U.S. patent application number 13/975184 was filed with the patent office on 2015-01-01 for catalytic isomerization of butane using ionic liquids.
This patent application is currently assigned to UOP LLC. The applicant listed for this patent is UOP LLC. Invention is credited to Alakananda Bhattacharyya, Stuart Smith.
Application Number | 20150005554 13/975184 |
Document ID | / |
Family ID | 52116237 |
Filed Date | 2015-01-01 |
United States Patent
Application |
20150005554 |
Kind Code |
A1 |
Smith; Stuart ; et
al. |
January 1, 2015 |
CATALYTIC ISOMERIZATION OF BUTANE USING IONIC LIQUIDS
Abstract
Processes for the disproportionation and isomerization of a
C.sub.4 hydrocarbon feed using a liquid catalyst comprising an
ionic liquid and a carbocation promoter are described. The ionic
liquid is unsupported, and the reactions occur at temperatures
below about 300.degree. C.
Inventors: |
Smith; Stuart; (Lake Zurich,
IL) ; Bhattacharyya; Alakananda; (Glen Ellyn,
IL) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
UOP LLC |
Des Plaines |
IL |
US |
|
|
Assignee: |
UOP LLC
Des Plaines
IL
|
Family ID: |
52116237 |
Appl. No.: |
13/975184 |
Filed: |
August 23, 2013 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
61841266 |
Jun 28, 2013 |
|
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|
Current U.S.
Class: |
585/310 ;
585/734; 585/740; 585/745; 585/747 |
Current CPC
Class: |
C07C 6/10 20130101; C07C
2527/128 20130101; C07C 2527/08 20130101; C07C 2527/24 20130101;
C07C 5/2702 20130101; C07C 5/2751 20130101; C07C 2527/138 20130101;
C07C 2/58 20130101; C07C 6/10 20130101; C07C 2527/14 20130101; C07C
2527/125 20130101; C07C 2527/11 20130101; C07C 4/06 20130101; C07C
9/12 20130101; C07C 9/18 20130101; C07C 9/16 20130101; C07C 5/2751
20130101; C07C 9/16 20130101; C07C 5/277 20130101; C07C 2527/12
20130101; C07C 6/10 20130101; C07C 2527/054 20130101; C07C 6/10
20130101; C07C 2527/122 20130101 |
Class at
Publication: |
585/310 ;
585/740; 585/734; 585/747; 585/745 |
International
Class: |
C07C 6/10 20060101
C07C006/10; C07C 5/27 20060101 C07C005/27 |
Claims
1. A hydrocarbon conversion process comprising: isomerizing a
hydrocarbon feed comprising normal C.sub.4 alkane or branched
C.sub.4 alkane by contacting the hydrocarbon feed with a liquid
catalyst in a reaction zone under isomerization conditions to form
a product mixture having a ratio of branched C.sub.4 alkane to
normal C.sub.4 alkane of at least about 0.3:1 in 1 hr, wherein the
liquid catalyst comprises an unsupported ionic liquid and a
carbocation promoter, and wherein a mass ratio of liquid catalyst
to hydrocarbon feed is less than 0.75:1.
2. The process of claim 1 wherein the ionic liquid comprises an
organic cation and an anion and wherein the organic cation is
selected from the group consisting of: ##STR00002## where
R.sup.1-R.sup.21 are independently selected from C.sub.1-C.sub.20
hydrocarbons, C.sub.1-C.sub.20 hydrocarbon derivatives, halogens,
and H.
3. The process of claim 1 wherein the ionic liquid comprises an
organic cation and an anion and wherein the anion is derived from
halides, sulfates, bisulfates, nitrates, sulfonates,
fluoroalkanesulfonates, or combinations thereof.
4. The process of claim 1 wherein the ionic liquid comprises an
organic cation and an anion and wherein the anion is selected from
the group consisting of 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.-.
5. The process of claim 1 wherein the carbocation promoter
comprises a haloalkane, a mineral acid, or combinations
thereof.
6. The process of claim 5 wherein the haloalkane comprises
2-chloro-2-methylpropane, 2-chloropropane, 2-chlorobutane,
2-chloro-2-methylbutane, 2-chloropentane, 1-chlorohexane,
3-chloro-3-methylpentane, or combinations thereof.
7. The process of claim 1 further comprising stirring the
hydrocarbon feed and the liquid catalyst while contacting the
hydrocarbon feed with the liquid catalyst.
8. The process of claim 1 wherein a molar ratio of the carbocation
promoter to ionic liquid is in a range of about 0:1 to about
3:1.
9. The process of claim 1 further comprising separating the ionic
liquid from the product mixture.
10. The process of claim 9 further comprising regenerating the
separated ionic liquid.
11. The process of claim 1 wherein a concentration of acid within
the liquid catalyst is less than about 2.5 M.
12. The process of claim 1 further comprising disproportionating
the hydrocarbon feed concurrently with isomerizing the hydrocarbon
feed.
13. The process of claim 1 wherein the hydrocarbon feed comprises a
mixture of at least C.sub.4 and C.sub.5 alkanes.
14. The process of claim 1 wherein a conversion rate for volume is
at least about 60 in the absence of an added metal salt.
15. A hydrocarbon conversion process comprising: isomerizing a
hydrocarbon feed comprising normal C.sub.4 alkane by contacting the
hydrocarbon feed with a liquid catalyst in a reaction zone under
isomerization conditions to form a product mixture comprising at
least about 10 wt % branched C.sub.4 alkanes in 1 hr based on the
normal C.sub.4 alkane in the hydrocarbon feed, wherein the liquid
catalyst comprises an unsupported ionic liquid and a carbocation
promoter, and wherein a mass ratio of liquid catalyst to
hydrocarbon feed is less than 0.75:1.
16. The process of claim 15 wherein the ionic liquid comprises an
organic cation and an anion and wherein the organic cation is
selected from the group consisting of: ##STR00003## where
R.sup.1-R.sup.21 are independently selected from C.sub.1-C.sub.20
hydrocarbons, C.sub.1-C.sub.20 hydrocarbon derivatives, halogens,
and H.
17. The process of claim 15 wherein the ionic liquid comprises an
organic cation and an anion and wherein the anion is derived from
halides, sulfates, bisulfates, nitrates, sulfonates,
fluoroalkanesulfonates, or combinations thereof.
18. The process of claim 15 wherein the carbocation promoter
comprises a haloalkane, a mineral acid, or combinations
thereof.
19. The process of claim 15 wherein a concentration of acid within
the liquid catalyst is less than about 2.5 M.
20. The process of claim 15 further comprising disproportionating
the hydrocarbon feed concurrently with isomerizing the hydrocarbon
feed.
Description
[0001] This application claims the benefit of Provisional
Application Ser. No. 61/841,266, entitled METHOD FOR TUNING PRODUCT
COMPOSITION BASED ON VARYING TYPES AND RATIOS OF FEED, filed Jun.
28, 2013, which is incorporated herein by reference.
BACKGROUND OF THE INVENTION
[0002] The Reid vapor pressure (RVP) of gasoline has been utilized
by the Environmental Protection Agency as a means of regulating
volatile organic compounds emissions by transportation fuels and
for controlling the formation of ground level ozone. As these
regulations become more stringent and as more ethanol (which has a
high vapor pressure) is blended into gasoline, C.sub.5 paraffins
need to be removed from the gasoline pool. Moreover, the need to
remove components may also extend to some C.sub.6 paraffins. This
may result in refiners being oversupplied with C.sub.5 paraffins
and possibly C.sub.6 paraffins.
[0003] Disproportionation reactions offer a possible solution to
this problem. The disproportionation of paraffins (e.g., isopentane
(iC.sub.5)) involves reacting two moles of hydrocarbon to form one
mole each of two different products, one having a carbon count
greater than the starting material and the other having a carbon
count less than the starting material, as shown in FIG. 1. The
total number of moles in the system remains the same throughout the
process, but the products have different carbon counts from the
reactants. Additional secondary disproportionation-type reactions
can occur in which two hydrocarbons having different carbon numbers
react to form two different hydrocarbons having different carbon
numbers from those of the feed where the total number of carbons in
the products does not change from the total number in the feed
(e.g., pentane and octane reacting to form hexane and heptane).
[0004] There are a number of different catalysts that have been
shown to produce the desired paraffin disproportionation reaction,
including zeolites, sulfated zirconias, AlCl.sub.2/SiO.sub.2, ionic
solids, platinum on chlorided Al.sub.2O.sub.3/Ga.sub.2O.sub.3
supports, supported ionic liquids, Pt/W/Al.sub.2O.sub.3 and
HF/TiF.sub.4. However, these processes have a number of
disadvantages. The processes using zeolites, sulfated zirconias,
AlCl.sub.2/SiO.sub.2, ionic solids, and platinum on
Al.sub.2O.sub.3/Ga.sub.2O.sub.3 supports require elevated
temperatures (e.g., 120-450.degree. C.) to carry out the
transformation. The HF/TiF.sub.4 system is capable of
disproportionation at 51.degree. C., but it utilizes dangerous HF.
The supported ionic liquid is active from about 85-125.degree. C.
and is composed of the Bronsted acidic trimethylammonium cation.
Since the ionic liquid's organic cation is composed of this
Bronsted acid, the acid concentration within this catalyst is
stoichiometric with respect to the ionic liquid and quite high.
Moreover, the supported ionic liquid is deactivated by leaching of
the ionic liquid from the support. Additionally, the use of a
support increases the cost of the catalyst and may result in a
chemical reaction of the support with the acidic ionic liquid over
time, as happens when AlCl.sub.3 is immobilized on silica.
[0005] Isomerization processes have been used to improve the low
octane numbers (RON) of light straight run naphtha. Isomerization
processes involve reacting one mole of a hydrocarbon (e.g., normal
pentane) to form one mole of an isomer of that specific hydrocarbon
(e.g., isopentane), as shown in FIG. 2. The total number of moles
remains the same throughout this process, and the product has the
same number of carbons as the reactant.
[0006] Current isomerization processes use chlorided alumina,
sulfated zirconia, or zeolites in conjunction with platinum.
Process temperatures range from about 120.degree. C. for chlorided
alumina up to about 260.degree. C. for zeolite type catalysts.
These reactions are run at temperatures which allow the feed to
reach equilibrium. At lower temperatures, the equilibrium favors
the branched isomers possessing the higher octane number.
[0007] Isomerization processes utilizing ionic liquids have been
developed. For example, US 2003/019767 describes an isomerization
process for a paraffin hydrocarbon feed using an ionic liquid as a
catalyst. The ionic liquid is formed from an N-containing
heterocyclic and/or N-containing aliphatic organic cation and an
inorganic anion derived from metal halides. The examples show a
catalyst:hydrocarbon weight ratio of 1:1 or 1.5:1. The hydrocarbon
feeds examined were normal pentane, normal heptane, normal octane,
and 3-methylhexane.
[0008] US 2004/059173 teaches an isomerization process for linear
and/or branched paraffin hydrocarbons. The catalyst comprises an
ionic liquid. Over 25 wt % of a cyclic hydrocarbon additive is
included. The ionic liquid is formed from an N-containing
heterocyclic and/or N-containing aliphatic organic cation and an
inorganic anion derived from metal halides. The ionic
liquid:hydrocarbon ratio in the examples is fixed at 1:1 volume
ratio. Metal salt additives or Bronsted acids can be included. The
feed is a mixture of C.sub.7 hydrocarbons.
[0009] U.S. Pat. No. 7,053,261 discusses isomerization of linear
and/or branched paraffin hydrocarbons using an ionic liquid
catalyst in combination with a metal salt additive. The ionic
liquid is formed from an N-containing heterocyclic and/or
N-containing aliphatic organic cation and an inorganic anion
derived from metal halides. The ionic liquid:hydrocarbon ratio in
the examples is fixed at 1:1 volume ratio. The results of the gas
chromatograph on the paraffin phase were not reported. The feed is
a mixture of C.sub.7 hydrocarbons.
[0010] All of these references describe isomerization of the feed;
none describes disproportionation reactions. All of the references
describe the use of ionic liquids having an acid concentration of
at least about 3.0 M. The Bronsted acidic ionic liquid used in US
Publication 2003/0109767 was [trimethylammonium][Al.sub.2Cl.sub.7],
which has a molar concentration of HCl that ranges from 3.0-4.1 M
if the density is in the range of 1.1 to 1.5 g/mL. For US
Publications 2004/0059173 and U.S. Pat. No. 7,053,261 the Bronsted
acidic ionic liquid used was
[trimethylammonium][Al.sub.1.8Cl.sub.6.4], which has a molar
concentration of HCl that ranges from 3.3-4.5 M if the density is
in the range of 1.1 to 1.5 g/mL. These estimated densities are
within the ranges measured for similar ionic liquids.
[0011] None of the references indicate the composition of the
product mixture; as a result, it is unclear what was actually
formed in the reactions. Assuming that all of the other products
were disproportionation products (which is unlikely to be correct
as Ibragimov et al. teach that cracking occurs in addition to
disproportionation (see below), but it sets an upper limit on the
greatest possible conversion, yield, etc. for the
disproportionation products). The conversion rates corrected for
mass or volume were calculated as follows: using the reported
iso-selectivity, the selectivity to other compounds was calculated
as (100-iso-selectivity). The % conversion was determined from the
reported %-iso yield and % iso-selectivity. The % conversion thus
determined was used to determine the reaction rate by the following
formula: volume rate=(% conversion/time (h)).times.(mL HC/mL IL) or
as mass rate=(% conversion/time (h)).times.(g HC/g IL). The %
conversion was then used with the computed selectivity to other
compounds to set an upper limit on the yield of disproportionation
products. The yield of the other compounds and yield of isomers was
then calculated using the calculated selectivity to other compounds
and the total yield. Since the reaction rate is dependent on the
ratio of ionic liquid:hydrocarbon, the rates were corrected
according to these ratios.
[0012] With respect to US 2003/0109767, the corrected conversion
rates for mass were very low. For n-C.sub.5, the corrected
conversion rate for mass ranged was between 3.5 and 18.2. For
n-C.sub.7, it ranged from 2.6 to 9.3, for n-C.sub.8, it was 3.3,
and for 3-methylhexane, it was 4.7. For US 2005/059173, the
corrected conversion rates for volume ranged from 0.6 to 47.1 for
the C.sub.7 mixture. For U.S. Pat. No. 7,053,261, the corrected
conversion rates for volume ranged from 5.4 to 371.3 in the
presence of an additional metal salt.
[0013] Isomerization is also described in "Isomerization of Light
Alkanes Catalysed by Ionic Liquids: An Analysis of Process
Parameters," Ibragimov et al., Theoretical Foundations of Chemical
Engineering (2013), 47(1), 66-70. The desired reaction is stated to
be isomerization, and the main isomerization products from n-hexane
are said to isobutane, isopentane, and hexane isomers. However,
isobutane and isopentane are not the isomerization products of
n-hexane as isomerization has been defined above. In addition, the
article discusses the fact that a significant amount of an
undesirable disproportionation reaction begins to occur after about
2-3 hrs. The article indicates that the disproportionation reaction
dominates when the ratio of catalyst to hydrocarbon ratio is 2:1,
and that cracking and disproportionation dominate at 333K. Because
cracking is occurring, the number of moles formed is increased. The
optimum isomerization temperature was 303K. The maximum volume rate
they obtained was 26 at their high mixing speeds (900 rpm or more)
at 0.5 hr.
[0014] Some processes involve isomerization and then a cracking
reaction in which one mole of a hydrocarbon forms two moles of
product, each with a lower carbon number than the starting
material. In FIG. 3, the products are illustrated as an alkene and
an alkane. Additionally, the total number of moles increases
throughout the process.
[0015] Alkylation processes involving ionic liquids are also known.
In alkylation reactions, one mole of an alkane and one mole of an
alkene react to form one mole of an alkane having a carbon number
equal to the sum of the carbon numbers of the starting alkane and
alkene, as shown in FIG. 4. In an alkylation process, the total
number of moles in the system is reduced.
[0016] There is a need for improved processes for
disproportionation and isomerization of hydrocarbons.
SUMMARY OF THE INVENTION
[0017] One aspect of the invention is a hydrocarbon conversion
process. In one embodiment, the process includes isomerizing a
hydrocarbon feed comprising normal C.sub.4 alkane or branched
C.sub.4 alkane by contacting the hydrocarbon feed with a liquid
catalyst in a reaction zone under isomerization conditions to form
a product mixture having a ratio of branched C.sub.4 alkane to
normal C.sub.4 alkane of at least about 0.3:1 in 1 hr, wherein the
liquid catalyst comprises an unsupported ionic liquid and a
carbocation promoter, and wherein a mass ratio of liquid catalyst
to hydrocarbon feed is less than 0.75:1.
[0018] In another embodiment, the process includes isomerizing a
hydrocarbon feed comprising normal C.sub.4 alkane by contacting the
hydrocarbon feed with a liquid catalyst in a reaction zone under
isomerization conditions to form a product mixture comprising at
least about 10 wt % branched C.sub.4 alkanes in 1 hr based on the
normal C.sub.4 alkane in the hydrocarbon feed, wherein the liquid
catalyst comprises an unsupported ionic liquid and a carbocation
promoter, and wherein a mass ratio of liquid catalyst to
hydrocarbon feed is less than 0.75:1.
BRIEF DESCRIPTION OF THE DRAWINGS
[0019] FIG. 1 illustrates the disproportionation reaction of
iso-pentane.
[0020] FIG. 2 illustrates the isomerization reaction of
n-pentane.
[0021] FIG. 3 illustrates a cracking reaction of n-pentane.
