Peat

Review Peat Peter J. Spedding Department of Chemical Engineering, The Queen’s University Gardens, Belfast, BT9 5DL (Received 13 April 1987; revised 15 October 7987)

of Belfast,

21 Chlorine

Advances in the use, production and understanding of peat are detailed for the past decade. There has been a renewed interest in the use of peat not only as a fuel but as a basic raw material that has led to considerable work being done to increase knowledge on the formation of peat and its reactions under various conditions. (Keywords:

peat; fossil fuel; review)

Peat is a low rank fuel formed from vegetable matter in bogs and fens; it is characterized by the material, the conditions under which it is formed and its degree of decomposition. From early times, peat has been used as a fuel, particularly in Russia, Finland, Ireland and in other parts of Europe. It has been exploited intensively in agriculture and in a host of other, smaller, ways. Currently there is a renewed interest in the material because of its potential as a general source of hydrocarbons and other more particular organic raw materials used industrially. The known reserve of peat is large. For example, the USA has peat energy resources that are larger than those from natural gas, crude oil, coal, lignite and oil shale combined’. Peatlands comprise a significant portion of the land surface in many regions of the world (Table I). The important peat resources are found in the northern hemisphere, particularly in the USSR, but significant reserves have been discovered in Brazil, Indonesia, Thailand and other tropical and subtropical regions*. Peat is viewed as being coal in the making. However, unlike coal, it is invariably found with significant moisture content at the surface of the ground, within a depth of between 2 and 15 metres. In recent years, a number of significant reviewsje9 and conference proceedings’ O-l9 ha ve been published on different aspects of peat and its use. ORIGIN

OF PEAT

Peat is formed largely from inhibited decomposition of various plant materials in the waterlogged environment of marshes, bogs and swamps. Given et a1.20-22 identified plant material such as cellulose and lignin derivatives in the large-scale and fine-grained humic materials in peat. A comparison 2o of the compositions of peat and of the living plants in peat swamps shows that the higher plant ccnstituents are altered extensively in the swamp environments. The importance of biological processes in peat formation was illustrated by the presence of CL--E, diaminopimelic acid, which is a constituent of the mureide complex of bacterial cell walls.

0016-2361/88/070883-18S3.00 c 1988 Butterworth & Co. (Publishers)

Ltd.

.23 showed that the structure of vitrinites found in RaJ peat bears some similarity to that of lignin found in while Morita and Measures24 used laser plants, fluorescence to identify both cellulose and lignin compounds in peat. A number of authors25-27 have discussed in general the manner in which environmental factors affect the transformation of plant material into the various types of peat that are found. Averina and Polikarpova28 used spectroscopic data to show the presence of plant pigments in peat and Table 1

World

resources

Country Canada USA Finland Sweden Norway UK Ireland FRG Iceland Netherlands Japan New Zealand Denmark Italy France Switzerland Austria Belgium Australia Luxembourg Africa Bangladesh China Indonesia Malaysia Other Far Eastern Countries West Indies, Central America South America

of peat* Area (h, x 106)

Dry weight (Tonne x 109)

150.00 59.64 10.40 7.00 3.00 1.58 1.18 1.11 1.00 0.28 0.25 0.15 0.12 0.12 0.09 0.055 0.022 0.018 0.015 0.0002 3.803 0.06 4.159 17.000 2.500

600.00 238.56 41.60 28.00 12.00 6.32 4.72 4.44 4.00 1.12 1.00 0.60 0.48 0.48 0.36 0.22 0.088 0.072 0.060 0.0008 15.21 0.24 12.64 68.00 10.00

0.43 1 2.888 6.176

Total energy (GJ x 10”) 1194.00 474.73 82.78 55.72 22.80 12.58 9.39 8.84 7.96 2.23 1.99 1.19 0.80 0.80 0.57 0.44 0.18 0.14 0.12 0.002 30.20 0.48 33.11 135.32 19.90

1.72

3.43

11.55 24.70

23.00 49.16

* USSR data not available

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Peat: P. J. Spedding Table 2 Peat content (1980)

production

x IO3 tonne

per annum

at 40 7; moisture

Country

Fuel

Horticulture

Total

USSR Ireland Finland FRG China USA Canada Poland Sweden Czechoslovakia GDR UK France Denmark Norway New Zealand Others Total approximate

80,000 5570 3100 250 800 0 0 0 0 0 0

120,000 380 500 2000 1300 800 490 280 270 270 170 170 100 110 83 10 2900 130,000

200,000 5950 3600 2250 2100 800 490 280 270 270 170

: 0 1 0 100 90,000

170 150 110 84 10 3000 220,000

absorption spectra to provide evidence of bacterial action in the formation ofpeat. Ivantsiv and Uzhenkovz9, on the other hand, used differential thermal analysis to identify the actual species from which peat was formed. Lukoshko et u1.30-32 showed that peats of all ages contained cellulose and hemicellulose originating from plant material, but more recent peats were rich in nitrogen and fulvic acids while older peats were richer in humic acids. In the initial microbiological decomposition stages of peat formation the content of dioxone lignin* falls rapidly. Thereafter condensation polymerization reactions, and other reactions such as oxidation, decarboxylation and demethoxylation, become more important as the peat matures. Andrejko et al. 33-36 have examined the origin of mineral matter in peat employing a scanning electron microscope (SEM) technique36v37 and have developed a deposition model that allows prediction of mining characteristics and production criteria. Slater3* showed that mineral content can arise by ingress from surrounding strata, while Shchirov39 gave evidence for the importance of hydrostatic conditions in the formation of peat and other fuels. There is no doubt that the origins of peat are now well established and indeed models have been developed for prediction purposes4’. Ruyter4’ has studied the kinetics of the coalification process in the laboratory and has proposed a model for the hydrothermal process that continues after the initial biological reaction has occurred. Several workers42s43 have studied the radiocarbon contents of peat beds while Naumova et a1.44 determined the effects of radiation on peat. Reserves of peat are large, and its use dates from olden times in parts of the northern hemisphere such as the USSR, Finland, Germany and Ireland, where peat is extensively used for agriculture and as a fuel (Table 2). Since the energy crisis of 1973, renewed interest has been taken in peat reserves and a number of surveys have been reported 29,40,45-53, but much of the newer information is covered in routine Government documents except where new discoveries or developments have been made or are envisaged. Luttig 54 has pointed out that many of the peat * CAS No. 8068-03-9

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reserves in Germany are inaccessible because of prior use of the land but immense reserves exist nevertheless5’, and as the results of surveys become available it is clear that past estimates of available peat resources have been extremely conservative.

