U.S. patent number 3,625,879 [Application Number 05/001,099] was granted by the patent office on 1971-12-07 for benzene from pyrolysis gasoline.
This patent grant is currently assigned to Gulf Research & Development Company. Invention is credited to William A. Horne, Ronald V. Luzar.
United States Patent |
3,625,879 |
Horne , et al. |
December 7, 1971 |
**Please see images for:
( Certificate of Correction ) ** |
BENZENE FROM PYROLYSIS GASOLINE
Abstract
A process for the production and recovery of benzene from
pyrolysis naphtha produced by high-temperature cracking of ethane,
propane, naphtha or gas oil to produce ethylene. The process
comprises the steps of hydrogenating a selected cut of pyrolysis
naphtha to saturate olefins, reforming the hydrocarbon product from
the hydrogenation step to convert benzene precursors to aromatic
compounds and partially crack the nonaromatic hydrocarbons present
and thereafter hydrodealkylating the hydrocarbon product from the
reforming step to convert the alkyl aromatics to benzene and
further crack nonaromatic compounds including those boiling at
about the benzene boiling point, so that benzene may then be
separated from the hydrodealkylation effluent by conventional
distillation.
Inventors: |
Horne; William A. (Oakmont,
PA), Luzar; Ronald V. (Broomall, PA) |
Assignee: |
Gulf Research & Development
Company (Pittsburgh, PA)
|
Family
ID: |
21694362 |
Appl.
No.: |
05/001,099 |
Filed: |
January 7, 1970 |
Current U.S.
Class: |
585/251; 208/68;
208/70; 585/252; 585/254; 585/258; 585/265; 585/275; 585/276;
585/322; 585/419; 585/420; 585/433; 585/483; 585/486; 585/807;
208/17 |
Current CPC
Class: |
C10G
69/08 (20130101); C10G 59/02 (20130101) |
Current International
Class: |
C10G
59/00 (20060101); C10G 59/02 (20060101); C10G
69/08 (20060101); C10G 69/00 (20060101); C10g
037/10 (); C10g 039/00 () |
Field of
Search: |
;208/57,62,66,68,69,70
;260/672R |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Levine; Herbert
Claims
We claim:
1. A process for increasing the benzene yield from a hydrocarbon
material comprising generally from about six to about 12 carbon
atoms per molecule obtained as the byproduct from the pyrolysis
cracking of hydrocarbons to produce primarily ethylene which
comprises:
hydrogenating said hydrocarbon material in the presence of hydrogen
generated within said process under hydrogenating conditions
including a hydrogenating temperature and a hydrogenation pressure
in the presence of a hydrogenation catalyst to saturate olefinic
hydrocarbons;
reforming said hydrocarbon material under reforming conditions
including a reforming temperature higher than said hydrogenating
temperature and a reforming pressure lower than said hydrogenating
pressure in the presence of a reforming catalyst to increase
aromatic content of said hydrocarbon material and to produce
hydrogen;
hydrodealkylating said hydrocarbon material in the presence of
hydrogen from said reforming step under hydrodealkylating
conditions including a temperature higher than said reforming
temperature and a pressure lower than said reforming pressure to
hydrodealkylate aromatic compounds and also crack remaining
nonaromatic hydrocarbons to obtain an effluent comprising benzene
and hydrogen;
recycling said hydrogen to said hydrogenation step; and
recovering benzene from said effluent by distillation.
2. A process in accordance with claim 1 wherein said hydrogenating
temperature is from about 125.degree. F. to about 800.degree. F.;
said reform temperature is from about 850.degree. F. to about
1,100.degree. F.; and said hydrodealkylating temperature is from
about 1,100.degree. F. to about 1,400.degree. F.
3. A process in accordance with claim 1 wherein
said hydrogenating total pressure is from about 300 to about 1,000
p.s.i.g.; said reforming total pressure is from about 150 to about
700 p.s.i.g.; and said hydrodealkylating total pressure is from
about 300 to about 1,000 p.s.i.g.
4. A process in accordance with claim 1 wherein
said hydrogenating conditions includes a hydrogen to hydrocarbon
mol ratio of about 1:1 to about 10:1; said reforming conditions
includes a hydrogen to hydrocarbon mol ratio of about 1:1 to about
10:1; and said hydrodealkylating conditions includes a hydrogen to
hydrocarbon mol ratio of about 3:1 to about 10:1.
5. A process in accordance with claim 1 wherein
said hydrogenating temperature is from about 200.degree. F. to
about 600.degree. F. and said hydrogenating total pressure is from
about 400 to about 800 p.s.i.g.; said reforming temperature is from
about 900.degree. F. to about 1,000.degree. F. and said reforming
total pressure is from about 300 about 700 p.s.i.g.; and said
hydrodealkylating temperature is from about 1,140.degree. F. to
about 1,350.degree. F. and said hydrodealkylating total pressure is
from about 350 to about 600 p.s.i.g.
