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Naphthalene Is An Organic Compound With Formula C10H8
Naphthalene Is An Organic Compound With Formula C10H8
Naphthalene Is An Organic Compound With Formula C10H8
Faculty of Engineering
Chemical Department
introduction
Naphthalene: is an organic compound with formula C10H8. It is the simplest polycyclic
aromatic hydrocarbon, and is a white crystalline solid with a characteristic odor that is
detectable at concentrations as low as 0.08 ppm by mass. As an aromatic hydrocarbon,
naphthalene's structure consists of a fused pair of benzene rings. It is best known as the
main ingredient of traditional mothballs.
History: In the early 1820s, two separate reports described a white solid with a pungent
odor derived from the distillation of coal tar. In 1821, John Kidd cited these two disclosures
and then described many of this substance's properties and the means of its production. He
proposed the name naphthaline, as it had been derived from a kind of naphtha (a broad
term encompassing any volatile, flammable liquid hydrocarbon mixture, including coal tar).
Naphthalene's chemical formula was determined by Michael Faraday in 1826. The structure
of two fused benzene rings was proposed by Emil Erlenmeyer in 1866, and confirmed by
Carl Gräbe three years later.
( Naphthalene )
Because of this resonance, the molecule has bilateral symmetry across the plane of the
shared carbon pair, as well as across the plane that bisects bonds C2-C3 and C6-C7, and
across the plane of the carbon atoms. Thus there are two sets of equivalent hydrogen
atoms: the alpha positions, numbered 1, 4, 5, and 8, and the beta positions, 2, 3, 6, and 7.
Two isomers are then possible for mono-substituted naphthalenes, corresponding to
substitution at an alpha or beta position. Bicyclo[6.2.0]decapentaene is a structural isomer
In terms of regiochemistry, electrophiles attack at the alpha position. The selectivity for
alpha over beta substitution can be rationalized in terms of the resonance structures of the
intermediate: for the alpha substitution intermediate, seven resonance structures can be
drawn, of which four preserve an aromatic ring. For beta substitution, the intermediate has
only six resonance structures, and only two of these are aromatic. Sulfonation gives the
"alpha" product naphthalene-1-sulfonic acid as the kinetic product but naphthalene-2-
sulfonic acid as the thermodynamic product. The 1-isomer forms predominantly at 25 °C,
and the 2-isomer at 160 °C. Sulfonation to give the 1- and 2-sulfonic acid occurs readily:
E-F:The gas particles continue to absorb more energy and move faster.
The temperature increases as heating continues.
R:The substance exists only in liquid state as all the gas particles have condensed into liquid.
T:All the liquid freezes into solid. The particles are now closely packed in an orderly manner.
T-U:Once all the liquid has become solid, the temperature falls once again until it reaches room
temperature. The substance is in the solid state here.
U :The substance reaches room temperature and remain at this temperature as long as the room
temperature remain the same
Supercooling
may b some of u still blu abt supercooling.... the most easier to show u s/cooling is ice...u put some
water into the freezer, after 20min, it seems oredi freeze, but if press it with yo finger, the upper
layer of ice will break, inside still remain water... this is what we call supercooling.
supercooling occur bcos the cooling temperature is not uniform. to avoid this , the boiling
tube which is placed in the conical flask must continuously stirredthroughout the cooling
process.
This invention relates to the preparation of naphthalene from hydrocarbon stocks and more
particularly to the dealkylation of hydrocarbon stocks which comprise alkyl naphthalenes for
the purpose of conversion to naphtha lene. Petroleum fractions which boil within the range
of 400-550 F. generally contain substantial amounts of alkyl naphthalenes, such as mono-,
di-, and trimethyl naphthalenes and in smaller quantity, the ethyl naphtha lenes. Recycle
fractions, which are formed in the crack ing of petroleum stocks and which include this
boiling range, often contain major proportions of aromatic hy drocarbons that are mainly
alklyl naphthalenes. Such fractions typically may have aromatic contents varying within the
range of 25-97% but usually contain between 50% and 95% aromatics depending upon the
particular operation in which the petroleum fractions are produced. These hydrocarbon
charge stocks are obtained in both catalytic and thermal cracking processes and in opera
tions in which combinations of catalytic and thermal cracking steps are utilized. Stocks
having high alkyl naphthalene contents can also be obtained by extracting straight run
petroleum fractions of appropriate boiling ranges, such as kerosene, or catalytic fractions
such as catalytic gas oil, with solvents, such as furfural or sulfur dioxide, or by selective
adsorption with silica gel. These aromatic concentrates may contain up to 100% aromatic
hydrocarbons. The present invention is directed to the preparation of naphthalene from
aromatic hydrocarbon charge stocks which comprise a mixture of alkyl naphthalenes and
which can be derived from such sources as referred to above. The charge stock generally
boils within the range of 400 550 F. but more preferably in the range of 440-515 F. and
preferably is composed mainly of alkyl naphtha lenes in which the alkyl groups appear at
both the alpha and beta positions on the naphthalene nucleus. It has been proposed
heretofore to prepare naphtha lene by subjecting aromatic hydrocarbon stocks contain ing
alkyl naphthalenes to high temperature dealkylation in the presence of hydrogen. As a
general rule, the de alkylation conditions employed can effect only a partial dealkylation in
one pass of the alkyl naphthalenes through the reactor. In order to increase the yield of
naphthalene, it is desirable to fractionate the reaction product to obtain the desired
naphthalene product and also to recover another fraction comprising unconverted and only
partially converted alkyl naphthalenes. The re covered alkyl naphthalenes can be recycled to
the de alkylator to effect further conversion. It has now been found that when the alkyl
naphtha lenes, which are separately recovered from the dealkyl ator reaction product, are
recycled for further reaction along with additional charge stock, the overall rate of
dealkylation is substantially reduced. This is for the reason that under the dealkylation
conditions employed, which generally include a temperature in the range of 1100-1500 F.
