U.S. patent application number 13/115950 was filed with the patent office on 2011-12-22 for cracking catalysts, additives, methods of making them and using them.
This patent application is currently assigned to Intercat, Inc.. Invention is credited to Mehdi Allahverdi, Guido Aru, Paul Diddams, Xunhua Mo, William Reagan, Shanthakumar Sithambaram.
Application Number | 20110309286 13/115950 |
Document ID | / |
Family ID | 45004793 |
Filed Date | 2011-12-22 |
United States Patent
Application |
20110309286 |
Kind Code |
A1 |
Allahverdi; Mehdi ; et
al. |
December 22, 2011 |
CRACKING CATALYSTS, ADDITIVES, METHODS OF MAKING THEM AND USING
THEM
Abstract
Collection enhanced materials, down stream additives, and
methods of making the enhanced materials and down stream additives
are provided. In one embodiment, a down stream additive is provided
that includes an active phase component and at least one of a
collection enhancing component. In other embodiments, the down
stream additive may have attrition index from about two (2) to
about ten (10) and/or an average diameter from about 20 .mu.m to
about 60 .mu.m. In other embodiments, the down stream additive may
have an active phase component which is incompatible with a process
performed in an FCC unit. In yet another embodiment, a collection
enhanced material having an average diameter from about 60 .mu.m to
about 300 .mu.m is provided that includes an active component and a
collection enhancing component.
Inventors: |
Allahverdi; Mehdi; (Pooler,
GA) ; Aru; Guido; (Conifer, CO) ; Diddams;
Paul; (Prague, CZ) ; Mo; Xunhua; (Savannah,
GA) ; Reagan; William; (Montgomery, IL) ;
Sithambaram; Shanthakumar; (Pooler, GA) |
Assignee: |
Intercat, Inc.
Manasquan
NJ
|
Family ID: |
45004793 |
Appl. No.: |
13/115950 |
Filed: |
May 25, 2011 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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61396255 |
May 25, 2010 |
|
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|
61428654 |
Dec 30, 2010 |
|
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61437866 |
Jan 31, 2011 |
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Current U.S.
Class: |
252/62.55 ;
252/182.32; 252/500; 252/512; 252/513; 252/62.51R; 502/2 |
Current CPC
Class: |
B01D 2255/20723
20130101; B01D 53/8609 20130101; B01D 2255/2045 20130101; B01D
2255/2092 20130101; B01D 2255/20738 20130101; B01D 2255/1023
20130101; Y10T 137/0318 20150401; B01D 2255/2027 20130101; B01J
20/08 20130101; B01D 2255/1021 20130101; B01D 2255/20776 20130101;
Y10T 137/7722 20150401; B01D 2255/702 20130101; C10G 2300/405
20130101; B01D 53/8628 20130101; B01D 2255/1026 20130101; B01D
2255/9202 20130101; G05D 7/00 20130101; Y10T 137/0324 20150401;
B01D 2255/104 20130101; B01D 2255/30 20130101; B01J 20/041
20130101; B01D 2251/2067 20130101; B01D 2255/50 20130101; B01D
2255/20707 20130101; C10G 11/187 20130101; Y02C 20/10 20130101;
B01D 2255/2022 20130101; B01D 2255/20761 20130101; C10K 1/32
20130101; B01D 2255/106 20130101; B01J 20/06 20130101; B01D
2255/1025 20130101; B01D 2255/906 20130101; B01D 2251/2062
20130101; B01D 2255/1028 20130101 |
Class at
Publication: |
252/62.55 ;
502/2; 252/62.51R; 252/500; 252/182.32; 252/513; 252/512 |
International
Class: |
B01J 35/02 20060101
B01J035/02; B01J 23/30 20060101 B01J023/30; B01J 29/04 20060101
B01J029/04; B01J 23/46 20060101 B01J023/46; B01J 23/44 20060101
B01J023/44; B01J 23/50 20060101 B01J023/50; B01J 23/52 20060101
B01J023/52; B01J 23/42 20060101 B01J023/42; B01J 31/02 20060101
B01J031/02; H01F 1/00 20060101 H01F001/00; H01B 1/00 20060101
H01B001/00; H01F 1/04 20060101 H01F001/04; C09K 3/00 20060101
C09K003/00; H01B 1/02 20060101 H01B001/02; B01J 23/22 20060101
B01J023/22 |
Claims
1. A flue gas additive comprising: an active phase component; and a
member selected from the group consisting of A) the flue gas
additive further comprises a collection enhancing component having
a characteristic selected from the group consisting of increased
magnetic susceptibility, encouragement of clumping, and low
electrical resistivity; B) the flue gas additive has an attrition
index from about two (2) to about ten (10); C) the flue gas
additive has an average diameter from about 20 .mu.m to about 60
.mu.m; and D) the flue gas additive has an active phase component
selected from the group consisting of copper, sodium, potassium,
nickel, vanadium, and iron.
2. The flue gas additive of claim 1 comprising the collection
enhancing component, wherein the collection enhancing component
comprises a low electrical resistivity component comprising an
inert ionic compound.
3. (canceled)
4. The flue gas additive of claim 2, wherein the inert ionic
compound has a characteristic selected from the group consisting of
substantially maintaining the functionality of the active phase
component, substantially affixed to the active phase component
during transport through a processing environment, and
substantially chemically stable in a processing environment.
5. The flue gas additive of claim 1 comprising the collection
enhancing component, wherein the collection enhancing component
comprises a low electrical resistivity component having a
resistivity value less than or equal to 2.00E+08 ohm-cm at a
temperature of 850 degrees Celsius.
6-8. (canceled)
9. The flue gas additive of claim 1 comprising the collection
enhancing component, wherein the collection enhancing component
comprises a magnetic susceptibility increasing component selected
from the group consisting of iron, stable iron compounds or other
transition metals, and rare earth ions.
10. The flue gas additive of claim 1 comprising the collection
enhancing component, wherein the collection enhancing component
comprises a clumping encouragement component selected from the
group consisting of fluxing agents, vanadium, sodium, and calcium
oxide.
11-13. (canceled)
14. The flue gas additive of claim 1, wherein the flue gas additive
has an attrition index in a range from about two (2) to about ten
(10).
15-16. (canceled)
17. The flue gas additive of claim 14 further comprising: a
collection enhancing component selected from the group consisting
of a magnetic susceptibility increasing component, clumping
encouragement component and a low electrical resistivity
component.
18. The flue gas additive of claim 17 comprising the collection
enhancing component, wherein the collection enhancing component has
a weight percent in a range from greater than 0 to about 20 percent
of the flue gas additive.
19. The flue gas additive of claim 14, wherein the active phase
component is selected from the group consisting of copper, sodium,
potassium, nickel, vanadium, and iron.
20-30. (canceled)
31. A collection enhanced material comprising: an active phase
component; a collection enhancing component comprises a component
selected from the group consisting of a low electrical resistivity
component, and magnetic susceptibility increasing component; and
wherein the collection enhanced material have an average diameter
in a range from about 60 .mu.m to about 300 .mu.m.
32. The collection enhanced material of claim 31, wherein the
collection enhancing component comprises a low electrical
resistivity component comprising an inert ionic compound.
33-34. (canceled)
35. The collection enhanced material of claim 31, wherein the
collection enhancing component comprises a low electrical
resistivity component, and wherein the low electrical resistivity
component has a resistivity value less than or equal to about
2.00E+08 ohm-cm at a temperature of about 850 degrees Celsius.
36. The collection enhanced material of claim 31, wherein the
active phase component is selected from the group consisting of
SO.sub.x reducing component, NO.sub.x reducing component, and
combinations thereof.
37. (canceled)
38. The collection enhanced material of claim 31, wherein the
collection enhancing component comprise a member selected from the
group consisting of an active phase component comprising an
embedded collection enhancing component, an active phase component
comprising an incorporated collection enhancing component, and an
active phase component comprising at least a partial collection
enhancing component coating.
39-40. (canceled)
41. The collection enhanced material of claim 31, wherein the
collection enhancing component comprises a plurality of components
selected from the group consisting of a magnetic susceptibility
increasing component, a clumping encouragement component, and a low
electrical resistivity component.
42-43. (canceled)
44. The collection enhanced material of claim 31, wherein the
collection enhanced material has an attrition index in a range from
about two (2) to about ten (10).
45-46. (canceled)
47. The collection enhanced material of claim 44 further
comprising: a collection enhancing component selected from the
group consisting of a magnetic susceptibility increasing component,
clumping encouragement component, and a low electrical resistivity
component.
48-50. (canceled)
51. The collection enhanced material of claim 31 further
comprising: a support phase component selected from the group
consisting of hydrotalcite, alumina, high acidic matrix catalyst,
silica, silica alumina, TiO.sub.2, active carbon, micro porous
material, zeolites, germanium aluminophosphate (AlPO), and
combinations of one or more thereof.
52-55. (canceled)
56. The collection enhanced material of claim 31, wherein the
active phase component is selected from the group consisting of
SCR-type catalysts having ceramic material carriers and active
catalytic components, oxides of base metals, oxides of vanadium,
oxides of tungsten, zeolites, ruthenium, rhodium, palladium,
silver, osmium, iridium, platinum, gold, zeolite-based SCRs, iron-
and copper-exchanged zeolite urea SCRs, and vanadium-urea SCRs.
57-63. (canceled)
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application claims benefit of U.S. Provisional Patent
Application Ser. No. 61/396,255, filed May 25, 2010, U.S.
Provisional Patent Application Ser. No. 61/428,654, filed Dec. 30,
2010, and U.S. Provisional Patent Application Ser. No. 61/437,866,
filed Jan. 31, 2011, which are incorporated by reference in their
entireties.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] Embodiments of the invention generally relate to one or more
collection enhanced materials, down stream additives, methods of
making such, apparatuses for adding such when used with one or more
units, and methods of using such in one or more units, such as
fluidized units.
[0004] 2. Description of the Related Art
[0005] FIG. 1 is a schematic diagram of a conventional fluid
catalytic cracking system 130. The fluid catalytic cracking system
130 generally includes a fluid catalytic cracking (FCC) unit 100
coupled to a catalyst addition system 110, a petroleum feed stock
source 104, an exhaust gas system 114, and a distillation system
116.
[0006] The FCC unit 100 includes a regenerator 150 and a reactor
152. The reactor 152 primarily houses the catalytic cracking
reaction of the petroleum feed stock and delivers the cracked
product in vapor form to the distillation system 116. Spent
catalyst from the cracking reaction is transferred from the reactor
152 to the regenerator 150 to regenerate the catalyst by removing
coke and other materials. The regenerated catalyst is then
reintroduced into the reactor 152 to continue the petroleum
cracking process. Exhaust gas from the regenerator 150 exits the
FCC unit 100 through an exhaust path 108, traveling through the
exhaust system 114 until exiting the exhaust system 114 to the
environment through an exhaust flue 106.
[0007] The catalyst addition system 110 maintains a continuous or
semi continuous addition of fresh base catalyst to the inventory
circulating between a regenerator and a reactor. The catalyst
addition system 110 generally includes a vessel 112 coupled to the
FCC unit 100 by a feed line 118. An additive addition system 120
may also be utilized to maintain a continuous or semi continuous
addition of fresh additives to the FCC unit 100, for example, for
emission control. The additive addition system 120 is typically
disposed near the catalyst addition system 110 and generally
includes a vessel 122 coupled to the FCC unit 100 by the feed line
118.
[0008] During the catalytic cracking process, there is a dynamic
balance of the total amount of the base cracking catalyst within
the FCC unit and desire to maintain the activity level of the base
cracking catalyst within the FCC unit. The amount of base cracking
catalyst within the FCC unit may increase over time, which may
result in the catalyst bed level within the regenerator reaching an
upper operating limit. The catalyst bed level may reach an upper
operating limit when the catalyst addition rate for maintenance of
catalyst activity or level exceeds the lost catalyst and the excess
catalyst is periodically withdrawn from the FCC unit. Conversely,
the amount of base catalyst within the FCC unit may decrease
significantly over time, causing the performance and desired output
of the FCC unit to diminish, and in extreme cases the FCC unit may
become inoperable. For example, fresh base cracking catalyst is
periodically added to the FCC unit to replace base catalyst lost in
various ways or to replenish base catalyst which has become
deactivated over time. Catalyst and additives become fines (also
called particulate matter and hereinafter referred to as "PM") by
attrition during gradual transfer to and from the reactor 152 and
regenerator 150. Fines transfer more easily out of the FCC unit
with the waste or product streams. Fines exiting the regenerator
through the exhaust flue may be considered an environmental hazard.
As such, one or more particle removal devices are typically
utilized to prevent fines from exiting the exhaust flue. These
particle removal devices may include third stage separators (TSS)
and electrostatic precipitators (ESP). In many refineries, the ESP
is the final device used to reduce the level of PM emitted to
atmosphere from the FCC flue gas stream by absorbing PM.
[0009] To improve ESP collection of PM, a refiner generally
increases the power to the ESP, and/or injects ammonia into or
upstream of the ESP. Increased power usage is expensive and
increases CO.sub.2 emissions Ammonia is effective, but excess
ammonia can lead to ammonia emission through the flue stack, which
is also under scrutiny as an environmental pollutant. Thus,
increasing the efficiency of the ESP with ammonia is not considered
a viable long term solution.
[0010] Additionally, refineries must also meet Environmental
Protection Agency (EPA) SO.sub.x emissions regulations. However,
low levels of SO.sub.x emissions in the FCC unit flue gas stream
causes an increase in the emission of PM. Thus, as refineries try
to reduce SO.sub.x emissions to meet environmental regulations,
operating costs increase along with an increase in the amount of PM
released to the environment through the flue stack.
[0011] Thus, a need exists for a cost effective way to meet EPA
SO.sub.x emissions regulations without increasing PM emissions or
increasing ammonia usage. A need also exists for collection
enhanced materials, down stream additives, methods of making such,
apparatuses for adding such to one or more units, and methods of
using such in one or more units, such as fluidized units.
[0012] BRIEF DESCRIPTION
[0013] The purpose and advantages of embodiments of the invention
will be set forth and apparent from the description of exemplary
embodiments that follow, as well as will be learned by practice of
the embodiments of the invention. Additional advantages will be
realized and attained by the methods and systems particularly
pointed out in the written description and claims hereof, as well
as from the appended drawings.
[0014] Embodiments of the invention generally include collection
enhanced materials, down stream additives, methods of making the
enhanced materials and down stream additives, apparatuses for
handling enhanced materials and down stream additives when used
with one or more units, and methods for using the same to improve
the operation of units, such as fluidized units, among others.
[0015] In one embodiment, a down stream additive includes an active
phase component and having one or more characteristics such as
below either individually or in a combination of two or more
thereof. Examples of characteristics include, but are not limited
to: A) the down stream additive further comprises a collection
enhancing component having one or more characteristics such as
increased magnetic susceptibility, encouragement of clumping, and
low electrical resistivity; B) the down stream additive has an
attrition index from about two (2) to about ten (10); C) the down
stream additive has an average diameter from about 20 .mu.m to
about 60 .mu.m; and D) the active phase component includes one or
more elements such as copper, sodium, potassium, nickel, vanadium,
and iron.
[0016] In another embodiment of the invention, a collection
enhanced material includes an active component and a collection
enhancing component having one or more characteristics such as
increased magnetic susceptibility, and low electrical resistivity,
and wherein the collection enhanced material having an average
diameter from about 60 .mu.m to about 300 .mu.m, either
individually or in a combination of two or more thereof.
DESCRIPTION OF THE DRAWINGS
[0017] The accompanying figures, which are incorporated in and
constitute part of this specification, are included to illustrate
and provide a further understanding of the different embodiments of
the materials, method and system of the invention. Together with
the description, the drawings serve to explain the principles of
the invention.