6. A process in accordance with claim 1 which includes separating
hydrogen sulfide formed in the hydrogenating step from the effluent
of said hydrogenating step by contacting said effluent with a
material selective for the removal of hydrogen sulfide.
7. A process in accordance with claim 1 which includes
hydrogenating said effluent from a hydrodealkylating step under
hydrogenating conditions including a temperature of about
200.degree. F. to about 700.degree. F. in the presence of a
hydrogenating catalyst to saturate olefins produced in said
hydrodealkylation step.
8. A process for increasing the benzene yield from a hydrocarbon
material comprising generally from about six to about 10 carbon
atoms per molecule obtained as the byproduct from the pyrolysis
cracking of hydrocarbons to produce primarily ethylene which
comprises:
hydrogenating said hydrocarbon material in the presence of hydrogen
generated within said process under hydrogenating conditions
including a hydrogenating temperature and a hydrogenation pressure
in the presence of a hydrogenation catalyst to saturate olefinic
hydrocarbons;
reforming said hydrocarbon material under reforming conditions
including a reforming temperature higher than said hydrogenating
temperature and a reforming pressure lower than said hydrogenating
pressure in the presence of a reforming catalyst to increase
aromatic content of said hydrocarbon material and to produce
hydrogen;
hydrodealkylating said hydrocarbon material in the presence of
hydrogen from said reforming step under hydrodealkylating
conditions including a temperature higher than said reforming
temperature and a pressure lower than said reforming pressure to
hydrodealkylate aromatic compounds and also crack remaining
nonaromatic hydrocarbons including those boiling close to benzene
to obtain an effluent comprising benzene and hydrogen;
recycling said hydrogen to said hydrogenation step; and
recovering benzene from said effluent by distillation.
9. A process in accordance with claim 8 wherein
said hydrogenating temperature is from about 125.degree. F. to
about 800.degree. F.; said reform temperature is from about
850.degree. F. to about 1,100.degree. F.; and said
hydrodealkylating temperature is from about 1,100.degree. F. to
about 1,400.degree. F.
10. A process in accordance with claim 8 wherein
said hydrogenating total pressure is from about 300 to about 1,000
p.s.i.g.; said reforming total pressure is from about 150 to about
700 p.s.i.g.; and said hydrodealkylating total pressure is from
about 300 to about 1,000 p.s.i.g.
11. A process in accordance with claim 8 wherein
said hydrogenating condition includes a hydrogen to hydrocarbon mol
ratio of about 1:1 to about 10:1; said reforming conditions
includes a hydrogen to hydrocarbon mol ratio of about 1:1 to abut
10:1; and said hydrodealkylating conditions includes a hydrogen to
hydrocarbon mol ratio of about 3:1 to about 10:1.
12. A process in accordance with claim 8 wherein
said hydrogenating temperature is from about 200.degree. F. to
about 600.degree. F. and said hydrogenating total pressure is from
about 400 to about 800 p.s.i.g.; said reforming temperature is from
about 900.degree. F. to abut 1,000.degree. F. and said reforming
total pressure is from about 300 to about 700 p.s.i.g.; and said
hydrodealkylating temperature is from about 1,140.degree. F. to
about 1,350.degree. F. and said hydrodealkylating total pressure is
from about 350 to about 600 p.s.i.g.
13. A process in accordance with claim 8 which includes separating
hydrogen sulfide formed in the hydrogenating step from the effluent
of said hydrogenating step by contacting said effluent with a
material selective for the removal of hydrogen sulfide.
14. A process in accordance with claim 8 which includes
hydrogenating said effluent from the hydrodealkylating step under
hydrogenating conditions including a temperature of about
200.degree. F. to about 700.degree. F. in the presence of a
hydrogenating catalyst to saturate olefins produced in said
hydrodealkylation step.
15. A process for increasing the benzene yield from a hydrocarbon
material comprising generally about six to 10 carbon atoms per
molecule obtained from a byproduct of the pyrolysis cracking of
hydrocarbon to produce primarily ethylene which comprises:
hydrogenating said hydrocarbon material in the presence of hydrogen
generated within said process under hydrogenating conditions
including an average hydrogenating temperature of about 650.degree.