[0022] FIG. 4 illustrates an alkylation reaction of isobutane and
isobutene.
[0023] FIG. 5 is a schematic of one embodiment of the process of
present invention.
DETAILED DESCRIPTION OF THE INVENTION
[0024] A process for the disproportionation and/or isomerization of
a hydrocarbon feed using a liquid catalyst comprising ionic liquids
and carbocation promoters is described. The ionic liquids are
unsupported and allow the reactions to occur at temperatures below
about 300.degree. C.
[0025] The disproportionation reaction involves contacting a
hydrocarbon feed comprising a C.sub.n alkane with a liquid catalyst
in a reaction zone to form a product mixture containing C.sub.n-
alkanes and C.sub.n+ alkanes, wherein the liquid catalyst comprises
an unsupported ionic liquid and a carbocation promoter, and wherein
n=4-12.
[0026] The isomerization reaction involves contacting the
hydrocarbon feed comprising a normal C.sub.n alkane (or iso C.sub.n
alkane) with a liquid catalyst in a reaction zone to form a product
mixture containing iso C.sub.n alkanes (or normal C.sub.n alkanes),
wherein the liquid catalyst comprises an unsupported ionic liquid
and a carbocation promoter, and wherein n=4-12.
[0027] Disproportionation and isomerization occur simultaneously.
There is a substantial disproportionation reaction for some
hydrocarbon, which can be seen by the fact that significant amounts
of C.sub.n+ and C.sub.n- alkanes form. In some embodiments, the
product mixture can contain at least about 3 wt % C.sub.n+ alkanes
in 1 hr based on the C.sub.n alkane fraction in the hydrocarbon
feed, or at least 5 wt %, or at least about 7 wt %, or at least
about 10%, or at least about 15 wt %, or at least about 20 wt %.
There is a corresponding formation of the C.sub.n- fraction. There
can be at least about 3 wt % C.sub.n- alkanes in 1 hr based on the
C.sub.n alkane fraction in the hydrocarbon feed, or at least 5 wt
%, or at least about 7 wt %, or at least about 10%, or at least
about 15 wt %, or at least about 20 wt %. The percentages are based
on the C.sub.n alkane fraction in the hydrocarbon feed.
[0028] It is more complex to evaluate the C.sub.n+ and C.sub.n-
fractions when the feed comprises more than one C.sub.n alkane.
When the feed comprises more than one C.sub.n alkane, the amount of
C.sub.n+ alkane based on the highest carbon number in the feed can
be used. For example if, the feed comprises C.sub.5 and C.sub.6,
the amount of C.sub.n+ can be evaluated using the C.sub.7 fraction.
When the feed comprises C.sub.5 and C.sub.8, the increase may be
evaluated using the C.sub.9 fraction.
[0029] For a feed comprising C.sub.5, at least about 5 wt % each of
C.sub.4- and C.sub.6+ forms within 30 min, or at least about 10 wt
%, or at least about 15 wt %. At least about 10 wt % each of
C.sub.4- and C.sub.6+ forms within 1 hr, or at least about 15 wt %,
or at least about 20 wt %.
[0030] For a feed comprising C.sub.7, at least about 3 wt % each of
C.sub.6- and C.sub.8+ forms within 1 hr, or at least about 5 wt %,
or at least about 7 wt %.
[0031] Longer reaction times may be needed for C.sub.4 hydrocarbons
due to slower reaction rates. In some embodiments, for a feed
comprising normal C.sub.4, at least about 0.2 wt % each of C.sub.3
and C.sub.5+ forms in 32 hr, or at least about 0.25 wt %, or at
least about 0.3 wt %. In some embodiments, for a feed comprising
normal C.sub.4, at least about 1 wt % each of C.sub.3 and C.sub.5+
forms in 50 hr, or at least about 1.5 wt %, or at least about 2.0
wt %. In some embodiments, at least about 0.2 wt % each of C.sub.3
and C.sub.5+ forms in 1 hr, or at least about 0.3 wt %. In some
embodiments, at least about 0.5 wt % each of C.sub.3 and C.sub.5+
forms in 8 hr, or at least about 0.6 wt %, or at least about 0.7 wt
%, or at least about 0.8 wt %, or at least about 0.9 wt %. In some
embodiments, at least about 1.0 wt % each of C.sub.3 and C.sub.5+
forms in 25 hr, or at least about 1.1 wt %, or at least about 1.2
wt %, or at least about 1.3 wt %.
[0032] Another indication of the existence of the
disproportionation reaction is that the number of moles in the
product is nearly equal to the number of moles initially
present.
[0033] There can also be a substantial isomerization reaction,
which can be seen by the fact that significant amounts of iso
C.sub.n alkanes form from normal C.sub.n alkanes, and normal
C.sub.n alkanes form from iso C.sub.n alkanes initially. The
product mixture can contain at least about 2 wt % normal C.sub.n
alkanes in 1 hr based on the iso C.sub.n fraction in the
hydrocarbon feed, or at least about 3 wt %, or at least 4 wt %, or
at least about 5 wt %, or at least about 7 wt %, or at least about
10 wt %. The product mixture can contain at least about 5 wt % iso
C.sub.n alkanes in 1 hr based on the normal C.sub.n fraction in the
hydrocarbon feed, or at least about 10 wt %, or at least about 15
wt %, or at least about 20 wt %.
[0034] For normal C.sub.5 isomerization, at least about 10 wt % of
iso C.sub.5 forms within 30 min, or at least about 15 wt %. At
least about 15 wt % iso C.sub.5 forms within 1 hr, or at least
about 20 wt %.
[0035] For iso C.sub.5 isomerization, at least about 2 wt % of
normal C.sub.5 forms within 1 hr min, or at least about 3 wt %, or
at least about 4 wt %, or at least about 5 wt %.
[0036] For normal C.sub.7 isomerization, at least about 5 wt % of
iso C.sub.7 forms within 1 hr, or at least about 10 wt %,
[0037] For normal C.sub.4 isomerization, at least about 10 wt % of
iso C.sub.4 forms within 1 hr, or at least about 15 wt %, or at
least about 20 wt %. For normal C.sub.4 isomerization, at least
about 30 wt % of iso C.sub.4 forms within 8 hr, or at least about
35 wt %, or at least about 40 wt %, or at least about 45 wt %, or
at least about 50 wt %.
[0038] The conversion rate for volume can be calculated as volume
rate=(% conversion/time (h)).times.(mL HC/mL IL), where the mL of
IL is determined by taking the mass of the ionic liquid and
carbocation promoter and dividing by the density of the pure ionic
liquid. The conversion rate for volume for some conversions is at
least about 60 in the absence of an added metal salt, or at least
about 70, or at least about 80, or at least about 90, or at least
about 100, or at least about 120, or at least about 140, or at
least about 160, or at least about 180, or at least about 200, or
at least about 250, or at least about 300, or at least about 350,
or at least about 400, or at least about 450, or at least about
500.
[0039] The conversion rate for mass can be calculated as mass
rate=(% conversion/time (h)).times.(g HC/g IL), where the mass of
the IL is taken to be the summed mass of the IL and carbocation
promoter. The conversion rate for mass in the absence of an added
metal salt for some conversions is at least about 20, or at least
about 30, or at least about 40, or at least about 50, or at least
about 60, or at least about 70, or at least about 80, or at least
about 90, or at least about 100, or at least about 110, or at least
about 120, or at least about 130, or at least about 140, or at
least about 150, or at least about 175, or at least about 200, or
at least about 220 or at least about 230, or at least about 240, or
at least about 250, or at least about 250.
[0040] The present invention provides a method of
disproportionating a hydrocarbon feed using less ionic liquid,
which is expensive, and obtaining better results at a faster rate.
It also provides a method of isomerizing a hydrocarbon feed using
less ionic liquid, and obtaining better results at a faster
rate.
[0041] The hydrocarbon feed can be straight chain paraffins,
branched chain paraffins, cycloparaffins, naphthenes, or
combinations thereof. The hydrocarbon feed may contain a single
C.sub.n alkane, such as pentane, or mixtures of two or more
alkanes, such as pentane and hexane, or pentane, hexane, and
heptane.
[0042] In some embodiments, the hydrocarbon feed can be a mixture
of 2, 3, 4, 5, or 6 or more consecutive carbon numbers. Typically,
there will be one, two, or three carbon numbers that form most of
the feed. For example, there could be greater than about 50% of one
carbon number, or greater than about 60%, or greater than about
70%, or greater than about 80%. In some embodiments, two or three
carbon numbers (or more) could form greater than about 50% of the
feed, or greater than about 60%, or greater than about 70%, or
greater than about 80%.
[0043] In some embodiments, the C.sub.n alkane can be substantially
pure C.sub.n alkane, e.g., greater than about 90% of a C.sub.n
alkane, such as pentane, or greater than about 95%, or greater than
about 97%, or greater than about 98%, or greater than about
99%.
[0044] In some embodiments, the C.sub.n alkane can be substantially
pure normal C.sub.n alkane or substantially pure iso C.sub.n
alkane, e.g., greater than about 90% of a specific normal or iso
C.sub.n alkane, such as normal pentane, or greater than about 95%,
or greater than about 97%, or greater than about 98%, or greater
than about 99%.
[0045] In other embodiments, mixtures of normal C.sub.n alkane and
iso C.sub.n alkane (both a single C.sub.n alkane, such as pentane,
and two or more C.sub.n alkanes, such as pentane and hexane) are
used. The ratio of normal C.sub.n alkane to iso C.sub.n alkane is
typically in the range of about 90:10 to about 10:90, or about
80:20 to about 20:80, or about 70:30 to about 30:70, or about 60:40
to about 40:60, or about 50:50.
[0046] As discussed above, the disproportionation reaction of a
C.sub.n alkane produces C.sub.n- and C.sub.n+ alkanes. For example,
the disproportionation of C.sub.5 produces C.sub.4- and C.sub.6+
alkanes. The presence of the C.sub.n+ fraction distinguishes the
disproportionation reaction (FIG. 1) from isomerization reactions
which produce isomers of the C.sub.n starting material (FIG. 2), or
isomerization and cracking which produces isomers of the C.sub.n
starting material and C.sub.n- alkanes due to cracking (FIGS. 2 and
4). The hydrocarbon feed can be dried to remove water before being
contacted with the liquid catalyst. The feed can also be treated to
remove undesirable reactive compounds such as alkenes, dienes,
nitriles, and the like using known treatment processes.
[0047] The hydrocarbon feed can be a fluid. The fluid can be a
liquid, a vapor, or a mixture of liquid and vapor. When a liquid or
liquid-vapor mixture is used, the method is one of the few
liquid-liquid disproportionation methods available.
[0048] The processes can produce mixtures of alkanes having
desirable RVP and RON. The RVP and RON values are calculated on the
C.sub.5+ fraction. The RVP was calculated as the vapor pressure for
the system when the vapor:liquid ratio is 4:1 by volume using the
Peng Robinson fluid properties model. The RON was calculated with
linear volumetric blending, and the RON values used for this
calculation were based on the values listed in Phillips 66
Reference Data for Hydrocarbons and Petro-Sulfur Compounds,
Bulletin No. 521.
[0049] In one embodiment, the product mixture of alkanes has an RVP
in the range of about 1 to about 25, or about 8 to about 16, and an
RON in a range of about 50 to about 110, or about 60 to about 100.
In another embodiment, the product mixture of alkanes has a similar
RVP and RON. The octane numbers can be increased by isomerization
of the linear paraffins to the corresponding branched
compounds.
[0050] In some embodiments, the RVP of the product mixture is less
than the RVP of the hydrocarbon feed. In some embodiments, the RVP
is reduced at least about 5 numbers compared to the hydrocarbon
feed, or at least about 7 numbers, or at least about 8 numbers. For
example, the RVP for pure (i.e., greater than 99%) normal pentane
is 15.6, and the RVP for the product mixture made from
substantially pure normal pentane is 13.0 to 13.5. The RVP for pure
(i.e., greater than 99%) isopentane is 20.4, and the RVP for the
product mixture made from substantially pure isopentane is 12.3 to
12.5.
[0051] When the mass ratio of branched alkanes to normal alkanes
(i/n) produced from converted pentane feed is in the range of about
6:1 to about 17:1, the selectivity for isoparaffins is in the range
of about 70 to about 90%, and when it is in the range of about 7:1
to about 17:1, the selectivity for isoparaffins is in the range of
about 80 to about 90%. The high branched to normal ratios for
alkanes obtainable with this system are notable, especially in
comparison to the methods employing dehydrogenation and metathesis
catalysts to effect disproportionation. Generally, when these
catalysts are employed, the major isomers formed within the
C.sub.n- and C.sub.n+ systems are normal paraffins. The formation
of large amounts of normal paraffins is typically not desired due
to their low octane numbers.
[0052] The formula for calculating the i/n ratio of the product for
pure alkanes is (wt. % iC.sub.n-+x wt. % iC.sub.n+wt. %
iC.sub.n+)/(wt. % nC.sub.n-+y wt. % nC.sub.n+wt. % nC.sub.n+) with
n- greater than or equal to 4, x=1 and y=0 when C.sub.n=normal
alkane and x=0 and y=1 when C.sub.n=isoalkane. For example, for
C.sub.5, the calculation would be (wt. % iC.sub.4+x wt. %
iC.sub.5+wt. % iC.sub.6+wt. % iC.sub.7+wt. % iC.sub.8)/(wt. %
nC.sub.4+y wt. % nC.sub.5+wt. % nC.sub.6+wt. % nC.sub.7+wt. %
nC.sub.8); where x=1 and y=0 when C.sub.n=nC.sub.5 and x=0 and y=1
when C.sub.n is iC.sub.5). Although C.sub.9+ alkanes will be
present in small amounts, they should not substantially affect the
i/n ratio as reported. In addition, the C.sub.3- compounds are not
included because they don't have normal and iso isomers.
[0053] The lower reactivity of normal pentane (nC.sub.5) has made
it generally difficult to for the development of a commercial
process using nC.sub.5. However, disproportionation of nC.sub.5 at
reasonable rates has been demonstrated in more than one embodiment
of the present invention.
[0054] In order for these reactions to proceed, a stable
carbocation likely needs to be present. Carbocations readily
undergo skeletal rearrangement at low temperatures. Even at
-90.degree. C., rapid rearrangement is observed for degenerate 1,
2-methide shifts. Frequently, carbocations are transient
intermediates and are short-lived. However, persistent carbocations
have been observed in superacidic media.
[0055] Ionic liquids offer a number of unique features which make
them particularly well suited as reaction mediums for low
temperature disproportionation and isomerization. These features
include: (1) extremely low volatility, resulting in little to no
solvent loss, (2) high chemical diversity, allowing for specific
properties to be readily incorporated into the solvent, (3) good
thermal stability, (4) readily recyclable, (5) wide liquid ranges,
and (6) in some cases (e.g., 1-ethyl-3-methylimidazolium
chloroaluminates), they have been shown to be superacidic.
[0056] The liquid hydrocarbon feed comprises a C.sub.n alkane where
n=4-12. A normal C.sub.n alkane is converted to a product mixture
comprising iso C.sub.n hydrocarbons, normal and iso C.sub.n-
hydrocarbons and normal and iso C.sub.n+ hydrocarbons, and an iso
C.sub.n alkane is converted to a product mixture comprising normal
C.sub.n hydrocarbons, normal and iso C.sub.n- hydrocarbons and
normal and iso C.sub.n+ hydrocarbons. A blend of normal and iso
C.sub.n alkane is converted to a product mixture comprising normal
and iso C.sub.n hydrocarbons, normal and iso C.sub.n- hydrocarbons
and normal and iso C.sub.n+ hydrocarbons, and the highest
concentration of C.sub.n+ hydrocarbons is the C.sub.n+1
hydrocarbon. For example, for a feed of n-pentane, the product
mixture would be isopentane, C.sub.4- hydrocarbons and C.sub.6+
hydrocarbons, and for a feed of isopentane, the product mixture
would be n-pentane, C.sub.4- hydrocarbons and C.sub.6+
hydrocarbons, with the highest concentration being C.sub.6
hydrocarbons for the C.sub.n+ fractions. A feed comprising a blend
of n-pentane and isopentane would produce a product mixture of
n-pentane and isopentane, C.sub.4- hydrocarbons and C.sub.6+
hydrocarbons. The process is particularly useful for conversion of
C.sub.4, C.sub.5, C.sub.6, and C.sub.7 alkanes.
[0057] The liquid catalyst comprises an ionic liquid and a
carbocation promoter. The ionic liquid is in liquid form; unlike
prior art processes, it is not supported on an oxide support. In
addition, the ionic liquids employed herein do not contain Bronsted
acidic organic cations, so the acid concentration within the
present systems is less than prior art processes using ionic
liquids containing Bronsted acidic organic cations. The acid
concentration within the liquid catalyst is less than about 2.5 M,
or less than about 2.25 M, or less than about 2.0 M, or less than
about 1.75 M, or less than about 1.5 M.
[0058] One or more ionic liquids can be used.
[0059] The ionic liquid comprises an organic cation and an anion.
Suitable organic cations include, but are not limited to:
##STR00001##
where R.sup.1-R.sup.21 are independently selected from
C.sub.1-C.sub.20 hydrocarbons, C.sub.1-C.sub.20 hydrocarbon
derivatives, halogens, and H. Suitable hydrocarbons and hydrocarbon
derivatives include saturated and unsaturated hydrocarbons, halogen
substituted and partially substituted hydrocarbons and mixtures
thereof. C.sub.1-C.sub.8 hydrocarbons are particularly
suitable.
