U.S. patent application number 13/225589 was filed with the patent office on 2012-05-03 for process for the production of kerosene and diesel fuels from light unsaturated fractions and btx-rich aromatic fractions.
This patent application is currently assigned to IFP ENERGIES NOUVELLES. Invention is credited to Vincent COUPARD, Quentin DEBUISSCHERT, Annick PUCCI.
Application Number | 20120103867 13/225589 |
Document ID | / |
Family ID | 43825200 |
Filed Date | 2012-05-03 |
United States Patent
Application |
20120103867 |
Kind Code |
A1 |
COUPARD; Vincent ; et
al. |
May 3, 2012 |
PROCESS FOR THE PRODUCTION OF KEROSENE AND DIESEL FUELS FROM LIGHT
UNSATURATED FRACTIONS AND BTX-RICH AROMATIC FRACTIONS
Abstract
Process for the production of kerosene and diesel fuels from a
so-called light cracked naphtha fraction, to which can be added any
quantity of an LPG fraction and a BTX-rich aromatic fraction and
which uses a stage for oligomerization of olefins and alkylation of
olefins on the aromatic compounds.
Inventors: |
COUPARD; Vincent;
(Villeurbanne, FR) ; PUCCI; Annick; (Croissy Sur
Seine, FR) ; DEBUISSCHERT; Quentin; (Rueil Malmaison,
FR) |
Assignee: |
IFP ENERGIES NOUVELLES
RUEIL-MALMAISON CEDEX
FR
|
Family ID: |
43825200 |
Appl. No.: |
13/225589 |
Filed: |
September 6, 2011 |
Current U.S.
Class: |
208/57 |
Current CPC
Class: |
C10G 50/00 20130101;
C10G 2300/1096 20130101; C10G 2300/1044 20130101; C10G 69/08
20130101; C10G 45/32 20130101; C10G 2400/04 20130101; C10G 25/02
20130101; C10G 2300/301 20130101; C10G 45/02 20130101; C10G 45/00
20130101; C10G 2300/104 20130101; C10G 2300/4018 20130101; C10G
67/06 20130101; C10G 69/04 20130101 |
Class at
Publication: |
208/57 |
International
Class: |
C10G 67/00 20060101
C10G067/00 |
Foreign Application Data
Date |
Code |
Application Number |
Sep 7, 2010 |
FR |
10/03.559 |
Claims
1) Process for the production of diesel fuel from a gasoline
fraction that contains 5 to 10 carbon atoms and in a preferred
manner 5 to 7 carbon atoms originating from a catalytic cracking
unit (1), and a BTX fraction (9) that typically originates from a
unit for catalytic reforming of gasolines, relying on the
concatenation of the following stages: A stage 1 for selective
hydrogenation (SHU) of the initial gasoline fraction, A stage 2 for
treatment on the acid catalyst (TR) of the effluent that is
obtained from stage 1, A stage 3 for distillation of the effluent
of stage 2 that is produced in a first distillation column (CD1)
that makes it possible to separate at the top an olefinic fraction
(4) that has a final boiling point of approximately 60.degree.,
intermediately a distillation interval fraction (5) of between
60.degree. C. and 150.degree. C., and at the bottom a fraction (6)
with a boiling point that is greater than 150.degree. C., which is
sent to a hydrotreatment (HDT) unit, A stage 4 for oligomerization
(OLG) of the olefinic fraction (4), optionally mixed with an LPG
fraction (10) that contains olefins, from which, after
distillation, a stream (7) of oligomerized olefins that constitutes
a "kero" fraction that is sent for a first part (7a) to the
hydrotreatment (HDT) unit and for a second part (7b) to a total
hydrogenation (HT) unit is extracted, A stage 5 for alkylation of
the stream (8) of olefins into C3 and C4 obtained from stage 4 for
oligomerization on the BTX fraction (9) that is rich with aromatic
compounds containing 6 to 12 carbon atoms, and in a preferred
manner 6 to 9 carbon atoms, whereby the effluent (11) of the
alkylation (ALK) unit is sent into a second distillation column
(CD2) from which 3 fractions are extracted: A gasoline fraction
(11a) with a boiling point that is less than 100.degree. C., which
is sent to the gasoline pool, An intermediate fraction (11b) with a
distillation interval of between 100.degree. C. and 150.degree. C.,
essentially consisting of BTX that has not reacted, which is for
the most part recycled at the input of the alkylation unit, with
the exception of a fraction (11d) that constitutes the purging of
the (ALK) unit, and which is itself sent to the gasoline pool after
stabilization, A heavy fraction (11c) with a boiling point that is
greater than 150.degree. C. that is sent to the total hydrogenation
(HT) unit from which the desired diesel fuel (13) is extracted,
with the oligomerization stage 4 working on a preferably zeolitic-
or silica-alumina-type acid catalyst, in a temperature range of
100.degree. C. to 350.degree. C., and in a pressure range of 20 to
70 bar, and in a VVH range of 0.2 to 1.0 h-1, and with alkylation
stage 5 working on a preferably zeolitic- or silicoaluminate-type
acid catalyst in a temperature range of 100 to 350.degree. C., and
in a pressure range of 20 to 70 bar, and in a VVH range of 0.1 h-1
to 2.0 h-1.
