U.S. patent number 3,900,390 [Application Number 05/409,216] was granted by the patent office on 1975-08-19 for metal, sulfur and nitrogen removal from hydrocarbons utilizing moving-bed reactors.
This patent grant is currently assigned to Universal Oil Products Company. Invention is credited to Frank H. Adams, Robert F. Anderson.
United States Patent |
3,900,390 |
Adams , et al. |
* August 19, 1975 |
Metal, sulfur and nitrogen removal from hydrocarbons utilizing
moving-bed reactors
Abstract
Hydroprocessing of hydrocarbon charge stocks which contain
sulfur and various metals is performed using two moving-bed
reactors connected in series; intermittently fresh catalyst is
added to and used catalyst is removed from the second reactor, the
used catalyst is regenerated and charged to the first reactor for
use in metals removal and initial hydrotreating of the charge
stock.
Inventors: |
Adams; Frank H. (Lagrange Park,
IL), Anderson; Robert F. (Lagrange Park, IL) |
Assignee: |
Universal Oil Products Company
(Des Plaines, IL)
|
[*] Notice: |
The portion of the term of this patent
subsequent to March 5, 1991 has been disclaimed. |
Family
ID: |
26961815 |
Appl.
No.: |
05/409,216 |
Filed: |
October 24, 1973 |
Related U.S. Patent Documents
|
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
|
282999 |
Aug 23, 1972 |
3795607 |
Mar 5, 1974 |
|
|
Current U.S.
Class: |
208/210;
208/251H; 208/254H |
Current CPC
Class: |
C10G
45/18 (20130101); B01J 37/14 (20130101); B01J
8/12 (20130101) |
Current International
Class: |
B01J
8/08 (20060101); B01J 8/12 (20060101); C10G
45/02 (20060101); B01J 37/14 (20060101); B01J
37/00 (20060101); C10G 45/18 (20060101); C10g
023/08 () |
Field of
Search: |
;208/209,211,213,210,216,251H,254H,89 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Gantz; Delbert E.
Assistant Examiner: Crasanakis; G. J.
Attorney, Agent or Firm: Hoatson, Jr.; James R. Erickson;
Robert W. Page, II; William H.
Parent Case Text
CROSS REFERENCE TO RELATED APPLICATION
This application is a continuation-in-part of our copending
application, Ser. No. 282,999, filed Aug. 23, 1972, which issued as
U.S. Pat. No. 3,795,607 on Mar. 5, 1974, all the teachings of which
copending application are incorporated herein by specific reference
thereto.
Claims
We claim as our invention:
1. A process for the catalytic hydroprocessing of hydrocarbons
containing metal, sulfur and nitrogen impurities therein, said
process having at least two moving-bed reactors operated with
series hydrocarbon flow which comprises the steps of:
a. passing a hydrocarbon charge stock and hydrogen through a first
moving-bed reaction zone to contact regenerated catalyst
hereinafter described, said catalyst flowing downward in said first
reaction zone to remove metal impurities from said charge
stock;
b. passing a portion of the reaction effluent from the first
reaction zone to the top of a second moving-bed reaction zone to
contact therein fresh catalyst flowing downward in said second
reaction zone to remove sulfur and nitrogen impurities from said
effluent;
c. removing used catalyst from the bottom of said second reaction
zone;
d. contacting said used catalyst with an oxygen-containing gas in a
regeneration zone to burn off accumulated carbon deposits to form
regenerated catalyst;
e. passing regenerated catalyst formed in step (d) into said first
reaction zone as said regenerated catalyst of step (a); and,
f. withdrawing said regenerated catalyst containing said metal
impurities from the bottom of said first reaction zone.
