US007838712B2

(12) United States Patent (10) Patent No.: US 7,838,712 B2

BouVart et al. (45) Date of Patent: Nov. 23, 2010

(54) STEAM-CRACKING OF MODIFIED (58) Field of Classification Search ................. 196/110,

NAPHTHA 196/116; 208/14, 130, 210, 211, 212, 218,
208/227, 233,237, DIG. 1; 364/501; 422/197,
(75) Inventors: François Bouvart, Senlis (FR); Robert 422/204: 585/259, 648, 1,650, 652
See application file for complete search history.
Duchesnes, Paris (FR); Claude Gutle,
Courbevoie (FR) (56) References Cited
U.S. PATENT DOCUMENTS
(73) Assignees: Total Petrochemicals Research Feluy,
Seneffe (Feluv) (BE); Total Raffinage 3,511,771 A * 5, 1970 Hamner ....................... 208/89
3,786,110 A 1/1974 Oleszko
Marketing, Puteaux (FR) 4,257.105. A * 3/1981 Stewart et al. .............. 7OO 274
4.956,509 A * 9/1990 Harandi et al. .... ... 585,300
(*) Notice: Subject to any disclaimer, the term of this 5,124,003 A * 6/1992 Martens et al. ............. 196110
patent is extended or adjusted under 35 5,582,714. A 12, 1996 Forte .......................... 208,237
U.S.C. 154(b) by 1306 days. 6,007,704 A * 12/1999 Chapus et al. .............. 208,218
FOREIGN PATENT DOCUMENTS
(21) Appl. No.: 10/501,266 DE 37 08332 A 9, 1988
OTHER PUBLICATIONS
(22) PCT Filed: Jan. 9, 2003
International Search Report dated Jul. 1, 2003.
(86). PCT No.: PCT/FR03/00047 * cited by examiner
S371 (c)(1), Primary Examiner Prem C Singh
(2), (4) Date: Apr. 11, 2005 (74) Attorney, Agent, or Firm Sughrue Mion, PLLC
(87) PCT Pub. No.: WO03/057802 (57) ABSTRACT
Disclosed is a method for steam-cracking naphtha, according
PCT Pub. Date: Jul. 17, 2003 to which a charge of hydrocarbons containing a portion of
paraffinic naphtha, which is modified by adding a combina
(65) Prior Publication Data tion of a first component containing a portion of gasoline and
US 2006/OO89518A1 Apr. 27, 2006 a second component containing a portion of at least one
hydrocarbonated refinery gas, and a paraffin-rich change con
(30) Foreign Application Priority Data taining at least one paraffin selected among propane, butane,
or a mixture thereof are fed through a steam cracker in the
Jan. 10, 2002 (FR) ................................... O2 OO244 presence of vapor. Also disclosed is a hydrocarbon composi
tion Suitable for steam cracking, containing a portion of a
(51) Int. Cl. paraffinic naphtha, which is modified by adding a combina
CD7C 4/02 (2006.01) tion of a first component containing a portion of gasoline and
CIOL I/O (2006.01) a second component containing a portion of at least one
CIG 9/36 (2006.01) hydrocarbonated refinery gas and a paraffin-rich charge con
(52) U.S. Cl. ........................... 585/648; 585/1585/259; taining at least one paraffin selected among propane, butane,
585/650:585/652; 208/14; 208/130; 208/210; or a mixture thereof.
208/211; 208/212; 208/218: 208/227, 208/233;
208/237; 208/DIG. 1 20 Claims, No Drawings
 US 7,838,712 B2
1. 2
STEAM-CRACKING OF MODIFIED in the raw materials, and the yields of ethylene (compared to
NAPHTHA the ethylene introduced into the feedstock) and propylene are
not particularly high.
The present invention concerns a method for steam-crack U.S. Pat. No. 3,786,110 describes a method of producing
ing naphtha, a composition of hydrocarbons suitable for unsaturated hydrocarbons obtained by pyrolysis, where the
steam-cracking, a method for controlling a steam cracker, undesirable fractions are reduced by adding to the pyrolysis
instrumentation for controlling a steam cracker, and a method products a polymerization inhibitor containing asphaltic
for processing a Sulfurous gasoline feedstock. hydrocarbons.
