research article ft-ir investigation of the structural

Hindawi Publishing CorporationJournal of CombustionVolume 2013 Article ID 134234 14 pageshttpdxdoiorg1011552013134234

Research ArticleFT-IR Investigation of the Structural Changes of Sulcis andSouth Africa Coals under Progressive Heating in VacuumCorrelation with Volatile Matter

Aldo DrsquoAlessio Anna Maria Raspolli-Galletti Domenico Licursi and Marco Martinelli

Dipartimento di Chimica e Chimica Industriale Universita di Pisa Via Risorgimento 35 56126 Pisa Italy

Correspondence should be addressed to Aldo DrsquoAlessio aldodcciunipiit

Received 30 January 2013 Revised 27 May 2013 Accepted 31 May 2013

Academic Editor Peter F Nelson

Copyright copy 2013 Aldo DrsquoAlessio et al This is an open access article distributed under the Creative Commons Attribution Licensewhich permits unrestricted use distribution and reproduction in any medium provided the original work is properly cited

The analysis of gas evolving during the pyrolysis of two very different rank coals was studied by using FT-IR spectroscopy Thesecoals coming from Sulcis (Sardinia Italy) and from South Africa respectively were subjected to progressive heating up to 800∘C invacuumThe thermal destruction of coal was followed bymonitoring the production of gases in this range of temperatureThe gasesevolving in the heating from room temperature to 800∘Cwere collected at intervals of 100∘C and analysed by infrared spectroscopyThe relative pressures 119875

119903(119894)

= 119875(119894)

119875max(119894)(119879) were plotted against temperature These graphs clearly show the correlation amongqualitative gas composition temperature and the maximum value of emissions thus confirming FT-IR analysis as a powerful keyfor pyrolysis monitoring

1 Introduction

Pyrolysis represents the first step inmost solid fuel conversionprocesses including combustion gasification and liquefac-tion and has a significant influence on every subsequent stagefor the recovery of valuable chemicals and energy [1] Coalhas been used for a long period both as fossil fuel and as rawmaterial by the chemical industry Currently petroleum andnatural gas represent the two main energy sources but it iswell-known that these supplies have no longer kept pace withthe ever-increasing energy demand of many nations As aresult an imperative need to rely on a well-known energysource such as coal is paramount Unfortunately impuritiesof coal such as sulphur and nitrogen derivatives are releasedinto the atmosphere causing problems such as acid rains andsmog The unburnt mineral matter can also be released intothe air as particulate However what concerns the mostis CO

2emissions which are believed to influence climate

change Due to the role that coal plays in the energyproduction it would be worthwhile to reduce the negativeeffects of air pollution caused by CO

119909and NO

119909emissions by

increasing the efficiency of coal conversion [2ndash4]

Coal pyrolysis is considered an effective way for its cleanuse because desulfurized char and tar can be obtained at theend of the reaction Coal tar can be utilized as rawmaterial forthe industrial synthesis of dyes plastics synthetic fibres finechemicals and cosmetic products due to its good activity asa cosmetic biocide [5] It is also a type of raw material fromwhich phenols naphthalenes and anthracene can be extract-ed for the production of washing oil cementitious agent andcatalytically hydrogenated products to obtain gasoline dieseloil and so forth Therefore it is necessary to deepen the un-derstanding of the pyrolysis process by investigating bothraw materials and the originated products in order to opti-mize the reaction conditions

The study of pyrolysis is also of interest for its possibleapplication to innovativematerials such as biomass Both coaland biomass have complex structures containing a number ofdifferent constituentsThese constituents show their inherentindividual characteristics during thermal processes and eachone contributes to the apparent thermal characteristics of thefeedstock On the other hand when coal and biomass aretreated as blend in processes such as copyrolysis cocombus-tion or cogasification some positive synergistic interactions

2 Journal of Combustion

may take place leading to significant variations in the thermalreactivity of the resulting samples or in the physical orchemical properties of the products [6ndash8]

Coal thermal degradation generates gaseous liquid andsolid products The primary decomposition products whichare initially formed probably decompose in turn and theresulting fragments react furtherwith each other andwith thesolid residue to form the observed tars liquors water vaporsgases and char Due to these secondary reactions the decom-position products which are eventually observed may be farremoved from the original coal structure offering few cluesto the chemical constitution of coal In this context pyrolysisof coal under reduced pressures has been used to minimizethese secondary reactions [9ndash12]

Among the variables of processes which characterize thepyrolysis temperature and time have the most remarkableeffect on the structural changes ascribed to organic andinorganic parts of coals [13ndash15]

Coal undergoes many physical and chemical changeswhen gradually heated from ambient temperature to approx-imately 1000∘C [16] The temperature ranges for the variouspyrolysis events significantly depend on the heating rate Atslow heating rate (about 5∘Cs) the maximum devolatiliza-tion occurs at around 400∘C whereas increasing the heatingrate up to about 10∘Cs this maximummight not occur until900∘C This is a ldquoconventionalrdquo pyrolysis and employs lowheating rates and modest residence times (about 5ndash30 min-utes) for the recovery of char This technology is still widelyused because it provides a clean feedstock of combustiongasification for electric power generation On the other handldquofastrdquo pyrolysis employs respectively very high heating rates(up to 1000∘Cs) and very short residence times (05ndash5 s)minimizing the formation of char and breaking the bonds ofthe molecular species recovering mainly liquid and gaseousproducts [17]

Fourier Transform Infrared Spectroscopy (FT-IR) playsan important role in the elucidation of chemical structure ofcoal chars and gas evolving during oxidation and pyrolysisprocesses [18ndash21] This research closely links to the appli-cation of FT-IR on the pyrolysis of new green materialssuch as biomass since the chemical groups are similar andchar is among the final products obtained The chemicalcharacterization of the evolved gas in the pyrolysis process byFT-IR spectroscopy is therefore an important tool for under-standing the properties of these materials

Many pyrolysis processes were extensively investigated[22] and the thermal decomposition of the functional groupspresent in the coals was widely studied by using infraredspectroscopy [23 24]

Recently many researchers have applied integrated tech-niques such as thermogravimetry (TG) and derivativethermogravimetry (DTG) differential scanning calorimetry(DSC) andFourier Transform Infrared Spectroscopy (FT-IR)in order to study the pyrolysis of coal [4 25 26]

Among all these studies Carangelo et al [27] andSolomon et al [28] investigated hydrocarbons structure andthe kinetics of gas evolution by using a TGFT-IR techniqueto study the pyrolysis of coal char tar and oil shaleThey identified the individual gaseous species such as CO

CO2 H2O CH

4 C2H6 C2H4 C2H2 C3H8 benzene heavy

paraffins heavy olefins HCN HCl NH3 SO2 CS2 COS

CH3OH CH

3COOH and CH

3COCH

3 Pitkanen et al [29]

studied various fuels such as coal peat wood chips and barkwith FT-IR spectrometry combined with TG FT-IR spectraand TG curves indicated that the main evolved gases wereCO2and H

2O while there were many minor gases such as

CO2 CH4 C2H6 CH3OH CH

3COOH and HCOOH

Many chromatographic techniques were developed tostudy coals and coal-derived products These included gaschromatography and liquid chromatography [30] A flameionization detector (FID) [31] was mostly used to detect coalcompounds coming out from a chromatographic columnAlso gas chromatography coupled with mass spectrometry(GC-MS) was frequently used to study coals [32 33] Finallythe development of analytical chemistry fostered the use ofcombined methods based on pyrolysis gas chromatographycoupled with mass detection (Py-GC-MS) [31 34]

However among all these analytical techniques infraredspectroscopy remains one of the most simple and effectiveones to evaluate and monitor the pyrolysis products In aprevious study [35] we investigated the structural changesof two bituminous coals a Sulcis and a South Africa one byFT-IR spectroscopy under slowly heating temperature pro-grammed mode from 25 to 800∘C under vacuum In thisresearch the analysis of gas evolving during the pyrolysis oftwo different rank coals by using FT-IR spectroscopy wasstudied under the same heating conditions The main aim ofthis work is to establish the correlation between the evolutionof vapors and gases and the structural changes of thefunctional groups during the pyrolysis process

2 Materials and Methods

Coal samples were ground with a ball mill for 15 minutesand subsequently sieved in order to obtain samples of average70 120583m granulometric size

Ultimate and proximate analysis of these two types of coalwere performed by a Perkin-Elmer analyser mod 240 and aThermoanalyser Mettler TA 1 respectively

In order to confirm the results of the IR analysis thegas chromatographymass spectrometry (GC-MS) analysisof some condensates was performed by using the gas-chromatograph Hewlett-Packard HP 6890 equipped with aMSDHP 5973 detector and with a GC column PhenomenexZebron with a 100 methyl polysiloxane stationary phase(column length 30m inner diameter 025mm and thicknessof the stationary phase 025120583m) The transport gas washelium 55 and the flow was 1mLmin The temperature ofthe injection port was set at 250∘C carrier pressure at 100 kPaand split flow at 340msminus1 The oven was heated at 30∘C for5min and then the temperature was raised at 5∘Cmin up to250∘C

The apparatus used in the pyrolysis experiments is shownin Figure 1

One hundred grams of each sample were put in a quartzpipe of a temperature-controlled furnace All the equipmentswere conditioned with a cycle of vacuum-nitrogen at roomtemperature Subsequently the apparatus was put under

Journal of Combustion 3

Flowmeter

Coal

Couple

Temperatureregulator

N2

a b c

d e f

g

Figure 1 System used for heating coals up to 800∘C (a) cooling trap with water + salts at minus15∘C (b) cooling trap with solid CO2

(s) + acetoneat minus77∘C (c) cooling trap with liquid nitrogen at minus180∘C (d) (e) (f) and (g) taps

vacuum and the working temperature was set The sameprocedure was repeated for all temperatures (from 100∘C to800∘C) performing the same thermal gradient for all experi-ments (nominal heating rate equal to 2∘Cs) and maintainingthe samples at these temperatures for a period of thirtyminutes

About the collection of the reaction products the firstfraction was collected in a first cooling trap with a water +salts bath at aboutminus15∘C (trap a in Figure 1) and subsequentlythe other fractions were collected in the cooling traps with asolid CO

2+ acetone bath at about minus77∘C (trap b in Figure 1)

and with a liquid nitrogen bath at minus180∘C (trap c in Figure 1)respectively Finally the noncondensable gases were collectedfrom the last taps (taps dndashg in Figure 1)

FT-IR spectra of the vapors and gases were recorded witha FT-IR Perkin-Elmermod 2000 spectrometer One hundredscans of 1 cmminus1 resolution were set and the average signalsobtained were stored on a magnetic disk for further analysis

The quantitative analysis of the various gaseous com-ponents was carried out by means of infrared spectroscopyusing a 1moptical path gas cell withCsIwindowsThe gas cellwas evacuated and the gas was introduced by means of thetap g of Figure 1 A suitablemercurymanometer connected tothe gas cell has allowed the introduction of a known quantityof gas and the measurement of its relative pressure atroom temperature In this way direct correlations betweenabsorbance and relative pressure of the individual compo-nents were obtained

3 Results and Discussion

The Sulcis mines represent the only reserve of coal in Italy(Sardinia Italy) Therefore this coal was studied for itsremarkable abundance On the other hand South Africacoal was considered in this work thanks to its well-knowndifferent chemical composition with respect to that of Sulciscoal In addition many experimental data are reported in theliterature for these two types of coals and now this study willfurther contribute to supplement our previous results [35]

In Table 1 data of ultimate and proximate analysis of thesetwo types of coal are reported

The data corresponding to the proximate analysis of theSulcis coal show a higher amount of volatiles and ashes and

Table 1 Elemental and proximate analysis data of investigatedcoalslowast

Coal Elemental analysis (wt db) Proximate analysis (wt)C H N S O M Cf Vm A

Sulcis 528 42 14 59 115 82 401 356 160SouthAfrica 665 36 17 06 86 25 478 233 165lowast

As minus receiveddb on dry basis M moisture Cf carbon Fixed A ashes Vm volatilematterOxygen content was calculated by difference O = 100 minusC minusH minusN minus S minus ash

a lower quantity of fixed carbon These data immediatelyevidence substantial differences of Sulcis coal with respectto the South Africa one Furthermore also ultimate dataanalysis shows that Sulcis coal is completely different fromthe South African one in particular for carbon and sulphurcontent

In a previous investigation on these coals [35] the relatedstructural changes associated with the organic and inorganicparts were analyzed In detail the analysis of the lowtemperature ash (LTA) and the application of FT-IR sub-traction technique for Sulcis coal revealed a high concentra-tion of sulphates carbonates and pyrite SiO