2. A process for the catalytic hydroprocessing of hydrocarbons
containing metal, sulfur and nitrogen impurities therein, said
process having at least two moving-bed reactors operated with
series hydrocarbon flow which comprises the steps of:
a. passing a hydrocarbon charge stock and hydrogen through a first
moving-bed reaction zone to contact regenerated catalyst
hereinafter described, said catalyst flowing downward in said first
reaction zone to remove metal impurities from said charge
stock;
b. passing a portion of the reaction effluent from the first
reaction zone to the top of a second moving-bed reaction zone to
contact therein fresh catalyst flowing downward in said second
reaction zone to remove sulfur and nitrogen impurities from said
effluent;
c. removing used catalyst from the bottom of said second reaction
zone;
d. contacting said used catalyst with an oxygen-containing gas in a
regeneration zone to burn off accumulated carbon deposits to form
regenerated catalyst;
e. passing regenerated catalyst formed in step (d) into said first
reaction zone as said regenerated catalyst of step (a); and,
f. withdrawing spent catalyst from the bottom of said first
reaction zone.
3. A process for the catalytic hydroprocessing of hydrocarbons
containing metal, sulfur and nitrogen impurities therein, said
process using at least two moving-bed reactors operated in series
hydrocarbon flow, which comprises the steps of:
a. passing a hydrocarbon charge stock and hydrogen through a first
moving-bed reaction zone to contact regenerated catalyst
hereinafter described, said catalyst flowing downward in said first
reaction zone to remove metal impurities from said charge
stock;
b. passing a portion of the reaction effluent from the first
reaction zone to the top of a second moving-bed reaction zone to
contact therein a mixture of fresh and regenerated catalyst flowing
downward in said second reaction zone to remove sulfur and nitrogen
impurities from said effluent;
c. removing used catalyst from the bottom of said second reaction
zone;
d. contacting said used catalyst with an oxygen-containing gas to
burn off accumulated carbon deposits to form regenerated catalyst
in a regeneration zone;
e. passing a portion of said regenerated catalyst formed in step
(d) into said first reaction zone as said regenerated catalyst of
step (a);
f. passing a portion of said regenerated catalyst formed in step
(d) into said second reaction zone; and,
g. withdrawing spent catalyst from the bottom of said first
reaction zone.
4. A process for the catalytic hydroprocessing of hydrocarbons
containing metal, sulfur and nitrogen impurities therein, said
process using at least two moving-bed reactors operated in series
hydrocarbon flow, which comprises the steps of:
a. passing a hydrocarbon charge stock and hydrogen through a first
moving-bed reaction zone to contact regenerated catalyst
hereinafter described, said catalyst flowing downward in said first
reaction zone to remove metal impurities from said charge
stock;
b. passing a portion of the reaction effluent from the first
reaction zone to the top of a second moving-bed reaction zone to
contact therein a mixture of fresh and regenerated catalyst flowing
downward in said second reaction zone to remove sulfur and nitrogen
impurities from said effluent;
c. removing used catalyst from the bottom of said second reaction
zone;
d. contacting said used catalyst with an oxygen-containing gas to
burn off accumulated carbon deposits to form regenerated catalyst
in a regeneration zone;
e. passing a portion of said regenerated catalyst formed in step
(d) into said first reaction zone as said regenerated catalyst of
step (a);
f. passing a portion of said regenerated catalyst formed in step
(d) into said second reaction zone; and,
g. withdrawing said regenerated catalyst containing said metal
impurities from the bottom of said first reaction zone.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention pertains to the hydrotreating and hydrorefining of
hydrocarbons to remove metals, sulfur, and nitrogen and to the
hydrocracking of hydrocarbons. Optimal usage of a catalyst being
fouled by metals deposition is achieved through continuous
operation of moving-bed reactors with transfer of regenerated
catalyst between reactors before it is discarded. Regeneration of
the catalyst is accomplished by burning off carbon, followed by
optional reduction and sulfiding of the base metal on the catalyst
prior to use.
2. Description of the Prior Art
The advantages of a moving-bed system in vapor phase reforming
operations are described in U.S. Pat. Nos. 3,470,090 and 3,647,680,
and various catalyst transferring routes are described in U.S. Pat.
No. 2,370,234. In another group of references, U.S. Pat. Nos.
3,607,725; 3,679,574 and 3,686,093, the catalyst moves through
fluidized reaction zones countercurrently to the feed and hydrogen
in the performance of hydrocracking and metals removal operations.
A recently disclosed moving-bed desulfurization process is
presented in U.S. Pat. No. 3,730,880.
