Viscosity pyrolysis products

At temperatures above the softening point, isotropic pitch often displays Newtonian flow characteristics (18,19), but this may well depend upon the concentration of any insoluble particles (i.e., primary QI in the case of coal tar based materials) present within the pitch. A high concentration of QI could lead to non-Newtonian character as a result of the particle-particle attractive forces. Figure 3 shows n -T curves for a variety of pitch materials and their pyrolysis products. Pyrolysis increases the Tg of the system and shifts the viscosity-temperature curve to higher temperatures. 

Approximately 50% of the pyrolysis product boils below the initial boiling point of the diesel fuel, which is entirely consistent with the specific gravity and viscosity results. The pour point (-39 C) of the product was also considerably lower than a number 2 diesel fuel (-27 C). It is lower than the average value (-2rC) of diesel fuel in the Great Lakes and Eastern Region of Canada and similar to the average value (-39 C) in the Western Region of Canada. 

The vacuum pyrolysis of thin samples of polytetrafluoroethylene follows first-order kinetics with monomer as the major decomposition product in the temperature range from 360—510° C (Siegle, Muus, and Lin). The rate constant does not depend on either the molecular weight or the type of polymer and is characterized by an activation enthalpy of 83.0 kcal/mole and a frequency factor of 3 x 1019 sec-1. The melt viscosity decreases during pyrolysis. 

In a number of processes the plastics prior to pyrolysis are dissolved into product oil for example, so that the viscosity is quite controllable. Other options, though today somewhat obsolete, are the use of a molten lead, tin or salt bath. Unfortunately, residues accumulate on top of this bath, and periodic shut-down for cleaning is inevitable. The process has been used commercially for PMMA. 

The quality of the product is of primary importance in developing a recycling technology converting plastics into fuels by pyrolysis. Today the characterization of a liquid fuel from any sources is obviously based on the qualification methods and standards of fuels from mineral oil. The properties of the pyrolysis-derived fuels from plastics are expected to be similar to conventional fuels (energy content, viscosity, density, octane and cetane number, flash-point, etc.). However, in addition to the familiar ranking values it is necessary to know more about the chemical composition of the plastic pyrolysis oil, because of the peculiarities as follows ... 

These results provide additional confirmation for the mechanism of pyrolysis of simple polyolefins. The absence of monomer in the volatile products, the maxima in the rate curves, and the sharp decrease in the intrinsic viscosity for linear polymethylene (29) and polypropylene (2, 6, 13, 30) all point to an essentially random scission, due to pronounced intermolecular chain transfer, Equation 2. However, deviations appear when a, the fraction of bonds broken, or, what amounts to the same, the number average DP is examined as a function of time. For small a, the former relation should be one of simple proportionality and hnearity in 1/P. Instead, for both polypropylene (6) and polymethylene [see Figure 5, in (29)] curvature appears, indicating a reduction of the scission rate after an initial period of rapid degradation. For polypropylene this has been interpreted as a breaking of weak and normal bonds. Between 250° and 280° C., one weak link per 2.4 X 10 is found (6). At 295° C., the existence of more than two types of bonds would have to be postulated. 

While all pyrolysis oil production reactor systems produce similar materials, each reactor produces a unique compound slate. The first decision, especially for a potential chemical or fuel producer, rather than a reactor developer, is to determine what products to make and which reactor system to use. The operating parameters of any reactor system designed to produce pyrolysis oil, especially temperature, can be altered to change the pyrolysis oil product composition and yield. Different feedstocks will produce different pyrolysis oil compositions and by-products, e.g. amorphous silica from rice hulls or rice straw, fatty acids from pine. Finally, feedstock pretreatment and/or catalysis, or reactor-bed catalysis can be used to improve specific product yields (7). Reactor system developers need to examine what they can produce and make this information available to chemical manufacturers and suppliers/owners of biomass feedstocks. This assumes that analysis of die entire liquid product from thermal conversion can be made, including quantitative analysis for any compounds that are being considered for recoveiy. Physical characterization - pH, viscosity, solids content, etc.is also needed. However, what can be produced is of no value, if it cannot be recovered or used economically. This involves examining the trade-offs between yield and current commercial value, recovery costs, and potential commercial value,... 

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