U.S. patent application number 12/137441 was filed with the patent office on 2009-01-01 for high shear process for the production of chlorobenzene.
This patent application is currently assigned to H R D CORPORATION. Invention is credited to Rayford G. Anthony, Ebrahim Bagherzadeh, Gregory Borsinger, Abbas Hassan, Aziz Hassan.
Application Number | 20090005619 12/137441 |
Document ID | / |
Family ID | 40161416 |
Filed Date | 2009-01-01 |
United States Patent
Application |
20090005619 |
Kind Code |
A1 |
Hassan; Abbas ; et
al. |
January 1, 2009 |
HIGH SHEAR PROCESS FOR THE PRODUCTION OF CHLOROBENZENE
Abstract
Use of a high shear mechanical device incorporated into a
process for the production of chlorobenzene is capable of
decreasing mass transfer limitations, thereby enhancing the
chlorobenzene production process. A system for the production of
chlorobenzene from benzene and chlorine, the system comprising a
reactor and an external high shear device, the outlet of which is
fluidly connected to the inlet of the reactor; the high shear
device capable of providing a emulsion of chlorine gas bubbles
within liquid benzene
Inventors: |
Hassan; Abbas; (Sugar Land,
TX) ; Bagherzadeh; Ebrahim; (Sugar Land, TX) ;
Anthony; Rayford G.; (College Station, TX) ;
Borsinger; Gregory; (Chatham, NJ) ; Hassan; Aziz;
(Sugar Land, TX) |
Correspondence
Address: |
CONLEY ROSE, P.C.;David A. Rose
P. O. BOX 3267
HOUSTON
TX
77253-3267
US
|
Assignee: |
H R D CORPORATION
Houston
TX
|
Family ID: |
40161416 |
Appl. No.: |
12/137441 |
Filed: |
June 11, 2008 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
60946524 |
Jun 27, 2007 |
|
|
|
Current U.S.
Class: |
570/208 ;
422/129 |
Current CPC
Class: |
B01J 2219/00083
20130101; B01J 8/025 20130101; B01J 19/1806 20130101; B01F 13/1016
20130101; B01J 8/20 20130101; B01J 2219/00779 20130101; B01J
19/0066 20130101; C07C 17/12 20130101; C07C 25/06 20130101; B01J
8/222 20130101; B01J 2219/00006 20130101; B01F 7/00766 20130101;
B01F 13/1013 20130101; C07C 17/12 20130101 |
Class at
Publication: |
570/208 ;
422/129 |
International
Class: |
C07C 17/00 20060101
C07C017/00; B01J 19/00 20060101 B01J019/00 |
Claims
1. A method for producing chlorobenzene, comprising: obtaining a
high shear device having at least one rotor/stator set configured
for producing a tip speed of at least 5 m/s, wherein the high shear
device comprises at least one rotor and at least on stator; forming
an emulsion of benzene and chlorine gas; wherein said benzene
comprises a pressurized liquid solution, and said chlorine gas
comprises bubbles in the emulsion with a mean diameter of less than
about 5 .mu.m; introducing said emulsion into a reactor comprising
a catalyst; and reacting said emulsion at a temperature less than
about 40.degree. C. in said reactor, from which a product
comprising chlorobenzene is removed.
2. The method of claim 1 said pressurized benzene solution is
pressurized to least about 203 kPa.
3. The method of claim 1 wherein said chlorine gas bubbles have an
average diameter of less than about 1.5 .mu.m.
4. The method of claim 1 wherein said high shear device has a tip
speed of at least about 5 m/s.
5. The method of claim 4 wherein said high shear device produces a
localized pressure of about 1000 MPa at the tip.
6. The method of claim 1 wherein forming said emulsion comprises
subjecting said oxidant gas bubbles and pressurized aqueous
solution to a shear rate of greater than about 20,000 s.sup.-1.
7. The method of claim 1 wherein forming said emulsion comprises an
energy expenditure of at least 1000 W/m.sup.3.
8. The method of claim 1 wherein the emulsion comprises a
micro-foam.
9. The method of claim 1 wherein the catalyst comprises one chosen
from the group consisting of Lewis acids, metallic chlorides,
iodine, or combinations thereof.
10. The method of claim 1, further comprising treating the product
with hydrochloric acid.
11. The method of claim 10, further comprising distilling the
product at least once to remove the chlorobenzene.