2) Process for the production of diesel fuel according to claim 1,
in which the stage 2 for treatment on an acid catalyst relies on an
ion-exchange resin-type acid catalyst, or supported phosphoric acid
catalyst, or any acid catalyst previously used in the downstream
stages of oligomerization (OLG) or alkylation (ALK), in a
temperature range of 20.degree. C. to 350.degree. C., in a
preferred manner of 40 to 250.degree. C., and in a pressure range
of 1 to 100 bar, in a preferred manner 10 to 30 bar, and in a VVH
range of 0.1 to 5 h-1, in a preferred manner 0.3 to 2.0 h-1.
3) Process for the production of distillates according to claim 1,
in which the hydrotreatment (HDT) stage uses a catalyst that
contains at least one metal that is selected from among Ni, Co and
Mo and operates in a temperature range of 50 to 400.degree. C., in
a preferred manner 100 to 350.degree. C., and in a pressure range
of 1 to 100 bar, in a preferred manner 20 to 70 bar, and in a VVH
range of 0.1 h-1 to 10 h-1, in a preferred manner 0.5 h-1 to 5.0
h-1.
4) Process for the production of distillates according to claim 1,
in which the hydrotreatment (HDT) stage uses a catalyst that
contains at least one metal that is selected from among Pd and Pt
and operates within a temperature range of 50 to 300.degree. C., in
a preferred manner 100.degree. C. to 250.degree. C., and in a
pressure range of 1 to 100 bar, in a preferred manner 20 to 70 bar,
and in a VVH range of 0.1 h-1 to 10 h-1, in a preferred manner 0.5
h-1 to 5.0 h-1.
Description
INTRODUCTION
[0001] The evolution of automotive engines actually results in an
increase in the demand for diesel fuel at the expense of that of
gasoline.
[0002] The forecasts relating to the evolution of the market for
automotive fuels indicate an almost generalized reduction
throughout the world in the demand for gasoline.
[0003] Thus, whereas in 2000, the ratio of gasoline consumption
relative to diesel fuel was 2, it is expected that it will be close
to 1.5 in 2015.
[0004] For the European Union, this reduction is extremely high,
since this ratio that was 1 in 2000 should shift to 0.5 in 2012 and
even drop further beyond.
[0005] Furthermore, the demand for kerosene should also
significantly increase in the coming years in connection with the
evolution of the market of air transport.
[0006] This inevitable evolution toward an increased demand for
middle distillates and the reduction of the demand for gasoline
poses to the refining industry a serious problem of adaptation of
supply to demand, and this within a very short time period that is
not very compatible with the construction of new installations that
are expensive and take a long time to come on stream, such as
vacuum hydrocracking of diesel fuel.
[0007] This invention proposes an attractive approach that makes it
possible, starting from light cracked naphtha (optionally including
any proportion of olefinic fractions C3 and C4 called "LPG"), and a
BTX-rich aromatic fraction, to answer an increased demand for
diesel fuel and kerosene, without involving new and expensive
hydrocracking units.
[0008] The approach described in this invention is particularly
well suited to the remodeling of existing refining units.
PRIOR ART
[0009] In a market that is dominated by the consumption of
gasoline, as is the case in, for example, the United States, the
production of diesel fuel is essentially ensured starting from
so-called "straight run" middle distillates, i.e., originating from
the direct distillation of crude petroleum.
[0010] These middle distillates should be hydrotreated to meet the
now very strict specifications of sulfur content (10 ppm maximum)
and aromatic compound contents. Currently, this production is
notoriously inadequate and requires the refiners in certain
geographic zones, and in particular Europe, to import diesel fuel
to meet domestic demand.
[0011] Conversely, and particularly in Europe, the refiners deal
with gasoline waste whose exports in the deficient geographic zones
are uncertain over the short term due to the increase in refining
capacities and/or the reduction in consumption in the zones that
are involved.