The petrochemical industry requires monomers (building A method of steam-cracking naphtha capable of furnishing
blocks) composed for example of olefins, diolefins and aro 10 a commercially acceptable yield of olefins, in particular light
matics. In Europe, olefins are primarily obtained by Steam olefins such as ethylene and propylene, while reducing the
cracking feedstocks obtained from refineries. The available quantity of paraffinic naphtha feedstock material required, is
feedstocks are primarily naphtha including paraffins, isopar therefore necessary in the technology.
affins and aromatics. A naphtha feedstock usable in steam Refineries produce a broad range of products. Depending
cracking is known in the industry as including a petroleum 15 on the technical demands of the local markets and other
fraction the lightest components of which include five carbon commercial considerations, some of these products can be of
atoms and which have a final boiling point of around 200°C., little commercial value and are therefore considered to be
the naphtha including high carbon-index components having "Surplus. Currently products like gasolines and certain gas
a boiling point of at least 200° C. The steam-cracking of eous hydrocarbons are considered to be obtained in quantities
naphtha yields light olefins such as ethylene and propylene, that are too large. Although products of this type can be used
and diolefins such as butadiene, as well as gasolines contain in certain petrochemical processes, they are not currently
ing aromatics. used in steam-cracking operations because, for liquid prod
When a typical naphtha is subjected to steam-cracking, the ucts, they do not have the required quantity of paraffins.
cracked product typically has the following composition (in Ethane and propane are used as feedstocks for steam
% by weight) when it leaves the furnace: 25
cracking, especially in the United States where natural gas,
from which they are extracted, is abundant. These paraffins
generate a large quantity of ethylene (more than 50%) when
% by weight (approx.) they are steam cracked, which results in processing these
30
feed-stocks in units that are specifically sized for this type of
Hydrogen 1 feedstock. Some refinery hydrocarbon gases such as FCC
Methane 16
Acetylene O.2 gases contain Substantial quantities of paraffins (ethane and
Ethylene 22 propane) and olefins (ethylene, propylene). However, when
Ethane 5 they are steam cracked as such, they have a tendency to
Methylacetylene, O.3 generate cracked gaseous effluents having a composition that
Propadiene 35
Propylene 14 is different from that of the effluents from steam-cracking
Propane O.S normal naphtha. This poses a problem, because it generates
Butadiene
C4
4
5
an imbalance in the downstream section (especially the dis
C5 4
tillation columns) of a steam cracker cracking naphtha.
Benzene 9 40 Butane and propane are also used, either alone or in mix
Toluene 5 ture with the naphtha, as feedstock for steam crackers. When
Non-aromatic gasoline 2 they are used exclusively, however, the problem of imbalance
Aromatic gasoline 6 in the downstream section of a naphtha Steam cracker also
Fuel oil 6
becomes apparent. Depending on the availability of the refin
Total 1OO
45 ery or the market, there can be an excess of these liquefied
gases and it is therefore worthwhile to use them as feedstock
for a steam cracker.
The most interesting fractions in the cracked product are
the light olefins, that is, the ethylene and propylene. Their DE-A-3708332, already cited, does not deal with the tech
yield is directly related to the presence of paraffins in the nical problem that consists of producing an effluent that has a
feedstock. When paraffins in Straight chains are present, the 50 composition that corresponds with the one produced by
formation of ethylene is favored. When isoparaffins are steam-cracking naphtha. In the examples of DE-A-3708332,
present, the formation of propylene is favored. The relative when the ethylene is added (alone) to the naphtha, the com
yield in propylene is expressed as the weight ratio of the position of the effluent, particularly with regard to ethylene
propylene to the ethylene, and is typically between 0.5 and and propylene, is substantially altered as compared to the
O.75. 55 cracking of naphtha alone under the same conditions, which
Recently, because of the increased need for olefins, the can result in significantly reducing the capacity of the steam
Supply of the paraffinic naphtha feedstock in a petrochemical cracking unit.
plant fed from a refinery has tended to be somewhat limited. A petrochemical process that increases the economic value
DE-A-3708332 describes a method of thermal cracking of the "Surplus” refinery products. Such as gasolines and
ethylene in a steam cracker, where the ethylene is mixed with 60 gaseous hydrocarbons, is also necessary for the technology.
the naphtha in order to prepare a feedstock composed essen The invention seeks at least partially to meet these needs.
tially of naphtha and 10 to 80% by weight ethylene, option To that end, the invention proposes a method for steam
ally containing, in addition to the naphtha, fractions from cracking naphtha, said method comprising the passage in a
gas-oil (boiling temperature up to 350° C.) and/or recycled steam cracker, in the presence of steam, of a feedstock of
byproducts from a petrochemical plant that can have up to 65 hydrocarbons comprising a paraffinic naphtha modified by
50% naphtha. This method has the disadvantage that it the addition of the combination of a first component including
requires relatively large quantities of ethylene (at least 10%) a gasoline and of a second component including at least one of
 US 7,838,712 B2
3 4
a hydrocarbon refinery gas and a feedstock rich in paraffins ing process to produce products that are economically ben
including at least one paraffin selected from propane and eficial and useful, to wit, light olefins, while making only
butane or a mixture thereof. minor modifications to the Steam-cracking unit since the
The invention also proposes a composition of hydrocar overall balance of materials is only slightly modified.
bons appropriate for steam-cracking, comprising a paraffinic 5 Forms of embodiment of the invention will now be
naphtha modified by the addition of the combination of a first described, solely by way of example, with reference to the
component including a gasoline, and of a second component appended drawing in which:
including at least one of a hydrocarbon refinery gas and a FIG. 1 diagrammatically shows a unit for the Steam-crack
feed-stock rich in paraffins including at least one paraffin ing of feedstocks containing naphtha according to one form
selected from propane and butane or a mixture thereof. 10 of embodiment of the invention.
