U.S. patent number 3,617,495 [Application Number 04/821,164] was granted by the patent office on 1971-11-02 for process for production of olefins and acetylene.
This patent grant is currently assigned to Marathon Oil Company. Invention is credited to Joe T. Kelly, deceased, Carle C. Zimmerman, Jr..
United States Patent |
3,617,495 |
Zimmerman, Jr. , et
al. |
November 2, 1971 |
PROCESS FOR PRODUCTION OF OLEFINS AND ACETYLENE
Abstract
Ethylene, acetylene, and petroleum coke are manufactured by
distilling a crude oil to produce a more volatile straight run
naphtha and a less-volatile reduced crude oil; feeding the straight
run naphtha to a hydrocarbon pyrolysis furnace to produce products
comprising acetylene, ethylene, and hydrogen; coking the reduced
crude to produce petroleum coke and a coker naphtha; separating a
portion of the hydrogen from the hydrocarbon pyrolysis furnace
effluent; using a portion of the hydrogen to hydrotreat the coker
naphtha so as to produce hydrotreated oils having a substantially
lower aromatic and olefin content than the coker naphtha; and
feeding a portion of the hydrotreated oils into the hydrocarbon
pyrolysis furnace.
Inventors: |
Zimmerman, Jr.; Carle C.
(Littleton, CO), Kelly, deceased; Joe T. (late of Littleton,
CO) |
Assignee: |
Marathon Oil Company (Findlay,
OH)
|
Family
ID: |
25232683 |
Appl.
No.: |
04/821,164 |
Filed: |
April 25, 1969 |
Current U.S.
Class: |
208/80; 208/50;
208/96 |
Current CPC
Class: |
C10G
49/007 (20130101); C10B 55/00 (20130101); C10G
69/00 (20130101) |
Current International
Class: |
C10B
55/00 (20060101); C10G 69/00 (20060101); C10G
49/00 (20060101); C10g 031/00 () |
Field of
Search: |
;208/50,51,80
;260/683 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Gantz; Delbert E.
Assistant Examiner: Bruskin; R. M.
Claims
What is claimed is:
1. An improved process for the operation of a hydrocarbon pyrolysis
furnace consisting essentially of
a. distilling a crude oil to produce a naphtha and a reduced crude,
which is less volatile than said naphtha,
b. feeding at least a portion of said naphtha to said hydrocarbon
pyrolysis furnace operating at about 900.degree. to
about2800.degree. F. to produce products comprising ethylene and
hydrogen,
c. coking said reduced crude to produce petroleum coke and a coker
naphtha,
d. separating at least a portion of said hydrogen from said
hydrocarbon pyrolysis furnace effluent,
e. utilizing at least a portion of said separated hydrogen to
hydrotreat said coker naphtha to produce a hydrotreated oil having
a lower olefin content than said coker naphtha,
f. feeding at least a portion of said hydrotreated oil into said
hydrocarbon pyrolysis furnace.
2. The process of claim 1 wherein a portion of the aromatics
contained in the hydrotreated oils withdrawn from the hydrotreater
are removed in an extraction step prior to introducing said
hydrotreated oils into said hydrocarbon pyrolysis furnace.
3. The process of claim 2 wherein aromatics are removed by
extraction with a solvent selected from the group consisting of
ethylene glycol, propylene glycol, tetramethylene sulfone,
dimethylformamide, N-methyl pyrrolidone, sulfur dioxide,
dicyanobutene, dimethylacetamide, furfural, furfuryl alcohol,
tetrahydrofurfuryl alcohol, phenol, and mixtures thereof.
4. The process of claim 1 wherein the volatile straight run naphtha
boils in the range of from about 85.degree. F. to about 400.degree.
F.
5. The process of claim 1 wherein the less volatile reduced crude
oil boils above 650.degree. F.
6. The process of claim 1 wherein the hydrocarbon pyrolysis furnace
is operated at temperatures of from about 600.degree. to about
3,000.degree. F, and at pressures of from about 0.05 to about 50
atmospheres.
7. The process of claim 1 wherein the coker naphtha boils in the
range of from about 100 to about 400.degree. F.
8. The process of claim 1 wherein the hydrotreater is operated at
temperatures of from about 600.degree. to about 750.degree. F. and
at pressures of from about 300 to about 1,500 p.s.i.g.
9. The process of claim 1 wherein the coker is operated at
temperatures of from about 800.degree. to about 1,100.degree. F.
and at pressures of from about 10 to about 70 p.s.i.g.