Processing hydrocarbons by passage with hydrogen over beds of
catalyst is described in detail in the prior art. Specific examples
are U.S. Pat. No. 2,767,121 which teaches the manner in which a
naphtha boiling range charge stock is treated for sulfur and
nitrogen removal and to saturate olefins in the preparation of
charge stock for a catalytic reforming unit. In U.S. Pat. No.
2,717,857, a process for the desulfurization of gas oil fractions
(material boiling over 400.degree.F., the normal end point for
gasoline) is discussed. Heavy oil hydrotreating processes and
techniques are also described in U.S. Pat. Nos. 3,501,396;
3,471,397; 3,371,029; 3,375,189 and 3,429,801. A catalyst
especially useful for the hydrorefining of heavy residual oil is
described, along with a process using the catalyst, in U.S. Pat.
No. 3,525,684.
Processes for the purposes outlined above have traditionally been
performed using a fixed bed of catalyst contained in one or more
reaction vessels. This procedure has two inherent disadvantages to
operation which it is the object of this invention to remove. As
the catalyst in a fixed bed system is used, its activity gradually
decreases and results in a continued lessening in the quality of
the product unless the reaction conditions are modified. Second,
when it is no longer possible to maintain adequate product quality,
the catalytic material must be replaced while processing is
switched to another "swing" reactor or while the process is not
operating. The catalytic desulfurization of residual fuel oils is
hindered by fouling of the catalyst by coke, metals removed from
the oil, salt, scale and other plant trash. In addition to reducing
the activity of the catalyst, deposits of such material increase
the pressure drop in the reactor resulting in higher operating
expenses and interfere with the uniform distribution of hydrogen
and oil across the catalyst, thereby causing channeling, hot spots
and further catalyst deactivation. Shut downs due to these problems
are very costly due to the loss of production and catalyst
replacement expense. A technique resorted to in the prior art to
avoid this problem is the use of guard reactors prior to the main
desulfurization reactor. These reactors are used on a swing basis,
meaning only one is in the process flow at any time while the other
is being regenerated or refilled with new catalyst. In the
processing of crude oils containing a high concentration of metals,
the deactivation of the catalyst due to the metal content of the
oil is as serious a problem as deactivation due to carbon
deposition on the catalyst even though it may occur at a slower
rate. The regeneration of the catalyst by burning off the carbon
does not result in a full restoration of the catalytic activity of
the catalyst since the metals are not removed. It is an object of
this invention to provide a means whereby hydrotreating of a
metal-containing residual crude oil can be performed on a
continuous basis, with catalyst being circulated from a second
reaction zone to a first reaction zone and then discarded when
completely spent. In this manner, metals removed in the guard
reactor and particulate material filtered out in the guard reactor
are not admitted to the main, second, reaction zone.
SUMMARY OF THE INVENTION
Hydrotreating is accomplished in a two reactor moving-bed system
using series flow of the charge stock and two step reverse series
flow of the catalyst between reactors to provide initial metals
removal and clean up of the charge stock in the first reactor
containing the regenerated used catalyst and the remainder of the
hydrotreating in the second reactor containing the fresh catalyst.
The process comprises the steps of passing the hydrocarbon charge
stock and hydrogen through the first moving-bed reaction zone
containing regenerated catalyst, passing some effluent from the
first reaction zone through the second reaction zone containing
fresh catalyst, while intermittently removing used catalyst from
the bottom of the second reaction zone, separating this used
catalyst from the effluent of said second reaction zone, contacting
the used catalyst with an oxygen-containing gas to burn off
accumulated carbon deposits to thereby regenerate the catalyst, and
passing said regenerated catalyst into the first reaction zone from
which spent catalyst is sent to a metals recovery unit.