The invention also proposes a method for controlling a According to the invention, a method for the Steam-crack
steam cracker, said method comprising the Supply to a steam ing of naphtha uses a feedstock composed of hydrocarbons,
cracker of steam and of a feed-stock of hydrocarbons com comprising a paraffinic naphtha modified by a gasoline in
prising a paraffinic naphtha modified by the addition of the combination with a hydrocarbon refinery gas and/or butane or
combination of a first component including a gasoline, and of 15
propane or a mixture thereof.
a second component including at least one of a hydrocarbon The paraffinic naphtha to be used in the method of the
refinery gas and a feed-stock rich in paraffins including at invention includes 10 to 60% by weight of n-paraffins, 10 to
least one paraffin selected from propane and butane or a 60% by weight of isoparaffins, 0 to 35% by weight of naph
mixture thereof, and the continuous control of the supply of thenes, 0 to 1% by weight of olefins and 0 to 20% by weight
paraffinic naphtha, of the second component and of the gaso of aromatics. A typical paraffinic naphtha to be used in the
line in the feedstock, in order to give the effluent a desired method of the invention includes about 31% by weight of
target composition. n-paraffins, 35% by weight of isoparaffins (giving a total
Moreover, the invention proposes an instrumentation for paraffinic content of 66% by weight), 26% by weight of
controlling a steam cracker, said instrumentation comprising naphthenes, 0% by weight of olefins (typically 0.05% by
means of furnishing a steam cracker with a hydrocarbon 25
weight of olefins) and 8% by weight of aromatics.
feedstock comprising a paraffinic naphtha modified by the According to the invention, this starting feedstock of par
addition of the combination a gasoline and of at least one of a affinic naphtha is modified by adding to it a gasoline and a
hydrocarbon refinery gas and/or butane or propane or a mix hydrocarbon refinery gas and/or butane or propane or a mix
ture thereof, and means for continuously controlling the pro ture thereof.
portions of the paraffinic naphtha, of the refinery gas and/or of 30
butane or propane or the mixture thereof, and of the gasoline The gasoline is preferably a fraction from an FCC (fluid
in the feedstock, in order to give the effluent a desired target ized-bed catalytic cracking) unit of an oil refinery (hereinafter
composition. called FCC gasoline), which advantageously has not been
The invention also proposes a method for processing a given a hydrogenation treatment (called "hydro-refining in
feedstock of sulfurous gasoline, which method includes the 35 the industry), which increases the paraffins content of the
following phases: combining a sulfurous gasoline feedstock gasoline by hydrogenating the unsaturated functions (like
with a naphtha feedstock to obtain a composite feed-stock; those present in the olefins and diolefins) of the gasoline. The
causing the composite feedstock to pass into a steam cracker, advantage of using a non-hydro-refined FCC gasoline is that
in the presence of steam, to produce an effluent, the effluent by avoiding a hydrogenation process, production costs are
containing at least light olefins, the light olefins having at 40 reduced by eliminating or reducing the use of hydrogen and
least one olefin between C2 and C4, and C5+ hydrocarbons; by avoiding the need for additional hydro-refining capacity.
and separating from the effluent a first fraction that is practi The FCC gasoline is a fraction or a mixture of fractions
cally free of sulfur and includes the light olefins, and a second from the FCC unit typically having a distillation range of
fraction that contains sulfur and includes the C5-- hydrocar between 30 and 160° C., preferably a fraction or mixture of
bons. 45 fractions that reach boiling in a range of between 30 and 65°
The invention is based on the surprising discovery by the C., 65 to 105° C. and 105 to 145° C. The choice of the
Applicant that by selecting certain quantities and qualities of particular FCC gasoline or mixture thereof to be used can be
these gasolines and gaseous hydrocarbons and by using them determined based on the requirements at any time for the
as feedstocks in combination with naphtha, it is possible to various fractions produced by the refinery. For example, some
steam crack the composite feedstock in order to produce a 50 gasoline fractions have an octane deficit and could be better
composition for the cracked product (called “pallet of prod upgraded in a steam cracker rather than having to increase the
ucts” in the industry) which strongly resembles a pallet of octane index in the refinery. In addition, the FCC gasoline to
products resulting from the steam-cracking, under similar be used can have a sulfur content that would be too high for
conditions, of a feedstock of just paraffinic naphtha. The gasolines to be used in automobiles and would require hydro
composition of the effluent produced according to the inven 55 gen desulfurization treatment, which is costly because it con
tion falls within a range of +90%, and preferably +0% by Sumes hydrogen and requires the corresponding capacity on a
weight, for each component, compared to that of the effluent, desulfurization unit.
