U.S. patent application number 14/566058 was filed with the patent office on 2016-06-16 for contaminant removal from kerosene streams with lactamium based ionic liquids.
The applicant listed for this patent is UOP LLC. Invention is credited to Soumendra Mohan Banerjee, Alakananda Bhattacharyya, Erin M. Broderick, Rajeswar R. Gattupalli, Beckay J. Mezza.
Application Number | 20160168483 14/566058 |
Document ID | / |
Family ID | 56107954 |
Filed Date | 2016-06-16 |
United States Patent
Application |
20160168483 |
Kind Code |
A1 |
Broderick; Erin M. ; et
al. |
June 16, 2016 |
CONTAMINANT REMOVAL FROM KEROSENE STREAMS WITH LACTAMIUM BASED
IONIC LIQUIDS
Abstract
A process for removing a contaminant from a kerosene stream
using a lactamium based ionic liquid is described. The process
includes contacting the kerosene stream comprising the contaminant
with a lean kerosene-immiscible lactamium ionic liquid to produce a
mixture comprising the kerosene and a rich kerosene-immiscible
lactamium ionic liquid comprising at least a portion of the removed
contaminant; and separating the mixture to produce a kerosene
effluent and a rich kerosene-immiscible lactamium ionic liquid
effluent comprising the rich kerosene-immiscible lactamium ionic
liquid.
Inventors: |
Broderick; Erin M.;
(Arlington Heights, IL) ; Bhattacharyya; Alakananda;
(Glen Ellyn, IL) ; Mezza; Beckay J.; (Arlington
Heights, IL) ; Banerjee; Soumendra Mohan; (New Delhi,
IN) ; Gattupalli; Rajeswar R.; (Arlington Heights,
IL) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
UOP LLC |
Des Plaines |
IL |
US |
|
|
Family ID: |
56107954 |
Appl. No.: |
14/566058 |
Filed: |
December 10, 2014 |
Current U.S.
Class: |
208/90 ;
208/280 |
Current CPC
Class: |
C10G 17/07 20130101;
C10G 21/20 20130101 |
International
Class: |
C10G 17/07 20060101
C10G017/07; C10G 67/08 20060101 C10G067/08; C10G 55/06 20060101
C10G055/06 |
Claims
1. A process for removing a contaminant from a kerosene stream
comprising: contacting the kerosene stream comprising the
contaminant with a lean kerosene-immiscible lactamium ionic liquid
to produce a mixture comprising the kerosene and a rich
kerosene-immiscible lactamium ionic liquid comprising at least a
portion of the removed contaminant; and separating the mixture to
produce a kerosene effluent and a rich kerosene-immiscible
lactamium ionic liquid effluent comprising the rich
kerosene-immiscible lactamium ionic liquid; wherein the
kerosene-immiscible lactamium ionic liquid comprises at least one
of: a reaction product of a lactam compound having a general
formula ##STR00022## wherein R is hydrogen, an alkyl group having
from 1 to 12 carbon atoms, an amine, an ether, or a silyl group, n
is 1 to 8; and a Bronsted acid HX; or a Bronsted acid HX, where X
is a halide, and a metal halide; or a reaction product of a lactam
compound having a general formula ##STR00023## wherein the ring has
at least one C--C double bond, R is hydrogen, an alkyl group having
from 1 to 12 carbon atoms, an amine, an ether, or a silyl group, n
is 1 to 8, and a Bronsted acid HX; or a Bronsted acid HX, where X
is a halide, and a metal halide; or a reaction product of a lactam
compound having a general formula ##STR00024## wherein R is
hydrogen, an alkyl group having from 1 to 12 carbon atoms, an
amine, an ether, or a silyl group, n is 1 to 8, m is 1 to 8, and
the rings can be saturated or unsaturated; and at least one of a
Bronsted acid HX; or a Bronsted acid HX, where X is a halide, and a
metal halide.
2. The process of claim 1 wherein the lactam reaction product is at
least one of carboxylates, nitrates, phosphates, phosphinates,
phosphonates, imides, cyanates, borates, sulfates, sulfonates,
acetates, and halides.
3. The process of claim 1 wherein the lactam reaction product is
the halometallate and wherein a metal in the halometallate is at
least one of Sn, Al, Zn, Mn, Fe, Ga, Cu, Ni, and Co.
4. The process of claim 1 wherein a ratio of the Bronsted acid HX
to the lactam compound is about 1:1 to about 3:1.
5. The process of claim 1 wherein the kerosene stream has a boiling
point in a range of about 140.degree. C. to about 210.degree.
C.
6. The process of claim 1 wherein the contacting step is conducted
at a temperature in a range of about 20.degree. C. to about
80.degree. C.
7. The process of claim 1 further comprising passing at least a
portion of the kerosene effluent to a kerosene conversion
process.
8. The process of claim 1 further comprising: regenerating the rich
kerosene-immiscible lactamium ionic liquid effluent; and recycling
the regenerated kerosene-immiscible lactamium based ionic liquid to
the contacting step.
9. The process of claim 1 wherein a ratio of the kerosene to the
kerosene-immiscible lactamium ionic liquid is in a range of about
1:1,000 to about 1,000:1.
10. The process of claim 1 further comprising contacting the rich
kerosene-immiscible lactamium ionic liquid effluent with a
regeneration solvent to form an extract stream comprising the
contaminant and a stream of lean kerosene-immiscible lactamium
ionic liquid.
11. The process of claim 10 wherein the regeneration solvent
comprises water, naphtha, gasoline, diesel, kerosene, light cycle
oil, and light coker gas oil.
12. The process of claim 10 further comprising separating the
stream of lean kerosene-immiscible lactamium ionic liquid from the
regeneration solvent.
13. The process of claim 12 further comprising recycling the stream
of lean kerosene-immiscible lactamium ionic liquid to the
contacting step.
14. The process of claim 13 reactivating the stream of lean
kerosene-immiscible lactamium ionic liquid with an acid before
recycling the stream of lean kerosene-immiscible lactamium ionic
liquid to the contacting step.
15. The process of claim 1 wherein the ionic liquid has the general
formula (III) and wherein at least one ring has at least one C--C
double bond.
16. A process for removing a contaminant from a kerosene stream
comprising: contacting the kerosene stream comprising the
contaminant with a lean kerosene-immiscible lactamium ionic liquid
to produce a mixture comprising the kerosene and a rich
kerosene-immiscible lactamium ionic liquid comprising at least a
portion of the removed contaminant; and separating the mixture to
produce a kerosene effluent and a rich kerosene-immiscible
lactamium ionic liquid effluent comprising the rich
kerosene-immiscible lactamium ionic liquid; regenerating the rich
kerosene-immiscible lactamium ionic liquid effluent to form a
stream of lean kerosene-immiscible lactamium ionic liquid;
recycling the stream of lean kerosene-immiscible lactamium ionic
liquid to the contacting step; and passing at least a portion of
the kerosene effluent to a kerosene conversion process; wherein the
kerosene-immiscible lactamium ionic liquid comprises at least one
of: a reaction product of a lactam compound having a general
formula ##STR00025## wherein R is hydrogen, an alkyl group having
from 1 to 12 carbon atoms, an amine, an ether, or a silyl group, n
is 1 to 8; and a Bronsted acid HX; or a Bronsted acid HX, where X
is a halide, and a metal halide; or a reaction product of a lactam
compound having a general formula ##STR00026## wherein the ring has
at least one C--C double bond, R is hydrogen, an alkyl group having
from 1 to 12 carbon atoms, an amine, an ether, or a silyl group, n
is 1 to 8, and a Bronsted acid HX; or a Bronsted acid HX, where X
is a halide, and a metal halide; or a reaction product of a lactam
compound having a general formula ##STR00027## wherein R is
hydrogen, an alkyl group having from 1 to 12 carbon atoms, an
amine, an ether, or a silyl group, n is 1 to 8, m is 1 to 8, and
the rings can be saturated or unsaturated; and a Bronsted acid HX;
or a Bronsted acid HX, where X is a halide, and a metal halide.