F. and a hydrogenating pressure of about 800 p.s.i.g. in the
presence of a supported hydrogenating catalyst selected from the
group consisting of metal from Group VI and the Iron Group metals
from Group VIII of the Periodic table, their oxides and sulfides to
saturate olefinic hydrocarbons;
reforming aid hydrocarbon material under reforming conditions
including an average reforming temperature of about 925.degree. F.
and a reforming pressure of about 500 p.s.i.g. in the presence of a
reforming catalyst selected from the group consisting of metals
from Group VI and metals from Group VIII of the Periodic table,
their oxides and sulfides supported on a base to increase aromatic
content of said hydrocarbon material and to produce hydrogen;
hydrodealkylating said hydrocarbon material in the presence of
hydrogen from said reforming step under hydrodealkylating
conditions including an average temperature of about 1,250.degree.
F. and a pressure of about 450 p.s.i.g. to hydrodealkylate aromatic
hydrocarbons and also crack remaining nonaromatic hydrocarbons
including those boiling close to benzene to obtain an effluent
comprising benzene and hydrogen;
recycling said hydrogen to said hydrogenating step; and
removing benzene from said effluent by distillation.
16. A process in accordance with claim 15 which includes separating
hydrogen sulfide formed in the hydrogenating step from the effluent
of said step by contacting said effluent with an adsorbent
comprising zinc oxide.
17. A process in accordance with claim 15 which includes
hydrogenating said effluent from the hydrodealkylating step under
hydrogenating conditions including a temperature of about
200.degree. F. to about 700.degree. F. and in the presence of a
hydrogenating catalyst selected from the group consisting of metals
from Group VI and the Iron Group metals from Group VIII of the
Periodic table, their oxides and sulfides supported on a base to
saturate olefins produced in said hydrodealkylating step.
Description
BACKGROUND OF THE INVENTION
This invention relates to a process for the production of benzene
from pyrolysis naphtha by hydrogenating a selected cut of pyrolysis
naphtha, reforming the hydrogenated product and hydrodealkylating
the reformed product. The benzene thus produced and the benzene
originally contained in the pyrolysis naptha feed to the process
can then be separated from the hydrodealkylated product by
conventional fractional distillation, thereby eliminating the step
of solvent extraction normally employed in recovering benzene from
pyrolysis naphtha.
The increased demand for ethylene and changes in ethylene
manufacturing technology has produced an increased amount of
pyrolysis naphtha which is a byproduct of ethylene manufacturing.
Only a small quantity of pyrolysis gasoline byproduct is produced
when ethane is used as the sole starting material for the
production of ethylene. However, when propane is used as the
starting material approximately 25 pounds of pyrolysis naphtha is
produced for each 100 pounds of ethylene product. When naphtha is
used as a starting material about 45 pounds of byproduct material
is produced for each 100 pounds of ethylene product. The modern
trend in ethylene manufacturing technology indicates that it is
more desirable to use mixtures of ethane and propane, naphtha or
gas oil as a starting material and this trend coupled with the
increased demand for ethylene obviously increases the amount of
byproduct pyrolysis naphtha the ethylene manufacturer has
available.
One of the problems encountered in the utilization of the byproduct
is that the byproduct contains an amount of highly unsaturated
hydrocarbon compounds, such as acetylenes, aliphatic diolefins,
vinyl substituted aromatics, and cyclic diolefins and these
compounds polymerize readily at temperatures above about
260.degree. F. or at ambient temperatures over a long period of
time. The highly unsaturated hydrocarbons also readily polymerize
when contacted with air and/or light. The polymeric compounds thus
formed are termed gums and render the pyrolysis naphtha unsuitable
as a motor fuel blending component and make additional processing
of the byproduct difficult. The acetylene produced in the ethylene
product is usually removed under mild hydrogenating conditions
before the ethylene is separated from the product. The mild
hydrogenating conditions do not, however, remove higher molecular
weight acetylenes or other gum-forming compounds and these remain
in the pyrolysis naphtha byproduct. The prior art solution to
making the pyrolysis naphtha a suitable motor fuel blending
component is to hydrogenate under conditions that will saturate the
gum-forming compounds but will not saturate the monoolefin or
aromatic compounds. It is not desirable to saturate the monoolefin
compounds because these are valuable as motor fuel blending agents
and the aromatic compounds present are also valuable in motor fuel.
The prior art hydrogenation obviously requires extraneous hydrogen.
As benzene and the other aromatics contained in the pyrolysis
naphtha became more valuable as petrochemicals than as motor fuel
blending agents, the aromatics were separated from the completely
hydrogenated pyrolysis naphtha by selective distillation,
adsorption or solvent extraction.
