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This paper demonstrates that the exclusive aromatic character of high temperature tar, is not only due to the disappearance, by post-cracking, of the paraffinic fraction of primary tars. The main pathway to aromatic compounds formation is the Diels-Alder reaction on short chain olefins, mainly butadiene and propene. Radiochromatography was used to determine the radio-active content of each of the cracking products.
This paper demonstrates that the exclusive aromatic character of high temperature tar, is not only due to the disappearance, by post-cracking, of the paraffinic fraction of primary tars. The main pathway to aromatic compounds formation is the Diels-Alder reaction on short chain olefins, mainly butadiene and propene. Radiochromatography was used to determine the radio-active content of each of the cracking products.
This paper demonstrates that the exclusive aromatic character of high temperature tar, is not only due to the disappearance, by post-cracking, of the paraffinic fraction of primary tars. The main pathway to aromatic compounds formation is the Diels-Alder reaction on short chain olefins, mainly butadiene and propene. Radiochromatography was used to determine the radio-active content of each of the cracking products.
El s e vi e r Sci ence Pu b l i s h e r s B. V. , Ams t e r d a m - P r i n t e d i n T h e Ne t h e r l a n d s
AROMATICHYDROCARBONSFORMATIONDURINGCOALPYROLYSIS Professor R. CYPRES Department of Carbochemistry, Universit~ libre de Bruxelles, Avenue F.D. Roose- velt 50, B-1050 Bruxelles (Belgium). SUMMARY The present paper demonstrates that the exclusive aromatic character of high temperature tar, is not only due to the disappearance, by post-cracking, of the paraffinic fraction of primary tars, but that cracking reactions contribute to form mono- and polycyclic aromatics. Aromatisation of the neutral and acid oil fractions of low temperature tar, was studied. The main pathway to aromatic compounds formation is the Diels-Alder reaction on short chain olefins, mainly butadiene and propene. The olefins are formed by post-cracking reactions of long chain paraffins in the primary tars and of cyclopentadiene, which is one of the primary cracking products of the phenols. These mechanisms were demonstrated by the cracking of pure compounds to investigate their fate in the post-cracking reactions occurring during coal carbonization. N-decane was chosen as representative of long chain aliphatics and 1,3-butadiene, 1-butene and iso-butene for the short chain olefins. Phenols, labelled in specific position by carbon 14 and tritium, were cracked. Radiochromatography was used to determine the radio-active content of each of the cracking products. Cyclopentadiene and COare the primary cracking pro- ducts of phenols. Cyclopentadiene is not stable at phenols' cracking tempera- tures. Direct formation of naphthalene from cyclopentadiene was observed at temperatures as low as 550C. Fragments of the cyclopenta~nylradical undergo Diels-Alder reaction to form light aromatics. I. INTRODUCTION Most of the loss in weight during coal carbonization is completed at tempe- ratures much lower than that attained in coke oven retorts. The composition of the primary tar is very different from that of high temperature tar. Post- cracking reactions or secondary reactions occur when the primary volatile mat- ter passes through the hot coke and along the hot walls. Donald MacNeil (ref. 1) gave a general discussion on the characteristics of low and high temperature tar. Not only does the tar yield fall with increasing carbonization temperature, but the properties of tar change markedly. The pitch yield increases from 20-30 % to 60-70 %, the tar acid content falls from 20-25 % to 1.5-4 %. Post-cracking reactions are also the cause of increase in aromaticity, disappearance of aliphatic hydrocarbons, decrease of the ratio of substituted to unsubstituted aromatics and phenols,in high temperature tars. 0378- 3820/ 87/ $03. 