17. The process of claim 16 wherein regenerating the rich
kerosene-immiscible lactamium ionic liquid effluent comprises
contacting the rich kerosene-immiscible lactamium ionic liquid
effluent with a regeneration solvent to form an extract stream
comprising the contaminant and the stream of lean
kerosene-immiscible lactamium ionic liquid.
18. The process of claim 16 reactivating the stream of lean
kerosene-immiscible lactamium ionic liquid with an acid before
recycling the stream of lean kerosene-immiscible lactamium ionic
liquid to the contacting step.
19. The process of claim 17 wherein the lactam reaction product is
at least one of carboxylates, nitrates, phosphates, phosphinates,
phosphonates, imides, cyanates, borates, sulfates, sulfonates,
acetates, and halides.
20. The process of claim 17 wherein a ratio of the Bronsted acid HX
to the lactam compound is about 1:1 to about 3:1.
Description
BACKGROUND OF THE INVENTION
[0001] Various hydrocarbon streams, such as vacuum gas oil (VGO),
light cycle oil (LCO), and naphtha, may be converted into higher
value hydrocarbon fractions such as diesel fuel, jet fuel, naphtha,
gasoline, and other lower boiling fractions in refining processes
such as hydrocracking and fluid catalytic cracking (FCC). However,
hydrocarbon feed streams for these materials often have high
amounts of nitrogen which are more difficult to convert. For
example, the degree of conversion, product yields, catalyst
deactivation, and/or ability to meet product quality specifications
may be adversely affected by the nitrogen content of the feed
stream. Catalytic hydrogenation reactions, such as in a
hydrotreating process unit, are is known to reduce the nitrogen
content of these hydrocarbon feed streams, but hydrogenation
processes require high pressures and pressure.
[0002] More specifically, refiners in some parts of the world are
seeking to upgrade low value Coker kerosene to high value
feedstocks such as normal paraffins. Since Coker kerosene contains
high levels of Sulfur (S) and Nitrogen (N) it needs to be
hydrotreated to reduce the levels of S and N before treatment in an
adsorption separation unit, such as the Molex process licensed by
UOP LLC, to separate the normal paraffins from non-normal
hydrocarbons. Feed specifications for the Molex unit require severe
hydrotreating to reduce the sulfur level to less than 1.0 wppm and
the nitrogen level to 0.5 wppm (maximum). Coker kerosene also
contains olefins and diolefins, which tend to become saturated
during the hydtrotreating process and increases the normal paraffin
yield. One of the feed specifications for the Molex process is that
the Bromine Index (BI) of the feed should be in the range of 50 to
100 to extend the life of the adsorbent. In order to meet all three
specifications of S, N and BI, hydrotreating at pressures in the
range of 7584 to 8274 kPa (1100 to 1200 psig) is required.
[0003] Various processes using ionic liquids to remove sulfur and
nitrogen compounds from hydrocarbon fractions are also known. U.S.
Pat. No. 7,001,504 discloses a process for the removal of
organosulfur compounds from hydrocarbon materials which includes
contacting an ionic liquid with a hydrocarbon material to extract
sulfur containing compounds into the ionic liquid. U.S. Pat. No.
7,553,406 discloses a process for removing polarizable impurities
from hydrocarbons and mixtures of hydrocarbons using ionic liquids
as an extraction medium. U.S. Pat. No. 7,553,406 also discloses
that different ionic liquids show different extractive properties
for different polarizable compounds. U.S. Pat. No. 8,709,236
discloses a process for removing nitrogen from fuel streams with
caprolactamium liquids.
[0004] There remains a need in the art for improved processes that
enable the removal of contaminants from kerosene streams including
coker kerosene streams.
SUMMARY OF THE INVENTION
[0005] The invention involves a process for removing at least one
type of contaminant from a kerosene stream. In one embodiment, the
process includes contacting the kerosene stream comprising the
contaminant with a lean kerosene-immiscible lactamium ionic liquid
to produce a mixture comprising the kerosene and a rich
kerosene-immiscible lactamium ionic liquid comprising at least a
portion of the removed contaminant; and separating the mixture to
produce a kerosene effluent and a rich kerosene-immiscible
lactamium ionic liquid effluent comprising the rich
kerosene-immiscible lactamium ionic liquid. The kerosene-immiscible
lactamium ionic liquid comprises at least one of: a reaction
product of a lactam compound having a general formula
##STR00001##
wherein R is hydrogen, an alkyl group having from 1 to 12 carbon
atoms, an amine, an ether, or a silyl group, n is 1 to 8, and a
Bronsted acid HX; or a Bronsted acid HX, where X is a halide, and a
metal halide; or a reaction product of a lactam compound having a
general formula
##STR00002##
wherein the ring has at least one C--C double bond, R is hydrogen,
an alkyl group having from 1 to 12 carbon atoms, an amine, an
ether, or a silyl group, n is 1 to 8, and a Bronsted acid HX; or a
Bronsted acid HX, where X is a halide, and a metal halide; or a
reaction product of a lactam compound having a general formula
##STR00003##
wherein R is hydrogen or an alkyl group having from 1 to 12 carbon
atoms, an amine, an ether, or a silyl group, n is 1 to 8, m is 1 to
8, and the rings can be saturated or unsaturated; and a Bronsted
acid HX; or a Bronsted acid HX, where X is a halide, and a metal
halide.
[0006] The contaminants that are removed include compounds
containing nitrogen and sulfur. Nitrogen and sulfur compounds are
the main contaminants that are removed.
BRIEF DESCRIPTION OF THE DRAWINGS
[0007] FIG. 1 is a simplified flow scheme illustrating various
embodiments of the invention.
[0008] FIG. 2A shows a simplified flow scheme of an extraction
zone.
[0009] FIG. 2B shows another embodiment of an extraction zone.
[0010] FIG. 3 shows an embodiment of a flow scheme including
separation of olefins and paraffins after removal of sulfur and
nitrogen contaminants.
DETAILED DESCRIPTION OF THE INVENTION
[0011] In general, the invention may be used to remove contaminants
from a kerosene stream using a lactamium based ionic liquid.
[0012] The kerosene stream typically has a boiling point in the
range of about 150.degree. C. to about 300.degree. C. Examples of
kerosene streams include, but are not limited to, at least one of
kerosene and low quality coker kerosene.
[0013] The term "contaminant" means one or more species found in
the kerosene material that is detrimental to further processing.
Contaminants include, but are not limited to, nitrogen and sulfur.
The total sulfur content may range from 0.1 to 7 wt % and more
typically from 2.2 to 3.5 wt %, the nitrogen content may be from
about 40 to 30,000 wppm and more typically from 600 to 900
wppm.