Although selective distillation can be employed to separate
compounds boiling very closely to each other, it is usually
expensive and of little commercial importance. Adsorption and
solvent extraction as applied to the recovery of benzene from
pyrolysis naphtha both suffer from essentially the same inherent
defects and therefore will be discussed together as solvent
extraction. To separate the aromatics by solvent extraction, it is
necessary to first saturate not only the gum-forming compounds but
also to saturate the monoolefins, again increasing in the
extraneous hydrogen requirements. In addition to saturating the
monoolefins the sulfur containing hydrocarbons must be removed,
again increasing the extraneous hydrogen requirements. The olefins
must be saturated and sulfur containing hydrocarbons removed
because the order of solubility of hydrocarbon material in a
solvent that is selective for aromatics is as follows: the least
soluble material is the paraffinic material followed in order of
increasing solubility by naphthenes, olefins, diolefins,
acetylenes, sulfur bearing molecules, and aromatics. After solvent
extraction, the impure benzene could be separated by distillation,
but it is noted that this process only recovers the indigenous
benzene and does not produce more benzene than was contained in the
original pyrolysis naphtha starting material. The reason that
solvent extraction was employed rather than simple distillation is
that the pyrolysis naphtha contains nonaromatic compounds boiling
close to benzene and they are not removed by the hydrogenation
step. Further, hydrogenation conditions employed by the prior art
in some cases were of such severity that when monoolefins were
saturated some aromatics were saturated to produce compounds
boiling close to benzene, for example, benzene was converted to
cyclohexane.
In the process of this invention, by selecting certain sequential
processing steps and operating conditions for each step, the need
for solvent extraction is eliminated and high purity benzene can be
separated from the product by simple distillation.
Therefore, an object of this invention is to eliminate solvent
extraction from the process for producing benzene from pyrolysis
naphtha. Another object of this invention is to increase the yield
of benzene from pyrolysis naphtha over and above the quantity of
benzene inherently contained in the pyrolysis naphtha starting
material. Another object of this invention is to effect substantial
heat savings by performing the sequence of process steps at
ascending temperature levels so that no intermediate cooling is
required between the steps. Another object of this invention is to
operate the sequence of process steps at attenuating pressure
levels so that compression is not required between the processing
steps. A further object of this invention is to minimize the total
hydrogen consumption and minimize the amount of extraneous hydrogen
required while increasing the yield of benzene from pyrolysis
naphtha.
SUMMARY OF THE INVENTION
A process is described for increasing the yield of benzene from a
feed stock of pyrolysis naphtha. Pyrolysis naphtha is a byproduct
in the manufacture of ethylene where ethane, ethane and propane,
naphtha or gas oil is dehydrogenated or cracked at high
temperatures to produce ethylene. The process initially comprises
the hydrogenation of a selected cut of pyrolysis naphtha comprising
from about six to 12 carbon atoms per molecule or about six to 10
carbon atoms per molecule to saturate olefins. Hydrogen sulfide
formed from the sulfur compounds in the hydrogenation step can be
removed from the hydrogenation effluent if the quantity is of
sufficient magnitude to impair the life of the catalyst in the
subsequent reformer stage. The hydrogenation effluent is then
reformed at a temperature higher than the hydrogenation temperature
and a pressure slightly less than the hydrogenation pressure to
convert benzene precursors to aromatic compounds and to partially
crack the nonaromatic compounds. The reformer effluent is then
charged to a hydrodealkylation stage maintained at a temperature
higher than the reformer temperature and a pressure slightly less
than the reformer pressure to further convert alkyl aromatics to
benzene and crack all remaining nonaromatic compounds including
those boiling close to benzene, such as thiophene, isoheptanes,
2,2-dimethylpentane, 2,4-dimethylpentane, 2,2,3-trimethylbutane,
etc. The effluent from the hydrodealkylation unit can by
hydrogenated to saturate trace olefins produced in the
hydrodealkylation step or passed directly to a hydrocarbon recovery
section where benzene is separated from the other hydrocarbons by
distillation. Reforming conditions are selected so that hydrogen
production is maximized and the need for extraneous hydrogen in the
hydrogenation and hydrodealkylation steps is minimized.
BRIEF DESCRIPTION OF THE DRAWING
The drawing discloses one preferred embodiment of the process to
maximize the yield of benzene from pyrolysis naphtha.
DETAILED DESCRIPTION OF THE INVENTION
The subject yields a maximum amount of high purity benzene from
pyrolysis naphtha by conserving the amount of benzene contained in
the original pyrolysis naphtha feed and further by converting
precursors of benzene to aromatic and/or alkyl aromatic compounds
in the reforming step and further by converting the alkyl aromatic
compounds to benzene in the hydrodealkylation step. Thereby the
quantity of benzene contained in the original feed is not only
retained but also enhanced by the quantity of benzene produced in
the processing steps of this invention. Further, nonaromatic
compounds including those boiling at about the benzene boiling
point are cracked to lower boiling hydrocarbons and/or converted to
aromatic compounds which allows the recovery of benzene
substantially free of close-boiling materials by conventional
distillation.
