U.S. patent application number 10/394596 was filed with the patent office on 2003-11-20 for calcining apparatus and process of use.
This patent application is currently assigned to Environmental Projects, Inc.. Invention is credited to Denham, Dale Lee JR., Hazen, Wayne C., Pruszko, Rudolph.
Application Number | 20030215379 10/394596 |
Document ID | / |
Family ID | 26737852 |
Filed Date | 2003-11-20 |
United States Patent
Application |
20030215379 |
Kind Code |
A1 |
Denham, Dale Lee JR. ; et
al. |
November 20, 2003 |
Calcining apparatus and process of use
Abstract
Disclosed is an apparatus for the calcination of materials using
low temperature heating and indirect heating for calcination. Also
disclosed are a variety of processes for calcination of materials
which have-reduced emissions of pollutants compared to conventional
processes.
Inventors: |
Denham, Dale Lee JR.;
(Arvada, CO) ; Pruszko, Rudolph; (Green River,
WY) ; Hazen, Wayne C.; (Denver, CO) |
Correspondence
Address: |
SHERIDAN ROSS PC
1560 BROADWAY
SUITE 1200
DENVER
CO
80202
|
Assignee: |
Environmental Projects,
Inc.
|
Family ID: |
26737852 |
Appl. No.: |
10/394596 |
Filed: |
March 21, 2003 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10394596 |
Mar 21, 2003 |
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10263335 |
Oct 1, 2002 |
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10263335 |
Oct 1, 2002 |
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09151694 |
Sep 11, 1998 |
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6479025 |
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60058643 |
Sep 11, 1997 |
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Current U.S.
Class: |
423/421 ;
422/139; 422/198; 422/239; 422/600 |
Current CPC
Class: |
C01D 7/00 20130101; C01D
7/35 20130101 |
Class at
Publication: |
423/421 ;
422/188; 422/198; 422/139; 422/239 |
International
Class: |
C01D 007/00; B01J
008/04 |
Claims
What is claimed is:
1. An indirect heat calcination apparatus for calcining a material
comprising: a) a feed inlet; b) a calcining chamber interconnected
to said feed inlet; c) an indirect heating element within said
calcining chamber for transferring heat from a heated fluid to said
material; d) a bed plate located below said indirect heating
element within said calcining chamber; and e) a product collection
chute interconnected to said calcining chamber.
2. The apparatus of claim 1, further comprising: f) a plurality of
bed plate holes on said bed plate; and g) a gas inlet for
introducing a fluidizing gas into said apparatus through said bed
plate holes.
3. The apparatus of claim 2, wherein said bed plate holes are
selected from the group consisting of angled bed plate holes and
bed plate holes comprising deflector plates.
4. The apparatus of claim 1, further comprising a gas plenum.
5. The apparatus of claim 1, further comprising an exhaust port
located above said calcining chamber.
6. The apparatus of claim 1, further comprising an expansion
chamber interconnected to said exhaust port and said calcining
chamber.
7. The apparatus of claim 1, wherein said indirect heating element
further comprises a fluid inlet port and a fluid outlet port.
8. The apparatus of claim 1, wherein said apparatus comprises a
plurality of calcining zones, and wherein said calcining zones are
defined by compartmental walls.
9. The apparatus of claim 8, wherein each of said calcining zones
comprises means for controlling the flow of fluidizing gas and each
of said means is separately controlled.
10. The apparatus of claim 8 further comprising an interconnecting
opening near the bottom of alternating compartmental walls.
11. The apparatus of claim 10, wherein compartmental walls without
interconnecting openings are shorter than walls with
interconnecting openings.
12. The apparatus of claim 1, further comprising a means for
fluidizing said material with a flow of fluidization gas.
13. The apparatus of claim 12, further comprising means for
increasing the flow of fluidization gas to selectively fluidize
dense material.
14. The apparatus of claim 1, further comprising a means for
removing at least a portion of impurities on a density separation
basis.
15. A process for treating a saline mineral, wherein said saline
mineral comprises insoluble impurities, comprising the steps of:
(a) introducing a feedstream comprising said saline mineral and
insoluble impurities through a feed inlet to a calcining chamber;
(b) heating said saline mineral to a temperature of less than about
350.degree. C. by contacting said saline mineral with an indirect
heating element to calcine said saline mineral; (c) removing said
calcined saline mineral from said calcining chamber through a
product collection chute.