[0014] The ionic liquid can remove one or more of the contaminants
in the kerosene feed. The kerosene feed will usually comprise a
plurality of nitrogen compounds of different types in various
amounts. Thus, at least a portion of at least one type of nitrogen
compound may be removed from the kerosene feed. The same or
different amounts of each type of nitrogen compound can be removed,
and some types of nitrogen compounds may not be removed. In an
embodiment, the nitrogen content of the kerosene feed is reduced by
at least about 3 wt %, at least about 5 wt %, or at least about 10
wt %, or at least about 15 wt %, at least about 20 wt %, or at
least about 30 wt %, or at least about 40 wt %. In some cases, the
nitrogen content of the kerosene feed is reduced by at least about
60 wt % or at least 75 wt %. In some instances it may be necessary
to employ multiple cycles to treatment to achieve the desired
reduction of nitrogen content. Different ionic liquids and
different treatment conditions may also be needed to achieve the
desired reduction of nitrogen content.
[0015] The kerosene feed will typically also comprise a plurality
of sulfur compounds of different types in various amounts. Thus, at
least a portion of at least one type of sulfur compound may be
removed from the kerosene feed. The same or different amounts of
each type of sulfur compound may be removed, and some types of
sulfur compounds may not be removed. When the ionic liquid is made
with a Bronsted acid only, there is little sulfur removal. More
sulfur removal occurs when the ionic liquid anion contains a
halometallate. In an embodiment, the sulfur content of the kerosene
feed is reduced by at least about 1 wt %, or at least about 2 wt %,
or at least 3 wt %, or at least 5 wt %, or at least 10 wt %, or at
least 20 wt %, or at least 30 wt %, or at least 35 wt %, or at
least 40 wt %. In some cases, the sulfur content of the kerosene
feed is reduced by at least about 60 wt % or at least 75 wt %. In
some instances it may be necessary to employ multiple cycles to
treatment to achieve the desired reduction of sulfur content.
Different ionic liquids and different treatment conditions may also
be needed to achieve the desired reduction of sulfur content.
[0016] The kerosene feed will usually contain various metals,
including, but not limited to, iron. In an embodiment, the metal
content of the kerosene feed can be reduced by at least about 10%
on an elemental basis, or at least about 20 wt %, or at least about
25 wt %, or at least about 30 wt %, or at least about 40 wt %, or
at least about 50%. The metal removed may be part of a hydrocarbon
molecule or complexed with a hydrocarbon molecule.
[0017] Processes according to the invention remove contaminants
from kerosene streams. That is, the process removes at least one
contaminant. It is understood that the kerosene will usually
comprise a plurality of contaminants of different types in various
amounts. Thus, the process removes at least a portion of at least
one type of contaminant. The process may remove the same or
different amounts of each type of contaminant, and some types of
contaminants may not be removed.
[0018] Lactamium based ionic liquids are used to extract one or
more contaminants from the kerosene stream. Lactamium based ionic
liquids suitable for use in the instant invention are immiscible in
the kerosene stream being treated. As used herein the term
"immiscible ionic liquid" means the formation of two phases that
can be separated.
[0019] Lactam compounds can be converted to ionic liquids through
reactions with strong acids followed by a second reaction with a
metal halide if needed.
[0020] The ionic liquids have a lactam cation. One type of
lactamium based ionic liquid catalyst has the general formula:
##STR00004##
wherein R is hydrogen, an alkyl group having from 1 to 12 carbon
atoms, an amine, an ether, or a silyl group, n is 1 to 8, and
X.sup.- is an anion group of a Bronsted acid HX or a
halometallate.
[0021] Another way to represent this compound is:
##STR00005##
wherein R is hydrogen, an alkyl group having from 1 to 12 carbon
atoms, an amine, an ether, or a silyl group, n is 1 to 8, and
X.sup.- is an anion group of a Bronsted acid HX or a
halometallate.
[0022] Formula (I) is intended to cover both representations.
[0023] Another type of lactamium based ionic liquid has the general
formula:
##STR00006##
wherein the ring has at least one C--C double bond, R is hydrogen,
an alkyl group having from 1 to 12 carbon atoms, an amine, an
ether, or a silyl group, n is 1 to 8, and X.sup.- is an anion group
of a Bronsted acid HX or a halometallate.
[0024] The ring has at least one double bond. Larger rings may have
more than one double bond. The double bond can be between any two
adjacent carbons capable of forming a double bond.
[0025] Another way to represent this compound is
##STR00007##
wherein the ring has at least one C--C double bond, R is hydrogen,
an alkyl group having from 1 to 12 carbon atoms, an amine, an
ether, or a silyl group, n is 1 to 8, and X.sup.- is an anion group
of a Bronsted acid HX or a halometallate.
[0026] Formula (II) is intended to cover both representations.
[0027] Examples of Formula (II) ionic liquids include, but are not
limited to, 1,5-dihydro-pyrrol-2-one ionic liquids,
1,5-dihydro-1-methyl-2H-pyrrol-2-one based ionic liquids,
1,3-dihydro-2H-pyrrol-one ionic liquids, and
1,3-dihydro-1-methyl-2H-pyrrol-2-one based ionic liquids.
[0028] Another type of lactamium based ionic liquid has the general
formula:
##STR00008##
wherein R is hydrogen, an alkyl group having from 1 to 12 carbon
atoms, an amine, an ether, or a silyl group, n is 1 to 8, m is 1 to
8, X.sup.- is an anion group of a Bronsted acid HX or a
halometallate, and the rings can be saturated or unsaturated.
[0029] The heterocyclic ring (ring with n) can be saturated or
unsaturated. The hydrocarbon ring (ring with m) can be saturated,
unsaturated, or aromatic. If the ring is unsaturated, the C--C
double bond can be between any two adjacent carbons capable of
forming a double bond. There can be one or more C--C double bonds
in either ring or in both rings.
[0030] Another way to represent this compound is
##STR00009##
wherein R is hydrogen, an alkyl group having from 1 to 12 carbon
atoms, an amine, an ether, or a silyl group, n is 1 to 8, m is 1 to
8, X.sup.- is an anion group of a Bronsted acid HX or a
halometallate, and the rings can be saturated or unsaturated.
[0031] Formula (III) is intended to cover both representations.
[0032] Examples of Formula (III) ionic liquids include, but are not
limited to, octahydro-2H-indol-2-one ionic liquids,
octahydro-1-methyl-2H-indol-2-one based ionic liquids, and
2-oxindole ionic liquids, and 1,3-dihydro-1-methyl-2H-indol-2-one
based ionic liquids.
[0033] Suitable X.sup.- groups include, but are not limited to,
carboxylates, nitrates, phosphates, phosphinates, phosphonates,
imides, cyanates, borates, sulfates (including bisulfates),
sulfonates (including fluoroalkanesulfonates), acetates, halides,
halometallates, and combinations thereof. Examples include, but are
not limited to, following tetrafluoroborate, triflate,
trifluoroacetate, chloroacetate, nitrate, hydrogen sulfate,
hydrogen phosphate, dicyanoimide, methylsulfonate, and combinations
thereof. Suitable halides include, but are not limited to, bromide,
chloride, and iodide. Halometallates are mixtures of halides, such
as bromide, chloride, and iodide, and metals. Suitable metals
include, but are not limited to, Sn, Al, Zn, Mn, Fe, Ga, Cu, Ni,
and Co. In some embodiments, the metal is aluminum, with the mole
fraction of aluminum ranging from 0<Al<0.25 in the anion.