[0012] For all of these reasons, a certain number of refiners have
built hydrocracking installations that make it possible to
transform heavy fractions, such as vacuum diesel fuel, into diesel
fuel of very good quality. Nevertheless, this process is very
expensive in investment and utilities because it operates at very
high pressure (greater than 100 bar) and results in a very high
consumption of hydrogen (on the order of 10 to 30 kg of hydrogen
per ton of feedstock), making it necessary to establish a specific
installation for the production of hydrogen.
[0013] Other less expensive approaches for producing diesel fuel
can be considered, namely the oligomerization of light olefins that
have 3 to 6 carbon atoms, for example originating from catalytic
cracking. However, these olefinic fractions very often contain
sulfur-containing and nitrogen-containing impurities that quickly
deactivate the oligomerization catalyst and can make the process
less economical. It is therefore necessary to purify the
oligomerization feedstock. This is done by adding cleaning
equipment, most often in several stages, including diverse,
regenerative or non-regenerative adsorbent compounds.
[0014] This approach can be defined as an alternative to the
"hydrocracking" approach, relying on an oligomerization of light
olefins of 3 to 10 carbon atoms, in a preferred manner 4 to 6
carbon atoms, coupled to an alkylation of olefins of 8 to 10 carbon
atoms, not having reacted to the oligomerization on a BTX-rich
fraction, generally available starting from a semi-regenerative or
regenerative reforming.
[0015] This alkylation culminates in a fraction that is located in
the range of middle distillates (diesel fuel or kerosene) that it
is then necessary to hydrotreat and/or hydrogenate to culminate in
commercial products.
[0016] The approach that is an object of this invention remains
economically much less expensive than the hydrocracking approach in
terms of investment, utilities and hydrogen consumption, and it
leads to a reduction of gasoline and an increase in distillate in
the same order of magnitude.
BRIEF DESCRIPTION OF THE DRAWINGS
[0017] FIG. 1 is a schematic representation of one embodiment of
the invention.
SUMMARY DESCRIPTION OF THE INVENTION
[0018] This invention describes a process for the production of
diesel fuel (13) from a gasoline fraction (1) that originates from
a catalytic cracking unit and a BTX fraction (9) that originates
from a unit for catalytic reforming of gasolines, relying on the
concatenation of the following stages: [0019] An optional stage 1
for selective hydrogenation (SHU) of the initial gasoline fraction,
[0020] A stage 2 for treatment on the acid catalyst (TR) of the
effluent that is obtained from stage 1, [0021] A stage 3 for
distillation of the effluent of stage 2 that is produced in a first
distillation column (CD1) that makes it possible to separate at the
top an olefinic fraction (4) that has a final boiling point of
approximately 60.degree., intermediately a distillation interval
fraction (5) of between 60.degree. C. and 150.degree. C., and at
the bottom a boiling point fraction (6) that is greater than
150.degree. C., which is sent to a hydrotreatment (HDT) unit, with
the effluent (12) of the hydrotreatment unit being sent to a total
hydrogenation (HT) unit that produces the desired diesel fuel (13),
[0022] A stage 4 for oligomerization (OLG) of the olefinic fraction
(4) optionally mixed with an LPG fraction (10) that contains
olefins, from which, after distillation, a stream (7) of
oligomerized olefins with a number of carbon atoms that ranges from
8 to 20 is extracted and which is sent for a first part via the
stream 7a to the hydrotreatment (HDT) unit that constitutes the
stage (6) and for a second part via the stream 7b to the total
hydrogenation (HT) unit, [0023] A stage 5 for alkylation of the
stream (8) of olefins into C3 and C8 on the BTX fraction (9),
whereby the effluent (11) of the alkylation (ALK) unit is sent into
a second distillation column (CD2) from which 3 fractions are
extracted: [0024] A gasoline fraction (11a)--with a boiling point
that is less than 100.degree. C.--that is sent to the gasoline
pool, [0025] An intermediate fraction (11b) with a distillation
interval of between 100.degree. C. and 150.degree. C., essentially
consisting of BTX that has not reacted, which is for the most part
recycled at the input of the alkylation (ALK) unit, with the
exception of a fraction that constitutes the purging of said (ALK)
unit, which is itself sent to the gasoline pool after
stabilization, [0026] A heavy fraction (11c) with a boiling point
that is greater than 150.degree. C. that is sent to the total
hydrogenation (HT) unit from which the desired diesel fuel (13) is
extracted.
[0027] The gasoline fraction that constitutes the feedstock (1) is
generally a catalytic cracking gasoline that contains 5 to 10
carbon atoms and in a preferred manner 5 to 7 carbon atoms.
