U.S. patent number 3,862,898 [Application Number 05/383,620] was granted by the patent office on 1975-01-28 for process for the production of olefinically unsaturated hydrocarbons.
This patent grant is currently assigned to Pullman Incorporated. Invention is credited to Harold B. Boyd, James R. Lambrix.
United States Patent |
3,862,898 |
Boyd , et al. |
January 28, 1975 |
**Please see images for:
( Certificate of Correction ) ** |
PROCESS FOR THE PRODUCTION OF OLEFINICALLY UNSATURATED
HYDROCARBONS
Abstract
Hydrocarbon feedstock containing petroleum residuum is
catalytically cracked in a heavy oil cracking unit to produce a
naphtha feed suitable for processing by steam pyrolysis to olefins.
By the process integration disclosed, internal gas compression
energy requirements for olefins recovery are furnished by steam
generated in the heavy oil cracking unit.
Inventors: |
Boyd; Harold B. (Houston,
TX), Lambrix; James R. (Houston, TX) |
Assignee: |
Pullman Incorporated (Chicago,
IL)
|
Family
ID: |
23513955 |
Appl.
No.: |
05/383,620 |
Filed: |
July 30, 1973 |
Current U.S.
Class: |
208/73; 208/72;
208/77; 208/130; 585/648; 208/113; 502/44 |
Current CPC
Class: |
C10G
51/02 (20130101); C10G 2400/20 (20130101) |
Current International
Class: |
C10G
51/00 (20060101); C10G 51/02 (20060101); C10g
037/04 () |
Field of
Search: |
;208/72,73,77,113,130
;260/683R,677A ;252/417 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Primary Examiner: Gantz; Delbert E.
Assistant Examiner: Spresser; C. E.
Claims
1. A process for the production of olefinically unsaturated
hydrocarbons which comprises the steps of:
a. introducing a hydrocarbon feedstock comprising petroleum
residuum into the catalytic cracking zone of a heavy oil cracking
unit in the presence of fluidized cracking catalyst at cracking
conditions to produce a catalytically cracked effluent including a
cracked naphtha fraction;
b. regenerating said fluidized cracking catalyst in the
regeneration zone of the heavy oil cracking unit;
c. producing high pressure steam in said regeneration zone by
indirect heat exhange;
d. passing the cracked naphtha fraction to a thermal pyrolysis zone
and thermally cracking said fraction to produce a thermally cracked
effluent containing olefinically unsaturated hydrocarbons;
e. expanidng said high pressure steam from step (c) to provide at
least part of the gas compression energy required for recovery of
the olefinically unsaturated hydrocarbons; and
2. The process of claim 1 wherein at least a portion of the
expanded high pressure steam is mixed with the cracked naphtha
fraction fed to the
3. The process of claim 1 wherein the catalytic cracking zone
includes a
4. The process of claim 1 wherein the olefinically unsaturated
hydrocarbon
5. The process of claim 1 wherein the hydrocarbon feedstock is
crude
6. The process of claim 1 wherein the hydrocarbon feedstock is a
pertroleum
7. The process of claim 1 wherein the hydrocarbon feedstock is
an
8. An integrated process for the production of olefinically
unsaturated hydrocarbons and aromatic compounds comprising the
steps of:
a. introducing hydrocarbon feedstock containing petroleum residuum
into the catalytic cracking zone of a heavy oil cracking unit in
the presence of fluidized cracking catalyst at cracking conditions
to produce catalytically cracked effluent including a cracked
naphtha fraction;
b. passing the cracked naphtha fraction to a thermal pryrolysis
zone at thermal cracking conditions to produce a thermally cracked
effluent containing pyrolysis oil, olefinically unsaturated
hydrocarbons and aromatic compounds;
c. separating pyrolysis oil from the thermally cracked
effluent;
d. passing pyrolysis oil to the catalytic cracking zone of the
heavy oil cracking unit; and
e. recovering olefinically unsaturated hydrocarbons and aromatic
compounds.