when said effluent is non-modified paraffinic naphtha. It is preferable to use a non-hydrorefined FCC gasoline
In reality, therefore, according to the invention part of the because, in the refinery, where there is a need for hydrorefined
paraffinic naphtha feedstock is replaced by a combination of 60 gasoline for other uses, this can cause bottlenecks in the
a gasoline feedstock and a hydrocarbon refinery gas feed processing by the hydro-refining unit. By reducing the quan
stock and/or a butane or propane feedstock or mixture of the tity of non-hydro-refined gasoline present in the refinery, that
tWO. is, by consuming the non-hydro-refined gasoline in the steam
This offers the combined advantages of (a) reducing the cracking process of the invention, the hydro-refining equip
quantity of paraffinic naphtha feeds needed for the steam 65 ment and units can be unblocked, thus improving the man
cracking process, and (b) using the gaseous hydrocarbon agement of flows in the refinery while reducing the needs for
products and "surplus' gasoline products in the steam-crack hydrogen.
 US 7,838,712 B2
5 6
Typically the non-hydro-refined FCC gasoline includes C. The quantity of steam can also fall within a range known in
from 0 to 30% by weight of n-paraffins, from 10 to 60% by the industry, typically between 25 and 60% by weight on the
weight of isoparaffins, from 0 to 80% by weight of naph basis of the weight of the hydrocarbon feedstock.
thenes, from 5 to 80% by weight of olefins and from 0 to 60% With reference to FIG. 1 of the appended drawing, the hot
by weight of aromatics. More typically, the non-hydrorefined 5 section of a steam cracking unit to be used in the method of the
FCC gasoline includes approximately 3.2% by weight of invention is represented diagrammatically. The Steam crack
n-paraffins, 19.2% by weight of isoparaffins (giving a total ing unit, generally indicated by 2, includes a heating unit
paraffins content of 22.4% by weight), 18% by weight of composed of furnaces 4, which are provided with coils 6
naphthenes, 30% by weight of olefins and 29.7% by weight of having a first intake 8 for the feedstock of hydrocarbons to be
aromatics. 10 cracked and a second intake 10 for the steam. An outlet
However, if a hydro-refined FCC gasoline were used, a conduit 12 from the heating unit is connected to a first frac
Substantial quantity of hydrogen would be needed to hydro tionating column 14. The first fractionating column 14
genate it and the hydrorefined composition would resemble includes a gasoline reflux 15 and outlets for the various frac
typical naphtha used for Steam-cracking. tionated products, including a top outlet 16 for the light
With regard to the hydrocarbon refinery gas that is added, 15 hydrocarbons and a bottom outlet 18 for the heavy hydrocar
in combination with the FCC gasoline and/or the butane or bons, which can be returned through 19 after cooling in the
propane or a mixture of the two, to the paraffinic naphtha to conduit 12 in order to control the temperature or drawn offat
produce a composite feedstock for the steam-cracking, this 17 in the form of heavy products called pyrolysis oil.
hydrocarbon gas is rich in C and C. hydrocarbons, particu In this simplified description and in the presentation of the
larly in paraffins (ethane and propane) and in olefins (ethylene following examples, only the feeds from outside the steam
and propylene). Preferably the refinery gas has the following cracker, commonly called fresh feeds, are considered, and not
composition ranges: 0 to 5% by weight of hydrogen, 0 to 40% the possible recycling of products coming from the steam
by weight of methane, 0 to 50% by weight of ethylene, 0 to cracker itself. Such as ethane, which is often re-cracked until
80% by weight of ethane, 0 to 50% by weight of propylene, 0 it disappears.
to 80% by weight of propane and 0 to 30% by weight of 25 If desired, the entire composite feedstock of naphtha, refin
butane. A typical composition of refinery gas of this type is ery gas and/or butane or propane or a mixture of the two, and
approximately 1% by weight of hydrogen, 2% by weight of gasoline can be fed through the common intake 8 of hydro
nitrogen, 0.5% by weight of carbon monoxide, 0% by weight carbons, or alternatively, the four components naphtha, FCC
of carbon dioxide, 10% by weight of methane, 15% by weight gasoline, refinery gas and/or butane or propane or a mixture
of ethylene, 32% by weight of ethane; 13% by weight of 30 thereof can be cracked separately in specific tubular coils. In
propylene, 14% by weight of propane, 2% by weight of one particular form of embodiment, the naphtha and the FCC
isobutane, 4% by weight of n-butane, 3% by weight ofbutene, gasoline, for the one part, the butane and/or propane or a
2% by weight of n-pentane, and 1.5% by weight of n-hexane. mixture of the two, and the refinery gas, for the other part, are
With regard to the butane and/or propane or the mixture cracked separately. The reason for this is that the naphtha and
thereofthat is added to the paraffinic naphtha, in combination 35 the FCC gasoline are typically cracked a temperatures that are
with the FCC gasoline and optionally the refinery gas, in close to each other, typically within the range of 750 to 850°
order to produce a composite feedstock for steam-cracking, C., while the butane, propane and refinery gases that contain
this butane and/or propane or the mixture thereof can contain the ethane and propane should be cracked at higher tempera
olefinic compounds Such as butenes and/or propylene, or tures, typically within the range of 800 to 900° C. The two
saturated compounds such as butanes (normal and/or iso) 40 effluents can be combined at the outlet of the heating unit
and/or propane. Preferably the butane and/or propane or the before the first fractionating column.