50 1987 El s e vi e r Sci ence Pu b l i s h e r s B. V. The reactions accounting for these changes are globally attributed to cracking reactions as dealkylation, dehydroxylation of phenols, dehydrogenation of hydroaromatics and cycloparaffins, etc. Cracking is responsible for the soot formation, a sort of carbon black present in high temperature tars. The goal of this paper is to demonstrate that the mechanisms of the post- cracking of paraffins and phenols from the primary tars, lead to the formation of single ring aromatics as well as condensed polycyclic aromatics. Not only is the aromaticity of high temperature tars due to the disappearance of alipha- tics and of an important fraction of phenols, but also to the formation of aro- matics at high temperature. 2. CRACKINGOFTHEPARAFFINS Literature on paraffinic hydrocarbons cracking is very abundant especially because of its interest in petroleum industry. The content of aliphatic hydrocarbons in coal and primary tars has also been often discussed. It has been in the last years taken up again by numerous researchers, amongst whom Ladner (ref. 2) and Calkins (refs. 3-4). The l atter demonstrated the presence of polymethylenic chains in coal. It was shown that their concentration in coal correlated with the observed yields of ethylene, propylene and butadiene on flash pyrolysis of the coal at 850C and 0.5 s con- tact time. At 600C or lower, the tars produced by flash pyrolysis contained the polymethylene precursors of the ethylene, propylene and butadiene. These polymethylene compounds were identified as a series of n-olefin-paraffin pairs from molecular weight C14-C26 and even higher. Calkins found that certain coals, as the Cannel coal, contain up to 18 % of (-CH2-) n. The amounts reported by other researchers have been generally much less than those figures. Calkins attributes this to the fact that most of the polymethylene is chemically bound or trapped and non-extractable. Kossiakov and Rice (ref. 5) have formulated a theory, based on their experimen- tal results, of long chain paraffin thermal cracking. They have shown that the primary mechanism is a free-radical reaction following the scheme R CH2 - CH2 CH2 - R' R"" - - R - CH2 - CH- CH2 - R' + R"H R - CN2 - CH- CH2 - R' ~ R - CH2 - CH= CH2 + R" The paraffin molecule looses a H" radical, which is extracted by an already formed R"" radical. The secondary radical, which has the dimension of the original molecule, decomposes in a small new radical R'' and an olefin. The chain reaction continues. Depending on reaction temperatures, the formed ole- fin is stable or not. With increasing temperature cracking continues and tends to accumulate olefins in C2, C 3 and C 4. Kossiakov and Rice have demonstrated that radical decomposition reactions are much more rapid than bi-molecular reactions. The loss of hydrogen occurs on CH2 and not on CH3. The so formed radical decomposes by rupture in 8 position with respect to the C bearing the unpaired electrons. In our laboratory much work was done on thermal cracking of n-decane by Bredael (refs. 6-7) for the long chain aliphatics and on butane and isobutene (ref. 8) for the short chain ones. The results obtained are in agreement with Kossiakov and Rice's theory. But the contribution of Bredael and other researchers in our i nst i t ut e is important with respect to the formation of aromatic hydrocar- bons. I t was shown that the l at t er are formed at temperatures above 700C for 2 s contact time, or lower temperatures with increasing contact time, by Diels- Alder reactions between the l i ght olefins formed by successive cracking of the paraffins. There is no cycl i zati on of aliphatics to cycloparaffins which would be dehydrogenated to aromatics. Fig. 1 shows the pyrolysis of n-decane, as a function of temperature, for 2 seconds contact time. 100 G ~G INJ. 600 700 800 900 C 50 G ~G INJ. LI(~UID OLEFIN S f ARC)MATIC~ 600 700 800 900 C Fig. 1. n-Decane pyrolysis (2 s C.T.). Fi g. 2 gi ves the molar yi el ds of aromatics f or i sothermal cracki ng at 850C, wi t h i ncreasi ng cont act t i me. Table I gi ves the molar y i e l d of the l i g h t cracki ng products of n-decane, bet - ween 600C and 900C f or 2 s cont act ti me. The concent rat i on of l i g h t ol ef i ns i ncreases wi t h temperature. At 900C onl y et hyl ene remains i mport ant not wi t hst andi ng i t s concent rat i on i s decreasing mar- kedl y between 825 and 900C. The ol ef i ns from pentene to nonene are al l pre- sent at l ower temperature. Thei r concent rat i on i s decreasi ng wi t h i ncreasi ng temperature. They have disappeared at 825C. Cycl ool ef i ns ( l , 3- cycl ohexadi ene, 1, 3-cycl opent adi ene and 4- met hyl - l - cycl ohexene) have been detected but di sap- peared r api dl y , whi l e the aromati cs are formed. The f ol l owi ng schema gi ves the mechanisms of f ormat i on of benzene, tol uene and al kyl ar omat i cs by Di el s- Al der r eact i on wi t h the l i g h t ol ef i ns, produced by the thermal degradati on of the alkanes : ( + l, - 0 O - - O Besides the monocyclic aromat i cs, naphthalene and al kyl - napht hal ene are formed, as seen on Fi g. 2. Condensation react i ons may cont i nue. This i s the mechanism f or the f ormat i on of hi gher condensed pol ycycl i c molecules and of the pi t ch. 1,3-butadi ene pl ays an i mport ant r ol e i n the f ormat i on of C 6 cycl ool ef i ns. To demonstrate t hi s , we have cracked pure butane, 1-butene and 1,3-butadi ene i n an i ner t gas stream. As shown i n Fi g. 3, high y i el ds of aromati cs are produced. The l i q u i d phase amounts to 60 % i n wei ght of i nj ect ed butadi ene. The curves of but adi ene' s disappearance and aromatics f ormat i on are symmet ri cal . The p r i - mary compounds of the B.T.X. f ormat i on are vi nyl cycl ohexene and ethyl benzene. Cracking of l -but ene y i el ds l ess l i q u i d phase. 3. PHENOL'S CONTRIBUTION TO AROMATIC HYDROCARBONS FORMATION Much work was done i n our i n s t i t u t e on the cracki ng of phenols. The f i r s t goal was to study the v al or i s at i on of hi gher phenols from low temperature t ar s ( r ef s. 9-10) by t h e i r sel ect i ve degradati on i nt o cresol s and phenol. The second was to study the mechanisms of t hei r aromati c r i ng opening, and t h e i r Fig. 2. lO M ~ M INd. B E N Z E N E ~.~ NAPHTHALENE STYRENE / ~ A TOLU ENE / ~ / D I M E T H Y L N A P H T H A - / f ~ LENES / J - ~ I N D E N E . / / / / ~~ ~'-'METHYLNAPHTHA- . . , L E N E S l 2 3 C.T.