10. An improved process for the operation of a hydrocarbon
pyrolysis furnace consisting essentially of
a. distilling a crude oil to produce a more volatile naphtha
boiling at about 100.degree. to about 400.degree. F. and a less
volatile reduced crude oil boiling above 600.degree. F,
b. feeding said naphtha to said hydrocarbon pyrolysis furnace
operating at about 900.degree. to about 2,800.degree. F. to produce
products comprising ethylene and hydrogen,
c. coking said reduced crude oil at from about 850.degree. to about
1,050.degree. F. to produce petroleum coke and a coker naphtha
boiling in the range of from about 100.degree. to about 400.degree.
F.
d. separating at least a portion of said hydrogen from said
hydrocarbon pyrolysis furnace effluent,
e. utilizing at least a portion of said separated hydrogen to
hydrotreat said coker naphthas at from about 600.degree. to about
750.degree. F. and at pressures of from about 300 to about 800
p.s.i.g, to produce a hydrotreated oil having a lower aromatic
content and olefin content than said coker naphtha,
f. feeding said hydrotreated oils to an extractor wherein the
aromatics are withdrawn, and
g. introducing at least a portion of said extracted, hydrotreated
oils into said hydrocarbon pyrolysis furnace at from about
900.degree. to about 2,800.degree. F.
Description
BACKGROUND OF THE INVENTION
Coker naphthas, derived from the coking of reduced crude, can be
used as feedstocks in hydrocarbon pyrolysis furnaces but they are
uneconomic, inferior feeds due to their high olefin content. They
produce more polymers and tars than do paraffins, and
correspondingly less ethylene and acetylene. This invention
upgrades coker naphthas as commercial hydrocarbon pyrolysis
feedstocks by hydrotreating to substantially saturate their olefin
content, producing a stream with a paraffin content of about 90-95
percent. The paraffin feed causes less polymer and tar deposition
in the pyrolysis furnace while it produces higher yields of
acetylene and ethylene.
SUMMARY OF THE INVENTION
The operation of a hydrocarbon pyrolysis furnace is substantially
improved by distilling a crude oil to produce a straight-run
naphtha and a reduced crude, feeding the straight-run naphtha to
the hydrocarbon pyrolysis furnace in order to produce products
comprising ethylene, acetylene, or ethylene and acetylene, and
hydrogen, coking the reduced crude to produce petroleum coke and a
coker naphtha, separating a portion of the hydrogen from the
hydrocarbon pyrolysis effluent, using a portion of the separated
hydrogen to hydrotreat the coker naphtha so as to produce a
hydrotreated oil having a substantially lower olefin content than
the coker naphtha, and feeding a portion of the hydrotreated oils
into the hydrocarbon pyrolysis furnace.
DESCRIPTION OF THE DRAWING
The drawing is a schematic representation of the invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
In the drawing, distillation unit 1, operating at atmospheric
pressure, produces light petroleum ends boiling in the range of
from about 40.degree. to about 85.degree. F. a light naphtha
boiling in the range of from about 85.degree. to about 200.degree.
F. and a heavy naphtha boiling in the range of from about
200.degree. to about 400.degree. F.
Hydrocarbon pyrolysis furnace 2 is any suitable pyrolysis furnace
referred to in Acetylene, Its Properties, Manufacture and Uses by
S. A. Miller, V. I, Chapter 5, pp. 383-448; 451-471. For instance,
feed may be charged to a steam cracker to produce ethylene, or it
may be thermally cracked in a Wulff furnace to produce ethylene or
acetylene, or ethylene and acetylene. Any type of furnace which can
be used to pyrolyze a distilled crude oil to obtain hydrocarbon
gases is encompassed within the concept of the invention.
Operating temperatures for pyrolysis range from about 600.degree.
to about 3,000.degree. F., depending upon the type of furnace used
and the type of products desired with about 900.degree. to about
2,800.degree. F. being preferred. Pressures range from about 0.05
to about 50 atmospheres, but preferably are about 0.15 to about 5
atmospheres, and most preferably, about 0.4 to about 2.5
atmospheres.
Separations train 3 is a standard unit known to the art where the
pyrolysis gases are separated through absorption, drying, partial
condensation, and/or distillation into the desired products.
H.sub.2 purification unit 4 recovers hydrogen from stream F by
various known techniques such as adsorption, distillation, or, by
catalytically reacting the hydro carbon content of stream F with
steam to convert the hydrocarbons into CO and H.sub.2. A
representative physical separation technique is illustrated in
"Hydrocarbon Processing," 46:11, (Nov., 1967), pp. 160, 190. A
catalytic process for the recovery of hydrogen is well-explained in
the work, Industrial Chemicals, 2nd Ed., by Faith, Keyes, and
Clark, John Wiley & Sons, N.Y., Apr., 1961, pp. 440-449.
CO.sub.2 may be removed from the crude hydrogen product by
absorption with carbonates or alcohol amines. Any commercial
H.sub.2 purification process which may be used to recover hydrogen
from a mixed hydrocarbon stream is operable with the invention.