and more usually 1200-1400° F., the alkyi substituents which are in the alpha position are re
moved from the naphthalene nucleus at a rate which is roughly about twice as fast as the
rate of removal of beta substituents. Hence the alkyl naphthalenes that are recovered after
the reaction are considerably enriched
with respect to components having beta substituents; and this material when recycled is
substantially more refrac tory than the original charge stock. The present invention provides
an improved process for producing naphthalene in which a substantially in creased overall
rate of dealkylation of alkyl naphthalenes is attained. According to the invention, the alkyl
naph thalenes recovered from the dealkylation product are sub jected to an isomerization
operation in which the condi tions are effective to shift the position of alkyl groups on the
naphthalene nucleus. The isomerization results in an alkyl naphthalene product having an
increased ratio of alpha to beta substituents. This isomerization product is recycled to the
dealkylation step, with the result that a higher conversion per pass of the alkyl naphthalenes
to naphthalene is achieved. The invention is described more specifically with ref erence to
the accompanying drawing which is a schematic flowsheet illustrating a preferred
processing operation for producing naphthalene from a hydrocarbon stock con taining alkyl
naphthalenes. The process as illustrated in the drawing involves a preliminary catalytic
hydrocracking-desulfurization step adapted to condition the alkyl naphthalene charge mate
rial prior to a thermal dealkylation step for producing the naphthalene. The charge, which
enters the system through line 10, is a gas oil fraction boiling in the range of 400-550 F. and
containing alkyl naphthalenes, and preferably is a catalytic gas oil aromatic extract boiling in
the range of 440-515 F. and containing a major proportion of dicyclic aromatics together
with a minor proportion of aromatics having only one aromatic ring and only a small amount
or no saturated hydrocarbons. For example, a preferred charge may contain 60% di cyclic
aromatics, 35% monocyclic aromatics and 5% Saturates. The heated charge together with
hydrogen from line 11 passes through line 12 to a catalytic hydrocracker 13 which
preferably contains a desulfurization catalyst such as cobalt molybdate on alumina or
molybdenum desulfide on alumina. The conditions for conducting this catalytic conditioning
step include a temperature within the range of 800-980 F., a pressure of 150-1000 p.s.i.g.,
with a range of 200-500 p.s.i.g. preferred, a hydrogen to hydro carbon mole ratio of 3:1 to
25:1 and preferably 5:1 to 15:1, and a liquid hourly space velocity of 0.5 to 10 (vol umes of
charge per hour per bulk volume of catalyst). The hydrogen consumption under these
conditions should be between 65-500 s.c.f. per barrel of liquid feed per per cent sulfur in the
feed and preferably between 200 and 400 s.c.f. per barrel. This conditioning step effects
cracking of most of the saturates and some of the monocyclic aro matics and also converts
most of the sulfur in the hydro carbon stock to hydrogen sulfide. From hydrocracker 13 the
reaction product preferably is sent through line 14 to fractionator 15 from which normally
gaseous components are removed overhead through line 7 and a C-400 F. gasoline fraction
is ob tained from line 18. The 400--° F. fraction which con tains the alkyl naphthalenes is
removed via line 16 and sent to thermal dealkylator 21. Alternatively all of the reaction
product from hydrocracker 13 can be sent to the dealkylator as indicated by dashed line 27.