9. An integrated process for the production of olefinically
unsaturated hydrocarbons comprising the steps of:
a. introducing hydrocarbon feedstock containing petroleum residuum
into the catalytic cracking zone of a heavy oil cracking unit in
the presence of fluidized cracking catalyst to produce a
catalytically cracked effluent including a cracked naphtha
fraction;
b. regenerating said fluidized cracking catalyst in the
regeneration zone of a heavy oil cracking unit;
c. producing high pressure steam in said regeneration zone by
indirect heat exchanage;
d. passing the cracked naphtha fraction to a thermal pyrolysis zone
to produce a thermally cracked effluent containing olefinically
unsaturated hydrocarbons;
e. cooling thermally cracked effluent in a quench zone;
f. producing high pressure steam in the quench zone by indirect
heat exchange;
g. exapnding high pressure steam from steps (c) and (f) to provide
the gas compression energy required for a recovery of olefinically
unsaturated hydrocarbons; and
10. The process of claim 9 wherein a portion of the expanded high
pressure
11. The rpocess of claim 9 wherein
a. flue gas is recovered from the regeneration zone and passed to a
carbon monoxide boiler;
b. high pressure steam is produced in the carbon monoxide boiler;
and
c. high pressure steam is recovered as a product of the process.
Description
This invention relates to the integration of fluid catalytic
cracking of heavy hydrocarbon oils containing petroleum residuum
and thermal pyrolysis of hydrocarbons to produce olefinically
unsaturated hydrocarbons such as ethylene and propylene.
Heretofore, it has been known to convert naphtha, ethane, or
porpane feedstocks to olefins by themal pyrolysis with steam.
Conventional processes are broadly disclosed in the Nov. 13, 1965
issue of "Chemical Week," pages 70-80.
It has also been known to fractionate a crude petroleum oil and
pyrolytically convert selected distillate fractions to olefins
according to U.S. Pat. No. 3,409,540. In this process, however,
residuum from such fractionation is diverted to fuel oil use and no
attempt is made to derive pyrolysis feed from it. Moreover, in
order to minixmize residum production, a heavy gas oil cut form the
fractionator is hydrocracked and certain separation products from
hydrocracking are thereby rendered suitable for pyrolysis feed.
In a related process disclosed in U.S. Pat. No. 3,617,495, residuum
from crued oil distillation is coked and coker naphtha so produced
is made suitable for pyrolysis feed by hydrotreatment. In this
process, however, relatively large amounts of fuel oil are produced
from the distillation zone and from the coker. The coke and fuel
oil resulting from these operations cannot be readily utilized in
ethylene production.
It is an object of this invention to provide a more efficient and
less expensive process for the manufacture of olefins and aromatic
compounds. Another object of the invention is to integrate
catalytic cracking of heavy hydrocarbons with thermal pyrolysis of
light hydrocarbon feeds to efficiently produce olefins and aromatic
compounds. Another object of the invention is to provide a process
for olefins production from residual feedstocks. Yet another object
of this invention is to provide internal compression energy
requirments for recovery of olefins produced by thermal pyrolysis
from components of crude petroleum oil that are unsuitable
pyrolysis feeds. Further objects and advantages of the invention
will be apparent from the drawings and the following
description.
According to the invention, a heavy hydrocarbon containing
petroleum residuum is converted to cracked products including
naphtha in a heavy oil cracking unit having a fluid catalytic
cracking zone and a catalyst regenreration zone. The naphtha is
passed to a non-catalytic thermal pyrolysis zone and converted to
thermally cracked effluent containing large quantities of olefins
having from 2 to 4 carbon atoms. The olefins are recovered in a
known manner by process gas compression and refrigeration. In
addition, high pressure steam is produced in the regeneration zone
of the heavy oil cracking unit and the steam so produced is
utilized in olefins recovery.
FIG. 2 is a schematic diagram of a petrochemical refinery and
discloses the production of C.sub.2 -C 4 olefins and aromatic
compounds from crude petroleum oil wherein a substantial part of
the thermal pyrolysis feed is derived from a residue fraction of
the crude oil.
FIG. 3 is a schematic diagram of steam generation and use within
the petrochemical refinery concept of FIG. 2 and discloses a total
energy concept with fulfillment of the entire gas compression
energy requirements of the process through internal process
generation of steam with consequent fuel and power savings.
The heavy oil cracking (HOC) unit comprises a fluid catalytic
cracking zone 1 and a catalyst regeneration zone 2. Fluidized
cracking catalyst circulating between the two zones may be of
conventional type such as activated clay, silica-alumina,
silica-zirconia, and alumina-boria, however, natural and synthetic
zeolitic catalysts, particularly of the molecular sieve, matrix
type having an average particle size range of from about 40 to
about 100 microns, are preferred cracking catalysts.
