TECHNICAL FIELD OF INVENTION
[0001] The present invention relates to a method for the efficacious decoking of flame cracking
reactors without interruption of the normal operation of such reactors.
BACKGROUND OF THE INVENTION
[0002] During hydrocarbon cracking processes. carbonaceous deposits are formed on the reactor
walls. Eventually, such carbonaceous deposits, if left to build to undesirable levels,
can seriously restrict the flow of hydrocarbon vapors through the reaction zone vessel
causing the pressure within the reactor vessel to increase to dangerous levels. Consequently,
when a dangerous pressure level is reached, the reactor must be shut down. Many processes
have been developed in the art of hydrocarbon cracking for dealing with this coking
problem.
[0003] U.S. Patents Numbers 3.557.241 and 3.365.387 disclose the introduction of sufficient
steam and/or water to at least one tube of the cracking furnace while simultaneously
reducing the hydrocarbon feed to that tube. The tube is then put back into service.
The treatment of the tube is effected at temperatures ranging from as low as 370°C
(700°F) to about 1100°C (2
000°F). Such heat is supplied by external firing of the reactor tubes. Both patents
utilize a separate and distinct feed line for introducing steam and/or water for the
so-called "on-stream decoking procedure". These lines are controlled by a valve which
is put into service on only those occasions when the individual tube in question being
decoked is undergoing such a cleaning operation.
[0004] While both patents claim a multiplicity of tubes may be decoked at one time. U.S.
Patent No. 3,557.241. specifically states that it "contemplates the decoking of only
a single tube at a time..." (Column 2. Lines 34-36), which is time consuming. Utilizing
this method the furnace will be decoking during virtually all of its operational time.
Furthermore, utilizing these two methods, decoking a multiplicity of tubes at one
time could cause a reduction in the production throughput of the system.
[0005] U.S. Patent No. 3,920,537, deals with the coke deposition evolving from hydrocarbon
cracking operations by "periodically contacting the coke deposit with a jet of relatively
cold, high-pressure water." The patent describes jetting the high-pressure cold water
against the coke deposit in an amount sufficient to thermally shock and break up the
coke deposit, typically at a pressure in excess of about 350 kg/cm
2. This type of decoking technique, however, is only particularly useful where the
coke deposition occurs on surfaces having temperatures of approximately 370°C (700-F)
to 538°C (1,000°F).
[0006] German Patent Application 2923326 (See European Patent Application 0021167) discloses
a method for decoking of equipment used in the thermal cracking of hydrocarbons which
involves a two-step procedure utilizing steam and oxygen. The first step, involves
conducting the gas flow of steam and oxygen through the equipment in an amount such
that the temperature of the coke deposits on the heat exchanging surfaces of the cracking
gas cooler are in the range of the prevailing thermocracking operating temperature.
The second step involves intensifying the gas flow such that the temperature of the
coke deposits on the heat exchanging surface of the cracking gas cooler is increased.
Though this patent does involve a two step process, the second step merely involves
the decoking of a separate piece of equipment, e.g., the heat exchanger.
[0007] U.S. Patent 4,203,778 effects decoking of furnace tubes by the use of a turbulent
stream of impact resistant, non-angular, non-abrasive particles entrained in a gas
stream. The particles are entrained at a concentration of 0.1 to 1.0 kg per kg of
gas and the gas is introduced into the inlet end of the furnace tubes at a gas flow
rate corresponding to an inlet velocity of 4.2 - 6.1 km/minute
[0008] The prior art decoking procedures in the hydrocarbon cracking field, operate under
certain process constraints. The prior art utilizes decoking procedures wherein the
reactors are made of metal. These processes are operated at reaction temperatures
not exceeding about 1100°C. Because the reactors are made of metal, the heat for the
decoking reactors are transferred through the walls. They usually require taking the
reaction train equipment out of service and specially treating that equipment so as
to reduce or eliminate the coking problem. Furthermore, in most cases, these processes
require the dismantling of equipment or the addition of equipment in order to effect
decoking. Such procedures are exceedingly time consuming, and add materially to the
cost of the operation of the hydrocarbon cracking apparatus.
[0009] There have been developed in the art processes for cracking hydrocarbons which utilize
a flame cracking reactor. Such a flame cracking reactor system is depicted in U.S.