(S) Isothermal n-decane cracking (T= 850C). TABLE I . Molar yi el d of l i ght cracking products of n-decane f or 2 s C.T. (M per i00 M i nj ect ed). H 2 CH4 C2H6 C2H 4 C3H8 C3H6 C4H10 1-C4H 8 1,3-C4H 6 1-C5H10 I-C6H12 1-C7H14 1-C8H16 1-C9H18 Benzene Toluene n-CIoH22 600C 650C 725C 825C 900C 1.3 4.4 4.8 6.8 0.3 2.7 2.5 2.5 2.4 1.9 1.7 0.8 89.3 4.4 19.2 16.1 35.8 0.9 14.3 7.9 24.7 65.2 28.5 143.0 0.7 54.9 16.2 72.2 195.1 18.2 206.4 17.1 1.5 0.5 4.9 7.5 4.1 3.7 1.4 64.5 6.9 10.1 6.3 2.5 1.3 1.2 0.5 - 9.3 - 4.2 21.2 145.3 192.7 2.4 129.4 8.1 1.4 14.8 6.1 I00 80 60 40 20 400 G 9~G INJ. ~ ~ ~ LIQUID / ' ~ ~ . ~ G A S / \~ 3.BUTAD IENE / / ,, . . . 600 800 TC I00 80 60 40 20 400 G ~ G (LIQ.) CS 60O 800 Toc 25 20 15 I0 G~G INd. C 600 BENZENE ETHYLENE 800 900 TC Fi 9 . 3. Cracking of C4 ol ef i ns . A. Cracking of 1,3-butadi ene : Ponderal y i e l d . B. Cracking of 1,3-butadi ene : Composition of the l i qui d phase. C. Cracking of 1-butene : Ethyl ene, propene and benzene y i el ds . cont r i but i on to the f ormat i on of monocyclic and condensed pol ycycl i c aromati c hydrocarbons. Cracking was performed i n i ner t gas at atmospheric pressure and al so under hydrogen pressure. Phenols are stable up to 700C and contact times not exceed- ing 2 seconds. Their main cracking products are, in the l i qui d phase, benzene, toluene, phenol and naphthalene, and in the gas phase, CO, H 2 and CH 4. The cracking mechanism is generally described as a combination of dehydroxylation and deal kylation of the higher phenols, and secondary reactions between water and CH 3" radicals, giving CO, H 2 and CH 4. Experimental cracking results show that CO is also formed in i nert gas cracking of C6H5OH. CO appears as to be the most abundant primary product in that case. This cannot be explained by dehydroxylation and dealkylation reactions. one sees that the cracking reactions of C6H50H into C6H 6 + H20 + CO H I-OH or b6n4....CH 3 into C6H50H + CH 4 + CO or C6HsCH 3 + H20 or C6H 6 + CH 4 + H20 ---OH Considering C6HsOH and C6H4__.CH3, are not balanced i f no hydrogen is present, what is the case~in cracking in a stream of i nert gas. Deal kylation and dehydroxylation are not primary mecha- nisms. With C6H5OH, CO detected at low cracking yi el ds, has to come from the aromatic ring. The molecule has also to provide the hydrogen necessary to give CH4, H20, C6H 6, etc. We have f i r st studied the thermal evolution of the primary products, detec- ted low cracking yi el ds, and followed the formation of secondary molecules, which represent the main cracking products, as a function of temperature and contact time, in i nert gas. As to show in which position of the starting molecule cracking occurs, phenols labelled in specific position by carbon 14 and tri ti um were used (refs. 11-13). The radi oacti vi ty of the cracking products is measured by radiochromatography. The radioactive 3H and 14C content (R.C.) in the cracking products is expressed as R.C. = molar speci fi c act i vi t y of product X in mCi/mole molar specific act i vi t y of the labelled phenol mCi/mole Cracking of C6H5-OH at low conversion yi el ds, showed that the primary compounds formed are cyclopentadiene, dibenzofurane and water, in the l i qui d phase and CO and H 2 in the gas phase. With increasing conversion only CO and H 2 are increas- ing, while cyclopentadiene and dibenzofurane remain in low concentration. The primary mechanism of phenols cracking is the simultaneous formation of CO and cyclopentadiene given by the reaction ~ H ~ + CO . H H H H With i ncreasi ng temperature phenol proceeds from the enol to the ketone form. This leads to the r upt ur e of the cycl e wi t h CO el i mi nat i on from the carbon i beadng the hydroxyl group, and f ormat i on of a cycl opent adi enyl r adi cal gi vi ng small amounts of cycl opentadi ene. This was demonstrated by l abel l i ng the phe- nol s i n d i f f e r e n t speci f i c posi t i ons, as shown on Fi g. 4. 