[0018] FIG. 1 is a schematic diagram of a conventional fluid
catalytic cracking system;
[0019] FIG. 2 is a schematic diagram of an exemplary unit
illustrating how materials of the present invention interface with
a unit in accordance with an embodiment of the invention;
[0020] FIG. 3A is a simplified schematic of a collection enhanced
material in accordance with an embodiment of the invention;
[0021] FIG. 3B is a simplified schematic of a collection enhanced
material in accordance with another embodiment of the
invention;
[0022] FIG. 3C is a simplified schematic of a collection enhanced
material in accordance with another embodiment of the
invention;
[0023] FIG. 4 is a graph of a low electrical resistivity component
having less than or equal to about a resistivity value at a given
temperature in accordance with an embodiment of the invention;
[0024] FIG. 5 is another graph of a low electrical resistivity
component having less than or equal to about a resistivity value at
a given temperature in accordance an embodiment of the
invention;
[0025] FIG. 6 is a simplified schematic of a down stream additive
in accordance with an embodiment of the invention;
[0026] FIG. 7 is a flow diagram of a method for making collection
enhanced material in accordance with another embodiment of the
invention;
[0027] FIG. 8 is a flow diagram of a method for making collection
enhanced material in accordance with another embodiment of the
invention;
[0028] FIG. 9 is a schematic diagram of an addition system
integrated with a flue gas exhaust gas stream in accordance an
embodiment of the invention;
[0029] FIG. 10 is a schematic diagram of a vessel of the addition
system of FIG. 9 in accordance with an alternative embodiment of
the invention;
[0030] FIG. 11 is a schematic diagram of a vessel of the addition
system of FIG. 9 in accordance with an alternative embodiment of
the invention;
[0031] FIG. 12 is a schematic diagram of a vessel of the addition
system of FIG. 9 in accordance with an alternative embodiment of
the invention;
[0032] FIG. 13 is a schematic diagram of a vessel of the addition
system of FIG. 9 in accordance with an alternative embodiment of
the invention;
[0033] FIG. 14 is a schematic diagram of one embodiment of an
electrostatic precipitator in accordance an embodiment of the
invention;
[0034] FIG. 15 is a down stream addition system integrated in a
flue gas exhaust gas stream in accordance an embodiment of the
invention;
[0035] FIG. 16 is a circulating fluid bed separator with a
dedicated regenerator which may be utilized in a down stream
addition system in accordance an embodiment of the invention;
[0036] FIGS. 17A-17C are schematic diagrams of one or more addition
systems interfaced with one or more units in accordance with
alternative exemplary embodiments of the invention;
[0037] FIGS. 18A-18B are schematic diagrams for coupling an
addition system to one or more units in accordance with exemplary
alternative embodiments of the invention;
[0038] FIG. 19 is a flow diagram of a method of providing at least
one of a collection enhanced material and down stream additive to a
gaseous exhaust stream of a unit in accordance with embodiments of
the invention;
[0039] FIG. 20 is a flow diagram of a method of removing at least
one of a collection enhanced material and down stream additive to a
gaseous exhaust stream of a unit in accordance with embodiments of
the invention;
[0040] FIG. 21 is a flow diagram of a method of recycling at least
a portion of material removed from a gaseous exhaust stream of a
unit back to the gaseous exhaust stream without passing through the
unit in accordance with embodiments of the invention.
[0041] To facilitate understanding, identical reference numerals
have been used, where possible, to designate identical elements
that are common to the figures, except that suffixes may be added,
when appropriate, to differentiate such elements. The images in the
drawings are simplified for illustrative purposes and are not
depicted to scale. It is contemplated that features or steps of one
embodiment may be beneficially incorporated in other embodiments
without further recitation.
DETAILED DESCRIPTION
[0042] In the following description, like reference characters
designate like or corresponding parts throughout the several views
shown in the figures. It is also understood that terms such as
"top," "bottom," "outward," "inward," and the like are words of
convenience and are not to be construed as limiting terms.
[0043] Approximating language, as used herein throughout the
specification and claims, may be applied to modify any quantitative
or qualitative representation that could permissibly vary without
resulting in a change in the basic function to which it is related.
Accordingly, a value modified by a term such as "from about" or "to
about" is not to be limited to a specified precise value, and may
include values that differ from the specified value. In at least
some instances, the approximating language may correspond to the
precision of an instrument for measuring the value.
[0044] Reference will now be made in detail to exemplary
embodiments of the invention which are illustrated in the
accompanying figures and examples. Referring to the drawings in
general, it will be understood that the illustrations are for
describing a particular embodiment of the invention and are not
intended to limit the invention thereto.
[0045] Whenever a particular embodiment of the invention is said to
comprise or consist of at least one element of a group and
combinations thereof, it is understood that the embodiment may
comprise or consist of any of the elements of the group, either
individually or in combination with any of the other elements of
that group, including any stable reaction products of any
combination of elements of the group. Furthermore, when any
variable occurs more than one time in any constituent or in
formula, its definition on each occurrence is independent of its
definition at every other occurrence. Also, combinations of
substituents and/or variables are permissible only if such
combinations result in stable compounds.
[0046] An embodiment of the invention includes materials which
enhance the collection of PM in an exhaust stream of a unit and/or
reduce emissions in an exhaust stream of a unit. Materials of the
present invention are generally grouped according to the
interaction of the materials with the unit. FIG. 2 is an exemplary
unit illustrating context of various embodiments of the materials
of the invention. Once the distinction between different
embodiments of the materials has been established, details for each
embodiment of the materials of the invention will follow.
[0047] FIG. 2 is a schematic diagram of one embodiment of a unit
200 having one or more reaction zones 202 defined in detailed
therein. The unit 200 includes an exhaust system 204 through which
a gaseous exhaust stream is routed through a flue stack 206 to the
environment. The exhaust system 204 includes a particle removal
device 208, which may include one or more third stage separators
(TSS) and/or ESPs. The particle removal device 208 removes PM,
which may at least partially include the materials of the present
invention, from the exhaust stream. At least some embodiments of
the materials of the present invention are suitable for recycling
through the reaction zone 202 of the unit 200 and/or recycling
through the exhaust system 204 handling the gaseous exhaust stream
exiting the unit 200.
[0048] As discussed above, materials of the present invention which
enhance the collection of PM in the exhaust stream exiting the unit
and/or reduce emissions in the exhaust stream of the unit are
grouped according to the interaction of the materials with the
unit. A first group of materials of the present invention are
hereinafter referred to as collection enhanced materials (CEM),
illustrated below in FIG. 3A utilizing reference numeral 300. CEM
300 generally are material having an attribute that makes the
collection of CEM by the particle removal device 208 from the
exhaust stream exiting the unit 200 through the exhaust system 204
more efficient relative to conventional catalysts and additives.
CEM 300 as described herein is a virgin material, meaning that the
material has never been exposed to a process for which it has been
intended, for example, as a cracking catalyst within an FCC unit.
In some embodiments, CEM 300 is recycled after exposure, wherein
the term recycled CEM will be utilized to provide distinction from
virgin CEM. CEM 300 includes two subgroups, collection enhanced
catalysts (CEC) and collection enhanced additives (CEA).
Collection Enhanced Materials (CEM)
[0049] In an embodiment of the invention illustrated in FIG. 3A,
CEM 300 comprises one or more active phase components 302 and one
or more collection enhancing components 304. The one or more
collection enhancing components 304 comprise one or more low
electrical resistivity components 306 and one or more magnetic
susceptibility increasing components 308, either individually or in
a combination of two or more thereof
[0050] In one embodiment of the CEM 300 as illustrated in FIG. 3A,
the active phase component 302 and the one or more collection
enhancing components 304 are in contact. Optional additional
collection enhancing components 304 are shown in phantom in FIG.
3A. In an embodiment, the one or more collection enhancing
components 304 in contact with the active phase component 302
comprises one or more low electrical resistivity components 306. In
another embodiment, the one or more collection enhancing components
304 in contact with the active phase component 302 comprises one or
more magnetic susceptibility increasing components 308. In yet
another embodiment, the one or more collection enhancing components
304 in contact with the active phase component 302 comprises one or
more low electrical resistivity components 306 and one or more
magnetic susceptibility increasing components 308. Embodiments of
the invention are not limited by how one or more collection
enhancing components 304 are in contact with the active phase
component 302. In an embodiment, the one or more collection
enhancing components 304 and the active phase component 302 are in
contact in a manner such as, but not limited to, coating,
incorporating, and embedding, etc., either individually or in
combination of two or more thereof. For example, CEM 300 may
comprise an active phase component 302 comprising an embedded
collection enhancing component 304, an active phase component
comprising 302 an incorporated collection enhancing component 304,
and an active phase component 302 comprising at least a partial
collection enhancing component coating, either individually or in
combination of two or more thereof. Embodiments of the invention
are also not limited by the shape, size, or form of the one or more
collection enhancing components 304, the one or more low electrical
resistivity components 306 and the one or more magnetic
susceptibility increasing components 308, or by the shape, size, or
form of the CEM 300 itself. Non-limiting examples of the form of
the low electrical resistivity components 306, the magnetic
susceptibility increasing components 308, and the CEM 300 include,
but are not limited to, liquid, powder, and formed solid shapes
such as microspheres, beads, and extrudates, either individually or
in a combination of two or more forms. Furthermore, in some
embodiments, the size or shape of the CEM 300 has varying
dimensions of depth, width, and length.
[0051] In another embodiment of the CEM 300 as illustrated in FIG.
3A, the active phase component 302 includes one or more collection
enhancing components 304. In an embodiment, the active phase
component 302 comprises one or more collection enhancing components
304 such as one or more low electrical resistivity components 306.
In another embodiment, the active phase component 302 comprises one
or more collection enhancing components 304 such as one or more
magnetic susceptibility increasing components 308. In yet another
embodiment, the active phase component 302 comprises one or more
collection enhancing components 304 such as one or more low
electrical resistivity components 306 and one or more magnetic
susceptibility increasing components 308. Embodiments of the
invention are not limited by how one or more collection enhancing
components 304 are part of the active phase component 302.
[0052] In an embodiment, low electrical resistivity components 306
include, but are not limited to, one or more inert ionic compounds.
In another embodiment, low electrical resistivity components 306
include, but are not limited to, one or more cations and one or
more anions, either individually or in combination of two or more
thereof Non-limiting examples of cations include elements such as
from periodic table columns 1A, 2A, 3A, and 4A, either individually
or in combination of two or more thereof. In one embodiment,
non-limiting examples of anions include elements such as from
periodic table columns 5B and 6B, either individually or in
combination of two or more thereof. In another embodiment, low
electrical resistivity components 306 include, but are not limited
to, magnesium sulphate and calcium sulphate, either individually or
in combination of two or more thereof
[0053] In an embodiment, the low electrical resistivity component
306 has a characteristic of substantially maintaining the
functionality of the active phase component 302. In another
embodiment, the low electrical resistivity component 306 has a
characteristic of remaining substantially affixed to the active
phase component 302 during transport through a processing
environment of the unit 200 to the particle removal device 208. In
another embodiment, the low electrical resistivity component 306
has a characteristic of being substantially chemically stable under
the operating conditions present in the reaction zone 202 of the
unit 200.
[0054] In another embodiment, low electrical resistivity components
306 include compositions having a resistivity about less than or
equal to a resistivity value at a given temperature, for example,
as illustrated in a graph 400 of resistivity and temperature
provided in FIG. 4. In the embodiment illustrated in FIG. 4, the
low electrical resistivity components 306 include compositions
having a resistivity about less than or equal to a resistivity
value at a given temperature as shown by line 402. In a particular
embodiment, the low electrical resistivity component 306 has a
resistivity value of less than or equal to about 2.00E+08 ohm-cm at
a temperature of about 850 degrees Celsius. In another embodiment,
the low electrical resistivity component 306 has a resistivity
value of less than or equal to about 3.50E+08 ohm-cm at a
temperature of about 800 degrees Celsius. In yet another
embodiment, the low electrical resistivity component 306 has a
resistivity value of less than or equal to about 3.00E+13 ohm-cm at
a temperature of about 300 degrees Celsius. In another embodiment,
the low electrical resistivity component 306 has a resistivity
value of less than or equal to about 1.00E+16 ohm-cm at a
temperature of about 14 degrees Celsius.
[0055] In another embodiment as shown in a graph 500 illustrated in
FIG. 5, low electrical resistivity components 306 include
compositions having a resistivity about less than or equal to about
a resistivity value at a given temperature as shown by line 502
illustrated in a graph 500 of resistivity and temperature provided
in FIG. 5. Line 502 represents the resistivity value at a given
temperature for CEM 300 having a metal low electrical resistivity
component 306. Other embodiments of CEM 300 have resistivity values
equal to or below the resistivity value indicated by line 502. The
other lines for various other materials provided on graph 500 are
provided for comparison, including an example of a conventional
catalyst illustrated by line 504.
[0056] In another embodiment, the collection enhancing component
304 includes one or more magnetic susceptibility increasing
components 308. Magnetic susceptibility increasing components 308
include iron, stable iron compounds, transition metals, and rare
earth ions, either individually or in a combination of two or more
thereof. Other magnetic susceptibility increasing components 308
include manganese, chromium, nickel, and cobalt, either
individually or in a combination of two or more thereof. Virgin
conventional catalysts and additives generally contain some iron,
rare earths, or other magnetically active materials when they are
made; however, this magnetism will be treated as "background" as
the CEM 300 is relatively more magnetic through the inclusion of a
magnetic susceptibility increasing component 308 that has the
specifically intended characteristic of increasing the magnetism
over and above the background level. In one embodiment for example,
the magnetic susceptibility increasing component 308 has a magnetic
susceptibility of at least about 500 cgs per atomic weight at about
20 degrees Celsius. It is known that conventional catalysts and
additives may have magnetic material deposited while present within
the unit. However, the virgin CEM 300 (and other materials of the
invention) as described herein excludes materials which have been
exposed to processes performed in the unit, and are thereby free of
materials that may be deposited thereon during use inside a unit,
for example, metals and coke deposited during cracking processes
performed in an FCC unit. As such, the magnetic susceptibility
increasing components 308 are part of the CEM 300 (and other
materials of the invention) in its virgin state. In an embodiment,
the magnetic susceptibility increasing component 308 comprises any
stable reaction products of one or more magnetic susceptibility
increasing components 308. In another embodiment, the magnetic
susceptibility increasing component 308 comprises any stable
reaction products of one or more magnetic susceptibility increasing
components 308. In another embodiment, the collection enhancing
component 304 comprises any stable reaction products of one or more
low electrical resistivity components 306 and one or more magnetic
susceptibility increasing components 308, either individually or in
a combination of two or more thereof. In some embodiments, the
particle removal device 208 is adapted to magnetically attract the
CEM 300 when CEM 300 having increased magnetic susceptibility is
utilized.
[0057] In an embodiment, CEM 300 comprises any stable reaction
products of one or more collection enhancing components 304 and one
or more active phase components 302. In another embodiment, the
collection enhancing component 304 comprises any stable reaction
products of one or more low electrical resistivity components 306
and one or more magnetic susceptibility increasing components 308,
either individually or in a combination of two or more thereof
[0058] In another embodiment, the active phase component 302 of the
CEM 300 is in contact with the one or more collection enhancing
components 304. In one embodiment, the combined weight percent of
the one or more low electrical resistivity components 306 and/or
one or more magnetic susceptibility increasing components 308 is in
a range from greater than 0 to about 20 weight percent of the CEM
300. In another embodiment, the combined weight percent of the one
or more low electrical resistivity components 306 and/or one or
more magnetic susceptibility increasing components 308 is in a
range from greater than 0 to about 15 weight percent of the CEM
300. In yet another embodiment, the combined weight percent of the
one or more low electrical resistivity components 306 and/or one or
more magnetic susceptibility increasing components 308 is in a
range from greater than 0 to about 10 weight percent of the CEM
300. In a particular embodiment, the combined weight percent of the
one or more low electrical resistivity components 306 and/or one or
more magnetic susceptibility increasing components 308 is in a
range from greater than 0 to about 5 weight percent of the CEM 300.
When stating the combined weight percent of the one or more low
electrical resistivity components 306 and/or one or more magnetic
susceptibility increasing components 308 is in a range from a
certain weight percentage of the CEM 300, the one or more such
components 306, 308 may be embedded in, incorporated in, or coat
the active phase component, and is not limited by how the
component(s) is/are in contact with, or are part of the active
phase component 302 of the CEM 300.
[0059] In an embodiment, each active phase component 302 with the
one or more collection enhancing components 304 comprise properties
independent of any other active phase component 302 of the CEM
300.
[0060] The above embodiments include an active phase component 302
with one or more collection enhancing components 304. In an
embodiment, the one or more collection enhancing components 304 is
in contact with at least one or more other collection enhancing
components 304 which differ from each other to preferentially have
a synergistic, unexpected combined effect of decreasing the
electrical resistance of CEM 300 and/or increasing magnetic
properties. In one embodiment, a plurality of collection enhancing
components 304 which differ from each other, and have a
synergistic, unexpected combined effect of decreasing the
electrical resistance of CEM 300, increasing the magnetic
properties of CEM 300, or both compared to conventional catalysts
and additives.
[0061] The active phase component 302 comprises one of a host
catalyst component or host additive component. In an embodiment,
the host catalyst component or host additive component generally
comprises a conventional catalyst or additive which is modified to
include one or more low electrical resistivity components and/or
one or more magnetic susceptibility increasing components thereby
becoming the CEM 300, and thereby resulting in the CEM 300 having
an enhanced collection efficiency by the particle removal device
208 as compared to a conventional unmodified catalyst or
additive.
[0062] In an embodiment, the active phase component 302 of the CEM
300 comprises one or more collection enhancing components 304. The
one or more collection enhancing components 304 comprises low
electrical resistivity components 306 and/or the one or more
magnetic susceptibility increasing components 308, either
individually or in combination of two or more thereof. The one or
more low electrical resistivity components 306 and/or the one or
more magnetic susceptibility increasing components 308 modify the
active phase component 302 by, but not limited to, a physical
process step(s) rather than the changes in the actual weight
percent content of active phase component 302. For example,
modifying could refer to 1) the order of providing ingredients to
the spray dryer slurry, such as providing the one or more low
electrical resistivity components 306 and/or the one or more
magnetic susceptibility increasing components 308 to the final
slurry last or first; and 2) spraying a low electrical resistivity
component 306 and/or magnetic susceptibility increasing component
308 on the active phase component 302 such that the low electrical
resistivity component 306 and/or magnetic susceptibility increasing
component 308 at least partially coats the active phase component
302, for example, with microspheres.