Hydrotreater 5 is any standard hydrotreater which may be equipped
for a one- or two-stage operation. When two stages are used, the
hydrotreater should operate at temperatures of from about
600.degree. to about 675.degree. F. in the first stage, and at
pressures in the range of from about 350 to about 800 p.s.i.g.
Preferred temperatures and pressures for the first stage of
hydrotreatment are from about 620.degree. to about 660.degree. F.
and from about 500 to about 800 p.s.i.g. In the second stage
temperatures range from about 680.degree. to about 720.degree. F.
and pressures range from about 350 to about 800 p.s.i.g.
If desired, the hydrotreatment can be done in a single stage if the
coker naphtha is diluted with a straight-run naphtha. The operating
conditions applied are those required in the second stage of a
two-stage operation.
The ratio of hydrogen to hydrocarbon feed is about 1,000-4,000
standard cubic feet per barrel (s.c.f./b.), but preferably is about
2,500-3,500 s.r.f./b.
Catalysts for hydrotreatment are selected from the group consisting
of cobalt, nickel, molybdenum, and combinations thereof.
The catalyst load is 1 to about 10 pounds of hydrocarbon feed per
one pound of catalyst per hour, but preferably is 4 to about 7
pounds of hydrocarbon feed per pound of catalyst per hour for the
first stage of hydrotreatment, and 2 to about 5 pounds of feed per
pound of catalyst per hour for the second stage.
Coker 6 is a conventional delayed coker which operates at pressures
of from 10 to about 70 p.s.i.g. but preferably operates at
pressures of from 20 to 50 p.s.i.g., and at temperatures in the
range of from about 800.degree. to about 1100.degree. F. but
preferably at temperatures of from about 850.degree. to about
1050.degree. F.
Extractor 7 can be any solvent extraction system operable with the
invention. Commercial solvents such as ethylene glycol, propylene
glycol, dimethylformamide, n-methyl pyrrolidone, tetramethylene
sulfone, sulfur dioxide, dicyanobutene, dimethylacetamide,
furfural, furfuryl alcohol, tetrahydrofurfuryl alcohol, phenol, or
the like, and/or mixtures thereof are appropriate. "Hydrocarbon
Processing," 47:9, Sept., 1968, presents flow charts of two
commercial extraction systems at pages 189 and 190 which can
conveniently be employed.
Having described the apparatus of the invention, the preferred
embodiment of the process may now be explained.
As depicted in the drawing, 100 pounds of crude oil are introduced
into distillation unit 1 through line 20. 45.97 pounds of reduced
crude and gas oil are withdrawn from distillation unit 1 and sent
to coker 6 through line 11. 23.80 pounds of fuel oils are removed
through line 10. 26.59 pounds of light and heavy naphthas are
withdrawn from distillation unit 1 as stream A and 3.64 pounds of
light ends are withdrawn as stream B. These streams enter
hydrocarbon pyrolysis furnace 2 from which stream C is withdrawn
and introduced into separations train 3.
5.21 pounds of C.sub.2 H.sub.2 are removed from separations train 3
as stream D, and 7.61 pounds of C.sub.2 H.sub.4 are removed as
stream E. 8.12 pounds of aromatic oils and tars are removed from
separations train 3 and introduced into coker 6 through line
30.
11.4 pounds of CO, H.sub.2 and CH.sub.4 are removed from
separations train 3 and introduced into H.sub.2 purification unit
4, from which 9.12 pounds of fuel gas are removed as stream G. 2.28
pounds of H.sub.2 is withdrawn from H.sub.2 purification unit 4
through line 40 and introduced into hydrotreater 5, which receives
10.02 pounds of coker naphtha, stream H, from coker 6. 29.86 pounds
of fuel oil are removed from coker 6 through line 60, 9.90 pounds
of coke are withdrawn through line 62, and 4.31 pounds of fuel gas
are removed from coker 6 through line 61.
2.10 pounds of fuel gas are withdrawn from hydrotreater 5 through
line 50, and 10.20 pounds of hydrotreated oils are removed from the
hydrotreater as stream I and introduced into hydrocarbon pyrolysis
furnace 2, or, optionally, they are introduced into extractor 7
from which 1.35 pounds of aromatics are withdrawn through line 70,
while the paraffins and naphthenes are removed as stream J which is
sent to hydrocarbon pyrolysis furnace 2.
The composition of stream A through J are tabulated in table 1 .
All values are in pounds per 100 pounds of crude oil feed.
##SPC1##
MODIFICATIONS OF THE INVENTION
For the sake of clarity, the invention has been described in terms
of a preferred embodiment. It is not intended to limit the process
to the particular operation shown. Rather, all equivalents obvious
to those skilled in the art are to be included within the scope of
the invention as claimed.
* * * * *