[0060] The anion can be derived from halides, sulfates, bisulfates,
nitrates, sulfonates, fluoroalkanesulfonates, and combinations
thereof. The anion is typically derived from metal and nonmetal
halides, such as metal and nonmetal chlorides, bromides, iodides,
fluorides, or combinations thereof. Combinations of halides
include, but are not limited to, mixtures of two or more metal or
nonmetal halides (e.g., AlCl.sub.4.sup.- and BF.sub.4.sup.-), and
mixtures of two or more halides with a single metal or nonmetal
(e.g., AlCl.sub.3Br). 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.-.
[0061] The ionic liquid is combined with one or more carbocation
promoters. In some embodiments, the carbocation promoter is added
to the ionic liquid. In other embodiments, the carbocation promoter
is generated in situ. However, in situ production might not provide
reproducible results if the activity is dependent only on the minor
impurities of the synthetic precursors.
[0062] Suitable carbocation promoters include, but are not limited
to, halo-alkanes, mineral acids alone or combined with alkenes, and
combinations thereof. Suitable halo-alkanes include but are not
limited to 2-chloro-2-methylpropane, 2-chloropropane,
2-chlorobutane, 2-chloro-2-methylbutane, 2-chloropentane,
1-chlorohexane, 3-chloro-3-methylpentane, or combinations thereof.
In some embodiments, the carbocation promoters are not cyclic
alkanes.
[0063] Suitable mineral acids include, but are not limited to, HCl,
HBr, H.sub.2SO.sub.4, and HNO.sub.3. Although HF can also be used,
it is less desirable due to safety issues. If the mineral acid is
not strong enough to protonate off a hydrogen from a C--H bond,
isobutene or another alkene can be added with the mineral acid to
produce the desired carbocation promoter. The mineral acid can be
generated in situ by the addition of a compound that reacts with
the ionic liquid. In situ acid generation can also occur as a
result of reaction with water present in the system. The mineral
acid may also be present as an impurity in the ionic liquid. In
some embodiments, the acid concentration within the liquid catalyst
is less than about 2.5 M, or less than about 2.25 M, or less than
about 2.0 M, or less than about 1.75 M, or less than about 1.5
M.
[0064] 2-chloropropane, and 2-chlorobutane were used successfully
as carbocation promoters. HCl was generated in situ by the addition
of methanol to the ionic liquid, resulting in the partial
degradation of the Al.sub.2Cl.sub.7.sup.- anion with concomitant
formation of HCl. This method was sufficient to catalyze the
disproportionation.
[0065] The molar ratio of the carbocation promoter to the ionic
liquid in the liquid catalyst is typically in the range of about
0:1 to about 3:1, or about 0.1:1 to about 1:1. This relates to
forming the carbocation promoter from the halo-alkane or mineral
acid. This ratio is important relative to the specific type of
anion. For example, if the anion is AlCl.sub.4.sup.-, a reaction is
unlikely to occur or will be poor because the aluminum is fully
coordinated. However, if the anion is Al.sub.2Cl.sub.7.sup.-, there
is some aluminum present that can coordinate to the carbocation
promoter's anion, assisting in generating the carbocation from the
carbocation promoter.
[0066] The mass or volume ratios of liquid catalyst (ionic liquid
and carbocation promoter) to hydrocarbon feed are less than 1:1.
This is desirable because the ionic liquid is an expensive
component in the process. In some embodiments, the mass ratio of
liquid catalyst to hydrocarbon feed is not more than about 0.75:1,
or not more than about 0.7:1, or not more than about 0.65:1, or not
more than about 0.60:1, or not more than about 0.55:1, or not more
than about 0.50:1. In some embodiments, the volume ratio of ionic
liquid to hydrocarbon feed is not more than about 0.8:1, or not
more than about 0.7:1, or not more than about 0.6:1, or not more
than about 0.5:1, or not more than about 0.45:1, or not more than
about 0.4:1, or not more than about 0.35:1, or not more than about
0.3:1, or not more than about 0.25:1.
[0067] The hydrocarbon feed is contacted with the liquid catalyst
at temperatures below the decomposition temperature of the ionic
liquids. The temperature is typically about 300.degree. C. or less,
or about 275.degree. C. or less, or about 250.degree. C. or less,
or about 225.degree. C. or less, or about 200.degree. C. or less,
or about 175.degree. C. or less, or about 150.degree. C. or less,
or about 125.degree. C. or less, or about 100.degree. C. or less,
or about 90.degree. C. or less, or about 80.degree. C. or less, or
about 70.degree. C. or less, or about 60.degree. C. or less, or in
the range of about 0.degree. C. to about 200.degree. C., or about
0.degree. C. to about 175.degree. C., or about 0.degree. C. to
about 150.degree. C., or about 10.degree. C. to about 150.degree.
C., or about 25.degree. C. to about 150.degree. C., or about
30.degree. C. to about 150.degree. C., or about 40.degree. C. to
about 150.degree. C., or about 50.degree. C. to about 150.degree.
C., or about 55.degree. C. to about 150.degree. C.
[0068] The pressure in the reaction zone is typically in the range
of about 0 MPa to about 20.7 MPa. In some embodiments, the pressure
should be sufficient to ensure that the hydrocarbon feed is in a
liquid state. Small amounts of vapor may also be present, but this
should be minimized. In some embodiments, increased amounts of
vapor are acceptable.
[0069] The reaction typically takes places in the presence of a
gas. Suitable gases include, but are not limited to nitrogen,
hydrogen, argon, helium, hydrogen chloride and the like.
[0070] For some hydrocarbons, the residence time in the reaction
zone is generally less than about 10 hr, or less than 7 hr, or less
than 5 hr, or less than 4 hr, or less than 3 hr, or less than 2 hr,
or less than 1 hr. In some embodiments, butanes may react more
slowly than hydrocarbons with higher numbers of carbons.
Significant isomerization of normal C.sub.4 takes place within 1
hr. Substantial amounts of disproportionation of normal C.sub.4 may
take longer in some embodiments. For example, disproportionation
may take at least about 0.5 hr, or at least about 1 hr, or at least
about 2 hr, or at least about 3 hr, or at least about 5 hr, or at
least about 10 hr, or at least about 15 hr, or at least about 20
hr, or at least about 25 hr, or at least about 30 hr, or at least
about 35 hr, or at least about 40 hr, or at least about 45 hr, or
at least about 50 hr.
[0071] The reaction time and conversion are based on the time
needed to reach equilibrium of the initial reaction products, such
as 2-methylpentane and isobutane from the disproportionation of
isopentane. The reaction time is a function of the degree of
mixing, the reaction temperature, the concentration of the
carbocation promoter, the molar ratio of the carbocation promoter
to ionic liquid, and the mass/volume ratio of ionic liquid to
hydrocarbon being reacted. Generally, increasing any of these
conditions will increase the reaction rate. Under some conditions,
greater than 90% conversion is possible.
[0072] The % selectivity for the disproportionation reaction is
defined as: [(sum of the wt % C.sub.n- and C.sub.n+
compounds)/(100-wt % C.sub.n feed)].times.100. For some
embodiments, the % selectivity for the disproportionation reaction
is typically at least about 40%, or at least about 45%, or at least
about 50%, or at least about 55%, or at least about 60%, or at
least about 65%, or at least about 70%, or at least about 75%, or
at least about 80%, or at least about 85%, or at least about 90%,
or at least about 94%.
[0073] For blends, the selectivity for the disproportionation
reaction would be similar as above. For example, for a blend
consisting of 50% isopentane and 50% n-pentane, the % selectivity
for the disproportionation reaction is defined as: [(sum of the wt.
% C.sub.4- and C.sub.6+ compounds)/(100-wt. % feed)].times.100,
where the C.sub.6 feed is taken to be the summed wt. % of
isopentane and n-pentane. A simple equation similar to this may not
be adequate for more complex blends.
[0074] The % selectivity for the isomerization reaction to
isoparaffins (S.sub.iso-isom) is defined as (z(wt. % isoparaffin
C.sub.6))/(100-wt. % C.sub.6 feed).times.100, where z=0 when the
C.sub.n, feed is isoparaffin and z=1 when the C.sub.n, feed is
n-paraffin. The % selectivity for isoparaffin disproportionation is
defined as (wt % isoparaffins of C.sub.n-+wt % isoparaffins
C.sub.n+)/(100-wt % C.sub.n, feed).times.100 (S.sub.iso-disp). The
% selectivity for isoparaffins is defined as (wt. % isoparaffins of
C.sub.n-+wt. % isoparaffins C.sub.6++z(wt. % isoparaffin
C.sub.6))/(100-wt. % C.sub.6 feed).times.100, where z=0 when the
C.sub.n feed is isoparaffin and z=1 when the C.sub.n feed is
n-paraffin (S.sub.isoparaffin); or
S.sub.isoparaffin=S.sub.iso-isom+S.sub.iso-disp. For some
embodiments, the selectivity for isoparaffins is typically at least
about 40%, or at least about 45%, or at least about 50%, or at
least about 55%, or at least about 60%, or at least about 65%, or
at least about 70%, or at least about 75%, or at least about 80%,
or at least about 85%, or at least about 90%.
[0075] For blends, the selectivity for isoparaffins would be
similar as above. For example, for a blend consisting of 50%
isopentane and 50% n-pentane, the % selectivity for the
isoparaffins reaction is defined as: [(sum of the wt. % iC.sub.4
and iC.sub.6+ compounds)/(100-wt. % C.sub.n feed)].times.100, where
the C.sub.6 feed is taken to be the summed wt. % of isopentane and
n-pentane. A simple equation similar to this may not be adequate
for more complex blends.
[0076] The selectivity is highly dependent on the type of feed
used. For example, for iC.sub.5, the selectivity for the
disproportionation reaction typically can be in the range of about
92-94%. However, the selectivity for the disproportionation
reaction for nC.sub.5 is much lower, e.g., in the range of about
67-76% because a substantial amount of isomerization to isopentane
occurs.
[0077] Conversion for the disproportionation and isomerization
reactions is defined as 100-wt % C.sub.n feed. The conversion is
typically at least about 50%, or at least about 55%, or at least
about 60%, or at least about 65%, or at least about 70%, or at
least about 75%, or at least about 80%, or at least about 85%, or
at least about 90%.
[0078] For blends, the conversion would be the same as above. For
example, for a blend consisting of 50% isopentane and 50%
n-pentane, the % conversion is equal to 100-wt % C.sub.n feed,
where the C.sub.n feed taken to be the summed wt % of isopentane
and n-pentane.
[0079] For example, with an iC.sub.5 feed, initially the products
are primarily the isoparaffins of the C.sub.4 and C.sub.6 compounds
along with some nC.sub.5. Because iC.sub.5 is more
thermodynamically preferred, the amount of nC.sub.5 that forms is
relatively small, and the dominating pathway is disproportionation.
Since the kinetic products are isoparaffins, the selectivity for
isoparaffins can be similar to disproportionation. However, the
mixture is not completely at equilibrium, so as the product
continues to react, some of the initially formed isoparaffins of
the disproportionation products begin to convert to their
corresponding n-paraffins. As this occurs, the selectivity for
isoparaffins decreases, but the selectivity for disproportionation
does not.
[0080] With a feed of nC.sub.5, the initial products are again
primarily the isoparaffins of the C.sub.4 and C.sub.6 compounds and
iC.sub.5. Because nC.sub.5 is thermodynamically disfavored, the
amount of iC.sub.5 that forms is substantially greater relative to
the formation of nC5 from the iC5 feed. In this case, significant
amounts of nC.sub.5 are converted to iC.sub.5. Since the initial
products are isoparaffins, the selectivity for isoparaffins remains
high. However, since a significant portion of nC.sub.5 is converted
to iC.sub.5, the selectivity for disproportionation is less than it
was when iC.sub.5 is used. As the reaction progresses, iC.sub.5 and
nC.sub.5 continue to disproportionate and the selectivity for
disproportionation increases during the reaction. Conversely, the
selectivity for isoparaffins decreases as the mixture equilibrates
because the initially formed isoparaffin disproportionation
products convert to their normal isomers.
[0081] With nC.sub.4, the initial product is primarily iC.sub.4.
Small but significant amounts of C.sub.3 and nC.sub.5 and iC.sub.5
form over longer reaction times, e.g., about 2 hr or more, or about
3 hr or more, or about 5 hr or more, or about 10 hr or more, or
about 15 hr or more, about 20 hrs or more, or about 25 hrs or more,
or about 30 hrs or more, or about 35 hrs or more, or about 40 hrs
or more, or about 45 hrs or more, or about 50 hrs or more.
[0082] For butanes, the mass ratio of branched butane to normal
butane (iC.sub.4/nC.sub.4) produced from converted normal butane
feed is typically at least about 0.3:1 in 1 hr. It is typically at
least about 0.5:1, or at least about 0.75:1, or at least about 1:1,
or at least about 1.1:1, or at least about 1.2:1, or at least about
1.3:1, or at least about 1.4:1, or at least about 1.5:1, or at
least about 1.6:1, or at least about 1.7:1, or at least about
1.8:1, or at least about 1.9:1, or at least about 2:1, or at least
about 2.5:1, or at least about 3:1, or at least about 5:1, or at
least about 7.5:1, or at least about 10:1, or at least about
15:1.
[0083] At higher temperatures, the relative concentration of normal
paraffins increases, which ultimately results in decreased
selectivities for isoparaffins relative to lower temperatures.
[0084] Although the reaction will proceed simply by contacting the
hydrocarbon feed and the liquid catalyst, the reaction rate is
generally too slow to be commercially viable. The reaction rate can
be substantially increased by increasing the stirring speed of the
reaction. This indicates that under some conditions the rate of
reaction is mass transfer limited and is not reflective of the true
elementary steps of the reaction. In addition to simply stirring
the reaction mixture, a baffle can be included in the reactor to
aid in obtaining good mixing. The baffle helps to prevent a vortex
from forming in the reactor. The formation of a vortex would reduce
the amount of mixing even in the presence of stirring.
[0085] One embodiment of the process 100 is a continuous-flow
reactor as shown in FIG. 5. Feed 105, including the liquid
hydrocarbon and carbocation promoter (if present), passes over a
drying bed 110 and is continuously introduced to the reactor 115
while simultaneously withdrawing product 120. The liquid catalyst
(or ionic liquid alone) 112 is introduced to the reactor 115. The
carbocation promoter can be added with the hydrocarbon feed, or
with the ionic liquid, or both. The reactor desirably includes a
stirrer 160 to mix the hydrocarbon feed 105 and the liquid
catalyst. The gaseous products 150 can be separated in the reactor
115. The effluent 120 is sent to a settler 125, where the heavier
ionic liquid phase separates as a bottom layer 130. The used ionic
liquid stream 165 can be recycled to the reactor 115 and/or the
regenerator 135. The upper hydrocarbon layer phase 140 is removed
from the settler 125, yielding the liquid product 145. The gaseous
products 170 are separated in settler 125. These gaseous products
170 can be combined with gaseous products 150 which could then be
used as feed in alkylation units (not shown). The used ionic liquid
165 can be regenerated in regenerator 135 to remove deactivated
liquid catalyst so it can be reused. Fresh ionic liquid 155 can be
added to the regenerated ionic liquid stream 175 as needed and sent
to the reactor 115. Fresh ionic liquid can also be added to the
regenerator 135, as needed.
[0086] The ionic liquid can be regenerated in a variety of ways.
The ionic liquid containing the conjunct polymer could be contacted
with a reducing metal (e.g., Al), an inert hydrocarbon (e.g.,
hexane), and hydrogen and heated to about 100.degree. C. The
conjunct polymer will be transferred to the hydrocarbon phase,
allowing for the conjunct polymer to be removed from the ionic
liquid phase. See e.g., U.S. Pat. No. 7,651,970; U.S. Pat. No.
7,825,055; U.S. Pat. No. 7,956,002; US 2007/0142213; US
2007/0249486, each of which is incorporated herein by reference.
Another method involves contacting the ionic liquid containing the
conjunct polymer with a reducing metal (e.g., Al) in the presence
of an inert hydrocarbon (e.g. hexane) and heating to about
100.degree. C. The conjunct polymer will be transferred to the
hydrocarbon phase, allowing for the conjunct polymer to be removed
from the ionic liquid phase. See e.g., U.S. Pat. No. 7,674,739 B2;
US 2007/0249485 A1; US 2010/0147740 A1, each of which is
incorporated herein by reference. Still another method of
regenerating the ionic liquid involves contacting the ionic liquid
containing the conjunct polymer with a reducing metal (e.g., Al),
HCl, and an inert hydrocarbon (e.g. hexane), and heating to about
100.degree. C. The conjunct polymer will be transferred to the
hydrocarbon phase, allowing for the conjunct polymer to be removed
from the IL phase. See e.g., US 2007/0142217, which is incorporated
herein by reference. The ionic liquid can be regenerated by adding
a homogeneous metal hydrogenation catalyst (e.g.,
(PPh.sub.3).sub.3RhCl) to the ionic liquid containing the conjunct
polymer and an inert hydrocarbon (e.g. hexane). Hydrogen would be
introduced, and the conjunct polymer would be reduced and
transferred to the hydrocarbon layer. See e.g., US 2007/0142218,
which is incorporated herein by reference. Another method for
regenerating the ionic liquid involves adding HCl, isobutane, and
an inert hydrocarbon to the ionic liquid containing the conjunct
polymer and heating to about 100.degree. C. The conjunct polymer
would react to form an uncharged complex, which would transfer to
the hydrocarbon phase. See e.g., US 2007/0142216, which is
incorporated herein by reference. The ionic liquid could also be
regenerated by adding a supported metal hydrogenation catalyst
(e.g. Pd/C) to the ionic liquid containing the conjunct polymer and
an inert hydrocarbon (e.g. hexane). Hydrogen would be introduced
and the conjunct polymer would be reduced and transferred to the
hydrocarbon layer. See e.g., US 2007/0142215, which is incorporated
herein by reference. Still another method involves adding a
suitable substrate (e.g. pyridine) to the ionic liquid containing
the conjunct polymer. After a period of time, an inert hydrocarbon
would be added to wash away the liberated conjunct polymer. In
another method, the ionic liquid precursor would be added to the
ionic liquid containing the conjunct polymer followed by an inert
hydrocarbon. After a given time of mixing, the hydrocarbon layer
would be separated, resulting in a regenerated ionic liquid. See,
e.g., US 2007/0142211, which is incorporated herein by reference.