The catalytic cracking zone 1 is preferably a transfer line reactor
and is most preferably a riser reactor of the type described in
U.S. Pat. No. 3,607,127. The riser type unit is more fully depicted
in FIG. 2 of the drawings.
In operation of the HOC unit, residue containing hydrocarbon
feedstock is fed to the lower part of the riser reactor at a
temperature of from about 150.degree.F to about 750.degree.F and is
admixed with the cracking catalyst in the presence of fluidizing
steam. Typical cracking conditions include a temperature range from
about 850.degree.F to about 1,200.degree.F, pressure from about 10
psig. to about 50 psig., catalyst to oil ratio of from about 3:1 to
15:1, and space velocity of from about 0.5 to 1,000. Normally from
50 to 95 percent of the cracking reaction takes place in the riser
reactor with the remainder occurring in the disengaging and
stripping zones located generally in the upper part of the heavy
oil cracking unit. Cracked effluent including a cracked naphtha
fraction leaving the riser reactor disengages from catalyst in the
upper part of the HOC unit and exits through a series of cyclone
separators that return entrained catalyst to a fluid bed
regeneration zone below the disengaging zone. Severe cracking
conditions are employed in order to maximize conversion of the
feedstock to naphtha boiling range hydrocarbons for thermal
pyrolysis feed. Generally, at least 65 volume percent and most
preferably 80 to 100 percent of the feed is cracked to light
hydrocarbons boiling in the naphtha range, gases including
hydrogen, cycle oil, and coke.
Following disengagement from cracked effluent, catalyst
contaminated with coke and occluded hydrocarbons passes downwardly
through a stripping zone. The stripping zone is fitted with
suitable baffling and steam sparging means to strip occluded
cracked effluent which passes over head while catalyst coated with
coke and some non-volatile hydrocarbons passes downwardly into
regeneration zone 2 located in the lower part of the HOC unit.
In the regeneration zone catalyst is contacted with an
oxygen-containing gas, preferably air, furnished by a regenerator
air blower or compressor (see reference numeral 46 in FIG. 2). Air
furnished by this blower will normally be at a pressure of from
about 20 psia. to about 70 psia. and delivered at a rate of from
about 11 pounds to about 13 pounds per pound of coke burned from
the catalyst. The air delivery rate is varied in order to maintain
regeneration zone temperatures of from about 1,000.degree.F to
about 1,400.degree.F and at which temperature materials coated on
the catalyst are burned off to desired levels of residual coke on
regenerated catalyst. Such levels will generally be from about 0.05
to about 0.4 weight percent, preferably from about 0.05 to about
0.15 weight percent. Following regeneration, catalyst is returned
to the riser reactor.
In view of the generally high carbon content of residue fractions
processed by the HOC unit and the formation of additional carbon or
coke during cracking, coke deposits on the cracking catalyst will
normally be heavy. Due to combustion of this carbon, a substantial
amount of heat is evolved during regeneration of cracking catalyst
which is recovered through indirect heat exchange as high pressure
steam, preferably at a pressure of from about 1,000 psia. to about
2,000 psia. by introducing boiler feed water to steam coils or
tubes located within the regeneration zone (see reference numerals
50, 51, and 52 in FIG. 2). In most instances the steam coils will
be interconnected to a suitable flash drum and auxiliary equipment
(not shown).
High pressure steam so produced is utilized in expansion turbine
drives shown generally be reference numeral 3 employed in gas
compression required for olefins recovery. In an integrated
petrochemical refinery as shown in FIG. 2, later described, the
quantity of high pressure steam from the regeneration zone of the
HOC unit is sufficient to provide at least a major part of the gas
compression energy requirements of the process and will generally
provide about two-thirds of this requirement in terms of the weight
flow rate of steam generated and expanded in compressor turbine
drives. The term gas compression energy is intended to mean the
total energy expended in compressing pyrolysis effluent gas to the
pressure required for olefins recovery in addition to te
refrigeration compression required for chilling pyrolysis effluent
in order to perform product separations by fractionation.
