Stirred reactor, pyrolysis

To model a packed bed of wood particles pyrolysis and char conversion schemes can be selected from the database. Homogenous reactions within the void space are modelled by describing each volume cell in the numerical grid of the flow model as a continuous stirred reactor. Due to the lack of reliable kinetic data for the conversion of gaseous species under packed bed conditions, only the conversion of hydrogen and carbon monoxide is currently taken into account. For the combustion of hydrogen an infinite rate is assumed whereas the conversion of carbon monoxide is calculated according to [17]. 

We have studied the pyrolysis of 2-2 dimethyl-propane (neopentane) in the gaseous phase at about 500 C and at small extents of reaction. The kinetic parameters obtained from these investigations in a continuous stirred reactor have been compared to the values previously determined from batch experiments (12 to 19). 

Process development on fluidized-bed pyrolysis was also carried out by the ConsoHdation Coal Co., culminating in operation of a 32 t/d pilot plant (35). The CONSOL pyrolysis process incorporated a novel stirred carbonizer as the pyrolysis reactor, which made operation of the system feasible even using strongly agglomerating eastern U.S. biturninous coals. This allowed the process to bypass the normal pre-oxidation step that is often used with caking coals, and resulted in a nearly 50% increase in tar yield. Use of a sweep gas to rapidly remove volatiles from the pyrolysis reactor gave overall tar yields of nearly 25% for a coal that had Eischer assay tar yields of only 15%. 

The majority of the cyanuric acid produced commercially is made via pyrolysis of urea [57-13-6] (mp 135°C) primarily employing either directiy or indirectly fired stainless steel rotary kilns. Small amounts of CA are produced by pyrolysis of urea in stirred batch or continuous reactors, over molten tin, or in sulfolane. The feed to the kilns can be either urea soHd, melt, or aqueous solution. Since conversion of urea to CA is endothermic and goes through a plastic stage, heat and mass transport are important process considerations. The kiln operates under slight vacuum. Air is drawn into the kiln to avoid explosive concentrations of ammonia (15—27 mol %). 

Beside continuous horizontal kilns, numerous other methods for dry pyrolysis of urea have been described, eg, use of stirred batch or continuous reactors, ribbon mixers, ball mills, etc (109), heated metal surfaces such as moving belts, screws, rotating dmms, etc (110), molten tin or its alloys (111), dielectric heating (112), and fluidized beds (with performed urea cyanurate) (113). AH of these modifications yield impure CA. 

A novel reactor for pyrolysis of a PE melt stirred by bubbles of flowing nitrogen gas at atmospheric pressure permits uniform temperature depolymerisation. Sweep-gas experiments at temperatures 370-410 C allowed pyrolysis products to be collected separately as reactor residue (solidified PE melt), condensed vapour, and uncondensed gas products. MWDs determined by GPC indicated that random scission and repolymerisation (crosslinking) broadened the polymer-melt MWD. 19 refs. USA... 

Houser and Lee [J. Phys. Chem., 71 (3422), 1967] have studied the pyrolysis of ethyl nitrate using a stirred flow reactor. They iiave proposed the following mechanism for the reaction. 

Recently, Barton and coworkers investigated the mechanism of the 1,2-silyl migration in a related system through a combination of experiment and theory40. Pyrolysis of 12 at 600 °C cleanly produced a mixture of 12 and methylenedisilacyclopentene 13 (25%) (equation 12). A kinetic study of this reaction was conducted over the temperature range of 520-600 °C in a stirred flow reactor. The Arrehnius parameters for the first order formation of 13 were logA = 12.5 s-1 and Ea = 54 kcalmol-1. In the pyrolysis of a related all-carbon system 14, decomposition occurred at 550 °C but no isomerization to the methylene cyclopentene 15 was observed up to 700 °C (equation 13). 

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... 

The stirred tank reactor, possibly with external heating loop and/or reflux cooler, is widely proposed as a plastics liquid phase pyrolysis reactor. Both BASF [15] and Professor Bockhom [6] have used a cascade of well-mixed reactors to produce a step-by-step pyrolysis of resin mixtures. 

BASF low-temperature pyrolysis of mixed plastics, using a battery of stirred tank reactors for liquefaction. 

Flnidized-bed processes are either bnbbling or internally circulating. The fluidized-bed reactor is very versatile for the pyrolysis of polyolefins. Nevertheless one of the problems with fluidized-bed pyrolysis of post-consumer plastics relates to the stickiness of the sand particles (the fluidization medium) that becomes coated with fused plastic. In order to solve these problems, new reactors have been proposed, snch as the conical spouted bed, the conical rotary reactor, a sphere circnlation reactor and a reactor with mechanical particle stirring. 

The 1973 petroleum crisis intensified research on coal liquefaction and conversion processes. The technology developed in this field was later harnessed in chemical recycling of plastics. Mastral et al. [32], for example, employed two different batch reaction systems (tubing bomb reactors and magnetically stirred autoclave) and a continuous reactor (swept fixed bed reactor). Chemical recycling techniques such as pyrolysis [28, 33-38] or coliquefaction with coal [39, 40] convert plastic wastes into hydrocarbons that are valuable industrial raw materials. 

ABSTRACT A novel reactor configuration has been developed in our laboratory which addresses the heat transfer limitations usually encountered in vacuum pyrolysis technology. In order to scale-up this reactor to an industrial scale, a systematic study on the heat transfer, the chemical reactions and the movement of the bed of particles inside the reactor has been carried out over the last ten years. Two different configurations of moving and stirred bed pilot units have been used to scale-up a continuous feed vacuum pyrolysis reactor, in accordance with the principle of similarity. A dynamic model for the reactor scale-up was developed, which includes heat transfer, chemical kinetics and particle flow mechanisms. Based on the results of the experimental and theoretical studies, an industrial vacuum pyrolysis reactor, 14.6 m long and 2.2 m in diameter, has been constructed and operated. The operation of the pyrolysis reactor has been successful, with the reactor capacity reaching the predicted feed rate of 3000 kg/h on a biomass feedstock anhydrous basis. 

This report by Conlin raised a lot of questions in my mind, but these questions remained dormant until in a futile attempt to prepare a,a-silylenevinylene polymers we accidentally synthesized 1,3-di-methylene-l,3-disilacyclobutane 5. This serindipitious synthesis allowed us to establish a two-case generality for the isomerization of methylenesilacyclobutanes since gas-phase pyrolysis of 5 cleanly and solely produced methylenedisilacyclopentene 7 (Eq. 9). This isomerization was kinetically followed in a stirred-flow reactor to afford Arrhenius parameters that clearly revealed this to be a concerted reaction. (Well, maybe not that clearly since you wouldn t bet your life on a log A of 12.5, but there certainly aren t any 54 kcal/mol sigma bonds in 5.)... 

Figures 2 and 3 show the variations in the experimental selectivities as a function of the space time for the pyrolysis of neopentane in a stirred flow reactor at a temperature of 1008 K and at a neopentane pressure of 2.19 x 10 Pa.

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. 

Pyrolysis of 2, 2-Dimethylpropane in a Continuous Flow Stirred Tank Reactor... 

---