mixture thereof contain more than 50% by weight of satu The method of the invention can function continuously and
rated compounds in order to maximize the production of light offers the advantage of eliminating the excess gasoline from
olefins such as ethylene and propylene. The butane and pro the refinery, and also reducing the need at the refinery for a
pane are preferably n-butane and n-propane. 45 desulphurization process. The gasoline contains Sulfur, and
According to the method of the invention, the parts of after the steam-cracking process, in which the gasoline fur
naphtha, refinery gas, butane or propane or a mixture thereof, nishes part of the feedstock, the most-interesting light olefins
and gasoline are combined to form a composite feedstock that in the effluent are free of sulfur, while the sulfur remains
is then processed by Steam-cracking. Preferably, the compos concentrated in the C5-- part of the effluent flow. Conse
ite feedstock includes from 5 to 95% by weight of naphtha, 5 50 quently the use of gasoline as part of a feedstock to be steam
to 95% by weight of a mixture of refinery gas, butane or cracked to produce the lightest olefins leads to a partial des
propane or a mixture of thereof, and gasoline. Typically, the ulfurization of the gasoline portion of the feedstock, because
mixture of refinery gas, butane or propane or a mixture the sulfur is concentrated in the fraction with the highest
thereof, and gasoline that is added to the naphtha includes up carbon number and of least commercial interest of the efflu
to 60% by weight of refinery gas and/or butane or propane or 55 ent, to wit, the C5-- flow.
a mixture thereof, and at least 40% by weight of gasoline, In a related way, according to another aspect, the invention
more typically up to 50% by weight of refinery gas and/or proposes a method for processing a Sulfurous gasoline feed
butane or propane or a mixture thereof, and up to 50% by stock, which method comprises the following phases: com
weight of gasoline. In a more preferred manner, the naphtha bining a Sulfurous gasoline feedstock with a naphtha feed
composite includes 80% by weight of naphtha, 7% by weight 60 stock to provide a composite feedstock; causing the
of refinery gas and/or butane or propane or a mixture thereof, composite feedstock to pass through a steam cracker, in the
and 13% by weight of non-hydrorefined FCC gasoline. presence of steam, to produce an effluent, the effluent con
The composite feedstock of naphtha, gasoline, refinery gas taining at least light olefins, the light olefins having at least
and/or butane or propane or a mixture thereof, is typically one of the C2 to C4 olefins, and C5+ hydrocarbons; and
processed by Steam-cracking under conditions similar to 65 separating from the effluent a first fraction that is practically
those known in the industry, to wit, at a temperature of free of sulfur and includes the light olefins, and a second
between 780 and 880° C., preferably between 800 and 850° fraction that contains the sulfur and includes the C5+ hydro
 US 7,838,712 B2
7 8
carbons. In this way, the sulfur is redistributed in the higher 1.5% by weight n-hexane.
carbon number fraction, producing a lower carbon number The non-hydro-refined FCC gasoline has the following
olefinic fraction free of sulfur, which is an effective way to approximate starting composition:
partially desulfurize the gasoline feedstock. 3% by weight n-paraffins,
Moreover, the method offers the advantage that the steam 5 19% by weight isoparaffins (giving a total paraffinic con
cracking process at least partially dehydrogenates the ethane tent of 22% by weight),
present in the refinery gas, the dehydrogenation being accom 18% by weight naphthenes,
plished at a temperature high enough to effectively produce 30% by weight olefins,
ethylene. 30% by weight aromatics.
The invention also offers the advantage that by adding to 10
After steam-cracking, the overall effluent from the set of
the feedstock naphtha that contains no olefins or only a small furnaces at outlet 12 without recycling the ethane produced
quantity thereof, non-hydro-refined gasoline that contains a by the Steam cracker, has the composition shown in Table 1.
relatively high quantity of olefins, typically from 5 to 80% by
weight of olefins; the composite feedstock for the steam TABLE 1
cracking has a higher overall content of olefins compared to 15
the naphtha alone, and this results in a lower use of energy to Composition of the Effluent of Example 1
produce light olefins (that is, ethylene and propylene) from % by weight
this feedstock, compared to steam-cracking paraffins or par (approx.)
affinic feedstocks into light olefins of this type.