COMPOSITION

AND NATURE

The classification or taxonomy of peat has been, and continues to be, a problem because of the wide variations in the vegetation from which peat is derived and of differences in the environment in which it was formed. Also, the nature and extent of completion of biological and other reactions strongly affect classification of the peat. Broad classifications based on the original vegetation are used26*27: for example sphagnum moss, which is a major constituent of fibric peats and is useful in agriculture; sedge and other swamp plants which are the major constituents of humic peats; and saphric peats in which the original vegetation is decomposed beyond botanical recognition, giving a material useful as a fuel. Also the degree of decomposition is used to identify peat, for example, black peat, white peat. German practice has been to classify peat on the basis of its degree of decomposition. Several studies have been reported on the petrology of peat 56,57 Carlson et aLs6 suggested the possibility of developing maceral analysis of peat along the lines used for coal. In addition, determination of the classification of peat and its degree of humification would allow the prediction of fuel properties. Cohen5’, on the other hand, showed how petrological factors reflect the compositions of wax, lignocellulose, elemental carbon and the degree of humification. Simpler classifications have been reported 58,59 that are limited to fuel usage. Raymond et al.36,37 used petrography and SEM techniques in an

attempt to classify peats. Markova60 and others29 have shown that differential thermal analysis and thermogravimetry provide a relationship between observed maxima and fuel rank. Cameron and Schruben4’ reported a direct correlation between the sulphur content and ash contents of peats, while an inverse relation existed between calorific value and ash content. Veski et ~1.~~ claimed that classifications could be achieved on the basis of the composition of peat while Teichmueller and Durand62 showed how fluorescence microscopy could be used to assess fuel rank. Nieminen et al. 63 have suggested a correlation between the extent of metamorphism using the Russian GOST method and calorific value and composition. There are a number of chemical compounds that reflect the chemical changes associated with the genesis of peat, and are useful as diagnostic chemical markers for differentiating and classifying peats. The abundances of mono-hydroxy, dihydroxy and methoxy-hydroxy benzoic acids are related to the degree of decomposition while the reducing sugar content, consisting of glucose, xylose and glucuronic acid, follows an inverse relation to the degree of decomposition64. Analysis The most extensive data on chemical composition of peat are based on proximate analysis of the type used for coals. For peat, the analysis consists of determination of the percentages of material soluble in hot water, benzene-

Peat: P. J. Spedding ethanol mixture (i.e. bitumens), 2% HCl (i.e. hemicellulose), 80% H,SO, (i.e. cellulose) and the insoluble residue (i.e. lignin-humic complexes). The individual fractions obtained are subjected to other methods of analysis. Much work has been done to link proximate analysis with the botanical origin, and the degree of decomposition, of peat. A number of workers have reported on analytical methods used to study peat5s65-68. According to Schelkoph et al. 66 the determination of moisture and calorific value presents no problems but the determination of ash can be a problem because peat is easily oxidized and certain components of the ash are readily volatilized. Blomquist et a1.6* emphasized that analysis is important to an understanding of the handling characteristics and potential uses of peat. Lehtovaara et ~1.~~ employed chromatographic methods of analysis on the liquid washings containing the residues of calorimetry to determine the sulphur contents of peat. The method is reported to be both fast and accurate, showing a variation of f0.005 wt %. Ekman and Ketola” detailed a routine method of lipid analysis for peat using chromatography and mass spectrometry. The main components identified were long chain free and esterified carboxylic acids and alcohols as well as ohydroxy acids. Andrejko et al.‘l compared the various ashing techniques used for peats and concluded that the existing temperature of 750°C recommended by ASTM and the equivalent DIN method are satisfactory for fuel use, but that low temperature ashing should be employed where minerals are to be identified. Liu and Han72 introduced a routine method of ash determination based on using low energy X-ray beam scattering. of peat has been Thermogravimetric analysis reported 29,60*73-75. Ranta and Nyroenen73 have shown how to calculate important parameters such as ignition temperature and combustion rates from the data obtained. Persson et al.” have applied statistical techniques as well to attempt correlations between chemical and physical properties of peats. Fluorescence studies have been used for identification of components in peat 24*62.Similarly, the SEM technique has been used to study the mineral matter in peat36*37. Eloranta et ~1.‘~ studied paramagnetic species in peat deposits using electron paramagnetic resonance (EPR) techniques. The main ions identified were Fe3+ and MnZf. At temperatures above 353 K, the radical concentration was observed to increase dramatically. Lishtvan et al.” used a rapid desorbtion method to determine the general characteristics of peat. Spectroscopic analysis has proved to be useful in identifying materials and bonds within peat’s, However the material possesses a complex nature and interpretation of data is difficult. Chemical composition The chemical composition of peat and its distribution pattern over the whole peat deposit are required if the potential of any deposit is to be fully realised. Cohen and Andrejko76 suggested a correlation between the premaceral content of peat and the traditional proximate and ultimate analysis. Other correlations have been developed linking ash and sulphur contents40.79 and calorific value79.

Table 3

Peat

fuel products

Product Sod peat

Milled peat Peat briquettes PDF K-Fuel

Moisture content (%)

Bulk density (kg m-?

Calorilic values (MJ kg-‘)

3w 4cL55 lo-15 %I0 l-5

30@400 30@-400 700-800 750-800 750-800

11-14 8-11 17-18 20-24 25-30

Pihlaja et ~1.~~ reviewed the mapping of peat lands in relation to chemical composition. The nitrogen content of peat is of importance as far as its use as a fertilizer is concerned. Studies showed that soluble ammonium salts were predominant in fen type peats, while nitrites were at a highest concentration in bogsal. Other workers reported on the distribution of nitrogen in peat bedsE2. Both Cohen et ~1.~~ and Given and Millers4 have shown that the sulphur in peat occurs mainly as metal pyrites crystals that are lodged within peat tissue in the body of the material. Sulphur has been reported to be highest in brackish water peats. There have been a number of other reports on the inorganic content of peat and the distribution of particular compounds that it contains8~81~85-94. The analysis often used sophisticated instrumental techniques such as X-ray fluorescence spectroscopy87*88. Pihlaja et ~1.~~ and Luomala and Xetala96 have shown that between 2 and 4 kg of sterols are present in one tonne of dried peat. Of these, about 50% is /I-sitosterol*. Other workerss*23*91*97 have studied various organic constituents of peat. HARVESTING Nowadays peat is harvested mechanically as either sod peat or milled peat (Table 3). Modifications or new designs of machines for the various stages employed in the harvesting process undoubtedly occur but are not widely reported in the general scientific literature, appearing rather in trade publications associated with machine manufacturers. Two recent developments are the use of hydro-mining and screw feed extractors, which allow small deposits to be worked more economically. Fredriksson et 01.~~ found that the interfacial areas between ground water and peat deposits are regions to avoid in mining since salt concentrations tend to be higher. Slater3* confirmed these findings. Several studies have been carried out on the effect of submersion9’ of peat in water, and of drainage of water from peat99. Studies’ O” were made on the use of explosives to help dewater peat in situ, but the results were not practical. The cost of harvesting peat in a suitable form for combustion is hampering its utilization as a fuel in USA, according to Leppa”‘. Williams102 has suggested that in situ production of methane may be an alternative method of utilizing peat lands. Other workers’ 03-’ OShave studied the formation of methane from peat bogs as well as of hydrocarbon compounds in the water phaselo6. The optimum pH condition for methane formation was found to be pH = 61°4. The water draining from peat deposits has been * CAS Nos. 83-96-5; 83-45-4; 83-48-7; 474-62-4