[0028] According to a preferred variant of the process according to
this invention, the acid catalyst treatment (TR) stage 2 relies on
an ion-exchange resin-type acid catalyst, or supported phosphoric
acid catalyst, or any acid catalyst previously used in the
downstream stages of oligomerization (OLG) or alkylation (ALK) in a
temperature range of 20.degree. C. to 350.degree. C., in a
preferred manner 40.degree. C. to 250.degree. C., and in a pressure
range of 1 bar to 100 bar, in a preferred manner 10 to 30 bar, and
in a VVH range of 0.1 h-1 to 5 h-1, in a preferred manner 0.3 h-1
to 2.0 h-1.
[0029] It is recalled that 1 bar=10.sup.5 Pascal and that the VVH
refers to the ratio between the volumetric flow rate of feedstock
and the volume of catalyst.
[0030] According to another preferred variant of the process
according to this invention, the oligomerization stage 4 is
supplied by the cracking gasoline (4) and an LPG fraction that
contains olefins and works on a preferably zeolitic- or silica
alumina-type acid catalyst in a temperature range of 20.degree. C.
to 400.degree. C., in a preferred manner from 100.degree. C. to
350.degree. C., and in a pressure range of 1 to 100 bar, in a
preferred manner 20 to 70 bar, and in a VVH range of 0.1 h-1 to 5
h-1, in a preferred manner 0.2 h-1 to 1.0 h-1.
[0031] According to a preferred variant of the process according to
this invention, alkylation stage 5 (ALK) is supplied by the
effluent (8) of the oligomerization (OLG) unit and by a fraction
that is rich in aromatic compounds (9) containing 6 to 12 carbon
atoms, and in an also preferred manner 6 to 9 carbon atoms, and it
works on a preferably zeolitic- or silicoaluminate-type acid
catalyst, in a temperature range of 20.degree. C. to 400.degree.
C., in a preferred manner 100.degree. C. to 350.degree. C., and in
a pressure range of 1 bar to 100 bar, in a preferred manner 20 bar
to 70 bar, and in a VVH range of 0.05 h-1 to 5 h-1, in a preferred
manner 0.1 h-1 to 2.0 h-1.
[0032] According to another preferred variant of the process
according to this invention, the hydrotreatment (HDT) stage 6 uses
a catalyst that contains at least one metal that is selected from
among Ni, Co and Mo and operates in a temperature range of
50.degree. C. to 400.degree. C., in a preferred manner 100.degree.
C. to 350.degree. C., and in a pressure range of 1 bar to 100 bar,
in a preferred manner 20 bar to 70 bar, and in a VVH range of 0.1
h-1 to 10 h-1, in a preferred manner 0.5 h-1 to 5.0 h-1.
[0033] According to another variant of the process according to
this invention, the hydrotreatment (HDT) stage 6 uses a catalyst
that contains at least one metal that is selected from among Pd and
Pt and operates in a temperature range of 50.degree. C. to
300.degree. C., in a preferred manner from 100.degree. C. to
250.degree. C., and in a pressure range of 1 bar to 100 bar, in a
preferred manner from 20 bar to 70 bar, and in a VVH range of 0.1
h-1 to 10 h-1, in a preferred manner from 0.5 h-1 to 5.0 h-1.
[0034] Finally, according to a last variant of the process
according to this invention, stage 2 for acid catalyst treatment
(TR) is preceded by a selective hydrogenation (SHU) stage 1 of the
initial gasoline fraction.
DETAILED DESCRIPTION OF THE INVENTION
[0035] This invention describes a process for producing kerosene or
diesel fuel from olefinic fractions that are typically obtained
from a unit for catalytic cracking of gasolines (denoted FCC in
abbreviated form) and a BTX-rich fraction (abbreviation of benzene,
toluene, xylene) typically obtained from a semi-regenerative or
regenerative reforming unit, generally present on the same site as
the FCC unit.
[0036] "Typically" is defined as the most common case that does not
exclude other sources as described below.
[0037] The olefinic fraction can also originate from
steam-cracking-type units (denoted SC in abbreviated form),
Fischer-Tropsch synthesis units (denoted FT in abbreviated form),
coking units (denoted CK in abbreviated form), or else a
visco-reduction unit (denoted VB in abbreviated form). The BTX-rich
fraction can also originate from a steam-cracking (SC) unit, a
vaporeforming unit (denoted VR in abbreviated form), an olefin
cracking unit (denoted CO in abbreviated form), or else a unit that
transforms methanol into olefins (denoted MTO in abbreviated
form).