Another method involves adding the ionic liquid containing the
conjunct polymer to an electrochemical cell containing two aluminum
electrodes and an inert hydrocarbon. A voltage would be applied and
the current measured to determine the extent of reduction. After a
given time, the inert hydrocarbon would be separated, resulting in
a regenerated ionic liquid. See, e.g., US 2010/0130804, which is
incorporated herein by reference.
[0087] The contacting step may be practiced in laboratory scale
experiments through full scale commercial operations. The process
may be operated in batch, continuous, or semi-continuous mode. The
contacting step can take place in various ways, with both
concurrent and co-current flow processes being suitable. The order
of addition of the reactants is not critical. For example, the
reactants can be added individually, or some reactants may be
combined or mixed before being combined or mixed with other
reactants.
[0088] Disproportionation of nC.sub.5 and iC.sub.5 has also been
achieved at temperatures as low as 45.degree. C. The reaction was
faster with iC.sub.5 than with nC.sub.5. Gas chromatograph (GC)
analysis revealed that the primary compounds formed were
isoparaffins using the analytical method ASTM UOP690-99; very few
C.sub.3- hydrocarbons formed. The products of the reaction for
n-C.sub.5 were broadly divided into the following categories:
C.sub.3-, n-C.sub.4, iC.sub.4, iC.sub.5, C.sub.6 paraffins
(C.sub.6P) and C.sub.7+ hydrocarbons. The products of the reaction
for iso C.sub.5 were broadly divided into the following categories:
C.sub.3-, n-C.sub.4, iC.sub.4, nC.sub.5, C.sub.6 paraffins
(C.sub.6P) and C.sub.7+ hydrocarbons. The selectivity to these
products was constant over a wide range of isopentane conversions.
However, at higher conversions, the selectivity to C.sub.6
paraffins decreased, while the selectivity to iC.sub.4 and C.sub.7+
hydrocarbons increased, which is likely the result of secondary
disproportionation-type reactions. An analysis of both the
headspace and the liquid phase revealed that C.sub.3- hydrocarbons
form in small amounts.
[0089] In some places, demand for iC.sub.4 exceeds supply, and
disproportionation could help alleviate this problem.
[0090] For iso-pentane conversion, the selectivity to the various
products (product selectivity being defined as [wt %
compound/(100-wt % C.sub.n, feed)]*100) was nearly constant up to
about 52% conversion at 55.degree. C. Higher isopentane conversions
resulted in decreased selectivity to C.sub.6 paraffins and higher
selectivities to iC.sub.4 and C.sub.7+ hydrocarbons, which was
likely the result of secondary disproportionation-type
reactions.
[0091] With iso-pentane conversion, the extent of isomerization to
n-pentane was minimal, but observable, because the reactant was
already present in the more thermodynamically favored state. It was
consistently observed that the selectivity for isomerization of
isopentane to n-pentane centered around 7%, regardless of the %
conversion of isopentane.
[0092] A significant stir rate dependence on the reaction rate was
observed. Under the conditions used, the benefits of increased
mixing began to taper off at stir rates greater than 700 rpm, which
indicates that much of the kinetics of the reaction below 700 rpm
is mass transfer limited.
[0093] The other products that form during the disproportionation
reaction of isopentane were mainly isobutane and C.sub.6+
isoparaffins. The selectivity to these products was also nearly
constant with isopentane conversion. However, at higher
conversions, the selectivity to the C.sub.6 paraffins decreased,
while there was a concomitant increase in selectivity for isobutane
and C.sub.7+ isoparaffins. It is important to note that very little
C.sub.3- formed in the reactions at 55.degree. C. as revealed by a
headspace analysis and by the analytical method ASTM UOP980-07.
[0094] Under similar conditions (e.g., volume of ionic liquid,
temperature, stir rate, etc.), the rate of nC.sub.5 conversion is
dependent on the type of ionic liquid used, as the same reaction
proceeds at a much greater conversion rate in
[1-butyl-1-methylpyrrolidinium][Al.sub.2Cl.sub.7] than in
[tributyl(hexyl)phosphonium][Al.sub.2Cl.sub.6Br]([(.sup.nBu).sub.3P(Hex)]-
[Al.sub.2Cl.sub.6Br]). Despite the increase in reactivity, the
selectivities for the products were similar to what was observed
with the ionic liquid
[(.sup.nBu).sub.3P(Hex)][Al.sub.2Cl.sub.6Br].
[0095] Isomerization and disproportionation of n-hexane has been
found to occur at temperatures as low as 45.degree. C. in several
different ionic liquids (e.g.,
[(.sup.nBu).sub.3P(Hex)][Al.sub.2Cl.sub.6Br],
[1-butyl-1-methylpyrrolidinium][Al.sub.2Cl.sub.7],
[1-butyl-3-methylimidazolium][Al.sub.2Cl.sub.7] and
trihexyl(tetradecyl)phosphonium heptachloroaluminate
([(n-Hex).sub.3P(tetradecyl)][Al.sub.2Cl.sub.7])). The promoter
used in all of these reactions, except for
[1-butyl-3-methylimidazolium][Al.sub.2Cl.sub.7], was
2-chloro-2-methylpropane, which served to generate the active
tert-butyl cation. Trace amounts of water or HCl present in
[1-butyl-3-methylimidazolium][Al.sub.2Cl.sub.7] was sufficient for
the catalysis to occur. A wide range of compounds were formed,
including naphthenes, n-paraffins, isoparaffins and even some
aromatic complexes, but the major products are paraffins.
[0096] Increasing the concentration of 2-chloro-2-methylpropane
increased the conversion, and the yield for the higher and lighter
molecular weight complexes. The major light components formed were
identified by headspace analysis as iC.sub.4, iC.sub.5,
2-methylpentane and unreacted nC.sub.6. However, it did little to
change the selectivity for isomerization. Similarly, increasing the
reaction time, temperature, and ratio of mass of ionic liquid to
mass of hydrocarbon feed increased the overall conversion. It is
desirable to minimize the amount of ionic liquid used due to the
cost and potential increase in the amount of feed processed per
unit ionic liquid.
EXAMPLES
Example 1
Experimental Set Up
[0097] Unless otherwise indicated, the set-up included a 300 mL
Hastelloy C autoclave equipped with a Hastelloy C mechanical
stirrer, Hastelloy C baffle, pressure gauge, Hastelloy C
thermowell, thermocouple, Hastelloy C dipleg that was connected to
the autoclave using a stainless steel nut and stainless steel
connector, gold faced inconel rupture disc and stainless steel
valves to introduce the feed and withdraw a liquid aliquot for GC
analysis. The rupture disc vented to a knock out pot. The house
nitrogen passed through a pressure regulator to a high surface
sodium column and was then split: feeding to the charger for feed
introduction or to a line for various uses (i.e.,
2-methyl-2-chloropropane/C.sub.5P introduction). The dipleg was
constructed such that the height positions it in the paraffin
layer. Upon opening the valve, the withdrawn paraffin layer passed
through a column of silica, to the GC valve and then through a
metering valve into a waste container. The reaction mixture was
analyzed using the GC method described in ASTM UOP690-99. All peaks
were integrated with a response factor of 1. Due to the presence of
LPG in the liquid sample and sampling from a heated autoclave, the
concentration of LPG present within the sample can be understated
from the true values. Despite this potential deviation, the
conclusions herein remain valid. The S.sub.isoparaffin was
calculated by summing the wt % contribution of the C4-C8
isoparaffins that are separable using the ASTM UOP690-99 method,
but does not include the contributions from the C9+ fraction.
Consequently, these values represent lower limits for the
selectivity. Similarly, the S.sub.iso-disp were determined using
this analytical method and is also a lower limit. The RVP was
calculated on the C.sub.5+ fraction as the vapor pressure for the
system when the vapor:liquid ratio is 4:1 by volume using the Peng
Robinson fluid properties model. The RON was calculated on the
C.sub.5+ fraction with linear volumetric blending and the RON
values used for this calculation were based on the values listed in
Phillips 66 Reference Data for Hydrocarbons and Petro-Sulfur
Compounds, Bulletin No. 521.
Example 2
Synthesis of [(.sup.nBu).sub.3P(Hex)][Al.sub.2Cl.sub.6Br]
[0098] An oven-dried round bottom flask was charged with
[(.sup.nBu).sub.3P(Hex)][Br]. The material was attached to a rotary
evaporator and dried under vacuum at 110.degree. C. for at least 14
h. The dried [(.sup.nBu).sub.3P(Hex)][Br] was immediately brought
into a nitrogen glovebox and stored there. A synthesis was achieved
by massing 17.589 g (47.88 mmol) of [(.sup.nBu).sub.3P(Hex)][Br]
into an oven-dried flask equipped with a stir bar in the nitrogen
glovebox. To this was added 12.775 g (95.81 mmol) of AlCl.sub.3 at
ambient temperature. The mixture was stirred and the solids slowly
reacted over the course of one week to produce a homogenous
pale-yellow liquid.
Example 3
Synthesis of [1-butyl-1-methylpyrrolidinium][Al.sub.2Cl.sub.7]
[0099] An oven-dried round bottom flask was charged with
[1-butyl-1-methylpyrrolidinium][Cl]. The material was attached to a
rotary evaporator, dried under vacuum at 110.degree. C. for at
least 14 h, and then sealed under vacuum with a connecting adapter.
The dried [1-butyl-1-methylpyrrolidinium][Cl] was immediately
brought into a nitrogen glovebox and stored there. A synthesis was
achieved by massing 57.14 g (322 mmol) of
[1-butyl-1-methylpyrrolidinium][Cl] into an oven-dried flask
equipped with a stir bar in the nitrogen glovebox. To this was
added 83.93 g (629 mmol) of AlCl.sub.3 at ambient temperature and
the mixture stirred. The solids reacted to produce a homogenous
liquid.
Example 4
Synthesis of with
[1-butyl-3-methylimidazolium][Al.sub.2Cl.sub.7]
[0100] An oven-dried round bottom flask was charged with
1-butyl-3-methylimidazolium chloride. The material was attached to
a rotary evaporator, dried under vacuum at 110.degree. C. for at
least 14 h and then sealed under vacuum with a connecting adapter.
Afterwards, the dried 1-butyl-3-methylimidazolium chloride was
stored in a nitrogen glovebox. A synthesis was achieved by massing
50.04 g (286 mmol) of 1-butyl-3-methylimidazolium chloride into an
oven-dried flask equipped with a stir bar in the nitrogen glovebox.
To this was added 76.40 g (573 mmol) of AlCl.sub.3 at ambient
temperature, and the mixture stirred. The solids react to produce a
homogenous liquid.
Example 5
iC.sub.5--Stir Rate Effect at 350 rpm with
[(.sup.nBu).sub.3P(Hex)][Al.sub.2Cl.sub.6Br]
[0101] A 300 mL stainless steel autoclave, stainless steel baffle,
and 75 mL stainless steel sample cylinder were dried in a
120.degree. C. oven for at least 8 h. The dried autoclave and
sample cylinder were brought into a nitrogen glovebox and allowed
to cool to ambient temperature. The autoclave was charged with
50.39 g of [(.sup.nBu).sub.3P(Hex)][Al.sub.2Cl.sub.6Br], and the
autoclave head was attached. To the sample cylinder, 1.451 g of
2-chloro-2-methylpropane, which had previously been dried over
activated sieves, was added. The sample cylinder was closed under
nitrogen, and both the autoclave and sample cylinder were removed
from the glovebox. The autoclave was charged with 119 g of
iso-pentane from a pressurized feed charger without displacing the
nitrogen present in the autoclave. The iso-pentane passed over a
high surface sodium column to remove any water before entering the
autoclave. Similarly, the nitrogen used to pressurize the charger
and for all other work passed over a separate high surface sodium
column. The sample cylinder was charged with 18 g of iso-pentane
using the same method described above and attached to the
autoclave. The autoclave was heated to 55.degree. C., and the
2-chloro-2-methylpropane/iso-pentane solution in the sample
cylinder was added with an over-pressure of nitrogen. After
complete addition, the initial pressure in the autoclave was 145
psi (1 MPa), and the autoclave was then set to stir at 350 rpm. The
reaction was monitored periodically by GC. In order to analyze the
paraffinic layer, the stirring was stopped, and the product was
allowed to settle for 5 minutes. An aliquot was sampled directly
from the autoclave by opening a valve from the autoclave, passing
the paraffinic layer through a SiO.sub.2 column, and then passing
it directly into a GC sample loop. The mass ratio of liquid
catalyst to iso-pentane was 0.38 and the volume ratio was 0.19. The
mass rate of reaction was 38, and the volume rate was 75 after 1.4
h. The results of the run are shown in Tables 1 and 2.
TABLE-US-00001 TABLE 1 Disproportionation and Isomerization of
iso-Pentane at 55.degree. C., 350 rpm, wt % of reaction mixture t %
S. (h) Conv. C3- iC4 nC4 iC5 nC5 C6P C7+ i/n Disp.
S.sub.isoparaffin 1.4 20 0.00 7.20 0.02 80.46 1.31 6.84 4.13 11.2
93 82 2.7 28 0.01 10.38 0.04 72.48 2.04 9.93 5.09 9.94 92 84 4.4 36
0.01 13.64 0.07 64.29 2.70 12.75 6.54 9.48 92 85
TABLE-US-00002 TABLE 2 Time (h) 1.4 2.7 4.4 NA Wt. % feed C3P 0.00
0.01 0.01 0.00 C4P 7.22 10.43 13.71 0.00 C5P 81.77 74.53 66.99
99.86 C6P 6.84 9.94 12.74 0.00 C7P 1.67 2.47 3.32 0.00 C8P 0.52
0.73 1.00 0.00 C9+ 1.56 1.51 1.80 0.00 C5N 0.00 0.00 0.00 0.00 C6N
0.00 0.00 0.00 0.00 C7N 0.01 0.00 0.00 0.00 C8N 0.34 0.34 0.38 0.00
C6A 0.00 0.00 0.00 0.00 C7A 0.00 0.00 0.00 0.00 C8A 0.05 0.05 0.05
0.00 nC4-nC5 0.00 0.00 0.00 0.14 unknowns mmoles (based on wt. %)
C3P 0 0 0 0 C4P 124 179 236 0 C5P 1133 1033 928 1384 C6P 79 115 148
0 C7P 17 25 33 0 C8P 5 6 9 0 C9+ 12 12 14 0 C5N 0 0 0 0 C6N 0 0 0 0
C7N 0 0 0 0 C8N 3 3 3 0 C6A 0 0 0 0 C7A 0 0 0 0 C8A 0 0 1 0 nC4-nC5
0 0 0 2 unknowns Total mmoles 1374 1374 1372 1386
Example 6
iC5--Stir Rate Effect at 700 rpm with
[(.sup.nBu).sub.3P(Hex)][Al.sub.2Cl.sub.6Br]
[0102] A 300 mL stainless steel autoclave, stainless steel baffle,
and 75 mL stainless steel sample cylinder were dried in a
120.degree. C. oven for at least 8 h. The dried autoclave and
sample cylinder were brought into a nitrogen glovebox and allowed
to cool to ambient temperature. The autoclave was charged with
50.352 g of [(.sup.nBu).sub.3P(Hex)][Al.sub.2Cl.sub.6Br], and the
autoclave head was attached. To the sample cylinder, 1.453 g of
2-chloro-2-methylpropane, which had previously been dried over
activated sieves, was added. The sample cylinder was closed under
nitrogen, and both the autoclave and sample cylinder were removed
from the glovebox. The autoclave was charged with 112 g of
iso-pentane from a pressurized feed charger without displacing the
nitrogen present in the autoclave. The iso-pentane passed over a
high surface sodium column to remove any water before entering the
autoclave. Similarly, the nitrogen used to pressurize the charger
and for all other work passed over a separate high surface sodium
column. The sample cylinder was charged with 15 g of iso-pentane
using the same method described above and attached to the
autoclave. The autoclave was heated to 55.degree. C., and the
2-chloro-2-methylpropane/iso-pentane solution in the sample
cylinder was added with an over-pressure of nitrogen. After
complete addition, the initial pressure in the autoclave was 115
psi (0.793 MPa), and the autoclave was then set to stir at 700 rpm.
The reaction was monitored periodically by GC. In order to analyze
the paraffinic layer, the stirring was stopped, and the product was
allowed to settle for 5 minutes. An aliquot was sampled directly
from the autoclave by opening a valve from the autoclave, passing
the paraffinic layer through a SiO.sub.2 column, and then passing
it directly into a GC sample loop. The mass ratio of liquid
catalyst to iso-pentane was 0.40 and the volume ratio was 0.20. The
mass rate of reaction was 47, and the volume rate was 93 after 1.5
h. The results of the run are shown in Tables 3 and 4.