Suitable anions include, but are not limited to, AlCl.sub.4.sup.-,
Al.sub.2Cl.sub.7.sup.-, Al.sub.3Cl.sub.10.sup.-,
AlCl.sub.3Br.sup.-, Al.sub.2Cl.sub.6Br.sup.-,
Al.sub.3Cl.sub.9Br.sup.-, AlBr.sub.4.sup.+, Al.sub.2Br.sub.7.sup.-,
Al.sub.3Br.sub.10.sup.-, GaCl.sub.4.sup.-, Ga.sub.2Cl.sub.7.sup.-,
Ga.sub.3Cl.sub.10.sup.-, GaCl.sub.3Br.sup.-,
Ga.sub.2Cl.sub.6Br.sup.-, Ga.sub.3Cl.sub.9Br.sup.-,
CuCl.sub.2.sup.-, Cu.sub.2Cl.sub.3.sup.-, Cu.sub.3Cl.sub.4.sup.-,
ZnCl.sub.3.sup.-, FeCl.sub.3.sup.-, FeCl.sub.4.sup.-,
Fe.sub.3Cl.sub.7.sup.-, PF.sub.6.sup.-, and BF.sub.4.sup.-.
[0034] In some embodiments when making a halometallate, the
lactamium compound is reacted with a Bronsted acid HX, such as HCl,
where X is a halide to form a lactam halide. The lactam halide is
then reacted with a metal halide to form the lactam
halometallate.
[0035] As is understood by those of skill in the art, the
particular Bronsted acid used will depend on the anion desired.
Suitable Bronsted acids include for example, sulfuric acid,
p-toluenesulfonic acid, hydrochloric acid, hydrobromic acid, nitric
acid, phosphoric acid, tetrafluoroboric acid, triflic acid,
trifluoroacetic acid, chloroacetic acid, and methanesulfonic
acid.
[0036] The lactamium ionic liquid comprises at least one of: a
reaction product of a lactam compound having a general formula
##STR00010##
wherein R is hydrogen, an alkyl group having from 1 to 12 carbon
atoms, an amine, an ether, or a silyl group, n is 1 to 8; and a
Bronsted acid HX; or a Bronsted acid HX, where X is a halide, and a
metal halide; or a reaction product of a lactam compound having a
general formula
##STR00011##
wherein the ring has at least one C--C double bond, R is hydrogen,
an alkyl group having from 1 to 12 carbon atoms, an amine, an
ether, or a silyl group, n is 1 to 8, and a Bronsted acid HX; or a
Bronsted acid HX, where X is a halide, and a metal halide; or a
reaction product of a lactam compound having a general formula
##STR00012##
wherein R is hydrogen, an alkyl group having from 1 to 12 carbon
atoms, an amine, an ether, or a silyl group, n is 1 to 8, m is 1 to
8, and the rings can be saturated or unsaturated; and a Bronsted
acid HX; or a Bronsted acid HX, where X is a halide, and a metal
halide.
[0037] A lactamium based ionic liquid can be made by reacting a
lactam compound having a general formula
##STR00013##
wherein R is hydrogen, an alkyl group having from 1 to 12 carbon
atoms, an amine, an ether, or a silyl group, and n is 1 to 8; with
a Bronsted acid HX; or a Bronsted acid HX, where X is a halide, and
a metal halide.
[0038] Another lactamium based ionic liquid can be made by reacting
a lactam compound having a general formula
##STR00014##
wherein the ring has at least one C--C double bond, R is hydrogen,
an alkyl group having from 1 to 12 carbon atoms, an amine, an
ether, or a silyl group, and n is 1 to 8, with a Bronsted acid HX;
or a Bronsted acid HX, where X is a halide, and a metal halide.
[0039] Another lactamium based ionic liquid can be made by reacting
a lactam compound having a general formula
##STR00015##
wherein R is hydrogen, an alkyl group having from 1 to 12 carbon
atoms, an amine, an ether, or a silyl group, n is 1 to 8, m is 1 to
8, and the rings can be saturated or unsaturated; with a Bronsted
acid HX; or a Bronsted acid HX, where X is a halide, and a metal
halide.
[0040] The heterocyclic ring (ring with n) can be saturated or
unsaturated. The hydrocarbon ring (ring with m) can be saturated,
unsaturated, or aromatic. If the ring is unsaturated, the C--C
double bond can be between any two adjacent carbons capable of
forming a double bond. There can be one or more C--C double bonds
in either ring or in both rings.
[0041] The reaction can take place at temperatures in the range of
about -36.degree. C. to the decomposition temperature of the ionic
liquid, or about -20.degree. C. to less than the decomposition
temperature of the ionic liquid, or about 0.degree. to about
200.degree. C., or about 0.degree. to about 150.degree. C., or
about 0.degree. to about 120.degree. C., or about 20.degree. to
about 80.degree. C.
[0042] The reaction typically takes place at atmospheric pressure,
although higher or lower pressures could be used if desired. When
making halometallate compounds, the reaction should take place in
an inert atmosphere. The reaction typically takes about 1 minute to
multiple days, depending on the ionic liquid. Those made with the
Bronsted acid typically take minutes to hours, while the
halometallates typically take minutes to one or more days. The
reaction may be practiced in laboratory scale experiments through
full scale commercial operations. The process may be operated in
batch, continuous, or semi-continuous mode.
[0043] In some embodiments, the reaction can take place in the
absence of a solvent. In other embodiments, it can take place in
the presence of a solvent. The contacting can take place in the
presence of one or more solvents. Suitable solvents for
non-halometallate ionic liquids include, but are not limited to
water, toluene, dichloromethane, liquid carboxylic acids such as
acetic acid or propanoic acid, alcohols, such as methanol and
ethanol, and combinations thereof. When water is used as the
solvent, an additional product may form. The products can be
separated using known separation techniques Non-protic solvents,
such as dichloromethane, are suitable for use with
halometallates.
[0044] The ratio of the Bronsted acid to the lactam compound is
about 1:1 to about 3:1. In some embodiments, when making a
halometallate using a Bronsted acid followed by the addition of a
metal halide, the ratio of Bronsted acid to the lactam compound is
about 1:1. In general, increasing the acid:lactam ratio increased
the contaminant removal.
[0045] Consistent with common terms of art, the ionic liquid
introduced to the contaminant removal step may be referred to as a
"lean lactamium ionic liquid" generally meaning a
kerosene-immiscible lactamium ionic liquid that is not saturated
with one or more extracted contaminants. Lean lactamium ionic
liquid may include one or both of fresh and regenerated lactamium
ionic liquid and is suitable for accepting or extracting
contaminants from the kerosene feed. Likewise, the lactamium ionic
liquid effluent may be referred to as "rich lactamium ionic
liquid", which generally means a kerosene-immiscible lactamium
ionic liquid effluent produced by a contaminant removal step or
process or otherwise including a greater amount of extracted
contaminants than the amount of extracted contaminants included in
the lean lactamium ionic liquid. A rich lactamium ionic liquid may
require regeneration or dilution, e.g. with fresh lactamium ionic
liquid, before recycling the rich lactamium ionic liquid to the
same or another contaminant removal step of the process.