[0063] Advantages of the CEM 300 described above reduces the amount
of PM escaping collection by the particle removal device 208 from
the gaseous exhaust stream exiting the unit 200 through the exhaust
system 204 since the portion of PM in the gaseous exhaust stream
that comprises CEM 300 is readily collectable. Not to be limited by
theory, gas and PM entrained in the gaseous exhaust stream enter
the ESP of the particle removal device 208. High voltage discharge
electrodes of the ESP ionize the gas molecules (negative
ions/anions). The gas ions adsorb onto the surface of the PM,
giving the PM a negative charge. Charged PM is attracted to and
sticks to the collection plates of the ESP. As the collection
plates of the ESP are grounded, the charge of the PM slowly
dissipates. The collection plates are periodically "rapped" to
cause the PM to drop off of the collection plate and fall to the
bottom of the ESP, where the PM is collected and removed from the
ESP.
[0064] Different gases, such as, but not limited to, NH.sub.3,
SO.sub.x, NO.sub.x, and H.sub.2O, may be charged or ionized to
varying degree. In one embodiment, such gases charge-up easily,
thereby providing sufficient ions to increase the rate of
charging-up of PM. For ESP efficiency, gases such as, but not
limited to, SO.sub.x, NO.sub.x, and H.sub.2O are present in
sufficient quantity to create enough ions to charge-up the PM
quickly.
[0065] The "resistivity" of the PM is the property that determines
how "resistant" the particles are to charging. PM having low
resistivity is less resistant to charging, and consequently, more
easily charged resulting in good capture efficiency by the ESP.
Thus, PM having low resistivity, such as in certain embodiments of
CEM 300, is desirable to enable better collection at the ESP.
[0066] In an embodiment of CEM 300, one or more collection
enhancing components 304 are physically separate and distinct
particles which means that the collection enhancing component 304
has a primary functionality distinct from the active phase
component 302 in a single particle system.
[0067] In another embodiment in contrast to the multi-particle
particle system, one or more collection enhancing components 304
are part of the CEM 300 as a single particle system. In an
embodiment of the single particle system, the collection enhancing
component 304 is in contact with and affixed to the active phase
component 302. The collection enhancing components 304 may be
affixed to the active phase component 302 by such as but not
limited to incorporating, coating, and embedding the collection
enhancing components 304 in or onto the active phase component 302.
In yet another embodiment as a single particle system, the active
phase component 302 has a primary functionality distinct from the
primary functionality of the collection enhancing component 304.
For comparative distinction, when collection enhancing components
304 are incorporated within or as part of the active phase
component 302 in a single particle system instead of as physically
separate and distinct particles from the active phase component 302
in a multi-particle particle system, dual or multiple
characteristics of the active phase component 302 and the
collection enhancing components 304 co-exist within the same single
particle by virtue of the proximity of the components.
Collection Enhanced Catalysts (CEC)
[0068] FIG. 3B schematically depicts CEC 310 according to an
embodiment of the invention. In an embodiment, CEC 310 comprises an
active phase component 312 and a collection enhancing component
304. In another embodiment, CEC 310 comprises any stable reaction
products of one or more collection enhancing components 304 and one
or more active phase components 312. In an embodiment, the
collection enhancing component 304 comprises one or more low
electrical resistivity components 306 and one or more magnetic
susceptibility increasing components 308, either individually or in
a combination of two or more thereof. The optional additional
collection enhancing components 304 are shown in phantom in FIG.
3B.
[0069] In one embodiment, the active phase component 312 of the CEC
310 is in contact with the one or more collection enhancing
components 304. In an embodiment, the one or more collection
enhancing components 304 in contact with the active phase component
312 comprises one or more low electrical resistivity components
306. In another embodiment, the one or more collection enhancing
components 304 in contact with the active phase component 312
comprises one or more magnetic susceptibility increasing components
308. In yet another embodiment, the one or more collection
enhancing components 304 in contact with the active phase component
312 comprises one or more low electrical resistivity components 306
and one or more magnetic susceptibility increasing components 308.
Embodiments of the invention are not limited by how one or more
collection enhancing components 304 are in contact with the active
phase component 312. In an embodiment, the one or more collection
enhancing components 304 contact the active phase component 312 in
a manner such as, but not limited to, coating, incorporating, and
embedding, etc., either individually or in combination of two or
more thereof. Embodiments of the invention are also not limited by
the shape, size, or form of the one or more collection enhancing
components 304, the one or more low electrical resistivity
components 306 and/or the one or more magnetic susceptibility
increasing components 308, or by the shape, size, or form of the
CEC 310 itself. Non-limiting examples of the form of the one or
more low electrical resistivity components 306, the one or more
magnetic susceptibility increasing components 308, and/or the CEC
310 include, but are not limited to, liquid, powder, and formed
solid shapes such as microspheres, beads, and extrudates, either
individually or in a combination of two or more forms. Furthermore,
in some embodiments, the size or shape of the CEC 310 has varying
dimensions of depth, width, and length.
[0070] In another embodiment, the one or more collection enhancing
components 304 are illustrated in FIG. 3B as part of the active
phase component 312 of the CEC 310. In an embodiment, the one or
more collection enhancing components 304 as part of the active
phase component 312 comprises one or more low electrical
resistivity components 306. In another embodiment, the one or more
collection enhancing components 304 as part of the active phase
component 312 comprises one or more magnetic susceptibility
increasing components 308. In yet another embodiment, the one or
more collection enhancing components 304 as part of the active
phase component 312 comprises one or more low electrical
resistivity components 306 and one or more magnetic susceptibility
increasing components 308. Embodiments of the invention are not
limited by how one or more collection enhancing components 304 are
part of the active phase component 312.
[0071] Collection enhancing components 304 suitable for use in CEC
310 include the low electrical resistivity components 306 and
increased magnetic susceptibility components 308 as described
above, either individually or in a combination of two or more
thereof. In one embodiment, the CEC 310 comprises one or more low
electrical resistivity components 306 having a resistivity value
less than or equal to 2.00E+08 ohm-cm at a temperature of 850
degrees Celsius. In another embodiment, the CEC 310 comprises one
or more low electrical resistivity components 306 having a
resistivity about less than or equal to about a resistivity value
at a given temperature as shown by line 502 illustrated in a graph
500 of resistivity and temperature provided in FIG. 5. In yet
another embodiment, the CEC 310 comprises one or more increased
magnetic susceptibility components 308 having a magnetic
susceptibility of at least about 500 cgs per atomic weight at about
20 degrees Celsius. In one embodiment, the active phase component
312 of CEC 310 comprises a zeolite, an inert material, and a
binder. The inert material may be a clay, for example, kaolin. The
binder may include alumina, silica alumina, or other suitable
material, either individually or in a combination of two or more
thereof.
Collection Enhanced Additives (CEA)
[0072] FIG. 3C schematically depicts CEA 320 according to an
embodiment of the invention. In an embodiment, CEA 320 comprises an
active phase component 322 and a collection enhancing component
304. In another embodiment, CEA 320 comprises any stable reaction
products of one or more collection enhancing components 304 and one
or more active phase components 322. In an embodiment, the
collection enhancing component 304 comprises one or more low
electrical resistivity components 306 and one or more magnetic
susceptibility increasing components 308, either individually or in
a combination of two or more thereof.
[0073] In one embodiment, the active phase component 322 of the CEA
320 is in contact with the one or more collection enhancing
components 304. Optional additional collection enhancing components
304 are shown in phantom affixed to the active phase component 322
in FIG. 3C. In an embodiment, the one or more collection enhancing
components 304 in contact with the active phase component 322
comprises one or more low electrical resistivity components 306. In
another embodiment, the one or more collection enhancing components
304 in contact with the active phase component 322 comprises one or
more magnetic susceptibility increasing components 308. In an
embodiment, the one or more collection enhancing components 304 in
contact with the active phase component 322 comprises one or more
low electrical resistivity components 306 and one or more magnetic
susceptibility increasing components 308. Embodiments of the
invention are not limited by how one or more collection enhancing
components 304 are in contact with the active phase component 322.
In an embodiment, the one or more collection enhancing components
304 contact the active phase component 322 in a manner such as, but
not limited to, coating, incorporating, and embedding, etc., either
individually or in combination of two or more thereof Embodiments
of the invention are also not limited by the shape, size, or form
of the one or more collection enhancing components 304, the one or
more low electrical resistivity components 306 and/or the one or
more magnetic susceptibility increasing components 308, or by the
shape, size, or form of the CEA 320 itself. Non-limiting examples
of the form of the one or more low electrical resistivity
components 306, the one or more magnetic susceptibility increasing
components 308, and/or the CEA 320 include, but are not limited to,
liquid, powder, and formed solid shapes such as microspheres,
beads, and extrudates, either individually or in a combination of
two or more forms. Furthermore, in some embodiments, the size or
shape of the CEA 320 has varying dimensions of depth, width, and
length.
[0074] In another embodiment, the one or more collection enhancing
components 304 are illustrated in FIG. 3C as part of the active
phase component 322 of the CEA 320. In an embodiment, the one or
more collection enhancing components 304 as part of the active
phase component 322 comprises one or more low electrical
resistivity components 306. In another embodiment, the one or more
collection enhancing components 304 as part of the active phase
component 322 comprises one or more magnetic susceptibility
increasing components 308. In yet another embodiment, the one or
more collection enhancing components 304 as part of the active
phase component 322 comprises one or more low electrical
resistivity components 306 and one or more magnetic susceptibility
increasing components 308. Embodiments of the invention are not
limited by how one or more collection enhancing components 304 are
part of the active phase component 322.
[0075] Collection enhancing components 304 suitable for use in CEA
320 include the low electrical resistivity components 306 and
increased magnetic susceptibility components 308 described above.
In one embodiment, the CEA 320 comprises one or more low electrical
resistivity components 306 having a resistivity value less than or
equal to 2.00E+08 ohm-cm at a temperature of 850 degrees Celsius.
In another embodiment, the CEA 320 comprises one or more increased
magnetic susceptibility components 308 having a magnetic
susceptibility of at least about 500 cgs per atomic weight at about
20 degrees Celsius.
[0076] In one embodiment, the active phase component 322 of CEA 320
comprises a functionality that reduces at least one of SO.sub.x,
NO.sub.x, or other undesirable emission from the unit. In one
embodiment, the active phase component 322 comprises a
functionality that oxidizes SO.sub.2 to SO.sub.3 and absorbs
SO.sub.3. In another embodiment, the active phase component 322 for
the reduction of SO.sub.x comprises a Mg-based pick-up agent and an
oxidation catalyst, which may be Ce-based or V-based. The Mg-based
pick-up agent may be a spinel, such as magnesium aluminum oxide,
MgO solid solution structures, and a hydrotalcite. Other examples
of active phase component 322 for reducing SO.sub.x include
oxidants, such as magnesium, aluminum, Ce, Cr, Zr, V, and Fe,
either individually or in a combination of two or more thereof.
[0077] In another embodiment, the active phase component 322
comprises a functionality that reduces NO emissions. Active phase
components 322 having a functionality that reduces NO emissions may
include high CeO content (i.e., greater than about 15 weight
percent) alumina additives, Cerium supported on alumina, copper
supported on zeolite, copper supported on alumina, and copper
supported on hydrotalcite, and active metals on a support, either
individually or in a combination of two or more thereof. In yet
another embodiment, the active phase component 322 comprises a
functionality that both reduces SO.sub.x and reduces NO.sub.x.
Down Stream Additives (DSA)
[0078] Another group of materials of the present invention
hereinafter referred to as down stream additive (DSA) is
schematically illustrated in FIG. 6 as DSA 600. Generally, DSA 600
have a characteristic of enhancing collection of the DSA 600 by the
particle removal device 208 from the exhaust stream exiting the
unit 200 and/or reduces emissions in the exhaust stream of the unit
200 as shown in FIG. 2. DSA 600 as described herein is a virgin
material, meaning that the material has never been exposed to a
process for which it has been intended, for example, to an exhaust
gas stream of a unit. In some embodiments, DSA 600 is recycled
after exposure, and the term recycled DSA 600 will be utilized to
provide distinction from virgin DSA 600. DSA 600 is generally first
introduced into the exhaust stream passing through the exhaust
system 204 without first passing through the unit 100 using the DSA
addition system 210. In some embodiments, DSA 600 is also
introduced to the reaction zone 202 of the unit 200 using a second
conventional additive addition system 120. In the embodiments where
DSA 600 is introduced to the reaction zone 202 of the unit 200,
introduction to the reaction zone 202 of the unit 200 occurs after
introduction of the DSA 600 to the exhaust system 204 in such that
the DSA 600 is recycled DSA 600.
[0079] In an embodiment, DSA 600 comprises one or more active phase
components 602 and one or more collection enhancing components 604.
In an embodiment, DSA 600 comprises any stable reaction products of
one or more collection enhancing components 604 and one or more
active phase components 602. The one or more collection enhancing
components 604 comprises one or more low electrical resistivity
components 306, one or more magnetic susceptibility increasing
components 308, and one or more clumping encouragement components
606, either individually or in combination of two or more thereof.
Examples of suitable low electrical resistivity components 306 and
magnetic susceptibility increasing components 308 identified above
for use with CEM 300 are also suitable for use as a collection
enhancing component in DSA 600.
[0080] In an embodiment, the one or more clumping encouragement
components 606 comprises a characteristic that encourages clumping
includes so-called fluxing agents, like vanadium, sodium, and
calcium oxide, either individually or in combination of two or more
thereof. Clumping of the DSA 600 within the exhaust stream
increases the size and weight of the DSA 600, making the DSA 600
more easily removed from the exhaust gas stream, particularly by
particle removal devices which may employ a cyclonic separator.
[0081] In one embodiment, the active phase component 602 of the DSA
600, when present, is in contact with the one or more collection
enhancing components 604. Optional additional collection enhancing
components 604 are shown in phantom affixed to the active phase
component 602 in FIG. 6. In an embodiment, the one or more
collection enhancing components 604 in contact with the active
phase component 602 comprises one or more low electrical
resistivity components 306. In another embodiment, the one or more
collection enhancing components 604 in contact with the active
phase component 602 comprises one or more magnetic susceptibility
increasing components 308. In another embodiment, the one or more
collection enhancing components 604 in contact with the active
phase component 602 comprises one or more clumping encouragement
components 606. In yet another embodiment, the one or more
collection enhancing components 604 in contact with the active
phase component 602 comprises one or more low electrical
resistivity components 306, one or more magnetic susceptibility
increasing components 308, and one or more clumping encouragement
components 606, in a combination of two or more thereof.
Embodiments of the invention are not limited by how one or more
collection enhancing components 604 are in contact with the active
phase component 602. In an embodiment, the one or more collection
enhancing components 604 contact the active phase component 602 in
a manner such as, but not limited to, coating, incorporating, and
embedding, etc., either individually or in combination of two or
more thereof. For example, DSA 600 may comprise an active phase
component 602 comprising an embedded collection enhancing component
604, an active phase component comprising 602 an incorporated
collection enhancing component 604, and an active phase component
602 comprising at least a partial collection enhancing component
coating, either individually or in combination of two or more
thereof. Embodiments of the invention are also not limited by the
shape, size, or form of the one or more collection enhancing
components 604, the one or more low electrical resistivity
components 306, the one or more magnetic susceptibility increasing
components 308, and/or the one or more clumping encouragement
components 606, or by the shape, size, or form of the DSA 600
itself Non-limiting examples of the form of the one or more low
electrical resistivity components 306, the one or more magnetic
susceptibility increasing components 308, the one or more clumping
encouragement components 606 and/or the DSA 600 include, but are
not limited to, liquid, powder, and formed solid shapes such as
microspheres, beads, and extrudates, either individually or in a
combination of two or more forms. Furthermore, in some embodiments,
the size or shape of the DSA 600 has varying dimensions of depth,
width, and length.
[0082] In another embodiment, the one or more collection enhancing
components 604 are illustrated in FIG. 6 as part of the active
phase component 602 of the DSA 600. In an embodiment, the one or
more collection enhancing components 604 as part of the active
phase component 602 comprises one or more low electrical
resistivity components 306, one or more magnetic susceptibility
increasing components 308, and one or more clumping encouragement
components 606, either individually or in a combination of two or
more thereof. Embodiments of the invention are not limited by how
one or more collection enhancing components 604 are part of the
active phase component 602.
[0083] In another embodiment, DSA 600 comprises an attrition index
in the range of about two (2) to about ten (10), wherein the
attrition index is determined according to ASTM D5057-10. In a
particular embodiment, DSA 600 comprising an attrition index in the
range of about two (2) to about ten (10) also comprises one or more
collection enhancing components 604 affixed to the active phase
component 602. The attrition index in the range from about two (2)
to about ten (10) promotes the breaking of the virgin DSA 600
provided to the gaseous exhaust stream, thereby reducing the size
of the DSA 600 while in the gaseous exhaust stream due to collision
of the DSA 600 with the walls of the conduit 1004 and other PM
(such as, but not limited to, other DSA 600). The high attrition
index allows the particle size of the virgin DSA 600 to be large
enough for efficient handling prior to entry into the gaseous
exhaust stream, while once added to the gaseous exhaust stream,
allows for an increase in the particle surface area and making more
active phase components available for NO.sub.x and/or SO.sub.x
reduction, or other emission control.