TABLE-US-00003 TABLE 3 Disproportionation and Isomerization of
iso-Pentane at 55.degree. C., 700 rpm, wt % of reaction mixture t %
S. (h) Conv. C3- iC4 nC4 iC5 nC5 C6P C7+ i/n Disp.
S.sub.isoparaffin 1.5 28 0.02 10.35 0.04 72.07 1.94 9.83 5.74 10.5
93 83 2.7 39 0.02 14.84 0.10 61.22 2.82 13.35 7.65 9.5 93 84 4.4 52
0.03 20.18 0.18 47.98 3.66 16.71 11.25 9.1 93 84
TABLE-US-00004 TABLE 4 Time (h) 1.5 2.7 4.4 NA Wt. % feed C3P 0.02
0.02 0.03 0.00 C4P 10.39 14.93 20.35 0.00 C5P 74.02 64.05 51.64
99.86 C6P 9.83 13.34 16.71 0.00 C7P 2.55 3.79 5.53 0.00 C8P 0.82
1.25 1.99 0.00 C9+ 1.99 2.17 3.13 0.00 C5N 0.00 0.00 0.00 0.00 C6N
0.00 0.00 0.00 0.00 C7N 0.00 0.01 0.01 0.00 C8N 0.33 0.37 0.51 0.00
C6A 0.00 0.00 0.00 0.00 C7A 0.00 0.00 0.01 0.00 C8A 0.06 0.06 0.09
0.00 nC4-nC5 0.00 0.00 0.00 0.14 unknowns mmoles (based on wt. %)
C3P 0 0 1 0 C4P 179 257 350 0 C5P 1026 888 716 1384 C6P 114 155 194
0 C7P 25 38 55 0 C8P 7 11 17 0 C9+ 16 17 24 0 C5N 0 0 0 0 C6N 0 0 0
0 C7N 0 0 0 0 C8N 3 3 5 0 C6A 0 0 0 0 C7A 0 0 0 0 C8A 1 1 1 0
nC4-nC5 0 0 0 2 unknowns Total mmoles 1371 1370 1363 1386
Example 7
iC5--Stir Rate Effect at 1700 rpm with
[(.sup.nBu).sub.3P(Hex)][Al.sub.2Cl.sub.6Br]
[0103] A 300 mL stainless steel autoclave, stainless steel baffle,
and 75 mL stainless steel sample cylinder were dried in a
120.degree. C. oven for at least 8 h. The dried autoclave and
sample cylinder were brought into a nitrogen glovebox and allowed
to cool to ambient temperature. The autoclave was charged with
50.398 g of [(.sup.nBu).sub.3P(Hex)][Al.sub.2Cl.sub.6Br], and the
autoclave head was attached. To the sample cylinder 1.453 g of
2-chloro-2-methylpropane, which had previously been dried over
activated sieves, was added. The sample cylinder was closed under
nitrogen, and both the autoclave and sample cylinder were removed
from the glovebox. The autoclave was charged with 106 g of
iso-pentane from a pressurized feed charger without displacing the
nitrogen present in the autoclave. The iso-pentane passed over a
high surface sodium column to remove any water before entering the
autoclave. Similarly, the nitrogen used to pressurize the charger
and for all other work passed over a separate high surface sodium
column. The sample cylinder was charged with 23 g of iso-pentane
using the same method described above and attached to the
autoclave. The autoclave was heated to 55.degree. C., and the
2-chloro-2-methylpropane/iso-pentane solution in the sample
cylinder was added with an over-pressure of nitrogen. After
complete addition, the initial pressure in the autoclave was 139
psi (0.958 MPa), and the autoclave was set to stir at 1700 rpm. The
reaction was monitored periodically by GC. In order to analyze the
paraffinic layer, the stirring was stopped, and the product was
allowed to settle for 5 minutes. An aliquot was sampled directly
from the autoclave by opening a valve from the autoclave, passing
the paraffinic layer through a SiO.sub.2 column, and then passing
it directly into a GC sample loop. The mass ratio of liquid
catalyst to iso-pentane was 0.40 and the volume ratio was 0.20. The
mass rate of reaction was 41, and the volume rate was 82 after 2.5
h. The results of the run are shown in Tables 5 and 6.
TABLE-US-00005 TABLE 5 Disproportionation and Isomerization of
iso-Pentane at 55.degree. C., 1700 rpm, wt % of reaction mixture t
% S. (h) Conv. C3- iC4 nC4 iC5 nC5 C6P C7+ i/n Disp.
S.sub.isoparaffin 2.5 41 0.01 15.70 0.13 58.64 2.94 14.48 8.09 9.6
93 84 3.7 49 0.02 19.55 0.19 50.66 3.51 16.73 9.34 9.3 93 85
TABLE-US-00006 TABLE 6 Time (h) 2.5 3.7 NA Wt. % feed C3P 0.01 0.02
0.00 C4P 15.83 19.74 0.00 C5P 61.58 54.17 99.86 C6P 14.48 16.73
0.00 C7P 4.06 4.97 0.00 C8P 1.31 1.59 0.00 C9+ 2.30 2.33 0.00 C5N
0.00 0.00 0.00 C6N 0.00 0.00 0.00 C7N 0.01 0.00 0.00 C8N 0.36 0.39
0.00 C6A 0.00 0.00 0.00 C7A 0.00 0.01 0.00 C8A 0.06 0.07 0.00
nC4-nC5 0.00 0.00 0.14 unknowns mmoles (based on wt. %) C3P 0 0 0
C4P 272 340 0 C5P 854 751 1384 C6P 168 194 0 C7P 41 50 0 C8P 11 14
0 C9+ 18 18 0 C5N 0 0 0 C6N 0 0 0 C7N 0 0 0 C8N 3 3 0 C6A 0 0 0 C7A
0 0 0 C8A 1 1 0 nC4-nC5 0 0 2 unknowns Total mmoles 1368 1371
1386
Example 8
iC5--Stir Rate at 700 rpm with
[(.sup.nBu).sub.3P(Hex)][Al.sub.2Cl.sub.6Br] in Hastelloy C
Autoclave at 55.degree. C.
[0104] A 300 mL Hastelloy C autoclave, Hastelloy C baffle, and 75
mL stainless steel sample cylinder were dried in a 120.degree. C.
oven for at least 8 h. The dried autoclave and sample cylinder were
brought into a nitrogen glovebox and allowed to cool to ambient
temperature. The autoclave was charged with 50.416 g of
[(.sup.nBu).sub.3P(Hex)][Al.sub.2Cl.sub.6Br], and the autoclave
head was attached. To the sample cylinder 1.422 g of
2-chloro-2-methylpropane, which had previously been dried over
activated sieves, was added. The sample cylinder was closed under
nitrogen, and both the autoclave and sample cylinder were removed
from the glovebox. The autoclave was charged with 114 g of
iso-pentane from a pressurized feed charger without displacing the
nitrogen present in the autoclave. The iso-pentane passed over a
high surface sodium column to remove any water before entering the
autoclave. Similarly, the nitrogen used to pressurize the charger
and for all other work passed over a separate high surface sodium
column. The sample cylinder was charged with 16 g of iso-pentane
using the same method described above and attached to the
autoclave. The autoclave was heated to 55.degree. C., and the
2-chloro-2-methylpropane/iso-pentane solution in the sample
cylinder was added with an over-pressure of nitrogen. After
complete addition, the initial pressure in the autoclave was 140
psi (0.965 MPa), and the autoclave was set to stir at 700 rpm. The
reaction was monitored periodically by GC. In order to analyze the
paraffinic layer, the stirring was stopped, and the product was
allowed to settle for 5 minutes. An aliquot was sampled directly
from the autoclave by opening a valve from the autoclave, passing
the paraffinic layer through a SiO.sub.2 column, and then passing
it directly into a GC sample loop. The mass ratio of liquid
catalyst to iso-pentane was 0.40 and the volume ratio was 0.20. The
mass rate of reaction was 70, and the volume rate was 140 after 0.5
h. The results of the run are shown in Tables 7 and 8.
TABLE-US-00007 TABLE 7 Disproportionation and Isomerization of
iso-Pentane at 55.degree. C., 700 rpm, Hastelloy C autoclave, wt. %
of reaction mixture t % S. (h) Conv. C3- iC4 nC4 iC5 nC5 C6P C7+
i/n Disp. S.sub.isoparaffin 0.5 14 0.00 5.04 0.01 85.85 0.94 4.98
3.16 11.4 93 82 2.8 38 0.14 14.04 0.11 62.48 3.13 12.89 7.08 8.1 92
83 4.5 54 0.03 20.70 0.25 46.32 4.41 16.82 11.45 7.6 92 82
TABLE-US-00008 TABLE 8 Time (h) 0.5 2.8 4.5 NA Wt. % feed C3P 0.00
0.14 0.03 0.00 C4P 5.05 14.16 20.94 0.00 C5P 86.79 65.61 50.73
99.86 C6P 4.99 12.88 16.83 0.00 C7P 1.19 3.60 5.73 0.00 C8P 0.38
1.15 2.05 0.00 C9+ 1.30 2.07 3.08 0.00 C5N 0.00 0.00 0.00 0.00 C6N
0.00 0.00 0.00 0.00 C7N 0.00 0.01 0.01 0.00 C8N 0.25 0.33 0.50 0.00
C6A 0.00 0.00 0.00 0.00 C7A 0.00 0.00 0.01 0.00 C8A 0.02 0.03 0.05
0.00 nC4-nC5 0.00 0.00 0.00 0.14 unknowns mmoles (based on wt. %)
C3P 0 3 1 0 C4P 87 244 360 0 C5P 1203 909 703 1384 C6P 58 150 195 0
C7P 12 36 57 0 C8P 3 10 18 0 C9+ 10 16 24 0 C5N 0 0 0 0 C6N 0 0 0 0
C7N 0 0 0 0 C8N 2 3 4 0 C6A 0 0 0 0 C7A 0 0 0 0 C8A 0 0 1 0 nC4-nC5
0 0 0 2 unknowns Total mmoles 1375 1371 1364 1386
Example 9
iC5--Stir Rate at 700 rpm with
[1-Butyl-1-methylimidazolium][Al.sub.2Cl.sub.7] at 55.degree. C. in
a Hastelloy C Autoclave
[0105] A 300 mL Hastelloy C autoclave, Hastelloy C baffle, and 75
mL stainless steel sample cylinder were dried in a 120.degree. C.
oven for at least 8 h. The dried autoclave and sample cylinder were
brought into a nitrogen glovebox and allowed to cool to ambient
temperature. The autoclave was charged with 55.310 g of
[1-butyl-1-methylimidazolium][Al.sub.2Cl.sub.7], and the autoclave
head was attached. To the sample cylinder 2.311 g of
2-chloro-2-methylpropane, which had previously been dried over
activated sieves, was added. The sample cylinder was closed under
nitrogen, and both the autoclave and sample cylinder were removed
from the glovebox. The autoclave was charged with 111 g of
iso-pentane from a pressurized feed charger without displacing the
nitrogen present in the autoclave. The iso-pentane passed over a
high surface sodium column to remove any water before entering the
autoclave. Similarly, the nitrogen used to pressurize the charger
and for all other work passed over a separate high surface sodium
column. The sample cylinder was charged with 28 g of iso-pentane
using the same method described above and attached to the
autoclave. The autoclave was heated to 55.degree. C., and the
2-chloro-2-methylpropane/iso-pentane solution in the sample
cylinder was added with an over-pressure of nitrogen. After
complete addition, the initial pressure in the autoclave was 150
psi (1.034 MPa), and the autoclave was set to stir at 700 rpm. The
reaction was monitored periodically by GC. In order to analyze the
paraffinic layer, the stirring was stopped, and the product was
allowed to settle for 5 minutes. An aliquot was sampled directly
from the autoclave by opening a valve from the autoclave, passing
the paraffinic layer through a SiO.sub.2 column, and then passing
it directly into a GC sample loop. The mass ratio of liquid
catalyst to iso-pentane was 0.41 and the volume ratio was 0.20. The
mass rate of reaction was 150, and the volume rate was 310 after
0.6 h. The results of the run are shown in Tables 9 and 10.
TABLE-US-00009 TABLE 9 Disproportionation and Isomerization of
iso-Pentane at 55.degree. C., 700 rpm, with
[1-butyl-3-methylimidazolium][Al.sub.2Cl.sub.7] in a Hastelloy C
autoclave, wt. % of reaction mixture t % S. (h) Conv. C3- iC4 nC4
iC5 nC5 C6P C7+ i/n Disp. S.sub.isoparaffin 0.6 37 0.01 13.86 0.08
62.83 3.11 11.50 8.59 8.2 92 80 1.7 69 0.04 27.55 0.56 31.04 5.47
18.18 17.15 6.9 92 80 2.9 75 0.07 31.33 1.10 24.52 5.47 18.13 19.38
6.6 93 79 4.5 76 0.09 32.31 1.56 23.41 5.34 18.37 18.90 6.4 93
80
TABLE-US-00010 TABLE 10 Time (h) 0.6 1.7 2.9 4.5 NA Wt. % feed C3P
0.01 0.04 0.07 0.09 0.00 C4P 13.95 28.12 32.44 33.88 0.00 C5P 65.94
36.51 29.98 28.75 99.86 C6P 11.50 18.17 18.12 18.38 0.00 C7P 3.68
7.80 8.61 8.65 0.00 C8P 1.37 3.36 4.18 4.25 0.00 C9+ 3.01 5.09 5.43
5.09 0.00 C5N 0.00 0.00 0.00 0.00 0.00 C6N 0.00 0.00 0.00 0.00 0.00
C7N 0.01 0.01 0.01 0.01 0.00 C8N 0.45 0.84 0.93 0.86 0.00 C6A 0.00
0.00 0.00 0.00 0.00 C7A 0.00 0.03 0.04 0.04 0.00 C8A 0.08 0.06 0.23
0.06 0.00 nC4-nC5 0.00 0.00 0.00 0.00 0.14 unknowns mmoles (based
on wt. %) C3P 0 1 2 2 0 C4P 240 484 558 583 0 C5P 914 506 416 398
1384 C6P 133 211 210 213 0 C7P 37 78 86 86 0 C8P 12 29 37 37 0 C9+
23 40 42 40 0 C5N 0 0 0 0 0 C6N 0 0 0 0 0 C7N 0 0 0 0 0 C8N 4 7 8 8
0 C6A 0 0 0 0 0 C7A 0 0 0 0 0 C8A 1 1 2 1 0 nC4-nC5 0 0 0 0 2
unknowns Total mmoles 1365 1357 1361 1368 1386
Example 10
iC5 [(.sup.nBu).sub.3P(Hex)][Al.sub.2Cl.sub.6Br] in Hastelloy C
Autoclave at 95.degree. C.
[0106] A 300 mL Hastelloy C autoclave, Hastelloy C baffle, and 75
mL stainless steel sample cylinder were dried in a 120.degree. C.
oven for at least 8 h. The dried autoclave and sample cylinder were
brought into a nitrogen glovebox and allowed to cool to ambient
temperature. The autoclave was charged with 50.419 g of
[(.sup.nBu).sub.3P(Hex)][Al.sub.2Cl.sub.6Br], and the autoclave
head was attached. To the sample cylinder 3.680 g of
2-chloro-2-methylpropane, which had previously been dried over
activated sieves, was added. The sample cylinder was closed under
nitrogen, and both the autoclave and sample cylinder were removed
from the glovebox. The autoclave was charged with 102 g of
iso-pentane from a pressurized feed charger without displacing the
nitrogen present in the autoclave. The iso-pentane passed over a
high surface sodium column to remove any water before entering the
autoclave. Similarly, the nitrogen used to pressurize the charger
and for all other work passed over a separate high surface sodium
column. The sample cylinder was charged with 15 g of iso-pentane
using the same method described above and then attached to the
autoclave. The autoclave was heated to 95.degree. C., and the
2-chloro-2-methylpropane/iso-pentane solution in the sample
cylinder was added with an over-pressure of nitrogen. After
complete addition, the initial pressure in the autoclave was 165
psi (1.138 MPa), and the autoclave was set to stir at 1700 rpm. The
reaction was monitored periodically by GC. In order to analyze the
paraffinic layer, the stirring was stopped, and the product was
allowed to settle for 5 minutes. An aliquot was sampled directly
from the autoclave by opening a valve from the autoclave, passing
the paraffinic layer through a SiO.sub.2 column, and then passing
it directly into a GC sample loop. The mass ratio of liquid
catalyst to iso-pentane was 0.46 and the volume ratio was 0.23. The
mass rate of reaction was 260, and the volume rate was 520 after
0.6 h. The results of the run are shown in Tables 11 and 12.
