U.S. patent number 3,718,709 [Application Number 05/060,149] was granted by the patent office on 1973-02-27 for process for producing ethylene.
This patent grant is currently assigned to Societa Italiana Resine S.I.R. S.p.A.. Invention is credited to Massimo Simonetta.
United States Patent |
3,718,709 |
Simonetta |
February 27, 1973 |
PROCESS FOR PRODUCING ETHYLENE
Abstract
Hydrocarbons having a boiling point above 300.degree. C (fuel
oils) are vaporized by means of direct superheated steam; after
separation of any liquid components a further amount of superheated
steam is added to obtain a feed at 450.degree. -550.degree. C for a
tubular pyrolysis reactor operating at 700.degree.-800.degree.C.
The total steam content in the feed is 0.5 to 5.0 parts by weight
steam per part by weight of the hydrocarbon.
Inventors: |
Simonetta; Massimo (Milan,
IT) |
Assignee: |
Societa Italiana Resine S.I.R.
S.p.A. (Milan, IT)
|
Family
ID: |
11143934 |
Appl.
No.: |
05/060,149 |
Filed: |
July 31, 1970 |
Related U.S. Patent Documents
|
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
|
705578 |
Feb 12, 1958 |
|
|
|
|
Foreign Application Priority Data
|
|
|
|
|
Feb 23, 1967 [IT] |
|
|
12962 A/67 |
|
Current U.S.
Class: |
585/652;
208/130 |
Current CPC
Class: |
C10G
9/16 (20130101); C10G 2400/20 (20130101) |
Current International
Class: |
C10G
9/16 (20060101); C10G 9/14 (20060101); C10G
9/00 (20060101); C07c 003/00 () |
Field of
Search: |
;260/683 ;208/130 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Gantz; Delbert E.
Assistant Examiner: Nelson; J.
Parent Case Text
CROSS REFERENCE
This application is a continuation-in-part of applicant's copending
application Ser. No. 704,578, filed Feb. 12, 1958, now abandoned.
Claims
What is claimed is:
1. A process for the production of a gaseous mixture containing
above 40 wt. percent ethylene comprising:
a. vaporizing up to 50 wt. % of a heavy fuel oil hydrocarbon
mixture having an initial boiling point above 300.degree.C by
admixing said mixture with 0.1 to 0.5 parts by weight of
superheated steam per part by weight of hydrocarbon
b. separating liquid components from gaseous components by passing
said mixture through a gas-liquid separator at a temperature of
300.degree. to 45.degree.C
c. admixing said gaseous components with a further amount of
superheated steam to obtain a feed mixture of steam and
hydrocarbons having a temperature of from 450.degree. to
550.degree.C, the total proportion of steam present in said feed
mixture being from 0.5 to 5.0 parts by weight per part by weight of
hydrocarbon,
d. pyrolyzing said feed mixture at a temperature of 700.degree. to
800.degree.C for from 1 to 3 seconds to produce normally gaseous
hydrocarbons in an amount of up to 50 wt. percent of the weight of
hydrocarbons subjected to pyrolysis, and
e. recovering said normally gaseous hydrocarbons from the pyrolysis
product obtained.
2. The process of claim 1 wherein the hydrocarbon mixture is a
heavy fuel oil.
3. The process according to claim 1 wherein the proportion of steam
present in said feed mixture is from 1.5 to 3.0 parts by weight per
part by weight of the hydrocarbon.
4. The process according to claim 1 wherein said feed mixture is
pyrolyzed for from 1.5 to 2 seconds.
5. The process according to claim 1 wherein said normally gaseous
hydrocarbons are quenched to about 300.degree. to 400.degree.C.
6. The process according to claim 5 wherein said normally gaseous
hydrocarbons are quenched with water.
7. The process according to claim 1 whereby deposits of coke are
reduced.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention concerns the production of ethylene by
pyrolysis of fuel oils.
More particularly, this invention concerns the production of
gaseous mixtures having an ethylene content exceeding 40 percent by
weight, by pyrolysis, in the presence of steam, of heavy
hydrocarbon mixtures having an initial boiling point in excess of
300.degree.C, particularly heavy fuel oils.
2. Description of the Prior Art
In latter years, ethylene has attained very great importance in a
variety of fields, such as the preparation of plastic materials or
in modern processes for obtaining products formerly prepared from
acetylene. For these reasons, the demand for this compound has been
greatly increased and production techniques have been
correspondingly improved.