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Peat: P. J. Spedding

investigated’ O’, particularly composition’ OS-l ’ ‘, and nich”’ reported on the surfactants of the strength While cationic compounds surfactants in this regard. influence at all’ ’ 3-1 ’ 5.

with regard to its chemical biological activity’ “. Moregulation by the use of and quality of peat as mined. are not as effective as anionic non-ionic materials have no

Drying

Much of the peat that is mined or harvested is subjected to drying in the open air with the peat being either spread or stacked (i.e. windrowed). To facilitate the drying process, the peat is turned from time to time. Peat possesses the ability to resist ingress of atmospheric precipitation so rehydration is minimal. Nevertheless partial coverage by plastic sheet etc. is used to protect the stored material from the gross effects of the weather. As mined, peat normally contains considerable amounts of water, typically between 82 and 94 wt “/,. The water-retaining capacity of peat depends on the type of material from which it was formed, the degree of decomposition, the content of cations, and its ion exchange properties ’ l6 . Excessive mechanical movement can destroy the structure of the peat and hinder dewatering. Coagulants such as iron, aluminium and calcium salts together with a flocculant such as polyacrylonitrile aid dewatering by opening up channels in the peat and facilitating water flow” ‘. The process of water removal is dependent on pH, and an optimum value of 3.7 has been suggested to avoid the formation of gelatinous precipitates that hinder the dewatering process ’ l8 . Anionic surfactants hinder dewatering in contrast to the cationic and nonionic surfactants which aid the process”‘-’ 24. The dewatering is linked to the effect of charged metal humates at the surface of the peat that prevent hydrogen bonding121.125. Chitosan and other cationic polysaccharides aid the dewatering process’ “. The slow drying of drained peat bogs has been studied by Bazin”’ who showed that water permeability was substantially reduced by drying. Several other workers98y99 have also shown that drainage of peat bogs adversely affects peat quality. Ultra violet radiation in sunlight adversely affects peat quality by promoting oxidation, for example by increasing the peroxide concentration, and promoting carbohydrate decomposition, thus increasing the self-ignition potential”‘. Rapid drying of peat increases its porosity and promotes the formation of a coke-like structure on the surface. The process aids self-ignition through the breakdown of polysaccharides to sugars129. Herein lies an explanation as to why small particles of peat shrink more than larger particles under severe drying conditions’ 3o and why such vigorous drying conditions lead to loss of volatiles and hence calorific value63. Sharp ’ 31,132 has shown that a freeze-thaw cycle helps the dewatering process by breaking down the colloidal peat structure. Indeed it has been shown133 that the behaviour of water in the region of its freezing point is modified by its association with peat. Zimmerman’ 34 has pointed out the order of magnitude difference between the actual amount of peat and the amount of water with which it is associated when it is mined (~90 wt y0 water). Mechanical dewatering, particularly using pulsating pressure in a belt press

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system, allowed the water content to be reduced economically to about 70 %, i.e. the removal of 80 % of the original moisture. Pentti and Timo135 give data on the operation of belt press dewatering of peat. They point out that among other operational parameters temperature has the important effect of increasing the dewatering rate. Wranger and Jonsson’ 36 detail a countercurrent process for dewatering peat by a combination of mechanical dewatering, preheating, separation and thermal drying using waste heat from a peat-fired furnace. Similar processes have been proposed by Leppa13’ using these general techniques. Petersson’ 38 has suggested the use of oil to cause the release of water from the peat. Decantation and deoiling on a belt press is claimed to reduce the water content to 15%. Solvent extraction13g-141 has been used to dewater peat either alone or in conjunction with mechanical dewatering. In either case, solvent losses are reported to be high. Solvents that have been used are butanol, ibutanol, amyl alcohol, methyl ethyl ketone, diethyl ketone and benzene.

SELF

HEATING

AND COMBUSTION

Peat is a relatively reactive fuel, and when transported or stock-piled can begin to self-heat; if this is not corrected it can lead to spontaneous ignition. Lishtvan et a1.‘42-151 have employed DTA, X-ray and spectroscopic analysis (i.r. and EPR) to study the self-heating process in the laboratory and have conducted field trials. Self-heating in peat starts with biodegradation of lignin and carbohydrate complexes. The biological activity results in the breaking of peat-metal bonds and an increase in mobility of cations, particularly calcium and iron ions, eventually resulting in the formation of ferrous oxalate which decomposes to give pyrophoric ferrous oxide, This series of reactions proceeds at increasingly higher temperatures, as the peat bed is heating, towards the final stage of self-ignition. Vuorio and Weckman”’ confirmed these reaction processes and determined an activation energy (ER= 53OOR) for the dominant exothermal reaction. The effects of moisture, ions and ion exchange processes were also confirmed153. Mal er al.’ 54 suggested that one of the first steps in the process was the hydrolysis of carbohydrates to sugars which subsequently reacted with amino acids under the influence of Fe,O, catalyst. Excess moisture was found to retard the reaction between sugars and amino acids. Falyushin et a1.155-158 detailed the effects of selfheating on peat. These were loss of calorific value and bitumens and an increase in water-soluble compounds and humic acids. DTA studies suggested159 that humic acids were converted to oxalic acid salts, which were readily reduced by sugars to give pyrophoric compounds of iron. Proper mixing of the stored peat, high water content and high humidity14* reduce the risk of autoignition. Treatment of peat with ammoniai6’ and other nitrogen compounds161 had a similar effect in reducing the risk of autoignition, while metal salt solutions162 and sulphur compounds163 had the opposite effect. Electric field effects164 and redox potential changes’65 also occur in stored peat, and may be of importance in monitoring the progress of self-heating. Addition of surfactants can help