Patent No. 4,136.015. In particular, this patent refers to the "Advanced Cracking
Reactor" (ACR) process. As characterized in said patent:
"In the 'Advanced Cracking Reactor' (ACR) process, a stream of hot gaseous combustion
products is developed in a first-stage combustion zone. The hot gaseous combustion
products may be developed by the burning of a wide variety of fluid fuels (e.g. gaseous,
liquid and fluidized solids) in an oxidant and in the presence of super-heated steam.
The hydrocarbon feedstock to be cracked is then injected and mixed in a second stage
zone into the hot gaseous combustion product stream to effect the cracking reaction.
Upon quenching in a third stage zone, the combustion and reaction products are then
separated from the stream."
[0010] The ACR process is described in varying detail in the following patents: U.S. Patent
No. 3,408,417; U.S. Patent No. 3,419,632: U.S. Patent No. 4,136,015: U.S. Patent No.
3,674,679: U.S. Patent No. 3,795,713: U.S. Patent No. 3,855,339: U.S. Patent No. 4,142.963:
U.S. Patent No. 4,150,716: U.S. Patent No. 4,240,898: U.S. Patent No. 4,321,131: U.S.
Patent No. 4,134,824; and U.S. Patent No. 4,264,435.
[0011] In addition to the aforementioned patents which are specifically directed to the
ACR process, other patents directed to the cracking of hydrocarbons by a flame-cracking
process include U.S. Patent No. 2,698,830. U.S. Patent No. 3,565,970, and U.S. Patent
No. 2,371,147.
[0012] - In the operation of such flame-cracking processes for converting hydrocarbons into
more volatile components, it is necessary to effect the reaction in a reaction zone
that contains a protective surface of a high-temperature resistant material which
is also resistant to the products of the reaction. Illustrative of such materials
are graphite, silicon carbide, alumina, zirconia. magnesia, calcium oxide and the
like. All of these materials are extremely resistant to high temperatures but have
low thermal conductivity. The continuous operation of the ACR process and a flame-cracking
reaction process in general, causes coke deposition on the reactor walls. For example,
U.S. Patent No. 4,136.015 utilizes a reaction zone in which the stream therein is
maintained at supersonic velocity flows. Coke formation in a system such as this,
will materially alter the nature of the flows, thereby rendering the reaction process
less controllable.
[0013] There is described herein a process whereby the coking problem can be effectively
controlled and which circumvent the physical limitations of the aforementioned ceramic
linings, i.e., low thermal conductivity. Furthermore this invention provides a method
of decoking without alteration or dismantling of the reaction assembly.
SUMMARY OF THE INVENTION
[0014] This invention is an improvement in the continuous process of cracking hydrocarbon
feeds in a flame cracking reactor.
[0015] This invention involves a method for effecting on-line decoking during a flame-cracking
reaction such as that embodied in the ACR process. Processes such as the ACR, involve
the combustion of a carbonaceous or hydrogen-containing fuel with oxygen and the resulting
combustion product stream is mixed with superheated steam to produce a heat carrier.
The heat carrier is contacted with converging hydrocarbon feedstock'streams in a zone
juxtaposed and openly connected to the zone in which the flame is formed. The mixture
is then passed into an reaction zone wherein cracking takes place. Carbon deposits
are formed on the reactor walls during the operation of the reactor.
[0016] This invention involves periodically stopping the flow of hydrocarbon feedstock streams
utilized in the flame cracking reaction process (e.g., the ACR process) while maintaining
the temperature of the heat carrier flow to the reactor at an appropriate rate and
at about 1000°C to 2000°C for a period of time sufficient to reduce the carbon deposits
to a predetermined level. The combustion gases may be produced by burning a fuel derived
from the products of the cracking process or an alternative process fuel. The normal
operation of the process may then resume by restarting the flow of feedstock and re-adjusting
the combustion products to their normal flow and temperature.
[0017] The removal of certain deposits, commonly referred to as decoking, is carried out
by periodically adjusting the fuel rate or the oxygen rate or the fuel to oxygen ratio
to produce combustion products which have the desired composition and properties of
temperature and velocity. Additionally, the steam rate can be changed to modify the
operating temperature and velocity. The mixture of combustion products and steam constitute
decoking gases.