TABLE-US-00011 TABLE 11 Disproportionation and Isomerization of
iso-Pentane at 95.degree. C., wt % of reaction mixture % S. RVP t
(h) Conv. C3- iC4 nC4 iC5 nC5 C6P C7+ i/n Disp. S.sub.isoparaffin
RON (psi) 0.6 72 0.37 27.78 1.72 28.32 4.2 16.21 21.36 6.3 94 73
80.0 12.5 1.8 76 0.82 31.73 3.91 23.66 5.4 17.15 17.29 4.6 93 76
77.6 12.3 3.1 77 1.05 31.50 5.12 23.14 5.71 17.1 16.38 4.0 92 74 ND
ND 4.6 77 1.21 31.56 6.14 22.79 5.90 16.91 15.42 3.7 92 73 ND
ND
TABLE-US-00012 TABLE 12 Time (h) 0.6 1.8 3.1 4.6 NA Wt. % feed C3P
0.37 0.82 1.05 1.21 0.00 C4P 29.50 35.64 36.62 37.70 0.00 C5P 32.51
29.06 28.85 28.69 99.86 C6P 16.22 17.16 17.10 16.91 0.00 C7P 7.66
8.19 7.96 7.56 0.00 C8P 3.42 3.88 3.79 3.57 0.00 C9+ 9.74 4.63 4.04
3.81 0.00 C5N 0.00 0.00 0.00 0.00 0.00 C6N 0.00 0.00 0.00 0.00 0.00
C7N 0.01 0.02 0.02 0.02 0.00 C8N 0.51 0.56 0.53 0.48 0.00 C6A 0.00
0.00 0.00 0.00 0.00 C7A 0.04 0.04 0.04 0.03 0.00 C8A 0.01 0.02 0.02
0.02 0.00 nC4-nC5 0.00 0.00 0.00 0.00 0.14 unknowns mmoles (based
on wt. %) C3P 8 19 24 27 0 C4P 508 613 630 649 0 C5P 451 403 400
398 1384 C6P 188 199 198 196 0 C7P 76 82 79 75 0 C8P 30 34 33 31 0
C9+ 76 36 31 30 0 C5N 0 0 0 0 0 C6N 0 0 0 0 0 C7N 0 0 0 0 0 C8N 5 5
5 4 0 C6A 0 0 0 0 0 C7A 0 0 0 0 0 C8A 0 0 0 0 0 nC4-nC5 0 0 0 0 2
unknowns Total mmoles 1343 1391 1402 1411 1386
Example 11
nC5 with [(.sup.nBu).sub.3P(Hex)][Al.sub.2Cl.sub.6Br] at 95.degree.
C. in a Hastelloy C Autoclave
[0107] A 300 mL Hastelloy C autoclave, Hastelloy C baffle, and 75
mL stainless steel sample cylinder were dried in a 120.degree. C.
oven for at least 8 h. The dried autoclave and sample cylinder were
brought into a nitrogen glovebox and allowed to cool to ambient
temperature. The autoclave was charged with 50.409 g of
[(.sup.nBu).sub.3P(Hex)][Al.sub.2Cl.sub.6Br], and the autoclave
head was attached. To the sample cylinder 3.679 g of
2-chloro-2-methylpropane, which had previously been dried over
activated sieves, was added. The sample cylinder was closed under
nitrogen, and both the autoclave and sample cylinder were removed
from the glovebox. The autoclave was charged with 102 g of
n-pentane from a pressurized feed charger without displacing the
nitrogen present in the autoclave. The n-pentane passed over a high
surface sodium column to remove any water before entering the
autoclave. Similarly, the nitrogen used to pressurize the charger
and for all other work passed over a separate high surface sodium
column. The sample cylinder was charged with 15 g of n-pentane
using the same method described above and then attached to the
autoclave. The autoclave was heated to 95.degree. C., and the
2-chloro-2-methylpropane/n-pentane solution in the sample cylinder
was added with an over-pressure of nitrogen. After complete
addition, the initial pressure in the autoclave was 160 psi (1.103
MPa), and the autoclave was then set to stir at 1700 rpm. The
reaction was monitored periodically by GC. In order to analyze the
paraffinic layer, the stirring was stopped, and the product was
allowed to settle for 5 minutes. An aliquot was sampled directly
from the autoclave by opening a valve from the autoclave, passing
the paraffinic layer through a SiO.sub.2 column, and then passing
it directly into a GC sample loop. The mass ratio of liquid
catalyst to n-pentane was 0.46 and the volume ratio was 0.24. The
mass rate of reaction was 130, and the volume rate was 240 after 1
h. The results of the run are shown in Tables 13 and 14.
TABLE-US-00013 TABLE 13 Disproportionation and Isomerization of
n-Pentane at 95.degree. C., wt % of reaction mixture % S. t (h)
Conv. C3- iC4 nC4 iC5 nC5 C6P C7+ i/n Disp. S.sub.isoparaffin
S.sub.isoisom 1.0 59 0.42 18.63 1.71 19.46 41.34 10.27 8.14 16.9 67
90 33 2.2 70 0.94 22.7 3.08 20.83 29.43 12.54 10.30 12.1 70 87 30
3.5 76 0.91 25.1 4.06 21.56 23.72 13.57 11.03 10.4 72 86 28 4.8 80
1.05 26.39 4.78 21.83 20.06 14.26 11.63 9.4 73 86 27 8.0 85 1.35
27.64 6.10 21.68 14.82 14.78 12.84 8.0 74 83 25
TABLE-US-00014 TABLE 14 NA Time (h) 1.0 2.2 3.5 4.8 8.0 feed Wt. %
C3P 0.42 0.94 0.91 1.05 1.35 0.00 C4P 20.35 25.78 29.16 31.17 33.74
0.00 C5P 60.81 50.26 45.28 41.90 36.50 99.60 C6P 10.27 12.55 13.59
14.25 14.78 0.00 C7P 4.17 5.17 5.67 5.96 6.24 0.00 C8P 1.63 2.11
2.40 2.57 2.82 0.00 C9+ 2.02 2.71 2.58 2.67 4.10 0.00 C5N 0.00 0.00
0.00 0.00 0.00 0.00 C6N 0.00 0.00 0.00 0.00 0.00 0.00 C7N 0.01 0.02
0.02 0.02 0.02 0.00 C8N 0.26 0.32 0.36 0.38 0.41 0.00 C6A 0.00 0.00
0.00 0.00 0.00 0.00 C7A 0.01 0.02 0.02 0.02 0.02 0.00 C8A 0.06 0.13
0.03 0.03 0.04 0.00 nC4-nC5 0.00 0.00 0.00 0.00 0.00 0.34 unknowns
nC5-nC6 0.00 0.00 0.00 0.00 0.00 0.05 unknowns mmoles (based on wt
%) C3P 10 21 21 24 31 0 C4P 350 444 502 536 580 0 C5P 843 697 628
581 506 1380 C6P 119 146 158 165 172 0 C7P 42 52 57 59 62 0 C8P 14
18 21 23 25 0 C9+ 16 21 20 21 32 0 C5N 0 0 0 0 0 0 C6N 0 0 0 0 0 0
C7N 0 0 0 0 0 0 C8N 2 3 3 3 4 0 C6A 0 0 0 0 0 0 C7A 0 0 0 0 0 0 C8A
1 1 0 0 0 0 nC4-nC5 0 0 0 0 0 5 unknowns nC5-nC6 0 0 0 0 0 1
unknowns Total 1396 1403 1409 1413 1412 1386 mmoles
Example 12
nC5 with [1-butyl-1-methylpyrrolidinium][Al.sub.2Cl.sub.7] at
95.degree. C.
[0108] A 300 mL Hastelloy C autoclave, Hastelloy C baffle, and 75
mL stainless steel sample cylinder were dried in a 120.degree. C.
oven for at least 8 h. The dried autoclave and sample cylinder were
brought into a nitrogen glovebox and allowed to cool to ambient
temperature. The autoclave was charged with 52.795 g of
[1-butyl-1-methylpyrrolidinium][Al.sub.2Cl.sub.7] and the autoclave
head was attached. To the sample cylinder 5.24 g of
2-chloro-2-methylpropane, which had previously been dried over
activated sieves, was added. The sample cylinder was closed under
nitrogen, and both the autoclave and sample cylinder were removed
from the glovebox. The autoclave was charged with 98 g of n-pentane
from a pressurized feed charger without displacing the nitrogen
present in the autoclave. The n-pentane passed over a high surface
sodium column to remove any water before entering the autoclave.
Similarly, the nitrogen used to pressurize the charger and for all
other work passed over a separate high surface sodium column. The
sample cylinder was charged with 33 g of n-pentane using the same
method described above and attached to the autoclave. The autoclave
was heated to 95.degree. C., and the
2-chloro-2-methylpropane/n-pentane solution in the sample cylinder
was added with an over-pressure of nitrogen. After complete
addition, the initial pressure in the autoclave was 260 psi (1.793
MPa), and the autoclave was set to stir at 1700 rpm. The reaction
was monitored periodically by GC. In order to analyze the
paraffinic layer, the stirring was stopped, and the product was
allowed to settle for 5 minutes. An aliquot was sampled directly
from the autoclave by opening a valve from the autoclave, passing
the paraffinic layer through a SiO.sub.2 column, and then passing
it directly into a GC sample loop. The mass ratio of liquid
catalyst to n-pentane was 0.44 and the volume ratio was 0.21. The
mass rate of reaction was 220, and the volume rate was 450 after
0.6 h. The results of the run are shown in Tables 15 and 16.
TABLE-US-00015 TABLE 15 Disproportionation and Isomerization of
n-Pentane at 95.degree. C. with
[1-butyl-1-methylpyrrolidinium][Al.sub.2Cl.sub.7], wt. % of
reaction mixture % S. RVP t (h) Conv. C3- iC4 nC4 iC5 nC5 C6P C7+
i/n Disp. S.sub.isoparaffin S.sub.isoisom RON (psi) 0.6 57 0.49
18.16 2.44 18.55 42.87 10.02 7.48 13.0 68 89 32 ND ND 1.9 84 1.22
28.59 5.73 22.01 15.60 14.75 12.00 8.7 74 85 26 76.1 13.5 3.2 89
1.70 30.42 7.70 21.66 10.57 15.38 12.54 7.1 76 83 24 77.1 13.2 4.4
91 1.96 30.79 8.72 21.31 9.06 15.51 12.65 6.5 76 81 23 77.4
13.0
TABLE-US-00016 TABLE 16 Time (h) 0.6 1.9 3.2 4.4 NA Wt. % feed C3P
0.49 1.22 1.70 1.96 0.00 C4P 20.60 34.32 38.12 39.51 0.00 C5P 61.41
37.61 32.23 30.37 99.60 C6P 10.02 14.76 15.39 15.50 0.00 C7P 3.93
6.04 6.24 6.25 0.00 C8P 1.52 2.64 2.85 2.89 0.00 C9+ 1.71 2.97 3.00
3.05 0.00 C5N 0.00 0.00 0.00 0.00 0.00 C6N 0.00 0.00 0.00 0.00 0.00
C7N 0.01 0.01 0.02 0.02 0.00 C8N 0.25 0.39 0.41 0.41 0.00 C6A 0.00
0.00 0.00 0.00 0.00 C7A 0.01 0.02 0.02 0.02 0.00 C8A 0.04 0.01 0.02
0.02 0.00 nC4-nC5 0.00 0.00 0.00 0.00 0.34 unknowns nC5-nC6 0.00
0.00 0.00 0.00 0.05 unknowns mmoles (based on wt. %) C3P 11 28 39
44 0 C4P 354 591 656 680 0 C5P 851 521 447 421 1380 C6P 116 171 179
180 0 C7P 39 60 62 62 0 C8P 13 23 25 25 0 C9+ 13 23 23 24 0 C5N 0 0
0 0 0 C6N 0 0 0 0 0 C7N 0 0 0 0 0 C8N 2 4 4 4 0 C6A 0 0 0 0 0 C7A 0
0 0 0 0 C8A 0 0 0 0 0 nC4-nC5 0 0 0 0 5 unknowns nC5-nC6 0 0 0 0 1
unknowns Total mmoles 1402 1421 1435 1441 1386
Example 13
nC7--Stir Rate at 1700 rpm with
[(.sup.nBu).sub.3P(Hex)][Al.sub.2Cl.sub.6Br] at 55.degree.
C.-80.degree. C. in a Hastelloy C Autoclave
[0109] A 300 mL Hastelloy C autoclave, Hastelloy C baffle, and 75
mL stainless steel sample cylinder were dried in a 110.degree. C.
oven for at least 8 h. The dried autoclave and sample cylinder were
brought into a nitrogen glovebox and allowed to cool to ambient
temperature. The autoclave was charged with 50.425 g of
[(.sup.nBu).sub.3P(Hex)][Al.sub.2Cl.sub.6Br], 201 mL of n-heptane
(pre-dried by storing over activated 3A MS for several days) and
then the autoclave head was attached. The sample cylinder was
charged with 8.833 g of a 82.29 wt % n-heptane and 17.71 wt %
2-chloro-2-methylpropane mixture, both of which had previously been
dried over activated sieves. The sample cylinder was closed under
nitrogen, and both the autoclave and sample cylinder were removed
from the glovebox. The autoclave was heated to 55.degree. C., and
then the 2-chloro-2-methylpropane/n-heptane solution in the sample
cylinder was added with an over-pressure of nitrogen. The nitrogen
used to provide this overpressure was passed over a high surface
sodium column. After complete addition, the initial pressure in the
autoclave was 340 psi (2.34 MPa), and the autoclave was set to stir
at 1700 rpm. The reaction was monitored by GC. In order to analyze
the paraffinic layer, the stirring was stopped, and the product was
allowed to settle for 5 minutes. An aliquot was sampled directly
from the autoclave by opening a valve from the autoclave, passing
the paraffinic layer through a SiO.sub.2 column, and then passing
it directly into a GC sample loop. After about 24 the temperature
was increased to 80.degree. C. At the end of the reaction (45 h),
an aliquot was sampled directly from the autoclave by opening a
valve from the autoclave, passing the paraffinic layer through a
SiO.sub.2 column, and into a sample cylinder. The sample cylinder
was then charged to about 300 psi using nitrogen prior to offline
analysis. The mass ratio of liquid catalyst to n-heptane was 0.36
and the volume ratio was 0.20. The mass rate of reaction was 2, and
the volume rate was 3 after 45 h. The results of the run are shown
in Table 17 and were determined using the UOP980 method
offline.
TABLE-US-00017 TABLE 17 Disproportionation and Isomerization of
n-heptane at 55-80.degree. C., 1700 rpm, with
[(.sup.nBu).sub.3P(Hex)][Al.sub.2Cl.sub.6Br] in a Hastelloy C
autoclave, wt % of reaction mixture S. % S. Isom. t (h) Conv. C3-
iC4 nC4 iC5 nC5 C6P nC7 C7P C8P Heavies i/n Disp. C7P 0.0 NA 0.00
0.00 0.00 0.04 0.00 0.00 99.25 99.55 0.00 NA NA NA (feed) 45 26
0.07 3.90 0.14 3.31 0.16 2.89 73.44 15.14
Example 14
nC7--Stir Rate at 1700 rpm with
[1-Butyl-1-methylimidazolium][Al.sub.2Cl.sub.7] at 95.degree. C. in
a Hastelloy C Autoclave
[0110] A 300 mL Hastelloy C autoclave, Hastelloy C baffle, and 50
mL stainless steel sample cylinder were dried in a 110.degree. C.
oven for at least 5 h and then placed in a glovebox antechamber and
evacuated over night. The autoclave and sample cylinder were then
brought into a nitrogen glovebox. The autoclave was charged with
55.335 g of [1-butyl-1-methylimidazolium][Al.sub.2Cl.sub.7], 211 mL
of n-heptane (pre-dried by storing over activated 3A MS for at
least 1 week) and then the autoclave head was attached. The sample
cylinder was charged with 15.358 g of a 62.30 wt % n-heptane and
37.70 wt % 2-chloro-2-methylpropane mixture, both of which had
previously been dried over activated sieves. The sample cylinder
was closed under nitrogen, and both the autoclave and sample
cylinder were removed from the glovebox. The autoclave was heated
to 95.degree. C., and then the 2-chloro-2-methylpropane/n-heptane
solution in the sample cylinder was added with an over-pressure of
nitrogen. The nitrogen used to provide this overpressure was passed
over a high surface sodium column. After complete addition, the
initial pressure in the autoclave was 280 psi (1.93 MPa), and the
autoclave was set to stir at 1700 rpm. The reaction was monitored
by GC. In order to analyze the paraffinic layer, the stirring was
stopped, and the product was allowed to settle for 5 minutes. An
aliquot was sampled directly from the autoclave by opening a valve
from the autoclave, passing the paraffinic layer through a
SiO.sub.2 column, and then passing it directly into a GC sample
loop. The mass ratio of liquid catalyst to n-heptane was 0.40 and
the volume ratio was 0.21. The mass rate of reaction was 110, and
the volume rate was 210 after 1 h. The results of the run are shown
in Tables 18 and 19 and were determined using the UOP690 method.
Alternatively, the aliquot could be introduced to a sample
cylinder, after passing through the SiO.sub.2 column, and analyzed
offline. If this method was used, after introduction of the sample
to the sample cylinder, the cylinder would then be charged to about
300 psi using nitrogen prior to offline analysis and analyzed using
the UOP980 method.
TABLE-US-00018 TABLE 18 Disproportionation and Isomerization of
n-heptane at 95.degree. C., 1700 rpm, with
[1-butyl-3-methylimidazolium][Al.sub.2Cl.sub.7] in a Hastelloy C
autoclave, wt. % of reaction mixture % nC8- S. t (h) Conv. C3- iC4
nC4 iC5 nC5 C6P nC7 C7P C8P nC10 C10+ i/n Disp. S.sub.isoisom 0.0
NA 0.00 0.00 0.00 0.04 0.00 0.00 99.25 99.55 0.00 NA NA NA (feed)
1.0 44 0.58 7.63 0.89 7.58 0.77 7.06 66.21 3.26 3.07 2.43 15 77
22
TABLE-US-00019 TABLE 19 Time (h) 1.0 NA Wt. % Feed C3P 0.58 0.00
C4P 8.52 0.00 C5P 8.35 0.04 C6P 7.06 0.00 C7P 66.21 99.55 C8P 3.26
0.00 C9P 1.62 0.00 C10P 1.40 0.00 C10+ 2.43 0.00 C5N 0.00 0.00 C6N
0.00 0.01 C7N 0.03 0.40 C8N 0.40 0.00 C6A 0.00 0.00 C7A 0.06 0.00
C8A 0.04 0.00 nC4-nC5 0.00 nC5-nC6 0.00 0.00 unknowns mmoles (based
on wt. %) C3P 13 0 C4P 147 0 C5P 116 1 C6P 82 0 C7P 661 993 C8P 29
0 C9P 13 0 C10P 10 0 C10+ 16 0 C5N 0 0 C6N 0 0 C7N 0 4 C8N 4 0 C6A
0 0 C7A 1 0 C8A 0 0 nC4-nC5 0 nC5-nC6 0 0 unknowns Total mmoles
1090 998
Example 15
nC4--Stir Rate at 1700 rpm with
[(.sup.nBu).sub.3P(Hex)][Al.sub.2Cl.sub.6Br] in Hastelloy C
Autoclave at 95.degree. C.-105.degree. C.