According to another aspect of the invention, a Software H2
Methane
O.9
16.0
program, using linear or non-linear programming, is used to Acetylene O.2
continuously control the steam-cracking conditions, in par Ethylene 22.0
ticular to control the parts of the paraffinic naphtha, the refin Ethane 5.3
ery gas, the butane and/or propane or the mixture of the two, Methylacetylene-propadiene
Propane
O.3
O6
and the FCC gasoline in the feedstock, so that the effluent has 25
Propylene 12.5
the desired target composition. For example, the target com Butadiene 3.4
position can have appreciably the same effluent composition C4 4.4
for the important components, that is, +20% by weight, pref C5 3.8
Benzene 8.9
erably +10% by weight compared to that of the unmodified Toluene 6.3
feedstock. The software can also control the flow of the refin 30
Non-aromatic gasoline 2.0
ery gas and/or control the quantities of FCC gasoline and/or Aromatic gasoline 6.9
butane or propane or mixture of the two, taken from the Fuel oil 6.5
refinery for shipment of excess quantities, for example, to
storage tanks. By contrast, when 100% of the same naphtha is subjected
The invention will now be described in more detail with 35
reference to the following two examples. to steam-cracking under the same conditions, the effluent
obtained had the composition shown in Table 2.
Example 1 TABLE 2
In this example, a composite feedstock having 80% by 40 Non-hydro-refined
weight naphtha and 20% mixture of refinery gas and non Naphtha Refinery Gas FCC gasoline
hydrorefined FCC gasoline, at a ratio by weight one third gas Hydrogen O.8 2.6 O6
and two thirds gasoline, was Subjected to steam-cracking. Methane 15.2 27.4 13.6
The naphtha has the following approximate starting com Acetylene O.2 O.2 O.1
position: 45 Ethylene 21.8 43.5 12.5
Ethane S.O 12.5 3.1
31% by weight n-paraffins, MAPD 0.4 O.1 O.3
35% by weight isoparaffins (giving a total paraffinic con Propylene 14.2 2.7 7.5
tent of 66% by weight), Propane O.6 O.S O.3
26% by weight naphtalenes, Butadiene 3.7 1.7 2.2
C4 S.1 0.4 2.5
0.05 wt olefins, 50
C5 4.3 O6 2.2
0% by weight diolefins, Benzene 9.1 3.8 1O.O
8% by weight aromatics. Toluene 5.4 O.S 14.9
The refinery gas has the following approximate starting Non-aromatic gasoline 2.4 O.1 1.1
composition: Aromatic gasoline
Fuel oil
5.8
6.O
1.4
2.0
16.8
12.3
1% by weight hydrogen, 55
2% by weight nitrogen,
0.5% by weight carbon monoxide, As can be seen, the effluent resulting from the Steam
0% by weight carbon dioxide, cracking of the combination of three feedstocks of paraffinic
10% by weight methane, naphtha, refinery gas and non-hydro-refined FCC gasoline
15% by weight ethylene, 60 very strongly resembles the effluent produced by steam
32% by weight ethane, cracking paraffinic naphtha alone.
13% by weight propylene, Thus, the composition of the effluent from the composite
14% by weight propane, feedstock of Example 1 is similar (+10% by weight for each
2% by weight isobutane, component) to that of naphtha alone, but part of the naphtha
4% by weight n-butane, 65 has been replaced by the addition of the refinery gas and the
3% by weightbutene, FCC gasoline for the reasons and advantages indicated above.
2% by weight n-pentane, It can be seen that the high yields of ethylene and propylene
 US 7,838,712 B2
10
obtained by the method according to the invention are similar
to those that can be obtained simply by Steam-cracking par TABLE 4-continued
affinic naphtha. Non-hydro-refined
Table 2 also shows, by contrast, the compositions of the Naphtha Butane FCC gasoline
effluents obtained by Steam-cracking of refinery gas alone,
and separately, the FCC gasoline alone. As can be seen, the Butadiene 3.7 2.8 2.2
steam-cracking of the non-hydro-refined FCC gasoline pro C4
C5
S.1
4.3
11.2
2.2
2.5
2.2
duces a low yield of ethylene and propylene, and the steam Benzene 9.1 2.2 1O.O
cracking of refinery gas produces a highyield of ethylene, but Toluene 5.4 O6 14.9
a low yield of propylene. However, when the three feedstocks 10 Non-aromatic gasoline 2.4 O.8 1.1
of naphtha, refinery gas and non-hydro-refined FCC gasoline Aromatic gasoline 5.8 O.S 16.8
Fuel oil 6.0 O6 12.3
are combined, the composition of the effluent very strongly
resembles that of normal naphtha.
As can be seen, the effluent resulting from the Steam
Example 2 15 cracking of the combination of three feedstocks of paraffinic
naphtha, butane and non-hydro-refined FCC gasoline very
In this example, a composite feedstock having 60% by strongly resembles the effluent produced by Steam-cracking
weight naphtha and 40% by weight mixture of butane and paraffinic naphtha alone.
non-hydro-refined FCC gasoline, in a ratio by weight half gas Thus, the composition of the effluent from the composite
and half gasoline, is Subjected to steam cracking. feedstock of Example 2 is similar (+10% by weight for each
The naphtha has the same starting composition as in the component) to that of naphtha alone, but part of the naphtha
preceding example. has been replaced by the addition ofbutane and FCC gasoline
The butane in this example is normal pure butane, as can be for the reasons and advantages indicated above. It can be seen
produced at the output of a refinery alkylation unit. that the high yields of ethylene and propylene obtained by the
The non-hydro-refined FCC gasoline has the same starting 25 method according to the invention are similar to those that can
composition as in the preceding example. be obtained simply by Steam-cracking paraffinic naphtha.