16. The process of claim 15, wherein said calcining chamber further
comprises (i) a bed plate located below said indirect heating
element and said bed plate comprises a plurality of bed plate holes
and (ii) a gas inlet for introducing a fluidizing gas into said
calcining chamber through said bed plate holes.
17. The process of claim 15, wherein said calcining chamber further
comprises a gas plenum.
18. The process of claim 15, wherein said calcining chamber further
comprises an exhaust port located above said calcining chamber.
19. The process of claim 15, wherein said calcining chamber further
comprises an expansion chamber interconnected to said exhaust port
and said calcining chamber.
20. The process of claim 15, wherein said indirect heating element
further comprises a fluid inlet port and a fluid outlet port.
21. The process of claim 15, wherein said calcining chamber
comprises a plurality of calcining zones, and wherein said
calcining zones are defined by compartmental walls.
22. The process of claim 21, wherein said calcining zones further
comprise interconnecting openings near the bottom of said
alternating compartmental walls.
23. The process of claim 15, wherein said calcining chamber further
comprises means for fluidizing said material.
24. The process of claim 15, wherein said calcining chamber further
comprises means for removing at least a portion of impurities on a
density separation basis.
25. A process for producing sodium carbonate from a feedstream
containing trona and insoluble impurities, comprising the steps of:
(a) heating said feedstream in a calcining apparatus to a
temperature of less than about 350.degree. C. to form anhydrous
sodium carbonate; (b) contacting said anhydrous sodium carbonate
with a saturated sodium carbonate brine solution to form sodium
carbonate monohydrate crystals; and (c) separating at least a
portion of said sodium carbonate monohydrate crystals from at least
a portion of said insoluble impurities to form an impurity
stream.
26. The process of claim 25, wherein said temperature of heating is
from about 120.degree. C. to about 250.degree. C.
27. The process of claim 25, wherein a heat source in said heating
step is not in direct fluid communication with said feedstream.
28. The process of claim 25, wherein said calcining apparatus is a
fluidized bed reactor.
29. The process of claim 25, further comprising the step of
comminuting said feedstream to provide a comminuted feedstream
before step (a).
30. The process of claim 29, wherein particles in said comminuted
feedstream have a particle size of less than about 1/4 inch.
31. The process of claim 29, wherein said feedstream is sized into
3 or more size fractions.
32. The process of claim 25, wherein said heating step comprises
the steps of: heating a fluid; and bringing the heated fluid into
thermal communication with said feedstream.
33. The process of claim 32, wherein said step of heating said
fluid comprises the steps of: (i) combusting an energy source to
produce heat and combustion gas; (ii) transferring at least a
portion of the heat to the fluid; and (iii) directing at least a
portion of the combustion gas through a combustion gas outlet which
is not in direct fluid communication with said calcining
vessel.
34. The process of claim 33, wherein said step of heating said
feedstream further comprises the steps of: removing calcining gas
from said heating step through a calcining gas outlet; and
combining at least a portion of said calcining gas with at least a
portion of said combustion gas.
35. The process of claim 34, further comprising the steps of
removing said calcining gas from said heating step and condensing
at least a portion of water vapor from said calcining gas.
36. The process of claim 35, wherein particulates are removed from
the said calcining gas during said condensing step.
37. The process of claim 35, wherein said step of condensing at
least a portion of said water vapor comprises the step of
condensing said portion of water vapor by cooling said calcining
gas.
38. The process of claim 25, further comprising the step of
separating a portion of said impurities from said trona before step
(a) by a process selected from the group consisting of magnetic
separation, electrostatic separation, density separation,
calorimetric separation and size purification.
39. The process of claim 25, wherein the temperature of said
saturated sodium carbonate brine solution is from about 35.degree.
C. to about 112.degree. C.
40. The process of claim 25, wherein the temperature of said
saturated sodium carbonate brine solution is at least about
95.degree. C.
41. The process of claim 25, wherein said separation of said sodium
carbonate monohydrate crystals from said saturated sodium carbonate
brine solution is by size separation.
42. The process of claim 41, wherein said sodium carbonate
monohydrate crystals separated from said saturated sodium carbonate
brine solution have a particle size of at least about 100 mesh.
43. The process of claim 41, wherein a non-recovered portion from
said size separation step comprises insoluble impurities and said
sodium carbonate monohydrate crystals having a particle size of
less than about 100 mesh.