The 400-- F. fraction from line 16 is admixed with a recycle fraction from line 33, as
hereinafter specified, and the mixture passes through line 20 together with hy drogen
introduced via line 19 into dealkylator 21. In the preferred embodiment the dealkylation is
effected ther mally without a catalyst. The conditions for this opera tion include a pressure
of 150-1000 p.s.i.g., preferably 200-800 p.s.i.g., a hydrogen to hydrocarbon mole ratio
within the range of 3:1 to 25:1 and preferably 5:1 to 3 15:1, a residence time of 2-300
seconds with a preferred residence time of 10-60 seconds, and a temperature above 1000
F., preferably within the range of 1200-1400 F., sufficient to effect dealkylation of alkyl
naphthalenes. In this reaction, as previously stated, only a partial dealkyla tion occurs and
the alkyl groups which are in the alpha position on the naphthalene nucleus are removed at
about twice the rate as those in the beta position. Hence the reaction product which leaves
the reactor through line 22 contains, in addition to the desired naphthalene, unreacted
naphthalenes and partially dealkylated naphthalenes, and the alkyl naphthalene portion of
the mixture is enriched with respect to beta alkyl groups as compared with the charge
material fed to dealkylator 21. The reaction product from line 22 passes to fraction ator 23
from which gases and a C5-400° F. aromatic gaso line cut are removed, respectively, from
lines 26 and 25. The desired naphthalene product is taken from line 24 as material boiling in
the 400-450 F. range. Typically this fraction is composed predominantly of naphthalene and
has a freezing point of 78.6 C. and a sulfur content of the order of 0.06%. The 450-- F.
material withdrawn from fractionator 23 via line 28 is composed mainly of monomethyl and
di methyl naphthalenes with the alkyl groups in the beta position predominating. This
stream also contains a small amount of material boiling above dimethylnaphtha lenes which
desirably should be removed. Hence the stream is passed through line 28 to fractionator 29
from which the mono- and dialkyl naphthalenes are obtained overhead through line 30 and
the higher boiling material is removed as bottoms via line 32. In order to increase the yield
of naphthalene from the process, the unconverted alkyl naphthalenes should be
continuously recycled to the dealkylation zone. How ever, direct recycling will result in a
relatively low over all rate of conversion in the dealkylator due to the high beta alkyl content
of this material. Accordingly, the present invention provides a means of increasing the over
all rate of the dealkylation reaction by first subjecting the alkyl naphthalenes to catalyic
isomerizaion in zone 31. This effects a shift of a substantial portion of the alkyl groups to the
alpha position. For example, (3-methyl naphthalene is partly converted to o-
methylnaphthalene. Likewise, 2,3-dimethylnaphtlalene is partly converted to 1,3- and 1,4-
dimethylnaphthalene, and 2,6-dimethyl and 2,7-dimethylnaphthalenes are partly converted
to alpha methyl naphthalenes such as the 1,5-, 1,6-, 1,7- and 1,8- isomers. It should be
noted, however, that the isomeriza tion does not effect any shift of an alkyl group from one
of the aryl rings to the other in the same molecule, al though some amount of
disproportionation between sepa rate molecules may occur. One manner of effecting the
isomerization in zone 31 is to contact the alkyl naphthalenes with any solid acidic cracking
catalyst Such as silica-alumina, silica-magnesia, silica-zirconia and acid activated clays. The
reaction temperature should be in the range of 300-500 C. and more preferably 350-400° C.
The liquid space velocity can vary between 0.1 and 20 volume hydrocarbon per volume
catalyst per hour and more preferably is main tained in the range of 0.5-6.0. It is desirable to
conduct the isomerization at a low hydrocarbon partial pressure and generally in the range
of 0.05-0.5 atmosphere, as otherwise coking tends to occur rapidly with resultant de
activation of the catalyst. The low partial pressure can be maintained either by holding a
vacuum in isomeriza tion zone 31 or by introducing an inert diluent along with
hydrocarbons, for example, nitrogen, hydrogen, methane, propane, butanes, and the like.
Whenever the activity of the catalyst has dropped enough to require regeneration, this can
be done in conventional manner merely by blow ing air through the hot catalyst to burn off
the coke de posits. Thereafter the catalyst can be re-used for further isomerization.