Generally, the compression energy required for these purposes will
be about equally divided between process gas compression and
refrigeration compression. High pressure steam may drive
turbo-generators and indirectly provide such gas compression energy
requirements through electro-mechanical means, however, direct
steam turbine drives to the compressors will generally be
preferred.
A major part of the steam expanded through the turbines is
condensed and recycled through a boiler feed water system.
Preferably, a portion of this steam is further expanded to reduced
pressure ranging from about 100 psia. to about 200 pisa. for use as
steam diluent of hydrocarbon feed to thermal pyrolysis zone 4.
A cracked naphtha fraction separated from catalytically cracked
effluent leaving the HOC until may be passed directly to thermal
pyrolysis zone 5, however, the fraction will normally contain
olefinic materials that tend to form coke and to polymerize
excessively when subjected to pyrolytic conversion. Preferably the
cracked naphtha fraction is hydrotreated, as will be later
described. The cracked naphtha fraction is then admixed with
diluent steam from the expansion turbines and introduced to thermal
pyrolysis zone 5 which will be subsequently discussed in connection
with FIG. 2.
Thermally cracked effluent from the pyrolysis zone is then cooled
and passed to process gas compression zone 6 and pressurized to
from about 400 psia. to about 650 psia. to facilitate fractionation
of products. Separations of hydrogen, fuel gases, ethane, propane,
mixed C.sub.4 compounds, and products including ethylene and
propylene are than performed in product recovery zone 7 by known
chilling and separation steps . A typical separations process is
described in the Nov. 13, 1965 issue of "Chemical Week," 77-80.
In a preferred embodiment the integrated process is carried out
according to the following example.
Referring now to FIG. 2, 690,000 1lb./hr. of desalted whole
petroleum crude oil containing 2.6 weight percent sulfur is
introduced through line 25 to thermal distillation zone 26. A
gaseous overhead fraction comprising predominantly C.sub.3 and
C.sub.4 paraffinic hydrocarbons is removed through line 27. A
straight-run naphtha fraction boiling between about 85.degree.F and
about 450.degree.F is removed from the distillation zone through
lines 28 and 34 and passed to thermal pyrolysis zone 35. A light
gas oil fraction boiling in the range from about 300.degree.F to
about 650.degree.F is also removed from the distillation zone and
passed through lines 29 and 34 to pyrolysis zone 35. A heavy gas
oil fraction boiling in the range from about 550.degree.F to about
1,000.degree.F is removed from a lower section of the distillation
zone through line 30 and hydrodesulfurized in zone 31 with hydrogen
introduced through line 32. The hydrodesulfurizer may utilize
cobalt-molybdenum or alumina catalyst and is operated at
temperatures ranging from about 550.degree.F to 750.degree.F and
pressure ranging from about 200 psia. to about 600 psia.
Desulfurized gas oil is then passed to the thermal pyrolysis zone
through lines 33 and 34. If desired, portions of the naphtha or gas
oil fractions may be diverted to other uses, however, in an
integrated petrochemical refinery of the type described herein, it
is preferred to pass these fractions to the thermal pyrolysis zone
in order to maximize olefins and aromatic hydrocarbons
production.
From the bottom of thermal distillation zone 26, 365,000 1lb./hr.
of a petroleum residuum fraction boiling above about 600.degree.F
is removed through line 36 and passed through line 37 to catalytic
cracking zone 38 of heavy oil cracking unit 39. The catalytic
cracking zone in FIG. 2 is illustrated as a riser reactor.
Alternately, all or part of the residue fraction from thermal
distillation zone 26 may be passed through a solvent deasphalting
zone, for example a propane deasphalting unit, to obtain a
deasphalted oil which is subsequently charged to the HOC unit. This
step will generally not be used when asphaltene and metals content
of the residue fraction is not excessively high.
The residuum fraction is fed to the lower part of riser 38 to a
temperature of from about 150.degree.F to about 750.degree.F and is
admixed with circulating, regenerated cracking catalyst and with
fluidizing steam introduced from line 40 at about 100 psia. Cracked
effluent including a cracked naphtha fraction laeaving riser 38
disengages from the catalyst in disengaging zone 41 and passes
upwardly through cyclones (not shown) for recovery through line
43.
