U.S. patent number 3,617,478 [Application Number 05/056,264] was granted by the patent office on 1971-11-02 for suppression of coke formation in a thermal hydrocarbon cracking unit.
This patent grant is currently assigned to Jefferson Chemical Company, Inc.. Invention is credited to Sidney Theodore Jones, James Ely King, Jr..
United States Patent |
3,617,478 |
King, Jr. , et al. |
November 2, 1971 |
**Please see images for:
( Certificate of Correction ) ** |
SUPPRESSION OF COKE FORMATION IN A THERMAL HYDROCARBON CRACKING
UNIT
Abstract
Coke formation and deposits in the inline heat exchanger of a
thermal hydrocarbon cracking unit comprised of a thermal-cracking
zone, a quenching apparatus and the heat exchanger are removed and
prevented by introducing an aqueous solution of an alkali metal
salt or hydroxide into the hydrocarbon flow at a point downstream
of the cracking zone of the unit.
Inventors: |
King, Jr.; James Ely (Groves,
TX), Jones; Sidney Theodore (Port Neches, TX) |
Assignee: |
Jefferson Chemical Company,
Inc. (Houston, TX)
|
Family
ID: |
22003271 |
Appl.
No.: |
05/056,264 |
Filed: |
July 20, 1970 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
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872220 |
Oct 29, 1969 |
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Current U.S.
Class: |
208/48AA;
585/650; 585/950; 585/648 |
Current CPC
Class: |
C07C
4/04 (20130101); C07C 5/321 (20130101); C07C
4/06 (20130101); C10G 9/16 (20130101); C07C
2527/232 (20130101); C07C 2523/04 (20130101); Y10S
585/95 (20130101) |
Current International
Class: |
C07C
4/04 (20060101); C07C 5/00 (20060101); C07C
4/06 (20060101); C07C 5/32 (20060101); C10G
9/16 (20060101); C10G 9/00 (20060101); C07C
4/00 (20060101); C10g 009/16 (); C07c 005/18 ();
C07c 011/06 () |
Field of
Search: |
;208/48 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Gantz; Delbert E.
Assistant Examiner: Schmitkons; G. E.
Parent Case Text
Cross-Reference to Related Application
This application is a continuation-in-part of our copending
application Ser. No. 872,220 filed Oct. 29, 1969, now abandoned.
Claims
We claim:
1. In a thermal hydrocarbon cracking process wherein the
hydrocarbon cracking apparatus comprises a thermal-cracking zone, a
quenching apparatus and an in-line heat exchanger arranged in
series such that the gaseous effluent from the cracking zone flows
through the quenching apparatus and then through the exchanger, the
improvement which comprises
introducing an aqueous solution of alkali metal salt which yields
an alkaline product on hydrolysis or an alkali metal hydroxide into
the hydrocarbon flow at a point downstream of the cracking
zone.
2. A process according to claim 1 wherein the aqueous solution is
of potassium carbonate, potassium bicarbonate, sodium carbonate,
sodium hydroxide or potassium hydroxide.
3. A process according to claim 2 wherein the aqueous solution is
of potassium carbonate, sodium carbonate, potassium hydroxide or
sodium hydroxide and the solution is introduced into the
hydrocarbon flow at the quenching apparatus.
4. A process according to claim 3 wherein the potassium carbonate,
sodium carbonate, potassium hydroxide or sodium hydroxide is fed to
the apparatus in a proportion of 1 to 200 p.p.m. of the hydrocarbon
feed to the cracking zone.
5. A process according to claim 4 wherein the potassium carbonate,
sodium carbonate, potassium hydroxide, or sodium hydroxide is in a
proportion of about 20 to 30 p.p.m. of the hydrocarbon feed.
6. A process according to claim 3 wherein potassium carbonate is
introduced into the hydrocarbon flow at the quenching
apparatus.
7. A process according to claim 6 wherein potassium carbonate is
fed to the apparatus in a proportion of 1 to 200 p.p.m. of the
hydrocarbon feed to the cracking zone.
8. A process according to claim 7 wherein the potassium carbonate
is in a proportion of about 20 to 30 p.p.m. of the hydrocarbon
feed.
9. A process according to claim 8 wherein a coke collecting vessel
is mounted beneath the quenching apparatus and open thereto.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention is a method for prolonging the cycle time between
shutdowns of a thermal-cracking unit in which ethylene and
propylene are made by the thermal cracking of lower alkanes.