[0046] In an embodiment, the invention is a process for removing
contaminants from a kerosene feed stream comprising a contacting
step and a separating step. In the contacting step, a kerosene feed
stream comprising a contaminant and a kerosene-immiscible lactamium
ionic liquid are contacted or mixed. The contacting may facilitate
transfer or extraction of the one or more contaminants from the
kerosene feed stream to the lactamium ionic liquid. Although a
lactamium ionic liquid that is partially soluble in the kerosene
may facilitate transfer of the contaminant from the kerosene to the
ionic liquid, partial solubility is not required. Insoluble
kerosene/lactamium ionic liquid mixtures may have sufficient
interfacial surface area between the kerosene and lactamium ionic
liquid to be useful. In the separation step, the mixture of
kerosene and lactamium ionic liquid settles or forms two phases, a
kerosene phase and a lactamium ionic liquid phase, which are
separated to produce a kerosene-immiscible lactamium ionic liquid
effluent and a kerosene effluent. The kerosene may be contacted
with the lactamium ionic liquid at a low pressure of 1 to 2
kg/cm.sup.2 g and temperatures in a range of 40.degree. to
80.degree. C.
[0047] In one embodiment of the invention, the feed is a Coker
kerosene feed having a composition as shown in the following
table:
TABLE-US-00001 Specific Gravity @ 15.degree. C., g/mL 0.822 Sulfur,
wt % 2.05-3.0 Nitrogen, ppm wt 663-900 Diene Content, wt % 1.9-2.2
Diene Value, gI2/100 g 2.8-3.2 Bromine Number, g/100 g 57.6
Aromatics, wt % 22.75 Mono, wt % 22.1 Di, wt % 5.3 Tri(+), wt % 0.1
Silicon as SiO2, wppm 2-3
[0048] The ionic liquid extraction stages carried out in ionic
liquid treating vessels may be located in a delayed Coker unit to
allow for simpler routing of the ionic liquid extract which may be
routed to the coke drum within the Coker.
[0049] The olefins that are obtained from the process of this
invention have a wide application to a refinery. A stream of
olefins may be used to alkylate low value C5-C6 naphtha to diesel.
In addition, the use of the ionic liquid instead of prior art
hydrotreating significantly reduces the need for hydrogen and
reduces emissions of carbon dioxide.
[0050] The process may be conducted in various equipment which is
well known in the art and suitable for batch or continuous
operation. For example, in a small scale form of the invention,
kerosene and a kerosene-immiscible lactamium ionic liquid may be
mixed in a beaker, flask, or other vessel, e.g., by stirring,
shaking, use of a mixer, or a magnetic stirrer. The mixing or
agitation is stopped and the mixture forms a kerosene phase and a
lactamium ionic liquid phase which can be separated, for example,
by decanting, centrifugation, or use of a pipette to produce a
kerosene effluent having a lower contaminant content relative to
the incoming kerosene. The process also produces a
kerosene-immiscible lactamium ionic liquid effluent comprising the
one or more contaminants.
[0051] The contacting and separating steps may be repeated, for
example, when the contaminant content of the kerosene effluent is
to be reduced further to obtain a desired contaminant level in the
ultimate kerosene product stream from the process. Each set, group,
or pair of contacting and separating steps may be referred to as a
contaminant removal step. Thus, the invention encompasses single
and multiple contaminant removal steps. A contaminant removal zone
may be used to perform a contaminant removal step. As used herein,
the term "zone" can refer to one or more equipment items and/or one
or more sub-zones. Equipment items may include, for example, one or
more vessels, heaters, separators, exchangers, conduits, pumps,
compressors, and controllers. Additionally, an equipment item can
further include one or more zones or sub-zones. The contaminant
removal process or step may be conducted in a similar manner and
with similar equipment as is used to conduct other liquid-liquid
wash and extraction operations. Suitable equipment includes, for
example, columns with: trays, packing, rotating discs or plates,
and static mixers. Pulse columns and mixing/settling tanks may also
be used.
[0052] FIG. 1 is a flow scheme illustrating various embodiments of
the invention and some of the optional and/or alternate steps and
apparatus encompassed by the invention. Kerosene stream 2 and
kerosene-immiscible lactamium ionic liquid stream 4 are introduced
to and contacted and separated in contaminant removal zone 100 to
produce kerosene-immiscible lactamium ionic liquid effluent stream
8 and kerosene effluent stream 6 as described above. The lactamium
ionic liquid stream 4 may be comprised of fresh lactamium ionic
liquid stream 3 and/or one or more lactamium ionic liquid streams
which are recycled in the process as described below. In an
embodiment, a portion or all of kerosene effluent stream 6 is
passed via conduit 10 to a kerosene conversion zone 800. Kerosene
conversion zone 800 may, for example, comprise at least one of a
fluid catalytic cracking and a hydrocracking process, which are
well known in the art.
[0053] The contact step can take place at a temperature in the
range of about 20.degree. C. to the decomposition temperature of
the lactamium based ionic liquid, or about 20.degree. to about
120.degree. C., or about 20.degree. to about 80.degree. C.
[0054] The contacting time is sufficient to obtain good contact
between the lactamium based ionic liquid and the kerosene feed. The
contacting time is typically in the range of about 1 to about 60
minutes, or about 5 to about 30 minutes.
[0055] An optional kerosene washing step may be used, for example,
to recover lactamium ionic liquid that is entrained or otherwise
remains in the kerosene effluent stream by using water to wash or
extract the ionic liquid from the kerosene effluent. In this
embodiment, a portion or all of kerosene effluent stream 6 (as
feed) and a water stream 12 (as solvent) are introduced to kerosene
washing zone 400. The kerosene effluent and water streams
introduced to kerosene washing zone 400 are mixed and separated to
produce a washed kerosene stream 14 and a spent water stream 16,
which comprises the lactamium ionic liquid. The kerosene washing
step may be conducted in a similar manner and with similar
equipment as used to conduct other liquid-liquid wash and
extraction operations as discussed above. Various kerosene washing
step equipment and conditions such as temperature, pressure, times,
and solvent to feed ratio may be the same as or different from the
contaminant removal zone equipment and conditions. In general, the
kerosene washing step conditions will fall within the same ranges
as given below for the contaminant removal step conditions. A
portion or all of the washed kerosene stream 14 may be passed to
kerosene conversion zone 800.
[0056] An optional lactamium ionic liquid regeneration step may be
used, for example, to regenerate the ionic liquid by removing the
contaminant from the ionic liquid, i.e. reducing the contaminant
content of the rich lactamium ionic liquid. In an embodiment, a
portion or all of kerosene-immiscible lactamium ionic liquid
effluent stream 8 (as feed) comprising the contaminant and a
regeneration solvent stream 18 are introduced to ionic liquid
regeneration zone 500. The kerosene-immiscible lactamium ionic
liquid effluent stream 8 and regeneration solvent stream 18 are
mixed and separated to produce an extract stream 20 comprising the
contaminant, and a regenerated lactamium ionic liquid stream 22.
The lactamium ionic liquid regeneration step may be conducted in a
similar manner and with similar equipment as used to conduct other
liquid-liquid wash and extraction operations as discussed below.
Various lactamium ionic liquid regeneration step conditions such as
temperature, pressure, times, and solvent to feed may be the same
as or different from the contaminant removal conditions. In
general, the ionic liquid regeneration step conditions will fall
within the same ranges as given below for the contaminant removal
step conditions.