12. A method for producing chlorobenzene, the method comprising:
forming an emulsion of chlorine gas bubbles in aqueous solution
comprising benzene by introducing liquid benzene and chlorine gas
into a high shear device and subjecting the mixture of liquid
benzene and chlorine gas to a shear rate of at least 20,000
s.sup.-1.
13. The method of claim 12 wherein the high shear device comprises
at least one rotor and at least one stator.
14. A system for the production of chlorobenzene, the system
comprising; a pump positioned upstream of a dispersible chlorine
gas inlet; a high shear device which produces an emulsion of
chlorine gas in an aqueous solution, the dispersion having an
average bubble diameter of less than about 5 .mu.m; and a reactor
maintained at a temperature of less than about 40.degree. C. for
the chlorination reaction of benzene to chlorobenzene; the reactor
fluidly connected to the outlet of the high shear device.
15. The system of claim 14 wherein the high shear device is
configured to produce an emulsion.
16. The system of claim 14 wherein the high shear device comprises
a tip speed of at least about 5 m/sec.
17. The system of claim 14 wherein said high shear device produces
a localized pressure of at least about 1000 MPa at the tip.
18. The system of claim 14 wherein said high shear device subjects
said oxidant gas bubbles and pressurized aqueous solution to a
shear rate of greater than about 20,000 s.sup.-1.
19. The system of claim 14 wherein said high shear device comprises
an energy expenditure of at least 1000 W/m.sup.3.
20. The system of claim 14 wherein said high shear feed stream
comprises a micro-foam.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit under 35 U.S.C. .sctn.
119(e) of U.S. Provisional Patent Application No. 60/946,524 filed
Jun. 27, 2007, the disclosure of which is hereby incorporated
herein by reference.
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
[0002] Not Applicable.
BACKGROUND OF THE INVENTION
[0003] 1. Technical Field
[0004] The present disclosure relates generally to the production
of chlorobenzene by chlorination of benzene and, more particularly,
to apparatus and methods for producing chlorobenzene via
chlorination of benzene in a high shear process. More specifically,
the disclosure pertains still more particularly to the reduction of
mass transfer limitations for converting benzene to
chlorobenzene.
[0005] 2. Background of the Invention
[0006] Chlorobenzene is used as a solvent with applications in
certain pesticide formulations, automotive and industrial
degreasers, and as a chemical intermediate to make herbicides,
rubber, and dyes. Benzene reacts with chlorine in the presence of a
catalyst at room temperature, replacing one of the hydrogen atoms
on the benzene ring with a chlorine atom. The catalyst is typically
aluminum chloride or iron.
[0007] Iron is altered during the reaction such that chlorine forms
iron (III) chloride, FeCl.sub.3.
2Fe+3Cl.sub.2.fwdarw.2FeCl.sub.3 (1)
[0008] This compound acts as the catalyst and behaves like aluminum
chloride, AlCl.sub.3, in the reaction. The reaction between benzene
and chlorine in the presence of either aluminum chloride or iron
gives chlorobenzene, or, written more compactly:
C.sub.6H.sub.6+Cl.sub.2.fwdarw.C.sub.6H.sub.5Cl+HCl. (2)
C.sub.6H.sub.5+Cl.sub.2.fwdarw.C.sub.6H.sub.4Cl+HCl. (3)
C.sub.6H.sub.5Cl.sub.2+Cl.sub.2.fwdarw.C.sub.6H.sub.3Cl+HCl.
(4)
As reaction (2) is the desired reaction, certain parameters must be
maintained in the reactor. In certain cases, dichlorobenzene can be
formed if reaction temperatures are not controlled properly.
[0009] There is a need in the industry for improved methods of
producing chlorobenzene from benzene and chlorine whereby costs may
be reduced via operation at lower temperature and/or pressure,
increased product yield, decreased reaction time, and/or reduced
capital and/or operating costs.
SUMMARY OF THE INVENTION
[0010] A high shear system and method for accelerating the
production of chlorobenzene is disclosed. The disclosed high shear
method reduces mass transfer limitations, thereby improving
reaction conditions in the reactor such as the reaction rate,
temperature, pressure, contact time, and/or product yield. In
accordance with certain embodiments of the present disclosure, a
method is provided that enhances the rate of a liquid phase process
for the production of chlorobenzene from benzene by providing for
more optimal time, temperature, and pressure conditions than are
currently used.
[0011] The method employs a high shear mechanical device to provide
enhanced time, temperature, and pressure conditions resulting in
accelerated chemical reactions between multiphase reactants.
[0012] In an embodiment, the method comprises the use of a
pressurized high shear device to provide for production of
chlorobenzene without the need for large volume reactors.