Catalyst with coke and occluded hydrocarbons deposited thereon
passes downwardly through the disengaging zone to stripping zone 42
for removal of occluded hydrocarbons which pass overhead with the
cracked effluent. Stripped catalyst then passes to regeneration
zone 44 where coke and non-volatile hydrocarbonaceous materials are
burned from the catalyst with air introduced through line 45 from
regenerator air blower 46. Flue gases containing carbon monoxide
from the regeneration step leave zone 44 through line 47 for
further use and treatment.
Heat produced during regeneration is removed by passing boiler feed
water through line 50 to coils 51 located within the regeneration
zone and thereby producing steam by indirect heat exchange at a
high pressure of about 1,500 psia. which is removed at a rate of
650,000 1lb./hr. through line 52.
Cracked effluent removed from the HOC unit through line 43 is
introduced to cracker fractionator 53 at a temperature of about
1,000.degree.F and pressure of about 20 psia. A volatitle overhead
stream comprising hydrogen and paraffinic hydrocarbons lighter than
C.sub.4 is removed from the cracker fractionator through line 54.
In conventional refinery operations, C.sub.2 and lighter materials
would be used as plant fuel or compressed and diverted to other
process facilities. Here, the stream is combined with overhead in
line 27 from thermal distillation zone 26 and integrated into
olefins production as later described.
Decant oil is removed from the bottom of a cracker fractionator 53
through line 55 and is preferably passed to catalytic cracking zone
38 of the HOC unit through line 37. Alternately, all or a part of
this oil may be diverted to other uses, for example, carbon black
production or auxiliary fuel. A cycle oil suitable for further
processing to commercial fuel oil is removed by way of line 56.
The principal product of the HOC unit, a cracked naphtha fraction
boiling between about 85.degree.F and about 450.degree.F is removed
from the cracker fractionator through line 57 at the rate of
127,000 lb./hr. and passed to hydrotreating zone 58 for olefins
saturation and desulfurization in the presence of a catalyst with
hydrogen introduced to the hydrotreating zone. Additionally, 92,000
lb./hr. of pyrolysis gasoline from downstream process sources later
described is passed to hydrotreatment zone 58 for similar
processing. Hydrotreating will serve to prepare the feed for
pyrolytic conversion by saturating olefins, partially saturating
aromatic compounds, and by removing sulfur contained in the
fraction by hydrodesulfurization. A substantial part of the
hydrogen required in hydrotreating may be obtained from the
hydrogen produced in the HOC unit and later recovered in the
product separation zone.
Hydrotreating is generally performed in one or more stages at
temperatures ranging from about 450.degree.F to about 800.degree.F
and pressures from about 100 psia. to 1,500 psia. Preferred
hydrotreating catalysts comprise one or more hydrogeneration metals
supported on a suitable carrier material. Oxides or sulfides of
molybdenum, tungsten, cobalt, nickel, and iron supported on such
supports as alumina and silica-alumina are used. The most preferred
catalysts are cobalt molybdate or alumina and nickel molybdate on
alumina. The catalyst can be employed in the form of a fixed bed or
a fluidized bed. Liquid phase or mixed phase conditions can be
used. Space velocities are from about 1 to about 15 volumes of feed
per volume of catalyst per hour and hydrogen addition rates are
from about 50 to about 2,000 SCF/bbl. A number of hydrogen treating
processes of varying degrees of severity are disclosed in
"Hydrocarbon Processing," September 1972, pages 150-184.
A hydrotreated naphtha fraction containing predominantely C.sub.5
paraffinic hydrocarbons is recovered from the hydrotreating zone
and passed through line 59 to thermal pyrolysis zone 35 at the rate
of 35,000 lb./hr.
A hydrocarbon stream containing naphtha and aromatic compounds is
also separated in hydrotreating zone 58 and passed through line 60
to an aromatics extraction and separation zone 61 which may
typically utilize solvent extraction by, for example, ethylene
glycol, furfural, or dimethyl formamide. Proudct separations in
extraction zone 61 yields 39,000 lb./hr. of benzene, 24,000 lb./hr.
of toluene, and 12,000 lb./hr. of xylene. 104,000 lb./hr. of
paraffinic raffinate resulting from aromatics extraction is then
passed through lines 62 and 59 to thermal pyrolysis zone 35.