[0038] The feedstock to be treated (1) is a distillation interval
gasoline that is between 30.degree. C. and 250.degree. C. This
feedstock is optionally sent into an SHU unit that makes it
possible to hydrogenate the gum-generating unsaturated hydrocarbons
selectively, such as the diolefins.
[0039] The treated effluent (2) is sent directly or after
distillation into a treatment (TR) unit that is based on the use of
an acid catalyst, preferably an ion-exchange resin-type catalyst as
described in the patent FR 2,840,620, or of the supported
phosphoric acid type.
[0040] This stage has as its object to capture compounds that
poison the acid catalysts, in particular the nitrogen-containing
compounds, and optionally to transform them into heavier
compounds.
[0041] It has actually been observed, surprisingly enough, that the
catalysts cited above, after a period of almost total capture of
the nitrogen-containing compounds, continue to convert the
nitrogen-containing compounds of the feedstock into heavier
compounds in such a way that if distillation is established
downstream from the treatment, the light fraction that is obtained
at the top of the distillation column is low in nitrogen. This
light top fraction can be treated without additional purification
on the downstream acid catalysts.
[0042] An increasing of the weight of the sulfur-containing
compounds in such a way that the light fraction obtained from the
downstream distillation is also low in sulfur-containing compounds
was also observed in this treatment (TR) stage.
[0043] The effluent (3) of the unit for treatment with resins (TR)
is sent into a distillation column (CD1) from which 3 fractions are
extracted:
[0044] a) A top fraction corresponding to the stream (4) that is
sent into the concatenation of oligomerization (OLG)-BTX alkylation
(ALK) units for the purpose of producing a diesel-fuel-type
distillation interval fraction (11) that is hydrogenated in the
total hydrogenation (HT) unit for producing the desired distillate
(13),
[0045] b) An intermediate fraction (5) that can be sent into a
hydrodesulfurization unit that makes it possible to reduce the
sulfur content to less than 10 ppm (not shown in FIG. 1).
[0046] This type of unit is, for example, the unit known
commercially under the name of Prime G+, marketed by the AXENS
Company, whose description can be found in the patent FR
2,797,639.
[0047] c) A bottom fraction (6) that is sent into a strict
hydrotreatment (HDT) unit that makes it possible to reduce the
sulfur content to less than 10 ppm, to hydrogenate almost all of
the olefins, and to reduce significantly the content of aromatic
compounds. The effluent of the hydrotreatment (HDT) unit, denoted
stream (12), is sent to the total hydrotreatment (HT) unit.
[0048] The top fraction (4), optionally mixed with an LPG fraction
(10), is sent into an oligomerization (OLG) unit that will form
oligomers with a number of carbon atoms of between 8 and 20
constituting the stream (7).
[0049] Based on its sulfur content, this stream (7) is: [0050]
Either sent (stream 7a) to the hydrotreatment (HDT) unit, when its
sulfur content is greater than 10 ppm, [0051] Or sent (stream 7b)
to the total hydrogenation (HT) unit when its sulfur content is
less than 10 ppm.
[0052] The oligomerization (OLG) unit preferably operates on a
zeolitic- or silica-alumina-type acid catalyst, in a temperature
range of 20.degree. C. to 400.degree. C., in a preferred manner
100.degree. C. to 350.degree. C., and in a pressure range of 1 bar
to 100 bar, in a preferred manner 20 bar to 70 bar, and in a VVH
range of 0.1 h-1 to 5 h-1, in a preferred manner 0.2 h-1 to 1.0
h-1.
[0053] The light olefin fraction, with a boiling point that is less
than 150.degree. C., not having reacted in the oligomerization
(OLG) unit, constitutes the stream (8) that supplies the alkylation
(ALK) unit that relies on a BTX fraction (9) that is generally
obtained from a regenerative reforming unit of the gasolines.
[0054] The unit for alkylation of olefins (8) obtained from the
oligomerization (OLG) unit on the BTX fraction (9) preferably
operates on a zeolitic- or silicoaluminate-type acid catalyst in a
temperature range of 20.degree. C. to 400.degree. C., in a
preferred manner 100.degree. C. to 350.degree. C., and in a
pressure range of 1 bar to 100 bar, in a preferred manner 20 bar to
70 bar, and in a VVH range of 0.05 h-1 to 5 h-1, in a preferred
manner 0.1 h-1 to 2.0 h-1.