[0013] These and other embodiments, features, and advantages will
be apparent in the following detailed description and drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0014] For a more detailed description of the preferred embodiment
of the present invention, reference will now be made to the
accompanying drawings, wherein:
[0015] FIG. 1 is a cross-sectional diagram of a high shear device
for the production of chlorobenzene.
[0016] FIG. 2 is a process flow diagram according to an embodiment
of the present disclosure including a high shear device for
production of chlorobenzene.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Overview
[0017] A system and method employs an external high shear
mechanical device to provide rapid contact and mixing of chemical
ingredients in a controlled environment in the reactor/mixer
device. The high shear device reduces the mass transfer limitations
on the reaction and thus increases the overall reaction rate.
[0018] Chemical reactions involving liquids, gases and solids rely
on the laws of kinetics that involve time, temperature, and
pressure to define the rate of reactions. In cases where it is
desirable to react two or more raw materials of different phases
(e.g. solid and liquid; liquid and gas; solid, liquid and gas), one
of the limiting factors in controlling the rate of reaction
involves the contact time of the reactants. In the case of
heterogeneously catalyzed reactions there may be the additional
rate limiting factor of having the reaction products removed from
the surface of the catalyst to enable the catalyst to catalyze
further reactants.
[0019] In conventional reactors, contact time for the reactants
and/or catalyst is often controlled by mixing which provides
contact between two or more reactants involved in a chemical
reaction. A reactor assembly that comprises an external high shear
mixer makes possible decreased mass transfer limitations and
thereby allows the reaction to more closely approach kinetic
limitations. When reaction rates are accelerated, residence times
may be decreased, thereby increasing obtainable throughput.
Alternatively, where the current yield is acceptable, decreasing
the required residence time allows for the use of lower
temperatures and/or pressures than conventional processes.
High Shear Device
[0020] High shear devices (HSD) such as a high shear mixer, or high
shear mill, are generally divided into classes based upon their
ability to mix fluids. Mixing is the process of reducing the size
of inhomogeneous species or particles within the fluid. One metric
for the degree or thoroughness of mixing is the energy density per
unit volume that the mixing device generates to disrupt the fluid
particles. The classes are distinguished based on delivered energy
density. There are three classes of industrial mixers having
sufficient energy density to consistently produce mixtures or
emulsions with particle or bubble sizes in the range of 0 to 50
.mu.m.
[0021] Homogenization valve systems are typically classified as
high energy devices. Fluid to be processed is pumped under very
high pressure through a narrow-gap valve into a lower pressure
environment. The pressure gradients across the valve and the
resulting turbulence and cavitations act to break-up any particles
in the fluid. These valve systems are most commonly used in milk
homogenization and can yield average particle size range from about
0.01 .mu.m to about 1 .mu.m. At the other end of the spectrum are
high shear mixer systems classified as low energy devices. These
systems usually have paddles or fluid rotors that turn at high
speed in a reservoir of fluid to be processed, which in many of the
more common applications is a food product. These systems are
usually used when average particle, globule or bubble, sizes of
greater than 20 microns are acceptable in the processed fluid.
[0022] Between low energy--high shear mixers and homogenization
valve systems, in terms of the mixing energy density delivered to
the fluid, are colloid mills, which are classified as intermediate
energy devices. The typical colloid mill configuration includes a
conical or disk rotor that is separated from a complementary,
liquid-cooled stator by a closely-controlled rotor-stator gap,
which is maybe between 0.025 mm and 10.0 mm. Rotors are usually
driven by an electric motor through a direct drive or belt
mechanism. Many colloid mills, with proper adjustment, can achieve
average particle, or bubble, sizes of about 0.01 .mu.m to about 25
.mu.m in the processed fluid. These capabilities render colloid
mills appropriate for a variety of applications including colloid
and oil/water-based emulsion processing such as that required for
cosmetics, mayonnaise, silicone/silver amalgam formation, or
roofing-tar mixing.
[0023] Referring now to FIG. 1, there is presented a schematic
diagram of a high shear device 200. High shear device 200 comprises
at least one rotor-stator combination. The rotor-stator
combinations may also be known as generators 220, 230, 240 or
stages without limitation. The high shear device 200 comprises at
least two generators, and most preferably, the high shear device
comprises at least three generators.
[0024] The first generator 220 comprises rotor 222 and stator 227.
The second generator 230 comprises rotor 223, and stator 228; the
third generator comprises rotor 224 and stator 229. For each
generator 220, 230, 240 the rotor is rotatably driven by input 250.
