, which considers multi‐phase products and lumped chamber parameters, was adopted to determine the discharging gas phase and condensed phase mass flow rates from the igniter. The data reduction model used experimentally obtained pressure‐time traces and the total burned mass as input data. The calculated instantaneous mass flow rates of the igniter at various initial temperatures showed that the initial temperature has a major influence on the igniter's performance. For the temperature range tested (−20 °C to 60 °C), the pressurization rate and the total mass flow rate of the igniter increased with temperature and ranged from 322 GPa/s to 721 GPa/s and 4.3 kg/s to 6.1 kg/s, respectively. It was found that the condensed‐phase products comprised the majority of the igniter discharge products. The mass fraction of the condensed‐phase products indicated a weak dependency on initial igniter temperature. Under similar test conditions, the recorded pressure‐time traces during igniter firings were found to be quite reproducible.     

Effects of hydrogen pressure on hydrogasification of Taiheiyo (Japan) coal

The non-isothermal hydrogasification of Taiheiyo coal is studied at hydrogen pressures up to 5 MPa and temperatures of 900 °C using a high-pressure thermobalance and tubular reactor. Gaseous products are analysed and liquid products obtained from the mass balance. Rates of formation of methane increased with temperature to two maxima, at 550 °C and at 750 °C. Corrections to rate are necessary because of appreciable weight losses. In the temperature range 650–800 °C the activation energy of methane formation is ≈ 115 kJ mol^?1. Below 55 °C, the pressure dependence of reaction is 0.3, becoming first order at higher temperatures. Rates of formation of methane and ethane indicate a similar mechanism of formation. Rates of formation of liquid hydrocarbons maximize at ≈ 450 °C and increase with hydrogen pressure.