Thermal pyrolysis zone 35 contains pyrolysis furnaces adapted fro
steam cracking of hydrocarbons varying from light paraffins to gas
oils to produce C.sub.2 to C.sub.4 olefins. In FIG. 2, the thermal
pyrolysis feed steams previously described are mixed with 310,000
lb./hr. of diluent steam from line 63 at a pressure of about 150
psia. Such steam is obtained from the discharge of gas compressor
turbines as later described. Diluent ratios are about 0.6 pounds of
steam per pound of naphtha feed, and 0.75 pounds of steam per pound
of gas oil feed. It is understood that individual furnaces within
the thermal pyrolysis zone may vary somewhat in detail design to
suit the particular feed streams involved. Typically, a pyrolysis
furnace will contain convection heating coils in which feed
materials are preheated to temperatures as high as 1,200.degree.F
and radiation sections in which preheated feed is converted to
olefins in the presence of diluent steam at temperatures in the
range of about 1,400.degree.F to about 2,000.degree.f depending on
the feedstock used and product mix desired. Residence time of
hydrocarbons in the furnaces is low, generally from about 0.2
seconds to about 2.0 seconds and maybe as low as 0.01 seconds.
Thermally cracked effluent containing C.sub.2 -C.sub.4 olefins,
pyrolysis gasoline, pryrolysis oil, hydrogen, and light paraffins
is passed from the thermal pyrolysis zone through line 64 to quench
zone 65 where the effluent is rapidly cooled to a temperature of
from about 600.degree.F to about 1,000.degree.F depending on the
pyrolysis feedstock. Boiler feed water is introduced to the quench
zone and passed in indirect heat exchange with the thermally
cracked effluent to produce 542,000 lb./hr. of steam at a pressure
of about 1,500 psia. which is removed through line 66.
Thermally cracked effluent is passed from quench zone 65 through
line 67 to effluent fractionator 68 where a pyrolysis oil bottoms
fraction is removed and passed to the catalytic cracking zone 38 of
the heavy oil cracking unit 39 at the rate of 43,000 lb./hr.
through lines 69, 36, and 37. An overhead fraction containing the
oil-depleted thermally cracked effluent is recovered from the
effluent fractionator through line 70 at a pressure of about 7
psig. and admixed with light hydrocarbons contained in lines 27 and
54. the combined effluent stream is then passed through line 27 to
a process gas compression zone 71 where pressure is increased from
7 psig. to 550 psia. in order to facilitate product separations. a
pyrolysis gasoline stream containing aromatic compounds,
principally aromatic hydrocarbons such as benzene, toluene, and the
xylenes, is separated from combined effluent in the gas compression
zone 71 and passed through line 72 to previously described
hydrotreating zone 58.
Following compression and pyrolysis gasoline removal, the combined
effluent is passed through line 73 to acid gas separation zone 74
for removal of carbon dioxide and hydrogen sulfide, thence through
line 75 to drying zone 76, and then through line 77 to chilling
zone 78 where the effluent stream is cooled by refrigeration
supplied from refrigeration compressors 79. Hydrogen is removed
from chilling zone 78 through line 80 at the rate of 7,000 lb./hr.
This hydrogen is utilized in hydrotreating zone 58,
hydrodesulfurization zone 31, and may be used for desulfurization
of fuel oil separated in the cracker fractionactor 53.
chilled pyrolysis effluent is then passed through line 81 to
product separation zone 82 where 152,000 lb./hr. of ethylene,
81,000 lb./hr. of propylene, and 91,000 lb./hr. of mixed C.sub.4
hydrocarbons are spearated by fractionation and removed as products
of the process. Additionally, 38,000 lb./hr. of ethane and 14,000
lb./hr. of propane are removed from the product recovery zone and
recycled via lines 83, 59, 33, and 34 to thermal pyrolysis zone 35.
A residual stream of pyrolysis gasoline is also removed through
line 84 and passed to hydrotreating zone 58.
A preferred embodiment of the total energy concept of the invention
follows.
Referring now to FIG. 3, which illustrates steam integration with
olefins production from crude oil, processing zones are those
previously described for FIG. 2, however, many of the
interconnecting process lines have been omitted for clarity.
Steam at a high pressure of about 1,500 psia. is recovered from the
regeneration zone 44 of the HOC unit 39 as previously described and
delivered at the rate of 650,000 lb./hr. through line 52 to high
pressure steam header designated by reference numeral 85.