[0084] In another embodiment, DSA 600 has an average diameter in a
range from about 20 .mu.m to about 60 .mu.m. In a particular
embodiment, DSA 600 comprising average diameter in a range from
about 20 .mu.m to about 60 .mu.m may also comprise an attrition
index in the range from about two (2) to about ten (10), one or
more collection enhancing components 604 affixed to the active
phase component 602, either alone or in combinations thereof. Since
the conventional catalyst/additive and catalyst/additive fines
present in the exhaust stream typically have an average diameter in
a range from less than about 10 .mu.m to about 15 .mu.m, which is
much smaller than the dimension of DSA 600, the size differential
between DSA 600 and conventional catalyst/additive and
catalyst/additive fines allows DSA 600 to be preferentially removed
from the gaseous exhaust stream. In the manner, the removed DSA 600
may be recycled without being diluted by other PM which may not
include an active phase component. DSA 600 having smaller average
diameters, such as in a range from about 20 .mu.m to about 60
.mu.m, results in greater surface area being available for emission
control reactions, thereby enhancing the reactivity and/or
absorption of the DSA 600.
[0085] However, DSA 600 having an average diameter in a range from
about 20 .mu.m to about 60 .mu.m is an exemplary range and is not
to be considered a limitation. In other embodiments, DSA 600 has an
average diameter in a range from about 20 .mu.m to about 300 .mu.m,
for example, from about 60 .mu.m to about 300 .mu.m. DSA 600 having
an average diameter greater than about 60 .mu.m provides greater
ease of handling.
[0086] In another embodiment, the active phase component 602 of DSA
600 comprises a material incompatible with a process being
performed in the unit having the exhaust gas stream into which the
DSA 600 is added. Materials used in the active phase component 602
which are incompatible with a process performed in an FCC unit may
cause a separate catalytic reaction that forms unwanted products
like hydrogen and methane. Examples of materials used in the active
phase component 602 which are incompatible with a process performed
in an FCC unit may include but are not limited to copper, sodium,
potassium, nickel, vanadium, and iron, either alone or in
combinations of two or more thereof
[0087] In an embodiment, the active phase component 602 of the DSA
600 has an emission reducing characteristic. In one embodiment, the
active phase component 602 comprises one or more emission reducing
components, such as, but not limited to, a SO.sub.x emission
reducing component, and a NO.sub.x emission reducing component,
either individually or in a combination of two or more thereof. For
example, the active phase component 602 may comprise a SO.sub.x
emission reducing component such as SO.sub.x removing additives
which oxidize SO.sub.2 to SO.sub.3 and absorb SO.sub.3. In an
embodiment of the DSA 600, the active phase component 602 includes
SOx removing additive comprising one or more sorbents and one or
more oxidants.
[0088] In one embodiment of the SO.sub.x removing additive,
non-limiting examples of sorbents include a spinel, a magnesium
aluminum oxide crystallizing with a periclase structure, a
precursor to a hydrotalcite or hydrotalcite-like material (HTL)
wherein the precursor has an X-ray diffraction pattern displaying
at least a reflection at a two theta peak position at about 43
degrees and about 62 degrees as described in U.S. Pat. No.
7,361,319 which is incorporated by reference herein in entirety, a
hydrotalcite, an HTL, a dehydrated or dehydroxylated hydrotalcite,
and a dehydrated or dehydroxylated HTL, as described in U.S. Pat.
No. 7,361,319 and 6,028,023 which are incorporated by reference
herein in entirety. It should be appreciated that embodiments of
the invention include one or more sorbents such as a spinel, a
magnesium aluminum oxide crystallizing with a periclase structure,
a precursor to a hydrotalcite or HTL, a hydrotalcite, an HTL, a
dehydrated or dehydroxylated hydrotalcite, and a dehydrated or
dehydroxylated HTL, either individually or in a combination of two
or more thereof
[0089] In a particular embodiment, the sorbent includes a spinel,
such as, but not limited to, MgAl.sub.2O.sub.4. Non-limiting
examples, for illustration and not limitation, of various types of
spinels are described in U.S. Pat. No. 4,469,589; U.S. Pat. No.
4,472,267; U.S. Pat. No. 4,492,677; U.S. Pat. No. 4,492,678; U.S.
Pat. No. 4,613,428; U.S. Pat. No. 4,617,175; U.S. Pat. No.
4,735,705; U.S. Pat. No 4,758,418; and U.S. Pat. No. 4,790,982
which are incorporated by reference herein in their entirety.
Particular examples of various types of spinels include, for
illustration and not limitation, those described in U.S. Pat. No.
4,790,982; U.S. Pat. No 4,758,418; U.S. Pat. No. 4,492,678; and
U.S. Pat. No. 4,492,677; which are incorporated by reference herein
in their entirety. In a particular embodiment when the sorbent
comprises substantially spinel, less than 100 percent of the
oxidants to be in the SO.sub.x removing additive are in the
slurry.
[0090] In a particular embodiment, the sorbent comprises
Al.sub.2O.sub.3 and MgO. Portions of the Al.sub.2O.sub.3 and MgO
may be chemically reacted or unreacted. The ratio of Mg/Al in the
SO.sub.x removing additive may readily vary. In one embodiment, the
sorbent comprises substantially aluminum and magnesium components.
In one embodiment, the concentration of magnesium to aluminum
ranges from about 0.25 to about 10 based on the total SO.sub.x
removing additive on a molar basis. In a particular embodiment, the
concentration of magnesium to aluminum ranges from about 0.5 to
about 2, based on the total SO.sub.x removing additive on a molar
basis. In yet another particular embodiment, the concentration of
magnesium to aluminum ranges from about 0.75 to about 1.5, based on
the total SO.sub.x removing additive on a molar basis.
[0091] The sorbent may comprise magnesium aluminum oxide. The
magnesium aluminum oxide may crystallize with a spinel structure
group. When the spinel includes a divalent metal (e.g., magnesium)
and a trivalent metal (e.g., aluminum), the atomic ratio of
divalent to trivalent metals in the spinel may range from about
0.17 to about 1, from about 0.25 to about 0.75, from about 0.35 to
about 0.65, and from about 0.45 to about 0.55. In one embodiment,
extra Mg content is present in the spinel structure such the Mg/Al
ratio is higher.
[0092] In one embodiment, the sorbent comprises calcium aluminum
oxide and magnesium aluminum oxide. In a particular embodiment, the
sorbent comprises substantially calcium and aluminum components. In
one embodiment, the concentration of calcium to aluminum ranges
from about 0.25 to about 4, based on the total SO.sub.x removing
additive on a molar basis. In a particular embodiment, the
concentration of calcium to aluminum ranges from about 0.5 to about
2, based on the total SO.sub.x removing additive on a molar basis.
In yet another particular embodiment, the concentration of calcium
to aluminum ranges from about 0.75 to about 1.5, based on the total
SO.sub.x removing additive on a molar basis.
[0093] In one embodiment, the sorbent portion also includes one or
more divalent components, either based on magnesium and/or calcium,
with a concentration of Al.sub.2O.sub.3 from about 18 percent to
about 84 percent on a weight percentage basis, described above. The
sorbent may crystallize in a periclase, a spinel, or other crystal
structure group.
[0094] In another embodiment, the sorbent includes a hydrotalcite
or hydrotalcite-like material (HTL). In a particular embodiment,
the hydrotalcite or HTL may be collapsed, dehydrated and or
dehydroxylated. Non-limiting examples and methods for making
various types of HTL are described in U.S. Pat. No. 6,028,023; U.S.
Pat. No. 6,479,421; U.S. Pat. No. 6,929,736; and U.S. Pat. No.
7,112,313; which are incorporated by reference herein in their
entirety. Other non-limiting examples and methods for making
various types of HTL are described in U.S. Pat. No. 4,866,019; U.S.
Pat. No. 4,964,581; and U.S. Pat. No. 4,952,382; which are
incorporated by reference herein in their entirety. Other methods
for making hydrotalcite-like compounds are described, for example,
by Cavani et al., Catalysis Today, 11:173-301 (1991), which is
incorporated by reference herein in its entirety.
[0095] In another embodiment of the SO.sub.x removing additive, the
sorbent comprises at least one hydrotalcite-like compound of
formula (I) or formula (II):
(X.sup.2+.sub.mY.sup.3+.sub.n(OH).sub.2m+2n)A.sub.n/a.sup.a-
bH.sub.2O (I)
(Mg.sup.2+.sub.mAl.sup.3+.sub.n(OH).sub.2m+2n)A.sub.n/a.sup.a- bH
.sub.2O (II)
where X is magnesium, calcium, zinc, manganese, cobalt, nickel,
strontium, barium, copper, or a mixture of two or more thereof; Y
is aluminum, manganese, cobalt, nickel, chromium, gallium, boron,
lanthanum, cerium, or a mixture of two or more thereof; A is
CO.sub.3, NO.sub.3, SO.sub.4, Cl, OH, Cr, I, SiO.sub.3, HPO.sub.3,
MnO.sub.4, HGaO.sub.3, HVO.sub.4, ClO.sub.4, BO.sub.3, or a mixture
of two or more thereof; a is 1, 2, or 3; b is between 0 and 10; and
m and n are selected so that the ratio of m/n is about 1 to about
10. The hydrotalcite-like compound of formula (II) can be
hydrotalcite (i.e., Mg.sub.6Al.sub.2(OH)16CO.sub.3 4H.sub.2O). In
one embodiment, the hydrotalcite-like compound of formula (I) or
formula (II) can be used per se as the SOx removing additive.
[0096] In another embodiment of the SO.sub.x removing additive, the
sorbent comprises a hydrotalcite-like compound of formula (III) or
formula (IV):
X.sup.2+.sub.mY.sup.3+.sub.4(OH).sub.2m+.sub.2n)OH.sub.n.sup.-
bH.sub.2O (III)
(Mg.sup.2+.sub.mAl.sup.3+.sub.4(OH).sub.2m+2n)OH.sub.n.sup.-
bH.sub.2O (IV)
wherein X is magnesium, calcium, zinc, manganese, cobalt, nickel,
strontium, barium, copper, or a mixture of two or more thereof; Y
is aluminum, manganese, cobalt, nickel, chromium, gallium, boron,
lanthanum, cerium, or a mixture of two or more thereof; b is
between 0 and 10; and m and n are selected so that the ratio of m/n
is about 1 to about 10. In one embodiment, the compound of formula
(IV) is Mg.sub.6Al.sub.2(OH).sub.18 4.5H.sub.2O. The
hydrotalcite-like compounds of formula (III) or formula (IV) can
contain minor amounts of anionic (e.g., CO.sub.3) impurities. In
one embodiment, the hydrotalcite-like compound of formula (III) or
formula (IV) can be used per se as the SO.sub.x removing
additive.
[0097] When more than one sorbent is present, the plurality of
sorbents may have various characteristics. For example, the
sorbents may include a spinel, a magnesium aluminum oxide
crystallizing with a periclase structure, a hydrotalcite, a
hydrotalcite-like material (HTL), and a dehydrated or
dehydroxylated HTL, either individually or in a combination of two
or more thereof. In one embodiment, the sorbents may be chemically
or physically separate and distinct from each other. In another
embodiment, the sorbents may be chemically or physically
reacted.
[0098] The sorbent may further comprise a support material. The
support material may be adjusted based on the FCC environment such
as high or low oxygen environment, mixed mode, or poor air
distribution. Examples of support material include, but are not
limited to, calcium aluminate, aluminum nitrohydrate, aluminum
chlorohydrate, magnesia, silica, silicon-containing compounds
(other than silica), alumina, titania, zirconia, clay, and a clay
phosphate material, either individually or in a combination of two
or more thereof. In one embodiment, the sorbent may be chemically
or physically separate and distinct from the support material. In
another embodiment, the sorbent may be chemically or physically
reacted with the support material.
[0099] The sorbent may further comprise a hardening agent. Examples
of hardening agents include, but are not limited to, aluminum
silicate, magnesium aluminate, magnesium silicate, aluminum
phosphate, and magnesium phosphate, either individually or in a
combination of two or more thereof. Another example of sorbents
includes magnesium and aluminum, either individually or in a
combination of two or more thereof.
[0100] In one embodiment, at least one sorbent and at least one
oxidant are distinct separate particle species as described in U.S.
Pat. No. 6,281,164. In one embodiment, distinct separate particle
species for respectively a sorbent and for an oxidant includes at
least a first particle for the sorbent and at least a second
particle for the oxidant. A need for relatively more SO.sub.x
sorbent may occur when a SO.sub.x additive is provided to an FCC
unit that is being used in a partial burn mode of operation.
[0101] In an embodiment of the SO.sub.x removing additive, examples
of oxidants include metals and mineral oxidants, either
individually or in a combination of two or more thereof. Examples
of oxidants include one or more metals such as but not limited to,
Ce, Fe, Mg, Al, Pt, Pd, Zr, Cu, Ba, Sr, Zn, Ca, Ni, Co, Mn, Cr, Mo,
W, Ag, Cd, Bi, Sb, Dy, Er, Eu, Gd, Ge, Au, Ho, Ir, La, Pb, Mn, Nd,
Nb, Os, Pr, Pm, Re, Rh, Ru, Sm, Sc, Se, Si, S, Ta, Te, Tb, Sn, Ti,
W, Tm, and one or more mineral oxidants such as bastnaesite, either
individually or in a combination of two or more thereof. In a
particular embodiment, the oxidant comprises Ce. In an embodiment,
Ce is in a range from about 0.1 weight percent to about 8.0 weight
percent of the total SO.sub.x removing additive based on a
CeO.sub.2 loss free basis. In another embodiment, Ce is in a range
from about 0.5 weight percent to about 4.0 weight percent of the
total SO.sub.x removing additive based on a CeO.sub.2 loss free
basis. In yet another embodiment, the concentration of Ce is about
4 weight percent of the total SO.sub.x removing additive based on a
CeO.sub.2 loss free basis.
[0102] In another embodiment, the SO.sub.x removing additive
includes a plurality of oxidants which differ from each other. The
plurality of oxidants may have various characteristics. In one
embodiment, the plurality of differing oxidants are in range from
about 0.1 weight percent to about 8.0 weight percent of the total
SO.sub.x removing additive based on an oxide loss free basis. In
another embodiment, the plurality of differing oxidants are in a
range from about 0.5 weight percent to about 4.0 weight percent of
the total SO.sub.x removing additive based on an oxide loss free
basis. In an embodiment, the plurality of differing oxidants are
individually in a range from about 0.5 weight percent to about 2.0
weight percent of the total SO.sub.x removing additive based on an
oxide loss free basis. In an embodiment, the plurality of differing
oxidants are individually in a range from about 0.5 weight percent
to about 1.0 weight percent of the total SO.sub.x removing additive
based on an oxide loss free basis. In a particular embodiment, the
plurality of differing oxidants are individually in a range from
about 0.5 weight percent to about 4.0 weight percent of the total
SO.sub.x removing additive based on an oxide loss free basis.
[0103] In another embodiment, oxidant includes group VIII metal
such as platinum, palladium, iridium, osmium, rhodium, and
ruthenium, either individually or in a combination of two or more
thereof. In another embodiment, oxidants include MgO,
Al.sub.2O.sub.3, CaO, BaO, P.sub.2O.sub.5, and SiO.sub.2, either
individually or in a combination of two or more thereof
[0104] Another example of oxidants include Ce, Cr, Zr, V, and Fe,
either individually or in a combination of two or more thereof.
Furthermore, in a particular embodiment optimal oxidant to
absorbent ratio (CeO:MgO) for DSA 600 will be different than the
oxidant to absorbent ratio used for conventional SO.sub.x emission
reducing additives provided to the reaction zone FCC unit.
[0105] In another embodiment, a sorbent and an oxidant are distinct
separate particle species in a multiple particle system. In another
embodiment, a sorbent and an oxidant are provided as a single
particle system.
[0106] In an embodiment, the DSA 600 includes a plurality of the
active phase component 602 such as Cu and SO.sub.x removing
additives comprising a hydrotalcite like sorbent and cerium.
[0107] In an embodiment, the active phase component 602 may
comprise a NO.sub.x emission reducing component such as NO.sub.x
removing additives. In a particular embodiment, the DSA 600
includes a plurality of the active phase components 602 such as Ce
and one or more NO.sub.x removing additives comprising one or more
sorbents and one or more oxidants described above. In a particular
embodiment, the DSA 600 includes a plurality of the active phase
components 602 such as Ce and one or more NO.sub.x removing
additives comprising a hydrotalcite like sorbent and Cu.
[0108] In another example, the active phase component 602 comprises
a NO emission reducing component. In one embodiment, DSA 600 may
include a NO.sub.x emission reducing component such as high CeO
(>15 weight percent) content alumina additives, copper supported
on zeolite, Cerium supported on alumina, copper supported on
alumina, copper supported on hydrotalcite, and active metals on a
support, either individually or in a combination of two or more
thereof. Non-limiting advantages of the invention include, but are
not limited to, the opportunity to reduce NO.sub.x emissions in a
partial burn unit.