6 ' I -"C : a ~ | (~ + 0 ' I i 2 - " c ~ " " : C O + ] " I . , : + t Cl l , 4-"C I II~ I - " C CII, F.i~.. 4. CO and C.P.D. f ormat i on. For the 1-14C phenol or p-cresol, the radioactive content (R.C.) of COis equal nearly to 1 and that of cyciopentadiene is 0., meaning that the t ot al i t y of the radi oacti vi ty from 14C in the phenol is found back in CO. Cyclopentadiene is not radioactive in that case. I f the carbon in position 2 is labelled, 2-14C phenol, j ust the contrary was measured : COwas not radioactive and cyclo- pentadiene had the same specific radi oacti vi ty as the phenol. The resonance between the enolic and ketonic form of the phenols, was demons- 9 trated by tritium transfer from the hydroxyl group, labelled as OT(T = ~H) to the o- and p-positions. Cracki.ng of C6H50T gave cyclopentadiene, whose R.C. was 1. All the T atoms, from -OT, have migrated on the carbons 2 and 4, before cracking. As only small quantities of cyclopentadiene are formed in the cracking pro- ducts, whereas the COconcentration increases regularly with cracking yields, i t had to be proved that cyclopentadiene is unstable in the experimental condi- tions at which phenols begin to crack, and also that the cracking products from cyclopentadiene are the same as those from phenols (benzene, toluene, naphtha- lene, indene, etc.). This was confirmed by studying the thermal behaviour of pure cyclopentadiene, as discussed in the fourth part of this paper. The second primary reaction in phenols cracking is the formation of small amounts of dibenzofurane (D.B.F.). The reaction is + ~ H20 + + H 2 Hydrogen becomes available for secondary dealkylation and dehydroxylation reac- tions. Carbon 14, R.C. measured in D.B.F. was always twice that of the phenols. The tritium R.C. of the water for C6H50T crackings, decreased from 1.2 at 665C to 0.5 at 865C. It should be 2, according to the above reaction. This is due to the isotopic exchange between tritium from -OT and the H atoms from the aro- matic ring, which reduces the T content of the hydroxyl group. At higher tem- peratures secondary water formation with non-radioactive hydrogen reduces the R.C. of the water to 0.5 at 865C. The D.B.F. formation is always low, and more or less constant, with increas- ing temperature, around 0.5 M%, notwithstanding the fact that i t is, as showed by Braekman and Heyvaert (ref. 14) more stable than phenol. The contribution of D.B.F. formation, as primary reaction of phenols cracking, is limited to low temperature and is not important. Once hydrogen becomes available in the sys- tem by the cyclopentadiene route, as shown next, the direct dehydroxylation takes place. So there is no accumulation of D.B.F. Cracking of 2,4-xylenol under hydrogen pressure was studied by A. Progneaux (ref. 15), with the goal to determine the experimental conditions at which the yield of B.T.X. and light phenols are maximum. Our objective in hydropyrolysis pilot plant experiments, is to maximize their concentration in oi l . It is im- portant to avoid the dehydroxylation of cresols and phenol because of their commercial value, and because of the hydrogen consumption involved in the water formation. 2,4-xylenol was chosen as model substance of the behaviour of higher phenols. Hydrocracking was performed under 1MPa total pressure and 0.8 MPaH 2 partial pressure. 10 701 M/|00MOLES INJ. 60 o H20 E] PHENOL * CRESOLS 0 & B,T.X, 40 30 20 10 725 750 775 g00 025' T'C 120 ' 'M.