Additionally, 542,000 lb./hr. of 1,500 psia. steam is recovered
from quench zone 65 and delivered through line 66 to high pressure
steam header 85.
Since flue gas produced from the oxidation of coke in the HOC unit
regeneration zone will normally contain an appreciable amount of
carbon monoxide, it is preferably passed to CO boiler 48 and burned
with the aid of a high heat value fuel such as recovered fuel gas
to generate high pressure steam from boiler feed water. All or part
of the steam thus produced may be used in fulfilling the remaining
energy requirements of the process, providing energy required by
the regenerator air blower, or exported as a product of the
process. Accordingly, 650,000 lb./hr. of 1,500 psia. steam is
recovered from the CO boiler 48 and delivered through line 49 to
high pressure steam header 85.
100,000 lb./hr. of the high pressure steam from header 85 is passed
through line 86 and expanded through regenerator air blower 46.
Steam exhausted from turbine 87 is then returned through line 92 to
boiler feed water recovery system 93 where it is condensed, treated
and repressurized for distribution by suitable lines (not shown) to
the previously described steam generation zones.
High pressure steam is similarly passed from header 85 through line
88 at the rate of 281,000 lb./hr. to refrigeration zone turbines 89
which are mechanically connected to closed loop refrigeration
compressors shown generally by reference numeral 79. Steam
exhausted from these turbines is also returned through line 92 to
feed water recovery system 93.
678,000 lb./hr. of high pressure steam is passed from header 85
through line 90 to process gas turbine 91 which is mechanically
connected to process gas compressor 71. A minor portion of this
steam is returned through line 92 at the rate of 155,000 lb./hr. to
feed water recovery system 93. Since high pressure steam produced
in the regeneration zone 44, quench zone 65, and CO boiler 48 is in
excess of the gas compression energy requirements of the process
and the regenerator air blower requirement, 738,000 lb./hr. of high
pressure steam is exported by way of lines 85 and 96 as a product
of the process.
A major portion of the steam entering turbin 91 is partially
expanded to a medium pressure of about 450 psia. and passed through
line 94 at the rate of 523,000 lb./hr. to medium pressure steam
header 95. It is understood that an equivalent amount of steam
expanded to the medium pressure may be exhausted from any of the
high pressure steam turbines according to the specific conditions
involved.
210,000 lb./hr. of steam from header 95 is further reduced in
pressure to about 150 psia. through valve 97 and combined with
100,000 lb./hr. of steam from line 98 that is produced at
approximately the same pressure in cracker fractionator boiler 99
which removes heat from catalytically cracked effluent by
recirculation of the fractionator bottom contents. The combined
stream is then passed through line 63 to thermal pyrolysis zone 35
for use as process diluent stream.
The remaining medium pressure steam is delivered through line 95
and 100 to other internal process uses such as pump drives, process
heating, and fluidizing steam for the HOC unit.
Thus, the process embodiments of the present invention provide a
means for the conversion of heavy hydrocarbons to olefins and
aromatic compounds. Whole crude oil and petroleum fractions
containing substantial amounts of sulfur and metals can be
converted to desirable products such as ethylene, propylene,
benzene, toluene, and the xylenes. The heavy oil cracking concept
of the present invention is unique in that a residuum containing
hydrocarbon may be converted and treated to a feedstock suitable
for pyrolitic conversion to olefins in the presence of steam.
The embodiments of the invention are essentially selfsupporting
from an energy balance standpoint. The heavy oil cracking unit
provides very large quantities of steam which are utilized to
provide a major part of the gas compression energy requirements of
the process. In the petrochemical refinery embodiment of the
present invention, all of the internal gas compression energy and
heat requirements of the process are furnished from the heavy oil
cracking unit and the thermal pyrolysis quench zone and substantial
quantities of high pressure steam are exported as a product of the
process. The feed to the heavy oil cracking unit may be recycled to
extinction or a portion of the recycle material can be used as
plant fuel. The quantity of hydrogen required to saturate and
desulfurize the various intermediate fractions produced in the
preferred embodiments is much less than the quantity of hydrogen
which would be required to support a hydrocracking unit and
associated hydrodesulfurization units.
Obvious variations of process embodiments disclosed in the drawings
and the foregoing descriptions are intended to be included within
the scope of the disclosure and claims.
* * * * *