The generators 220, 230, 240 rotate about axis 260 in rotational
direction 265. Stator 227 is fixably coupled to the high shear
device wall 255.
[0025] The generators include gaps between the rotor and the
stator. The first generator 220 comprises a first gap 225; the
second generator 230 comprises a second gap 235; and the third
generator 240 comprises a third gap 245. The gaps 225, 235, 245 are
between about 0.025 mm (0.01 in) and 10.0 mm (0.4 in) wide.
Alternatively, the process comprises utilization of a high shear
device 200 wherein the gaps 225, 235, 245 are between about 0.5 mm
(0.02 in) and about 2.5 mm (0.1 in). In certain instances the gap
is maintained at about 1.5 mm (0.06 in). Alternatively, the gaps
225, 235, 245 are different between generators 220, 230, 240. In
certain instances, the gap 225 for the first generator 220 is
greater than about the gap 235 for the second generator 230, which
is greater than about the gap 245 for the third generator 240.
[0026] Additionally, the width of the gaps 225, 235, 245 may
comprise a coarse, medium, fine, and super-fine characterization.
Rotors 222, 223, and 224 and stators 227, 228, and 229 may be
toothed designs. Each generator may comprise two or more sets of
rotor-stator teeth, as known in the art. Rotors 222, 223, and 224
may comprise a number of rotor teeth circumferentially spaced about
the circumference of each rotor. Stators 227, 228, and 229 may
comprise a number of stator teeth circumferentially spaced about
the circumference of each stator. In embodiments, the inner
diameter of the rotor is about 11.8 cm. In embodiments, the outer
diameter of the stator is about 15.4 cm. In further embodiments,
the rotor and stator may have an outer diameter of about 60 mm for
the rotor, and about 64 mm for the stator. Alternatively, the rotor
and stator may have alternate diameters in order to alter the tip
speed and shear pressures. In certain embodiments, each of three
stages is operated with a super-fine generator, comprising a gap of
between about 0.025 mm and about 3 mm. When a feed stream 205
including solid particles is to be sent through high shear device
200, the appropriate gap width is first selected for an appropriate
reduction in particle size and increase in particle surface area.
In embodiments, this is beneficial for increasing catalyst surface
area by shearing and dispersing the particles.
[0027] High shear device 200 is fed a reaction mixture comprising
the feed stream 205. Feed stream 205 comprises an emulsion of the
dispersible phase and the continuous phase. Emulsion refers to a
liquefied mixture that contains two distinguishable substances (or
phases) that will not readily mix and dissolve together. Most
emulsions have a continuous phase (or matrix), which holds therein
discontinuous droplets, bubbles, and/or particles of the other
phase or substance. Emulsions may be highly viscous, such as
slurries or pastes, or may be foams, with tiny gas bubbles
suspended in a liquid. As used herein, the term "emulsion"
encompasses continuous phases comprising gas bubbles, continuous
phases comprising particles (e.g., solid catalyst), continuous
phases comprising droplets of a fluid that is substantially
insoluble in the continuous phase, and combinations thereof.
[0028] Feed stream 205 may include a particulate solid catalyst
component. Feed stream 205 is pumped through the generators 220,
230, 240, such that product dispersion 210 is formed. In each
generator, the rotors 222, 223, 224 rotate at high speed relative
to the fixed stators 227, 228, 229. The rotation of the rotors
pumps fluid, such as the feed stream 205, between the outer surface
of the rotor 222 and the inner surface of the stator 227 creating a
localized high shear condition. The gaps 225, 235, 245 generate
high shear forces that process the feed stream 205. The high shear
forces between the rotor and stator functions to process the feed
stream 205 to create the product dispersion 210. Each generator
220, 230, 240 of the high shear device 200 has interchangeable
rotor-stator combinations for producing a narrow distribution of
the desired bubble size, if feedstream 205 comprises a gas, or
globule size, if feedstream 205 comprises a liquid, in the product
dispersion 210.
[0029] The product dispersion 210 of gas particles, or bubbles, in
a liquid comprises an emulsion. In embodiments, the product
dispersion 210 may comprise a dispersion of a previously immiscible
or insoluble gas, liquid or solid into the continuous phase. The
product dispersion 210 has an average gas particle, or bubble, size
less than about 1.5 .mu.m; preferably the bubbles are sub-micron in
diameter. In certain instances, the average bubble size is in the
range from about 1.0 .mu.m to about 0.1 .mu.m. Alternatively, the
average bubble size is less than about 400 nm (0.4 .mu.m) and most
preferably less than about 100 nm (0.1 .mu.m).
