Reactor tubular pyrolysis

Other variables of importance in designing these tubular pyrolysis reactors include the mass velocity (or flow velocity) of the gaseous reaction mixture in the tubes, pressure, steam-to-hydrocarbon-feedstock ratio, heat flux through the tube wall, and tube configuration and spacing. Pressure drop in the reactor is of major importance, especially because of the extremely high flow velocities normally employed. 

Modern olefins plants now under design and construction employ indirectly fired tubular pyrolysis reactors. A typical furnace housing the reactor is illustrated schematically in Figure 2. 

The simulation of tubular pyrolysis reactors is well established (15). It is basically composed of differential equations governing energy, mass, and momentum balances. 

Chapters 10-12 cover important aspects of coke formation in metal tubular reactors during pyrolysis of hydrocarbons. Chapters 13 and 14 are concerned with coal and lignite pyrolysis. Chapters 15 and 16 deal with pitch formation from, respectively, heavy petroleum fraction and tar sand bitumen. Chapters 17 and 18 cover studies on the mechanisms of thermal alkylation and hydropyrolysis. Chapters 19 and 20 on oil shale deal with the properties of oil shale and shale oil as developed by techniques of microwave heating and thermal analysis. 

All modem olefins plants now under design and construction use indirectly fired tubular pyrolysis reactors. Although this type of reactor is presently undergoing several challenges (1,2), it should continue to hold a dominant position for many years to come. A tubular reactor may be simulated by a set of ordinary differential equations (3). Reaction... 

Figure 6. Surfaces formed on tubular reactors during pyrolysis of ethane at 800°C. (Top left,) Stainless steel 410—Surface A, (predominant deposit) (top right,) stainless steel 410—Surface A, (less frequent deposit) (middle left,) stainless steel 410—Surface B (middle right stainless steel 410—Surface C (bottom left,) Hastelloy X—Surface A (bottom right)...

This study was primarily focused on the volatility of tars that were prepared under conditions that minimize the extent of secondary reactions. Tars were produced using a fast pyrolysis technique (heating rate greater than 5 °C/sec). About 2 or 3 grams of sample on a wire mesh holder was pushed into the pre-heated tubular pyrolysis reactor. The sample temperature was measured by a thermocouple and the holder was pulled out from the heated region after the sample reached desired temperature. The final temperature was selected based on thermogravinietrig experiments at heating rate of 20 °C /min for each material studied and arc shown in Table 1. The inert gas (N ) flow was 300 ml/min at room temperature. That corresponds to the gas phase tar maximum... 

This reaction has been studied using batch reactors, perfectly stirred continuous reactors, tubular continuous reactors, BENSON type reactors, wall-less reactors and shock tubes. The reaction has been carried out at temperatures between 700 and 1300 K, at pressures of 0.1 Pa to 10 Pa and at reaction times of 10 s to 10 s. The effects of the nature and of the area of the reactor walls as well as those of various additives have also been studied. The diversity of the studies carried out by a dozen teams throughout the world, the particularly widespread range of operating conditions (600 K for the temperature, which represents 11 orders of magnitude for the rate of initiation, 8 orders of magnitude for the pressure and reaction duration) make the pyrolysis of neopentane into a model radical reaction. 

In this pyrolysis, sub atmospheric partial pressures are achieved by employing a diluent such as steam. Because of the corrosive nature of the acids (HE and HCl) formed, the reactor design should include a platinum-lined tubular reactor made of nickel to allow atmospheric pressure reactions to be mn in the presence of a diluent. Because the pyrolysate contains numerous by-products that adversely affect polymerization, the TFE must be purified. Refinement of TFE is an extremely complex process, which contributes to the high cost of the monomer. Inhibitors are added to the purified monomer to avoid polymerization during storage terpenes such as t7-limonene and terpene B are effective (10). 

Titanium disulfide can also be made by pyrolysis of titanium trisulfide at 550°C. A continuous process based on the reaction between titanium tetrachloride vapor and dry, oxygen-free hydrogen sulfide has been developed at pilot scale (173). The preheated reactants ate fed iato a tubular reactor at approximately 500°C. The product particles comprise orthogonally intersecting hexagonal plates or plate segments and have a relatively high surface area (>4 /g), quite different from the flat platelets produced from the reaction between titanium metal and sulfur vapor. The powder, reported to be stable to... 

Experiments of propane pyrolysis were carried out using a thin tubular CVD reactor as shown in Fig. 1 [4]. The inner diameter and heating length of the tube were 4.8 mm and 30 cm, respectively. Temperature was around 1000°C. Propane pressure was 0.1-6.7 kPa. Total pressure was 6.7 kPa. Helium was used as carrier gas. The product gas was analyzed by gas chromatography and the carbon deposition rate was calculated from the film thickness measured by electron microscopy. The effects of the residence time and the temperature... 

Recently, Stair and coworkers [10, 11] developed a method to produce gas-phase methyl radicals, and used this to study reactions of methyl groups on Pt surfaces [12] and on molybdenum oxide thin films [13]. In this approach, methyl radicals are produced by pyrolysis of azomethane in a tubular reactor locat inside an ulttahigh vacuum chamber. This method avoids the complications of co-adsorbcd halide atoms, it allows higher covraages to be reached, and it allows tiie study of reactions on oxide and other surfaces that do not dissociate methyl halides effectively. 

