Flash-pyrolysis

A report on the continuous flash pyrolysis of biomass at atmospheric pressure to produce Hquids iadicates that pyrolysis temperatures must be optimized to maximize Hquid yields (36). It has been found that a sharp maximum ia the Hquid yields vs temperature curves exist and that the yields drop off sharply on both sides of this maximum. Pure ceUulose has been found to have an optimum temperature for Hquids at 500°C, while the wheat straw and wood species tested have optimum temperatures at 600°C and 500°C, respectively. Organic Hquid yields were of the order of 65 wt % of the dry biomass fed, but contained relatively large quantities of organic acids. 

Fig. 10. Liquid-fuel production by flash pyrolysis usiag char recycle.

Table 17. Properties and Analysis of Liquid Fuel and No. 6 Fuel Oil Liquid fuel produced by flash pyrolysis using char recycle (Fig. 10).

Thermochemical Liquefaction. Most of the research done since 1970 on the direct thermochemical Hquefaction of biomass has been concentrated on the use of various pyrolytic techniques for the production of Hquid fuels and fuel components (96,112,125,166,167). Some of the techniques investigated are entrained-flow pyrolysis, vacuum pyrolysis, rapid and flash pyrolysis, ultrafast pyrolysis in vortex reactors, fluid-bed pyrolysis, low temperature pyrolysis at long reaction times, and updraft fixed-bed pyrolysis. Other research has been done to develop low cost, upgrading methods to convert the complex mixtures formed on pyrolysis of biomass to high quaHty transportation fuels, and to study Hquefaction at high pressures via solvolysis, steam—water treatment, catalytic hydrotreatment, and noncatalytic and catalytic treatment in aqueous systems. 

A process of polymerization of isomerized a-pinene or turpentine with vinylbenzenes has been disclosed (105). a-Pinene or turpentine is isomerized by flash pyrolysis at 518 5° C in a hot tube reactor to yield a mixture of predominantly dipentene and i7t-alloocimene... 

Thioketenes can be prepared in several ways, from carboxyHc acid chlorides by thionation with phosphoms pentasulfide [1314-80-3] 2 5 ketene dithioacetals by -elimination, from l,2,3-thiadia2oles with flash pyrolysis, and from alkynyl sulfides (thioacetylenes). The dimeri2ation of thioketenes to 2,4-bis(alkyHdene)-l,3-dithietane compounds occurs quickly. They can be cleaved back pyrolyticaHy (63). For a review see Reference 18. 

Table 4. Product Distribution for the Occidental Flash Pyrolysis Process...

Fig. 9. Lurgi-Rhurgas flash pyrolysis system, where 1 is a lift pipe 2, primary pyrolysis reactor 3, screw feeder 4, secondary pyrolysis reactor 5 and 7,...

The isomerization of oxaziridines (1) to acid amides with migration of a substituent from C to N is a general reaction and is always observed when no other reactions predominate under the relatively harsh conditions (heating to above 150 °C or photolysis). Even then one can make acid amide formation the main reaction by working at 300 °C (57JA5739) and by dilution techniques. For example, caprolactam (63) is formed in 88% yield by flash pyrolysis of oxaziridine (52) at about 300 °C, whereas decomposition of (52) at lower temperatures gives almost no (63) (77JPR274). 

The formation of transient benzazetidinones (251) in the photolysis and thermolysis of benzotriazin-4-ones (250) is well established (76AHC215) and the highly hindered adamantyl derivative has actually been isolated from flash pyrolysis of 4-adamantylbenzotriazinone (73JCS(Pl)868). A second route to such hindered benzazetidinones involves cyclization of the iminoketene valence tautomer (252 R = Bu ), the latter being generated by deprotonation of the anthranilium salts (253) (71JA1543). 

Perhaps the most firmly based report for the formation of an azete involves flash pyrolysis of tris(dimethylamino)triazine (303). This gave a red pyrolysate believed to contain the highly stabilized azete (304) on the basis of spectroscopic data. The putative azete decomposed only slowly at room temperature, but all attempts to trap it failed (73AG(E)847). Flash pyrolysis of other 1,2,3-triazines gives only acetylenes and nitriles and it is not possible to tell whether these are formed by direct <,2-l-<,2-l-<,2 fragmentation of the triazine or by prior extrusion of nitrogen and collapse to an azete (81JCR(S)162). 

Flash Pyrolysis Coal is rapidly heated to elevated temperatures for a brief period of time to produce oil, gas, and char. The increase in hydrogen content in the gases and hquids is the result of removing carbon from the process as a char containing a significantly reduced amount of hydrogen. Several processes have been tested on a rela-... 