[0030] Tip speed is the velocity (m/sec) associated with the end of
one or more revolving elements that is transmitting energy to the
reactants. Tip speed, for a rotating element, is the
circumferential distance traveled by the tip of the rotor per unit
of time, and is generally defined by the equation V (m/sec)=.pi.Dn,
where V is the tip speed, D is the diameter of the rotor, in
meters, and n is the rotational speed of the rotor, in revolutions
per second. Tip speed is thus a function of the rotor diameter and
the rotation rate.
[0031] For colloid mills, typical tip speeds are in excess of 23
m/sec (4500 ft/min) and can exceed 40 m/sec (7900 ft/min). For the
purpose of the present disclosure the term `high shear` refers to
mechanical rotor-stator devices, such as mills or mixers, that are
capable of tip speeds in excess of 5 m/sec (1000 ft/min) and
require an external mechanically driven power device to drive
energy into the stream of products to be reacted. A high shear
device combines high tip speeds with a very small shear gap to
produce significant friction on the material being processed.
Accordingly, a local pressure in the range of about 1000 MPa (about
145,000 psi) to about 1050 MPa (152,300 psi) and elevated
temperatures at the tip of the shear mixer are produced during
operation. In certain embodiments, the local pressure is at least
about 1034 MPa (about 150,000 psi). The local pressure further
depends on the tip speed, fluid viscosity, and the rotor-stator gap
during operation.
[0032] An approximation of energy input into the fluid (kW/l/min)
can be made by measuring the motor energy (kW) and fluid output
(1/min). In embodiments, the energy expenditure of a high shear
device is greater than 1000 W/m.sup.3. In embodiments, the energy
expenditure is in the range of from about 3000 W/m.sup.3 to about
7500 W/m.sup.3. The high shear device 200 combines high tip speeds
with a very small shear gap to produce significant shear on the
material. The amount of shear is typically dependent on the
viscosity of the fluid. The shear rate generated in a high shear
device 200 may be greater than 20,000 s.sup.-1. In embodiments, the
shear rate generated is in the range of from 20,000 s.sup.-1 to
100,000 s.sup.-1.
[0033] The high shear device 200 produces a gas emulsion capable of
remaining dispersed at atmospheric pressure for at least about 15
minutes. For the purpose of this disclosure, an emulsion of gas
particles, or bubbles, in the dispersed phase in product dispersion
210 that are less than 1.5 .mu.m in diameter may comprise a
micro-foam. Not to be limited by a specific theory, it is known in
emulsion chemistry that sub-micron particles, or bubbles, dispersed
in a liquid undergo movement primarily through Brownian motion
effects. The bubbles in the emulsion of product dispersion 210
created by the high shear device 200 may have greater mobility
through boundary layers of solid catalyst particles, thereby
facilitating and accelerating the catalytic reaction through
enhanced transport of reactants.
[0034] The rotor is set to rotate at a speed commensurate with the
diameter of the rotor and the desired tip speed as described
hereinabove. Transport resistance is reduced by incorporation of
high shear device 200 such that the velocity of the reaction is
increased by at least about 5%. Alternatively, the high shear
device 200 comprises a high shear colloid mill that serves as an
accelerated rate reactor. The accelerated rate reactor comprises a
single stage dispersing chamber. The accelerated rate reactor
comprises a multiple stage inline disperser comprising at least 2
stages.
[0035] Selection of the high shear device 200 is dependent on
throughput requirements and desired particle or bubble size in the
outlet dispersion 210. In certain instances, high shear device 200
comprises a Dispax Reactor.RTM. of IKA.RTM. Works, Inc. Wilmington,
N.C. and APV North America, Inc. Wilmington, Mass. Model DR 2000/4,
for example, comprises a belt drive, 4M generator, PTFE sealing
ring, inlet flange 1'' sanitary clamp, outlet flange 3/4'' sanitary
clamp, 2HP power, output speed of 7900 rpm, flow capacity (water)
approximately 300 l/h to approximately 700 l/h (depending on
generator), a tip speed of from 9.4 m/s to about 41 m/s (about 1850
ft/min to about 8070 ft/min). Several alternative models are
available having various inlet/outlet connections, horsepower, tip
speeds, output rpm, and flow rate.