Peat: P. J. Spedding

overcome certain difficulties with self-heating166. Smirnov and Kozlov 16’ have proposed a statistical method of predicting spontaneous combustion in stored peat. Pikhlak1’j8 on the other hand suggested a classification of peat based on its ignition tendency. Kiselev and Udilov’ 69 have studied the reaction kinetics disaccharides, carbonyl compounds and water-soluble exothermic reactions in peat briquette stores. Traditionally peat has been used as a fuel and in agriculture. However, the conversion of peat to other commercially useful products has been the object of extensive study for some time, even though such conversion adds considerably to the cost of what is already a low value product. Marsan”’ reported on the combustion of peat in large installations, particularly with regard to costs, and showed that increasing the water content, typically from 15 % to 40 %, overcame particulate pollution problems but reduced overall thermal efficiency by 20%. Hein er ~1.“’ gave details of pulverized peat firing and highlighted the difficulties of handling the fuel particularly peat with a high ash content. Honea ef ~1.“~ also highlighted the difficulties associated with combustion of high ash peats, particularly when the alkali metal contents are high. Belosel’skii et ~1.“~ studied the conversion of organic metal humate compounds in peat through to alkali metal oxides during the combustion process. Baryshev and Shpilevskaya’ 74 similarly followed the reactions of sulphur and calcium during combustion. Belov er aI.’ 75 reported on the formation of ash and ash deposition during combustion of peat. Siitonen et ~l.“‘,~ 76 have shown how to alter design of metal components handling peat in order to reduce wear in power stations liring peat. Schuster et ~1.“’ have suggested that grate temperatures are lower with peat, compared with other types of solid mineral fuels. In addition”‘, most existing large-scale installations can handle peat fuel but existing small domestic stoves need modification before efficient combustion can be achieved. Several reports have been presented on the use of peat as a boiler fue1179-182. Particular emphasis is placed on sources of difficulty in firing the potential peat 68*179~181*1*3.Anson et ~1.‘~~ have suggested the use of a 50% blend of peat with coal in order to eliminate firing problems that would otherwise require major plant modification to correct. Gibbs and Hampartsoumian’ 85-1 ** have given details of the effect of variables on the operation of and emissions from a fluidized bed combustion system. Engstrom et present operating experience on a circulating Ul. ’ 89+192 fluidized bed combustion boiler fired with peat. The main problem experienced was fuel handling49*192. A recent development has been to embody peat into a slurry with a combustible liquid such as oi1193-196 or methanol’ 97-1 99. Peat does not agglomerate and dewater in the same way as coals when mixed with oil and requires the use of a stabilizer such as an electrolyte to maintain suspension of the solid. In one process, the peat was combined with spent lube oil to give a substantially solid fue1’93. When methanol is used as the fluid, its greater volatility compared with oil means that the degree of preheating must be limited. The suggestion is that the methanol would be made from peat in a chemical complex. For whichever fluid is used as the suspending medium, there is an upper critical water concentration for

the peat that must not be exceeded198*199. The corrosive properties of peat ash on steel have been examined in some detai1200, and it was observed that the greatest attack took place with fly ash in a reducing atmosphere at higher temperatures (SOO-IOOO’C). On the other hand, peat itself caused pitting corrosion of steel, maximum attack occurring at 50-55°C and 80-95 wt % water content2”. Briquetting and pelletizing of peat are often associated with mechanical dewatering or with water separation as in the Fleissner process202*203, which employs elevated temperature (~220°C) and the corresponding steam pressure. Patents exist204-209 on the formation of composite peat briquettes using cellulose waste and coal with the peat. In some cases, an oxidant was used in the preparations204T210. Terent’ev et ~1.~“~~~~ suggested that the briquetting process is aided by the use of additives such as surfactants or polymers. Ishi206 has found that the shape of a peat briquette is important in determining its combustion characteristics. Maslov et a1.213 reported that cellulose and humic substances in the peat tend to be converted to mono- and disaccharides, carbonyl compounds and water-soluble substances during the briquetting process. Karlsson214 has detailed a method of heat recovery during the processing while Lazarev et ul.” 5 have furnished data on the technology of peat briquetting.

AGRICULTURE Traditionally peat has been widely employed in agriculture (Table 2). The main uses are as litter spread in stables, as a soil conditioner, in the manufacture of substrateculturecontainers, and as a fertilizer. In general, little processing of the peat is required so that the product is a high volume low price material. Various types of peat and harvesting techniques are employed in order to develop the characteristics most suitable for the intended use. In Germany, as an example, the properties of and test methods for peat used in horticulture and agriculture are detailed in DIN 11 540/542 (1978). In general, sod (or chunk) peat has different properties from those of milled peat due to the more pronounced ‘corking’ of the peat particles during air drying. Thus the density of milled peat is slightly lower than that of the corresponding sod peat while the water capacity is much lower. In addition the freezing of strongly decomposed peat while on grass in the winter leads to rupturing of its structure and the hindering of contraction on drying (so desirable in a fuel peat). As a result, a high water absorption capacity is imparted which is attractive in horticultural use. Slightly decomposed peat is used as litter spread. It is air dried to about 50% moisture and baled by pressing. Strongly decomposed, freeze-treated peat is used for soil improvement or as a cultural substrate. The former use is achieved with or without additives but the latter use of peat invariably requires additives to aid the horticultural properties of the product. Generally the additives are lime, ash, clay or slag as well as nutrients and fertilizers containing nitrogen, phosphate and potassium, these usually being added in amounts of about 1 0A by weight. Moulding and extrusions of peat culture substrates is an important facet of the horticultural industry particularly

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in inner city areas where its use has shown a consistent increase over the years. There have been a number of general reports and articles on the use of peat in agriculture and horticulture216~21 ‘. Mixtures of fertilizer with peat 218-220 have been used in horticulture and as an animal feed substitute**l. Peat ash also has a possible use as a fertilizer***. Kabai223 claims that the addition of peat224 increases the release time of N/P/K from granulated fertilizer and provides better availability to plants. Treatment of peat with ammonia to increase its fertilizing power has been suggested by a number of workers225*226. Metal complex formation in peat has been shown to be important in release and adsorption of desirable fertilizing elements 227,228.Demidenko et a1.229suggested that peat-loam blends in soil increase fertility. Anisimov et al.*30 highlight the adverse effects on plant growth that can accrue from certain organic phenolic constituents in peat. The biologically active effects of humates in peat have been shown to be beneficial to plant growth231,232. Saari233 suggested that aerobic decomposition of peat improves the efficacy of the material in agriculture. Selennov and others234-236 have detailed developments of peat culture substrates for horticulture. Stevenson237 and Mathur and Farnham238 have described the importance of humus and humic materials in the genesis and properties of peat, and relevant conferences have been held on the general subject of humic substances”‘. WATER POLLUTION

CONTROL

The adsorptive properties of peat have been found useful in the control of water pollution under certain circumstances. Karlina240 and others241 claim that the adsorption of nitrogen compounds by peat is four to five times better than with soil by itself, while phosphates are absorbed 20 times more easily than in soil. There have been a number of reports on the use of peat to remove impurities from waste water242.243; in particular, metal ions244-249 and organic pollutants250-252 are mentioned. Several workers have studied the adsorption of metal ions on peat, and have concluded that adsorption of metal ions depends on pH253-255. McKay and Allen256 examined the adsorption of dyes on peat and developed models for the mass transfer processes involved257~258. Khonyak et ~1.~‘~investigated the effect on adsorption of the size of peat particles, and concluded that a particle diameter of 50pm gave the best adsorption characteristics. Kovzun et ~1.~~’examined the adsorption of metal ions from waste water onto oxidized peat granules formed with various binders. Sodium maleate was suggested as the most appropriate type ofbinder. The inclusion of the binder caused a slight reduction in the adsorptivity by reducing the number of active carboxylic acid sites on the oxidized peat. Lych et a1.261 reported on the adsorption of surfactants by peat while Shchebetkovskii and Bochkov262 examined the adsorption of radioactive cesium, cerium and iodine from non-ionic foams. Others have suggested the use of peat dykes to contain polluted run-off water263-265. Dewaxing increases the adsorptive power ofpeat, while drying and treatment with chemicals such as urea or