44. The process of claim 43, further comprising the step of
dissolving said sodium carbonate monohydrate crystals from said
non-recovered portion and separating said insoluble impurities from
said dissolved crystals.
45. The process of claim 44, further comprising the step of
recycling said dissolved sodium carbonate monohydrate crystals from
said non-recovered portion by introducing a stream containing said
dissolved sodium carbonate monohydrate crystals from said
non-recovered portion into said saturated sodium carbonate brine
solution.
46. The process of claim 41, further comprising the step of drying
or calcining said separated sodium carbonate monohydrate crystals
and converting said separated sodium carbonate monohydrate crystals
to anhydrous sodium carbonate crystals.
47. The process of claim 25, further comprising the step of gravity
purification of said impurity stream.
48. The process of claim 47, wherein said impurity stream has a
final density of at least about 20% solids.
49. A method for reducing emission of a pollutant during calcining
of a saline mineral comprising the steps of: (a) heating said
saline mineral in a calcining vessel to calcine said saline
mineral, wherein said step of heating said saline mineral produces
calcining gas comprising water vapor and a pollutant; (b) removing
said calcining gas from said calcining vessel through a calcining
gas outlet; and (c) condensing at least a portion of said water
vapor from said calcining gas, wherein at least a portion of said
pollutant is removed from said calcining gas during said condensing
step.
50. The method of claim 49, wherein a heat source for calcining
said saline mineral is not in direct fluid communication with said
saline mineral.
51. The method of claim 49, wherein said heating step occurs in a
fluidized bed reactor.
52. The method of claim 49, wherein the temperature of said heating
step is less than about 350.degree. C.
53. The method of claim 49, wherein the temperature of said heating
step is from about 120.degree. C. to about 250.degree. C.
54. The method of claim 49, wherein no portion of said saline
mineral is heated in excess of about 450.degree. C.
55. The method of claim 49, wherein said heating step comprises the
steps of: (i) heating a fluid; and (ii) bringing the heated fluid
into thermal communication with said saline mineral.
56. The method of claim 55, wherein said step of heating said fluid
comprises the steps of: (i) combusting an energy source to produce
heat and combustion gas; (ii) transferring at least a portion of
said heat to said fluid; (iii) directing at least a portion of said
combustion gas through said combustion gas outlet which is not in
direct fluid communication with said calcining vessel.
57. A method of reducing the amount of calcining gas exiting a
calcining system wherein said calcining gas is produced during
calcining of a saline mineral in a calcining vessel comprising the
steps of: (a) removing said calcining gas from said calcining
vessel through a calcining gas outlet; and (b) condensing at least
a portion of said calcining gas.
58. The method of claim 57, wherein said calcining step comprises
heating said saline mineral in said calcining vessel above its
calcining temperature with a heat source to calcine said saline
mineral, wherein said heat source is not in direct fluid
communication with said saline mineral and wherein said step of
heating said saline mineral produces said calcining gas comprising
water vapor.
59. The method of claim 58, wherein said step of condensing at
least a portion of said calcining gas comprises the step of
condensing said water vapor by cooling said calcining gas.
60. A process for producing sodium carbonate from a feedstream
containing trona and insoluble impurities, comprising the steps of:
(a) heating said feedstream in an inert atmosphere to form
anhydrous sodium carbonate; (b) contacting said anhydrous sodium
carbonate with a saturated sodium carbonate brine solution to form
sodium carbonate monohydrate crystals; and (c) separating at least
a portion of said sodium carbonate monohydrate crystals from at
least a portion of said insoluble impurities.
61. The process of claim 60, wherein said temperature of heating is
less than about 350.degree. C.
62. The process of claim 60, wherein said temperature of heating is
from about 120.degree. C. to about 200.degree. C.
63. The process of claim 60, wherein no portion of said feedstream
is heated in excess of about 450.degree. C.
64. The process of claim 60, wherein said heating step is conducted
in a fluidized bed reactor.
65. The process of claim 60, wherein said step of heating produces
a calcining gas comprising carbon dioxide and water vapor.
66. The process of claim 65, further comprising the step of
condensing water vapor from said calcining gas.
67. The process of claim 66, wherein said inert atmosphere
comprises said carbon dioxide.