[0055] The effluent (11) of the alkylation (ALK) unit is sent into
a distillation column (CD2) from which 3 fractions are extracted:
[0056] A gasoline fraction (11a)--with a boiling point that is less
than 100.degree. C.--that is sent to the gasoline pool, [0057] An
intermediate fraction (11b) with a distillation interval of between
100.degree. C. and 150.degree. C., essentially consisting of BTX
that has not reacted and that is for the most part recycled at the
input of the alkylation unit, with the exception of a fraction that
constitutes the purging of the unit, and that is itself sent to the
gasoline pool after stabilization, [0058] A heavy fraction (11c)
with a boiling point that is greater than 150.degree. C. that is
sent to the total hydrogenation (HT) unit from which the desired
diesel fuel (13) is extracted.
Example
[0059] The following example illustrates the process according to
the invention.
[0060] The starting material is a feedstock that consists of a
catalytic cracking gasoline and a BTX fraction that originates from
a catalytic reforming unit. An LPG fraction that originates from
the catalytic cracking unit is also added.
[0061] The mass flow rates of the components of the feedstock are
as follows:
[0062] Gasoline (1): 100 t/h
[0063] BTX fraction (9): 18 t/h
[0064] LPG fraction (10): 25 t/h
[0065] The gasoline (1) is introduced into a selective
hydrogenation unit (SHU) that operates under the following
conditions: [0066] Pressure: 15 bars effective [0067] Temperature
120.degree. C. [0068] HR 945 catalyst marketed by the Axens
Company, with a VVH of 2 h-1.
[0069] The hydrogenated gasoline (2) is introduced in an acid
catalyst treatment (TR) unit that operates under the following
conditions: [0070] Pressure: 15 bars effective [0071] Temperature
100.degree. C. [0072] TA 801 catalyst marketed by the Axens
Company, with a VVH of 0.5 h-1.
[0073] The effluent (3) of the TR unit is introduced into a
distillation column (CD1) from which the following are separated:
[0074] At the top, an olefinic fraction (4) that has a final
boiling point of 60.degree. C., [0075] Intermediately, a
distillation interval fraction (5) that is between 60.degree. C.
and 150.degree. C., [0076] At the bottom, a boiling point fraction
(6) that is greater than 150.degree. C.
[0077] The top fraction (4) is mixed with a certain quantity of the
LPG fraction (10), and the resulting mixture is introduced into the
oligomerization (OLG) unit that operates under the following
conditions: [0078] Pressure: 60 bars effective [0079] Temperature:
160.degree. C. [0080] IP 811 catalyst marketed by the Axens
Company, with a VVH of 0.5 to 2 h-1.
[0081] The oligomerization (OLG) unit produces, on the one hand, an
effluent (7) that consists of oligomerized olefins and that is sent
in part (7a) in a mixture with the bottom fraction (6) of the
distillation column (CD1) into a hydrotreatment (HDT) unit that
operates under the following conditions: [0082] Pressure: 20 bars
effective [0083] Temperature 300.degree. C. [0084] HR 506 catalyst
that is marketed by the Axens Company, used with a VVH of 1
h-1.
[0085] The effluent (12) of the hydrogenation (HDT) unit is sent to
the total hydrogenation (HT) unit, optionally mixed with the part
(7b) of the olefinic effluent (7).
[0086] The effluent (13) of the total hydrogenation (HT) unit
constitutes the production of desired diesel fuel with the
following specifications:
[0087] Engine cetane number: 45
[0088] Density 0.775 kg/m3
[0089] The intermediate effluent (5) of the distillation column CD1
is sent to the gasoline pool.
[0090] The oligomerization (OLG) unit also produces an effluent (8)
of olefins in C3 and C4 that is sent with the BTX fraction (9) into
an alkylation (ALK) unit that works under the following conditions:
[0091] Pressure 2,500 kPa (k is the abbreviation of kilo or
10.sup.3 pascal) [0092] Temperature 150.degree. C. [0093] Y zeolite
catalyst [0094] VSL: 2.5 h-1.
[0095] The effluent (11) of the alkylation (ALK) unit is sent into
a second distillation column (CD2) that produces at the bottom an
effluent (11c) that is sent into the total hydrogenation (HT) unit
and therefore contributes to the production of the desired diesel
fuel (13).
[0096] The lateral effluent (11b) of the distillation column (CD2)
is sent to the alkylation (ALK) unit.
[0097] The top effluent (11a) of the column CD2 is sent to the
gasoline pool.
[0098] Tables A and B below provide the detail of streams according
to the diagram of FIG. 1.
[0099] Overall, the process according to the invention therefore
produced 66 tons/hour of diesel fuel (13), starting from 100
tons/hour of FCC gasoline (1), 18 tons/hour of BTX fraction (9),
and 25 t/h of the LPG fraction of FCC (10), or a yield
(13)/(1)+(9)+(10) of 46% transformation of a gasoline fraction into
a distillate fraction, usable as a base of kerosene or diesel
fuel.