[0109] In some embodiments, the DSA 600 is substantially free of a
regeneration component such as vanadium. In one embodiment, DSA 600
is substantially free of one or more reductant metals. In a
particular embodiment, reductant metals include such as vanadium,
iron compounds, either individually or in a combination of two or
more thereof
[0110] It should be noted that some raw materials used in the
preparation of the DSA 600 may contain some level of such metals,
particularly iron. In another embodiment, the DSA 600 is
substantially free of iron, nickel, cobalt, manganese, tin, and
vanadium, either individually or in a combination of two or more
thereof. In another embodiment, the DSA 600 is substantially free
of nickel, titanium, chromium, manganese, cobalt, germanium, tin,
bismuth, molybdenum, antimony, and vanadium, either individually or
in a combination of two or more thereof
[0111] In one embodiment, the DSA 600 is substantially free of the
presence of vanadium to an amount of less than about 1 percent by
weight of the total DSA 600. "Substantially free" expressly allows
the presence of trace amounts of the respective referred substance
either individually or in a combination of two or more, such as
vanadium or iron, and is not to be limited to a specified precise
value, and may include values that differ from the specified value.
In one embodiment, substantially free expressly allows the presence
of trace amounts of vanadium. In a particular embodiment,
substantially free expressly allows the presence of trace amounts
of a respective referred substance, such as iron, nickel, cobalt,
manganese, tin, and vanadium, by less than about 10 percent by
weight, by less than about 5 percent by weight, by less than about
1 percent by weight, by less than about 0.5 percent by weight, and
less than about 0.1 percent by weight, either individually or in
combinations thereof. Substantially free expressly allows the
presence of the respective trace amounts of vanadium, iron, etc.,
but does not require the presence of the referred substance, such
as vanadium or iron.
[0112] An embodiment includes a method of providing the DSA 600
into the gaseous exhaust stream passing through the exhaust system
204 exiting the unit 200 to the flue stack 206 as shown in FIG. 2.
The method includes at least one factor such as, but not limited
to, continuity of providing the DSA 600, dispersion of the DSA 600,
means of providing the DSA 600, and size of the DSA 600, either
individually or in combination of two or more thereof. In another
embodiment, the continuity of providing the DSA 600 includes
providing the additive in less than 5 minute intervals, less than 3
minute intervals, less than 2 minute intervals, less than a 1
minute interval, and continuously providing DSA 600.
[0113] In another embodiment, dispersion of the DSA 600 means
heterogeneity greater than 90 percent dispersion, greater than 95
percent dispersion, etc. Embodiments of the invention include
various means of facilitating dispersion as known to one of
ordinary skill in the art, such as, but not limited to, having
multiple introduction points, liquid form, mixing, etc., and other
dispersion techniques for providing fluidized material.
[0114] In another embodiment, DSA 600 may be provided at multiple
introduction points, and at a plurality of points, either
individually or in a combination of two or more thereof. DSA 600
may be in the form of a powder, slurry, or liquid. In another
embodiment, average size of the DSA 600 is less than or equal to
about 20 microns.
[0115] Embodiments of the invention include increasing or
decreasing the amount of DSA 600 provided before an ESP but
downstream of the reaction zone 202 of the unit in response to
SO.sub.x levels in an FCC unit. Embodiments of the invention
include metering the amount of DSA 600 provided before the ESP but
downstream of the reaction zone 202 of the unit in response to
SO.sub.x levels exiting the FCC unit.
[0116] Embodiments of the invention include ability to recycle DSA
600 provided before an ESP but downstream of the reaction zone 202
of the unit. Embodiments of the invention which include recycling
include metering the amount of DSA 600 provided before the ESP but
of the reaction zone 202 of the unit and metering the amount of the
gas additive withdrawn and re-providing at least some of the
withdrawn DSA 600 before an ESP but downstream of the reaction zone
202 of the unit. Embodiments of the invention include withdrawing
an amount of DSA 600 before an ESP but downstream of the reaction
zone 202 of the unit in response to SO.sub.x level in an FCC
unit.
[0117] An embodiment of the invention includes providing DSA 600
before an ESP but downstream of reaction zone 202 of the unit,
either individually or in a combination of two or more, to one or
more fluidized units.
[0118] In an embodiment of DSA 600, one or more collection
enhancing components 604 are physically separate and distinct
particles which means that the collection enhancing component 604
has a primary functionality distinct from the active phase
component 602 in a single particle system.
[0119] In another embodiment in contrast to the multi-particle
particle system, one or more collection enhancing components 604
are part of the DSA 600 as a single particle system. In an
embodiment of the single particle system, the collection enhancing
component 604 is in contact with and affixed to the active phase
component 602. The collection enhancing components 604 may be
affixed to the active phase component 602 by such as but not
limited to incorporating, coating, and embedding the collection
enhancing components 604 in or onto the active phase component 602.
In yet another embodiment of a single particle system, the active
phase component 602 has a primary functionality distinct from the
primary functionality of the collection enhancing component 604.
For comparative distinction, when collection enhancing components
604 are incorporated within or as part of the active phase
component 602 in a single particle system instead of as physically
separate and distinct particles from the active phase component 602
in a multi-particle particle system, dual or multiple
characteristics of the active phase component 602 and the
collection enhancing components 604 co-exist within the same single
particle by virtue of the proximity of the components.
[0120] DSA 600 is not limited by the form. For example, DSA 600 may
be in the form of a powder, liquid, slurry, solution, dispersion or
other form, either individually or in combination of two or more
thereof
[0121] A support phase component of powder DSA 600, i.e., the basic
particle structure, may include without limitation, hydrotalcite,
alumina (high acidic matrix catalyst), silica, silica alumina,
TiO.sub.2, active carbon, micro porous material (zeolites), and/or
germanium aluminophosphate (AlPO), and/or pure active phase
components without a separate support phase component, either
individually or in combination of two or more thereof. The active
phase component 602 of DSA 600 in powder form may be deposited on
the support phase component or may be the support phase component
itself The active phase component 602 promotes absorption and
catalytic mechanisms. Active phase component 602 comprise materials
that include, by way of example and without limitation, lime,
gypsum, salts, and AlPO-type materials without composition derived
from their active components, among others. Non-limiting examples
of salt include cations, anions, etc., such as, but not limited to,
individually or in combination of two or more thereof. Examples of
salts include cations (Na, K, Ca, Cu, Ni, W, Fe, V, transition
metals, lanthanides (La, Ce)), anions (CO.sub.3, CHO.sub.3, oxides,
hydroxides, and acetates), promoters, or other components, e.g.,
noble metals. The active phase component 602 may also include other
types of catalytic materials. Examples of other catalytic materials
that may be used as the active phase component 602 of the DSA 600
itself include NH.sub.3.
[0122] Selective catalytic reduction (SCR)-type catalysts may also
be utilized as the active phase component 602. SCR catalysts may
have ceramic material carriers and active catalytic components. One
example of a ceramic material carrier is titanium oxide. The active
catalytic components may be oxides of base metals (such as vanadium
and tungsten), zeolites, and various precious metals (ruthenium,
rhodium, palladium, silver, osmium, iridium, platinum, and gold).
Some examples of zeolite-based SCRs include iron- and
copper-exchanged zeolite urea SCRs and vanadium-urea SCRs, either
individually or in combination of two or more thereof. SCR-type
catalysts advantageously utilize less material, and makes double
usage of existing NH.sub.3 addition or introduction. For SCR-type
catalysts, acidic supports may be beneficial, especially
microporous zeolites, aluminas, and silica aluminas, either
individually or in combination of two or more thereof.
[0123] As discussed above, DSA 600 comprises any stable reaction
products of one or more collection enhancing components 604 and one
or more active phase components 602. In an embodiment, collection
enhancing components 604 comprises any stable reaction products of
any combination of one or more low electrical resistivity
components 306, one or more magnetic susceptibility increasing
components 308, and one or more clumping encouragement components
606.
[0124] In an embodiment, DSA 600 is in a liquid or slurry form.
Non-limiting examples of DSA 600 in liquid and/or slurry form
include solutions of the above salts, ammonia and urea solutions,
either individually or in combination of two or more thereof.
Slurries and dispersions of the above solids allow smaller particle
sizes, i.e., particles having an average diameter less than about
60 .mu.m, to be added to the exhaust gas stream much more
efficiently as compared to dry DSA 600 of the same size.
[0125] DSA 600 includes one or more physical characteristics such
as, but not limited to, as discussed below. Examples of physical
characteristics of DSA 600 include good SO.sub.x and/or NO.sub.x
removal performance, which contribute to the reduction of unit
emissions to the environment. Small particle size, such as having a
diameter in a range from about 60 .mu.m to about 300 .mu.m, and
high surface area of DSA 600 provides ample active sites available
for reducing emissions. In an embodiment, the particles of DSA 600
may have a porous surface to increase the accessible surface area
for improved NO.sub.x and/or SO.sub.x removal performance.
[0126] As discussed above, one embodiment of DSA 600 has a high
attrition index as defined by ASTM D5757-10, i.e., an attrition
index in a range from about two (2) to about ten (10) or greater.
The high attrition index allows larger size particles to be
utilized in the vessel addition system for ease of handling and
dispensing, while promoting the fracture and size reduction with
corresponding increase in surface area of the DSA 600 once
entrained with flue gas within the conduit connecting the unit to
the flue stack. In the conduit, the high attrition index promotes
the fracture and splitting of the DSA 600 into smaller particles as
DSA 600 collides with the conduit walls and other particles. The
high attrition index and resulting particle size reduction within
the conduit increases the efficiency of the NO.sub.x and/or
SO.sub.x removal by increasing the exposed surface area of the DSA
600 exposed to the gaseous exhaust stream. In one embodiment, the
ASTM D5057-10 attrition index is in a range from about two (2) to
about ten (10). In another embodiment, the ASTM D5057-10 attrition
index is greater than about ten (10).
[0127] In an embodiment, DSA 600 has a high bulk density. For
example, the bulk density of DSA 600 exceeds about 1.0 grams/cc. In
another embodiment, the bulk density of DSA 600 exceeds about 1.5
grams/cc.
[0128] In some embodiments as discussed above, DSA 600 comprises a
modification that improves the retention of DSA 600 in at least one
of the electrostatic precipitator or the third stage separator. In
one example, DSA 600 comprises a modification that lowers the
electrical resistivity of the DSA particles to differ from the
electrical resistivity of catalyst fines present in the exhaust gas
stream. In an embodiment, DSA 600 is modified to have an electrical
resistivity to be less than about 1.times.10.sup.8 ohm-cm at 850
degrees Celsius to promote separation in the first stage of the
electrostatic precipitator preferentially to the catalyst fines. In
another embodiment, the magnetic susceptibility of DSA 600 is
modified to increase the retention of DSA 600 in the first stage of
the electrostatic precipitator as discussed above. In another
embodiment, the DSA 600 is modified to encourage
clumping/aggregation of the DSA 600. For example, a modification to
encourage clumping may be balanced with a high attrition index,
such that particles of DSA 600 which fracture and break-up upon
entry into the gaseous exhaust stream to promote NO.sub.x and/or
SO.sub.x removal may reclump downstream to make collection of the
DSA 600 present in the exhaust gas stream more efficient by
increasing the particle size of the fractured DSA 600 prior to
interfacing with the particle retention device.
[0129] As discussed above, an embodiment of DSA 600 is in powder
form and includes AlPOs. AlPOs are aluminophosphates with zeolite
type structures (highly microporous, high zeolite surface area,
etc.). A wide range of AlPOs compositions may be utilized, where
the active components are in the framework of the zeolite type
structure. Active components that are microporous materials provide
extremely high surface area which beneficially enhances performance
for the DSA 600. As with zeolites, AlPOs can be exchanged to
include other components within the micropores. Such AlPO materials
in the channels of the micropores could also be catalytically
active or promote an active framework.
[0130] Table I includes exemplary chemical compositions of
alternative DSAs.
TABLE-US-00001 TABLE I DOWN STREAM ADDITIVES Composition, wt %
Particle Size Distribution Name SiO.sub.2 Al.sub.2O.sub.3 MgO CaO
CeO.sub.2 V.sub.2O.sub.5 TiO.sub.2 Fe.sub.2O.sub.3 K.sub.2O CuO
0-20 um, % 0-40 um, % 0-80 um, % APS, um DSA-1 Fine 30.5 64 -- 0.4
-- -- 1.5 0.6 3 16 50 72 40 DSA-1 Coarse 1.7 7 36 99 DSA-2 Fine 23
55 0.8 21.2 3.7 30 89 51 DSA-2 Coarse 0.4 3 42 85 DSA-2.5 Coarse
20.5 52.5 0.9 8.6 0.4 0.2 16.9 1 4 45 87 DSA-5 Fine 24.5 54.5 21
6.7 58 94 37 DSA-5 Coarse 2.1 5 38 93 DSA-6 Fine 21.5 63.6 0.9 11.5
2.5 17 86 100 29 DSA-6.5 Coarse 19.5 57 0.8 10.4 2.3 10 1 8 40
95
[0131] DSA 600 of Table I were tested in a test rig that simulates
addition of DSA 600 to the exhaust system of a unit, such as
illustrated in FIG. 2. The test rig includes a 1-4 gram bed of DSA
600 disposed in a vertical quartz tube reactor. 130 ml/min of a
sample gas was provided through the bed at temperatures ranging
from about 25 degrees Celsius to about 650 degrees Celsius. The
sample gas included about 2035 ppm SO.sub.2, about 500 ppm NO, and
about 2 percent O.sub.2, with the balance being N.sub.2. After
passing through the DSA 600 bed disposed in the test rig, the
sample gas was tested using a gas analyzer to determine changes in
composition. Tables II-IV illustrate test results for various
embodiments of DSA 600 tested as described above. As shown in Table
II, significant NO.sub.x and SO.sub.x reduction (i.e., reduction
greater than or equal to about 70 percent) was observed for most
samples after about 600 seconds of exposure to the sample gas at
about 250 degrees Celsius.
TABLE-US-00002 TABLE II NO.sub.x and SO.sub.x Reduction of Virgin
DSA Additives Name NO.sub.x Reduction, % SO.sub.x Reduction, %
DSA-2 Complete Complete DSA-6 90% Complete DSA-5 80% Complete DSA-3
5% 95% DSA-4 70% Complete
TABLE-US-00003 TABLE III NO.sub.x and SO.sub.x Reduction of Virgin
DSA-2/Diluent Mixtures at Different Concentrations Material
Concentration, wt % NO.sub.x Reduction, % SO.sub.x Reduction, %
DSA-2 100 Complete Complete 10 55% Complete 5 10% 90% 1 0% 20%
TABLE-US-00004 TABLE IV NO.sub.x and SO.sub.x Reduction of DSA-1 at
Different Temperatures Material Temperature, C. NO.sub.x Reduction,
% SO.sub.x Reduction, % DSA-1 65 Complete Complete DSA-1 250 55%
Complete
[0132] As shown in Table IV, NO.sub.x and SO.sub.x reduction was
tested at different dilutions using an inert material added to the
bed of DSA 600. More than 50 percent NO.sub.x reduction and
substantially complete SO.sub.x reduction was observed after about
600 seconds of exposure to the sample gas at about 250 degrees
Celsius with concentrations of DSA 600 of 10 percent, with NO.sub.x
and SO.sub.x reduction diminishing with increased dilution. Table
IV illustrates the effect of reaction temperature on NO.sub.x and
SO.sub.x absorption using DSA 600 comprising about 6 percent
KHCO.sub.3 as an active phase component on a support phase
component. The tests indicate increased performance at higher
temperatures after about 600 seconds of exposure of the bed of DSA
600 to the sample gas.
TABLE-US-00005 TABLE V NO.sub.x and SO.sub.x Reduction of DSA-2.5
and DSA-6.5 Name NO.sub.x Reduction, % SO.sub.x Reduction, %
DSA-2.5 85 Complete DSA-6.5 85 N/A
[0133] The performance of DSA-2.5 and DSA-6.5 was tested using a 2
gram bed of the subject DSA disposed in a vertical quartz tube
reactor. 130 ml/min of a sample gas was provided through the bed at
250 degrees Celsius. The sample gas included about 800 ppm
SO.sub.2, about 400 ppm NO, about 2 percent O.sub.2, and about 1
percent H.sub.2O, with the balance being N.sub.2. After passing
through the bed of DSA, the sample gas was tested using a mass
spectrometer to determine changes in composition. Tables V
illustrate test results for various embodiments of DSA 2.5 and 6.5
tested as described above. As shown, significant NO.sub.x and
SO.sub.x reduction was observed for these samples after about 300
seconds of exposure to the sample gas at about 250 degrees
Celsius.
Method Of Making Collection Enhanced Materials (CEM)
[0134] For illustration and not limitation, FIG. 7 is a flow
diagram of a method 700 of making CEM 300 in accordance with
another embodiment of the invention. The method 700 is not limited
by the order or frequency of the steps unless expressly noted. As
depicted in FIG. 7, the method 700 of making CEM 300 begins at step
702 by optionally providing a collection enhancing component 304 to
a feed slurry containing an active phase component 302 for a CEM
300 before the feed slurry is formed into shaped particles. Step
720 comprises forming the slurry into shaped particles. The slurry
may be formed into shaped particles by techniques such as, but not
limited to, spray drying, granulation, extrusion, and
pelletization, either individually or a combination of two or more
thereof. The method is also not limited by the form of the shaped
particles. Examples of form of shaped particles include, but are
not limited to, particles, grains, pellets, powders, extrudate,
spheres, and granules, either individually or in a combination of
two or more. In one embodiment, the shaped particles are in the
form of microspheres. Step 730 comprises calcining the shaped
particles. Step 740 comprises optionally hydrating the calcined
shaped particles. Step 750 comprises optionally calcining the
microspheres again. Steps 740, 750 may be repeated as desired. Step
760 comprises optionally providing a collection enhancing component
304 to the active phase component 302 after feed slurry for the CEM
300 has formed into shaped particles. Although the collection
enhancing component 304 is described as optionally provided in both
steps 710, 760, providing collection enhancing component 304 to the
active phase component 302 is provided in at least one of steps
710, 760 during the method 700. Providing a collection enhancing
component 304 to the active phase component 302 at step 760 may be
achieved by techniques such as, but not limited to, hydration and
impregnation.