After steam cracking, the overall effluent from the set of Table 4 also shows, by contrast, the compositions of the
furnaces at outlet 12 without recycling the ethane produced effluents obtained by Steam cracking of butane alone, and
by the steam cracker has the composition shown in Table 3. separately, the FCC gasoline alone. It can be seen that the
30 steam-cracking of the non-hydro-refined FCC gasoline pro
TABLE 3 duces a low yield of ethylene and propylene, and that the
steam-cracking of butane produces a high yield of ethylene,
Composition of the Effluent of Example 2 propylene and C4, and low yields of heavy products. How
% by weight ever, when the three feedstocks of naphtha, butane and non
(approx.) hydro-refined FCC gasoline are combined, the composition
of the effluent very strongly resembles that of normal naph
H2 O.8 tha.
Methane 15.4 The invention claimed is:
Acetylene O.2
Ethylene 21.9 1. A method for steam-cracking naphtha comprising pass
Ethane 4.8 40 ing a feedstock of hydrocarbons through a steam cracker, in
Methylacetylene-propadiene
Propylene
0.4
14.1
the presence of Steam;
Propane O.S wherein said feedstock of hydrocarbons comprises
Butadiene 3.2 about 60% to about 80% by weight of a paraffinic naphtha,
C4 5.9 and
C5
Benzene
3.7
7.7
45 about 40% to about 20% by weight of a mixture of a first
Toluene 6.3
component, that is, a gasoline produced by a fluidized
Non-aromatic gasoline 2.1 bed catalytic cracking (FCC) unit and a second compo
Aromatic gasoline 6.9 nent including at least one hydrocarbon refinery gas and
Fuel oil 6.1 at least a feedstock rich in paraffins,
50 the paraffinic naphthahaving from 10 to 60% by weight of
By contrast, when 100% of the same naphtha was sub n-paraffins, from 10 to 60% by weight of isoparaffins,
jected to steam-cracking under the same conditions, the efflu from 0 to 35% by weight of naphthenes, from 0 to 1% by
ent obtained had the composition shown in Table 2 and weight of olefins, and from 0 to 20% by weight of
recalled in Table 4. aromatics,
55 the FCC gasoline being an unhydrogenated gasoline hav
TABLE 4 ing from 0 to 30% by weight of n-paraffins, from 10 to
60% by weight of isoparaffins, from 0 to 80% by weight
Non-hydro-refined of naphthenes, from 5 to 80% by weight of olefins and
Naphtha Butane FCC gasoline from 0 to 60% by weight of aromatics,
Hydrogen O.8 O.9 O.6 60 the refinery gas having from 0 to 5% by weight of hydro
Methane 15.2 18.8 13.6 gen, from 0 to 40% by weight of methane, from 0 to 50%
Acetylene O.2 0.4 O.1 by weight of ethylene, from 0 to 80% by weight of
Ethylene 21.8 32.7 12.5 ethane, from 0 to 50% by weight of propylene, from 0 to
Ethane S.O 5.9 3.1
MAPD 0.4 O.3 O.3 80% by weight of propane and from 0 to 30% by weight
Propylene 14.2 19.7 7.5 65 ofbutanes, and the feedstock rich in paraffins containing
Propane O6 0.4 O.3 at least 50% by weight of saturated hydrocarbons, said
feedstock containing at least propane or butane.
 US 7,838,712 B2
11 12
2. The method according to claim 1, in which the mixture 14. The composition of hydrocarbons according to claim
of the first and second components that is added to the naph 13, in which the feedstock includes about 80% by weight of
tha includes up to 60% by weight of the second component naphtha, about 7% by weight of the second component and
and at least 40% by weight of gasoline. about 13% by weight of gasoline.