2and a lower

concentration of clay minerals In the FT-IR spectra of theSouth Africa coal the absorption bands due to clay minerals(eg kaolinite nacrite dikite etc) can be observed Spectralchanges of the corresponding chars were mainly observed athigh temperatures when the decomposition of mineral mat-ter occurs On the other hand at low temperatures mineralmatter was not still degraded giving very intense bandsadsorptions due to its high extinction coefficient [35]

In the current research gases evolving during pyrolysis ofthese two kinds of coal in the temperature range from 25 to800∘Cat intervals of 100∘Cwere analyzed by using the appara-tus of Figure 1 by means of FT-IR spectroscopyThe IR spec-tra of liquid materials collected in the trap (a) revealed thatthey consist mainly of water and only a few traces of hydro-carbons This liquid fraction was not further analyzed by gaschromatography due to its low content of the organic com-ponents


The amounts of liquid materials (wt) collected in thecooling traps (a) and (b) in relation to the heating temper-ature for both coals are reported respectively in Figure 2(a)and in Figure 2(b)

Sulcis coal showed three maximum emissions at 100 500and 700∘C (Figure 2(a)) The first corresponding to 52 wtwas due almost exclusively to moisture while the other twowere constituted by hydrationwater associatedwithmineralsreleased at higher temperatures and hydrocarbons

On the other hand the South African coal gave anappreciable amount of liquids in the cooling trap (a) only athigher values of temperature over 500∘C (Figure 2(a)) whilemoisturewas collected in the trap (b) at a heating temperatureof 100∘C (Figure 2(b)) in relation to the contemporary emis-sion of ammonia detected by infrared analysis the presenceof which lowers the temperature of liquefaction of the vapors[36]This different behaviour of the South Africa coal may bedue to the presence of two kinds of nitrogenous compoundsone of which is easily decomposable by heating at low tem-perature This would suggest that in South Africa coal thereare ammonium salts that develop ammonia by increasingtemperature

The pressure data obtained relatively to vapors and gasesare plotted in Figures 3(a) and 3(b) as a function of tempera-ture

The pressure data were measured at room temperature byusing a mercury manometer The graph of Figure 3(a) showsthat for Sulcis coal a first type of products was evolved inthe temperature range between 25 and 600∘C with a max-imum at about 400∘C while from 600∘C to about 800∘Cother components were produced unlike the South Africalitanthrace which instead presented a maximum at about700∘C

The graph of Figure 3(b) shows a big quantitative dif-ference among gas fractions which were collected from thetwo coals in the trap (c) cooled at minus180∘C In particular thepressure of the gaseous components was higher for Sulcis coalrather than the South African one

The products obtained by heating at lower temperatureshave a different distribution The IR spectra of the con-densates collected in the cooling trap (b) coming from thedevolatilization of both coals at different temperatures areshown in Figure 4

Furthermore the qualitative distribution of the pyrolysisproducts collected in trap (b) is reported in Table 2 on thebasis of the intensities of their analytical infrared bands [3738] each reported in Table 3

The global comparison between the IR spectra ofFigure 4 reveals the presence of oxygenate compoundsmainly ketones and alcohols (acetone methyl ethyl ketonemethanol and ethanol) saturated (C

3ndashC5) unsaturated

(olefins) and aromatic (benzene toluene and xylenes)hydrocarbons and nitrogen derivatives (ammonia hydro-cyanic acid) Emission of oxygenates and hydrocarbonssignificantly begins at 300∘C and increases up to about600∘C and then decreases In particular acetone and methylethyl ketone were identified on the basis of the stretchingof the C=O group at about 2000ndash1500 cmminus1 as reportedin Table 3 Aromatics were identified from the analytical

bands at 1670ndash1430 cmminus1 and at 1100ndash800 cmminus1 due to thestretching and bending C=C of ring respectively (Table 3)Saturated hydrocarbons were identified from the analyticalband at 3200ndash2800 cmminus1 due to the stretching of CndashH bond(Table 3) Instead the unsaturated ones were identified fromthe analytical band at about 3200ndash3000 cmminus1 and at 1100ndash800 cmminus1 due to the stretching and bending (out of plane)of HndashC=C bond respectively (Table 3)

Nitrogen products (hydrocyanic acid and ammonia)were detected In particular at low wavenumbers (ie 750ndash650 cmminus1) hydrocyanic acid showed absorption bands whichsuffered interference due to other components (Figure 4) Itsrecognition was possible only by considering the analyticalband at 3312 cmminus1 due to the stretching of HndashCequivN bond asreported in Table 3

As regards ammonia it was recognized on the basis ofthe bands at 1250ndash680 cmminus1 due to the bending (in plane andout of plane) of NndashH bond as shown in Table 3 A first com-parison among the IR spectra reported in Figure 4 showedthat ammonia emission was different for these two kinds ofcoal In fact South Africa coal released vapors from 25 to300∘C showing IR absorption bands due to ammonia Onthe other hand the vapors emitted from Sulcis coal at lowtemperatures (25ndash200∘C) were mainly constituted by waterand only traces of oxygenate compounds Only starting from300∘C these vapors showed appreciable IR absorptions Thestrong emission of NH

3by heating South Africa coal at low

temperatures (25ndash100∘C) is due to the presence of bothorganic andmostly of inorganic nitrogen compounds the lat-ter being ammonium salts On the contrary Sulcis coal con-tains only organic nitrogen lacking the inorganic one andtherefore the unique nitrogen compound emitted at relativelylow temperatures (up to 300∘C) is HCN The different emis-sions of nitrogen compounds from these two kinds of coalsare also confirmed by higher NO

119909emissions observed from

the combustion of South Africa coal as underlined in aprevious work [35] Based on these considerations the smalldifference of total nitrogen content in these two samples(about 03 as reported in Table 1) is ascribed to theinorganic nitrogen component contained in the South Africacoal

The composition of the main pyrolysis products recov-ered from trap (b) was confirmed by GC-MS analysisAn example of a chromatogram obtained is reported inFigure 5(a)

In particular Figure 5(b) reports a detail of the light endspresent in the previous chromatogram

Figure 5(b) enlargement clearly evidences the presenceof C3ndashC5saturated hydrocarbons and of C

1ndashC3alcohols

Furthermore the presence of acetone and methyl ethylketone is confirmed

The analysis on the condensates from the Sulcis coalshowed a very similar GC profile once again evidencing ananalogous composition of the hydrocarbon fractions comingfrom the two different coals and the formation of aliphatichydrocarbons alcohols ketones and aromatics

The intensities of the analytical IR bands for the vaporswhich were collected in the liquid nitrogen trap (c) are


Table 2 Qualitative distribution of vapors collected in the cooling trap (b) with solid CO2 + acetone

Coal T (∘C) C6H6 Me-C6H5 n-Hydra Me2CO HCN Et-CO-Me NH3 Olefins

Sulcis

25100200300 w w w400 w w m m m w500 m m s m w w600 s s s m s w700 m m m w m m800 m w w w s

South Africa

25 m100 m200 w w300 w w400 m500 m s s w w m600 s s s w w m700 s m m m m800 w w w m

Intensity of analytical bands w weak m medium s strong Me methyl group Et ethyl groupa n-hydrocarbons

Table 3 Infrared absorptions range and analytical IR bands for considered vapors and gases

Sample Formula Range (cmminus1) Assignment Range (cmminus1) Assignment Analytical bands(cmminus1)

Methane CH4 3200ndash2900 ]CndashH 1350ndash1250 120575CndashH 3015 1307Hydrocarbons HC 3200ndash2800 ]CndashH 1450ndash1370 120575CndashH 2950Hydrocarbons uns C=C 3200ndash3000 ]=CndashH 1100ndash800 120574CndashH 1663 913 890lowast

Ethylene C2H4 3200ndash3000 ]=CndashH 1100ndash900 120574CndashH 1890 950Acetylene C2H2 3300ndash3250 ]CndashH 700ndash610 120574CndashH 730Carbon dioxide CO2 2500ndash2200 ]asC=O 700ndash600 120575C=O 2350Carbon monoxide CO 2250ndash2050 ]CO mdash mdash 2120Carbon disulpfhide CS2 1550ndash1450 ]C=S mdash mdash 1537sulphur Dioxide SO2 1400ndash1300 ]S=O 1250ndash1100 120575S=O 1133Carbonyl Sulphide COS 2100ndash1970 ]C=O 900ndash800 120575S=C=O 2070Benzene C6H6 1500ndash1400 ]C=C 1100ndash1000 r-ring 3030 674Toluene C6H5-CH3 1665ndash1430 ]C=C 800ndash650 r-ring 729 694

MAH C6H5-X 1665ndash1430 ]C=C 910ndash665 r-ring 741 769 796 910776lowastlowast

Methanol CH3-OH 3700ndash2400 ]OH 1050ndash950 ]CndashOH 1054Acetone CH3-CO-CH3 2000ndash1500 ]C=O 1200ndash1050 120575C=O 1220Ammonia NH3 1800ndash1400 119904HndashNndashH 1250ndash680 wNndashH 968Hydrocyanic acid HCN 3400ndash3200 ]CH]CN 750ndash650 120575CndashH 3312 712Nitrous oxide N2O 2300ndash2000 ]NN mdash mdash 2240Nitrogen oxide NO 2000ndash1800 ]N=O mdash mdash 1875Nitrogen dioxide NO2 1700ndash1550 ]NndashO mdash mdash 1625MAHmononuclear aromatic hydrocarbons X ethyl isopropyl groups ] stretching vibration deformations 120575 in plane 120574 out-of-plane r rocking s scissoringand w wagginglowastFor propylene isobutene lowastlowastFor o-Xylene m-Xylene p-Xylene isopropyl-benzene and ethyl-benzene


0 100 200 300 400 500 600 700 800 9000

1

2

3

4

5

6C

onde

nsat

e (w

t)

Temperature (∘C)

South AfricaSulcis

(a)

0 100 200 300 400 500 600 700 800 900

00

05

10

15

20

25

Con

dens

ate (

wt

)

Temperature (∘C)

South AfricaSulcis

(b)

Figure 2 (a) Amount (wt) of liquid materials collected in the cooling trap (a) against heating temperature (b) Amount (wt) of liquidmaterials collected in the cooling trap (b) against temperature

0 100 200 300 400 500 600 700 800 900

0

20

40

60

80

100

120

South AfricaSulcis

Pres

sure

(Tor

r)

Temperature (∘C)

(a)

0 100 200 300 400 500 600 700 800 9000

500

1000

1500

2000

2500

3000

3500

Pres

sure

(Tor

r)

Temperature (∘C)

South AfricaSulcis

(b)

Figure 3 (a) Pressure values against temperature of vapors released by coals and collected in the trap (b) cooled at minus77∘C (b) Pressure valuesagainst temperature of gases released by coals and collected in the trap (c) cooled at minus180∘C

reported in Table 4 while Figure 6 shows the correspondingIR spectra at different temperatures of emission

With the FT-IR analysis of this fraction products suchas CO

2 COS SO

2 Me2CO CS

2 HCN Me

2C=CH

2 C2H4

MeCH=CH2 C2H6 Et2O andC

3H8+C4H10were identified

The overall comparison between Figure 6 and Table 4shows that CO

2was emitted continuously by both coals at

all temperatures above 200∘C One of its bands of interestwas in the range 700ndash600 cmminus1 and it was due to the bendingof C=O bond (Table 3) Hydrocarbons were emitted at tem-peratures above 400∘C for both coals (Figure 6 and Table 4)Identification of unsaturated hydrocarbonswas performed by

evaluating the bands in the range 1100ndash800 cmminus1 due to thebending out of plane of CndashH bond (Table 3) Saturated onesshowed the absorption bands in the range 3200ndash2800 cmminus1due to the stretching of CndashH bond (Table 3)

SO2was emitted between 200 and 300∘C for Sulcis coal

(Figure 6 and Table 4) and it was identified on the basis ofthe band in the range 1400ndash1300 cmminus1 due to the stretchingof S=O bond (Table 3) On the other hand COS was emittedfrom Sulcis coal and it was recognized from the stretching ofC=Obond in the range 2100ndash1970 cmminus1 (Table 3) Finally CS

2

was emitted significantly from both coals between 500 and600∘C (Figure 6 and Table 4) and it was identified from the


Table 4 Qualitative distribution of vapors collected in the cooling trap (c) with liquid nitrogen

Coal T (∘C) CO2 COS SO2 Me2CO CS2 HCN Me2C=CH2 C2H4 MeCH=CH2 C2H6 Et2O C3H8 + C4H10

Sulcis

200 s m s m300 s s s m w w w400 s s m m m m s w w s m500 s s w w m w s m s m600 s s w w m w s m m m700 s s m m w800 s s w m

South Africa

100 m w200 w300 w400 s w w w w w w m500 s m m s m s s s s s600 s m m w w s s s s700 s m w m s w s m800 s w m m w