DESCRIPTION OF THE DRAWING
Hydrocarbon charge stock and hydrogen enter the process through
line 1 located at the top of the first reactor 2 and pass downward
through the reactor to exit by line 3 and transfer into a separator
18. Light vaporous material is removed from the separator via line
19, and the partially processed charge stock leaves by line 20 for
passage to the second reactor 4. Fresh makeup hydrogen from line 22
and purified hydrogen from line 29 are added via line 21 before the
partially processed charge stock enters the second reactor 4. The
light vaporous material leaving by line 19 is cooled by means not
shown and passed into a high pressure separator 23. Liquefied light
hydrocarbons are removed from the separator via line 24 and a
hydrogenrich vapor is removed via line 25. This vapor is passed
into a vapor-liquid contactor 26. An amine or caustic solution
enters the contactor via line 28 and removes H.sub.2 S from the
hydrogen-rich gas entering through line 25. Spent amine solution
leaves the contactor through line 27 and a purified hydrogen stream
leaves via line 29 to be charged to reactor 4. Hydrotreated
products leave the process by line 5 for passage to a second high
pressure separator or other processing as may be appropriate.
Fresh catalyst is fed to the system through line 6 by means of lock
hopper 7 used to equalize pressure on the catalyst before admission
to second reactor 4. This catalyst gradually travels downward
through the reactor and, as used catalyst, is removed from the
bottom of the reactor through means 8 and fed into lock hopper 9.
The separated catalytic material is then transported through line
10 into regeneration zone 11 located in a second lock hopper
wherein the catalyst is contacted with an oxygen-containing gas
such as air which enters by a means not shown. After suitable
carbon removal by oxidation has occurred in the regeneration zone,
catalytic material is first passed by line 12 into hopper 13 and
then pressurized through line 14 to the lock hopper 15 located at
the top of the first reactor. Catalyst added to the first reactor 2
through lock hopper 15 flows downward through the reactor wherein
initial metals removal from the charge stock is performed and
extraneous particulate matter is removed. Spent catalyst is removed
through means 16 and enters lock hopper 17 for removal from the
reactor system and passage to a metals recovery unit. For the
purpose of clarity and simplicity, controls, valves, heat
exchangers, and other equipment obviously necessary have not been
shown. The drawing and this description of the drawing are not
intended to in any way limit the manner in which the process may be
utilized. The regeneration zone may comprise a fluidized bed, a
moving-bed similar to the reaction zone, or a fixed bed as
previously indicated. Additional steps such as reduction and
sulfiding of the catalyst prior to its return to a reaction zone
are within the scope of this invention. Reduction and sulfiding can
be conducted in the transfer line 14 or in lock hopper 15 or within
the second reaction vessel itself.
DETAILED DESCRIPTION OF THE INVENTION
The broad field of hydroprocessing is divided into three main
subdivisions. The first is hydrotreating wherein materials such as
sulfur, nitrogen, and metals contained in various organic molecular
structures are removed from the charge stock with very little
molecular cracking. The second subdivision is hydrocracking,
wherein at least 50% of the charge stock is cracked into smaller
molecular weight components, such as the production of a naphtha
from a heavy distillate. Hydrorefining is between these two
extremes and results in molecular changes to up to 10% of the feed
together with impurity removal. Although there are many differences
in processing conditions or suitable catalysts and flow schemes for
these two different operations, they are basically alike in most
aspects.
The catalysts used in these processes are typically composed of a
base metal, which is defined to be a metal selected from the group
comprising nickel, iron, and cobalt, supported on an inorganic
oxide carrier. The manufacture and composition of these catalysts
is an art in itself and is not directly relevant to the practice of
the process of this invention. A typical catalyst may contain from
about 0.1 to 10% nickel or other metal or a combination of metals
from the base metal group, along with other metals such as
molybdenum or vanadium. The base material of the catalyst will
normally be a refractory inorganic oxide such as alumina, silica,
zirconia, boria, etc. or combinations of any of these materials,
particularly, alumina in combination with one or more of the other
oxides. The alumina is usually in excess with a weight ratio of
alumina to other components of from 1.5:1 to about 9:1 and
preferably from about 1.5:1 to about 3:1. The inclusion of a small
amount of silica is very common to increase the overall cracking
activity of the catalyst since silica itself is an effective
cracking catalyst even though used as a support for the metals.
Details of production of suitable catalysts are given in U.S. Pat.
No. 3,525,684.