[0036] Without wishing to be limited to a particular theory, it is
believed that the level or degree of high shear mixing is
sufficient to increase rates of mass transfer and may also produce
localized non-ideal conditions that enable reactions to occur that
would not otherwise be expected to occur based on Gibbs free energy
predictions. Localized non ideal conditions are believed to occur
within the high shear device resulting in increased temperatures
and pressures with the most significant increase believed to be in
localized pressures. The increase in pressures and temperatures
within the high shear device are instantaneous and localized and
quickly revert back to bulk or average system conditions once
exiting the high shear device. In some cases, the high shear mixing
device induces cavitation of sufficient intensity to dissociate one
or more of the reactants into free radicals, which may intensify a
chemical reaction or allow a reaction to take place at less
stringent conditions than might otherwise be required. Cavitation
may also increase rates of transport processes by producing local
turbulence and liquid micro-circulation (acoustic streaming). An
overview of the application of cavitation phenomenon in
chemical/physical processing applications is provided by Gogate et
al., "Cavitation: A technology on the horizon," Current Science 91
(No. 1): 35-46 (2006). The high shear mixing device of certain
embodiments of the present system and methods is operated under
what are believed to be cavitation conditions effective to
dissociate the benzene into free radicals exposed to chlorination
catalysts for the formation of the chlorobenzene product.
Description of High Shear Chlorobenzene Production Process and
System
[0037] The high shear chlorobenzene production process and system
of the present disclosure will now be described in relation to FIG.
2 which is a representative process flow diagram of a high shear
system (HSS) 100 for the production of chlorobenzene from benzene
and chlorine gas. FIG. 2 illustrates the basic components of a
representative high shear chlorobenzene production system. These
components comprise pump 5, high shear mixer 40, and reactor
10.
[0038] Pump 5 is used to provide a controlled flow throughout high
shear device (HSD) 40 and high shear system 100 for chlorobenzene
production. Pump inlet stream 21 comprises liquid benzene for
introduction to pump 5. In certain embodiments, pump inlet stream
21 comprises dry benzene. Pump 5 increases the pressure of the pump
inlet stream 21 to greater than about 203 kPa (about 2 atm);
alternatively, the inlet stream 21 is pressurized to greater than
about 304 kPa (about 3 atm). Additionally, pump 5 may build
pressure throughout HSS 100. In this way, HSS 100 combines high
shear with pressure to enhance reactant intimate mixing.
Preferably, all contact parts of pump 5 are stainless steel, for
example, 316 stainless steel. Pump 5 may be any suitable pump, for
example, a Dayton Pressure Booster Pump Model 2P372E, Dayton
Electric Co (Niles, Ill.).
[0039] The pressurized benzene liquid exits pump 5 via pump exit
stream 12. Pump exit stream 12 is in fluid communication with HSD
inlet stream 13. In certain instances, dispersible gas stream 22
comprising chlorine gas is introduced or injected to HSD inlet
stream 13. In some embodiments chlorine gas may continuously be fed
into exit stream 12 to form HSD inlet stream 13. HSD inlet stream
13 comprises a mixture of chlorine gas and catalyst in liquid
benzene. Dispersible gas stream 22 and pressurized pump exit stream
12 may be injected separately into HSD inlet stream 13 for
processing by high shear device 40. Furthermore, any suitable
chlorination catalyst known to those of skill in the art may be
introduced into HSD inlet stream 13 for processing by HSD 40. In
certain instances, the catalyst introduced comprises a Lewis acid
catalyst. The catalyst may be chosen from metallic chlorides and
iodine. In embodiments, the catalyst is selected from Lewis acids
selected from the group consisting of Fe, FeCl.sub.3, and
AlCl.sub.3. HSD inlet stream 13 is in fluid communication with the
high shear device 40.
[0040] HSD 40 serves to intimately mix the liquid benzene solution
with dispersible gas stream 22 and the catalyst. As discussed in
detail above, high shear device 40 is a mechanical device that
utilizes, for example, a stator rotor mixing head with a fixed gap
between the stator and rotor. In high shear device 40, chlorine gas
and benzene are mixed to form an emulsion comprising microbubbles
and nanobubbles of chlorine gas. In embodiments, the resultant
dispersion comprises bubbles in the submicron size. In embodiments,
the resultant dispersion has an average bubble size less than about
1.5 .mu.m. In embodiments, the mean bubble size is less than from
about 0.1 .mu.m to about 1.5 .mu.m. Not to be limited by a specific
method, it is known in emulsion chemistry that submicron particles
dispersed in a liquid undergo movement primarily through Brownian
motion effects. Thus it is believed that submicron gas particles
created by the high shear device 40 have greater mobility through
boundary layers of solid catalyst particles thereby facilitating
and accelerating the catalytic reaction through greater transport
of reactants. In embodiments, the high shear mixing produces gas
bubbles capable of remaining dispersed at atmospheric pressure for
about 15 minutes or longer depending on the bubble size. In
embodiments, the mean bubble size is less than about 400 nm; more
preferably, less than about 100 nm. HSD 40 serves to create an
emulsion of chlorine bubbles within high shear inlet stream 13
comprising aqueous aldehydes and chlorine gas. The emulsion may
further comprise a micro-foam.