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formaldehyde reduces it 266 Inoculation of the peat with bacteria of various types enhances the efficacy of the process of adsorption267. Peat has been used to recover oil and other petroleum products from water, particularly from large-scale oil spills 268-270. Several workers have suggested that the addition of alkaline earth metals aids the process271*272, while others273*274 ha ve suggested that the inclusion of certain polymers has the same effect. Details have been given of the quality of run-off water from peat lands275 and from briquetting plant276 and abatement methods have been suggested to treat the latter. The ion exchange properties of peat have been studied by Tummavuori et al. 277-279. The phenomena are little changed by harvesting and the freeze-thaw cycle but are primarily dependent on the pH of the aqueous environment280. A number of studies have been conducted on ion mobility in peat249,281-284. The property is useful when peat is employed for water pollution control, but serious use of peat as an ion exchange medium is made only after some form of processing of the as-mined peat. PYROLYSIS The conversion of peat into other useful products involves processing of some kind in a chemical plant. The peat is treated as a raw material that is converted into other useful products. General reviews of such processing of peat have been presented285-290. Peat coke of various grades is the most important product from the pyrolysis of peat, the rest of the materials formed being by-products. In general the coke is more reactive than that produced from other solid fuels, and less gas byproduct is produced, while the tar is aliphatic in nature compared with the more aromatic tars from coal. The process is more sensitive to variation in raw materials than other carbonization procedures; indeed most types of peat do not give satisfactory cokes. Old moss peats, high in free carbon and low in sulphur and phosphorus, are the only types suitable for coke formation, although a number of properties, such as oil adsorption and ion exchange of ‘white’ peat of low decomposition, are improved by mild thermal treatment. As peat is heated from ambient temperature to 1 10°C the free and absorbed water is evaporated. The peat shrinks as this takes place, and changes occur in the colloidal structure of the material. Above llO”C, polymerization of waxes and resins commences and the peat hardens and becomes less hydrophilic in character. Above 160°C CO, and CO is released along with colloidally bound water. Between 200°C and 320°C cellulose, pentosans and pectins decompose. These compounds contain bound oxygen in their structure which is released as water on thermal decomposition. At about 28O”C, tar begins to appear along with gases such as NH,, H,, CH, and higher hydrocarbons. From 320°C to 45O”C, lignins and bitumen, i.e. humic substances, decompose. The greater part of the tar and pyrolysis gases are evolved in this regime. By 7OO”C, all the aliphatic compounds have totally decomposed and the original peat has shrunk in volume by about 70% to give an approximate 40 wt ‘A yield of coke. The type of coke produced depends on the final temperature attained in the pyrolysis process. Up to

Peat: P. J. Spedding 300°C the coke is very soft; between 300°C and 600°C it is semi-coke, while coke itself is formed above 6OO”C, usually above 850°C when the coke hardensz91. Soft coke The production of this type of material is carried out in order to increase the ion exchange and oil sorption properties of the peat. Thun et ~1.‘~~ have discussed the production of soft coke and have shown that the oilbinding capacity and oil adsorption ability of the soft coke is approximately doubled by the treatment to give maximum effect at a pyrolysis temperature of 250°C. Semi-coke

and coke

The production, properties and uses of coke obtained from the pyrolysis of peat have been discussed by a number of workers292-294. The end uses of the coke are in metallurgy and as activated carbon products. However, it is not as simple to produce metallurgical quality coke from peat as has been assumed. Not only is the process very sensitive to changes in raw material and procedure but it must be thermally self-sufficient. Grumpelt295 points out that an indirectly heated shaft furnace is the only type of equipment that will produce an acceptable coke. The moisture content of peat was reported to have an effect on the granular structure of the resulting semicoke296. Other reports have been concerned with the effect on coking of steamz9’, organic additives298p299, and inorganic salts300-304. The last are useful for activated carbon production and catalyst preparation, besides aiding in the formation of coke. Auto-oxidative processes occurring during storage of peat have been reported to have a beneficial effect on coke reactivity and adsorptive properties 305*306but the calorific content of the peat was adversely affected by the self-heating process adversely affecting thermal self-sufficiency. Several workers have reported on the chemical processes taking place during pyrolysis of peat307*308. There have been several reports on the by-products from pyrolysis of peat although most are used to provide heat for the pyrolysis process. Activated carbon The economics of the manufacture of activated carbon from peat were presented by Sipilak et u1.311,312. Saler and Slabbert3’ 3 showed that peat gave a better activated carbon than lignite, coal or coconut shell. Mazina and Drozhalina314 demonstrated that moss peat, which was rich in humic acids, gave the best activated carbon. Steam-air is the best type of oxidant to use for the actual activation of the char because it penetrates deeply into the peat to give a uniform micropore structure. Drozhalina et a1.315 claimed that the strength of activated carbon was improved by inclusion of brown coal with the peat. Several workers316931 ’ have examined various metallic activators used in the manufacture of active carbon from peat. Both K,CO, and ZnCl, were shown to impart the greatest pore size and surface area to the carbon. Schnegula et al.3’8 suggested a gas desulphurization process based on this type of metal-promoted activated carbon. Kunin et a1.319 reported on the efficacy of sodium-promoted activated carbon from peat while Baranchikova et a1.320 used aluminium as the activator and reported on the resulting pore structure. Bloomzz7

used a peat-aluminium complex to adsorb phosphate for use in soil fertilization. Bel’kevich et ~1.~‘~ partially oxidized peat by chemical means and formed suitable sorbent particles by incorporating a binder such as sodium maleate. structure of Zhukov et a1.322 studied the porous activated carbon made from peat using a low angle X-ray scattering technique. Gaiduk et al.323 reported that peat would adsorb 328 to 354 mg of nitrogen dioxide gas per gram of peat, while oxidized peat would adsorb hydrogen sulphide but to a lesser extent. Drozhalina and examined the ability of activated Bulgakova3249325 carbon formed from a mixture of peat and brown coal to separate gases. Catalysts While certain substances are added to peat to aid the formation of activated carbon, and indeed these compounds may also aid the absorptive process, another development has been to use the char-metal complex as a catalyst. Schnegula et al. 3’8 developed a metal-doped catalyst from activated carbon that was used in gas desulphurization. Bel’kevich et a1.326*327 made a cobaltpeat catalyst for the dehydration of cyclohexanol, and found that the metal was covalently bonded to the modified peat. Kapteijn and Moulijn3” studied the gasification of activated peat carbon with K,CO, as a catalyst. Steglich et a1.329 studied Zn and Fe on peat carbon as catalysts for vinyl chloride synthesis while Kienneman and Chomet3jo used metal-doped peat coke catalysts for the methanation reaction. Bitumen and tar Peat contains bitumen compounds while tars are formed by the pyrolysis of peat to give cokes of various types. Grinberg et al. 331 investigated the formation of bitumen compounds in peat under simulated geothermal conditions of temperature and pressure. Luukkanen332 showed that the optimum yield of bitumen from pyrolysis of peat was obtained at water contents of between 30 and 60 wt %. Pobul and Klesment333 reported on the composition of bitumen obtained from peat, while Golubeva et al.334 used liquid extraction techniques to recover the bitumen fraction from peat; maximum yields were obtained at 35 wt y0 water content. Zubko et a/.335 investigated the aromatic components of tars obtained from peat. Other workers336-338 have reported on the chemistry of tars and bitumens from peat. Zubko339 detailed a method of producing electrode coke from peat tar products. Humic acids Humic acids are formed, as part of the peat, during the decomposition of plant residues that leads to formation of peat. These compounds can be used to characterize the decomposition process. They constitute a multicomponent mixture of highly diverse chemical compounds. Methods of separating and isolating the components in the humic acid fraction of peat have been outlined by a number of workers340-342. A number of methods have been detailed for identifying actual components and relating these to peat structure343-347. The pyrolysis of humic acids348 and structural changes during coalification have been studied349. Lishtvan et a1.350 studied the reactions of iron and humic acids of peat with