[0135] For example, in an embodiment, the optional collection
enhancing component 304 is provided at step 710 to the feed slurry
prior to forming shaped particles. In another embodiment, the
optional collection enhancing component 304 is provided at step 760
while forming the shaped particles at step 720. In another
embodiment, the optional collection enhancing component 304 is
provided at step 760 while calcining the shaped particles at step
730. In another embodiment, the optional collection enhancing
component 304 is provided at step 760 while hydrating the calcined
shaped particles at step 740. In another embodiment, the optional
collection enhancing component 304 is provided at step 760 while
calcining the hydrated shaped particles at step 750. In another
embodiment, the collection enhancing component 304 is provided at
step 710 and at step 760, wherein step 760 may be performed one or
more times. In yet another embodiment, the method includes
repeating step 760 providing the optional collection enhancing
component at desired frequency intervals and as many times as
desired, such as, but not limited to, after steps 710, 720, 730,
740, and 750, either individually or a combination of two or more
thereof.
Method Of Making Down Stream Additives (DSA)
[0136] For illustration and not limitation, FIG. 8 is a flow
diagram of a method 800 of making DSA 600 in accordance with
another embodiment of the invention. The method 800 is not limited
by the order or frequency of the steps unless expressly noted. The
method 800 begins at step 810 by providing an active phase
component 602 to be in a DSA 600 to feed slurry for the DSA 600
before slurry is formed into shaped particles. Step 820 comprises
forming the slurry into shaped particles. The slurry may be formed
into shaped particles by techniques such as, but not limited to,
spray drying, granulation, extrusion, and pelletization, either
individually or a combination of two or more thereof. The method is
also not limited by the form of the shaped particles. Examples of
form of shaped particles include, but are not limited to,
particles, grains, pellets, powders, extrudate, spheres, and
granules, either individually or in a combination of two or more.
In one embodiment, the shaped particles are in the form of
microspheres. Step 830 comprises optionally calcining the shaped
particles. Step 840 comprises optionally hydrating the calcined
shaped particles. Step 850 comprises optionally calcining the
microspheres again. Steps 840, 850 may be repeated as desired. Step
860 comprises optionally providing a collection enhancing component
304 to the active phase component 302 before and/or after the feed
slurry for the DSA 600 is formed into shaped particles.
[0137] For example, in an embodiment, the optional collection
enhancing component 304 is provided at step 810 to the feed slurry
prior to forming shaped particles. In another embodiment, the
optional collection enhancing component 304 is provided at step 860
while forming the shaped particles at step 820. In another
embodiment, the optional collection enhancing component 304 is
provided at step 860 while calcining the shaped particles at step
830. In another embodiment, the optional collection enhancing
component 304 is provided at step 860 while hydrating the calcined
shaped particles at step 840. In another embodiment, the optional
collection enhancing component 304 is provided at step 860 while
calcining the hydrated shaped particles at step 850. In another
embodiment, the collection enhancing component 304 is provided at
step 810 and at step 860, wherein step 860 may be performed one or
more times. In yet another embodiment, the method includes
repeating step 860 providing the optional collection enhancing
component at desired frequency intervals and as many times as
desired, such as, but not limited to, before and/or after steps
810, 820, 830, 840, and 850, either individually or a combination
of two or more thereof
Down Stream Addition Systems
[0138] FIG. 9 depicts one embodiment of a down stream addition
system 1010 interfaced with an exhaust gas stream 1060 of a
fluidized unit 1000. The fluidized unit 1000 is for illustration,
and may alternatively be another type of unit. For example as
recited herein, a "unit" refers to, but is not limited to, an FCC
unit, a fixed bed or moving bed unit, a bubbling bed unit, a unit
suitable for the manufacture of pyridine and its derivatives, a
unit suitable for the manufacture of acrylonitrile, and other units
suitable for industrial processes, etc., either individually or in
a combination of two or more thereof. In a particular embodiment,
the material of the present invention is provided to a plurality of
units that are FCC units. The FCC unit is adapted to promote
catalytic cracking of feed stock provided from a source and may be
configured in a conventional manner. In another embodiment, the
material of the present invention is provided to units designed to
crack gasoline range feed stocks into Liquefied Petroleum Gas (LPG)
such as, but not limited to, Superflex.TM. process, or crack heavy
feed into LPG instead of gasoline such as, but not limited to,
Indmax.TM. process. In another particular embodiment, the material
of the present invention is provided to units for processing
acrylonitrile. An example of a unit suitable for the manufacture of
acrylonitrile is a fluidized bed process. Similar units are also
used for manufacturing other chemicals such as pyridine. The unit
may also be a processing plant having a flue gas exhaust stream in
which particle reduction and/or flue gas emission reduction is
desirable. In an embodiment, the unit may be in the form of a
processing plant in which it would be desirable to have particle
reduction and/or flue gas emission reduction in a gaseous exhaust
gas stream. Non-limiting examples of such processing plants include
plants having gas streams from scrubbers that emit/capture sodium
sulfate or other pollutant, carbon black producing plants, fluid
cokers, and biofuel plants, among others.
[0139] In an embodiment, the exhaust gas stream 1060 of the
fluidized unit 1000 exits a regenerator 1002 of an FCC unit. The
exhaust gas stream 1060 is routed along a gaseous exhaust path 1040
defined between an outlet 1062 of the fluidized unit 1000 and a
flue gas stack 1016 of an exhaust system 1042 of the unit 1000. In
the embodiment depicted in FIG. 9, the gaseous exhaust path 1040
includes a pipe or conduit 1004 coupled to the outlet 1062 of the
fluidized unit 1000. The conduit 1004 is interfaced with one or
more particle removal devices 1028. Examples of particle removal
devices 1028 include, but are not limited to, a third stage
separator 1012, an electrostatic precipitator 1014 and filtration
device 1032, either individually or combinations of two or more
thereof. As shown in FIG. 9, three particle removal devices 1028
(i.e., third stage separator 1012, electrostatic precipitator 1014,
and filtration device 1032) are arranged in series. The number,
type and sequence of the one or more particle removal devices 1028
may be arranged to suit particular particle needs of the exhaust
stream. The exhaust gas stream 1060 exits the electrostatic
precipitator 1014 through the conduit 1004 into the flue gas stack
1016. In another embodiment, the one or more particle removal
devices 1028 include an ESP modified for magnetic material removal
or particle removal device operable to magnetically remove magnetic
PM, such as high gradient magnetic field separators and carousel
magnetic separators. Examples of a particle removal device operable
to magnetically remove magnetic PM are described in U.S. Pat. No.
4,407,773.
[0140] In an embodiment, the flue gas stack 1016 includes a sensor
1030 that provides a metric indicative of the composition of the
exhaust gas stream 1060. The metric indicative of the composition
of the exhaust gas stream 1060 is provided to a controller 1050
which controls the operation of the down stream addition system
1010 such that the amount of DSA 600 provided to the exhaust gas
stream 1060 is adjusted in response to the metric provided by the
sensor 1030, for example, by decreasing the amount of DSA 600
provided as emission of a pollutant diminishes or increasing the
amount of DSA 600 provided as emission of a pollutant
increases.
[0141] In an embodiment, the controller 1050 additionally includes
a communication device, such as a modem or antenna, which allows
the controller 1050 to provide information to a remove device, such
as a computer residing in a location far removed from the hazardous
processing area around the unit 1000. The information provided by
the controller 1050 allows monitoring of the amount of DSA 600
dispensed into the exhaust gas stream 1060, the inventory of the
DSA 600 within the down stream addition system 1010, events and the
like.
[0142] In the embodiment depicted in FIG. 9, the exhaust gas stream
1060 exits the regenerator 1002 of the fluidized unit 100 (e.g.,
the regenerator of an FCC unit) and passes through an optional heat
recovery unit 1006, such as a CO boiler, prior to entering the
third stage separator 1012 and electrostatic precipitator 1014. The
down stream addition system 1010 is coupled by a feed line 1024 to
the conduit 1004 at a location downstream of the heat recovery unit
1006 (if present) and prior to the third stage separator 1012.
Alternatively, the feed line 1024 may couple to the conduit 1004
upstream of the heat recovery unit 1006 to increase residence time
of the DSA 600 in the gaseous exhaust stream.
[0143] In an embodiment, the down stream addition system 1010
includes a vessel 1022 or device for dispensing DSA 600 into the
conduit 1004 carrying the exhaust gas stream 1060. The down stream
addition system 1010 may continuously dispense DSA 600 (or other
particulate matter) into the conduit 1004 or dispense DSA 600 into
the conduit 1004 in discrete amounts. Additions from the down
stream addition system 1010 may be made in metered (e.g., measured)
amounts to track the amount of DSA 600 being interfaced with the
exhaust gas stream 1060 using the controller 1050. In one
embodiment, catalyst addition systems may be adapted to operate as
down stream addition systems 1010. Non-limiting examples of
catalyst addition systems that may be adapted to operate as down
stream addition systems 1010 include, but are not limited to,
systems described in U.S. patent application Ser. No. 11/283,227,
filed Nov. 18, 2005, U.S. patent application Ser. No. 10/374,450,
filed Feb. 26, 2003, U.S. patent application Ser. No. 10/445,453,
filed May 27, 2003, U.S. patent application Ser. No. 10/717,250,
filed Nov. 19, 2003, U.S. patent application Ser. No. 11/008,913,
filed Dec. 10, 2004, U.S. patent application Ser. No. 10/717,249,
filed Nov. 19, 2003, and U.S. patent application Ser. No.
11/835,347, filed Aug. 7, 2007, all of which are incorporated by
reference in their entireties. An eductor may also be adapted to
function as part of a down stream addition system 1010 to add DSA
600, other additives, catalysts or other particulate matter to an
exhaust gas stream 1060 of a fluidized unit as further described
below. Non-limiting examples of eductors for use with fluidized
units such as an FCC unit that may be adapted for use in a down
stream addition system 1010 are described in U.S. patent
application Ser. No. 11/462,882, filed Aug. 7, 2008.
[0144] FIG. 10 depicts one embodiment of a vessel configured for
providing DSA 600 to the feed line 1024. The vessel 1022 includes a
first container 1402 and a second container 1404 coupled in
parallel to the feed line 1024. Each container 1402, 1404 includes
one or more sensors 1408 and a metering device 1410 which
communicate with the controller 1050, such that the DSA 600
provided from the vessel 1022 into the gas stream in the conduit
1004 may be precisely measured and historically tracked on a real
time basis. The sensors 1408 may be one or more of a level sensor
located to detect changes in the level of DSA 600 within the
containers 1402, 1404 that are indicative of the amount of DSA 600
provided to the conduit 1004; load cells interfaced with the
container 1402, 1404 to determine the weight gained or lost due to
DSA 600 additions for removal from the container 1402, 1404; and/or
a flow meter positioned to determine the amount of material leaving
the container 1402, 1404 and entering the feed line 1024 through
the metering device 1410. The metering device 1410 may be a valve
or positive displacement device which can operably be utilized to
provide discrete amounts of DSA 600 into a delivery line 1462
coupled to the feed line 1024, or alternatively, control the rate
and/or amount of material exiting the container 1402, 1404 and
entering the feed line 1024 from the delivery line 1462 in a batch
or continuous basis, such that the controller 1050 may control and
keep track of the amount of DSA 600 dispensed into the conduit 1004
through an outlet 1416 of the feed line 1024 using information
provided by the sensors 1408.
[0145] The feed line 1024 is coupled to a fluid source 1400, such
as plant air or a blower, which moves DSA 600 exiting the
containers 1402, 1404 through a check valve 1414 and into the
conduit 1004. Shut-off valves 1412 may be provided in order to
isolate the feed line 1024 from the conduit 1004 when desired. To
enhance distribution of DSA 600 within the conduit 1004, the outlet
1416 of the feed line 1024 may include a quill or a plurality of
outlet pipes or a quill comprising a plurality of outlet holes to
enhance mixing and distribution of the DSA 600 in the exhaust gas
stream 1060.
[0146] In an embodiment, DSA 600 is provided to the feed line 1024
through operation of the metering device 1410 of at least one of
the containers 1402, 1404. In a mode providing a continuous
addition of DSA 600 to the exhaust gas stream 1060, the metering
device 1410 coupled to the container 1402 is operated to allow a
continuous stream of DSA 600 to enter the conduit 1004 in a
regulated manner while the sensors 1408 interfaced with the
container 1402 provide a metric indicative of the amount of DSA 600
entering the exhaust stream to the controller 1050, which records
the rate and/or amount of DSA 600 being added and updates the
inventory of DSA 600 in the down stream addition system 1010.
Depending on the DSA 600 needs within the exhaust stream, the
controller 1050 may control the operation of the metering device
1410 to add more or less DSA 600, for example, in response to a
metric provided by the sensor 1030 described above. Once the amount
of DSA 600 within the container 1402 reaches a predefined amount,
the metering device 1410 coupled to the container 1402 is closed,
and the metering device 1410 coupled to the container 1404 is
opened to provide a substantially uninterrupted stream of DSA 600
to the conduit 1004 while the container 1402 is refilled with
additional DSA 600. Once the DSA 600 within the container 1404
reaches a predefined level, the metering device 1410 coupled to the
container 1404 is closed, and the metering device 1410 coupled to
the container 1402 is opened to provide a substantially
uninterrupted flow of DSA 600 to the exhaust stream.
[0147] In another embodiment, DSA 600 is provided intermittently in
batches. For example, the metering device 1410 coupled to the
container 1402 is operated to open and close at intervals, thereby
providing batches of DSA 600 to enter the conduit 1004. The sensors
1408 interfaced with the container 1402 provide a metric indicative
of the amount of each batch of DSA 600 entering the exhaust stream
to the controller 1050, which records the total of DSA 600 being
added and updates the DSA 600 inventory of the down stream addition
system 1010. In an embodiment, the down stream addition system 1010
provides the DSA 600 in less than 5 minute intervals between
batches, less than 3 minute intervals between batches, less than 2
minute intervals between batches, or less than 1 minute intervals
between batches. Once the amount of DSA 600 within the container
1402 reaches a predefined amount, batches of DSA 600 are then
provided from the container 1404 are provided to the conduit 1004
to provide a substantially uninterrupted stream of DSA batches to
the conduit 1004 while the container 1402 is refilled with
additional DSA 600.
[0148] FIG. 11 depicts another embodiment of the vessel 1022. The
vessel 1022 includes a container 1402 configured as described with
reference to FIG. 10. As such, the container 1460 is a metering
device 1410 which regulates DSA 600 dispensed from the container
1460 into the delivery line 1462 and feed line 1024, which
eventually provides the DSA 600 to the conduit 1004. However, when
the amount of DSA 600 in the container 1402 reaches a predefined
level, a predefined amount of DSA 600 is provided to the container
1402 so that the calculations of DSA 600 provided to the exhaust
stream flowing through the conduit 1004 can be accurately
maintained. In one embodiment, the container 1402 is recharged by a
feed system from the container 1404, which may be configured as a
feed addition system similar to that described with reference to
FIG. 10. Alternatively, the container 1402 may be recharged with
DSA 600 using an eductor 1422 or other device which may empty the
entire contents of a tote 1420 or other container having a known
quantity of DSA 600 which can be provided to the controller 1050 to
update or maintain the accuracy of the amount of DSA 600 within the
container 1402 and ultimately provided to the exhaust stream
flowing in the conduit 1004. In this manner the feed system
replenishes the vessel 1022 such that uninterrupted additions may
be made.
[0149] FIG. 12 depicts another embodiment of a vessel 1022 suitable
for providing DSA 600 in various forms such as liquid, solutions,
dispersions of solids, slurries, and the like, either individually
or combinations of two or more thereof. The vessel 1022 depicted in
FIG. 12 includes a container 1450 which is suitable for containing
a quantity of fluid and/or slurry. The container 1450 is interfaced
with at least one sensor 1408 and a metering device 1410 as
described above. In one embodiment, the at least one sensor 1408
and metering device 1410 may be integrated as a positive
displacement device 1452 which controls and/or meters the amount of
liquid and/or slurry and the like contained in the container 1450
and introduced into the exhaust gas stream 1060 flowing through the
conduit 1004.
[0150] FIG. 13 depicts another embodiment of a vessel 1022 suitable
for providing DSA 600 in various forms such as liquid, solutions,
dispersions of solids, slurries and the like, either individually
or combinations of two or more thereof. The vessel 1022 depicted in
FIG. 13 includes a container 1460 which is suitable for containing
a quantity of DSA 600 in the form of a fluid, slurry and/or powder.
The container 1460 may be a tote or other suitable container.