[0057] In an embodiment, the regeneration solvent stream 18
comprises a hydrocarbon fraction lighter than the kerosene and
which is immiscible with the lactamium ionic liquid. The lighter
hydrocarbon fraction may consist of a single hydrocarbon compound
or may comprise a mixture of hydrocarbons. In this embodiment,
extract stream 20 comprises the lighter hydrocarbon regeneration
solvent and the contaminant. In another embodiment, the
regeneration solvent stream 18 comprises water, and the ionic
liquid regeneration step produces extract stream 20 comprising the
contaminant and regenerated kerosene-immiscible lactamium ionic
liquid 22 comprising water and the lactamium ionic liquid. In an
embodiment wherein regeneration solvent stream 18 comprises water,
a portion or all of spent water stream 16 may provide a portion or
all of regeneration solvent stream 18. Regardless of whether
regeneration solvent stream 18 comprises a lighter kerosene
fraction or water, a portion or all of regenerated
kerosene-immiscible lactamium ionic liquid stream 22 may be
recycled to the contaminant removal step via a conduit not shown
consistent with other operating conditions of the process. For
example, a constraint on the water content of the
kerosene-immiscible lactamium ionic liquid stream 4 or the
lactamium ionic liquid/kerosene mixture in contaminant removal zone
100 may be met by controlling the proportion and water content of
fresh and recycled ionic liquid streams.
[0058] Optional ionic liquid drying step is illustrated by drying
zone 600. The ionic liquid drying step may be employed to reduce
the water content of one or more of the streams comprising ionic
liquid to control the water content of the contaminant removal step
as described above. In the embodiment of FIG. 1, a portion or all
of regenerated kerosene-immiscible lactamium ionic liquid stream 22
is introduced to drying zone 600. Although not shown, other streams
comprising ionic liquid such as the fresh lactamium ionic liquid
stream 3, kerosene-immiscible lactamium ionic liquid effluent
stream 8, and spent water stream 16, may also be dried in any
combination in drying zone 600. To dry the lactamium ionic liquid
stream or streams, water may be removed by one or more various well
known methods including distillation, flash distillation, and using
a dry inert gas to strip water. Generally, the drying temperature
may range from about 100.degree. C. to less than the decomposition
temperature of the ionic liquid, usually less than about
300.degree. C. The pressure may range from about 35 kPa(g) to about
250 kPa(g). The drying step produces a dried kerosene-immiscible
lactamium ionic liquid stream 24 and a drying zone water effluent
stream 26. Although not illustrated, a portion or all of dried
kerosene-immiscible lactamium ionic liquid stream 24 may be
recycled or passed to provide all or a portion of the
kerosene-immiscible lactamium ionic liquid introduced to
contaminant removal zone 100. A portion or all of drying zone water
effluent stream 26 may be recycled or passed to provide all or a
portion of the water introduced into kerosene washing zone 400
and/or ionic liquid regeneration zone 500.
[0059] FIG. 2A illustrates an embodiment of the invention which may
be practiced in contaminant removal or extraction zone 100 that
comprises a multi-stage, counter-current extraction column 105
wherein kerosene and kerosene-immiscible lactamium ionic liquid are
contacted and separated. The kerosene feed stream 2 enters
extraction column 105 through feed inlet 102 and lean lactamium
ionic liquid stream 4 enters extraction column 105 through ionic
liquid inlet 104. In the FIGURES, reference numerals of the streams
and the lines or conduits in which they flow are the same. Kerosene
feed inlet 102 is located below ionic liquid inlet 104. The
kerosene effluent passes through kerosene effluent outlet 112 in an
upper portion of extraction column 105 to kerosene effluent conduit
6. The kerosene-immiscible lactamium ionic liquid effluent
including the contaminants removed from the kerosene feed passes
through lactamium ionic liquid effluent outlet 114 in a lower
portion of extraction column 105 to lactamium ionic liquid effluent
conduit 8.
[0060] FIG. 2B illustrates another embodiment of contaminant
removal washing zone 100 that comprises a contacting zone 200 and a
separation zone 300. In this embodiment, lean lactamium ionic
liquid stream 4 and kerosene feed stream 2 are introduced into the
contacting zone 200 and mixed by introducing kerosene feed stream 2
into the flowing lean lactamium ionic liquid stream 4 and passing
the combined streams through static in-line mixer 155. Static
in-line mixers are well known in the art and may include a conduit
with fixed internals such as baffles, fins, and channels that mix
the fluid as it flows through the conduit. In other embodiments,
not illustrated, lean lactamium ionic liquid stream 4 may be
introduced into kerosene feed stream 2, or the lean lactamium ionic
liquid stream 4 and kerosene feed stream may be combined such as
through a "Y" conduit. In another embodiment, lean lactamium ionic
liquid stream 4 and kerosene feed stream 2 are separately
introduced into the static in-line mixer 155. In other embodiments,
the streams may be mixed by any method well known in the art,
including stirred tank and blending operations. The mixture
comprising kerosene and lactamium ionic liquid is transferred to
separation zone 300 via transfer conduit 7. Separation zone 300
comprises separation vessel 165 wherein the two phases are allowed
to separate into a rich lactamium ionic liquid phase which is
withdrawn from a lower portion of separation vessel 165 via
lactamium ionic liquid effluent conduit 8 and a kerosene phase
which is withdrawn from an upper portion of separation vessel 165
via kerosene effluent conduit 6. Separation vessel 165 may comprise
a boot, not illustrated, from which rich lactamium ionic liquid is
withdrawn via conduit 8.
[0061] Separation vessel 165 may contain a solid media 175 and/or
other coalescing devices which facilitate the phase separation. In
other embodiments, the separation zone 300 may comprise multiple
vessels which may be arranged in series, parallel, or a combination
thereof. The separation vessels may be of any shape and
configuration to facilitate the separation, collection, and removal
of the two phases. In a further embodiment, contaminant removal
zone 100 may include a single vessel wherein lean lactamium ionic
liquid stream 4 and kerosene feed stream 2 are mixed, then remain
in the vessel to settle into the kerosene effluent and rich
lactamium ionic liquid phases.
[0062] In an embodiment, the process comprises at least two
contaminant removal steps. For example, the kerosene effluent from
one contaminant removal step may be passed directly as the kerosene
feed to a second contaminant removal step. In another embodiment,
the kerosene effluent from one contaminant removal step may be
treated or processed before being introduced as the kerosene feed
to the second contaminant removal step. There is no requirement
that each contaminant removal zone comprises the same type of
equipment. Different equipment and conditions may be used in
different contaminant removal zones.
[0063] FIG. 3 shows an embodiment of the invention that includes
two contaminant removal stages. A Coker kerosene (full range)
stream 900 from a delayed Coker unit (not shown) is sent to a first
stage ionic liquid treating vessel 902. A treated Coker kerosene
stream 904 is then sent to a second stage ionic liquid treating
vessel 906. The purified Coker kerosene stream 930 is eventually
purified to a sulfur level at 1.0 wppm or less and a nitrogen level
at 0.5 wppm or less and may then sent to an olefin/paraffin
separation zone 932. A stream comprising C8 to C16 range olefins
may then be sent for uses in a refinery such as in alkylation
reactions. A stream 934 containing paraffins and aromatics is sent
to a separation unit 936 to produce a normal paraffin stream 938
and a stream 940 comprising other paraffins and aromatics to be
sent to be blended into a diesel stream (not shown). Regarding
ionic liquid treating vessels 902 and 906, the ionic liquid is
regenerated in ionic liquid regeneration vessels 914 and 920, with
streams of contaminated ionic liquid 910 and 928 and regenerated
ionic liquid 908 and 926 being shown. Contaminated extracts 916 and
922 are shown being combined into a stream 924 that may be recycled
to a delayed Coker (not shown).