Intensity of analytical bands w weak m medium s strong Me methyl group Et ethyl group

stretching of C=S bond in the range 1550ndash1450 cmminus1 showinga characteristic doublet

In our system thermal cracking of tar molecules causesring opening reactions thereby releasing nitrogen into thegas phase as NO

119909precursors primarily as HCN but also

as NH3and HNCO [39 40] The release of HCN can be

explained on the basis of the reaction

CO +NH3997888rarr HCN +H

2O (1)

Furthermore it has also been suggested that HCN canreact with H

2to form NH

3[41]

Sulfur is present in coal in organic phase (classified asaliphatic aromatic and thiophenic sulfur) and inorganicphase being pyrite (FeS

2) and sulphates [42] Coal pyrolysis

releases sulfur as gas species (H2S COS SO

2 and CS

2) and

mercaptans in the tar phase while the rest remains in thesolid matrix of the residual char [43] Generally H

2S is the

most abundant gaseous component and there is usually asignificant amount of mercaptans too [41] In other caseslarge amounts of SO

2are also revealed [44] The following

reactions can explain the formation of these compounds

CH4+4

119909S119909997888rarr CS

2+ 2H2S (119879=500ndash700∘C)

CH4+2

119909S119909997888rarr CS

2+ 2H2(119879 gt 700

∘C)

S +O2997888rarr SO

2

3S + 2H2O 997888rarr SO

2+ 2H2S

3S + 2CO2997888rarr 2COS + SO

2

(2)

where S119909indicates that the sulphur in the vapour state has a

various molecular complexity S2 S6 and S

8

In addition COS will be formed by secondary gas phasereactions [45 46]

H2S + CO 997888rarr COS +H

2

H2S + CO

2997888rarr COS +H

2O

(3)

In nitrogen atmosphere pyrite is transformed into ironsulfide at low sulphur content pyrrhotite FeS

119899(1 le 119899 le 2)

[47] and into the very reactive S∘ Both species may reactwith H

2produced from coal and forming H

2S or with the

carbonaceousmatrix to form organicinorganic sulfur whichremains trapped in tar or char [48]

In addition the following reactions may occur [49]

FeS2997888rarr FeS + S

FeS2+H2997888rarr FeS +H

2S

2SO2+ 4C 997888rarr 4CO + S

2

(4)

In this reaction environment a gas-solid reaction mayoccur between pyrite and the formed CO [46]

FeS2+ CO 997888rarr FeS + COS (5)

Finally the emission of CO119909can take place from the

following reactions

C + 12O2997888rarr CO

CO + 12O2997888rarr CO

2

C +O2997888rarr CO

2

C +H2O 997888rarr CO +H

2

C + 2H2O 997888rarr CO +H

2

(6)


25∘C

100∘C

300∘C

400∘C

500∘C

600∘C

700∘C

800∘C

NH3

NH3

NH3

NH3

AA

A

A

A

A

A

A

A

A

A

A

K

K

K

K K

K

K

K K

K

K

K

K

K

K

KK

K

K

K

K

H

H

H H

H

AH

AH

AH

NH3

NH3

NH3

KAH

AH

AH

H

H

H

1800 1000(cmminus1)

Figure 4 FT-IR spectra in 2000ndash400 cmminus1 region of vaporsobtained at different temperatures from Sulcis (mdash) and South Africa(- - -) coals sampled in the cooling trap (b) K = ketones A =aromatic hydrocarbons and H = aliphatic hydrocarbons (saturatedand unsaturated)

In the earlier reactions the adsorbed oxygen in thecarbonaceous matrix (deriving from air of the environment)is released during the pyrolysis process

Furthermore these components can be originated at hightemperatures by following the reactions [50]

CaCO3997888rarr CaO + CO

2(119879 gt 700

∘C)

CaSO4+ 2C 997888rarr CaS + 2CO

2(119879 = 700ndash800∘C)

CaSO4+ 4C 997888rarr CaS + 4CO (119879 = 800∘C)

(7)

The overall comparison of the IR spectra evidences thatboth coals present a similar qualitative composition of theproducts obtained at high values of temperature Moreover itis important to observe that the pyrolysis products for the twocoals are quantitatively different Sulcis coal releases higheramounts of pyrolysis products at a lower temperature thanthe South Africa one since the former is a lower rank coal Infact Sulcis coal is richer in volatile matter (119881

119898) than South

African coal as evidenced in Table 1 This aspect justifiesthe lower temperature of decomposition of the Sulcis coal(between 100 and 200∘C) than that of the South African one(between 300 and 400∘C) (Figures 2(a) and 2(b)) In factthe temperature at which the decomposition starts is directlyrelated to the average energy required to break the bonds inthe coal macrostructures

In agreement with the literature data [51] sulphur deriva-tives such as SO

2 COS and CS

2can be identified as pyrolysis

products In particular Sulcis coal emitted SO2 COS and

CS2 while South Africa coal released smaller quantities of

SO2and COS This is fully in agreement with their different

total sulphur content (59 versus 06 for Sulcis and SouthAfrica coal resp)

The evolved amount of these products is a function of thetemperature In fact while the quantity of COS constantlyincreases with temperature until 600∘C for both fossils SO

2

is mainly collected for Sulcis coal only between 200 and300∘C and in a small amount in the other case COS derivesfrom the organic sulphur (eg thioethers) while SO

2from

the inorganic matrix consisting mainly in elemental sulphursulphide sulphate and pyrite

In the case of South Africa coal it is important tonote that it has a singular behaviour at low temperaturesSmall quantities of CO

2and oxygenated compounds such as

acetone and diethyl ketone were revealed during the heatingat 100∘C These quantities decreased at 200∘C and disap-peared at 500∘C From 400∘C its decomposition was similarto the other coal This behaviour is in agreement with amolecular sieve structure type that contains some moleculessuch as CO

2 CO and other oxygenated compounds trapped

inside the pores of the solid matrix [52] Their formation isdue to absorbed oxygen by air of the environment In factas soon as fresh coal is mined and exposed to atmosphericconditions the process of slow oxidation due to contact withair inexorably sets in [18]

In Figure 7(a) pressure values of noncondensable gasesare reported as a function of temperature for both coals

Figure 7(a) shows that noncondensable gases comingfrom both types of coal are emitted significantly starting from400∘C and their trends are almost similar

In Figure 7(b) the FT-IR spectra of these noncondensablegases are shown at different temperatures of emission forSulcis and South Africa coals

The IR spectra of the noncondensable gases revealbands ascribed to methane and carbon monoxide and small


200 400 600 800 1000 1200 1400 1600 1800 2000 2200 2400Time

Abun

danc

e

Nap

htha

lene

Benz

alde

hyde

p-Xy

lene

m

-Xyl

ene

Ethy

lben

zene

Phen

ol

1-Pe

ntan

ol

Tolu

ene

keto

nes

alco

hols

and

olefi

nsA

lipha

tic h

ydro

carb

ons

Benz

ene

5

10

15

20

25

30

35

40

45

50

55

times105

(a)

150 200 250 300 350 400 450Time

Abun

danc

e

Thio

phen

e

Benz

ene

Etha

nol

Prop

ane

Met

hano

lBu

tane

Acet

one

2-Pr

opan

ol

Pent

ane

2-Bu

tene

Hex

ane

MEK

3-Pe

ntan

one

2-M

ethy

lpro

pano

l

times105

2468

1012141618202224262830323436384042444648505254

(b)

Figure 5 (a) GC-MS chromatogram of the condensate (trap b) coming from the devolatilization of the South Africa coal at 600∘C (b)Particularity of the light ends in the GC-MS chromatogram of the condensate (trap b) coming from the devolatilization of the South Africacoal at 600∘C


100∘C

500∘C

600∘C

700∘C800∘C

200∘C

300∘C

400∘C

EEE

E E E

CO2 CO2

CO2

CO2

CO2

CO2

CO2

CO2

CO2

CO2

CO2

CO2

CO2

CO2

CO2

SO2

SO2

SO2

SO2

SO2

SO2

SO2K

KK

K

K

K

H

H

H

H H

H

HH

HH H

H

H

HH

H H HH

H

H

HHH

H H H

CS2

CS2

CS2

CS2

CS2

CS2

CS2

1800 1400 1000(cmminus1)

1800 1400 1000(cmminus1)

1800 1400 1000(cmminus1)

Figure 6 FT-IR spectra in the 2000ndash400 cmminus1 region of gases obtained at different temperatures from Sulcis (mdash) and South Africa (- - -)coals sampled in the cooling trap (c) E = ethers K = ketones H = aliphatic hydrocarbons (saturated and unsaturated)

300 400 500 600 700 8000

100

200

300

400

500

South AfricaSulcis

Pres

sure

(tor

r)

Temperature (∘C)

(a)

600∘C700∘C

800∘C

600∘C

700∘C

800∘C

CH4

CH4

CH4

CH4

CO

CO

C=C

C=C

Ethane

Ethane

HCN

HCN

A

A

3000 2000 1600 1200 800(cmminus1)

(b)

Figure 7 (a) Plots of the pressure values of noncondensable gases against temperatures for Sulcis and South Africa coals (b) FT-IR spectra in3500ndash400 cmminus1 region of noncondensable gases obtained at various temperatures by Sulcis (mdash) and South Africa coals (- - -) A = acetylene


0 200 400 600 800

0

20

40

60

80

100Pr(i)=P(i)P

max

(i)(T

)

Temperature (∘C)

(CH3)COHCN

COCO2

(a)

0 200 400 600 8000

20

40

60

80

100

Pr(i)=P(i)P

max

(i)(T

)

Temperature (∘C)

(CH3)C=CH2

SO2

C2H4

COS

(b)

Figure 8 (a) Relative pressure values of (CH3

)2

CO HCN CO and CO2

against temperature for Sulcis coal (b) Relative pressure values of(CH3

)2

C=CH2

SO2

C2

H4

and COS against temperature for Sulcis coal

0 200 400 600 800

0

20

40

60

80

100

Pr(i)=P(i)P

max

(i)(T

)

Temperature (∘C)

COCO2

(CH3)2COHCN

(a)

0 200 400 600 800

0

20

40

60

80

100

Pr(i)=P(i)P

max

(i)(T

)

Temperature (∘C)

C2H4

CH3ndashCH=CH2

COS

(b)

Figure 9 (a) Relative pressure values of CO CO2

(CH3

)2

CO and HCN against temperature for South Africa coal (b) Relative pressurevalues of C

2

H4

CH3

ndashCH=CH2

and COS against temperature for South Africa coal

amounts of ethane unsaturated hydrocarbons and acetyleneFurthermore in the same spectra the absorption bands dueto HCN were found probably because a part of the totalHCN evolved during the pyrolysis process has not beencompletely condensed in the previous traps However whenthe temperature increases the HCN emission increases up toa maximum and then decreases This pattern is similar alsofor the other pyrolysis products recovered from the coolingtraps (b) and (c) In fact the global comparison between the

IR data of the condensates collected in the cooling trap (b)(with CO

2+ acetone) (Figure 4 Table 2) and those of the

condensates collected in the cooling trap (c) (with liquidnitrogen) (Figure 6 Table 4) shows that absorption bandsintensities of each pyrolysis product increase with the tem-perature until a maximum zone and then they decrease Inorder to better define the maximum emission for some of thepyrolysis products after having identified most of the vaporsand gases (Table 3) on the basis of assignments reported in


the literature [53] the analytical bands of interest were chosenand standard mixtures of the gas samples correspondingto the pyrolysis products were prepared These calibrationmixtures containing known amounts of gas were introducedinto an evacuated gas cell which was subsequently filled toa pressure of one atmosphere with nitrogen In Figures 8(a)8(b) 9(a) and 9(b) the relative pressure 119875

119903(119894)= 119875(119894)(119879119903)

119875max(119894)(119879119890) is plotted against temperature for Sulcis and SouthAfrica coal respectively 119875

(119894)is the partial pressure of 119894

component in the mix at room temperature (119879119903) and 119875max(119894)

is its pressure value at the temperature of extraction (119879119890)

These plots are very useful because they immediatelyidentify the main products of the thermal decompositionduring the carbonization process Therefore any similaritiesand differences in behavior between the coals during pyroly-sis can be put clearly in evidence The symmetric emission ofmany components as appears in Figures 8(a) 8(b) 9(a) and9(b) can be explained as follows by increasing the tempera-ture the rate of pyrolysis in the macrostructures increaseswith a consequent decrease of the functional groups fromwhich the products originated In this context it is possible tonote that South Africa coal presents a maximum value of gasemission at about 600∘C while Sulcis coal shows amaximumat around 400∘C releasing acetone and isobutene This is inagreement with spectral changes observed for their residualsobtained in the previous investigation [35]