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a view to investigating self-heating. Interest in separating humic acid fractions from peat is centred around using the material in biological processing. wux Ekman35’ has shown that wax in peat comes, in the main, from the leaves of certain shrubs. The chemical and physical properties of peat wax have been outlined by a number of workers352-357. Predominantly the wax consists of straight-chain aliphatic compounds with lipid groups present. The distribution profiles of wax are given field in western by Ketola et ul. 358 for a production Finland. Yields of 30 to 65 kg of wax per dry tonne of peat are usual. Several workers have reported on solvent extraction ofwax from peat359-36’ using a process that is combined with dewatering. Bott362 has reported on the use of liquid CO, to effect dewaxing of peat, while others363 have extended this work to the use of other solvents. The pour point of the recovered wax decreased with the severity of drying364. Initial oxidation of peat was found to increase the yield of wax by 25 y0 to 45 %36s-368 while ethylene oxide has been used to modify the peat wax chemically369~370. There is a definite interest in using peat wax as a raw material in the production of polymers, paints, waxes and polishes.

WET CARBONIZATION Originally, wet carbonization or wet coalification was developed to allow peat production to be independent of the seasons by replacing open air drying. The spreading and drying of peat in the field was replaced by thermal decomposition of the colloids holding a significant portion of the water. The reaction was carried out in aqueous suspension at about 22O”C, i.e. under 22 bar pressure. The freed water was separated from the solids by expression, giving a product with about 45 wt o/, water content that was similar in character to lignite. The technology gave briquettes at a thermal efficiency of about 50 %. There are several variations of the basic aqueous suspension dewatering process based on gas reactions. If the wet carbonization process is carried out with the addition ofair or oxygen (termed variously wet oxidation, wet combustion, wet gasification or partial combustion), the organic matter can be gasified or consumed to give heat and in the latter case fuel gases. If H, or CO/H, gas is used (up to 375°C and 100 bar) then a 60% yield of a coal-like residue can be produced (termed wet hydrogenation) or a 40% yield of a petroleum-like soft bitumen may be obtained (termed wet conversion or partial liquefaction). The latter CO/H, process can also be applied to sewage sludge. A number of workers have reported on dewatering of peat by the wet carbonization process371-376. The main problem is to obtain a high enough thermal efficiency to make the process economically viable, although little attention has been given to catalytic methods to reduce the heat requirements and to improve the quality of eflluent from the process. Wet oxidation with air or oxygen has been studied by a number of workers373p380, particularly with regard to the efficient use of waste heat; otherwise the process is not economica1381*382. The use of catalytic techniques can improve the thermal efficiency but the treatment of waste water is an important aspect of

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the overall process. Gallo et ~1.~~~ noted that the process involved two consecutive first order reactions. The hydrogen processes will be mentioned later.

REACTIONS

WITH

PEAT

Ma1 et u1.383*384 reacted peat with concentrated NH,OH solutions to achieve nitrogen fixation. Temperature was found to be the most important variable, and it was suggested that the optimum reaction condition was at 150°C Bel’kevich et ~1.~~~studied the reactions of amines with peat. Several workers386-388 have studied the acid hydrolysis of peat, Monosaccharides such as hexoses and pentoses were formed as well as amino acids and humic substances. The main thrust of the work appeared to be towards production of solutions, which could then be used as suitable substrates for biological conversion to various products. The types of monosaccharides formed often limited further use of the hydrolysis products. Gaiduk et a1.389 attempted to overcome the difficulties caused by hexose and pentose formation by using acidic oxidation conditions. Esters and carboxylic acids were formed as the main products while the concentration of oxalic acid rose with the intensity of the oxidation conditions. Bio-conversion

General reviews are available on the biological conversion of peat to various products390,391. An alkaline392-396 or acid397 hydrolysis of peat to aqueoussoluble organic materials is viewed as the first step of an anaerobic biological gasification process to produce fuel gas. Organic materials such as alcohols can be produced by the same technique3989399. Svensson4” gave data on the optimal conditions for the process. Viraraghavan et ul 40’ have detailed the economics of the process, while Chynoweth402 has suggested an in situ method of biogasification that does not require harvesting of the peat. A number of workers403-406 have used the hydrolysates of peat to prepare animal fodder, fodder yeasts and other biologically active products405,407-41 ‘, workers41 3~414 have including vitamins41 2. Several studied the mechanism of hydrolysis of peat based on an initial attack on ester bonds. Martin and Bailey415 examined the effects of process variables on the acid hydrolysis of peat. Several workers have studied the alkaline hydrolysis of peat in order to optimize yields416 and identify compounds produced417-419. Others have sought to separate and identify biologically active substances from peat420-423. Dalouche et ~1.~~~suggested that peat could be used with sewage sludge to remove odours from gases. Gmificution It is possible to react certain gases such as hydrogen with hot peat to produce fuel gases that can be converted into liquid organic products. Owing to its high reactivity and high content of volatiles, peat is one of the most effective raw materials to be used for fuel gas generation. The main processes that are used are the high temperature fluidized bed Winkler system425-428, the Fischer-Tropsch catalytic fluidized bed process429, the Institute of Gas Technology (IGT) two-stage fluidized bed system430-434, and the Lurgi pressure gasifier435. All