[0018] At the start of the decoking operation, the hydrocarbon feed rate is lowered to a
level consistent with the decreased burner flow. The feedstock stream is then completely
stopped for a period sufficient to reduce the carbon deposits to an acceptable level
for continued operation. Once ,the decoking operation is completed , the normal hydrocarbon
feed rate is resumed and the cracking operation is continued.
[0019] The method of this invention, as compared to conventional decoking methods, has the
advantage of allowing the operated machinery to be completely decoked in a short amount
of time, i.e., usually three hours or less. Thus, it does not require the removal
of downstream equipment and the reactor need not be disassembled, mechanically altered,
or connected to additional equipment.
DISCUSSION OF THE INVENTION
[0020] The operation of the flame-cracking reactions are well described in the references
previously cited. It is the purpose of this invention to eliminate a problem which
occurs during their continued operation: the coke formation that results during the
normal period of operation of these processes.
[0021] It is well known that carbon can react with a number of chemicals which are present
during a high-temperature hydrocarbon cracking reaction. Carbon, for example, will
react with water to form carbon monoxide and hydrogen. It reacts with carbon dioxide
to form carbon monoxide. Furthermore, carbon can be hydrogenated to methane by reaction
with hydrogen and can be oxidized to carbon dioxide and carbon monoxide by reaction
with oxygen. It is the purpose of this invention to utilize all of these known chemical
reactions to remove the carbon that has been deposited within an ACR or a typical
flame-cracking process reactor.
[0022] The,problem of effectuating carbon removal in the instant case is not as simple as
the application of the known chemical reactions stated above. During the operation
of flame-cracking reactors such as the ACR reactor. in particular, the temperature
of the reaction zone ranges as high as 2000°C, and even higher. As the temperature
within a reactor of this nature increases, carbon depositions along the wall can become
more graphitic in nature and consequently, a layer of carbon which is remarkably resistant
to chemical reactions can form. Indeed, such graphitic carbon could be used as an
insulating layer for such a reactor. The term graphitic carbon is intended to include
carbon which has undergone a sufficient amount of heat treatment such that its crystalline
structure becomes either graphite-like or as that of pure graphite.
[0023] The deposited coke can be eliminated by flowing a hot steam containing stream (such
as steam) over it for a time sufficient to convert at least a portion of said coke
to a gaseous material by chemical reaction. This can be best accomplished by controlling
the temperature and velocity of the gaseous stream formed by the burning of carbonaceous
ar hydrocarbon-containing fuel, and transporting those combustion products to the
reaction zone. Simultaneously, the temperature of the reaction zone must be maintained
at 1000°C to about 2000°C for a period of time sufficient to effectively reduce the
carbon deposit. Preferably, the velocity of the stream in the reaction zone should
be such as to provide a carbon removal rate sufficient to meet the process requirements
of a typical hydrocarbon cracking commercial facility. Minimally, the combustion product
velocity should be such as to provide for stable combustion of the carbonaceous or
hydrocarbon-containing fuel. The maximum velocity preferred would be a supersonic
velocity within the reaction zone.
[0024] In the preferred operation of the process. a higher velocity gas stream is preferred
for carbon removal. It is believed that such a high velocity stream enhances the gasification
of the carbon and also enhances the physical removal of particulate carbon from the
surface of the reactor walls.
[0025] The primary chemical reaction relied upon for carbon removal in the practice of this
invention is carbon gasification: the reaction of carbon with steam to form carbon
monoxide and hydrogen. This reaction to be most effective requires the presence of
enough steam within the combustion zone to efficaceously remove the deposited carbon.
In the typical case. the amount of steam which is present should be at least approximately
10 weight per cent versus the weight of the stream fed to the reaction zone. This
amount can be reduced should the velocity of that stream be increased. However, the
amount of steam can exceed 10 weight per cent and can be as high as 100 per cent of
the weight of the stream, e.g., use of hydrogen as a fuel for producing the hot gaseous
stream will provide that the stream is all water/steam.. This mechanism provides for
the actual physical removal of carbon by spalling,and thermoshock techniques which
will be discussed below.
