Fuel Processing Technology, 15 (1987) 1- 15 1

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.
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