3. The method according to claim 2, in which the mixture 15. The composition of hydrocarbons according to any of
of the first and second components includes up to 50% by claims 10 to 12, in which the second component consists of at
weight of the second component and at least 50% by weight least propane and butane.
of gasoline. 16. A method for controlling a steam cracker, said method
4. The method according to claim 2 or 3, in which the comprising:
mixture of the first and second components includes about 10 Supplying steam and a feedstock of hydrocarbons to a
one third in percentage by weight of the second component steam cracker,
and about two thirds in percentage by weight of gasoline. wherein the feedstock of hydrocarbons comprises about
5. The method according to any one of claims 1-3, in which 60% to about 80% by weight of a paraffinic naphtha and
the feedstock includes about 80% by weight naphtha, about about 40% to about 20% by weight of a mixture of a first
7% by weight of the second component and about 13% by 15 component, that is, a gasoline produced by a fluidized
weight of gasoline. bed catalytic cracking (FCC) unit, and a second compo
6. The method according to any one of claims 1-3, in which nent including at least one hydrocarbon refinery gas and
the FCC gasoline is a fraction or a mixture of fractions from at least a feedstock rich in paraffins,
an FCC unit having a distillation range of between 30 and the paraffinic naphthahaving from 10 to 60% by weight of
160° C. n-paraffins, from 10 to 60% by weight of isoparaffins,
7. The method according to any of claims 1 to 3, in which from 0 to 35% by weight of naphtalenes, from 0 to 1% by
the second component consists of at least propane and butane. weight of olefins and from 0 to 20% by weight of aro
8. The method according to any of claims 1 to 3, in which matics, the FCC gasoline being an unhydrogenated
the composite feedstock of naphtha, gasoline and of the sec gasoline having from 0 to 30% by weight of n-paraffins,
ond component is Subjected to steam-cracking under condi 25 from 10 to 60% by weightofisoparaffins, from 0 to 80%
tions including a temperature of between 780 and 880° C. by weight of naphthenes, from 5 to 80% by weight of
9. The method according to any of claims 1 to 3, in which olefins and from 0 to 60% by weight of aromatics, the
the quantity of steam is from 25 to 60% by weight based on refinery gas having from 0 to 5% by weight of hydrogen,
the weight of the feedstock of hydrocarbons. from 0 to 40% by weight of methane, from 0 to 50% by
10. A composition of hydrocarbons suitable for a steam 30 weight of ethylene, from 0 to 80% by weight of ethane,
cracking method, said composition comprising about 60% to from 0 to 50% by weight of propylene, from 0 to 80% by
about 80% by weight of a paraffinic naphtha and about 40% weight of propane and from 0 to 30% by weight of
to about 20% by weight of a mixture of a first component, that butanes, and the feedstock rich in paraffins containing at
is, a gasoline produced by a fluidized bed catalytic cracking least 50% by weight of saturated hydrocarbons, said
(FCC) unit and a second component including at least one 35
feedstock containing at least propane or butane; and
hydrocarbon refinery gas and at least a feedstock rich in a continuous control of the Supply of paraffinic naphtha, of
paraffins, the paraffinic naphtha having from 10 to 60% by the second component and of the gasoline in the feed
weight of n-paraffins, from 10 to 60% by weight of isoparaf stock, in order to give an effluent a desired target com
fins, from 0 to 35% by weight of naphthenes, from 0 to 1% by position.
weight of olefins and from 0 to 20% by weight of aromatics, 40
17. The method according to claim 16, in which the target
the FCC gasoline being an unhydrogenated gasoline having composition is appreciably the same composition of effluent,
from 0 to 30% by weight of n-paraffins, from 10 to 60% by that is +20% by weight for any given effluent component, as
weight of isoparaffins, from 0 to 80% by weight of naph the composition obtained with unmodified paraffinic naph
thenes, from 5 to 80% by weight of olefins and from 0 to 60% tha.
by weight of aromatics, the refinery gas having from 0 to 5% 45
18. The method according to claim 16 or 17, in which the
by weight of hydrogen, from 0 to 40% by weight of methane, second component and the gasoline are both furnished
from 0 to 50% by weight of ethylene, from 0 to 80% by weight directly by a refinery and also including control of sending the
of ethane, from 0 to 50% by weight of propylene, from 0 to second excess component to the flare and/or the control of the
80% by weight of propane and from 0 to 30% by weight of quantity of gasoline in the refinery.
butanes, and the feedstock rich in paraffins containing at least 50
19. The method according to any one of claims 16 to 17, in
50% by weight of saturated hydrocarbons, said feedstock which the supply of the components of the feedstock to the
containing at least propane or butane.
11. The composition of hydrocarbons according to claim steam cracker is controlled by software.
10, in which the mixture of the first and second components to 20. The method according to claim 1 or 16 for processing
the naphtha includes up to 60% of the second component and 55 Sulfurous gasoline wherein
at least 40% by weight gasoline. sulfurous gasoline produced by a fluidized bed catalytic
12. The composition of hydrocarbons according to claim cracking unit, and
11, in which the mixture of the first and second components effluent from the steam cracker containing at least light
includes up to 50% of the second component and at least 50% olefins, which have at least one olefin between C2 and
by weight of gasoline. 60 C4, and C5+ hydrocarbons, are separated into a first
13. The composition of hydrocarbons according to claim fraction, which is practically free of sulfur and includes
11 or 12, in which the mixture of the first and second com the light olefins, and a second fraction that contains
ponents that is added to the naphtha includes about one third sulfur and includes the C5-hydrocarbons.
in percentage by weight of the second component and about
two thirds in percentage by weight of gasoline. k k k k k