At 300∘C SO2emission coming from Sulcis coal is at its

maximumwhile this component only appears in traces in theother coal By comparing CO

2production of both coals it is

possible to note that this component is also predominant inthe case of Sulcis coal rather than in the South African oneaccording to the low rank of carbonization of the Italian coalIn fact it contains a great number of unities having oxygenso its infrared spectrum is similar to the one of a pit coal Byincreasing the temperature the release of CO

2increases in

agreement with the greater energy required to break theseunities

Some components such as acetone and hydrocyanicacid do not present a symmetric emission with temperaturebecause they have a different origin In particular for the pro-duction of HCN a first emission at 400∘C for Sulcis coal andat 500∘C for theAfrican onewas observed For Sulcis coal thepresence of functional amide groups (RndashCOndashNH

2) allows the

production of HCN by a dehydration reaction [54]

HndashCOndashNH2997888rarr HCN +H

2O (8)

This reaction occurs at about 400∘C in the presenceof components as alumina clay and zinc oxide and thesematerials are not difficult to to be found in coals

4 Conclusion

The investigated coals contain gaseous components trappedinto the interstices of the coal matrix as shown by infraredspectra of the gases collected at room temperature and at100∘C

The FT-IR spectroscopy is a powerful technique forinvestigation of coal pyrolysis since it allows to distinguish

the compositions of Sulcis and South Africa coals Thethermal treatment of these coals involves a first-stage pyrol-ysis in which structural changes and decomposition offunctional organic groups occur with the formation of tarand generation of vapors and gases From about 400∘C asecond pyrolysis process takes place proceeding with thethermal cracking of tar skeleton framework reactions in thepores between the coal matrix and gases dehydration of theminerals and changes in surface areas The quantity of thesegases is higher for Sulcis coal according to its rank and theelemental and proximate analyses Plots of pressures 119875

119903(119894)=

119875(119894)(119879119903)119875max(119894)(119879119890) against temperature show the correlation

among qualitative gas composition temperature and themaximum value of emission These plots are very usefulbecause they uniquely identify the main products of thethermal decomposition during the carbonization processFurthermore these data could be integrated in structuralmodels for coal pyrolysis to evaluate pyrolysis kinetics

References

[1] K Miura ldquoMild conversion of coal for producing valuablechemicalsrdquo Fuel Processing Technology vol 62 no 2 pp 119ndash135 2000

[2] B Avid B PurevsurenM Born J Dugarjav Y Davaajav andATuvshinjargal ldquoPyrolysis and TG analysis of Shivee Ovoo coalfrom Mongoliardquo Journal of Thermal Analysis and Calorimetryvol 68 no 3 pp 877ndash885 2002

[3] J W Patrick A Walker and S Hanson ldquoThe effect of coalparticle size on pyrolysis and steam gasificationrdquo Fuel vol 81no 5 pp 531ndash537 2002

[4] L Yang J Ran and L Zhang ldquoMechanism and kinetics ofpyrolysis of coal with high ash and low fixed carbon contentsrdquoJournal of Energy Resources Technology vol 133 no 3 ArticleID 031701 pp 1ndash7 2011

[5] R W Niemeier ldquoPetroleum coal tar and related productsrdquo inPattyrsquos Toxicology pp 325ndash370 John Wiley amp Sons New YorkNY USA 2012

[6] L S Pedersen H P Nielsen S Kiil et al ldquoFull-scale co-firingof straw and coalrdquo Fuel vol 75 no 13 pp 1584ndash1590 1996

[7] C Meesri and B Moghtaderi ldquoLack of synergetic effects in thepyrolytic characteristics of woody biomasscoal blends underlow and high heating rate regimesrdquo Biomass and Bioenergy vol23 no 1 pp 55ndash66 2002

[8] H Haykiri-Acma and S Yaman ldquoInteraction between biomassand different rank coals during co-pyrolysisrdquoRenewable Energyvol 35 no 1 pp 288ndash292 2010

[9] C A Ulloa A L Gordon and X A Garcıa ldquoThermogravimet-ric study of interactions in the pyrolysis of blends of coal withradiata pine sawdustrdquo Fuel Processing Technology vol 90 no 4pp 583ndash590 2009

[10] C-Z Li K D Bartle and R Kandiyoti ldquoVacuum pyrolysis ofmaceral concentrates in a wire-mesh reactorrdquo Fuel vol 72 no11 pp 1459ndash1468 1993

[11] L Zhang S Xu W Zhao and S Liu ldquoCo-pyrolysis of biomassand coal in a free fall reactorrdquo Fuel vol 86 no 3 pp 353ndash3592007

[12] D-M He L Zhang J Guan and Q M Zhang ldquoThe compara-tive study of Honghe lignite pyrolysis under the atmosphere ofmethanol and nitrogenrdquoAdvancedMaterials Research vol 512ndash515 pp 1784ndash1789 2012


[13] D M P Wu and D P Harrison ldquoVolatile products from lignitepyrolysis and hydropyrolysisrdquo Fuel vol 65 no 6 pp 747ndash7511986

[14] J B Howard ldquoFundamentals of coal pyrolysis and hydropyrol-ysisrdquo in Chemistry of Coal Utilization Secondary SupplementaryVolume pp 665ndash784 John Wiley amp Sons New York NY USA1981

[15] N Qiu H Li E Xu J Qin and L Zheng ldquoTemperature andtime effects on free radical concentration in organic matterevidence from laboratory pyrolysis experimental and geologicalsamplesrdquo Energy Exploration and Exploitation vol 30 no 2 pp311ndash330 2012

[16] R D Srivastava H G Mcllvried III and J C Winslow ldquoCoaltechnology for power liquid fuels and chemicalsrdquo in Kent andRiegelrsquos Handbook of Industrial Chemistry and Biotechnologychapter 19 pp 843ndash906 Springer Science + Business MediaNew York NY USA 11th edition 2007

[17] J Rezaiyan and N P Cheremisinoff ldquoPyrolysisrdquo in GasificationTechnologies A Primer for Engineers and Scientists pp 145ndash164CRC New York NY USA Taylor amp Francis Boca Raton FlaUSA 2005

[18] L Tognotti G Bertozzi L Petarca A DrsquoAlessio and EBenedetti ldquoLow-temperature oxidation of a bituminous coal itsstructural implicationsrdquo La Chimica e LrsquoIndustria vol 70 no 9pp 76ndash80 1988

[19] L Tognotti L Petarca A DrsquoAlessio and E Benedetti ldquoLowtemperature air oxidation of coal and its pyridine extractionproducts Fourier transform infrared studiesrdquo Fuel vol 70 no9 pp 1059ndash1067 1991

[20] A DrsquoAlessio and E Benedetti ldquoInfrared analysis of the struc-tural changes of Sulcis and other coals under progressiveheatingrdquo La Chimica e LrsquoIndustria vol 66 pp 689ndash693 1984

[21] A Karcz and S Porada ldquoThe influence of coal rank onformation of gaseous hydrocarbons in hydrogasif ication ofcoalrdquo Fuel vol 75 no 5 pp 641ndash645 1996

[22] K Murakami H Shirato and Y Nishiyama ldquoIn situ infraredspectroscopic study of the effects of exchanged cations onthermal decomposition of a brown coalrdquo Fuel vol 76 no 7 pp655ndash661 1997

[23] B J Meldrum and C H Rochester ldquoInfrared spectra ofcarbonaceous chars under carbonization and oxidation condi-tionsrdquo Fuel vol 70 no 1 pp 57ndash63 1991

[24] J B Ibarra R Moliner and A J Bonet ldquoFT-ir investigation onchar formation during the early stages of coal pyrolysisrdquo Fuelvol 73 no 6 pp 918ndash924 1994

[25] P Keliang X Wenguo and Z Changsui ldquoInvestigation onpyrolysis characteristic of natural coke using thermogravi-metric and Fourier-transform infrared methodrdquo Journal ofAnalytical and Applied Pyrolysis vol 80 no 1 pp 77ndash84 2007

[26] S S Idris NA RahmanK Ismail A B Alias Z A Rashid andM J Aris ldquoInvestigation on thermochemical behaviour of lowrank Malaysian coal oil palm biomass and their blends duringpyrolysis via thermogravimetric analysis (TGA)rdquo BioresourceTechnology vol 101 no 12 pp 4584ndash4592 2010

[27] R M Carangelo P R Solomon and D J Gerson ldquoApplicationof TG-FT-IR to study hydrocarbon structure and kineticsrdquo Fuelvol 66 no 7 pp 960ndash967 1987

[28] P R Solomon M A Serio and E M Suuberg ldquoCoal pyrolysisexperiments kinetic rates and mechanismsrdquo Progress in Energyand Combustion Science vol 18 no 2 pp 133ndash220 1992

[29] I Pitkanen J Huttunen H Halttunen and R VesterinenldquoEvolved gas analysis of some solid fuels by TG-FTIRrdquo Journalof Thermal Analysis and Calorimetry vol 56 no 3 pp 1253ndash1259 1999

[30] E Ekinci F Yardim M Razvigorova et al ldquoCharacterizationof liquid products from pyrolysis of subbituminous coalsrdquo FuelProcessing Technology vol 77-78 pp 309ndash315 2002

[31] L Bonfanti L Comellas J L Lliberia R Vallhonrat-MatalongaM Pich-Santacana and D Lopez-Pinol ldquoPyrolysis gas chro-matography of some coals by nitrogen and phosphorus flameionisation and mass spectrometer detectorsrdquo Journal of Analyt-ical and Applied Pyrolysis vol 44 no 1 pp 101ndash119 1997

[32] D Fabbri I Vassura and C E Snape ldquoSimple off-line flashpyrolysis procedure with in situ silylation for the analysisof hydroxybenzenes in humic acids and coalsrdquo Journal ofChromatography A vol 967 no 2 pp 235ndash242 2002

[33] G Gryglewicz P Rutkowski and J Yperman ldquoCharacterizationof sulfur compounds in supercritical coal extracts by gaschromatography-mass spectrometryrdquo Fuel Processing Technol-ogy vol 77-78 pp 167ndash172 2002

[34] Q yang SWu R Lou andG Lv ldquoAnalysis of wheat straw ligninby thermogravimetry and pyrolysis-gas chromatographymassspectrometryrdquo Journal of Analytical and Applied Pyrolysis vol87 no 1 pp 65ndash69 2010

[35] A DrsquoAlessio P Vergamini and E Benedetti ldquoFT-IR investiga-tion of the structural changes of Sulcis and South Africa coalsunder progressive heating in vacuumrdquo Fuel vol 79 no 10 pp1215ndash1220 2000

[36] R H Perry and C H Chilton Chemical Engineers HandbookMc Graw-Hill New York NY USA 8th edition 2007

[37] D N Kendall Applied Infrared Spectroscopy Reinhold NewYork NY USA 1966

[38] M V Zeller Infrared Methods in Air Analysis Perkin-ElmerCorporation Eden Prairie Minn USA 2000

[39] E B Ledesma C Li P F Nelson and J C Mackie ldquoRelease ofHCNNH

3

andHNCO from the thermal gas-phase cracking ofcoal pyrolysis tarsrdquo Energy and Fuels vol 12 no 3 pp 536ndash5411998

[40] L L Tan and C Li ldquoFormation of NO119909

and SO119909

precursorsduring the pyrolysis of coal and biomass Part I Effects ofreactor configuration on the determined yields of HCN andNH3

during pyrolysisrdquo Fuel vol 79 no 15 pp 1883ndash1889 2000[41] R Bassilakis Y Zhao P R Solomon and M A Serio ldquoSulfur

and nitrogen evolution in the Argonne coals experiment andmodelingrdquo Energy amp Fuels vol 7 no 6 pp 710ndash720 1993

[42] TMaffei S Sommariva E Ranzi and T Faravelli ldquoA predictivekinetic model of sulfur release from coalrdquo Fuel vol 91 no 1 pp213ndash223 2012

[43] J Yan J Yang and Z Liu ldquoSH radical the key intermediatein sulfur transformation during thermal processing of coalrdquoEnvironmental Science and Technology vol 39 no 13 pp 5043ndash5051 2005

[44] K Miura K Mae M Shimada and H Minami ldquoAnalysisof formation rates of sulphur-containing gases during thepyrolysis of various coalsrdquo Energy and Fuels vol 15 no 3 pp629ndash636 2001

[45] P Selsbo P Almen and I Ericsson ldquoQuantitative analysis ofsulfur in coal by pyrolysis-gas chromatography andmultivariatedata analysisrdquo Energy and Fuels vol 10 no 3 pp 751ndash756 1996

[46] L Duan C Zhao W Zhou C Liang and X Chen ldquoSulfurevolution from coal combustion in O