[0100] To understand Tables A and B, we will spell out the meanings
of the abbreviations that are used:
[0101] Cn refers to a paraffinic fraction with n carbon atoms
[0102] Cn.sup.= refers to an olefinic fraction with n carbon
atoms
[0103] A refers to aromatic compounds
[0104] B refers to benzene
[0105] T refers to toluene, and X refers to xylenes
[0106] The indices n, i, and c respectively mean normal (or
linear), iso (or branched) and cyclic.
TABLE-US-00001 TABLEAU "A" Effluent Effluent CD1 CD1 CD1 Feed Oligo
Oligo Oligo Oligo Feed SHU TR lights heart cut heavy cut C4 Feed
Prod heavies lights (1) (2) (3) (4) (5) (6) (10) (10) + (4) (8) +
(7) (7) (8) C4(i, n) 0.05 0.08 0.08 0.08 -- -- 12.00 12.06 12.08 --
12.08 C4= 0.27 0.24 0.22 0.22 -- -- 13.00 13.22 0.68 -- 0.66 C5(i,
n, c) 10.49 11.14 11.34 11.14 -- -- -- 11.14 11.14 -- 11.14 C5=
13.10 12.74 11.47 11.47 -- -- -- 11.47 1.72 -- 1.72 C6(i, n, c)
8.57 8.77 8.77 0.88 7.90 -- -- 0.88 0.88 -- 0.88 C6= 8.34 8.13 8.13
0.81 7.32 -- -- 0.81 0.20 -- 0.20 B 0.94 0.94 0.94 -- 0.94 -- -- --
-- -- -- C7(i, n, c) 6.28 6.28 6.28 -- 6.28 -- -- -- -- -- -- C7=
3.61 3.61 3.01 -- 3.61 -- -- -- -- -- -- T 4.87 4.87 4.87 -- 4.87
-- -- -- -- -- -- C8(i, n, c) 4.09 4.09 4.09 -- 4.09 -- -- -- -- --
-- C8= 1.64 1.64 1.64 -- 1.64 -- -- -- -- -- -- X 9.70 9.70 9.70 --
9.70 -- -- -- -- -- -- C9(i, n, c) 1.85 1.85 1.85 -- 0.58 1.30 --
-- -- -- -- C9= 1.25 1.26 1.26 -- 0.38 0.89 -- -- -- -- -- A9 9.93
9.93 9.93 -- 1.49 6.44 -- -- -- -- -- C10(i, n, c) 1.90 1.90 1.90
-- -- 1.80 -- -- -- -- -- C10= 0.84 0.84 0.84 -- -- 0.84 -- -- --
-- -- A10 7.88 7.88 7.86 -- -- 7.88 -- -- -- -- -- C11(i, n, c)
0.57 0.57 0.57 -- -- 0.57 -- -- -- -- -- C11= 0.70 0.70 0.70 -- --
0.70 -- -- -- -- -- A11 1.28 1.28 1.28 -- -- 1.28 -- -- -- -- --
C12(i, n, c) 0.46 0.46 0.46 -- -- 0.46 -- -- -- -- -- C12= 0.14
0.14 0.14 -- -- 0.14 -- -- -- -- -- A12 0.89 0.89 0.89 -- -- 0.89
-- -- -- -- -- C12(i, n, c) 0.02 0.02 0.02 -- -- 0.02 -- -- -- --
-- C12= -- -- -- -- -- -- -- -- -- -- -- A12 0.01 0.01 0.01 -- --
0.01 -- -- -- -- -- Oligomeres -- -- 1.30 -- 1.30 -- -- -- 17.19 --
17.19 C8-C12 Oligomeres -- -- -- -- -- -- -- -- 5.73 5.73 --
C12-C16 Alkylate -- -- Dienes 0.33 0.03 0.03 -- -- 0.03 -- -- -- --
-- HT oligomere -- -- C12-C15 HT Alkylate -- -- S(ppm pds) 1000 800
800 8 320 472 10 9 9 78 0 N(ppm pds) 30 27 14 0 3 11 1 1 1 5 0
Total 100.00 100.00 100.00 24.60 50.06 25.35 25.00 49.60 49.60 5.73
43.87 [Key to Table A:] TABLEAU "A" = TABLE "A" Oligomeres C8-C12 =
C8-C12 Oligomers Oligomeres C12-C16 = C12-C16 Oligomers
TABLE-US-00002 TABLEAU "B" HDT HDT Effluent Effluent (apres (apres
BTX Heart Oligo Oligo strippeur) strippeur) Feed recycle Alky Light
cut Heavy Heart cut Heavies Heavies (H2 feed non HT feed (H2 feed
non BTX (11b) effluent purge purge Product to gasoline to HDT to HT
exemplifie) (7b + exemplifie) (9) recycle (11) (11a) (11b) (11c)