By way of example as to the effectiveness of the above described isomerization procedure
in producing alpha substituted naphthalenes, when 2,3-dimethylnaphthalene was reacted
over a silica-alumina cracking catalyst at a temperature of 375 C., a liquid hourly space
velocity of about 0.3 and using heptane as diluent so that the partial pressure of the
dimethylnaphthalene was 0.046 atmos phere, the isomerization product had the following
com position: Mole percent 1,3-dimethylnaphthalene ------------ 43 1,4-dimethylnaphthalene
----- 34 2,3-dimethylnaphthalene----------- 20 1,2-dimethylnaphthalene -------- Negligible
Methylnaphthalenes------------- 3 These data show that at least 77% of the 2,3-isomer was
converted to products having an alpha substituent. The isomerization in Zone 31 can also be
effected at low temperature using HF--BF3 as catalyst. In practicing the isomerization in this
manner, the alkyl naphthalenes from line 30 are first dissolved in a suitable solvent, such as
benzene or heptane, and the mixture is contacted with the catalyst at a temperature
preferably in the range of 0-30 C. and generally for several hours. Only a small amount of BF
need be used and the HF can be present in a large molar excess over the BF3 to provide
sufficient catalyst volume for good contact. After the isomeriza tion the solvent can be
removed by distillation (not shown) and the isomerized product can be recycled through
line 33 to dealkylator 21. Generally, some amount of tarry material may be formed during
this type of isomerizing operation and it also can be removed by distillation prior to
recycling the isomerizate. By way of example, when a 10 weight percent solution of 2,3-
dimethylnaphthalene in benzene was contacted at 27 C. for 4 hours with BF in HF solution,
about 95% of the dimethylnaphthalene product was the 1,3-isomer. When 2,7-
dimethylnaphthalene was contacted similarly for 20 hours, about 20% of the product was
the 1,7- isomer. The above-described process can be modified by carry ing out the
dealkylation reaction in Zone 21 catalytically employing a desulfurization catalyst such as is
used in the hydrocracker 3. The presence of the catalyst in the latter step facilitates the
dealkylation reaction and in Some cases permits. it to be carried out at a lower tem perature
than that required for thermal dealkylation. The catalyst also effects the conversion of any
remaining sul fur into hydrogen sulfide and hence permits the prepara tion of naphthalene
having negligible sulfur content. The conditions for the catalytic dealkylation step include a
pressure of 150-1000 p.s.i.g. with a range of 200-500 p.s.i.g. preferred, a hydrogen to
hydrocarbon mole ratio of 5:1 to 25:1, a liquid hourly space velocity of 0.2-5.0, and a
temperature above 1000 F., usually between 1100 F. and 1200° F., sufficient to dealkylate
the alkyl naphthalenes and convert any remaining sulfur mainly in to hydrogen sulfide. In
both the hydrocracker and dealkylator of each of the foregoing embodiments, coking occurs
after a time to such extent that coke removal from the reaction zone is required. This can be
done in conventional manner by passing an oxygen-containing gas through the reaction
zone to burn out the coke. In the steps in which a desul furizing catalyst is used, burning of
coke from the cata lyst restores its catalytic activity. We claim: 1. Process for producing
naphthalene from an aroma tic hydrocarbon charge stock comprising a mixture of alkyl
naphthalenes which comprises subjecting said charge stock in the presence of hydrogen to a
temperature in the range of 1000-1500 F., whereby partial dealkylation of alkyl
naphthalenes occurs and alkyl groups in the alpha position are removed at a rate faster than
alkyl groups in the beta position; distilling the reaction product to obtain a naphthalene
fraction and an alkyl naphthalene fraction; subjecting said alkyl naphthalene fraction to
isomerizing conditions effective to shift the position of alkyl groups on the naphthalene
nucleus, whereby an alkyl naphthalene product having an increased content of alpha alkyl
naph thalenes is obtained; and recycling said alkyl naphthalene product to the partial
dealkylation step. 2. Process according to claim 1 wherein said partial dealkylation is
effected thermally without a catalyst at a temperature of 1200-1400 F., pressure of 200-800
p.s.i.g., hydrogen to hydrocarbon mole ratio of 3:1 to 25:1, and a residence time of 2-300
seconds. 3. Process according to claim 2 wherein said charge stock is an aromatic extract
separated from catalytic gas oil. 4. Process according to claim 3 wherein said charge stock
boils within the range of 400-550 F. 5. Process according to claim 1 wherein said isomeriz ing
conditions include contacting said alkylnaphthalene fraction with a solid acidic catalyst in
the presence of an inert diluent at a temperature of 300-500 C., hydro carbon partial
pressure of 0.05-0.5 atmosphere, and a liquid hourly space velocity of 0.1-20. 6. Process
according to claim 2 wherein said isomeriz ing conditions include contacting said
alkylnaphthalene fraction with a solid acidic catalyst in the presence of an inert diluent at a
temperature of 300-500 C., hydro carbon partial pressure of 0.05-0.5 atmosphere, and a
liquid hourly space velocity of 0.1-20.