[0026] Where the carbon deposit becomes graphitic. carbon removal might necessitate more
severe treatment such as, the utilization of gas streams with higher concentrations
of steam and the operation of such streams at higher velocities and temperatures to
induce cracks within the carbon structure which greatly increase the gasification
rate by providing more surface area per unit volume. Additionally, these cracks enhance
the potential for the flaking away of the carbon deposit from the reactor walls. In
the art, this phenomena is referred to as "spalling".
[0027] The elimination of carbonaceous deposits by spalling results from the achievement
of a thermal gradient across the carbon thickness. A natural temperature gradient
exists throughout the coke and the reactor walls and'by quickly increasing the temperature
of the decoking gases, this temperature gradient is increased. Gases with higher temperatures
and velocities will tend to cause more spalling as well as faster chemical reaction
rates. A high temperature gradient can be achieved by a rapid rise in the temperature
of the decoking gases in the reactor, that is, bringing the reactor to a maximum decoking
temperature during a short period of time. This greatly enhances the spalling effect.
causing thermal stress in the, form of cracking within the coke: thereby, allowing
it to more readily react with the steam and other reactants present in the decoking
gas.
DETAILED DESCRIPTION OF INVENTION
[0028] In order to describe the invention. references will be made to the drawings in U.S.
Patent No. 4,136.015 which graphically and schematically depict an ACR reaction assembly.
In particular Figure 3, thereof, shows a cross-sectional view of the critical components
typically found in an ACR reactor.
[0029] A cracking reactor utilizes the heat of combustion of a carbonaceous or hydrogen-containing
fuel with oxygen, either as pure oxygen gas, air, or oxygen mixed with other gases,
to heat a hydrocarbon feedstock to its appropriate cracking temperature. The combustion
fuel may comprise, for example, the gases produced by the high-temperature partial
combustion of coal or coke with oxygen, or any fluid hydrocarbon material such as
natural gas and/or hydrogen. These fuels and their combustion products are well-known
in the art.
[0030] The combustion products can be formed by mixing a gaseous hydrocarbon, or hydrocarbon
mixtures with oxygen utilizing a metal burner with a gas combustion chamber assembly
as set forth in copending U.S. Patent Application Serial No. 335,6l6, filed December
30, 1981. The combustion gases may be produced by burning a fuel derived from the
products of the cracking process or an alternative process fuel. The hydrocarbon feedstock
thereafter is introduced into the reactor, in a mixing zone, typically in a direction
angular to the flow of the combustion product stream. This admixing occurs preferably,
in a direction not only angular but countercurrent to the direction of the product
stream. The angular introduction of the hydrocarbon feed is described in particular
in U.S. Patent No. 4.142.963. U.S. Patent No. 3.674.679. U.S. Patent No. 3.4
08.417, U.S. Patent 3.419,632.
[0031] U.S. Patent No. 3,855,339, and U.S. Patent No. 4,136,015 both specifically apply
to feeding the hydrocarbon feed into the reactor in the form of an atomized spray
of liquid droplets in a manner such that said material is linearly injected in a radial
direction towards the center axis of the reactor. and countercurrently at an angle
of 120° to 150° to the passing direction of the heating medium stream which is the
combustion gases.
[0032] In practicing the preferred embodiment of the ACR process, the hydrocarbon feed to
be cracked is enveloped in a steam shroud, which not only enhances the introduction
of the feed to the reaction zone but also protects the metal injectors and inhibits
carbon deposition at the feed inlet points. The feed and the combustion product stream
are thoroughly intermixed and fed through the constricted throat into the diffuser/reactor
portion of the ACR reactor. The velocity of the stream through the throat is preferably
sonic velocity and develops supersonic velocity upon exit from the throat in the diffuser/reactor
section: all of which is described in considerable detail in U.S. Patent No. 4,136,015.
The effluent from the diffuser/reactor section as shown in Figure 1 of U.S. Patent
4,136,015 enters the quench zone. whereupon the reaction is stopped and product recovery
begins. This.is more specifically described in U.S. Patent No. 4,150,716.