At the present time, the pyrolysis of hydrocarbons is the process
which is by far the most used for the production of ethylene.
A number of industrial methods are known for the pyrolysis of
normally gaseous hydrocarbons such as the natural gases, ethane,
propane, butane or relatively light hydrocarbon liquids, for
example, the mixture of hydrocarbons found in commerce and known as
"Naphtha."
Certain pyrolysis processes utilize hydrocarbon mixtures (e.g.,
crude petroleum) containing low boiling liquid fractions. In said
processes, the low boiling liquid fractions are first separated
from their mother-mixture (for example by means of steam) and the
pyrolysis is carried out on only these separated fractions. In
pyrolysis processes carried out in the presence of steam, the
hydrocarbons are subjected to elevated temperatures for a very
short period, the products of the pyrolysis then being cooled
rapidly and finally fractionated.
These procedures are inconvenient in that they utilize primary feed
materials which are relatively expensive in the production of
pyrolysis products having a concentration of ethylene not greater
than about 30 percent by weight.
It has now been discovered that gaseous mixtures having an ethylene
content exceeding 40 percent by weight can be obtained by
high-temperature pyrolysis, in the presence of steam, of
hydrocarbon mixtures having an initial boiling point exceeding
300.degree.C, in particular by pyrolysis of heavy fuel oils.
SUMMARY OF THE INVENTION
The process of this invention comprises:
A. VAPORIZING AN AMOUNT UP TO 50 WT. PERCENT OF A HYDROCARBON
MIXTURE HAVING AN INITIAL BOILING POINT ABOVE 300.degree.C by
admixture with 0.1 to 0.5 parts by weight of superheated steam
(primary steam) per part by weight of the hydrocarbon mixture
charge;
b. separating liquid components from gaseous components at a
temperature of 300.degree. to 450.degree.C; point
c. admixing the gaseous components with a further amount of
superheated steam (secondary steam) thereby to obtain, as the feed
for a pyrolysis reaction, a mixture of steam and hydrocarbons at a
temperature of 450.degree. to 550.degree.C, which mixture contains
0.5 to 5.0 parts by weight of steam per each part by weight of
hydrocarbons;
d. pyrolysing said feed, for example, in a tubular reaction zone at
a temperature of 700.degree. to 800.degree.C over a period of from
1 to 3 seconds, thus producing from said feed an amount of normally
gaseous hydrocarbons up to 50 wt. percent with respect to the
hydrocarbons contained in the feed;
e. recovering said normally gaseous hydrocarbons from the pyrolysis
product obtained.
DETAILED DESCRIPTION OF THE INVENTION
As in previous processes of this type, the process of the present
invention is advantageously carried out by use of a cyclically
operated tube-furnace in which the periods of pyrolysis are
alternated with periods of regeneration to eliminate the deposits
of coke within the tubes, although the quantity of deposited coke
does not become excessive (less than 1 percent in proportion to the
oil introduced) in the tube furnace during operation of the present
process. This regeneration is conventional and is preferably
effected at temperatures of 750.degree. to 900.degree.C, by passing
a mixture of air and steam through the pyrolysis tube furnace.
In the process of the present invention, the hydrocarbon is first
preheated and then mixed with primary steam in a proportion of 0.1
to 0.5 parts by weight to each part by weight of hydrocarbon.
As a result, a mixture comprising a gaseous phase and a liquid
phase at 300.degree.-450.degree.C is obtained, from which the
liquid phase is subsequently separated in a gas/liquid separator
maintained within this temperature range. By operating under these
conditions, an amount of up to 50 wt. percent of hydrocarbon
components is vaporized. It should be pointed out that, considering
the nature of the hydrocarbon charge employed, a vaporization of an
amount exceeding 50 percent hydrocarbons would give rise to
undesirable deposits in the gas/liquid separator comprising
carbonaceous and/or pitchy residues. Moreover, the hydrocarbons
which would then be present in the feed to the pyrolysis furnace
would contain undesirably high amounts of fractions capable of
immediately coking in the furnace (with consequent clogging of the
furnace tubes). Thus, it is important to partially vaporize the
hydrocarbon charge using only a relatively small amount of steam
and to dilute the vaporized fraction with a further amount of steam
only subsequently to the initial vaporization and separation
steps.