[0111] A 300 mL Hastelloy C autoclave, Hastelloy C baffle, and 75
mL stainless steel sample cylinder were dried in a 110.degree. C.
oven for at least 8 h. The dried autoclave and sample cylinder were
brought into a nitrogen glovebox and allowed to cool to ambient
temperature. The autoclave was charged with 50.467 g of
[(.sup.nBu).sub.3P(Hex)][Al.sub.2Cl.sub.6Br], and the autoclave
head was attached. 3.692 g of 2-chloro-2-methylpropane, which had
previously been dried over activated 3A molecular sieves, was added
to the sample cylinder. The sample cylinder was closed under
nitrogen, and both the autoclave and sample cylinder were removed
from the glovebox. The autoclave was charged with 103.1 g of
n-butane from a pressurized feed charger without displacing the
nitrogen present in the autoclave. The sample cylinder was charged
with 10.9 g of n-butane using the same method described above and
attached to the autoclave. The autoclave was heated to 105.degree.
C. At this temperature, stirring was stopped, and the
2-chloro-2-methylpropane/iso-pentane solution in the sample
cylinder was added with an over-pressure of nitrogen. The nitrogen
used to pressurize the charger and for all other work passed over a
separate high surface sodium column. After complete addition, the
autoclave was set to stir at 1700 rpm, and the initial pressure in
the autoclave was 420 psi (2.90 MPa) and the temperature was
101.degree. C. The temperature was difficult to maintain above
100.degree. C., so the reaction was cooled to 95.degree. C. where
it was easier to maintain temperature. The reaction was in the
98-101.degree. C. region for about 1 h before being allowed to cool
to 95.degree. C. The reaction was monitored periodically by GC
offline. In order to analyze the paraffinic layer, the stirring was
stopped, and the product was allowed to settle for 5 minutes. An
aliquot was sampled directly from the autoclave by opening a valve
from the autoclave, passing the paraffinic layer through a
SiO.sub.2 column, and into a sample cylinder. The sample cylinder
was then charged to about 300 psi (2.07 MPa) using nitrogen prior
to offline analysis. The mass ratio of the liquid catalyst to
n-butane was 0.48, and the volume ratio of liquid catalyst to
n-butane was 0.22 using the following densities: 1.22 g/mL for the
liquid catalyst and 0.57 g/mL for n-butane. The mass reaction rate
was 5, and the volume reaction rate was 10. The results of the run
are shown in Table 20 and were determined using the ASTM UOP980
method.
TABLE-US-00020 TABLE 20 Disproportionation and Isomerization of
n-butane at 95.degree. C., 1700 rpm, Hastelloy C autoclave,wt. % of
reaction mixture t (h) C3- iC4 nC4 iC5 nC5 C6P C7+ iC4/nC4 0 0.01
0.18 99.09 0.00 0.00 0.00 0.60 0.00 (feed) 3.5 0.07 6.76 91.97 0.71
0.08 0.16 0.14 0.07 27.0 0.09 13.67 84.53 0.93 0.15 0.17 0.33
0.16
Example 16
iC4 and nC7 Reverse Disproportionation--Stir Rate at 1700 rpm with
[(.sup.nBu).sub.3P(Hex)][Al.sub.2Cl.sub.6Br] in Hastelloy C
Autoclave at 95.degree. C.
[0112] A 300 mL Hastelloy C autoclave, Hastelloy C baffle, and 75
mL stainless steel sample cylinder were dried in a 110.degree. C.
oven for at least 8 h. The dried autoclave and sample cylinder were
brought into a nitrogen glovebox and allowed to cool to ambient
temperature. The autoclave was charged with 50.428 g of
[(.sup.nBu).sub.3P(Hex)][Al.sub.2Cl.sub.6Br], 40.368 g of n-heptane
(pre-dried by storing over activated 3 A molecular sieves for
several days), and the autoclave head was attached. 1.501 g of
2-chloro-2-methylpropane, which had previously been dried over
activated 3 A molecular sieves, and 12.868 g of n-heptane were
added to the sample cylinder. The sample cylinder was closed under
nitrogen, and both the autoclave and sample cylinder were removed
from the glovebox. The autoclave was charged with 65 g of isobutane
from a pressurized feed charger without displacing the nitrogen
present in the autoclave. The autoclave was heated to 95.degree. C.
Once the temperature was reached, the
2-chloro-2-methylpropane/n-heptane solution in the sample cylinder
was added with an over-pressure of nitrogen. The nitrogen used to
pressurize the charger and for all other work passed over a
separate high surface sodium column. After complete addition,
stirring was set to 1700 rpm, and the initial pressure in the
autoclave was 360 psi (2.48 MPa). The reaction was monitored
periodically by GC. In order to analyze the paraffinic layer, the
stirring was stopped, and the product was allowed to settle for 5
minutes. An aliquot was sampled directly from the autoclave by
opening a valve from the autoclave, passing the paraffinic layer
through a SiO.sub.2 column, and then passing it directly into a GC
sample loop. At the end of the reaction, an aliquot was sampled
directly from the autoclave by opening a valve from the autoclave,
passing the paraffinic layer through a SiO.sub.2 column, and into a
sample cylinder. The sample cylinder was then charged to about 300
psi (2.07 MPa) using nitrogen prior to offline analysis. The mass
ratio of liquid catalyst to hydrocarbon feed was 0.44. The volume
ratio of liquid catalyst to hydrocarbon feed was 0.22 using the
following densities: 1.22 g/mL for the liquid catalyst, 0.68 g/mL
for n-heptane and 0.55 g/mL for isobutane. The mass reaction rate
was 2, and the volume reaction rate was 3 after 28 h. The results
of the run are shown in Table 21 and were determined using the ASTM
UOP980 method offline. The feed composition (t (0)) is based on the
mass of the added reagents.
TABLE-US-00021 TABLE 21 Reverse Disproportionation of n-Heptane and
iso-Butaneat 95.degree. C., 1700 rpm, Hastelloy C autoclave, wt %
of reaction mixture t (h) C3- iC4 nC4 iC5 nC5 C6P nC7 Heavies 0
(feed) 55 45 28 0.27 56.99 1.38 3.16 0.08 1.70 23.80 11.39
Example 17
nC4/nC5--Stir Rate at 1700 rpm with
[1-butyl-3-methylimidazolium][Al.sub.2Cl.sub.7] in Hastelloy C
Autoclave at 100.degree. C.
[0113] A 300 mL Hastelloy C autoclave, Hastelloy C baffle, and 75
mL stainless steel sample cylinder were dried in a 110.degree. C.
oven for at least 8 h. The dried autoclave and sample cylinder were
brought into a nitrogen glovebox and allowed to cool to ambient
temperature. The autoclave was charged with 55.387 g of
[1-butyl-3-methylimidazolium][Al.sub.2Cl.sub.7], and the autoclave
head was attached. 5.6 g of 2-chloro-2-methylpropane, which had
previously been dried over activated 3 A molecular sieves, was
added to the sample cylinder. The sample cylinder was closed under
nitrogen, and both the autoclave and sample cylinder were removed
from the glovebox. The autoclave was charged with 103 g of n-butane
from a pressurized feed charger without displacing the nitrogen
present in the autoclave, but was then vented down to 86 g of
n-butane. The sample cylinder was charged with 31 g of n-pentane
from a pressurized feed charger without displacing the nitrogen
present in the sample cylinder. The autoclave was heated to
103.degree. C. while stirring at 100 rpm. Once this temperature was
reached, stirring was stopped and the
2-chloro-2-methylpropane/n-pentane solution in the sample cylinder
was added with an over-pressure of nitrogen. The nitrogen used to
pressurize the charger and for all other work passed over a
separate high surface sodium column. After complete addition, the
reaction mixture was stirred at 1700 rpm and the temperature
increased to 110.degree. C. The pressure in the autoclave at this
point was 600 psi (4.14 MPa). After 0.1 h, during which time the
temperature fluctuated from 104-111.degree. C., stirring was
stopped, the reaction mixture was allowed to settle for 5 minutes,
and the paraffinic layer was analyzed by GC. An aliquot was sampled
directly from the autoclave by opening a valve from the autoclave,
passing the paraffinic layer through a SiO.sub.2 column, and then
passing it directly into a GC sample loop. The GC method employed
was UOP690. Afterwards, a liquid sample was removed by filtering
through a SiO.sub.2 column into a sample cylinder. The liquid
contained within the sample cylinder was pressurized with nitrogen
to 300 psi (2.07 MPa) and was then analyzed offline using an
analogous method. During sampling, the reaction cooled to
91.degree. C. Afterwards, the reaction was reheated to 100.degree.
C. with stirring at 1700 rpm, which took 0.7 h to achieve, and the
pressure at this point was 350 psi (2.41 MPa). The reaction was
continued for an additional 17.6 h at this temperature, and the
mixture was then analyzed is a similar manner. The results of the
run are shown in Table 22 and were determined using the UOP690
method online. The mass ratio of liquid catalyst to hydrocarbon
feed was 0.52, and the volume ratio was 0.23 using the following
densities: 1.34 g/mL for the liquid catalyst, 0.626 g/mL for
n-pentane and 0.57 g/mL for n-butane. The mass reaction rate was
650, and the volume reaction rate was 1500 after 0.1 h.
TABLE-US-00022 TABLE 22 Isomerization and disproportionation of a
n-butane/n-pentane feed at 100.degree. C., 1700 rpm, Hastelloy C
autoclave, wt. % of feed and reaction mixture nC4- nC5- nC8- nC9-
C3P iC4 nC4 iC5 nC5 C6P C7P C8P nC5 .sup.b nC6 .sup.b nC9 .sup.b
nC10 .sup.b nC10+ .sup.b HC nC5 .sup.a 0.00 0.00 0.00 0.03 99.05
0.00 0.00 0.00 0.88 0.03 0.00 0.00 0.00 nC4 .sup.a 0.01 0.17 99.71
0.00 0.00 0.00 0.00 0.00 0.10 0.00 0.00 0.00 0.00 time (h) 0.1 0.44
15.52 52.06 11.64 13.97 3.87 0.81 0.49 0.64 0.11 0.11 0.06 0.05
18.4 4.35 42.59 24.64 15.16 4.17 6.80 1.03 0.67 0.19 0.00 0.13 0.05
0.10 .sup.a Composition of the pure hydrocarbon feed, .sup.b
Unknowns within these ranges
Example 18
nC4/nC5--Stir Rate at 1700 rpm with
[1-butyl-3-methylimidazolium][Al.sub.2Cl.sub.7] in Hastelloy C
Autoclave at 100.degree. C.
[0114] A 300 mL Hastelloy C autoclave, Hastelloy C baffle, and 500
mL stainless steel sample cylinder were dried in a 110.degree. C.
oven for at least 8 h. The dried autoclave and sample cylinder were
brought into a nitrogen glovebox and allowed to cool to ambient
temperature. The autoclave was charged with 55.404 g of
[1-butyl-3-methylimidazolium][Al.sub.2Cl.sub.7], and the autoclave
head was attached. 11.821 g of 2-chloro-2-methylpropane, which had
previously been dried over activated 3 A molecular sieves, was
added to a 500 mL sample cylinder. The sample cylinder was closed
under nitrogen, and both the autoclave and sample cylinder were
removed from the glovebox. The sample cylinder was charged with
61.9 g of n-pentane, which was passed over a high surface sodium
column, followed by 200.9 g of n-butane from a pressurized feed
charger. The sample cylinder was then charged to about 600 psi
(4.14 MPa) with nitrogen. A portion of the stock solution was
analyzed by GC offline. The autoclave was charged with 130.3 g of
the n-butane/n-pentane/2-chloro-2-methylpropane stock solution at
room temperature, without displacing the nitrogen present in the
autoclave. The initial temperature and pressure were 26.degree. C.
and 340 psi (2.34 MPa). The reaction mixture was set to stir at
1700 rpm while the autoclave was heated to 100.degree. C.; it took
1.2 h to reach temperature, and the initial pressure was 980 psi
(6.76 MPa). After a total of 18.8 h, the pressure was 1090 psi
(7.52 MPa) within the autoclave. At this time, the reaction mixture
was cooled to 85.degree. C., which took 1.6 h, and it was then
analyzed by GC. In order to analyze the paraffinic layer, the
stirring was stopped, and the product was allowed to settle for 5
minutes. An aliquot was sampled directly from the autoclave by
opening a valve from the autoclave, passing the paraffinic layer
through a SiO.sub.2 column, and then passing it directly into a GC
sample loop. The GC method employed was UOP690. Afterwards, a
liquid sample was removed by filtering through a SiO.sub.2 column
into a sample cylinder. The liquid contained within the sample
cylinder was pressurized with nitrogen to about 300 psi (2.07 MPa)
and was then analyzed offline using an analogous method. The
results of the run are shown in Table 23 and were determined using
the UOP690 method. The GC of the feed (0.0 h in Table 23) is the
wt. % of the components in the 500 mL sample cylinder, without
integrating 2-chloro-2-methylpropane. The mass ratio of liquid
catalyst to hydrocarbon feed was 0.49, and the volume ratio was
0.21 using the following densities: 1.34 g/mL for the liquid
catalyst, 0.626 g/mL for n-pentane and 0.57 g/mL for n-butane. The
mass reaction rate was 6, and the volume reaction rate was 14 after
20.4 h.
TABLE-US-00023 TABLE 23 Isomerization and disproportionation of a
n-butane/n-pentane feed at 100.degree. C., 1700 rpm, Hastelloy C
autoclave, wt. % of feed and reaction mixture nC4- nC5- nC8- nC9-
(h) C3P iC4 nC4 iC5 nC5 C6P C7P C8P nC5 .sup.a nC6 .sup.a nC9
.sup.a nC10 .sup.a nC10+ .sup.a 0.0 0.01 0.13 73.81 0.01 25.26 0.00
0.00 0.00 0.21 0.01 0.00 0.00 0.06 20.4 1.35 40.64 33.77 13.40 3.78
5.30 0.73 0.57 0.08 0.00 0.10 0.04 0.09 .sup.a Unknowns within
these ranges
Example 19
nC4--Stir Rate at 1700 rpm with
[1-butyl-3-methylimidazolium][Al.sub.2Cl.sub.7] in Hastelloy C
Autoclave at 100.degree. C.
[0115] A 300 mL Hastelloy C autoclave, Hastelloy C baffle, and 75
mL stainless steel sample cylinder were dried in a 110.degree. C.
oven for at least 8 h. The dried autoclave and sample cylinder were
brought into a nitrogen glovebox and allowed to cool to ambient
temperature. The autoclave was charged with 55.394 g of
[1-butyl-3-methylimidazolium][Al.sub.2Cl.sub.7] and the autoclave
head was attached. 5.818 g of 2-chloro-2-methylpropane, which had
previously been dried over activated 3 A molecular sieves, was
added to the sample cylinder. The sample cylinder was closed under
nitrogen, and both the autoclave and sample cylinder were removed
from the glovebox. The autoclave was charged with 120 g of n-butane
from a pressurized feed charger, which was then vented down to 94 g
of n-butane in the autoclave. The sample cylinder was charged with
15 g of n-butane from a pressurized feed charger without displacing
the nitrogen present in the sample cylinder. The autoclave was
heated to 100.degree. C. while stirring at 138 rpm. Once the
temperature was achieved, stirring was stopped, and the
2-chloro-2-methylpropane/n-butane solution in the sample cylinder
was added with an over-pressure of nitrogen. The nitrogen used to
pressurize the charger and for all other work passed over a
separate high surface sodium column. After complete addition,
stirring was started again at 1700 rpm; the initial pressure in the
autoclave was 540 psi (3.72 MPa), and the temperature was
112.degree. C. After 0.2 h, during which time the temperature
fluctuated from 98-112.degree. C., stirring was stopped, the
reaction mixture was allowed to settle, and the paraffinic layer
was analyzed by GC. In order to analyze the paraffinic layer, the
stirring was stopped, and the product was allowed to settle for 5
minutes. An aliquot was sampled directly from the autoclave by
opening a valve from the autoclave, passing the paraffinic layer
through a SiO.sub.2 column, and then passing it directly into a GC
sample loop. The GC method employed was UOP690. Afterwards, a
liquid sample was removed by filtering through a SiO.sub.2 column
into a sample cylinder. The liquid contained within the sample
cylinder was pressurized with nitrogen to 300 psi (2.07 MPa) and
was then analyzed offline using an analogous method. After GC
analysis, the reaction was stirred at 1700 rpm and the temperature
had cooled to 96.degree. C. Reheating to 100.degree. C. took 0.6 h.
The reaction was continued for an additional 21.1 h at this
temperature. The mixture was then analyzed in a similar manner. The
results of the run are shown in Table 24 and were determined using
the UOP690 method online. The mass ratio of liquid catalyst to
hydrocarbon feed was 0.56, and the volume ratio was 0.24 using the
following densities: 1.34 g/mL for the liquid catalyst and 0.57
g/mL for n-butane. The mass reaction rate was 240, and the volume
reaction rate was 570 after 0.2 h.