[0064] The contaminant removal step may be conducted under
contaminant removal conditions including temperatures and pressures
sufficient to keep the kerosene-immiscible lactamium ionic liquid
and kerosene feeds and effluents as liquids. For example, the
contaminant removal step temperature may range between about
10.degree. C. and less than the decomposition temperature of the
lactamium ionic liquid, and the pressure may range between about
atmospheric pressure and about 700 kPa(g). When the
kerosene-immiscible ionic liquid comprises more than one lactamium
ionic liquid component, the decomposition temperature of the
lactamium ionic liquid is the lowest temperature at which any of
the lactamium ionic liquid components decompose. The contaminant
removal step may be conducted at a uniform temperature and pressure
or the contacting and separating steps of the contaminant removal
step may be operated at different temperatures and/or pressures. In
an embodiment, the contacting step is conducted at a first
temperature, and the separating step is conducted at a temperature
at least 5.degree. C. lower than the first temperature. In a
non-limiting example, the first temperature is about 80.degree. C.
Such temperature differences may facilitate separation of the
kerosene and lactamium ionic liquid phases.
[0065] The above and other contaminant removal step conditions such
as the contacting or mixing time, the separation or settling time,
and the ratio of kerosene feed to kerosene-immiscible lactamium
ionic liquid (lean lactamium ionic liquid) may vary greatly based,
for example, on the specific lactamium ionic liquid or liquids
employed, the nature of the kerosene feed (straight run or
previously processed), the contaminant content of the kerosene
feed, the degree of contaminant removal required, the number of
contaminant removal steps employed, and the specific equipment
used. In general, it is expected that contacting time may range
from less than one minute to about two hours; settling time may
range from about one minute to about eight hours. The weight ratio
of kerosene feed to lean lactamium ionic liquid introduced to the
contaminant removal step may range from about 1:10,000 to about
10,000:1, or about 1:1,000 to about 1,000:1, or about 1:100 to
about 100:1, or about 1:20 to about 20:1, or about 1:10 to about
10:1. In an embodiment, the weight of kerosene feed is greater than
the weight of lactamium ionic liquid introduced to the contaminant
removal step.
[0066] In an embodiment, a single contaminant removal step reduces
the contaminant content of the kerosene by more than about 10 wt %,
or more than about 20 wt %, or more than about 30 wt %, or more
than about 40 wt %, or more than about 50 wt %, or more than about
60 wt %, or more than about 70 wt %, or more than about 75 wt %, or
more than about 80 wt %, or more than about 85 wt %, or more than
about 90 wt %. As discussed herein, the invention encompasses
multiple contaminant removal steps to provide the desired amount of
contaminant removal.
[0067] The degree of phase separation between the kerosene and
lactamium ionic liquid phases is another factor to consider as it
affects recovery of the lactamium ionic liquid and kerosene. The
degree of contaminant removed and the recovery of the kerosene and
lactamium ionic liquid may be affected differently by the nature of
the kerosene feed, the variations in the specific lactamium ionic
liquid or liquids, the equipment, and the contaminant removal
conditions such as those discussed above.
[0068] The amount of water present in the
kerosene/kerosene-immiscible lactamium ionic liquid mixture during
the contaminant removal step may also affect the amount of
contaminant removed and/or the degree of phase separation, i.e.,
recovery of the kerosene and lactamium ionic liquid. In an
embodiment, the kerosene/kerosene-immiscible lactamium ionic liquid
mixture has a water content of less than about 10% relative to the
weight of the lactamium ionic liquid, or less than about 5%
relative to the weight of the lactamium ionic liquid, or less than
about 2% relative to the weight of the ionic liquid. In a further
embodiment, the kerosene/kerosene-immiscible lactamium ionic liquid
mixture is water free, i.e., the mixture does not contain
water.
[0069] Unless otherwise stated, the exact connection point of
various inlet and effluent streams within the zones is not
essential to the invention. For example, it is well known in the
art that a stream to a distillation zone may be sent directly to
the column, or the stream may first be sent to other equipment
within the zone such as heat exchangers, to adjust temperature,
and/or pumps to adjust the pressure. Likewise, streams entering and
leaving contaminant removal, washing, and regeneration zones may
pass through ancillary equipment such as heat exchanges within the
zones. Streams, including recycle streams, introduced to washing or
extraction zones may be introduced individually or combined prior
to or within such zones.
[0070] The invention encompasses a variety of flow scheme
embodiments including optional destinations of streams, splitting
streams to send the same composition, i.e. aliquot portions, to
more than one destination, and recycling various streams within the
process. Examples include: various streams comprising ionic liquid
and water may be dried and/or passed to other zones to provide all
or a portion of the water and/or ionic liquid required by the
destination zone. The various process steps may be operated
continuously and/or intermittently as needed for a given embodiment
e.g. based on the quantities and properties of the streams to be
processed in such steps. As discussed above the invention
encompasses multiple contaminant removal steps, which may be
performed in parallel, sequentially, or a combination thereof.
Multiple contaminant removal steps may be performed within the same
contaminant removal zone and/or multiple contaminant removal zones
may be employed with or without intervening washing, regeneration
and/or drying zones.
[0071] By the term "about," we mean within 10% of the value, or
within 5%, or within 1%.
[0072] While at least one exemplary embodiment has been presented
in the foregoing detailed description of the invention, it should
be appreciated that a vast number of variations exist. It should
also be appreciated that the exemplary embodiment or exemplary
embodiments are only examples, and are not intended to limit the
scope, applicability, or configuration of the invention in any way.
Rather, the foregoing detailed description will provide those
skilled in the art with a convenient road map for implementing an
exemplary embodiment of the invention. It being understood that
various changes may be made in the function and arrangement of
elements described in an exemplary embodiment without departing
from the scope of the invention as set forth in the appended
claims.
SPECIFIC EMBODIMENTS
[0073] While the following is described in conjunction with
specific embodiments, it will be understood that this description
is intended to illustrate and not limit the scope of the preceding
description and the appended claims.