Peat: P. J. Spedding these processes use air or oxygen and steam as the reacting gases. The IGT have carried out a considerable amount of work on peat gasification in single stage4j2 and two-stage gasifiers 430.43’.433.434. The latter process operates with a-peat feed containing about 35 wt Y0water and at a temperature below the ash slagging point. A steam/oxygen mixture is used to fluidize the second stage of the process while exit gases are used in the first stage to dry and carbonize the incoming peat. Hydrogen has also been used as the reactive gas436. The output stream can be used to make gaseous437 or liquid fuels431*436*437. The cost of the peat, and particularly of its transport, is crucial to the whole economics of the process438*439. This is in agreement with the conclusions of Rudolf et ~1.~~’ on the subject. However, it is known that the thermal efficiency of the IGT process is high (z 67 %). Hydrogasification of peat has been studied440-445 with results which were very different from those for other solid fossil fuels445. The Rockwell process is an example of this technique 446v447. Universal Oil Products (UOP) carried out comparison tests on the fluidized bed IGT and the entrained bed Rockwell processes. The IGT process proved to be the most efticient and cost effective448. Kuo449 had earlier been unable to demonstrate significant differences between the performances of the suggested that the Shell gasifier processes. Arpiainen4” was the best, but it was not currently economical. Raniere et ~1.~‘~ gave detailed experimental data on peat hydrogasification. Tarki et ~1.~” reported enhanced reactivity if metal catalysts were used to impregnate the feed material. Details have been given of the production of liquid hydrocarbons via the hydrogasification of , and Punwani et ~1.~” have peat 429,436,450,453,454 described an integrated plant to produce both gaseous and liquid hydrocarbons. A simple updraft gasifier has been built to produce power456*457 and supply domestic heating458*459. A model has been proposed for gasification of solid fossil fuei460 as well as details of the thermodynamics of the process461. A number of workers have examined the plasm0 gasification of peat in the liquid4‘j2 and gaseous phases463-466. 0th ers have detailed equipment designed specifically for gasification of peat467*468 and for its preparation and transport469. Purdy et ~1.~” have examined the waste water problems associated with peat gasification, while Ferrell et a1.471 have also reported on the air pollution aspects. A number of workers have suggested an integrated approach to energy production based on peat472-474, and Rekant4” has suggested a gasification process for peat based on reaction with CO,.

Liquefaction Several methods are available for forming liquid products directly from wet peat. Aqueous reaction with CO/H, under 5.5 to 8.3 MPa pressure at 100 to 400°C (termed hydrogenolysis) gives a liquid product. The reaction is complex but appears to operate through the formation of a formate although some hydrogenation takes place. Kalkreuth and Chornet476*477 examined the reaction and found that various components of the peat were liquefied at different temperatures; it was possible to operate so that little residue was left. Various catalysts

have been used with the reaction478.479 the best being CO/MO with Na,O promotion. The use of CO gas only 480-486 has been successful in liquefaction of peat, so indeed has been the reaction of takes place simulhydrogen alone4*(‘. Dewatering taneously so there is no need to dry the peat482~483~487~488 and it is not necessary to use a catalyst482. Paersch et ~1.~~~ reported on the kinetics of the reaction between CO and peat, while other workers have given details of the mechanisms involved487*490. Knickle49’ studied multiphase flow in connection with liquefaction processes, while Bjoernbom er ~11.~~~studied pretreatment of the fuel, i.e. before the actual liquefaction compared the liquefaction of process. Landsman various materials including sewage sludge. Belinko et ~1.~~~ studied the solid residues left after the liquefaction process. be carried out by solvent Liquefaction can extraction495*496, usually with supercritical fluidscapable of large dipole interaction 497-499. Not all the solid is dissolved and solvent loss is a potential problem. Duerkop et ul. 5oo have shown that the yields of oil obtained by using solvents are much higher than with the gas reaction system of liquefaction. Ash The formation and composition of ash from peat have been investigated 501*502.The formation of deposits in the convective sections of boilers using peat fuel have been studied503,504. The use of peat ash in bindersso and cement”’ has been suggested. There has also been a study of the effects of peat itself on cementso6.

AIR POLLUTION Peat deposits have been used to quantify the effects of atmospheric pollution. Various workers85*86,90 have attributed increases in metals in peat deposits to industrial pollution and in some cases to volcanic activity”. Madsenso and Oldfield et ~1.~‘~ measured the levels of mercury and iron in peat deposits and showed that deposition rates, have increased by up to two orders of magnitude in the past 100 years. Deposition of metals in the peat bogs or in snow around power stations fuelled by peat has been measured by a number of workers soy*slo. For example, the rate of deposition of iron varied from 88 to 567 x 10e6 kg me2 depending on distance from the source. Singh” ‘, on the other hand, correlated increased levels of radioactivity trapped in a peat deposit with the Pacific atomic tests. Attention has been directed to the air pollution generated by the burning of peat particularly in large installations’71~‘85. Stenby et ~1.“~ reviewed the environmental controls and economic factors to be considered if peat were to be used as an alternative fuel in existing power plants in the USA. 0therssL3 have given a more complete overview of the environmental problems associated with peat exploitation. Rudling and Loefroth514 detailed emission levels from a 100 MW peat-fuelled power station; the CO levels in the flue gas were of the order of 50 ppm with no detectable organic pollutants. These latter pollutants are present in flue gas from other solid fuels. Of course, the pollution levels would be expected to be higher with smaller units burning peat, which are less efficient and do not have efficient grit

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Peat: P. J. Spedding

removal systems. Nevertheless the results reflect the higher reactivity of peat as a fuel and emphasize the importance of efficient particle collectors such as electrostatic precipitators in combustion units using peat. Ketola et ~1.” 5 examined the organic vapours emitted from peat drying installations. Normal loadings of 3 to 5 mg of organic vapours per cubic metre of peat were obtained. In a power station, predrying would be carried out using waste heat and the fumes could be admitted to the furnace in the secondary air. Fredriksson et ~1.~~ have shown that peat in contact with ground water at the periphery of a deposit can have an increased concentration of salts such as thorium and uranium. Slater3* reported a similar trend regarding ash levels. Bypassing these zones during mining operations would eliminate the possibility of any undesirable contamination or high ash in the fuel . Ertugrul and Sober 516 have estimated that the effect on the environment of peat utilization certainly could be less than that of equivalent coal-powered systems, and at the worst would be equal. Moroz et uI.‘l’ and Kisil et ~11.~~ * suggested that pollution from peat dust arising during storage could be alleviated by the use of a suppressing agent containing inorganic salts and surfactants. Ottengraf and Van Der 0ever519 have shown that it is possible to remove organic components from flue gases by using a filter made from peat material. The activity of the filter can be maintained at a high level for periods of time up to many years. There are a number of specialized applications of peat and its by-products on which work has been reported. These are medicine520*521, drilling mud formulation522-525 particle board manufacture526, fibres527,528 ’ carbon-based fibres529-53’, molecular 8ieves532-5;5 iron production536-538, production of silicon539 ahd silicon alloys540,541, as a filler in plastics542, cement543 and insulation544, foundry sand545, semiconductors546, chromatography547, wood stain548*549, electrographic developer550, tanning551, as a fish food supplement552, and as a fire lighter materia1553.

1

8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24

25

26

27 28 29

30

CONCLUSION

31

A considerable amount of work has been done on peat in this decade that has enhanced the understanding of its characteristics and use. Certainly the emphasis on efficient use of fuel has highlighted the importance of peat, and has led to renewed interest in using it as a basic raw material. The impetus given can be expected to continue in the forseeable future. Data on heat characteristics, usage and possible world reserves are given in Tables l-3 (Ref. 554).