68. A method for the calcination and purification of trona,
comprising: (a) introducing a feedstream of trona and impurity
particles to a fluidized bed reactor at an elevated temperature to
calcine said trona to anhydrous sodium carbonate; (b) removing a
bottom stream of particles from said fluidized bed reactor; (c)
removing a top stream of particles from said fluidized bed reactor;
wherein the average density of particles in said top stream is less
than the average density of particles in said bottom stream, and
wherein the concentration of sodium carbonate in said top stream is
greater than in said bottom stream.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of U.S. Provisional
Application No. 60/058,643, filed Sep. 11, 1997.
FIELD OF THE INVENTION
[0002] The present invention relates to an apparatus for the
calcination of materials and uses therefor.
BACKGROUND OF THE INVENTION
[0003] A variety of industrial processes involve the use of
calcination to thermally decompose materials either to aid in the
purification of materials or for use in an industrial process.
Generally, calcination processes involve exposing the materials to
be calcined to heat to thermally decompose the materials. Thus,
calcination differs from thermal drying of materials in which free
water is driven off by exposure to increased temperatures. In
contrast, calcination involves changing the chemical composition of
the material.
[0004] A number of apparatus are known for calcination processes.
For example, rotary direct-fired calciners use an open flame as a
heat source and therefore, necessitate the use of combustion air.
Also, vertical fluid bed calciners use heated gas in direct contact
with the material to be calcined.
[0005] Despite the well-known use of calcination, a number of
problems exist in the use of conventional calcination processes.
For example, the emission of by-products such as particulates
causes pollution concerns. Additionally, a number of calcination
processes are not energy efficient because much of the energy from
the process is released to the atmosphere in the form of heat.
[0006] Further, many calcination processes which operate at high
temperatures, such as use of open flame calciners, unevenly heat
the material to be calcined. For example, in open flame rotary
calciners, material contacting the flame may experience a
temperature close to 1000.degree. C., even though the average
temperature in the calciner may be significantly below that
temperature. In this manner, some particles may not be fully
calcined and some may be combusted. Alternatively, some larger
particles may be calcined on the outside, but not on the inside of
the particle. This type of disadvantage can also have significant
negative effects on downstream processing because the material
exiting the calcination process is not uniform in its chemical
composition. Therefore, subsequent processing will have more
variable results than if the material from the calcination process
was uniform in nature.
[0007] As a result of the above disadvantages of known calcination
technology, there remains a need for improved calcination apparatus
and methods of use.
SUMMARY OF THE INVENTION
[0008] One embodiment of the present invention is an indirect heat
calcination apparatus for calcining materials. The apparatus
includes a feed inlet, a calcining chamber which is interconnected
to the feed inlet, an indirect heating element within the calcining
chamber to transfer heat from a heated fluid to the material, a bed
plate located below the indirect heating element within the
calcining chamber, and a product collection chute which is
connected to the calcining chamber. The apparatus can also include
a plurality of holes on the bed plate and a gas inlet for
introducing a fluidizing gas into the apparatus through the bed
plate holes. The apparatus can include an exhaust port located
above the calcining chamber. The exhaust port can also include an
expansion chamber for slowing the velocity of gas exiting the
calcining apparatus. The indirect heating element of the apparatus
can be, for example, coils within the calcining chamber which
conduct the heated fluid through the chamber. Thus, the indirect
heating element can include a fluid inlet port and a fluid outlet
port. The apparatus can also include a plurality of calcining zones
which are defined by compartmental walls.
[0009] The present invention includes a calcining process for
treating a saline mineral which includes introducing the saline
mineral to a calcining chamber, heating the saline mineral to a
temperature of less than about 350.degree. by contacting it with an
indirect heating element and removing the calcined material from
the chamber. In this embodiment, the calcining chamber can include
a bed plate located below the indirect heating element and having a
plurality of bed plate holes and a gas inlet for introducing a
fluidizing gas into the chamber through the bed plate holes. The
calcining apparatus can also include an exhaust port located above
the calcining chamber which can have an expansion chamber for
slowing the velocity of exiting gas. The apparatus can also include
a plurality of calcining zones defined by compartmental walls.
[0010] Other processes of the present invention include processes
for calcining material and subsequent processing of the material.
For example, such processing can include purification, such as
crystallization.
[0011] An additional process of the present invention is a method
for reducing the emission of pollutants during calcining. This
process includes heating a saline mineral in a calcining vessel
wherein the calcination step produces a gas comprising water vapor
and a pollutant. The calcining gas is removed from the calcining
vessel to an outlet and at least a portion of the water vapor in
the calcining gas is condensed. In this manner, a portion of the
pollutants in the calcining gas are removed. This process can also
include the use of a heat source for calcining which is not in
direct fluid communication with the material to be calcined. In
further a aspect, the material is calcined at temperatures less
than about 250.degree. C.