Specifically, this invention is a method for decreasing coke
buildup in the heat exchanger employed in the cracking unit by
introducing an aqueous solution of alkali metal salt or hydroxide
into the unit at a point downstream of the cracking zone.
2. Description of the Prior Art
Kohfeldt's s U.S. Pat. No. 2,893,941 (1959 ) discloses a process
for treating liquid hydrocarbons such as heavy naphtha, kerosene,
and gas oil which involves the steps of thermally cracking the
hydrocarbon in the presence of potassium carbonate and steam
wherein the potassium carbonate is added as an aqueous solution
preferably at a point upstream from the thermal-cracking zone. The
preferred Kohfeldt teaching was followed by adding an aqueous
potassium carbonate solution to a thermal-cracking unit for lower
alkanes at a point upstream of the cracking zone and the unit
became plugged with coke formation at the in-line heat exchanger
within 7 days. The operating time in a unit wherein no potassium
carbonate is used is about 7 days; therefore, Kohfeldt's preferred
process is unworkable in our unit for all practical purposes.
We have found that by adding an aqueous potassium carbonate
solution to the process in a unit for making ethylene and propylene
or other olefins at a point downstream of the cracking zone, the
furnace can operate without plugging for as long as 74 days, a more
than ten-fold improvement over introducing the carbonate to the
cracking unit as taught by Kohfeldt's preferred method. And the
reason for shutdown of the unit after 74 days operation was not
because of plugging due to coke formation in the heat exchanger but
because of coke formation in the reactor coil upstream of the
quench fitting. Comparable improvements are shown using other
alkali metal salts or hydroxides of our invention.
SUMMARY OF THE INVENTION
The invention is an improvement in a thermal hydrocarbon cracking
process comprised of a thermal-cracking zone, a quenching apparatus
and an in-line heat exchanger arranged in series such that the
gaseous effluent from the cracking zone flows through the quenching
apparatus and then through the exchanger. The improvement is
introducing an aqueous solution of alkali metal salt which yields
an alkaline product on hydrolysis or an alkali metal hydroxide into
the hydrocarbon flow at a point downstream of the cracking
zone.
DESCRIPTION OF THE DRAWING
The invention will be further illustrated with reference to the
accompanying drawings. In FIGS. 1 and 2, a feed gas is introduced
by means of line 1 into a cracking heater 2 where the gas is heated
at a temperature above 1400.degree. F. The effluent gases, at a
temperature about 1,530.degree. F., pass from the cracking heater 2
by means of line 3 to the quenching apparatus 4. Sufficient water
to cool the gases to 1,000.degree. -1,400.degree. F. is introduced
at the top of quenching apparatus 4 in a fine spray by means of
line 5 or alternatively by line 3. The addition of an alkali metal
salt or hydroxide to the prequench water successfully suppresses
the formation of heavy hydrocarbon and prevents coke and polymer
formation in the transfer line 6 which feeds the gases to the heat
exchanger 7 where they are cooled from the temperature of
1,000.degree. -1,400.degree. F. to a temperature of 400.degree.
-1,000.degree. F. Quenching apparatus 4 can contain a baffle 10
against which the quenched gases impinge. In the exchanger, the
heat removed from the gases is used to generate steam, which may
then be used in other plant operations. These cooled gases then
pass from heat exchanger 7 by means of line 8 to a quench tower
which forms no part of the present invention. Beneath quenching
apparatus 4, there can be located a coke collecting vessel 9 which
is shown in FIG. 1 as an integral part of the quenching
apparatus.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
In the production of olefinic hydrocarbons such as ethylene,
propylene and other cracked products by thermally cracking gaseous
and vaporizable liquid hydrocarbons in a tubular pyrolysis furnace
at high temperatures in the presence of steam and using short
residence time, often referred to as high severity cracking, which
is followed by immediate cooling or quenching of the cracked
effluent to minimize secondary reactions by direct or indirect
cooling means; coke deposits and other cracked deposits often form
at critical points in the apparatus. Such deposits cause
interruption of onstream time of the cracking furnace and produce a
serious economic problem. We have discovered that an aqueous
solution of an alkali metal salt which yields an alkaline product
on hydrolysis or an alkali metal hydroxide, for example, potassium
carbonate, potassium bicarbonate, sodium carbonate, sodium
bicarbonate, lithium carbonate, barium carbonate, potassium
hydroxide, sodium hydroxide, magnesium hydroxide, barium hydroxide
or lithium hydroxide injected in small quantities into the
hydrocarbon flow path of prequenching and subsequent cooling