Processing conditions for any hydrorefining operation are
determined by the charge stock, the catalyst used and the desired
result of the process. A broad range of conditions include a
temperature of from 500.degree.F. to 1000.degree.F., a pressure of
from 300 psig. to 4000 psig., and a liquid hourly space velocity of
0.5 to about 5.0. The liquid hourly space velocity is defined as
the volume of the liquid charged to the reactor divided by the
volume of the catalyst in the reactor. The exact reactor
temperature required is determined by the activity and age of the
catalyst. As a general rule, the operating pressure will be
increased with the boiling point of the material being processed.
In all hydrotreating operations, hydrogen is circulated through the
process at a rate of from about 1000 to about 25,000 standard cubic
feet per barrel of charge. This is to increase vaporization and
thereby improve processing results, to provide hydrogen for the
formation of ammonia and hydrogen sulfide from the nitrogen and
sulfur removed from the charge stock, and for the saturation of
olefinic hydrocarbons and cracking large molecules. The production
of hydrogen sulfide and ammonia makes it necessary to in some
manner remove these compounds from the process on a continuous
basis. Normal procedure to accomplish this is the injection of
water into the reactor effluent to dissolve the salts of these
impurities followed by cooling sufficient to form a water phase
which is decanted from a separatory vessel. A second method is the
treatment of the hydrogen recycle stream with a caustic solution to
scrub out the H.sub.2 S. The performance of these and other
suitable operations is well known to those skilled in the art and
warrants no further explanation.
In the processing of residual fractions of crude petroleum, it is
common that metals, most commonly nickel and vanadium, will be
present in this fraction at concentrations exceeding 100 ppm. by
weight. These metals are an impurity that must be removed prior to
further processing or use of the crude oil. This is commonly done
in the same process in which the sulfur and nitrogen are removed by
hydrocracking the large metal containing and usually thermally
stable molecules to break free the individual metal atoms. The
metal released in this manner accumulates on the catalyst and will
cause its eventual deactivation, and during a cycle of catalyst use
can be as serious a problem as the deactivation caused by carbon
disposition on the catalyst due to coking of the charged
hydrocarbon material. Metals deposited on the catalyst in this
manner are not removed by the burning off of the built up carbon
layers making it impossible to regenerate the used catalyst to an
activity equal to that of unused catalyst. Eventual replacement of
used catalyst is a very time consuming procedure which the present
invention eliminates.
Catalysts are also fouled by salt, scale, plant trash and
particulate impurities contained in the residual fuel oil. It is
therefore apparent that the initial catalyst acts not only as a
catalyst but also as a filter medium for the charged material. This
phenomenon causes interference with the uniform distribution of
hydrogen and oil across the catalyst bed resulting in channeling of
reactant flow, hot spots, and further catalyst deactivation. An
increased pressure drop through the reactor which increases the
expense of operation is also an undesirable result of this filter
action. Shut downs due to these problems are very costly in both
down time and catalyst replacement expense. A technique for
overcoming these disadvantages of the fixed bed methods used in the
prior art is a direct object of this invention.
The flow utilized in the present invention is series flow of the
charge stock through two reactors with catalyst movement in a two
step semi-countercurrent fashion wherein the fresh charge stock is
first contacted with regenerated used catalyst. Catalyst movement
is by gravity and therefore confined to a downward flow. Full
countercurrent flow of the reactants in a liquid phase is seldom
used in hydroprocessing of heavy oils because of the poor
conversions and increased catalyst deactivation rates which result.
However, countercurrent vaporized oil flow, though hard to
accomplish with heavy oils, would be desirable. The benefits of
this moving-bed system include longer process runs between
shutdowns, dictated only by mechanical problems or periodic
maintenance, the elimination of pressure drop build up, a more
consistent product and the ability to remove contaminants to a
lower level with an equal amount of catalyst.
The invention comprises using regenerated catalyst in a first
moving-bed reactor which is of small volume and serves as a guard
reactor for the main moving-bed hydrotreating reactor of the
process which used fresh catalyst. For this discussion, a
moving-bed reactor is defined as a reactor wherein a non-fluidized
bed of catalyst is slowly transferred from one end of the reactor
to the other end, in flow similar to plug flow of reactants, by the
addition of catalyst at the first end and removal at the second.