To the gaseous mixture thus obtained is added the secondary steam
in a proportion such that the weight ratio of steam/hydrocarbon at
the inlet to the pyrolysis furnace is between 0.5 to 5.0 and
preferably between 1.5 and 3.0 The temperature of the mixture may
vary between 450.degree. and 550.degree.C.
In the pyrolysis furnace, formed of tubes heated from the outside,
the hydrocarbons are pyrolysed, the temperature of the interior of
the tubes preferably being maintained between 700.degree. and
800.degree.C and the residence time of the mixture in the reactor
proper being maintained between 1 and 3 seconds, preferably 1.5 and
2 seconds.
By operating under these conditions, the hydrocarbons in the
pyrolysis furnace are converted to normally gaseous products in an
amount up to 50 wt. percent of the hydrocarbon feed. The
composition of the feed (steam: hydrocarbon) is to be maintained
within the limits stated hereinbefore, in order to avoid deposits
of coke in the furnace tubes. Moreover, the pyrolysis conditions
(relatively high temperatures and short residence times) prevent
coke formation in furnace tubes and contribute towards formation of
ethylene-rich pyrolysis gases from the specific hydrocarbon stock
employed.
The pyrolysis product leaving the pyrolysis reactor is quenched to
about 300.degree. to 400.degree.C, preferably by admixture of the
product with water to make use of the heat of vaporization of the
latter. The products are thus separated into liquids and gases
which are then fractionated.
The values set forth above with regard to the amount of hydrocarbon
stock to be vaporized by admixture with primary steam (50 wt.
percent) and the amount of conversion of hydrocarbon pyrolysis feed
into normally gaseous hydrocarbons (50 wt. percent) are to be
considered as maximums for operation in accordance with the present
invention. Any positive value less than these is operable in the
process of the present invention, the minimum acceptable values
being dictated by purely economical considerations.
Employing the process of the present invention, a pryolysis gas is
obtained in which the content of ethylene exceeds 40 percent by
weight, thus allowing subsequent separation to be effected in a
very economical manner.
Finally, the present process has the advantage of utilizing
inexpensive starting materials, such as heavy fuel oils or other
heavy petroleum fractions.
The following example illustrates the present invention without
limiting the scope thereof.
EXAMPLE
A pilot plant is fed with 100 kg/h of a fuel oil having the
following characteristics:
API: 20.4.degree.
Flow point:36.degree.C
Lower calorific value 9,800 calories/kg
Boiling point: 380.degree.C
The oil is preheated and mixed with about 23 kg/h superheated steam
at a temperature of 500.degree.C. The mixture, at a temperature of
360.degree.C and pressure of 1.1 atm. abs. is passed through a
gas-liquid separator.
The gaseous products obtained are admixed with about 93 kg/h of
superheated steam at a temperature of 780.degree.C. The new
mixture, containing about 27.degree. by weight hydrocarbons, is
introduced at a temperature of 530.degree.C and under 1.1 atm. abs.
into a pyrolysis reactor formed by a tube furnace heated from the
outside.
The pyrolysis conditions correspond to a residence time of the
mixture of 1.7 seconds, the products reaching the furnace outlet at
a temperature of about 770.degree.C. The products leaving the
reactor are quenched to about 400.degree.C in a mixing tower fed
with about 43 kg/h water which is instantly vaporized.
The heavier hydrocarbons are separated in a separating tower at a
temperature of about 110.degree. C, while the lighter products
constituting the pyrolysis gas, the water and the hydrocarbons
boiling at about the boiling point of petrol are successively
cooled in a heat exchanger.
In this manner, normally gaseous products are recovered which can
be separated by normal techniques at a rate of 24 to 24.5 kg/h,
calculated as dry products.
The pyrolysis product has the following composition determined by
gas chromatography :
methane 24.9% by weight ethylene 46.3% by weight ethane 4.5% by
weight C.sub.3 hydrocarbons 8.6% by weight C.sub.4 hydrocarbons
2.9% by weight benzene 3.8% by weight water 1.8% by weight CO 2.8%
by weight CO.sub.2 2.2% by weight hydrogen 2.2% by weight
In a series of tests with the pilot plant described, pyrolysis
periods of 10 to 12 hours can be alternated with regeneration
periods of 70 to 100 minutes. This regeneration operation is
effected at temperatures exceeding preferably by 100.degree. C the
pyrolysis temperature, that is to say between 750.degree. and
950.degree. C by passing air and steam at a rate of 20 to 50
m.sup.3 /h.
* * * * *