2

CO2

mixturerdquo Journal


of Analytical and Applied Pyrolysis vol 86 no 2 pp 269ndash2732009

[47] G L Hu K Dam S Wedel and J P Hansen ldquoDecompositionand oxidation of pyriterdquo Progress in Energy and CombustionScience vol 32 no 3 pp 295ndash314 2006

[48] P J Cleyle W F Caley L Stewart and S G whitewayldquoDecomposition of pyrite and trapping of sulphur in a coalmatrix during pyrolysis of coalrdquo Fuel vol 63 no 11 pp 1579ndash1582 1984

[49] M R Khan and T Kurata ldquoThe feasibility of mild gasifi-cation of coal research needsrdquo 1985 DOEMETC-854019NTISDE85013625

[50] S Furfari and R Cypres ldquoHydropyrolysis of a high-sulphur-high-calcite Italian Sulcis coal 2 Importance of the mineralmatter on the sulphur behaviourrdquo Fuel vol 61 no 5 pp 453ndash459 1982

[51] D Shao E J Hutchinson J Heidbrink W Pan and C ChouldquoBehavior of sulfur during coal pyrolysisrdquo Journal of Analyticaland Applied Pyrolysis vol 30 no 1 pp 91ndash100 1994

[52] J J Pitt ldquoStructure analysis of coalrdquo in Coal and ModernCoal processIng An Introduction pp 27ndash50 Academic PressLondon UK 1979

[53] C PoucherThe Aldrich Library of FT-IR Spectra John Wiley ampSons New York NY USA 1997

[54] V S Nguyen H L Abbott M M Dawley T M OrlandoJ Leszczynski and M T Nguyen ldquoTheoretical study of for-mamide decomposition pathwaysrdquo Journal of Physical Chem-istry A vol 115 no 5 pp 841ndash851 2011

International Journal of

AerospaceEngineeringHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

RoboticsJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014


Active and Passive Electronic Components

Control Scienceand Engineering

Journal of



RotatingMachinery


Hindawi Publishing Corporation httpwwwhindawicom

Journal ofEngineeringVolume 2014

Submit your manuscripts athttpwwwhindawicom

VLSI Design



Shock and Vibration


Civil EngineeringAdvances in

Acoustics and VibrationAdvances in



Electrical and Computer Engineering

Journal of

Advances inOptoElectronics


Volume 2014

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

SensorsJournal of


Modelling amp Simulation in EngineeringHindawi Publishing Corporation httpwwwhindawicom Volume 2014


Chemical EngineeringInternational Journal of Antennas and

Propagation




Navigation and Observation



DistributedSensor Networks



may take place leading to significant variations in the thermalreactivity of the resulting samples or in the physical orchemical properties of the products [6ndash8]

Coal thermal degradation generates gaseous liquid andsolid products The primary decomposition products whichare initially formed probably decompose in turn and theresulting fragments react furtherwith each other andwith thesolid residue to form the observed tars liquors water vaporsgases and char Due to these secondary reactions the decom-position products which are eventually observed may be farremoved from the original coal structure offering few cluesto the chemical constitution of coal In this context pyrolysisof coal under reduced pressures has been used to minimizethese secondary reactions [9ndash12]

Among the variables of processes which characterize thepyrolysis temperature and time have the most remarkableeffect on the structural changes ascribed to organic andinorganic parts of coals [13ndash15]

Coal undergoes many physical and chemical changeswhen gradually heated from ambient temperature to approx-imately 1000∘C [16] The temperature ranges for the variouspyrolysis events significantly depend on the heating rate Atslow heating rate (about 5∘Cs) the maximum devolatiliza-tion occurs at around 400∘C whereas increasing the heatingrate up to about 10∘Cs this maximummight not occur until900∘C This is a ldquoconventionalrdquo pyrolysis and employs lowheating rates and modest residence times (about 5ndash30 min-utes) for the recovery of char This technology is still widelyused because it provides a clean feedstock of combustiongasification for electric power generation On the other handldquofastrdquo pyrolysis employs respectively very high heating rates(up to 1000∘Cs) and very short residence times (05ndash5 s)minimizing the formation of char and breaking the bonds ofthe molecular species recovering mainly liquid and gaseousproducts [17]

Fourier Transform Infrared Spectroscopy (FT-IR) playsan important role in the elucidation of chemical structure ofcoal chars and gas evolving during oxidation and pyrolysisprocesses [18ndash21] This research closely links to the appli-cation of FT-IR on the pyrolysis of new green materialssuch as biomass since the chemical groups are similar andchar is among the final products obtained The chemicalcharacterization of the evolved gas in the pyrolysis process byFT-IR spectroscopy is therefore an important tool for under-standing the properties of these materials

Many pyrolysis processes were extensively investigated[22] and the thermal decomposition of the functional groupspresent in the coals was widely studied by using infraredspectroscopy [23 24]

Recently many researchers have applied integrated tech-niques such as thermogravimetry (TG) and derivativethermogravimetry (DTG) differential scanning calorimetry(DSC) andFourier Transform Infrared Spectroscopy (FT-IR)in order to study the pyrolysis of coal [4 25 26]

Among all these studies Carangelo et al [27] andSolomon et al [28] investigated hydrocarbons structure andthe kinetics of gas evolution by using a TGFT-IR techniqueto study the pyrolysis of coal char tar and oil shaleThey identified the individual gaseous species such as CO

CO2 H2O CH

4 C2H6 C2H4 C2H2 C3H8 benzene heavy

paraffins heavy olefins HCN HCl NH3 SO2 CS2 COS

CH3OH CH

3COOH and CH

3COCH

3 Pitkanen et al [29]

studied various fuels such as coal peat wood chips and barkwith FT-IR spectrometry combined with TG FT-IR spectraand TG curves indicated that the main evolved gases wereCO2and H

2O while there were many minor gases such as

CO2 CH4 C2H6 CH3OH CH

3COOH and HCOOH

Many chromatographic techniques were developed tostudy coals and coal-derived products These included gaschromatography and liquid chromatography [30] A flameionization detector (FID) [31] was mostly used to detect coalcompounds coming out from a chromatographic columnAlso gas chromatography coupled with mass spectrometry(GC-MS) was frequently used to study coals [32 33] Finallythe development of analytical chemistry fostered the use ofcombined methods based on pyrolysis gas chromatographycoupled with mass detection (Py-GC-MS) [31 34]

However among all these analytical techniques infraredspectroscopy remains one of the most simple and effectiveones to evaluate and monitor the pyrolysis products In aprevious study [35] we investigated the structural changesof two bituminous coals a Sulcis and a South Africa one byFT-IR spectroscopy under slowly heating temperature pro-grammed mode from 25 to 800∘C under vacuum In thisresearch the analysis of gas evolving during the pyrolysis oftwo different rank coals by using FT-IR spectroscopy wasstudied under the same heating conditions The main aim ofthis work is to establish the correlation between the evolutionof vapors and gases and the structural changes of thefunctional groups during the pyrolysis process

2 Materials and Methods

Coal samples were ground with a ball mill for 15 minutesand subsequently sieved in order to obtain samples of average70 120583m granulometric size

Ultimate and proximate analysis of these two types of coalwere performed by a Perkin-Elmer analyser mod 240 and aThermoanalyser Mettler TA 1 respectively

In order to confirm the results of the IR analysis thegas chromatographymass spectrometry (GC-MS) analysisof some condensates was performed by using the gas-chromatograph Hewlett-Packard HP 6890 equipped with aMSDHP 5973 detector and with a GC column PhenomenexZebron with a 100 methyl polysiloxane stationary phase(column length 30m inner diameter 025mm and thicknessof the stationary phase 025120583m) The transport gas washelium 55 and the flow was 1mLmin The temperature ofthe injection port was set at 250∘C carrier pressure at 100 kPaand split flow at 340msminus1 The oven was heated at 30∘C for5min and then the temperature was raised at 5∘Cmin up to250∘C

The apparatus used in the pyrolysis experiments is shownin Figure 1

One hundred grams of each sample were put in a quartzpipe of a temperature-controlled furnace All the equipmentswere conditioned with a cycle of vacuum-nitrogen at roomtemperature Subsequently the apparatus was put under


Flowmeter

Coal

Couple


N2

a b c

d e f

g



















2and a lower

























1ndashC3alcohols







Sulcis


South Africa










0 100 200 300 400 500 600 700 800 9000

1

2

3

4

5

6C

onde

nsat

e (w

t)

Temperature (∘C)

South AfricaSulcis

(a)

0 100 200 300 400 500 600 700 800 900

00

05

10

15

20

25

Con

dens

ate (

wt

)

Temperature (∘C)

South AfricaSulcis

(b)


0 100 200 300 400 500 600 700 800 900

0

20

40

60

80

100

120

South AfricaSulcis

Pres

sure

(Tor

r)

Temperature (∘C)

(a)

0 100 200 300 400 500 600 700 800 9000

500

1000

1500

2000

2500

3000

3500

Pres

sure

(Tor

r)

Temperature (∘C)

South AfricaSulcis

(b)




2 COS SO

2 Me2CO CS

2 HCN Me

2C=CH

2 C2H4









2





Sulcis


South Africa









2O (1)


2to form NH

3[41]




2 and CS

2) and


2S is the




CH4+4

119909S119909997888rarr CS

2+ 2H2S (119879=500ndash700∘C)

CH4+2

119909S119909997888rarr CS

2+ 2H2(119879 gt 700

∘C)

S +O2997888rarr SO

2

3S + 2H2O 997888rarr SO

2+ 2H2S


2

(2)



8



2

H2S + CO

2997888rarr COS +H

2O

(3)


119899(1 le 119899 le 2)



2S or with the





2S

2SO2+ 4C 997888rarr 4CO + S

2

(4)




following reactions

C + 12O2997888rarr CO


2

C +O2997888rarr CO

2


2


2

(6)


25∘C

100∘C

300∘C

400∘C

500∘C

600∘C

700∘C

800∘C

NH3

NH3

NH3

NH3

AA

A

A

A

A

A

A

A

A

A

A

K

K

K

K K

K

K

K K

K

K

K

K

K

K

KK

K

K

K

K

H

H

H H

H

AH

AH

AH

NH3

NH3

NH3

KAH

AH

AH

H

H

H

1800 1000(cmminus1)





2(119879 gt 700

∘C)


2(119879 = 700ndash800∘C)


(7)


119898) than South



2 COS and CS







2


2from












200 400 600 800 1000 1200 1400 1600 1800 2000 2200 2400Time

Abun

danc

e

Nap

htha

lene

Benz

alde

hyde

p-Xy

lene

m

-Xyl

ene

Ethy

lben

zene

Phen

ol

1-Pe

ntan

ol

Tolu

ene

keto

nes

alco

hols

and

olefi

nsA

lipha

tic h

ydro

carb

ons

Benz

ene

5

10

15

20

25

30

35

40

45

50

55

times105

(a)

150 200 250 300 350 400 450Time

Abun

danc

e

Thio

phen

e

Benz

ene

Etha

nol

Prop

ane

Met

hano

lBu

tane

Acet

one

2-Pr

opan

ol

Pent

ane

2-Bu

tene

Hex

ane

MEK

3-Pe

ntan

one

2-M

ethy

lpro

pano

l

times105

2468

1012141618202224262830323436384042444648505254

(b)



100∘C

500∘C

600∘C

700∘C800∘C

200∘C

300∘C

400∘C

EEE

E E E

CO2 CO2

CO2

CO2

CO2

CO2

CO2

CO2

CO2

CO2

CO2

CO2

CO2

CO2

CO2

SO2

SO2

SO2

SO2

SO2

SO2

SO2K

KK

K

K

K

H

H

H

H H

H

HH

HH H

H

H

HH

H H HH

H

H

HHH

H H H

CS2

CS2

CS2

CS2

CS2

CS2

CS2

1800 1400 1000(cmminus1)

1800 1400 1000(cmminus1)

1800 1400 1000(cmminus1)


300 400 500 600 700 8000

100

200

300

400

500

South AfricaSulcis

Pres

sure

(tor

r)

Temperature (∘C)

(a)

600∘C700∘C

800∘C

600∘C

700∘C

800∘C

CH4

CH4

CH4

CH4

CO

CO

C=C

C=C

Ethane

Ethane

HCN

HCN

A

A

3000 2000 1600 1200 800(cmminus1)

(b)



0 200 400 600 800

0

20

40

60

80

100Pr(i)=P(i)P

max

(i)(T

)

Temperature (∘C)

(CH3)COHCN

COCO2

(a)

0 200 400 600 8000

20

40

60

80

100

Pr(i)=P(i)P

max

(i)(T

)

Temperature (∘C)

(CH3)C=CH2

SO2

C2H4

COS

(b)