[0033] The fuel which is utilized to form the combustion product stream is typically a mixture
of hydrogen and methane. Typically, the oxidant is essentially pure oxygen. This combination
is reacted and then moderated by the addition of steam diluent to achieve a combustion
product stream having a temperature of about 1600° to about 2400'C. The combustion
product stream is thereafter contacted with the hydrocarbon feedstock which is fed
in an essentially countercurrent direction to that of the combustion product streams
through a number of injectors which openly connect to the interior of the ACR. Each
of these injectors is surrounded by concentric annular feed zones which introduce
the steam shroud which circumscribes the hydrocarbon feed. The shrouded hydrocarbon
feedstock stream mixes with the combustion product stream slightly above a throated
section within the ACR. This is more specifically described in Figure 3 of U.S. Patent
No. 4.136.015 and Figure 1 of U.S. Patent No. 4,142,963. An illustration of specific
injector arrangements utilized for the introduction of the hydrocarbon feedstock and
its steam shroud can be found in Figures 3a, 4a, and their corresponding Figures 3b
and 4b of U.S. Patent 4.142,963. The operative conditions by which such a reaction
is carried out are fully described in U.S. Patent 4.136.015.
[0034] The mixture of feedstock, combustion product stream and shroud steam flow through
the throated section of the ACR reactor to obtain sonic velocity and thereafter issue
into the diverging supersonic velocity diffuser/reaction zone wherein the cracking
reaction to produce the more volatile products is effected. It is within the expanded
reaction zone and the throated zone that the carbon deposits develop in quantities
sufficient to eventually adversely affect the overall process.
[0035] The process of this invention most efficiently removes deposited carbon products
within the aforementioned zones in a manner which does not require any dismantling
of apparatus or the inclusion into the apparatus of other equipment. The process of
this invention allows one to utilize the ACR process, for example, without having
to make any changes in any of the downstream apparatus normally associated therewith.
In the typical case. no uncoupling of downstream equipment is necessary during the
decoking operation as herein described.
[0036] In carrying out this preferred embodiment. the temperature which is achieved in the
combustion reaction is from about 1000°C to about 2400°C. These unusually high temperatures
would necessitate a lining capable of withstanding these high temperatures.
[0037] In the practice of this invention, it is preferable to maintain the highest concentration
of oxygen allowable so as to enhance the rate of decoking by the reaction of such
oxygen with the coke. The concentration of oxygen is limited by safety considerations
such as the flammability of the overall mixture.
[0038] The preferred embodiment of the present invention involves the practice of a two
stage method. The decoking is begun by reducing the burner flow capacity to approximately
70% of its usual mass flow rate, while maintaining the reactor at a temperature between
approximately l150°C-1200°C for a two hour period. The burner flow capacity is actually
the mass flow rate of the high temperature gas used in normal operation.
[0039] When utilizing this preferred embodiment, a steam purge is normally put through a
metal steam curtain just upstream of the quencher to protect it from high temperatures.
Once the inlet pressure is reduced to lower levels, indicating that decoking has been
completed in the reactor, throat and diffuser the burner flow capacity is raised in
the second stage of the process to approximately 90% and the decoking temperature
is increased to 1300°C for a period of one hour. The steam purge to the quencher is
then simultaneously decreased. It is this downstream decrease in the steam purge to
the quencher that allows the quench zone to be decoked.
[0040] As the coke deposition increases, the diameter of the throat decreases, and the overall
area of the reactor/diffuser section is reduced. Consequently, it is possible thereby,
with reduced velocity in the combustion gas stream to maintain the sonic conditions
in the throat and supersonic conditions in the reactor/diffuser section.
[0041] Utilizing the combustion products stream which has an extremely high temperature
will, of course, enhance the gasification of the coke deposited on the reactor walls.
However, such high temperatures can adversely affect the ceramic lining of the reactor
and, therefore, in choosing the conditions at which the decoking process is operated,
it is necessary to take into consideration the issue of mechanical integrity. The
most preferred method of effecting coke removal is to utilize the most stringent conditions
in terms of temperature, steam concentration, and the like that the particular reactor
assembly will accept. This then allows for decoking in the shortest period of time.
[0042] An alternate embodiment of the present invention involves the practice whereby decoking
is achieved by reducing the burner flow capacity to approximately 55%. The reactor
temperature is maintained between approximately 1150°C-1200°C for the entire decoking
period. A steam purge is put through the quencher steam curtain to protect it from
high temperatures and said steam purge remains at this level throughout the entire
decoking process.