Another novel feature of the process of this invention is that each
of the sequential processing steps, that is, hydrogenation
reforming and hydrodealkylation, are carried out at progressively
higher temperatures so that no intermediare cooling between steps
is required. Nor is intermediate cooling followed by subsequent
reheating required. In one embodiment of this invention, it is
necessary to cool the effluent from the hydrodealkylation step
before a final hydrotreating operation to saturate trace olefinic
compounds produced in the hydrodealkylation step, but then it is
not necessary to heat the effluent from the subsequent
hydrotreating step prior to product distillation. If a final
hydrotreating is not employed, the effluent from the
hydrodealkylation step would normally be cooled before
distillation, so it can be seen that even with the employment of a
final hydrogenation step, the overall thesis of heat savings is
valid.
Still another advantage of the process of this invention is that
the pressure employed in each of the steps is selected so that each
process step performs its intended function at a higher pressure
level than its subsequent step so that no depressurizing and
repressurizing are necessary. By careful selection of other process
conditions, the appropriate descending pressure levels can be
maintained notwithstanding pressure drops normally occurring
between process steps and in each process step.
The need for extraneous hydrogen is reduced by incorporation of
reforming within the sequence of processing steps. Since reforming
results in a net production of hydrogen via dehydrocyclization and
dehydrogenation reactions, hydrogen is produced in the reforming
step which is utilized in the hydrodealkylating and hydrogenation
steps. By proper selection of process conditions in the reforming
step, partial cracking of nonaromatic hydrocarbons can be
accomplished and the cracking of aromatic hydrocarbons can be
eliminated. Further, reforming conditions are controlled so that
aromatics are not saturated, thereby conserving hydrogen. For
example, if benzene were saturated to cyclohexane in the reformer
step the cyclohexane would be cracked in the hydrodealkylation step
requiring additional hydrogen to saturate the cracked cyclohexane.
It should be understood at this point that aromatic rings are not
hydrogenated in any of the processing steps, thereby conserving the
aromatics present in the original pyrolysis naphtha feed.
Total hydrogen requirements are minimized by selecting proper
operating conditions for the reforming unit as pointed out above
and also by selecting proper hydrogenating conditions so that all
gum-forming compounds and most but not necessarily all of the
monoolefins are saturated in the hydrogenation step and not the
aromatic rings.
Complete saturation of monoolefins would be necessary if the
pyrolysis naphtha were first hydrogenated and then solvent
extracted. But it is an advantage of our invention that complete
saturation of the monoolefins is not necessary. By not completely
saturating monoolefins, although we saturate monoolefins to a low
level of about 0.5 weight percent, we prevent saturation of
aromatic rings and thereby minimize hydrogen required as well as
conserve the hydrogen that would be consumed by saturating the
monoolefins.
Three distinctive process steps are employed to accomplish the
advantages outlined above, and though distinctive, the steps are
not exclusive as a great deal of cooperation exists among the steps
to accomplish desired objectives. To begin with, the hydrogenation
step is necessary to saturate gum-forming hydrocarbons that would
make additional processing difficult. In addition, most but not
necessarily all of the monoolefin hydrocarbons are saturated as
these hydrocarbons would tend to cause coke formation or rapid
catalyst aging in the reforming step. Further, sulfur containing
hydrocarbons are converted to hydrogen sulfide and hydrocarbon and
the hydrogen sulfide, if present in a quantity sufficient to impair
the reformer catalyst life, may be removed before the hydrogenation
effluent is fed to the reformer. It is important that under the
conditions employed in the hydrogenation step aromatic rings are
not hydrogenated. Therefore, the quantity of aromatics indigenous
to the pyrolysis naphtha feed pass unreacted to the reformer and
hence to the hydrodealkylation step and the naphthenes contained in
the pyrolysis naphtha and produced in the hydrogenation step are
converted to aromatics in the reforming step. The reforming step
performs the additional functions of: converting normal paraffins
containing six or more carbon atoms per molecule, to naphthenes by
isomerization and dehydrocyclization, and the naphthenes thus
formed to aromatics, cracking and dehydrogenating dicyclic
naphthenes to form aromatics, and partially cracking nonaromatic
hydrocarbons. The hydrodealkylation step not only converts to
benzene the alkyl aromatics formed in the reforming step and the
alkyl aromatics inherent in the pyrolysis naphtha feed but also
further cracks remaining nonaromatic materials including those that
boil close to benzene.