New catalyst is charged to the top of the main, second, reactor and
after a residence period determined by deactivation effects present
in both reactors, is removed from the bottom of the reactor and
regenerated. The regeneration process is meant to be the removal of
built up layers of coke from the catalyst. Secondary optional steps
associated with this regeneration are the reduction of the base
metal atoms contained on the catalyst from an oxidized state
resulting from the combustion necessary to remove carbon, and the
sulfiding of these metal atoms to reduce the cracking tendency of
the raw metals. Although cracking is often desired in the process,
the raw metals have a near uncontrollable catalytic activity which
results in poor processing results. The regenerated catalyst is
then fed into the first reactor for use as the initial cracking
catalyst and as a filter medium. Spent catalyst is withdrawn from
the bottom of this first reaction zone and sent to a metals
recovery unit or simply disposed of.
The deposition of carbon on the catalyst may cause deactivation at
a higher rate than the fouling of the catalyst by the accumulation
of metals removed from the charged material. In this situation, the
economic factors of process performance and catalyst cost may
dictate that regeneration of used catalyst from the second reactor
be performed at a rate greater than the total degradation rate in
the first reactor. Some portions of the regenerated catalyst would
therefore be returned to the second reactor rather than charged to
the first reactor. This rate of catalyst return would be set by the
relative deactivation rates and the desired average activity of the
two beds of catalyst which are interrelated to such factors as
utility expense, processing conditions, the average catalyst life,
the catalyst turnover rate in the first reactor and the relative
physical size of the two reactors. The complexity of these
relationships makes it impossible in this discussion to describe an
optimum catalyst turnover or recycle rate until constrained to a
specific catalyst, charge stock, product specification, and reactor
size.
The reverse of the above situation occurs when the rate of catalyst
fouling by metals deposition is very severe compared to carbon
build up. To maintain the desired catalyst activity in the first
reactor, it may be necessary to charge fresh catalyst to both the
first and second reactors.
Recycling of catalyst removed from the first reactor to the first
reactor after regeneration may be appropriate in the special
instances of the start up of the process with both reactors loaded
with fresh catalyst or with very excessive coke build up in the
first reactor.
The addition and removal of catalysts from the reaction zones is
performed in a lock hopper type apparatus comprising an enclosed
volume between two valves. In the addition step, catalyst from
above is allowed to fall into the lock hopper, the top valve is
closed, the pressure in the lock hopper is equalized with the
reaction zone and the bottom valve is then opened. In this manner,
catalyst can be intermittently added to, and removed from, either
reactor without upsetting the process due to changes in the
pressure or temperature of the reaction zone.
A lock hopper type device may also be used as the regeneration zone
between the two reactors. In operation, catalyst would enter the
regeneration zone which would then be sealed off, entrained oil
removed and an oxygen containing gas would be passed over the
catalyst which due to its high temperature would spontaneously
ignite and burn off hydrocarbon residue and coke layers. The
temperature of the catalyst being regenerated should not be allowed
to exceed 850.degree.F. to 900.degree.F. Undesirable flash flame
effects and resulting high temperatures are avoided by the
judicious use of nitrogen purges of the lock hopper before
regeneration, and the dilution of the air used in the regeneration
by nitrogen or recycled combustion gases. The oxygen concentration
of the gas used to regenerate the catalyst is normally maintained
below about 1 to 2%.
After the regeneration process, the metal contained on the catalyst
is in a highly oxidized state. The catalyst can be fed directly
into the first reactor at this point. It is desirable, however, to
perform the reduction and sulfiding gradually at controlled
conditions and rates which produce an increased catalytic activity
over that obtained by the direct insertion of the catalyst into a
reaction zone. The reduction can be performed by passing a gas such
as hydrogen or methane over the catalyst at an elevated temperature
to utilize the oxygen combined with metal in a combustion process.