[0043] Another alternate embodiment of the present invention involves a two stage process
whereby different temperature levels are utilized to facilitate the decoking process.
The burner flow capacity is reduced to approximately 70% while maintaining the reactor
at a temperature between approximately 1350°C-1400°C. Utilizing this alternate embodiment,
a steam purge is put through the quencher steam curtain to protect it from high temperatures.
The reactor is maintained at this temperature for a period of time sufficient to detect
a noticeable decrease in the pressure, indicating the decoking process is almost at
completion, in this instance usually about thirty minutes. The reactor temperature
is then elevated to approximately 1450°C for the remainder of the decoking period,
approximately one hour.
EXAMPLES
Example 1
[0044] A pilot-scale flame-cracking ACR reactor, with an ethylene capacity of 113,500
kg /yr., is operated with a whole distillate of Arabian Light crude as the feedstock.
A "whole distillate is a blend of the overhead product from the atmospheric and vacuum
distillation of a crude oil," i.e., a crude oil minus the residual oil obtained following
vacuum distillation. The burner uses essentially pure hydrogen and oxygen; steam is
added to moderate the temperature of the combustion products. Thus the effluent from
the burner consists mainly of superheated steam with small amounts of unconsumed hydrogen.
The reactor exit pressure is kept at 3,5 kg/cm
2
[0045] At the beginning of the run, the required inlet pressure to the reactor is 4.1 kg/cm
2 over a period of about six hours run time, the inlet pressure gradually increases
to about 5.
4 kg/cm
2 indicating the coke is depositing and is restricting the reactor.
[0046] To decoke the reactor, the burner is first adjusted to conditions which would result
in a reactor temperature of approximately 1200°C if no feed were being injected. Feed
to the reactor is stopped, and the reactor pressure is reduced to about 2.1 kg/cm
2 and held constant. Total burner effluent is reduced to about 66 percent of normal
operating rates. Without feed injection to absorb the endothermic heat of reaction,
the reactor temperature rises to about 1200°. At the start of the decoking process,
the inlet pressure is about 3.8 kg/cm
2: after about 10 minutes of decoking, the inlet pressure decreases to about 3.2 kg/cm2
indicating that the coke is being removed. Further operation does not result in another
decrease in inlet pressure. indicating that all the coke has been removed.
[0047] At this point the reaction could have been reinstated by reversing the above procedure.
However, the reactor is shut down and disassembled for inspection. The ceramic lining
of the reactor is found to be clean and substantially, free of traces of coke. No
damage to the reactor resulted from the decoking. Had the reactor been decoked according
to the prior art, the process would have taken at least two days and the coke would
not have been removed as completely as accomplished by the invention.
EXAMPLE 2
[0048] An ACR with an ethylene capacity of 2,270,000 kg/yr is operating with vacuum gas
oil as cracking feestock. The burner fuel is a mixture of gaseous hydrocarbons and
hydrogen, which is burned in substantially pure oxygen. Steam is added to moderate
the burner temperature. About five percent more than the stoichiometric quantity of
fuel is used, so the burner effluent consists mainly of high temperature carbon oxides
and steam, with a small amount of unconsumed fuel. The reactor outlet pressure is
kept at about 2.8 kg/cm
2. At the start of the run, inlet pressure is about 4.8 kg/cm: during the course of
several days operation, inlet pressure gradually increases to about 5.2 kg/cm
2 indicating that coke is depositing in the reactor.
[0049] To decoke the reactor, first the feed and burner are adjusted to about half the normal
flow rates. The feed is then turned off completely, and the burner adjusted to obtain
a temperature in the reactor of about 1150°C to 1200°C. A steam purge of about 227
kg/hr is put through the quencher steam curtain to protect it from high temperatures.
The reactor is maintained at these conditions for approximately three hours. At the
end of that time, the process is reversed and the reactor is returned to normal operating
conditions. The inlet pressure to the reactor has returned to about 4.8 kg/
em2 demonstrating that the coke has been removed.