)2

CO HCN CO and CO2


)2

C=CH2

SO2

C2

H4


0 200 400 600 800

0

20

40

60

80

100

Pr(i)=P(i)P

max

(i)(T

)

Temperature (∘C)

COCO2

(CH3)2COHCN

(a)

0 200 400 600 800

0

20

40

60

80

100

Pr(i)=P(i)P

max

(i)(T

)

Temperature (∘C)

C2H4

CH3ndashCH=CH2

COS

(b)


(CH3

)2


2

H4

CH3

ndashCH=CH2








119903(119894)= 119875(119894)(119879119903)










2increases in



2) allows the



2O (8)


4 Conclusion




119903(119894)=



References









































3



and SO119909









2

CO2














RoboticsJournal of





Journal of



RotatingMachinery





VLSI Design



Shock and Vibration







Journal of



Volume 2014


SensorsJournal of





Propagation










Flowmeter

Coal

Couple


N2

a b c

d e f

g



















2and a lower

























1ndashC3alcohols







Sulcis


South Africa










0 100 200 300 400 500 600 700 800 9000

1

2

3

4

5

6C

onde

nsat

e (w

t)

Temperature (∘C)

South AfricaSulcis

(a)

0 100 200 300 400 500 600 700 800 900

00

05

10

15

20

25

Con

dens

ate (

wt

)

Temperature (∘C)

South AfricaSulcis

(b)


0 100 200 300 400 500 600 700 800 900

0

20

40

60

80

100

120

South AfricaSulcis

Pres

sure

(Tor

r)

Temperature (∘C)

(a)

0 100 200 300 400 500 600 700 800 9000

500

1000

1500

2000

2500

3000

3500

Pres

sure

(Tor

r)

Temperature (∘C)

South AfricaSulcis

(b)




2 COS SO

2 Me2CO CS

2 HCN Me

2C=CH

2 C2H4









2





Sulcis


South Africa









2O (1)


2to form NH

3[41]




2 and CS

2) and


2S is the




CH4+4

119909S119909997888rarr CS

2+ 2H2S (119879=500ndash700∘C)

CH4+2

119909S119909997888rarr CS

2+ 2H2(119879 gt 700

∘C)

S +O2997888rarr SO

2

3S + 2H2O 997888rarr SO

2+ 2H2S


2

(2)



8



2

H2S + CO

2997888rarr COS +H

2O

(3)


119899(1 le 119899 le 2)



2S or with the





2S

2SO2+ 4C 997888rarr 4CO + S

2

(4)




following reactions

C + 12O2997888rarr CO


2

C +O2997888rarr CO

2


2


2

(6)


25∘C

100∘C

300∘C

400∘C

500∘C

600∘C

700∘C

800∘C

NH3

NH3

NH3

NH3

AA

A

A

A

A

A

A

A

A

A

A

K

K

K

K K

K

K

K K

K

K

K

K

K

K

KK

K

K

K

K

H

H

H H

H

AH

AH

AH

NH3

NH3

NH3

KAH

AH

AH

H

H

H

1800 1000(cmminus1)





2(119879 gt 700

∘C)


2(119879 = 700ndash800∘C)


(7)


119898) than South



2 COS and CS







2


2from












200 400 600 800 1000 1200 1400 1600 1800 2000 2200 2400Time

Abun

danc

e

Nap

htha

lene

Benz

alde

hyde

p-Xy

lene

m

-Xyl

ene

Ethy

lben

zene

Phen

ol

1-Pe

ntan

ol

Tolu

ene

keto

nes

alco

hols

and

olefi

nsA

lipha

tic h

ydro

carb

ons

Benz

ene

5

10

15

20

25

30

35

40

45

50

55

times105

(a)

150 200 250 300 350 400 450Time

Abun

danc

e

Thio

phen

e

Benz

ene

Etha

nol

Prop

ane

Met

hano

lBu

tane

Acet

one

2-Pr

opan

ol

Pent

ane

2-Bu

tene

Hex

ane

MEK

3-Pe

ntan

one

2-M

ethy

lpro

pano

l

times105

2468

1012141618202224262830323436384042444648505254

(b)



100∘C

500∘C

600∘C

700∘C800∘C

200∘C

300∘C

400∘C

EEE

E E E

CO2 CO2

CO2

CO2

CO2

CO2

CO2

CO2

CO2

CO2

CO2

CO2

CO2

CO2

CO2

SO2

SO2

SO2

SO2

SO2

SO2

SO2K

KK

K

K

K

H

H

H

H H

H

HH

HH H

H

H

HH

H H HH

H

H

HHH

H H H

CS2

CS2

CS2

CS2

CS2

CS2

CS2

1800 1400 1000(cmminus1)

1800 1400 1000(cmminus1)

1800 1400 1000(cmminus1)


300 400 500 600 700 8000

100

200

300

400

500

South AfricaSulcis

Pres

sure

(tor

r)

Temperature (∘C)

(a)

600∘C700∘C

800∘C

600∘C

700∘C

800∘C

CH4

CH4

CH4

CH4

CO

CO

C=C

C=C

Ethane

Ethane

HCN

HCN

A

A

3000 2000 1600 1200 800(cmminus1)

(b)



0 200 400 600 800

0

20

40

60

80

100Pr(i)=P(i)P

max

(i)(T

)

Temperature (∘C)

(CH3)COHCN

COCO2

(a)

0 200 400 600 8000

20

40

60

80

100

Pr(i)=P(i)P

max

(i)(T

)

Temperature (∘C)

(CH3)C=CH2

SO2

C2H4

COS

(b)


)2

CO HCN CO and CO2


)2

C=CH2

SO2

C2

H4


0 200 400 600 800

0

20

40

60

80

100

Pr(i)=P(i)P

max

(i)(T

)

Temperature (∘C)

COCO2

(CH3)2COHCN

(a)

0 200 400 600 800

0

20

40

60

80

100

Pr(i)=P(i)P

max

(i)(T

)

Temperature (∘C)

C2H4

CH3ndashCH=CH2

COS

(b)


(CH3

)2


2

H4

CH3

ndashCH=CH2








119903(119894)= 119875(119894)(119879119903)










2increases in



2) allows the



2O (8)


4 Conclusion




119903(119894)=



References









































3



and SO119909









2

CO2














RoboticsJournal of





Journal of



RotatingMachinery





VLSI Design



Shock and Vibration







Journal of



Volume 2014


SensorsJournal of





Propagation































1ndashC3alcohols







Sulcis


South Africa










0 100 200 300 400 500 600 700 800 9000

1

2

3

4

5

6C

onde

nsat

e (w

t)

Temperature (∘C)

South AfricaSulcis

(a)

0 100 200 300 400 500 600 700 800 900

00

05

10

15

20

25

Con

dens

ate (

wt

)

Temperature (∘C)

South AfricaSulcis

(b)


0 100 200 300 400 500 600 700 800 900

0

20

40

60

80

100

120

South AfricaSulcis

Pres

sure

(Tor

r)

Temperature (∘C)

(a)

0 100 200 300 400 500 600 700 800 9000

500

1000

1500

2000

2500

3000

3500

Pres

sure

(Tor

r)

Temperature (∘C)

South AfricaSulcis

(b)




2 COS SO

2 Me2CO CS

2 HCN Me

2C=CH

2 C2H4









2





Sulcis


South Africa









2O (1)


2to form NH

3[41]




2 and CS

2) and


2S is the




CH4+4

119909S119909997888rarr CS

2+ 2H2S (119879=500ndash700∘C)

CH4+2

119909S119909997888rarr CS

2+ 2H2(119879 gt 700

∘C)

S +O2997888rarr SO

2

3S + 2H2O 997888rarr SO

2+ 2H2S


2

(2)



8



2

H2S + CO

2997888rarr COS +H

2O

(3)


119899(1 le 119899 le 2)



2S or with the





2S

2SO2+ 4C 997888rarr 4CO + S

2

(4)




following reactions

C + 12O2997888rarr CO


2

C +O2997888rarr CO

2


2


2

(6)


25∘C

100∘C

300∘C

400∘C

500∘C

600∘C

700∘C

800∘C

NH3

NH3

NH3

NH3

AA

A

A

A

A

A

A

A

A

A

A

K

K

K

K K

K

K

K K

K

K

K

K

K

K

KK

K

K

K

K

H

H

H H

H

AH

AH

AH

NH3

NH3

NH3

KAH

AH

AH

H

H

H

1800 1000(cmminus1)





2(119879 gt 700

∘C)


2(119879 = 700ndash800∘C)


(7)


119898) than South



2 COS and CS







2


2from












200 400 600 800 1000 1200 1400 1600 1800 2000 2200 2400Time

Abun

danc

e

Nap

htha

lene

Benz

alde

hyde

p-Xy

lene

m

-Xyl

ene

Ethy

lben

zene

Phen

ol

1-Pe

ntan

ol

Tolu

ene

keto

nes

alco

hols

and

olefi

nsA

lipha

tic h

ydro

carb

ons

Benz

ene

5

10

15

20

25

30

35

40

45

50

55

times105

(a)

150 200 250 300 350 400 450Time

Abun

danc

e

Thio

phen

e

Benz

ene

Etha

nol

Prop

ane

Met

hano

lBu

tane

Acet

one

2-Pr

opan

ol

Pent

ane

2-Bu

tene

Hex

ane

MEK

3-Pe

ntan

one

2-M

ethy

lpro

pano

l

times105

2468

1012141618202224262830323436384042444648505254

(b)



100∘C

500∘C

600∘C

700∘C800∘C

200∘C

300∘C

400∘C

EEE

E E E

CO2 CO2

CO2

CO2

CO2

CO2

CO2

CO2

CO2

CO2

CO2

CO2

CO2

CO2

CO2

SO2

SO2

SO2

SO2

SO2

SO2

SO2K

KK

K

K

K

H

H

H

H H

H

HH

HH H

H

H

HH

H H HH

H

H

HHH

H H H

CS2

CS2

CS2

CS2

CS2

CS2

CS2

1800 1400 1000(cmminus1)

1800 1400 1000(cmminus1)

1800 1400 1000(cmminus1)


300 400 500 600 700 8000

100

200

300

400

500

South AfricaSulcis

Pres

sure

(tor

r)

Temperature (∘C)

(a)

600∘C700∘C

800∘C

600∘C

700∘C

800∘C

CH4

CH4

CH4

CH4

CO

CO

C=C

C=C

Ethane

Ethane

HCN

HCN

A

A

3000 2000 1600 1200 800(cmminus1)

(b)



0 200 400 600 800

0

20

40

60

80

100Pr(i)=P(i)P

max

(i)(T

)

Temperature (∘C)

(CH3)COHCN

COCO2

(a)

0 200 400 600 8000

20

40

60

80

100

Pr(i)=P(i)P

max

(i)(T

)

Temperature (∘C)

(CH3)C=CH2

SO2

C2H4

COS

(b)


)2

CO HCN CO and CO2


)2

C=CH2

SO2

C2

H4


0 200 400 600 800

0

20

40

60

80

100

Pr(i)=P(i)P

max

(i)(T

)

Temperature (∘C)

COCO2

(CH3)2COHCN

(a)

0 200 400 600 800

0

20

40

60

80

100

Pr(i)=P(i)P

max

(i)(T

)

Temperature (∘C)

C2H4

CH3ndashCH=CH2

COS

(b)


(CH3

)2


2

H4

CH3

ndashCH=CH2








119903(119894)= 119875(119894)(119879119903)










2increases in



2) allows the



2O (8)


4 Conclusion




119903(119894)=



References









































3



and SO119909









2

CO2














RoboticsJournal of





Journal of



RotatingMachinery





VLSI Design



Shock and Vibration







Journal of



Volume 2014


SensorsJournal of





Propagation












Sulcis


South Africa










0 100 200 300 400 500 600 700 800 9000

1

2

3

4

5

6C

onde

nsat

e (w

t)

Temperature (∘C)

South AfricaSulcis

(a)

0 100 200 300 400 500 600 700 800 900

00

05

10

15

20

25

Con

dens

ate (

wt

)

Temperature (∘C)

South AfricaSulcis

(b)


0 100 200 300 400 500 600 700 800 900

0

20

40

60

80

100

120

South AfricaSulcis

Pres

sure

(Tor

r)

Temperature (∘C)

(a)

0 100 200 300 400 500 600 700 800 9000

500

1000

1500

2000

2500

3000

3500

Pres

sure

(Tor

r)

Temperature (∘C)

South AfricaSulcis

(b)




2 COS SO

2 Me2CO CS

2 HCN Me

2C=CH

2 C2H4









2





Sulcis


South Africa









2O (1)


2to form NH

3[41]




2 and CS

2) and


2S is the




CH4+4

119909S119909997888rarr CS

2+ 2H2S (119879=500ndash700∘C)