Sensors 1408 are interfaced with the container 1460 and/or delivery
line 1462 coupling the container 1460 to the feed line 1024. The
container 1460 is also interfaced with a metering device 1410 as
described above. At least one eductor 1422 is interfaced with the
delivery line 1462 to move DSA 600 from the container 1460 to the
feed line 1024 and eventually to the conduit 1004. In one
embodiment, metering device 1410 and eductor 1422 may be an
integrated unit. The eductor 1422 is useful for moving particles of
DSA 600 having smaller size dimensions, for example DSA 600 having
an average particle size ranging down to about 30 .mu.m. Thus, the
eductor 1422 and metering device 1410 cooperate with container 1460
to function as the down stream addition system 1010.
[0151] Returning to FIG. 9, the length of a region of the conduit
1004 bounded by the feed line 1024 and the third stage separator
1012 defines a reaction zone 1008 in which DSA 600 or other
particulate matter such as but not limited to one or more DSA 600
or catalyst, either individually or in combination of two or more
thereof, provided by the down stream addition system 1010 may
interface with and react with the gases and other material
entrained in the exhaust gas stream 1060. Some non-limiting
examples of one or more considerations for the design of the
reaction zone 1008 include the length and diameter of the conduit
1004 defining the reaction zone 1008, and the reaction time
required for the DSA 600. Generally, a short reaction zone 1008
means less residence time for the DSA 600, and where space permits,
the reaction zone 1008 may be long enough to provide adequate
reaction time. Optionally, the DSA 600 may be recycled, and if the
DSA 600 is recycled back to the regenerator 1002; the reaction zone
or zones include the reaction zone 202 of the regenerator 1002
wherein the recycled DSA 600 may interact with the surrounding
matter. In one embodiment, the reaction zone 1008 defined in the
conduit 1004 is designed to minimize the use of DSA 600 such that
the capacity of the third stage separator 1012 and/or electrostatic
precipitator 1014 does not reach a saturation point due to excess
addition of DSA 600. It is contemplated that the reaction zone or
multiple reaction zones 202, 1008 may be in the regenerator 1002
and/or conduit 1004 of the same or multiple fluidized units 1000.
For example, the down stream addition system 1010 may be configured
to provide DSA 600 to reaction zones 202, 1008 in two or more
different fluidized units 1000, wherein the different units share
the same exhaust gas stream 1060 treated by the down stream
addition system 1010. It is also contemplated that the down stream
addition system 1010 may be configured to provide DSA 600 to
reaction zones 202, 1008 in two or more different fluidized units
1000, wherein at least two of the different units 1000 do not share
the same exhaust gas stream 1060 treated by the down stream
addition system 1010. One addition system that provides catalyst to
multiple units that may be adapted to provide DSA 600 to multiple
reaction zones 202, 1008 is described in U.S. patent application
Ser. No. 12/504,882, filed Jul. 17, 2009, which is incorporated by
reference in its entirety.
[0152] At the end of the reaction zone 1008, the third stage
separator 1012 removes particulate matter, including DSA 600, from
the exhaust gas stream 1060. Generally, the third stage separator
1012 removes both coarse and fine particles from the exhaust gas
stream 1060. Coarse particles are generally particles having an
average diameter in a range from about 70 .mu.m to about 80 .mu.m,
while fine particles are generally defined as having an average
diameter in a range from about 20 .mu.m to about 40 .mu.m. The
particulate removed from the third stage separator 1012 may be
discarded or recycled. In one embodiment, the particulate matter
separated by the third stage separator may be recycled back into
the generator of the fluidized unit 1000, to the vessel 1022 and/or
recycled for use in one or more other fluidized units 1000,
including those which do not share a common exhaust gas stream
1060. A recycling path between the third stage separator 1012 and
the unit 1000 is designated by reference numeral 1018. As discussed
above, recycled DSA 600 routed along the recycling path 1018 has
been exposed to the exhaust gas stream 1060 and is not to be
confused with virgin DSA 600.
[0153] Recycling DSA 600 primarily recovered from the third stage
precipitator has a number of advantages. For example, as
super-fines present in the exhaust gas stream have a diameter of
less than about 20 .mu.m, the relatively larger particle size of
recycled DSA 600 allows recycled DSA 600 to be removed and recycled
separately from the super-fine. Thus, the recycled DSA 600 is more
easily handled, and the concentration of active materials on the
recycled DSA 600 is more concentrated due to the lack of super-fine
particles.
[0154] The exhaust gas stream 1060 leaving the third stage
separator 1012 passes through the electrostatic precipitator 1014
prior to entering the flue gas stack 1016. The electrostatic
precipitator 1014 removes not only coarse and fine particles which
may still be entrained in the exhaust gas stream 1060, but also
removes super-fine particles. Super-fine particles are particles
having an average diameter less than about 20 .mu.m. The
electrostatic precipitator 1014 may include multiple stages to
preferentially separate particles of different size ranges in
different stages, as further discussed below. The particles removed
from the electrostatic precipitator 1014 may include virgin DSA 600
provided by the down stream addition system which has traveled
through the conduit 1004 for the first time. The particles removed
by the electrostatic precipitator 1014 may be recycled with or
separated from particles captured by the third stage separator
1012. Thus, particles removed from the exhaust gas stream 1060 by
the electrostatic precipitator 1014 may be recycled back into the
regenerator 1002 of the fluidized unit 1000, to the vessel 1022
and/or recycled for use in one or more other fluidized units,
including those which do not share a common exhaust gas stream
1060. A recycling path between the electrostatic precipitator 1014
and the unit 1000 is designated by reference numeral 1020. As
discussed above, recycled DSA 600 routed along the recycling path
1020 has been exposed to the exhaust gas stream 1060 and is not to
be confused with virgin DSA 600.
[0155] It is also contemplated that the particles removed from the
exhaust gas stream 1060 and residing on the collection plates of
the electrostatic precipitator 1014 form a dust cake comprising CEM
300 and/or DSA 600. The frequency of rapping to remove the dust
cake may be adjusted to increase the amount of CEM 300 and/or DSA
600 exposed to the exhaust gas stream 1060 by the dust cake,
thereby increasing the amount of emissions removed from the exhaust
gas stream 1060 without adding additional CEM 300 or DSA 600.
[0156] The exhaust gas stream 1060 leaving the electrostatic
precipitator 1014 passes through one or more filtration devices
1032, if present, prior to entering the flue gas stack 1016. The
one or more filtration devices 1032 may be positioned at other
locations on conduit 1004 relative to the locations of the
electrostatic precipitator 1014 and/or the third stage separator
1012. The filtration devices 1032 includes a plurality of filters
1036 disposed in a housing 1038. The exhaust gas stream 1060 flows
from the conduit 1004 into an inlet port of the housing 1038,
through the filters 1036, and then exits the housing 1038 through
an outlet port. The outlet port of the housing 1038 is coupled to
the conduit 1004 to the exhaust flue 1006.
[0157] The filters 1036 may be a bag filter, pleated filter,
ceramic filter, sintered metal filter or other filter suitable for
filtering the exhaust gas stream 1060. The filters 1036 remove PM
from in the exhaust gas stream 1060, which forms a dust cake of PM
on the on the upstream surface of the filter 1036. The dust cake
comprises virgin DSA 600, recycled DSA 600, virgin CEM 300, and
recycled CEM 300 present in the PM filtered from the exhaust gas
stream 1060. The dust cake is periodically removed from the
upstream surface of the filter 1036 by forcing a reverse jet of air
through the filter 1036 and/or by shaking the filter 1036 and/or
the housing 1038. The dust cake removed from the filter 1036 is
collected in the housing 1038 or a bin (not shown) connected
thereto.
[0158] The PM of dust cake removed from the filter 1036 collected
in the housing 1038 (which includes any virgin DSA 600, recycled
DSA 600, virgin CEM 300, and recycled CEM 300 present in the
exhaust gas stream 1060), may be recycled back into the regenerator
1002 of the fluidized unit 1000, to the vessel 1022 and/or recycled
for use in one or more other fluidized units, including those which
do not share a common exhaust gas stream 1060. A recycling path
between the electrostatic precipitator 1014 and the unit 1000 is
designated by reference numeral 1034. As discussed above, recycled
DSA 600 and/or recycled CEM 300 present in the dust cake routed
along the recycling path 1034 has been exposed to the exhaust gas
stream 1060, and is not to be confused with virgin DSA 600 and/or
virgin CEM 300.
[0159] The dust cake present on the filter 1036 provides a bed of
absorption media comprising DSA 600 and/or CEM 300 through which
the exhaust gas stream 1060 must pass through prior to entering the
flue gas stack 1016. Thus, the bed of absorption media present on
the filter 1036 provides another reaction zone through which the
exhaust gas stream 1060 must pass, resulting in a significant
increase of amount of SO.sub.x and/or NO.sub.x removed from the
exhaust gas stream 1060. For example, test data demonstrates that
the use of a filtration device 1032 to retain a dust cake of DSA
600 through which the exhaust gas stream 1060 was forced to flow
through resulted in a 40 percent drop in SO.sub.x emissions
relative to an exhaust gas stream untreated with DSA 600. This
relates to an 80 percent reduction on the treated exhaust gas
stream 1060.
[0160] In embodiments wherein the particulate matter withdrawn from
the third stage separator 1012, electrostatic precipitator 1014
and/or filtration device 1032 is recycled to the regenerator 1002
of an FCC unit, the flow of recycled DSA 600 may be described as
counter-current. For example, virgin DSA 600 is first used in the
flue gas exhaust gas stream 1060 within the conduit 1004 when the
DSA 600 is freshest (i.e., most reactive), then recycled into the
regenerator 1002 of the unit 1000 for a second use. Thus, the
sequence of use of the recycled DSA 600 is counter-current to the
direction of the exhaust gas flow leaving the regenerator 1002
toward the flue stack 1016.
[0161] FIG. 14 depicts one embodiment of an electrostatic
precipitator 1014 which may be utilized for removing DSA 600 from
the gaseous exhaust stream passing through the conduit 1004 into
the flue gas stack 1016. The electrostatic precipitator 1014
includes at least two stages, illustratively shown as a first stage
1572 and a second stage 1574. The first stage 1572 generally
removes coarser particles from the gaseous exhaust stream and
deposits the separated material into a bin 1576. The second stage
1574 of the electrostatic precipitator 1014 removes finer particles
from the exhaust gas stream 1060 passing through the electrostatic
precipitator 1014 which are not removed by the first stage 1572.
Particles removed from the second stage 1574 are deposited in a
second bin 1578.
[0162] Since the two stages 1572, 1574 remove different size ranges
of particles, the electrostatic precipitator 1014 may be utilized
to remove DSA 600 preferentially to catalysts by configuring the
size of the DSA 600 entering the electrostatic precipitator 1014 to
be in a different size range relative to catalyst, fines and other
particulate matter so that the DSA 600 may be removed in a separate
stage 1572, 1574 and collected in separate bins 1576, 1578. By
collecting the DSA 600 preferentially in one of the bins 1576,
1578, the collected DSA 600 removed from the exhaust gas stream
1060 is not diluted by catalyst or other material, and the DSA 600
may be more readily recycled back through the regenerator 1002 of
the fluidized unit 1000 without an adverse effect on the
calculation or tracking of virgin DSA 600 placed into the exhaust
gas stream 1060 traveling through the conduit 1004 and into the
flue gas stack 1016 by the vessel 1022.
[0163] In one embodiment, the size of the DSA 600 present in the
exhaust gas stream 1060 is in the size range from about 60 .mu.m to
about 300 .mu.m in average diameter. Since the catalyst and
catalyst fines present in the exhaust gas stream 1060 are typically
much smaller than the dimension of the DSA 600, for example,
typically having an average diameter in the size range less than
about 10 .mu.m to about 15 .mu.m, the DSA 600 is preferentially
removed from the exhaust stream in the first stage 1572 while the
catalyst fines are removed in the second stage 1574. Thus, the DSA
600 from the bin 1576 may be recycled as shown by path 1020 back to
the regenerator 1002 of the fluidized unit 1000 for further use
without excessive dilution by non-DSA material. Alternatively, the
DSA 600 from the bin 1576 may be recycled back to the vessel 1022
(or other addition system) for reintroduction into the gaseous
exhaust stream passing through the conduit 1004. CEM 300 may be
similarly recycled to either the regenerator 1002 of the fluidized
unit 1000 for further use and/or recycled for reintroduction into
gaseous exhaust stream 1060 passing through the conduit 1004.
[0164] It is also contemplated that DSA 600 may have a high
attrition index (ASTM D5757-10), which promotes the breaking of DSA
600 in the exhaust gas stream 1060 present in the conduit 1004,
thereby reducing the size of the DSA 600 while in the gaseous
exhaust stream due to collision with the walls of the conduit 1004
and other DSA 600. The high attrition index allows the particle
size of virgin DSA 600 to be large enough for ease of handling
prior to entry into the effluent gas stream 1060, while once added
to the effluent gas stream 1060 fractures and breaks into smaller
particles of DSA 600, thereby increasing the particle surface area
and making more active material available for NO.sub.x and/or
SO.sub.x reduction. In order to preferentially capture the
particles of DSA 600 in the first stage 1572 of the electrostatic
precipitator 1014 relative to other fines, a clumping or
aggregation agent may be introduced into the conduit 1004 upstream
of the first stage 1572 by a promoter source 1580. The DSA 600 may
additionally or alternatively include a clumping encouragement
component 606. The promoter source 1580 provides a material which
enhances the propensity of the particles DSA 600 to clump or
aggregate or increase in weight to make collection by the
electrostatic precipitator 1014 more effective. For example, the
promoter source 1580 may introduce water bearing a salt solution or
other material which would increase the weight or propensity to
clump or aggregate by the particles of DSA 600. Increasing the
weight of particles of DSA 600 makes removal of DSA 600 by the
third stage separator 1012 more effective. Clumping and aggregation
of particles of DSA 600 increases the particle diameter, which
makes the clumped particles of DSA 600 more likely to be separated
in the first stage 1572, as compared to the catalyst fines removed
in the second stage 1574. This technique may also be utilize prior
to the third stage separator 1012 to promote clumping, aggregation
or increase in weight to make collection by the electrostatic
precipitator 1014 more effective.
[0165] In another embodiment, the first stage 1572 of the
electrostatic precipitator 1014 may include a magnetic field
generator. The magnetic field generator interfaced with the first
stage 1572 removes DSA 600 which have been modified to be or
inherently are more magnetic than conventional catalyst and
additive fines. This enables the DSA 600 to be preferentially
removed in the first stage 1572 relative to the catalyst fines
removed in the second stage 1574.
[0166] FIG. 15 is another embodiment of a down stream addition
system 2010 coupled to an exhaust gas stream 1060 of a fluidized
unit 1000. In the embodiment depicted in FIG. 15, the addition
system 2010 is generally configured similarly to the down stream
addition system 1010 described above with reference to FIG. 9,
except that at least one circulating fluid bed vessel 2040 is
disposed in-line with conduit 1004 directing the exhaust gas stream
1060 between the fluidized unit 1000 and the electrostatic
precipitator 1014. The circulating fluid bed vessel 2040 includes a
housing 2042 that retains a bed of DSA 600 (i.e., a DSA bed 2044)
therein. The DSA bed 2044 provides a reaction zone for the DSA 600
to react with the exhaust gas stream 1060. The housing 2042 may
incorporate one or more third stage separators 2046, such as
cyclonic separators, within a plenum defined in the housing 2042
above the DSA bed 2044. Alternatively or in addition, a separate
third stage separator (such as the separator 1012 shown in FIG. 9)
may be disposed between the circulating fluid bed vessel 2040 and
the electrostatic precipitator 1014. DSA 600 may be provided to the
circulating fluid bed vessel 2040 either directly from the vessel
1022 of the addition system 2010 via a feed line 1026 (shown in
phantom) or via feed line 1024 which entrains the DSA 600 with the
exhaust gas stream 1060 entering the circulating fluid bed vessel
2040 through the conduit 1004.
[0167] In the embodiment depicted in FIG. 15, two circulating fluid
bed vessels 2040, 2050, each containing integrated third stage
separators 2046, are disposed in series prior to the electrostatic
precipitator 1014. The particle matter exiting the bed of the
circulating fluid bed vessel may be discarded or recycled. If two
circulating fluid bed vessels 2040, 2050 are used, each circulating
fluid bed vessel 2040, 2050 may be used for the addition of
different DSA 600 to prevent intermixing of the DSAs. For example,
a bed 2044 of SO.sub.x DSA may be used in the upstream circulating
fluid bed vessel 2040, while a bed 2054 of NO.sub.x DSA may be
disposed in a housing 2052 of the downstream circulating fluid bed
vessel 2050. Thus, intermixing in the reaction zone is minimized.
Moreover, the recycle streams 2048, 2058 may optionally be kept
separate, if desired. For example, recycled NO.sub.x DSA may be
kept from entering the regenerator 1002 while the SO.sub.x DSA is
recycled through the regenerator 1002 by routing the recycle path
2058 to a holding bin instead of to the regenerator 1002.