32 33

34

35

REFERENCES Anon Chem. Eng. News 1971,55, 39 Villwock, J. A., Dehnhardt, E. A., Loss, E. L. and Hofmeiste, R. T. Acta Geol. Leohold 1983, 6, 79-92 Bazin, E. T. and Kosov, V. I. in ‘Physics and Chemistry of Peat’, Kalin Gos. Univ. Kalinin, 1982 Drozhalina, D. in ‘Carbon Molecular Sieves Based on Peat’, Nanka i Tekhnika Moscow, 1984 Largin, I. F. (Ed.) in ‘Properties and Methods for the Study of Peat and Supropel Deposits’, Kalin Gos. Univ. Kalinin, 1983 Lazarev, A. V., Lykin, B. G., Dem’yanov, E. S. er al. in ‘Technology for the Production of Peat Briquets’, Nedra Moscow, 1984

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36

37 38 39 40

Lishtvan, I. I., Terent’ev, A. A., Bazin, E. J. and Golovach, A. A. in ‘Phvsiochemical Principles of Peat Production Technoloev’. __ Nanka i Tekhnika, Minsk, 1983 Mal, S. S. in ‘Carbohydrates and Nitrogen-containing Substances of Peat’, Nanka i Tekhnika, Minsk, 1982 Yatsevich, F. S. in ‘Peat,a raw material for Chemical Processing; Physic0 technical Principles’, Nanka i Technika, Minsk, 1981 IGT Proc. Exec. Conf. Manag. Assess. Peat Energy Resour., Chicago, IL, USA, 1979 1GT Symp. Peat Energy Alternative, Chicago, IL (Eds. J. W. White, B. F. Feingold and W. McGrew), 1980 Proc. Int. Peat Symp., Bemidji State Univ., Bemidji Minn, (Ed. C. H. Fuchman), 1981 Proc. U.S. Dept. Energy Tech. Contract Conf. Peat, Springfield, VA, USA, TR/80/031/001, 1980 Proc. U. S. Dept. Energy Tech. Contract Conf. Peat, Springfield, VA, USA, DOE/ET/l0159/T20, 1981 Int. Symp. Recent Technol. Use of Peat (Ed. G. W. Luttig), 1979 Proc. Int. Symp. Peat Util., Bemidji State Univ., Bemidji Minn, (Eds. C. H. Fuchman and S. A. Spigarelli), 1983 Proc. Int. Symp. Peat Agr. Hort., Bet Dagan, Israel (Ed. K. M. Schallinger), 1984 Proc. Int. Peat Congress, Dublin, 1984, 7 Proc. Symp. Tropical Peat Resources-Prospects, Potential. Int. Peat Sot., Helsinki, Finland, 1985 Casagrande, D. J. and Given, P. H. Geochim. Cosmochim. Acta 1980,44 (lo), 1493-1507 Given,P. H., ‘Natureofthecontribution ofpolymersofcell walls of the higher plants to coal formation’, DOE/ER/l0988-T, 1983 Given, P. H., Spackman, W., Painter, P. C., Rhoads, C. A. et al. Ado. Org. Geochem. 1984,6, 399407 Raj, S. A.C.S. Div. Fuel Chem. 1979, 24 (3), 251-9 Morita, H. and Measures, R. M., ‘Some observations on the laser fluorescence spectroscopy of peats’, Proc. Int. Symp. Peat Util., 1983, pp. 391-403 Mal, S. S., ‘Role of the chemical composition of peat-forming plants in the origin and low-temperature thermoanalysis ofpeat’, Nov. Protsessy Prod. Pererab Torfa., 1982,43-48 Babenko, V. P. in ‘Conversion of organic matter of ancient peat bogs under different geochemical conditions in the formation of genetic types of coal’, Ugol’n Basseiny Usloviya Ikh Form, (Ed. P. P. Timofeev). Izd. Nanka. Moscow, 1983. DV. 176-82 Zurek, S. Proc.‘Inl. Peat Cong. 1984, 7 (2), 6847 Averina, N. G. and Polikarpova, N. N. Vestsi Akad. Naauk BSSR Ser. Khim. Navuk 1981, (1), 102-106 Ivantsiv, 0. E. and Uzhenkov, G. A. in ‘Geochemical characteristics of peat-bog lithogenesis of the Carpathian Region’, Osad Porody Rudy, (Ed. E. F. Shnyukov), Naukova Dumk, Kiev, 1984, pp. 215-20 Lukoshko, E. S., Khoruzhik, A. V. and Pigulevskaya, L. V. Khim Tverd TopI 1981, (4), 3641 Lukoshko, E. S., Khoruzhik, A. V., Pigulevskaya, L. V. and Yankovskaya, N. S. ‘Chemical composition of buried interglacial peats and their recent analogs’, Nov. Protsessy Prod Pereab Torfa, (Ed. I. I. Lishtvan), Navka Tekh., Minsk, 1982 Lukoshko, E. S., Bambalov, N. N. and Smychnik, T. P. Khim Errd TopI 1986, (1), 8-14 Cohen, A. D. and Andrejko, M. J. in ‘Use of models based on modem peat deposits to predict the distribution of mineral matter in coal’, Los Alamos Natl. Lab. L.A.-9907-OBES. Min. Matter Peat DE84-002332, 1983, pp. 77-85 Andreijko, M. J., Cohen, A. D. iid Raymond, R. ‘Origin of mineral matter in neat’. Los Alamos Natl. Lab. LA-9907-OBES. Min. Matter PeaiDE84-002332, 1983. pp. 3-24 Upchurch, S. B., Strom, R. N. and Andrejko, M. J., ‘A model for silicification in peat-forming environments’, LOS Alamos Natl. Lab. LA-9907-OBES, Min. Matter Peat DE84-002332,1983,pp. 225-235 Raymond, R., Andrejko, M. J. and Bardin, S. W., ‘Techniques for- applying scanning electron microscopy to the study of mineral matter in oeat’. Los Alamos Natl. Lab. LA 9907-OBES, Min. Matter PeaiDE84-002332, 1983, pp. 169-178 Raymond, R. and Bardin, S. W. Microbeam Anal. 1983,18, 1518 Slater, F. M. Proc. Inr. Peat Cong. 1984, 7 (l), 450-467 Shchirov, V. T. Izv. Sev-Kavk Nauchn Tsentra Vyssh Shk Estestv Navki 1981, (3), 70-74 Cameron, C. L. and Schruben, P. G. ‘Procedures for setting up a model ofa typical freshwater peat deposit in Karst topography in Central Florida’, Proc. Symp. Tropical Peat Resources

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41 42 43 44

45

46 47 48 49

50 51

52

53 54

55

56

57

58

59 60 61 62 63 64 65 66

61

68

69 70 71

72 73 74

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