CH4+2

119909S119909997888rarr CS

2+ 2H2(119879 gt 700

∘C)

S +O2997888rarr SO

2

3S + 2H2O 997888rarr SO

2+ 2H2S


2

(2)



8



2

H2S + CO

2997888rarr COS +H

2O

(3)


119899(1 le 119899 le 2)



2S or with the





2S

2SO2+ 4C 997888rarr 4CO + S

2

(4)




following reactions

C + 12O2997888rarr CO


2

C +O2997888rarr CO

2


2


2

(6)


25∘C

100∘C

300∘C

400∘C

500∘C

600∘C

700∘C

800∘C

NH3

NH3

NH3

NH3

AA

A

A

A

A

A

A

A

A

A

A

K

K

K

K K

K

K

K K

K

K

K

K

K

K

KK

K

K

K

K

H

H

H H

H

AH

AH

AH

NH3

NH3

NH3

KAH

AH

AH

H

H

H

1800 1000(cmminus1)





2(119879 gt 700

∘C)


2(119879 = 700ndash800∘C)


(7)


119898) than South



2 COS and CS







2


2from












200 400 600 800 1000 1200 1400 1600 1800 2000 2200 2400Time

Abun

danc

e

Nap

htha

lene

Benz

alde

hyde

p-Xy

lene

m

-Xyl

ene

Ethy

lben

zene

Phen

ol

1-Pe

ntan

ol

Tolu

ene

keto

nes

alco

hols

and

olefi

nsA

lipha

tic h

ydro

carb

ons

Benz

ene

5

10

15

20

25

30

35

40

45

50

55

times105

(a)

150 200 250 300 350 400 450Time

Abun

danc

e

Thio

phen

e

Benz

ene

Etha

nol

Prop

ane

Met

hano

lBu

tane

Acet

one

2-Pr

opan

ol

Pent

ane

2-Bu

tene

Hex

ane

MEK

3-Pe

ntan

one

2-M

ethy

lpro

pano

l

times105

2468

1012141618202224262830323436384042444648505254

(b)



100∘C

500∘C

600∘C

700∘C800∘C

200∘C

300∘C

400∘C

EEE

E E E

CO2 CO2

CO2

CO2

CO2

CO2

CO2

CO2

CO2

CO2

CO2

CO2

CO2

CO2

CO2

SO2

SO2

SO2

SO2

SO2

SO2

SO2K

KK

K

K

K

H

H

H

H H

H

HH

HH H

H

H

HH

H H HH

H

H

HHH

H H H

CS2

CS2

CS2

CS2

CS2

CS2

CS2

1800 1400 1000(cmminus1)

1800 1400 1000(cmminus1)

1800 1400 1000(cmminus1)


300 400 500 600 700 8000

100

200

300

400

500

South AfricaSulcis

Pres

sure

(tor

r)

Temperature (∘C)

(a)

600∘C700∘C

800∘C

600∘C

700∘C

800∘C

CH4

CH4

CH4

CH4

CO

CO

C=C

C=C

Ethane

Ethane

HCN

HCN

A

A

3000 2000 1600 1200 800(cmminus1)

(b)



0 200 400 600 800

0

20

40

60

80

100Pr(i)=P(i)P

max

(i)(T

)

Temperature (∘C)

(CH3)COHCN

COCO2

(a)

0 200 400 600 8000

20

40

60

80

100

Pr(i)=P(i)P

max

(i)(T

)

Temperature (∘C)

(CH3)C=CH2

SO2

C2H4

COS

(b)


)2

CO HCN CO and CO2


)2

C=CH2

SO2

C2

H4


0 200 400 600 800

0

20

40

60

80

100

Pr(i)=P(i)P

max

(i)(T

)

Temperature (∘C)

COCO2

(CH3)2COHCN

(a)

0 200 400 600 800

0

20

40

60

80

100

Pr(i)=P(i)P

max

(i)(T

)

Temperature (∘C)

C2H4

CH3ndashCH=CH2

COS

(b)


(CH3

)2


2

H4

CH3

ndashCH=CH2








119903(119894)= 119875(119894)(119879119903)










2increases in



2) allows the



2O (8)


4 Conclusion




119903(119894)=



References









































3



and SO119909









2

CO2














RoboticsJournal of





Journal of



RotatingMachinery





VLSI Design



Shock and Vibration







Journal of



Volume 2014


SensorsJournal of





Propagation










0 100 200 300 400 500 600 700 800 9000

1

2

3

4

5

6C

onde

nsat

e (w

t)

Temperature (∘C)

South AfricaSulcis

(a)

0 100 200 300 400 500 600 700 800 900

00

05

10

15

20

25

Con

dens

ate (

wt

)

Temperature (∘C)

South AfricaSulcis

(b)


0 100 200 300 400 500 600 700 800 900

0

20

40

60

80

100

120

South AfricaSulcis

Pres

sure

(Tor

r)

Temperature (∘C)

(a)

0 100 200 300 400 500 600 700 800 9000

500

1000

1500

2000

2500

3000

3500

Pres

sure

(Tor

r)

Temperature (∘C)

South AfricaSulcis

(b)




2 COS SO

2 Me2CO CS

2 HCN Me

2C=CH

2 C2H4









2





Sulcis


South Africa









2O (1)


2to form NH

3[41]




2 and CS

2) and


2S is the




CH4+4

119909S119909997888rarr CS

2+ 2H2S (119879=500ndash700∘C)

CH4+2

119909S119909997888rarr CS

2+ 2H2(119879 gt 700

∘C)

S +O2997888rarr SO

2

3S + 2H2O 997888rarr SO

2+ 2H2S


2

(2)



8



2

H2S + CO

2997888rarr COS +H

2O

(3)


119899(1 le 119899 le 2)



2S or with the





2S

2SO2+ 4C 997888rarr 4CO + S

2

(4)




following reactions

C + 12O2997888rarr CO


2

C +O2997888rarr CO

2


2


2

(6)


25∘C

100∘C

300∘C

400∘C

500∘C

600∘C

700∘C

800∘C

NH3

NH3

NH3

NH3

AA

A

A

A

A

A

A

A

A

A

A

K

K

K

K K

K

K

K K

K

K

K

K

K

K

KK

K

K

K

K

H

H

H H

H

AH

AH

AH

NH3

NH3

NH3

KAH

AH

AH

H

H

H

1800 1000(cmminus1)





2(119879 gt 700

∘C)


2(119879 = 700ndash800∘C)


(7)


119898) than South



2 COS and CS







2


2from












200 400 600 800 1000 1200 1400 1600 1800 2000 2200 2400Time

Abun

danc

e

Nap

htha

lene

Benz

alde

hyde

p-Xy

lene

m

-Xyl

ene

Ethy

lben

zene

Phen

ol

1-Pe

ntan

ol

Tolu

ene

keto

nes

alco

hols

and

olefi

nsA

lipha

tic h

ydro

carb

ons

Benz

ene

5

10

15

20

25

30

35

40

45

50

55

times105

(a)

150 200 250 300 350 400 450Time

Abun

danc

e

Thio

phen

e

Benz

ene

Etha

nol

Prop

ane

Met

hano

lBu

tane

Acet

one

2-Pr

opan

ol

Pent

ane

2-Bu

tene

Hex

ane

MEK

3-Pe

ntan

one

2-M

ethy

lpro

pano

l

times105

2468

1012141618202224262830323436384042444648505254

(b)



100∘C

500∘C

600∘C

700∘C800∘C

200∘C

300∘C

400∘C

EEE

E E E

CO2 CO2

CO2

CO2

CO2

CO2

CO2

CO2

CO2

CO2

CO2

CO2

CO2

CO2

CO2

SO2

SO2

SO2

SO2

SO2

SO2

SO2K

KK

K

K

K

H

H

H

H H

H

HH

HH H

H

H

HH

H H HH

H

H

HHH

H H H

CS2

CS2

CS2

CS2

CS2

CS2

CS2

1800 1400 1000(cmminus1)

1800 1400 1000(cmminus1)

1800 1400 1000(cmminus1)


300 400 500 600 700 8000

100

200

300

400

500

South AfricaSulcis

Pres

sure

(tor

r)

Temperature (∘C)

(a)

600∘C700∘C

800∘C

600∘C

700∘C

800∘C

CH4

CH4

CH4

CH4

CO

CO

C=C

C=C

Ethane

Ethane

HCN

HCN

A

A

3000 2000 1600 1200 800(cmminus1)

(b)



0 200 400 600 800

0

20

40

60

80

100Pr(i)=P(i)P

max

(i)(T

)

Temperature (∘C)

(CH3)COHCN

COCO2

(a)

0 200 400 600 8000

20

40

60

80

100

Pr(i)=P(i)P

max

(i)(T

)

Temperature (∘C)

(CH3)C=CH2

SO2

C2H4

COS

(b)


)2

CO HCN CO and CO2


)2

C=CH2

SO2

C2

H4


0 200 400 600 800

0

20

40

60

80

100

Pr(i)=P(i)P

max

(i)(T

)

Temperature (∘C)

COCO2

(CH3)2COHCN

(a)

0 200 400 600 800

0

20

40

60

80

100

Pr(i)=P(i)P

max

(i)(T

)

Temperature (∘C)

C2H4

CH3ndashCH=CH2

COS

(b)


(CH3

)2


2

H4

CH3

ndashCH=CH2








119903(119894)= 119875(119894)(119879119903)










2increases in



2) allows the



2O (8)


4 Conclusion




119903(119894)=



References









































3



and SO119909









2

CO2














RoboticsJournal of





Journal of



RotatingMachinery





VLSI Design



Shock and Vibration







Journal of



Volume 2014


SensorsJournal of





Propagation












Sulcis


South Africa









2O (1)


2to form NH

3[41]




2 and CS

2) and


2S is the




CH4+4

119909S119909997888rarr CS

2+ 2H2S (119879=500ndash700∘C)

CH4+2

119909S119909997888rarr CS

2+ 2H2(119879 gt 700

∘C)

S +O2997888rarr SO

2

3S + 2H2O 997888rarr SO

2+ 2H2S


2

(2)



8



2

H2S + CO

2997888rarr COS +H

2O

(3)


119899(1 le 119899 le 2)



2S or with the





2S

2SO2+ 4C 997888rarr 4CO + S

2

(4)




following reactions

C + 12O2997888rarr CO


2

C +O2997888rarr CO

2


2


2

(6)


25∘C

100∘C

300∘C

400∘C

500∘C

600∘C

700∘C

800∘C

NH3

NH3

NH3

NH3

AA

A

A

A

A

A

A

A

A

A

A

K

K

K

K K

K

K

K K

K

K

K

K

K

K

KK

K

K

K

K

H

H

H H

H

AH

AH

AH

NH3

NH3

NH3

KAH

AH

AH

H

H

H

1800 1000(cmminus1)





2(119879 gt 700

∘C)


2(119879 = 700ndash800∘C)


(7)


119898) than South



2 COS and CS







2


2from












200 400 600 800 1000 1200 1400 1600 1800 2000 2200 2400Time

Abun

danc

e

Nap

htha

lene

Benz

alde

hyde

p-Xy

lene

m

-Xyl

ene

Ethy

lben

zene

Phen

ol

1-Pe

ntan

ol

Tolu

ene

keto

nes

alco

hols

and

olefi

nsA

lipha

tic h

ydro

carb

ons

Benz

ene

5

10

15

20

25

30

35

40

45

50

55

times105

(a)

150 200 250 300 350 400 450Time

Abun

danc

e

Thio

phen

e

Benz

ene

Etha

nol

Prop

ane

Met

hano

lBu

tane

Acet

one

2-Pr

opan

ol

Pent

ane

2-Bu

tene

Hex

ane

MEK

3-Pe

ntan

one

2-M

ethy

lpro

pano

l

times105

2468

1012141618202224262830323436384042444648505254

(b)



100∘C

500∘C

600∘C

700∘C800∘C

200∘C

300∘C

400∘C

EEE

E E E

CO2 CO2

CO2

CO2

CO2

CO2

CO2

CO2

CO2

CO2

CO2

CO2

CO2

CO2

CO2

SO2

SO2

SO2

SO2

SO2

SO2

SO2K

KK

K

K

K

H

H

H

H H

H

HH

HH H

H

H

HH

H H HH

H

H

HHH

H H H

CS2

CS2

CS2

CS2

CS2

CS2

CS2

1800 1400 1000(cmminus1)

1800 1400 1000(cmminus1)

1800 1400 1000(cmminus1)


300 400 500 600 700 8000

100

200

300

400

500

South AfricaSulcis

Pres

sure

(tor

r)

Temperature (∘C)

(a)