[0168] Utilization of a circulating fluid bed vessel advantageously
increases the residence time of the DSA 600 in the exhaust gas
stream 1060 without the need to continuously add DSA 600 to the
exhaust gas stream 1060. For example, the bed of DSA 600 may
include about 20 percent DSA 600 as opposed to about 1 to about 3
percent DSA 600 present in the reaction zone of the system
described in FIG. 6. Other advantages of using a circulating fluid
bed vessel include reduction in the amount of DSA 600 used by about
one quarter, for example, from about 1000 pounds/day for
continuously provided DSA 600 into the exhaust gas stream to about
100-250 pounds/day of DSA 600 utilized in a circulating fluid bed
vessel. Use of a circulating fluid bed vessel also minimize waste,
enhances the ability to recycle DSA 600, increases the efficiency
of DSA usage, prevents saturation of the electrostatic
precipitator, and reduces the requirements (frequency) of additions
and withdrawals, which extends equipment life and maintenance
requirements.
[0169] FIG. 16 is a schematic of another embodiment of a down
stream addition system 3000. The down stream addition system 3000
includes a circulating fluid bed vessel 2040 having a dedicated
regenerator 3002. The addition systems described above may also
utilize a dedicated regenerator 3002 as described below. The
circulating fluid bed vessel 2040 may optionally include one or
more third stage separators 2046, such as cyclone separators
disposed in the plenum above the DSA bed 2044. The particle removal
port positioned at the bottom of the circulating fluid bed vessel
2040 is coupled by a feed line 3048 to an inlet port of the
regenerator 3002 to allow DSA 600 exiting the circulating fluid bed
vessel to be recycled through the regenerator. Valves and/or
blowers, not shown, control the flow of material from the
circulating fluid bed vessel to the regenerator 3002 to prevent
blow-back. The DSA 600 from the circulating fluid bed vessel are
regenerated in the regenerator 3002 and returned to the circulating
fluid bed vessel for reuse via a return line 3004. Valves, not
shown, control the flow of material from the regenerator 3002 to
the circulating fluid bed vessel. It is also contemplated that any
of the lines 3004, 3048 coupling the circulating fluid bed vessel
and the regenerator 3002 may include a tee to enable a desired
amount of DSA 600 to be diverted for other uses prior to, or after
regeneration. Other uses for diverted DSA 600 include recycling the
DSA 600 through a fluidized unit 1000, for example, a regenerator
1002 of an FCC unit to which the exhaust gas stream 1060 is
directed though the circulating fluid bed vessel and/or one or more
other fluidized units. The use of a dedicated regenerator 3002
enables more efficient use of the DSAs, and less frequent
additions, thereby saving costs and extending the life of the
vessel 1022 of the addition system.
[0170] Returning to FIG. 9, the performance of the electrostatic
precipitator 1014 may be enhanced by selection of certain
variables, either individually or combination of two or more
thereof, to increase particle retention by the electrostatic
precipitator 1014. Examples of such variables include, but are not
limited to, modifying surface composition of the electrostatic
precipitator, increasing the residence time in the electrostatic
precipitator by increasing the size of the electrostatic
precipitator or decreasing the gas velocity (for example, minimum
residence time is about 3 seconds, typical is about 20 seconds,
maximum residence time is about 30 seconds), increasing the power
usage/voltage across the electrostatic precipitator, i.e., the
voltage delta across the anode and cathode (for example, setting
the voltage at a minimum of about 20,000V, such as about 40,000V,
up to a maximum of about 50,000V), increasing the cleaning/rapping
frequency of the electrostatic precipitator (for example, setting
the rapping frequency at a minimum of about once every 10 minutes,
such as about once per minute, to a maximum frequency of about once
per every 10 seconds), and increasing the adhesion/retention
(adhesion is ability to retain captured/absorbed PM while lower
electrical resistivity of particle matter helps the electrostatic
precipitator capture PM, among others). In yet other embodiments, a
conditioning agent may be added to the flue gas exhaust stream
prior to the electrostatic precipitator by a conditioning agent
provider 1090. The conditioning agent may be a polar gas molecule
which helps the electrostatic precipitator absorb/pick-up particle
matter. Non-limiting examples of conditioning agents include
H.sub.2O, steam, SO.sub.3, urea, salt solutions, NO.sub.R, and
NH.sub.3. Thus, use of the conditioning agent results in an
increased efficiency of the electrostatic precipitator that
advantageously provides a reduction in the amount of particular
matter exiting the stack to the atmosphere, while allowing more
efficient reclamation of DSA 600 for recycling.
[0171] FIGS. 17A-17C are schematic diagrams for one or more
addition systems interfaced with one or more units. In the
embodiment of FIG. 17A, a plurality of units, shown as 1500.sub.A,
1500.sub.B, and 1500.sub.N, wherein N is representative of one or
more additional units, are provided CEM 300 by at least one of an
addition system 110, 120. The CEM 300 provided by the addition
system 110, 120 is primarily virgin CEM 300; however, the addition
systems 110, 120 may be utilized to provide recycled CEM 300. The
addition system 110, 120 is coupled to the units 1500.sub.A,
1500.sub.B, and 1500.sub.N by feed lines 118.sub.A, 118.sub.B, and
118.sub.N. The gaseous exhaust of each units 1500.sub.A,
1500.sub.B, and 1500.sub.N travels via exhaust paths 1550.sub.A,
1550.sub.B, and 1550.sub.N (collectively exhaust path 1550) through
particle removal devices 1502.sub.A, 1502.sub.B, and 1502.sub.N to
a flue gas stack 1016.sub.A, 1016.sub.B, and 1016.sub.N. The
particle removal devices 1502.sub.A, 1502.sub.B, and 1502.sub.N
(collectively particle removal devices 1502) may be one or more of
any of the particle removal devices 1028 described above. A recycle
line 1508.sub.A, 1508.sub.B, and 1508.sub.N (1508 collectively)
optionally couples each particle removal devices 1502.sub.A,
1502.sub.B, and 1502.sub.N to the addition system 110, 120 which
allows the virgin CEM 300 provided by the addition system 110, 120
to be recycled back (as recycled CEM 300) through one or more of
the units 1500.sub.A, 1500.sub.B, and 1500.sub.N. The recycled CEM
300 may be alternatively added to units 1500.sub.A, 1500.sub.B, and
1500.sub.N by a second addition system 120 (not shown) to segregate
virgin and recycled CEM 300. In this manner, the addition system
110, 120 may be configured to service one or more of the units
1500.sub.A, 1500.sub.B, and 1500.sub.N with virgin CEM 300, while
the recycled CEM 300 may be collected from one or more of units
1500.sub.A, 1500.sub.B, and 1500.sub.N for recycling to any one or
more of the units 1500.sub.A, 1500.sub.B, and 1500.sub.N.
[0172] In the embodiment of FIG. 17B, a plurality of units, shown
as 1500.sub.A, 1500.sub.B, and 1500.sub.N are provided DSA 600 by
an DSA addition system 210. The DSA 600 provided by the addition
system 210 is primarily virgin DSA; however, the addition system
210 may also be utilized to provide recycled DSA. Although only one
addition system 210 is shown in FIG. 17B, virgin and recycled DSA
600 may be provided by separate addition systems 210. The DSA
addition system 210 is coupled to the units 1500.sub.A, 1500.sub.B,
and 1500.sub.N by feed lines 1024.sub.A, 1024.sub.B, and
1024.sub.N. The gaseous exhaust of each unit 1500.sub.A,
1500.sub.B, and 1500.sub.N travels via exhaust paths 1550.sub.A,
1550.sub.B, and 1550.sub.N (collectively exhaust path 1550) through
particle removal devices 1502.sub.A, 1502.sub.B, and 1502.sub.N to
one or more exhaust flues (not shown). A recycle line 1508.sub.A,
1508.sub.B, and 1508.sub.N (1508 collectively) optionally couples
each particle removal devices 1502.sub.A, 1502.sub.B, and
1502.sub.N to the DSA addition system 210 which allows the virgin
DSA 600 provided by the DSA addition system 210 to be recycled back
(as recycled DSA 600) through one or more of the exhaust paths
1550.sub.A, 1550.sub.B, and 1550.sub.N of the units 1500.sub.A,
1500.sub.B, and 1500.sub.N. The recycled DSA 600 may be
alternatively added to the exhaust path 1550 of the units
1500.sub.A, 1500.sub.B, and 1500.sub.N by a second DSA addition
system 210 (not shown) to segregate virgin and recycled DSA 600. In
this manner, the DSA addition system 210 may be configured to
service one or more of the units 1500.sub.A, 1500.sub.B, and
1500.sub.N with virgin DSA 600, while the recycled DSA 600 may be
collected from one or more of units 1500.sub.A, 1500.sub.B, and
1500.sub.N for recycling to any one or more of the units
1500.sub.A, 1500.sub.B, and 1500.sub.N without mixing the virgin
and recycled DSA 600. In other embodiments, the virgin and recycled
DSA 600 may be provided by a common DSA addition system 210.
[0173] In the embodiment of FIG. 17C, a plurality of units
1500.sub.A, 1500.sub.B, and 1500.sub.N have a common exhaust path
1550 into which are provided DSA 600 by a DSA addition system 210.
The DSA 600 provided by the addition system 210 is primarily virgin
DSA; however, the addition system 210 may be utilized to provide
recycled DSA. The gaseous exhaust of each units 1500.sub.A,
1500.sub.B, and 1500.sub.N travels via exhaust paths 1550 through a
common particle removal device 1502 to a flue gas stack 1016.
Recycle line 1508 couples the particle removal device 1502 to the
DSA addition system 210 which allows the virgin DSA 600 provided by
the DSA addition system 210 to be recycled back through the exhaust
path 1550 of the units 1500.sub.A, 1500.sub.B, and 1500.sub.N. The
recycled DSA 600 may be alternatively added to the exhaust path
1550 of the units 1500.sub.A, 1500.sub.B, and 1500.sub.N by a
second addition system 210 (not shown) to segregate virgin and
recycled DSA 600. The recycle line 1508 may additionally or
alternatively couple the particle removal device 1502 to the CEM
300 addition system 110, 120 which allows the recycled DSA 600 to
be recycled back through the units 1500.sub.A, 1500.sub.B, and
1500.sub.N. The recycled DSA 600 may be alternatively added by a
second addition system 120 (not shown) to segregate virgin CEM 300
and recycled DSA 600. It is also contemplated that recycled CEM 300
removed by the particle removal device 1502 may be provided to at
least one of the units 1500.sub.A, 1500.sub.B, and 1500.sub.N
and/or exhaust path 1550 in the same manner.
[0174] FIGS. 18A-18B are schematic diagrams of one embodiment for
coupling an addition system to one or more units as described in
FIGS. 17A-C. In the embodiment depicted in FIG. 18A, a down stream
addition system 1010 is provided which has a selector valve (or
valves) 1604 coupled to an outlet port 1612 of the vessel 1022. The
controller 1050 may operably change the state of the valve 1604
such that material (i.e., virgin DSA 600, recycled DSA 600, virgin
CEM 300, and recycled CEM 300) may be directed to a reaction zone
of a selected one or more of the units 1500.sub.A, 1500.sub.B, and
1500.sub.N and/or to a reaction zone of a selected one or more of
the exhaust paths 1550.sub.A, 1550.sub.B, and 1550.sub.N of the
units 1500.sub.A, 1500.sub.B, and 1500.sub.N. Similarly, the down
stream addition system 1010 has a selector valve (or valves) 1602
coupled to an inlet port 1600 of the vessel 1022. The controller
1050 may operably change the state of the valve 1602 such that
material (i.e., recycled DSA 600 and recycled CEM 300) recovered by
a particle removal device 1502 may be directed to a reaction zone
of a selected one or more of the unit 1500.sub.A, 1500.sub.B, and
1500.sub.N and/or to a reaction zone of a selected one or more of
the exhaust paths 1550.sub.A, 1550.sub.B, and 1550.sub.N of the
units 1500.sub.A, 1500.sub.B, and 1500.sub.N.
[0175] Additionally shown in FIG. 18A is an optional transportable
platform 1610 (shown in phantom) which may be utilized with any of
the addition systems described herein. The transportable platform
1610 may be a pallet, container, flat bed trailer, rail car, barge,
or other readily transportable platform which can support a down
stream addition system during both transport and use. The
transportable platform 1610 may also support at least one or more
of the controller 1050, a pressure regulating device 1620, and
power generator (not shown).
[0176] In the embodiment depicted in FIG. 18B, a down stream
addition system 1010 is provided which has a plurality of
compartments (shown as compartments 1652.sub.A, 1652.sub.N) in a
common vessel 1022. N is representative of one or more of the items
identified by the reference numeral. Each compartment 1652.sub.A,
1652.sub.N may be loaded through a separate inlet port 1600.sub.A,
1600.sub.N and may be emptied through respective dedicated outlet
ports 1612.sub.A, 1612.sub.N. Selector valves 1604 are coupled to
outlet ports 1612.sub.A, 1612.sub.N of the vessel 1022 to direct
the material exiting the vessel 1022 to a reaction zone of a
selected one or more of the units 1500.sub.A, 1500.sub.B, and
1500.sub.N and/or to a reaction zone of a selected one or more of
the exhaust paths 1550.sub.A, 1550.sub.B, and 1550.sub.N of the
units 1500.sub.A, 1500.sub.B, and 1500.sub.N. Similarly, the
selector valves 1602, 1660 coupled to the inlet ports 1600.sub.A,
1600.sub.N of the vessel 1022 direct material (i.e., recycled DSA
600, recycled CEM 300) recovered by a particle removal device 1502
into a selected compartment 1652.sub.A, 1652.sub.N for later
delivery to a reaction zone of a selected one or more of the unit
1500.sub.A, 1500.sub.B, and 1500.sub.N and/or to a reaction zone of
a selected one or more of the exhaust paths 1550.sub.A, 1550.sub.B,
and 1550.sub.N of the units 1500.sub.A, 1500.sub.B, and
1500.sub.N.
[0177] Embodiments of the invention additionally contemplate
methods that may be performed using at least one of CEM 300 and DSA
600. Embodiments of the methods may also be practiced utilizing the
additional systems described above with reference to FIGS. 9-18B,
or other suitable addition system, to enhance collection of PM
and/or reduce emissions of a unit.
[0178] FIG. 19 is a flow diagram of one embodiment of a method 1700
that may be practiced in accordance with the present invention. The
method 1700 generally provides at least one of CEM 300 and DSA 600
to a gaseous exhaust stream of a unit, such as the units described
above. The method 1700 begins at step 1702 by routing a gaseous
exhaust stream from an outlet of a unit to an exhaust flue through
an exhaust path. At step 1704, material such as DSA 600 or CEM 300
is introduced to the gaseous exhaust stream. In an embodiment, the
material is selected to enhance collection of PM from the gaseous
exhaust stream. In another embodiment, the material is selected to
reduce emissions of the unit. In yet another embodiment, the
material is selected to both to enhance collection of PM from the
gaseous exhaust stream while reducing emissions of the unit. In one
embodiment, CEM 300 is introduced to the gaseous exhaust stream
after passing through the unit. In another embodiment, CEM 300 is
introduced to the gaseous exhaust stream without passing through
the unit. In one embodiment, DSA 600 is introduced to the gaseous
exhaust stream without passing through the unit.
[0179] FIG. 20 is a flow diagram of another embodiment of a method
1800 that may be practiced in accordance with the present
invention. The method 1800 generally removes at least one of CEM
300 and DSA 600 from a gaseous exhaust stream of a unit, such as
the units described above. The method 1800 begins at step 1802 by
routing a gaseous exhaust stream through an exhaust path defined
between an outlet of a unit and an exhaust flue. At step 1804, a
material such as DSA 600 or CEM 300 is exposed to the gaseous
exhaust stream. At step 1806, at least a portion of the material
entrained in the gaseous exhaust stream is removed prior to
entering the exhaust flue. In one embodiment, the material is
exposed to the gaseous exhaust stream after passing through the
unit. In another embodiment, the material is exposed to the gaseous
exhaust stream without passing through the unit.
[0180] FIG. 21 is a flow diagram of another embodiment of a method
1900 that may be practiced in accordance with the present
invention. The method 1900 generally recycles material removed a
gaseous exhaust stream of a unit, such as the units described
above. The method 1900 begins at step 1902 by removing a material
from a gaseous exhaust stream exiting a unit. The method 1900
continues at step 1904 by recycling at least a portion of the
removed material back to the gaseous exhaust stream without passing
through the unit. The material recycled to the gaseous exhaust
stream without the recycled material passing through the unit may
be at least one of at least one of CEM 300 and DSA 600. In an
embodiment, the material is selected to enhance collection of PM
from the gaseous exhaust stream. In another embodiment, the
material is selected to reduce emissions of the unit. In yet
another embodiment, the material is selected to both to enhance
collection of PM from the gaseous exhaust stream while reducing
emissions of the unit. In still another embodiment, at least a
portion of the recycled material is passed through the unit prior
to reentering the exhaust gas stream.
[0181] Thus, one or more collection enhanced materials, down stream
additives, methods of making the same, apparatuses for handling the
same when used with one or more units, and methods for using the
same to improve the operation of units, such as fluidized units,
among others, has been provided. The materials of the present
invention advantageously reduce emission of pollutants.
Additionally, equipment, method and systems have been described
which allow for the efficient handling of said materials with
various units, thereby enabling refiners and other unit operators
to cost effectively control processes.
* * * * *