Phenolic and lignin pyrolysis products

Phenolic and Lignin Pyrolysis Products of Plants, Seston, and Sediment in a Georgia Estuary... 

As to the origins of the major N compounds identified, it is possible that at least a portion of some of these compounds are pyrolysis products of amino acids, peptides, proteins, [18] and porphyrins (a component of chlorophyll), [19] or originate from the microbial decomposition of plant lignins and other phenolics in the presence of ammonia. [20] Of considerable interest are the identifications aromatic and aliphatic nitriles. Nitriles can be formed from amines with the loss of 2 H2, from amides with the loss of H20, and also by reacting n-alkanoic acid with NH3. [21] The detection of long-chain alkyl- and dialkyl-nitriles points to the presence in the soil or SOM of long-chain amines... 

Lignin-derived compounds have been observed in pyrolysis products of low rank coals and associate woody tissue FI- 61. Mycke and Michaelis [2] isolated lignin-derived methoxyphenols from a Miocene coal by catalytic hydrogenolysis. Sigleo [S] reported the presence of phenolic compounds derived from iteration of lignin in pyrolysis products of silicified woody tissue as old as Triassic age. However,... 

The phenol, the cresol isomers, and the dimethylphenols, major pyrolysis products in e Moscow wood sample, are probably also derived frt>m lignin precursors that have been altered through coalification reactions. Hatcher [fr] have shown that an increase is observed in the relative proportion of phenols and cresols as rank of coaHfred wood samples increases to subbituminous coal. Comparing the distribution of pyrolysis products from the Moscow wood to that of other coalified wood samples of Hatcher allows us to deduce that the... 

The analysis of lignitic woods by analytical pyrolysis has shown that lignin structural units can be preserved as biomaikers in samples as old as Carboniferous age, or approximately 300 million years. At least half or more of the pyrolysis products in lignitic wood of Cretaceous age are methoxyphenols characteristic of lignin. The pn uct distributions in these Cretaceous samples indicate that the lignin is mainly altered in the 3-carbon side chains. Phenols, cresols, catechols, and other methylated phenols account for most of the remaining pyrolysis products. It is likely diat these products are also derived frx>m li in, especially lignin that has been altered by coalification reactions. 

Table 4.7.1 lists phenolic lignin-derived pyrolysis products according to their relative retention times on DB-1701 (0.25- and 1.0-//m films) and DB-5 (0.25-pm films) quartz capillary columns. 

All of the studies mentioned are directed to lignins derived from pulp and paper manufacture. This requires that a traditionally conservative pulp and paper industry embark on further development as a chemical producer. However, Helena Chum and her colleagues (Chapter 11) derive their phenolics from lignin by fast pyrolysis of wood rather than as byproducts from the pulp and paper industry. Opportunities might be better for development of adhesives from a chemical manufacturer drawing on waste wood as a raw material much the same as has developed in the production of furan resins derived from agricultural residues described by Bill McKillip (Chapter 29). 

The decomposition of lignin into aromatic repeat units is a long practiced art that reached its zenith around 1800 a.d. Production of chemicals by wood pyrolysis was extensively practiced until, between 1750 and 1850 a.d., coal slowly displaced wood as the major chemical source available to man. Wood is usually pyrolyzed at 260-4 lO C and lignin at 300-440 C to produce 50 wt % charcoal, 10-15% tar, and lesser amounts of 2-propanone, ethanoic acid, and methanol [16-181. The tar is often called wood creosote and is a complex mixture of substituted phenols and aromatics. It contains phenol, 2- and 4-methylphenol, 2,4-dimethylphenol, 2-methoxyphenol, 4-methyl-2-methoxyphenol, and 4-ethyl-2-methoxyphenol [19]. 

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