%M.InJ. 100 80 60 40 q 2o ~ 725 750 775 B00 ,> 8 2 5 I'C Fig. 5. Hydropyrolysis of 2,4-xylenol (PT =IMPa , t = 0.8 s). Fig. 5 shows the molar yield of cracking products as a function of temperature. The formation of cresols and phenol is maximum at 775C and decreases rapidly above 800C. B.T.X. and water are increasing regularly. The hydrogen influence is given in table I I , which compares the moles formed for 100 moles cracked under i MPa of helium and hydrogeD. I t appears that the water formation being almost the same in both cases, hydrogen does not lead to dehydroxylation but increases the phenol and cresols formation. Moreover, the amount of l i ght aromatic hydrocarbons (B.T.X.) is almost double under hydrogen than under helium. The presence of hydrogen also decreases the heavy compounds fraction in the liquid phase and the solid phase. TABLE I I . Yields comparison (moles formed / 100 moles cracked) under He and H 2 at P= 1MPa , T= 775C , t = 0.8 s. Cracking rate Phenol -cresols B.T.X. H20 CH4 CO He H 2 47 47 17 33 49 17 76 57 30 35 76 10 11 4. CRACKING OF CYCLOPENTADIENE (C.P.D.) ; As said before, cracking of pure C.P.D. was studied in our i nsti tute by Spielman (ref. 16) as to determine i f the cracking products of C.P.D. are the same as those from phenols, and i f i ts thermal i nst abi l i t y at the phenols' cracking temperatures explains that only low concentrations of C.P.D. are found in the phenols' cracking products. . . . . : Table I I I gives the cracking yields of C.P.D. between 550C and 740C for in- creasing contact time, at each temperature. Pulse injection technique was used. 1 ~l of C.P.D. was injected in the carrier gas, entrained through the reactor and di rectl y in the G.C. analyser. Table IV gives the composition of the gaseous products of C.P.D. for a continu- ous injection at 650C and 20 seconds C.T. I t can be seen that C.P.D. cracks at temperatures as low as 550C. At 740C and 3 s C.T. nearly 90 % of the in- jected C.P.D. has disappeared. The major cracking products are benzene, tolue- ne, indene and naphthalene. Their concentration increases with temperature and C.T. In the gas phase, the major constituent is cyclopentene. For instance, at 650C for 23.2 % of C.P.D. cracked under N 2 and 2s C.T., concentration of cyclopentene reaches 11.4 %. I t has to be noted that there is also 1.1% of n-butane and 0.4 % n-pentane. Obviously hydrogenation of the cyclopentadienyl radical and of i t s cracking fragments takes place. H 2 can only be produced in the system by the cracking process of the C.P.D. Weattribute this to the conversion of C.P.D. into naph- thalene according to the following reaction 2 C5H 6 ~ C10H8 + 2 H 2 The arguments in favour of thi s, are that naphthalene appears already in the cracking products of C.P.D. at low temperature and that naphthalene concentra- tions are always high, compared with the main other cracking products. The hydrogen made available by the reaction, hydrogenates cyclopentadiene to cyclo- pentene. The cyclopentadienyl radical or fragments of i t are also hydrogenated to alkanes (n-pentane 0.4 %, n-butane 1.1%). Experimental results show that the thermal degradation of C.P.D. and methyl- C.P.D. yields the same products as those observed in the pyrolysis of phenols at higher temperatures. Because C.P.D. begins to crack at much lower temperatures than phenols, only low concentrations of C.P.D. are found in the crackinq products of phenols. Benzene and toluene formation is 12 TABLE I I I . Cracking of C.P,D. (in mole %). Pulse injection ; sample size = 1 ~l C.P.D. METHANE ETHYLENE EYCLOPENTENE CYCLOPENTADIENE BENZENE TOLUENE STYRENE INDANE INDENE METHYLINDEN NAPHTHALENE 550C 600C 5" 14" 23" 34" 6" I0" 13" <0.5 <0.5 <0.5 0.5 <0.5 <0.5 <0.5 - < 0 . 