The starting material for this process, pyrolysis naphtha, is
produced as a byproduct from the manufacture of ethylene. For
example ethane and propane are fed to a thermal cracker or
pyrolysis furnace and heated to a temperature of about
1,200.degree. F. to about 1,800.degree. F., preferably between
about 1,350.degree. F. and 1,550.degree. F. Low pressures up to
about 200 p.s.i.a. are normally employed, a pressure below about 35
p.s.i.a. being satisfactory. The time of exposure to the high
temperatures is usually about 0.5 to 5 seconds, contact times of
0.1 to 1 second being preferred. The effluent from the pyrolysis
step contains hydrogen, normally gaseous hydrocarbons, normally
liquid hydrocarbons, carbon dioxide, varying amounts of sulfur
containing hydrocarbons and trace quantities of nitrogen and oxygen
containing hydrocarbons. The high temperature pyrolysis product is
rapidly cooled, usually by quenching with water or oil to a
temperature of about 400.degree. F. The gaseous product from the
quenching step is then compressed and caustic washed to remove the
carbon dioxide present. The caustic washed gases are then preheated
to a temperature normally between 150.degree. F. and 325.degree. F.
and then introduced into a catalytic hydrogenation zone which is
operated at mild hydrogenation conditions to selectively
hydrogenate acetylenes. The mild hydrogenation conditions comprise
a temperature of between 150.degree. F. and 325.degree. F. and a
flow rate of between 1,000 and 2,500 ft..sup.3 /hr./ft..sup.3 of
catalyst bed. The hydrogen and normally gaseous hydrocarbons
comprising fuel gas, ethane, ethylene, propane, propylene, butane
and butylenes are separated from the normally liquid byproduct
pyrolysis naphtha also known as aromatic distillate. The thus
obtained aromatic distillate forms the starting material for the
process of our invention.
The aromatic distillate has a boiling range of about 100.degree. F.
to about 700.degree. F. and preferably between about 100.degree. F.
and 375.degree. F. The amount and composition of the distillate is
dependent upon the type of feed selected for pyrolysis, the
pyrolysis temperature, contact time and pressure. The normally
liquid distillate is of such complexity that accurate and complete
analyses are difficult. It is felt that the complexity of this
material has, in part at least, obscured the feasibility of
producing benzene from it by the particular sequence of steps
employed in this invention.
The charge stock for the process of this invention comprises a
mixture of compounds comprising between about 6 and about 30
percent by weight of unsaturated compounds which readily thermally
polymerize. By an unsaturated compound which readily thermally
polymerizes is meant a compound which has a potential gum value of
over 500 milligrams per 100 milliliters of compound after 5 hours
as determined by ASTM test D-873. Examples of compounds that
readily thermally polymerize include unsaturated hydrocarbons, such
as vinyl substituted aromatics, aliphatic di- and triolefins, and
cyclic diolefins. Specific examples of these compounds are styrene,
isoprene, cyclopentadiene, etc. The charge stock also comprises
between about 20 and 30 percent by weight of benzene and many
precursors of benzene when the process steps of the subject
invention are employed. Precursors of benzene include substituted
dicyclopentadienes, toluene, styrene, indene, naphthenes, six to 10
carbon atom paraffins, olefins and diolefins, etc. Included in the
charge stock there may be small amounts of sulfur, nitrogen and
oxygen containing hydrocarbons, such as for example thiophenes,
pyrroles, pyridines and phenols. Normally, the amounts of nitrogen
and oxygen-containing compounds are negligible and the
sulfur-containing compounds are less than 0.1 percent and usually
between 0.05 and 0.005 weight percent of the charge stock. It is
one advantage of the process of this invention that these sulfur
compounds are converted to hydrogen sulfide and hydrocarbon during
the hydrogenation step, and if the hydrogen sulfide in the effluent
stream is of sufficiently high concentration to poison the reformer
catalyst it may be removed prior to reforming.
Referring now to the drawing, the aromatic distillate or pyrolysis
naphtha is introduced to the process system through line 10 where
it is depentanized in distillate tower 12, the overhead removed via
line 14 which after finishing can be added to the gasoline blending
pool. The bottoms from tower 12 are removed via line 16 to line 18
and introduced into tower 20 wherein the aromatic distillate is cut
to remove the hydrocarbons having 11 or more carbon atoms per
molecule. This cut corresponds to an end point of about 350.degree.
F. to about 400.degree. F. and preferably between about 360.degree.
F. to about 375.degree. F. The hydrocarbons having 11 or more
carbon atoms per molecule are removed via line 23 and are suitable
for use as a fuel oil cutter stock. The overhead from tower 20 is
removed via line 22 to line 24 to the hydrogenating section 26. The
product contained in line 22 can be heated to the desired
hydrogenation temperature by conventional means, not shown. The
hydrogenating step can comprise any hydrogenating process that will
saturate the readily polymerizable unsaturated compounds and
prevent their conversion to gums and further saturate most
monoolefins but does not saturate aromatic rings. A process as
described in McKinney et al., U.S. Pat. No. 3,216,924, is
satisfactory. In general, satisfactory hydrogenation processes fall
into two broad classes and the choice of the hydrogenation process
to be employed will depend to some extent on the amount of sulfur
contained in the feed stock and other factors apparent to one
skilled in the art. The particular hydrotreating process selected
is not critical as long as the results outlined above are obtained.