Authors have proposed a novel process not to dispose to landfill sites both waste PVC and waste glass but to utilize them to produce fuel and neutralize each other at the same moment. It has been successfully demonstrated that hydrogen chloride produced during flash pyrolysis of PVC was completely neutralized by the fixed glass bed and thus chlorine-lree fuel was produced [1-2]. To carry forward our proposed process we need to know the kinetics of the neutralization process. Also we have to solve the problem of formation of metal chlorides in the product char during pyrolysis of PVC, which is a critical issue for its thermal utilization. Consequently, in the present study the evaluations of neutralization kinetics of glass cullets and the decomposition of CaCl2 in char by steam were conducted. 

UV irradiation (A>300nm) of an argon matrix containing tetra-fluoromethane led to the formation of difluorocarbene CF2 (Milligan and Jacox, 1968a). It was shown that the IR spectrum of this species contains three bands at 1222 (i i), 1102 (v ), and 668 (i 2)cm . Some time later difluorocarbene was stabilized in a neon matrix at 4.2 K from the gas phase after vacuum flash pyrolysis (1300°C) of perfluoroethene (Snelson, 1970b). In this case the IR bands of CF2 differed from those in an argon matrix by less than 2 cm . ... 

The total energy, the structure, and the ionization pattern of the more stable phenyl derivative have been calculated.52,33 The controlled explosion of triazide(phenyl)silane in a flash-pyrolysis apparatus under approximately unimolecular conditions (p = 10-3 Pa, c = 10 2 3 mil/) can be carried out without danger.52,53... 

Pyrolysis method involves thermal decomposition of suitable precursors to produce free radicals. Pyrolysis sources based on continuous molecular beam nozzles are well developed (for example, methyl6 8 and benzyl9). Recently, Chen and co-workers have pioneered a flash pyrolysis/supersonic jet technique to produce free radical beams (Fig. I).10 In this radical... 

Fig. 1. Supersonic jet flash pyrolysis nozzles by Chen and co-workers. (From Kohn...

The photodissociation of jet-cooled methyl from a flash pyrolysis source has also been studied at 216.3 nm using the hign-n Rydberg atom time-of-flight technique by Wilson and co-workers.113 The H-atom time-of-flight spectrum indicates that predissociation of Cl l s(/)2 ) at 216.3 nm predom-... 

Koplitz and co-workers have studied the photolysis of C2H5 via the A2A (3s) state by using 248-nm photolysis radiation and hot ethyl radicals generated from photolysis of ethyl halides.125,126 Chen and co-workers have investigated the photodissociation of jet-cooled ethyl (produced by flash pyrolysis of ethyl iodide and n-propylnitrite) in the region of 245-264 nm... 

Deyerl and co-workers have also studied the photodissociation of the jet-cooled allyl radical produced in a flash pyrolysis source.148,149 The allyl radical is excited near 250 nm and H-atom product is detected by... 

As a proven technique for detecting reactive intermediates, flash pyrolysis seems to be the method of choice for direct detection or isolation of phosphenes. The result of thermal decomposition of (a-diazobenzyl)diphenylphosphine oxide (7) was nevertheless disappointing, since only triphenylmethane (75), fluorene (14), and benzophenone (75) but not the desired methyleneoxophosphorane 9 could be isolated 12). 

In contrast to the situation on flash pyrolysis, methyleneoxophosphoranes generated by thermolysis or photolysis in the presence of protic nucleophiles can be directly trapped to form corresponding derivatives of phosphinic acid (17- 19) however, the possibility of competing insertion of carbenes into the H/X bond of the additives is always present, giving phosphine oxides with X in the a-position (16- 18). Reaction branching at the carbene 16 was first observed on photolysis of 7 in water 13) and prompted detailed investigations on the phosphorylcarbene/ methyleneoxophosphorane rearrangement. 

Figure 6. Dependence of maximum tar yields and corresponding total volatile matter yields during flash pyrolysis on atomic hydrogen-to-carbon ratio for some Australian and V.S.A. coals (O, 9), black coals (X), brown coals (A), Pittsburgh No. 8 (USA.) ( ), Montana lignite (USA).

It is appropriate to conclude this section by reference to one aspect of the CSIRO flash pyrolysis project involving, again, brown coals. Here, it has been shown (28) that the presence of... 

Further reference to Fig. 6 shows that the latter tar yield now plots with the bituminous coals with reference to the effect of the atomic H/C ratio. Similarly a second brown coal sample (Loy Yang) which, as recovered from the seam, has a very low ash yield (0.4% dry ash-free basis), and most of the carboxyl groups in the acid form, plots with the bituminous coals in Fig. 6 however, when the sodium-salt is produced from this coal before flash pyrolysis the tar yield is almost complete supressed. 

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