5 < 0 . 5 - < 0 . 5 < 0 . 5 <0.5 1.0 2.8 3.5 0.9 1,8J 2.8 i 94.1 84. 9 78. 8 73. 3 74. 4 65. 6 51.8 <0.5 1.7 1.8 2.2 2.7 3.7 5.5 <0.5 0.7 0.9 1.5 1.2 2.1 2.8 <0,5 <0.5 <0.5 0.9 0.9 1.2 1.5 1.5 1.2 = 1.8 1.8 1.6 2.3 3.2 0,8 2.6 3.6 4,1 6.0 6.9 8.6 0.8 2.4 2.1 2.2 3. 3 3.8 6.2 < 0 . 5 1.7 2.4 3.8 4. 8 6. 8 10.5 6" ; < 0 . 5 < 0 . 5 1.5 65.6 3.1 1.2 0. 8 1.6 7.3 8. 8 5.7 650C 10" 15" 25" 1.0 1.6 3.5 < 0.5 < 0.5 0.8 2.2 3.1 3.9 44.4 38. 3 24.1 6.3 8.2 12.7 2.5 3,5 4. 6 1.6 1.7 1.8 3. 5 3.5 3.4 12.4 11. 9 13.1 8. 8 8. 4 7. 6 12.4 14.3 18.4 740C 3" 5" 7" 0. 8 2.3 4.3 < 0. 5 1.0 2.3 3.7 4. 4 6.7 10.8 3.3 0. 6 16.0 23. 2 30.3 5.7 7.4 8.8 2.6 2.6 2.5 1.3 0.8 0.5 19.4 14.3 8. 7 3.1 1.1 1.3 32.5 35.8 27.2 (?) TABLE IV, Composition of the gaseous pyrolysis products of cyclopentadiene (weight %). T= 650% , t = 20 s , continuous injection. W% Methane Ethane Ethylene Propane Acetylene n-Butane n-Pentane Cyclopentane Transbutene-2 Isobutene 1,3-Butadiene Pentene-1 Cyclopentene Unidentified 2-Methylbutadiene-l,3 Cyclopentadiene 2,6 0.4 1,5 0.2 0.2 1.1 0,4 0.5 0.5 0.5 0.5 0.7 11.4 0.9 0.9 77.8 13 due to a Diels-Alder reaction between the olefins from the cyclopentadienyl ra- di cal . The mechanism is the same as discussed earl i er. 5. CONCLUSION The exclusively aromatic character of high temperature tars is not only due to the disappearance, because of thei r post-cracking, of the paraffins present in low temperature tars. Phenols and the non-aromatic fraction of the neutral oi l s of primary tars contribute, at higher temperature, to the formation of mono- and polyaromatic hydrocarbons. The main processes are the Diels-Alder reaction of cyclisation of C 3 and C 4 olefins to cycloolefins, which dehydroge- nate to aromatics,and the decomposition of phenols in COand cyclopentadiene, which is an intermediate to monocyclic aromatics and to naphthalene. The formation of a high temperature tar from a primary tar is summarized in Fig. 6. PRIMARY TAR NBJ TRAJ. OILS ACID OILS OLEF IN S OF 5 T O n C PARAFFINS FRCM 3 tOn +IC ALKYLS I CYCLOOLEFINES \ ~ " i ARCM ATICS IN H IG H TI~tPERA'[URE TAR I CYCLOPENTAD I ENES l I NAPHTHALENE I Fig. 6. Aromatic hydrocarbons formation by postcracking of primary tars. 14 6. EXPERIMENTAL Thermal cracking of n-decane, C 4 olefins, labelled phenol and dibenzofu- rane were made in a tubular quartz reactor at atmospheric pressure in a stream of nitrogen. The partial pressures of the starting compounds was maintained at 0.033 MPa, and the residence time at 2 s. The C.P.D. was cracked in a pulse injection gold reactor di rectl y coupled with gas chromatography. The partial pressure of the starting compound varies from 0.007 to 0.026 MPa, the residence time was maintained at 2 s. Cracking of 2,4-xylenol was performed under 1MPa total pressure with 0.8 MPa H 2 partial pressure and 0.2 MPa 2,4-xylenol partial pressure. The resi- dence time was 2 s. The analysis of the liquid and gaseous cracking compounds were made by gas chromatography, radiochromatography for the radioactive materials, or gas- chromatography-mass spectrometry. ACKNOWLEDGEMENTS The author wishes to thank the Commission of the European Communities, Coal Directorate, for the financial assistance i t has provided in the framework of the 'Chemical and Physical Valorisation of Coal' programme of the ECSC. REFERENCES 1. D. 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