apparatus removes or prevents coke deposits and other cracked
deposits downstream from the cracking zone. These deposits have
been such a problem prior to our discovery that it was necessary to
shut down the unit at least every 7 days in order to remove the
coke deposits. Aqueous solutions of potassium carbonate, potassium
bicarbonate, sodium carbonate, sodium hydroxide or potassium
hydroxide are preferred in the practice of our invention. By adding
an aqueous solution of these salts or hydroxides downstream from
the cracking zone, i.e., in the cooling or quenching apparatus
including the quench and coke pots, the quench boilers and transfer
line exchangers and connecting piping in the cracked hydrocarbon
flow path, coking problems have been reduced significantly. In
addition, the quench water is cleaner and less oils are formed when
our improvement is used, illustrating a reduction in secondary
reactions which thereby abates water pollution because of the
reduction of total carbon going into the quench water. By reducing
the amount of carbon added to the quench water, less oxygen is
removed from the receiving water bodies which are, for example,
lakes and rivers. The determination of the amount of total carbon
in the quench water is determined by the Beckman Carbonaceous
Analyzer and shows a 28 percent reduction in organic carbon in the
water. The carbonates or hydroxides may be introduced into the unit
in a proportion of 1 to 200 parts per million of the hydrocarbon
feed to the cracking furnace. The preferred range of carbonate is
about 20-30 p.p.m. of the hydrocarbon feed.
To further illustrate the improvement of our invention, a
test-cracking furnace was put on stream, after decoking, under
normal operating conditions and an aqueous solution of potassium
carbonate, 25 to 30 p.p.m. based on the hydrocarbon feed, was
continuously injected into the quench pot via the quench water
nozzle. After 62 days of operation, the unit was shut down for
inspection and repairs. Inspection revealed less coke fouling than
normally found after only a few days operation with no potassium
carbonate treatment.
A second test showed similar results to those described above. A
test-cracking furnace was put on stream after decoking under normal
operating conditions. An aqueous solution of potassium carbonate,
25 to 30 p.p.m. based on hydrocarbon feed, was continuously
injected into the quench pot via the quench water nozzle. After 41
days on stream, the furnace was shut down prematurely for
inspection. Inspection revealed no coke deposits in the quench pot
or on the surface of the connecting pipe up and down stream of the
transfer line exchanger and there was less coke on the inlet tube
sheet of the transfer line exchanger that previously encountered
after only a few days operating time without using potassium
carbonate. A similar furnace run was made for cracking lower
alkanes wherein an aqueous solution of sodium carbonate, 25 to 30
p.p.m. based on hydrocarbon feed, was continuously injected into
the quench pot via the quench water nozzle. After 35 days of
operation, the unit was still running with no indication of coke
buildup in the in-line heat exchanger. A further similar furnace
run was made for cracking lower alkanes wherein an aqueous solution
of potassium hydroxide, 25 to 30 p.p.m. based on hydrocarbon feed,
was continuously injected into the quench pot via the quench water
nozzle. After 35 days of operation, the unit was still running with
no indication of coke buildup in the in-line heat exchanger.
Comparable results are obtained using other salts or hydroxides of
our invention.
In an attempt to carry out the addition of potassium carbonate to
the cracking zone as taught in the preferred method of Kohfeldt's
U.S. Pat. No. 2,893,941, a test-cracking furnace was put on stream
after decoking under normal operating conditions and an aqueous
solution of 25 to 30 p.p.m. potassium carbonate based on the
hydrocarbon feed was continuously injected into the cracking zone
with the hydrocarbon. The unit had to be shut down after 7 days of
operation due to plugging caused by coke formation in the transfer
line exchanger.
To further illustrate the improvement of our invention,
test-cracking furnaces for cracking lower alkanes were operated
under normal conditions while an aqueous solution of potassium
carbonate, 25 to 30 p.p.m. based on the hydrocarbon feed, was
continuously injected into the quench pots via the quench water
nozzles for a period of 3 months. The formation of heavy oils,
hydrocarbon polymer and aromatic distillate was measured and
compared to the same formation accumulated in 3 months in a unit
where no potassium carbonate was used. The data in the following
table illustrate the decrease in heavy hydrocarbon production when
our improvement is used. Even though the aromatic distillate
decreases when our process is used, better quality products in the
aromatic distillate are obtained. ##SPC1##
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