The most common type of commercial pyrolysis equipment is the direct fired tubular heater in which the reacting material flows through several tubes connected in series. The tubes receive thermal energy by being immersed in an oil or gas furnace. The pyrolysis products are cooled rapidly after leaving the furnace and enter the separation train. Constraints on materials of construction limit the maximum temperature of the tubes to 1500 °F. Thus the effluent from the tubes should be restricted to temperatures of 1475 °F or less. You may presume that all reactor tubes and return bends are exposed to a thermal flux of 10,000 BTU/... 

Tests were performed on pyrolysis of an oil in a heated tubular reactor. The reaction is pseudo first order with an activation energy of 56630 cal/gmol, so the specific rate is represented by... 

Conversion data were obtained in a tubular flow reactor for the pyrolysis of acetone at 520 C and 1 atm to form ketene. The reactor was 3.3 cm ID and 80 cm long. Find a rate equation. 

FIGURE 12.1. Schematic of tubular reactor setup for pyrolysis/catalytic/oxidation studies coupled to a molecular-beam mass spectrometer sampling system. 

Five biomass samples (hazelnut shell, cotton cocoon shell, tea factory waste, olive husk and sprace wood) were pyrolyzed in a laboratory-scale apparatus designed for the purpose of pyrolysis (Demirbas, 2001, 2002a). Figure 6.4 shows the simple experimental setup of pyrolysis. The main element of the experimental device is a vertical cylindrical reactor of stainless steel, 127.0 nun in height, 17.0 nun iimer diameter and 25.0 mm outer diameter inserted vertically into an electrically heated tubular furnace and provided with an electrical heating system power source, with a heating rate of about 5 K/s. The biomass samples ground... 

Figure 17.23. Representative temperature profiles in reaction systems (see also Figs. 17.20, 17.21(d), 17.22(d), 17.30(c), 17.34, and 17.35). (a) A jacketed tubular reactor, (b) Burner and reactor for high temperature pyrolysis of hydrocarbons (Ullmann, 1973, Vol. 3, p. 355) (c) A catalytic reactor system in which the feed is preheated to starting temperature and product is properly adjusted exo- and endothermic profiles, (d) Reactor with built-in heat exchange between feed and product and with external temperature adjustment exo- and endothermic profiles.

Production of Ethylene by Pyrolysis of Ethane in an Isothermal Tubular Reactor... 

Significant amounts of CH4 and C2H2 are also formed but will be ignored for the purposes of this example. The ethane is diluted with steam and passed through a tubular furnace. Steam is used for reasons very similar to those in the case of ethylbenzene pyrolysis (Section 1.3.2., Example 1.1) in particular it reduces the amounts of undesired byproducts. The economic optimum proportion of steam is, however, rather less than in the case of ethylbenzene. We will suppose that the reaction is to be carried out in an isothermal tubular reactor which will be maintained at 900°C. Ethane will be supplied to the reactor at a rate of 20 tonne/h it will be diluted with steam in the ratio 0.3 mole steam 1 mole ethane. The required fractional conversion of ethane is 0.6 (the conversion per pass is relatively low to reduce byproduct formation unconverted ethane is separated and recycled). The operating pressure is 1.4 bar total, and will be assumed constant, i.e. the pressure drop through the reactor will be neglected. 

Fast Pyrolysis of Methane in Tubular Reactor. We have conducted a series of experiments on fast pyrolysis of methane using ceramic (alumina) and quartz tubular reactors. 

To illustrate the concepts of determining, non-determining and negligible processes, the mechanism of the pyrolysis of neopentane will be discussed briefly here. Neopentane pyrolysis has been chosen because it has been studied by various techniques batch reactor [105— 108], continuous flow stirred tank reactor [74, 109], tubular reactor [110], very low pressure pyrolysis [111], wall-less reactor [112, 113], non-quasi-stationary state pyrolysis [114, 115], single pulse shock tube [93, 116] amongst others, and over a large range of temperature, from... 

For some widely practiced processes, especially in the petroleum industry, reliable and convenient computerized models are available from a number of vendors or, by license, from proprietary sources. Included are reactor-regenerator of fluid catalytic cracking, hydro-treating, hydrocracking, alkylation with HF or H2SO4, reforming with Pt or Pt-Re catalysts, tubular steam cracking of hydrocarbon fractions, noncatalytic pyrolysis to ethylene, ammonia synthesis, and other processes by suppliers of catalysts. Vendors of some process simulations are listed in the CEP Software Directory (AIChE, 1994). 

A chrome -alumel thermocouple was set in close proximity to the sample inside a reactor. The reactor was made of a quartz tube which was surrounded by a tubular furnace. In a typical coal pyrolysis run, the coal sample (20-30 mg) was placed in a platinum boat which was suspended from the quartz beam of the TGA balance. The coal particle size used was 100-200 mesh. Samples were heated to desired temperatures at linear heating rates or heated iso-thermally under various gaseous environments. 

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