After this step, the catalyst would be contacted with a sulfur
containing substance such as hydrogen sulfide or a sulfur
containing light cycle oil. U.S. Pat. No. 3,642,613 presents an
improved method for reduction and sulfiding of fresh catalyst with
an initial prewetting with a light cycle oil for an extended period
of about 18 hours while at a moderate temperature of about
300.degree.F., a pressure of 2000 psig. and a hydrogen circulation
rate of 5000 scf./Bbl. Following this, the temperature is raised to
450.degree.F. for a period of about 32 hours or until an
equilibrium concentration of H.sub.2 S is formed. The charge stock
is then cut into the process, the light cycle oil circulation is
discontinued and the reactor is raised to the temperature necessary
to perform the desired hydrotreating. In the present invention, the
charge stock would of course not be contacted with the catalyst
until it had been transferred to the reaction zone. The method of
sulfiding chosen is dependent on the increase in activity derived
compared to the increased costs and the comparative rates of
deactivation due to metals and coke disposition.
In some instances, it is desirable to perform a separation
operation on the first reactor's effluent before charging it to a
second reactor. This may be because the degree of cracking or
treating performed on the lighter petroleum fractions of the charge
stock renders any further catalytic contact unnecessary or
undesirable. Processes in which such separation operations are
performed are described in U.S. Pat. Nos. 3,429,801; 3,471,397 and
3,501,396 which were first presented in the prior art section.
Whether a separation operation is desirable will depend on the
degree to which the first reactor functions solely as a high
severity guard reactor.
The most desirable flow path for the hydrogen utilized in this
process may differ from the serial flow of the hydrocarbon stream.
This flow path would be determined by an attempt to optimize the
efficiency of the process by better control of the hydrogen and
hydrogen sulfide concentrations in the reactors. In a multipass
conversion system, it is desired to have a higher hydrogen purity
and lower hydrogen sulfide concentration in the final "clean-up"
stage. To accomplish this, hydrogen and light gases are withdrawn
from the effluent of a first reactor and purified. The purification
may comprise a partial condensation of the hydrocarbons followed by
passage of the remaining gaseous material through an absorption
zone. An amine or caustic solution is usually employed to remove
hydrogen sulfide. The purified hydrogen stream formed in this
manner and preferably also the make-up hydrogen are then added to
the hydrocarbon feed stream to the next reactor. The effluent
stream of the last reactor is also separated for the recovery of
hydrogen. This hydrogen stream is then recirculated for use in the
guard reactor or a first reactor wherein hydrogen purity is not as
critical and higher sulfur levels may be more easily tolerated.
This is the type of flow path depicted in the drawing.
Although the hydrogen purification step is shown in the drawing as
occurring between the guard reactor and the second reactor of a
two-reactor process, our invention is not so limited. There may for
instance be three reactors with the hydrogen separation being
performed between the last two in the sequence. This may be the
optimum case when the hydrogen sulfide concentration of the
hydrogen stream is raised by only a relatively small amount in its
passage through the guard reactor. Further still, the effluent of
one reactor may be split into two separate hydrocarbon fractions
which are further hydroprocessed in separate reactors operated at
different severity factors including different space velocities or
temperatures.
Our invention may be described as a process for the catalytic
hydroprocessing of hydrocarbons containing metal, sulfur and
nitrogen impurities therein, said process which comprises the steps
of: (a) passing a hydrocarbon charge stock and hydrogen through a
first moving-bed reaction zone to contact regenerated catalyst
hereinafter described, said catalyst flowing downward in said first
reaction zone to remove metal impurities from said charge stock;
(b) passing at least a portion of the reaction effluent from the
first reaction zone to the top of a second moving-bed reaction zone
to contact therein fresh catalyst flowing downward in said second
reaction zone to remove sulfur and nitrogen impurities from said
effluent; (c) removing used catalyst from the bottom of said second
reaction zone; (d) contacting said used catalyst with an
oxygen-containing gas in a regeneration zone to burn off
accumulated carbon deposits to form regenerated catalyst; (e)
passing regenerated catalyst formed in step (d) into said first
reaction zone as said regenerated catalyst of step (a); and, (f)
withdrawing used catalyst from the bottom of said first reaction
zone.
* * * * *