[0050] - During the decoking process, the downstream processing equipment, such as the gasoline
fractionator, is kept in standby mode. The decoking period is so short that the downstream
equipment is easily returned to normal operating conditions, with very little upset
to the overall process.
EXAMPLE 3
[0051] The reactor is operated and coking occurs as described in Example 2. The decoking
process is conducted similarly, except that the temperature in the reactor is adjusted
to about 1350°C to 1400°C. and the decoking is only carried out for about 30 minutes.
The steam purge through the quencher curtain as in Example 2 is used to protect the
quencher. After decoking, the reactor inlet pressure has again returned to its usual
level. demonstrating that the coke has been removed. Coke chips are later discovered
in a downstream strainer, indicating that some of the coke has been removed either
by spalling, or by the mechanical force of the decoking gas stream.
EXAMPLE 4
[0052] The reactor is operated and coking occurs as described in Examples 2 and 3. The decoking
process is conducted at about 1150°C to 1200°C for about two hours, and then at about
1350°C to 1400°C for about one hour. After decoking. the reactor is returned to normal
operating conditions by reversing the process, and the inlet pressure returns to its
normal level. During this entire process the quencher steam purge remains constant
at 22
7 kg/
hr.
[0053] No coke chips are discovered in any downstream equipment, indicating that the bulk
of the coke was removed by chemical reaction in the first two hours of the proces.
This avoids any possible problems of coke chips clogging downstream equipment. The
final hour at a higher temperature ensures that any traces of coke which are especially
resistant to chemical reaction are removed, because reaction rate increases greatly
with a 200°C increase in temperature.
EXAMPLE 5
[0054] The reactor is operated as described in EXAMPLE 2. After several days of operation,
the inlet pressure increases to about
5.2 kg/em
2. In addition, the pressure drop across the quencher increases from its normal value
of about
0.
35 kg/
cm2 to about 1.05 kg/cm
2 indicating that coke is depositing in the quencher. Decoking is begun with a reactor
temperature of about 1150° to 12
00°C. A steam purge of about 227 kg/hr is put through the quencher steam curtain to
protect it from high temperatures.
[0055] At the beginning of the decoking, the pressure drop across the quencher is about
0.7 kg/cm
2 After about two hours of decoking, the pressure drop across the reactor has dropped
to a level indicating that the reactor is effectively decoked. The pressure drop,
however, across the quencher remains about 0.7 kg/cm
2. At this point, the decoking temperature is increased to about 1350°C to 1400°C and
the steam purge to the quencher is decreased to 64 kg/hr. This decrease in the steam
purge to the quench zone enables said zone to be effectively decoked. The pressure
drop across the quencher begins to decrease almost immediately, indicating that coke
is being removed. The reactor is decoked for about another hour at these conditions.
After a total of about three hours decoking. the process is reversed and the reactor
is returned to normal operating conditions. Inlet pressure to the reactor has returned
to about 4.8 kg/cm
2 and pressure drop across the quencher has decreased to the original demonstrating
that the reactor and quencher have been effectively decoked.
[0056] Examples 2, 3 and 4 illustrate three possible embodiments of the invention for decoking
the reactor. Any of these three methods or some modification of these methods may
be used depending upon the circumstances. Example 2 describes a method which is unlikely
to cause excessive reactor wear because the temperatures never exceed about 1200°C.
Example 3 is effective in a shorter period of time, but causes some coke chips to
be carried out of the reactor into the downstream equipment. This may result in faster
reactor wear because of the use of higher temperatures. Example 4 eliminates the problem
of the coke chips and because of the increased temperature (for the last part of the
cycle), is very effective at removing the last vestiges of coke. However, this method
requires more time than the method of Example 3, and it exposes the reactor to higher
temperatures than the method of Example 2. -The method of Example 2C is thought to
be the most preferred embodiment at this time, but the other methods are acceptable
and may be preferred in some circumstances.
[0057] Example 5 illustrates how the invention can be extended to the decoking of downstream
equipment, which is not normally thought of as part of the main reactor section. The
decoking gases are conducted through that equipment and the temperature there is adusted.
The method of Example 5 is identical to that of Example 4, except that the flow of
purge steam through the quencher curtain just upstream of the quencher is reduced,
allowing the temperature in the quencher to rise to the level necessary for effective
decoking.