[0041] The emulsion exits HSD 40 by the HSD emulsion stream 18. The
HSD emulsion stream 18 may undergo further processing prior
introduction to the reactor 10. Before introduction to reactor 10,
the moisture content of benzene may be reduced. In certain
embodiments, the benzene in HSD emulsion stream 18 comprises dry
benzene. HSD emulsion stream 18 is introduced into reactor 10 by
reactor inlet stream 19. Reactor inlet stream 19 is in fluid
communication with reactor 10.
[0042] Forming the emulsion in the presence of a catalyst may
initiate the reaction process of chlorination. Chlorination
reactions will occur whenever suitable time temperature and
pressure conditions exist. In instances where a slurry based
catalyst is utilized, reaction is more likely to occur at points
outside reactor 10. In this sense chlorination could occur at any
point in the flow diagram of FIG. 2 where temperature and pressure
conditions are suitable for the reaction. Nonetheless a discrete
reactor 10 is often desirable to allow for increased residence
time, agitation and heating and/or cooling. In fixed bed catalyst
applications, the catalyst increases the rate of the chlorination
reaction.
[0043] Reactor 10 is configured for chlorobenzene production.
Reactor 10 may further comprise temperature control (i.e. heat
exchanger), stirring system, and level regulator as known to those
of skill in the art. In embodiments, inlet stream 15 is fluidly
coupled to the reactor 10. Inlet stream 15 may comprise additional
catalyst for catalyzing the chlorination of benzene to
chlorobenzene. As described herein, a Lewis acid may be added to
promote the production of chlorobenzene. In certain embodiments, in
the reactor 10, chlorine gas in reacts with dry benzene utilizing a
Lewis acid catalyst at a predetermined temperature to yield
chlorobenzene mixtures. In embodiments, chlorobenzene production is
continuous within the reactor. The reactor 10 is drained by product
stream 16.
[0044] A specified reaction temperature may be maintained in the
reactor 10, as known to those of skill in the art. In certain
embodiments, the reactor includes internally or externally
positioned heat exchangers. Alternatively, heat exchangers may be
positioned in any location along the production stream within HSS
100. Suitable locations for external heat transfer devices include
between the pump 5 and the high shear mixer 40, between the high
shear mixer 40 and the reactor 10, and between the reactor and
further processing systems. There are many types of heat transfer
devices that may be suitable; such exchangers might include shell
and tube, plate, and coil heat exchangers without limitation.
Further heat exchangers may be known to one skilled in the art.
[0045] The chlorination product stream 16 comprises chlorobenzene,
unconverted benzene, and HCl. Product stream 16 may be treated by
any means known in the art to recover any unreacted benzene, remove
produced HCl, and purify chlorinated benzene. In an embodiment
illustrated in FIG. 2, product stream 16 is fluidly coupled a
treatment system 99. Treatment system 99 comprises treatment vessel
30; the treatment vessel 30 is fluidly coupled to reactor 10 by
product stream 16. Further, the treatment vessel 30 is drained by
catalyst free stream 32 to a holding tank 50. Holding tank 50
stores the catalyst free chlorobenzene product prior to further
treatment. In the illustrated embodiment, holding tank 50 is in
fluid communication with a chlorobenzene distillation column(s) 60
via distillation inlet stream 33. The chlorobenzene distillation
column(s) 60 are in fluid connection with further processing
streams 80 by the chlorobenzene stream 65. Chlorobenzene
distillation column(s) 60 may be further in communication with a
reflux drum 90, by gas recycle system 62. Gas recycle system 62 is
fluid communication between reflux drum 90 and chlorobenzene
distillation column(s) 60. In certain instances, reflux drum 90 is
in fluidly coupled to treatment vessel 30 by water stream 92.
Reflux drum 90 additionally comprises recovered benzene stream 95
in fluid communication with secondary distillation column(s) 70.
Secondary distillation column(s) 70 may drain benzene holding tank
130 via stream 71 to feed recycle stream 20. Recycle stream 20 is
fluidly coupled to pump inlet stream 21.