The first class of satisfactory hydrogenating processes are those
employing catalysts comprising metals selected from Group VIa
and/or the iron group metals of Group VIII, their oxides and/or
sulfides unsupported or supported upon a noncracking support such
as clay, kieselguhr, alumina, etc. This class of process is
operated at a temperature of about 260.degree. F. to about
800.degree. F. and preferably about 400.degree. F. to about
600.degree. F. The process is not seriously affected by sulfur in
the feed stock, however, the catalyst is more active in the
sulfided state and therefore some sulfur in the feed stock is
desirable. Usually about 100 to 500 p.p.m. of sulfur in charge
stock is preferred. The second class of hydrogenation processes
utilizes a noble metal catalyst and generally operates at
temperatures of about 125.degree. F. to about 250.degree. F. At
such temperatures, the feed is in the liquid phase and the tendency
for the gum-forming compounds to polymerize is minimized. The
catalyst, however, is subject to partial deactivation when
relatively high sulfur content feeds are hydrogenated. In one
embodiment of the process of this invention the hydrogen sulfide
produced in the hydrogenation step is above about 10 p.p.m. of the
hydrocarbon effluent and preferably above about 1 p.p.m. can be
removed in a hydrogen sulfide removal zone (not shown) by any
suitable separation process including adsorption, extraction,
chemical combination, etc. A preferred method of removing the
hydrogen sulfide is to employ a porous adsorbent such as zinc
oxide. Additional hydrogenating conditions include a total reaction
pressure of about 300 to about 1,000 p.s.i.g., and preferably about
400 to about 800 p.s.i.g. The space velocity can range from 0.5 to
8 LHSV and preferably about 1 to 6 LHSV. The hydrogen purity is not
critical and can range from about 40 to 100 percent, preferably
about 70 to 95 percent. A hydrogen to hydrocarbon mol ratio of 1:1
to 10:1 is satisfactory with a ratio of 1.5:1 to 6:1 being
preferred. The hydrogenated product prior to reforming should have
a bromine number of about 0 to about 5, and preferably the bromine
number is about 0 to about 2.
The hydrotreating section effluent exists from the hydrotreating
section via line 30. The temperature of the product is raised by
heating means 32 to a reforming temperature higher than the
hydrogenation temperature and enters a reforming section 36 via
line 34 at a pressure slightly lower than the hydrogenation
pressure. Proper selection of reforming conditions is of upmost
importance to the successful practice of this invention. Reforming
conditions are mild enough so that aromatics are not saturated but
severe enough to crack some of the nonaromatic hydrocarbons. The
main purpose of the reforming step is to dehydrogenate naphthenes
present, isomerize and dehydrocyclize normal paraffins to produce
hydrogen, aromatics and alkyl aromatics. The hydrogen produced is
utilized in the other processing steps of this invention and the
alkyl aromatics produced are dealkylated in the hydrodealkylation
step and recovered as benzene. Some naphthenes such as
methylcyclopentane and cyclohexane boil near the benzene boiling
point and are converted to aromatics in the reforming step and,
therefore, are not cracked in the thermal hydrodealkylation step.
Some isomerization of normal paraffins occurs in the reforming step
and some of these isomers boil close to benzene so they must be
cracked in the hydrodealkylation step. Examples of isomers formed
would be isopentanes, 2,2-dimethylpentane, etc. All monoolefins
need not be saturated in the hydrogenation step prior to reforming,
however, it is a preferred practice to saturate most or
substantially all of the monoolefins as the monoolefins tend to
suppress the activity of the reformer catalyst. It is permissible
to leave unsaturated about 0 to 1 weight percent of the monoolefins
prior to reforming and preferably 0 to 0.5 weight percent. Not
saturating all monoolefins in the hydrogenation step conserves some
hydrogen when compared to prior art processes. It is essential to
the overall conversion of hydrogen that naphthenes such as
cyclohexane are dehydrogenated in the reforming step as these
compounds if fed to the hydrodealkylation step would crack and
therefore additional hydrogen would be consumed.
The reforming system 36 can be of a fixed or moving bed type and
employ a suitable reforming catalyst such as platinum group metals
on a support such as alumina with or without rhenium activation or
Group VI a oxides on a support such as clay, kieselguhr, alumina,
etc. and preferably promoted with halides such as chlorine or
fluorine. The reforming temperature can be from about 850.degree.