600∘C700∘C

800∘C

600∘C

700∘C

800∘C

CH4

CH4

CH4

CH4

CO

CO

C=C

C=C

Ethane

Ethane

HCN

HCN

A

A

3000 2000 1600 1200 800(cmminus1)

(b)



0 200 400 600 800

0

20

40

60

80

100Pr(i)=P(i)P

max

(i)(T

)

Temperature (∘C)

(CH3)COHCN

COCO2

(a)

0 200 400 600 8000

20

40

60

80

100

Pr(i)=P(i)P

max

(i)(T

)

Temperature (∘C)

(CH3)C=CH2

SO2

C2H4

COS

(b)


)2

CO HCN CO and CO2


)2

C=CH2

SO2

C2

H4


0 200 400 600 800

0

20

40

60

80

100

Pr(i)=P(i)P

max

(i)(T

)

Temperature (∘C)

COCO2

(CH3)2COHCN

(a)

0 200 400 600 800

0

20

40

60

80

100

Pr(i)=P(i)P

max

(i)(T

)

Temperature (∘C)

C2H4

CH3ndashCH=CH2

COS

(b)


(CH3

)2


2

H4

CH3

ndashCH=CH2








119903(119894)= 119875(119894)(119879119903)










2increases in



2) allows the



2O (8)


4 Conclusion




119903(119894)=



References









































3



and SO119909









2

CO2














RoboticsJournal of





Journal of



RotatingMachinery





VLSI Design



Shock and Vibration







Journal of



Volume 2014


SensorsJournal of





Propagation










25∘C

100∘C

300∘C

400∘C

500∘C

600∘C

700∘C

800∘C

NH3

NH3

NH3

NH3

AA

A

A

A

A

A

A

A

A

A

A

K

K

K

K K

K

K

K K

K

K

K

K

K

K

KK

K

K

K

K

H

H

H H

H

AH

AH

AH

NH3

NH3

NH3

KAH

AH

AH

H

H

H

1800 1000(cmminus1)





2(119879 gt 700

∘C)


2(119879 = 700ndash800∘C)


(7)


119898) than South



2 COS and CS







2


2from












200 400 600 800 1000 1200 1400 1600 1800 2000 2200 2400Time

Abun

danc

e

Nap

htha

lene

Benz

alde

hyde

p-Xy

lene

m

-Xyl

ene

Ethy

lben

zene

Phen

ol

1-Pe

ntan

ol

Tolu

ene

keto

nes

alco

hols

and

olefi

nsA

lipha

tic h

ydro

carb

ons

Benz

ene

5

10

15

20

25

30

35

40

45

50

55

times105

(a)

150 200 250 300 350 400 450Time

Abun

danc

e

Thio

phen

e

Benz

ene

Etha

nol

Prop

ane

Met

hano

lBu

tane

Acet

one

2-Pr

opan

ol

Pent

ane

2-Bu

tene

Hex

ane

MEK

3-Pe

ntan

one

2-M

ethy

lpro

pano

l

times105

2468

1012141618202224262830323436384042444648505254

(b)



100∘C

500∘C

600∘C

700∘C800∘C

200∘C

300∘C

400∘C

EEE

E E E

CO2 CO2

CO2

CO2

CO2

CO2

CO2

CO2

CO2

CO2

CO2

CO2

CO2

CO2

CO2

SO2

SO2

SO2

SO2

SO2

SO2

SO2K

KK

K

K

K

H

H

H

H H

H

HH

HH H

H

H

HH

H H HH

H

H

HHH

H H H

CS2

CS2

CS2

CS2

CS2

CS2

CS2

1800 1400 1000(cmminus1)

1800 1400 1000(cmminus1)

1800 1400 1000(cmminus1)


300 400 500 600 700 8000

100

200

300

400

500

South AfricaSulcis

Pres

sure

(tor

r)

Temperature (∘C)

(a)

600∘C700∘C

800∘C

600∘C

700∘C

800∘C

CH4

CH4

CH4

CH4

CO

CO

C=C

C=C

Ethane

Ethane

HCN

HCN

A

A

3000 2000 1600 1200 800(cmminus1)

(b)



0 200 400 600 800

0

20

40

60

80

100Pr(i)=P(i)P

max

(i)(T

)

Temperature (∘C)

(CH3)COHCN

COCO2

(a)

0 200 400 600 8000

20

40

60

80

100

Pr(i)=P(i)P

max

(i)(T

)

Temperature (∘C)

(CH3)C=CH2

SO2

C2H4

COS

(b)


)2

CO HCN CO and CO2


)2

C=CH2

SO2

C2

H4


0 200 400 600 800

0

20

40

60

80

100

Pr(i)=P(i)P

max

(i)(T

)

Temperature (∘C)

COCO2

(CH3)2COHCN

(a)

0 200 400 600 800

0

20

40

60

80

100

Pr(i)=P(i)P

max

(i)(T

)

Temperature (∘C)

C2H4

CH3ndashCH=CH2

COS

(b)


(CH3

)2


2

H4

CH3

ndashCH=CH2








119903(119894)= 119875(119894)(119879119903)










2increases in



2) allows the



2O (8)


4 Conclusion




119903(119894)=



References









































3



and SO119909









2

CO2














RoboticsJournal of





Journal of



RotatingMachinery





VLSI Design



Shock and Vibration







Journal of



Volume 2014


SensorsJournal of





Propagation










200 400 600 800 1000 1200 1400 1600 1800 2000 2200 2400Time

Abun

danc

e

Nap

htha

lene

Benz

alde

hyde

p-Xy

lene

m

-Xyl

ene

Ethy

lben

zene

Phen

ol

1-Pe

ntan

ol

Tolu

ene

keto

nes

alco

hols

and

olefi

nsA

lipha

tic h

ydro

carb

ons

Benz

ene

5

10

15

20

25

30

35

40

45

50

55

times105

(a)

150 200 250 300 350 400 450Time

Abun

danc

e

Thio

phen

e

Benz

ene

Etha

nol

Prop

ane

Met

hano

lBu

tane

Acet

one

2-Pr

opan

ol

Pent

ane

2-Bu

tene

Hex

ane

MEK

3-Pe

ntan

one

2-M

ethy

lpro

pano

l

times105

2468

1012141618202224262830323436384042444648505254

(b)



100∘C

500∘C

600∘C

700∘C800∘C

200∘C

300∘C

400∘C

EEE

E E E

CO2 CO2

CO2

CO2

CO2

CO2

CO2

CO2

CO2

CO2

CO2

CO2

CO2

CO2

CO2

SO2

SO2

SO2

SO2

SO2

SO2

SO2K

KK

K

K

K

H

H

H

H H

H

HH

HH H

H

H

HH

H H HH

H

H

HHH

H H H

CS2

CS2

CS2

CS2

CS2

CS2

CS2

1800 1400 1000(cmminus1)

1800 1400 1000(cmminus1)

1800 1400 1000(cmminus1)


300 400 500 600 700 8000

100

200

300

400

500

South AfricaSulcis

Pres

sure

(tor

r)

Temperature (∘C)

(a)

600∘C700∘C

800∘C

600∘C

700∘C

800∘C

CH4

CH4

CH4

CH4

CO

CO

C=C

C=C

Ethane

Ethane

HCN

HCN

A

A

3000 2000 1600 1200 800(cmminus1)

(b)



0 200 400 600 800

0

20

40

60

80

100Pr(i)=P(i)P

max

(i)(T

)

Temperature (∘C)

(CH3)COHCN

COCO2

(a)

0 200 400 600 8000

20

40

60

80

100

Pr(i)=P(i)P

max

(i)(T

)

Temperature (∘C)

(CH3)C=CH2

SO2

C2H4

COS

(b)


)2

CO HCN CO and CO2


)2

C=CH2

SO2

C2

H4


0 200 400 600 800

0

20

40

60

80

100

Pr(i)=P(i)P

max

(i)(T

)

Temperature (∘C)

COCO2

(CH3)2COHCN

(a)

0 200 400 600 800

0

20

40

60

80

100

Pr(i)=P(i)P

max

(i)(T

)

Temperature (∘C)

C2H4

CH3ndashCH=CH2

COS

(b)


(CH3

)2


2

H4

CH3

ndashCH=CH2








119903(119894)= 119875(119894)(119879119903)










2increases in



2) allows the



2O (8)


4 Conclusion




119903(119894)=



References









































3



and SO119909









2

CO2














RoboticsJournal of





Journal of



RotatingMachinery





VLSI Design



Shock and Vibration







Journal of



Volume 2014


SensorsJournal of





Propagation










100∘C

500∘C

600∘C

700∘C800∘C

200∘C

300∘C

400∘C

EEE

E E E

CO2 CO2

CO2

CO2

CO2

CO2

CO2

CO2

CO2

CO2

CO2

CO2

CO2

CO2

CO2

SO2

SO2

SO2

SO2

SO2

SO2

SO2K

KK

K

K

K

H

H

H

H H

H

HH

HH H

H

H

HH

H H HH

H

H

HHH

H H H

CS2

CS2

CS2

CS2

CS2

CS2

CS2

1800 1400 1000(cmminus1)

1800 1400 1000(cmminus1)

1800 1400 1000(cmminus1)


300 400 500 600 700 8000

100

200

300

400

500

South AfricaSulcis

Pres

sure

(tor

r)

Temperature (∘C)

(a)

600∘C700∘C

800∘C

600∘C

700∘C

800∘C

CH4

CH4

CH4

CH4

CO

CO

C=C

C=C

Ethane

Ethane

HCN

HCN

A

A

3000 2000 1600 1200 800(cmminus1)

(b)



0 200 400 600 800

0

20

40

60

80

100Pr(i)=P(i)P

max

(i)(T

)

Temperature (∘C)

(CH3)COHCN

COCO2

(a)

0 200 400 600 8000

20

40

60

80

100

Pr(i)=P(i)P

max

(i)(T

)

Temperature (∘C)

(CH3)C=CH2

SO2

C2H4

COS

(b)


)2

CO HCN CO and CO2


)2

C=CH2

SO2

C2

H4


0 200 400 600 800

0

20

40

60

80

100

Pr(i)=P(i)P

max

(i)(T

)

Temperature (∘C)

COCO2

(CH3)2COHCN

(a)

0 200 400 600 800

0

20

40

60

80

100

Pr(i)=P(i)P

max

(i)(T

)

Temperature (∘C)

C2H4

CH3ndashCH=CH2

COS

(b)


(CH3

)2


2

H4

CH3

ndashCH=CH2








119903(119894)= 119875(119894)(119879119903)










2increases in



2) allows the



2O (8)


4 Conclusion




119903(119894)=



References









































3



and SO119909









2

CO2














RoboticsJournal of





Journal of



RotatingMachinery





VLSI Design



Shock and Vibration







Journal of



Volume 2014


SensorsJournal of





Propagation










0 200 400 600 800

0

20

40

60

80

100Pr(i)=P(i)P

max

(i)(T

)

Temperature (∘C)

(CH3)COHCN

COCO2

(a)

0 200 400 600 8000

20

40

60

80

100

Pr(i)=P(i)P

max

(i)(T

)

Temperature (∘C)

(CH3)C=CH2

SO2

C2H4

COS

(b)


)2

CO HCN CO and CO2


)2

C=CH2

SO2

C2

H4


0 200 400 600 800

0

20

40

60

80

100

Pr(i)=P(i)P

max

(i)(T

)

Temperature (∘C)

COCO2

(CH3)2COHCN

(a)

0 200 400 600 800

0

20

40

60

80

100

Pr(i)=P(i)P

max

(i)(T

)

Temperature (∘C)

C2H4

CH3ndashCH=CH2

COS

(b)


(CH3

)2


2

H4

CH3

ndashCH=CH2








119903(119894)= 119875(119894)(119879119903)










2increases in



2) allows the



2O (8)


4 Conclusion




119903(119894)=



References









































3



and SO119909









2

CO2














RoboticsJournal of





Journal of



RotatingMachinery





VLSI Design



Shock and Vibration







Journal of



Volume 2014


SensorsJournal of





Propagation











119903(119894)= 119875(119894)(119879119903)










2increases in



2) allows the



2O (8)


4 Conclusion




119903(119894)=



References









































3



and SO119909









2

CO2














RoboticsJournal of





Journal of



RotatingMachinery





VLSI Design



Shock and Vibration







Journal of



Volume 2014


SensorsJournal of





Propagation





































3



and SO119909









2

CO2














RoboticsJournal of





Journal of



RotatingMachinery





VLSI Design



Shock and Vibration







Journal of



Volume 2014


SensorsJournal of





Propagation





















RoboticsJournal of





Journal of



RotatingMachinery





VLSI Design



Shock and Vibration







Journal of



Volume 2014


SensorsJournal of





Propagation









research article ft-ir investigation of the structural

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