[0074] A first embodiment of the invention is a process for
removing a contaminant from a kerosene stream comprising contacting
the kerosene stream comprising the contaminant with a lean
kerosene-immiscible lactamium ionic liquid to produce a mixture
comprising the kerosene and a rich kerosene-immiscible lactamium
ionic liquid comprising at least a portion of the removed
contaminant; and separating the mixture to produce a kerosene
effluent and a rich kerosene-immiscible lactamium ionic liquid
effluent comprising the rich kerosene-immiscible lactamium ionic
liquid; wherein the kerosene-immiscible lactamium ionic liquid
comprises at least one of a reaction product of a lactam compound
having a general formula
##STR00016##
wherein R is hydrogen, an alkyl group having from 1 to 12 carbon
atoms, an amine, an ether, or a silyl group, n is 1 to 8; and a
Bronsted acid HX; or a Bronsted acid HX, where X is a halide, and a
metal halide; or a reaction product of a lactam compound having a
general formula
##STR00017##
wherein the ring has at least one C--C double bond, R is hydrogen,
an alkyl group having from 1 to 12 carbon atoms, an amine, an
ether, or a silyl group, n is 1 to 8, and a Bronsted acid HX; or a
Bronsted acid HX, where X is a halide, and a metal halide; or a
reaction product of a lactam compound having a general formula
##STR00018##
wherein R is hydrogen, an alkyl group having from 1 to 12 carbon
atoms, an amine, an ether, or a silyl group, n is 1 to 8, m is 1 to
8, and the rings can be saturated or unsaturated; and at least one
of a Bronsted acid HX; or a Bronsted acid HX, where X is a halide,
and a metal halide. An embodiment of the invention is one, any or
all of prior embodiments in this paragraph up through the first
embodiment in this paragraph wherein the lactam reaction product is
at least one of carboxylates, nitrates, phosphates, phosphinates,
phosphonates, imides, cyanates, borates, sulfates, sulfonates,
acetates, and halides. An embodiment of the invention is one, any
or all of prior embodiments in this paragraph up through the first
embodiment in this paragraph wherein the lactam reaction product is
the halometallate and wherein a metal in the halometallate is at
least one of Sn, Al, Zn, Mn, Fe, Ga, Cu, Ni, and Co. An embodiment
of the invention is one, any or all of prior embodiments in this
paragraph up through the first embodiment in this paragraph wherein
a ratio of the Bronsted acid HX to the lactam compound is about 11
to about 31. An embodiment of the invention is one, any or all of
prior embodiments in this paragraph up through the first embodiment
in this paragraph wherein the kerosene stream has a boiling point
in a range of about 140.degree. C. to about 210.degree. C. An
embodiment of the invention is one, any or all of prior embodiments
in this paragraph up through the first embodiment in this paragraph
wherein the contacting step is conducted at a temperature in a
range of about 20.degree. C. to about 80.degree. C. An embodiment
of the invention is one, any or all of prior embodiments in this
paragraph up through the first embodiment in this paragraph further
comprising passing at least a portion of the kerosene effluent to a
kerosene conversion process. An embodiment of the invention is one,
any or all of prior embodiments in this paragraph up through the
first embodiment in this paragraph further comprising regenerating
the rich kerosene-immiscible lactamium ionic liquid effluent; and
recycling the regenerated kerosene-immiscible lactamium based ionic
liquid to the contacting step. An embodiment of the invention is
one, any or all of prior embodiments in this paragraph up through
the first embodiment in this paragraph wherein a ratio of the
kerosene to the kerosene-immiscible lactamium ionic liquid is in a
range of about 11,000 to about 1,0001. An embodiment of the
invention is one, any or all of prior embodiments in this paragraph
up through the first embodiment in this paragraph further
comprising contacting the rich kerosene-immiscible lactamium ionic
liquid effluent with a regeneration solvent to form an extract
stream comprising the contaminant and a stream of lean
kerosene-immiscible lactamium ionic liquid. An embodiment of the
invention is one, any or all of prior embodiments in this paragraph
up through the first embodiment in this paragraph wherein the
regeneration solvent comprises water, naphtha, gasoline, diesel,
kerosene, light cycle oil, and light coker gas oil. An embodiment
of the invention is one, any or all of prior embodiments in this
paragraph up through the first embodiment in this paragraph further
comprising separating the stream of lean kerosene-immiscible
lactamium ionic liquid from the regeneration solvent. An embodiment
of the invention is one, any or all of prior embodiments in this
paragraph up through the first embodiment in this paragraph further
comprising recycling the stream of lean kerosene-immiscible
lactamium ionic liquid to the contacting step. An embodiment of the
invention is one, any or all of prior embodiments in this paragraph
up through the first embodiment in this paragraph reactivating the
stream of lean kerosene-immiscible lactamium ionic liquid with an
acid before recycling the stream of lean kerosene-immiscible
lactamium ionic liquid to the contacting step. An embodiment of the
invention is one, any or all of prior embodiments in this paragraph
up through the first embodiment in this paragraph wherein the ionic
liquid has the general formula (III) and wherein at least one ring
has at least one C--C double bond.
[0075] A second embodiment of the invention is a process for
removing a contaminant from a kerosene stream comprising contacting
the kerosene stream comprising the contaminant with a lean
kerosene-immiscible lactamium ionic liquid to produce a mixture
comprising the kerosene and a rich kerosene-immiscible lactamium
ionic liquid comprising at least a portion of the removed
contaminant; and separating the mixture to produce a kerosene
effluent and a rich kerosene-immiscible lactamium ionic liquid
effluent comprising the rich kerosene-immiscible lactamium ionic
liquid; regenerating the rich kerosene-immiscible lactamium ionic
liquid effluent to form a stream of lean kerosene-immiscible
lactamium ionic liquid; recycling the stream of lean
kerosene-immiscible lactamium ionic liquid to the contacting step;
and passing at least a portion of the kerosene effluent to a
kerosene conversion process; wherein the kerosene-immiscible
lactamium ionic liquid comprises at least one of a reaction product
of a lactam compound having a general formula
##STR00019##
wherein R is hydrogen, an alkyl group having from 1 to 12 carbon
atoms, an amine, an ether, or a silyl group, n is 1 to 8; and a
Bronsted acid HX; or a Bronsted acid HX, where X is a halide, and a
metal halide; or a reaction product of a lactam compound having a
general formula
##STR00020##
wherein the ring has at least one C--C double bond, R is hydrogen,
an alkyl group having from 1 to 12 carbon atoms, an amine, an
ether, or a silyl group, n is 1 to 8, and a Bronsted acid HX; or a
Bronsted acid HX, where X is a halide, and a metal halide; or a
reaction product of a lactam compound having a general formula
##STR00021##
wherein R is hydrogen, an alkyl group having from 1 to 12 carbon
atoms, an amine, an ether, or a silyl group, n is 1 to 8, m is 1 to
8, and the rings can be saturated or unsaturated; and a Bronsted
acid HX; or a Bronsted acid HX, where X is a halide, and a metal
halide. An embodiment of the invention is one, any or all of prior
embodiments in this paragraph up through the second embodiment in
this paragraph wherein regenerating the rich kerosene-immiscible
lactamium ionic liquid effluent comprises contacting the rich
kerosene-immiscible lactamium ionic liquid effluent with a
regeneration solvent to form an extract stream comprising the
contaminant and the stream of lean kerosene-immiscible lactamium
ionic liquid. An embodiment of the invention is one, any or all of
prior embodiments in this paragraph up through the second
embodiment in this paragraph reactivating the stream of lean
kerosene-immiscible lactamium ionic liquid with an acid before
recycling the stream of lean kerosene-immiscible lactamium ionic
liquid to the contacting step. An embodiment of the invention is
one, any or all of prior embodiments in this paragraph up through
the second embodiment in this paragraph wherein the lactam reaction
product is at least one of carboxylates, nitrates, phosphates,
phosphinates, phosphonates, imides, cyanates, borates, sulfates,
sulfonates, acetates, and halides. An embodiment of the invention
is one, any or all of prior embodiments in this paragraph up
through the second embodiment in this paragraph wherein a ratio of
the Bronsted acid HX to the lactam compound is about 1:1 to about
3:1.
[0076] Without further elaboration, it is believed that using the
preceding description that one skilled in the art can utilize the
present invention to its fullest extent and easily ascertain the
essential characteristics of this invention, without departing from
the spirit and scope thereof, to make various changes and
modifications of the invention and to adapt it to various usages
and conditions. The preceding preferred specific embodiments are,
therefore, to be construed as merely illustrative, and not limiting
the remainder of the disclosure in any way whatsoever, and that it
is intended to cover various modifications and equivalent
arrangements included within the scope of the appended claims.
[0077] In the foregoing, all temperatures are set forth in degrees
Celsius and, all parts and percentages are by weight, unless
otherwise indicated.
* * * * *