F. to about 1,100.degree. F. and preferably is from about
900.degree. F. to 1,000.degree. F. The desired reforming pressure
is from about 150 p.s.i.g. to about 700 p.s.i.g. and preferably
from about 300 p.s.i.g. to about 700 p.s.i.g. Space velocity can be
from 1.0 to 5.0 LHSV or a more preferred range is from 1.5 to 4.0
LHSV. Hydrogen purity is not critical but should be above 40
percent and preferably about 70 percent. The hydrogen to
hydrocarbon ratio can be from 1:1 to about 10:1 and preferably from
5:1 to 10:1. A single bed reforming unit can be employed but it is
more desirable to employ a plurality of beds with heating means
between each bed to supply the endothermic reaction heat and to
raise the reforming temperature level as the hydrocarbon progresses
through the reforming unit. Higher reforming temperatures in the
later reforming stages promotes cracking.
The reformer effluent exits from the reforming section 36 via line
38 and is raised in temperature by heating means 40 to a
temperature higher than the reforming temperature. The reforming
effluent enters the hydrodealkylation section 44 through line 42 at
a pressure slightly less than the reformer pressure. The
hydrodealkylation section converts alkyl aromatics formed in the
reformer section and contained in the pyrolysis naphtha feed to
benzene. Examples of alkyl aromatics originally present or formed
in the reformer section include toluene, xylene, ethylbenzene,
mesitylene, etc. The pyrolysis feed contains a significant
percentage of alkyl aromatics and a substantial additional amount
is formed in the reforming section. The hydrodealkylation step
performs the additional function of cracking remaining nonaromatic
hydrocarbons including those boiling close to the boiling point of
benzene, such as isoheptanes, cyclohexane, thiophene, etc. The
hydrodealkylation system can be operated in one, two, or more
stages to control the exothermic heat of reaction. Recycled cooled
hydrogen can enter a second stage from vessel 54 through line 76 to
line 78 and hence into a second stage of system 44 to maintain the
initial temperature of stage 2 at about the same temperature as
stage 1. At the inlet of each stage or a single stage of section 44
the temperature of the mixture is about 1,100.degree. F. to about
1,400.degree. F., preferably about 1,140.degree. F. to about
1,350.degree. F. and the pressure is about 300 to 1,000 pounds per
square inch gauge, preferably about 350 to 600 pounds per square
inch gauge, while at the outlet of each stage or a single stage the
temperature of the mixture is about 1,325.degree. F. to about
1,400.degree. F. and the pressure is about 300 to 1,000 pounds per
square inch gauge, preferably about 350 to 600 pounds per square
inch gauge. The molar ratio of hydrogen to hydrocarbon in each
stage or a single stage is about 3:1 to 10:1, preferably about 4:1
to 7:1. Calculated on the basis of plug flow through each stage the
residence time of the mixture therein is about 20 to about 200
seconds, preferably about 25 to about 100 seconds.
The hydrodealkylation effluent exits section 44 via line 46 and
enters a hydrotreating finishing section 48 wherein small amounts
of olefins which are generated in the thermal hydrodealkylation
section are saturated. The olefins are usually present in amounts
of 10 to about 1,000 p.p.m. of total hydrocarbon. The hydrotreating
finishing section is only a preferred embodiment of this invention
and is not an essential step. The effluent from section 44 is
cooled prior to entering section 48 by heat exchange 45 to a
temperature of about 200.degree. F. to about 700.degree. F.
preferably about 250.degree. F. to about 600.degree. F. Section 48
contains a suitable hydrogenating catalyst such as metals selected
from Group VI and/or Group VIII supported on a support such as
alumina. The pressure of section 48 is only slightly less than the
pressure of section 44.
The finished hydrocarbon exits section 48 via line 50 through heat
exchanger 52 to vessel 54 where hydrogen is separated from the
hydrocarbon product and recycled after compression (compressor
means not shown) via line 76 to section 44 through line 78 and to
section 26 via line 80. Fresh externally supplied hydrogen such as
purified hydrogen produced in the pyrolysis step, enters line 80
via line 84 and is heated with recycle hydrogen in heater 82 before
entering section 26. The temperature of the product entering vessel
54 is about 100.degree. F. to about 150.degree. F., preferably
about 100.degree. F. to about 120.degree. F. Hydrocarbon product
exits vessel 54 via line 56 to vessel 58 wherein dissolved light
gases such as hydrogen and methane are separated from the product
via line 60. The bottoms from vessel 58 enters fractionator 64 via
line 62 and is stripped of hydrocarbons boiling below benzene the
overhead removed via line 66 and the bottoms via line 68. The
product benzene is separated from the remaining hydrocarbons in
fractionator 70 and removed via line 72. The benzene product has a
purity of about 99.8 percent to 100.0 percent benzene. The bottoms
from tower 70 are recycled to line 18 via line 74.
* * * * *