[0046] Treatment vessel 30 comprises a tank, vessel, or container
configured for acid and catalyst removal. In embodiments, the acid
and catalyst from product stream are removed with water before
introduction to holding tank 50. The products comprising
chlorobenzene from holding tank 50 are fed into chlorobenzene
distillation column(s) 60. Chlorobenzene stream 65 is removed for
further processing into final products such as rubber, dyes,
pesticides, and the like, without limitation. Alternatively,
Chlorobenzene stream 65 may be sent for further separation, for
example to a distillation column wherein monochlorobenzene may be
separated from other chlorobenzene isomers, such as
paradichlorobenzene, orthodichlorobenzene, and
trichlorobenzene.
[0047] In certain embodiments, treatment vessel 30 is in fluid
communication with solvent recovery system 110. Water is drained
from treatment vessel 30, with dissolved acids and catalyst, and is
sent via stream 105 to the solvent recovery system 110 for further
removal of the organics from the water.
[0048] Benzene-containing vapor in the gas recycle system 62 is
directed from distillation column 60, condensed, and sent to reflux
drum 90. In embodiments, a portion of benzene from reflux drum 90
is recycled to distillation column(s) 60 by gas recycle system 62.
Water stream 92 may be removed from reflux drum 90 for return to
treatment vessel 30 and/or continuing processing by solvent
recovery system 110. A portion of recovered benzene stream 95, from
reflux drum 90, may be supplemented by wet benzene from holding
tank 130. The stream 71 is sent to secondary distillation column(s)
70 with recovered benzene stream 95 to produce dry benzene. The dry
benzene makes up recycle stream 20, and may be injected into pump
inlet stream 21 for recycling through the high shear system,
comprising the high shear device 40.
[0049] In embodiments, use of the disclosed process comprising
reactant mixing via high shear device 40 allows greater conversion
of benzene to chlorobenzene and/or an increase in throughput. In
embodiments, there may be several high shear devices 40 used in
series. In embodiments, the method comprises incorporating high
shear device 40 into an established process thereby enabling the
increase in production (greater throughput) from a process operated
without high shear device 40. The superior dissolution provided by
the high shear mixing may allow improvements in operating
conditions such as temperature, pressure, and contact time while
maintaining, or increasing, reaction rate. In embodiments, the
method and system of this disclosure enable design of a smaller
and/or less capital intensive process than previously possible
without the incorporation of external high shear mixer 40. In
embodiments, the disclosed method reduces operating costs/increases
production from an existing process. Alternatively, the disclosed
method may reduce capital costs for the design of new processes.
Potential benefits of this modified system and method for the
production of chlorobenzene include, but are not limited to, faster
cycle times, increased throughput, reduced operating costs, and/or
reduced capital expense due to the possibility of designing smaller
reactors and/or operating the chlorobenzene production at lower
temperature and/or pressure.
[0050] While preferred embodiments of the invention have been shown
and described, modifications thereof can be made by one skilled in
the art without departing from the spirit and teachings of the
invention. The embodiments described herein are exemplary only, and
are not intended to be limiting. Many variations and modifications
of the invention disclosed herein are possible and are within the
scope of the invention. Where numerical ranges or limitations are
expressly stated, such express ranges or limitations should be
understood to include iterative ranges or limitations of like
magnitude falling within the expressly stated ranges or limitations
(e.g., from about 1 to about 10 includes, 2, 3, 4, etc.; greater
than 0.10 includes 0.11, 0.12, 0.13, and so forth). Use of the term
"optionally" with respect to any element of a claim is intended to
mean that the subject element is required, or alternatively, is not
required. Both alternatives are intended to be within the scope of
the claim. Use of broader terms such as comprises, includes,
having, etc. should be understood to provide support for narrower
terms such as consisting of, consisting essentially of, comprised
substantially of, and the like.
[0051] Accordingly, the scope of protection is not limited by the
description set out above but is only limited by the claims which
follow, that scope including all equivalents of the subject matter
of the claims. Each and every claim is incorporated into the
specification as an embodiment of the present invention. Thus, the
claims are a further description and are an addition to the
preferred embodiments of the present invention. The discussion of a
reference in the Description of Related Art is not an admission
that it is prior art to the present invention, especially any
reference that may have a publication date after the priority date
of this application. The disclosures of all patents, patent
applications, and publications cited herein are hereby incorporated
by reference, to the extent they provide exemplary, procedural or
other details supplementary to those set forth herein.
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