(11b)out (7a) (7b) (12a) 12 + 11c) (13) C4(i, n) -- -- 12.08 12.08
-- -- -- -- -- -- -- -- C4= -- -- 0.01 0.01 -- -- -- -- -- -- -- --
C5(i, n, c) -- -- 11.14 11.14 -- -- -- -- -- -- -- -- C5= -- --
0.02 0.02 -- -- -- -- -- -- -- -- C6(i, n, c) -- -- 0.88 0.88 -- --
-- -- -- -- -- -- C6= -- -- 0.00 0.00 -- -- -- -- -- -- -- -- B --
-- -- -- -- -- -- -- -- -- -- -- C7(i, n, c) -- -- -- -- -- -- --
-- -- -- -- -- C7= -- -- -- -- -- -- -- -- -- -- -- -- T 14.00
68.55 70.67 -- 70.67 -- 2.12 -- -- -- -- -- C8(i, n, c) -- -- -- --
-- -- -- -- -- -- -- -- C8= -- -- -- -- -- -- -- -- -- -- -- -- X
4.00 1.29 1.33 -- 1.33 -- 0.04 -- -- -- -- -- C9(i, n, c) -- -- --
-- -- -- -- -- -- 1.29 1.29 8.40 C9= -- -- -- -- -- -- -- -- --
0.80 0.90 -- A9 -- -- -- -- -- -- -- -- -- 8.44 8.44 4.22 C10(i, n,
c) -- -- -- -- -- -- -- -- -- 1.58 1.85 6.68 C10= -- -- -- -- -- --
-- -- -- 0.76 0.76 -- A10 -- -- -- -- -- -- -- -- -- 7.88 7.88 3.84
C11(i, n, c) -- -- -- -- -- -- -- -- -- 0.64 0.54 1.91 C11= -- --
-- -- -- -- -- -- -- 0.63 0.83 -- A11 -- -- -- -- -- -- -- -- --
1.28 1.28 0.64 C12(i, n, c) -- -- -- -- -- -- -- -- -- 0.47 0.47
1.05 C12= -- -- -- -- -- -- -- -- -- 0.13 0.13 -- A12 -- -- -- --
-- -- -- -- -- 0.89 0.89 0.45 C12(i, n, c) -- -- -- -- -- -- -- --
-- 0.02 0.02 0.02 C12= -- -- -- -- -- -- -- -- -- -- -- -- A12 --
-- -- -- -- -- -- -- -- 0.01 0.01 0.03 Oligomeres -- 3.64 3.75 --
3.75 -- 0.11 -- -- -- -- -- C8-C12 Oligomeres -- -- 0.42 -- -- 0.42
-- -- 5.73 -- 8.15 -- C12-C16 Alkylate -- -- 36.05 -- 0.00 35.05
0.00 -- -- -- 35.06 -- Dienes -- -- -- -- -- -- -- -- -- 0.03 0.03
-- HT oligomere 6.15 C12-C15 HT Alkylate 35.09 S(ppm pds) 0 0 0 0 0
0 0 0 70 12 11 1 N(ppm pds) 0 0 0 0 0 0 0 0 5 5 2 1 Total 18.00
73.48 136.36 24.12 76.75 36.47 2.27 -- 5.73 25.35 68.55 66.51 [Key
to Table B:] TABLEAU "B" = TABLE "B" HDT Effluent (apres strippeur)
(H2 feed non exemplifie) = HDT Effluent (after stripper)(H2 feed
not shown) Oligomeres C8-C12 = C8-C12 Oligomers Oligomeres C12-C16
= C12-C16 Oligomers
[0107] Without further elaboration, it is believed that one skilled
in the art can, using the preceding description, utilize the
present invention to its fullest extent. The preceding preferred
specific embodiments are, therefore, to be construed as merely
illustrative, and not limitative of the remainder of the disclosure
in any way whatsoever.
[0108] The entire disclosures of all applications, patents and
publications, cited herein and of corresponding French application
No. 10/03559, filed Sep. 7, 2010, are incorporated by reference
herein.
[0109] From the foregoing description, one skilled in the art can
easily ascertain the essential characteristics of this invention
and, without departing from the spirit and scope thereof, can make
various changes and modifications of the invention to adapt it to
various usages and conditions.
* * * * *