TABLE-US-00024 TABLE 24 Isomerization and disproportionation of
n-butane at 100.degree. C., 1700 rpm, Hastelloy C autoclave, wt. %
of feed and reaction mixture nC4- nC5- nC8- nC9- (h) C3P iC4 nC4
iC5 nC5 C6P C7P C8P nC5 .sup.a nC6 .sup.a nC9 .sup.a nC10 .sup.a
nC10+ .sup.a 0.0 0.01 0.17 99.71 0.00 0.00 0.00 0.00 0.00 0.10 0.00
0.00 0.00 0.00 0.2 0.37 21.55 72.71 3.04 0.77 0.79 0.19 0.31 0.11
0.00 0.02 0.00 0.05 21.9 0.85 52.78 38.09 5.06 1.38 0.78 0.07 0.30
0.11 0.00 0.07 0.05 0.15 .sup.a Unknowns within these ranges
Example 20
nC4--Stir Rate at 1700 rpm with
[1-butyl-3-methylimidazolium][Al.sub.2Cl.sub.7] in Hastelloy C
Autoclave at 90.degree. C.
[0116] A 300 mL Hastelloy C autoclave, Hastelloy C baffle, and 75
mL stainless steel sample cylinder were dried in a 110.degree. C.
oven for at least 8 h. The dried autoclave and sample cylinder were
brought into a nitrogen glovebox and allowed to cool to ambient
temperature. The autoclave was charged with 55.392 g of
[1-butyl-3-methylimidazolium][Al.sub.2Cl.sub.7], and the autoclave
head was attached. 5.823 g of 2-chloro-2-methylpropane, which had
previously been dried over activated 3 A molecular sieves, was
added to the sample cylinder. The sample cylinder was closed under
nitrogen, and both the autoclave and sample cylinder were removed
from the glovebox. The autoclave was charged with 117 g of n-butane
from a pressurized feed charger, which was then vented down to 101
g of n-butane in the autoclave. The sample cylinder was charged
with 15.7 g of n-butane from a pressurized feed charger without
displacing the nitrogen present in the sample cylinder. The
autoclave was heated to 90.degree. C. with stirring at 115 rpm.
Once the temperature had stabilized, stirring was stopped, and the
2-chloro-2-methylpropane/n-butane solution in the sample cylinder
was added with an over-pressure of nitrogen. The nitrogen used to
pressurize the charger and for all other work passed over a
separate high surface sodium column. After complete addition, the
initial pressure in the autoclave was 320 psi (2.21 MPa), and the
autoclave was set to stir at 1700 rpm. After 97 h, stirring was
stopped and the reaction mixture was allowed to settle and the
paraffinic layer was analyzed by GC. In order to analyze the
paraffinic layer, the stirring was stopped, and the product was
allowed to settle for 5 minutes. An aliquot was sampled directly
from the autoclave by opening a valve from the autoclave, passing
the paraffinic layer through a SiO.sub.2 column, and then passing
it directly into a GC sample loop. The GC method employed was
UOP690. Afterwards, a liquid sample was removed by filtering
through a SiO.sub.2 column into a sample cylinder. The liquid
contained within the sample cylinder was pressurized with nitrogen
to 300 psi (2.07 MPa) and was then analyzed offline using an
analogous method. The results of the run are shown in Table 25 and
were determined using the UOP690 method online. The mass ratio of
liquid catalyst to hydrocarbon feed was 0.52, and the volume ratio
was 0.22 using the following densities: 1.34 g/mL for the liquid
catalyst and 0.57 g/mL for n-butane. The mass reaction rate was
0.8, and the volume reaction rate was 2 after 97 h.
TABLE-US-00025 TABLE 25 Isomerization and disproportionation of
n-butane at 90.degree. C., 1700 rpm, Hastelloy C autoclave, wt. %
of feed and reaction mixture nC4- nC5- nC8- nC9- (h) C3P iC4 nC4
iC5 nC5 C6P C7P C8P nC5 .sup.a nC6 .sup.a nC9 .sup.a nC10 .sup.a
nC10+ .sup.a 0.0 0.01 0.17 99.71 0.00 0.00 0.00 0.00 0.00 0.10 0.00
0.00 0.00 0.00 97 0.33 33.74 60.38 3.03 0.77 0.61 0.14 0.45 0.11
0.00 0.08 0.06 0.10 .sup.a Unknowns within these ranges
Example 21
nC4--Stir Rate at 1700 rpm with
[1-butyl-3-methylimidazolium][Al.sub.2Cl.sub.7] in Hastelloy C
Autoclave at 100.degree. C.
[0117] A 300 mL Hastelloy C autoclave, Hastelloy C baffle, and 500
mL stainless steel sample cylinder were dried in a 110.degree. C.
oven for at least 8 h. The dried autoclave and sample cylinder were
brought into a nitrogen glovebox and allowed to cool to ambient
temperature. The autoclave was charged with 55.390 g of
[1-butyl-3-methylimidazolium][Al.sub.2Cl.sub.7], and the autoclave
head was attached. 8.754 g of 2-chloro-2-methylpropane, which had
previously been dried over activated 3 A molecular sieves, was
added to the 500 mL sample cylinder. The sample cylinder was closed
under nitrogen, and both the autoclave and sample cylinder were
removed from the glovebox. Nitrogen and any other gaseous compounds
were removed from the autoclave by evacuation using standard
Schlenk techniques on a Schlenk line. The sample cylinder was
charged with 165 g of n-butane. The autoclave was charged with 113
g of the n-butane/2-chloro-2-methylpropane stock solution at room
temperature. The initial temperature and pressure were 27.degree.
C. and 60 psi (0.41 MPa). The reaction mixture was set to stir at
1700 rpm while the autoclave was heated to 100.degree. C. It took 1
h to reach temperature, and the pressure was 320 psi (2.21 MPa).
After a total of 19.4 h, the pressure was 360 psi (2.48 MPa) within
the autoclave. At this time, the reaction mixture was analyzed by
GC. In order to analyze the paraffinic layer, the stirring was
stopped, and the product was allowed to settle for 5 minutes. An
aliquot was sampled directly from the autoclave by opening a valve
from the autoclave, passing the paraffinic layer through a
SiO.sub.2 column, and then passing it directly into a GC sample
loop. The GC method employed was UOP690. Afterwards, a liquid
sample was removed by filtering through a SiO.sub.2 column into a
sample cylinder. The liquid contained within the sample cylinder
was pressurized with nitrogen to about 300 psi (2.07 MPa) and was
then analyzed offline using an analogous method. The results of the
run are shown in Table 26 and were obtained using the UOP690
method. The mass ratio of liquid catalyst to hydrocarbon feed was
0.57, and the volume ratio was 0.24 using the following densities:
1.34 g/mL for the liquid catalyst and 0.57 g/mL for n-butane. The
mass reaction rate was 4, and the volume reaction rate was 9 after
19.4 h.
TABLE-US-00026 TABLE 26 Isomerization and disproportionation of
n-butane feed at 100.degree. C., 1700 rpm, Hastelloy C autoclave,
wt % of feed and reaction mixture time nC4- nC5- nC8- nC9- (h) C3P
iC4 nC4 iC5 nC5 C6P C7P C8P nC5 .sup.a nC6 .sup.a nC9 .sup.a nC10
.sup.a nC10+ .sup.a iC4/nC4 0.0 0.01 0.17 99.71 0.00 0.00 0.00 0.00
0.00 0.10 0.00 0.00 0.00 0.00 0.00 19.4 0.34 33.54 58.91 4.10 1.09
1.04 0.19 0.41 0.08 0.00 0.04 0.03 0.08 0.57 .sup.a Unknowns within
these ranges
Example 22
nC4--Stir Rate at 1700 rpm with
[1-butyl-3-methylimidazolium][Al.sub.2Cl.sub.7] in Hastelloy C
Autoclave at 100.degree. C.
[0118] A 300 mL Hastelloy C autoclave equipped with a Hastelloy C
dipleg and Hastelloy B nut and connector, Hastelloy C baffle, and
75 mL stainless steel sample cylinder were dried in a 110.degree.
C. oven for at least 8 h. The dried autoclave and sample cylinder
were brought into a nitrogen glovebox and allowed to cool to
ambient temperature. The autoclave was charged with 55.391 g of
[1-butyl-3-methylimidazolium][Al.sub.2Cl.sub.7] and the autoclave
head was attached. 5.894 g of 2-chloro-2-methylpropane, which had
previously been dried over activated 3 A molecular sieves, was
added to the sample cylinder. The sample cylinder was closed under
nitrogen, and both the autoclave and sample cylinder were removed
from the glovebox. The autoclave was charged with 104 g of n-butane
from a pressurized feed charger without displacing the nitrogen
present in the autoclave. The composition of the n-butane feed is
listed in Table 27, entry 1. The sample cylinder was charged with
15.25 g of n-butane from a pressurized feed charger without
displacing the nitrogen present in the sample cylinder. The
autoclave was heated to 100.degree. C. with stirring at 100 rpm.
Once the temperature was reached, stirring was stopped, and the
2-chloro-2-methylpropane/n-butane solution in the sample cylinder
was added with an over-pressure of nitrogen. The nitrogen used to
pressurize the charger and for all other work passed over a
separate high surface sodium column. Once the addition was
complete, stirring was set to 1700 rpm. Initially, the temperature
increased to 102.degree. C., and the pressure was 740 psi (5.10
MPa) within the autoclave. During the first 0.6 h, the temperature
fluctuated from 98-102.degree. C. After this time, the temperature
stabilized at 100.degree. C. and the initial pressure was 720 psi
(4.96 MPa). After an additional 7.2 h, the pressure had increased
to 830 psi (5.72 MPa), and the reaction mixture was analyzed by GC
(entry 2, Table 27). In order to analyze the paraffinic layer, the
stirring was stopped, and the product was allowed to settle for 5
minutes. An aliquot was sampled directly from the autoclave by
opening a valve from the autoclave, passing the paraffinic layer
through a SiO.sub.2 column, and then passing it directly into a GC
sample loop. The GC method employed was UOP690. Afterwards, a
liquid sample was removed by filtering through a SiO.sub.2 column
into a sample cylinder. The liquid contained within the sample
cylinder was pressurized with nitrogen to 300 psi (2.07 MPa) and
was then analyzed offline using an analogous method. Once the
stirring was recommenced, the temperature increased to 113.degree.
C., and, after 0.6 h, it stabilized at 100.degree. C. with a
pressure of 410 psi (2.83 MPa). The reaction was continued for an
additional 14.5 h at this temperature, and the mixture was analyzed
is a similar manner (entry 3, Table 27). Afterwards, the autoclave
was cooled to ambient temperature, and a portion of the product was
vented off. Fresh n-butane was added to the partially emptied
autoclave. The composition of this new mixture is shown in entry 4,
Table 27. The autoclave was then heated back to 100.degree. C. with
stirring at 1700 rpm, which took 1 h to achieve, and the pressure
was 300 psi (2.07 MPa). After an additional 16.9 h of reaction, the
product was analyzed. The results of the run are shown in Table 27
and were determined using the UOP690 method online. The mass ratio
of liquid catalyst to hydrocarbon feed was 0.51 and the volume
ratio was 0.22 using the following densities: 1.34 g/mL for the
liquid catalyst and 0.57 g/mL for n-butane. The mass reaction rate
was 15, and the volume reaction rate was 35 after 7.8 h.
TABLE-US-00027 TABLE 27 Isomerization and disproportionation of
n-butane at 100.degree. C., 1700 rpm, Hastelloy C autoclave, wt. %
of feed and reaction mixture time nC4- nC5- nC8- nC9- Entry (h) C3P
iC4 nC4 iC5 nC5 C6P C7P C8P nC5 .sup.a nC6 .sup.a nC9 .sup.a nC10
.sup.a nC10+ .sup.a iC4/nC4 1 0.0 0.01 0.17 99.71 0.00 0.00 0.00
0.00 0.00 0.10 0.00 0.00 0.00 0.00 0.00 2 7.8 0.97 52.69 39.89 4.18
1.13 0.62 0.07 0.23 0.12 0.00 0.00 0.00 0.05 1.32 3 22.9 1.38 57.72
33.11 5.19 1.41 0.70 0.05 0.18 0.12 0.00 0.00 0.00 0.07 1.74 4 22.9
0.66 31.01 64.14 3.03 0.75 0.35 0.00 0.01 0.00 0.00 0.00 0.00 0.00
0.48 5 40.8 0.72 50.72 42.75 3.75 1.02 0.48 0.04 0.19 0.12 0.00
0.02 0.01 0.07 1.19 .sup.a Unknowns within these ranges
Example 23
nC4--Stir Rate at 1700 rpm with
[1-butyl-3-methylimidazolium][Al.sub.2Cl.sub.7] in Hastelloy C
Autoclave at 100.degree. C. Using HCl
[0119] A 300 mL Hastelloy C autoclave equipped with a Hastelloy C
dipleg and Hastelloy B nut and connector, and Hastelloy C baffle
were dried in a 110.degree. C. oven for at least 8 h. The dried
autoclave and sample cylinder were brought into a nitrogen glovebox
and allowed to cool to ambient temperature. The autoclave was
charged with 55.390 g of
[1-butyl-3-methylimidazolium][Al.sub.2Cl.sub.7], and the autoclave
head was attached. The autoclave was closed under nitrogen and
removed from the glovebox. Nitrogen and any other gaseous compounds
were removed from the autoclave by evacuation using standard
Schlenk techniques and a Schlenk line. The autoclave was charged
with 2.5 g of anhydrous HCl at ambient temperature. Afterwards, 123
g of n-butane was added to the autoclave from a pressurized feed
charger. The reaction mixture was set to stir at 1700 rpm, and the
autoclave was heated to 100.degree. C. with stirring at 1700 rpm.
It took 1.2 h to reach temperature, and the initial pressure was
460 psi (3.17 MPa). After a total of 4.8 h, the pressure was 440
psi (3.03 MPa) within the autoclave, and an aliquot was removed for
GC analysis. In order to analyze the paraffinic layer, the stirring
was stopped, and the product was allowed to settle for 5 minutes.
An aliquot was sampled directly from the autoclave by opening a
valve from the autoclave, passing the paraffinic layer through a
SiO.sub.2 column, and then passing it directly into a GC sample
loop. The GC method employed was UOP690 (entry 2, Table 28). Entry
1 in Table 28 is the composition of the butane feed. Afterwards, a
liquid sample was removed by filtering through a SiO.sub.2 column
into a sample cylinder. The liquid contained within the sample
cylinder was pressurized with nitrogen to 300 psi (2.07 MPa) and
was then analyzed offline using an analogous method. Afterwards,
stirring was set to 1700 rpm, and the pressure was 320 psi (2.21
MPa). The reaction was continued for an additional 17.0 h; the
pressure was 320 psi (2.21 MPa) and had not increased. The reaction
temperature was increased to 120.degree. C.; it took 1 h to reach
temperature. At this temperature, the pressure within the autoclave
was 510 psi (3.52 MPa). The reaction was stirred at this
temperature for 3.9 h, and the pressure had increased to 530 psi
(3.65 MPa). The temperature was then increased to 130.degree. C. It
took 0.5 h to reach temperature, and the reaction was allowed to
continue at that temperature for an additional 2.7 h. Afterwards,
the temperature was decreased to 100.degree. C.; it took 0.7 h to
reach temperature. After maintaining the temperature at 100.degree.
C. for 0.1 h, the pressure within the autoclave was 350 psi (2.41
MPa), and the product mixture was analyzed in a similar manner
(entry 3, Table 28), as discussed above. Afterwards, stirring was
set to 1700 rpm, and the reaction mixture heated to 120.degree. C.
It took 1.1 h to reach temperature, and the pressure at this
temperature was 500 psi (3.45 MPa). The reaction mixture was
allowed to continue to react at this temperature for an additional
13.5 h. At this time, the pressure within the autoclave was 510 psi
(3.52 MPa). The reaction mixture was then cooled to 24.degree. C.
and analyzed by GC (entry 4, Table 28). The results of the run are
shown in Table 28 and were determined using the UOP690 method
online. The mass ratio of liquid catalyst to hydrocarbon feed was
0.47, and the volume ratio was 0.20 using the following densities:
1.34 g/mL for the liquid catalyst and 0.57 g/mL for n-butane. The
mass reaction rate was 3, and the volume reaction rate was 8 after
4.8 h.
TABLE-US-00028 TABLE 28 Isomerization and disproportionation of
n-butane at 100-130.degree. C. Using HCl, 1700 rpm, Hastelloy C
autoclave, wt. % of feed and reaction mixture time nC4- nC5- nC8-
nC9- iC4/ % C4P Entry (h) C3P iC4 nC4 iC5 nC5 C6P C7P C8P nC5
.sup.a nC6 .sup.a nC9 .sup.a nC10 .sup.a nC10+ .sup.a nC4 Conv. 1
0.0 0.01 0.17 99.71 0.00 0.00 0.00 0.00 0.00 0.10 0.00 0.00 0.00
0.00 0.00 0 2 4.8 0.01 7.37 92.45 0.00 0.00 0.00 0.00 0.00 0.16
0.00 0.00 0.00 0.00 0.08 7 3 30.7 0.34 57.95 40.95 0.46 0.13 0.00
0.00 0.02 0.12 0.00 0.00 0.00 0.00 1.42 59 4 45.3 2.11 59.83 33.93
3.00 0.82 0.13 0.00 0.00 0.12 0.00 0.00 0.00 0.00 1.76 66 .sup.a
Unknowns within these ranges
[0120] 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.
* * * * *