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] FIG. 1 is a graph illustrating the settling characteristics
of trona calcined in a CO.sub.2 atmosphere at various
temperatures;
[0013] FIG. 2 is a graph illustrating the settling characteristics
of trona calcined in an air atmosphere at various temperatures;
[0014] FIG. 3 a graph illustrating the settling characteristics of
trona calcined in a CO.sub.2 atmosphere at various temperatures and
treated to remove magnetic impurities; and
[0015] FIG. 4 is a table providing data for various settling and
compositional characteristics of trona calcined in a variety of
temperatures and atmospheres.
[0016] FIG. 5 is a side view of an indirect heat calcining
apparatus of the present invention.
[0017] FIG. 5A is an illustration of a one-piece exhaust port
containing an expansion chamber.
[0018] FIG. 6 is a plan view of an indirect heat calcining
apparatus of the present invention.
[0019] FIG. 7A is an illustration of a bed plate having a
fluidizing gas inlet holes.
[0020] FIG. 7B is an illustration of bed plate having a fluidizing
gas inlet holes and a gas-flow deflector
DETAILED DESCRIPTION OF THE INVENTION
[0021] In various embodiments of the present invention, processes
and apparatus involve the use of a calcining step with low
temperature heating of the feedstream at temperatures lower than
conventional calcination, such as in direct fired rotary kiln
calciners. More particularly, the calcining step of the present
invention includes heating a feedstream to a temperature of less
than about 350.degree. C., more preferably less than about
250.degree. C., and more preferably at a temperature from about
120.degree. C. to about 250.degree. C. As used herein, reference to
heating a feedstream to less than a certain temperature refers to
raising the temperature of the particles in the feedstream within
the stated temperature constraints, and not to the temperature of
the ambient atmosphere in the-calciner or to the temperature of the
heat transfer medium. Moreover, reference to heating a feedstream
to less than a certain temperature requires that no substantial
portion of particles in the feedstream be heated in excess of the
stated temperature constraints. Thus, it should be recognized that
while substantially the entire feedstream is maintained within the
temperature constraints, particles which actually come into contact
with a heat transfer surface, such as a heated tube, may exceed the
temperature constraints. More particularly, however, no more than
about 15 wt. % of the feedstream should be heated in excess of the
stated temperature constraints, more preferably no more than about
10 wt. %, and most preferably no more than about 5 wt %. In another
aspect, no portion of the material in the feedstream is heated in
excess of about 450 C.
[0022] Calcination in accordance with these temperature constraints
of the present invention provides a number of previously
unrecognized significant benefits. As discussed in more detail
below, the amount of pollutants from the calcination process is
reduced with low temperature calcination. For example, low
temperature calcination does not volatilize as many organic
compounds from insoluble impurities as mid and high temperature
calcination. Thus, fewer volatile organic compound (VOC) pollutants
are generated by calcination. Also, fewer soluble organic
compounds, such as sulfonates, are generated. Additionally,
benefits in subsequent processing are obtained.
[0023] In a preferred embodiment, the calcination temperature
constraints are more readily achieved by controlling the particle
size and particle size distribution of particles in the feedstream.
By having a relatively small particle size with a relatively narrow
particle distribution, particles in the feedstream can be evenly
heated to meet the temperature constraints as discussed above. More
particularly, the feedstream to the calciner is typically
comminuted to reduce the particle size. For example, the feedstream
can be comminuted to a particle size of less than about 1/4 inch,
alternatively, less than about 6 mesh, and alternatively, less than
about 20 mesh. In addition, the feedstream is preferably sized into
multiple size fractions for calcining. More particularly, the
feedstream is sized into 3 or more size fractions, more preferably
5 or more size fractions, and most preferably 7 or more size
fractions. In this manner, it is more likely that sufficient
heating of all the particles will occur to completely calcine them
without excessively heating smaller particles in excess of the
temperature constraints identified above. Thus, in a further
embodiment, the present process includes calcination of at least
about 95 wt. % of the feedstream, more preferably, at least about
98 wt. %, and most preferably, at least about 99.5 wt. %.
[0024] In a further embodiment of the present invention, the step
of calcining is conducted by heating a feedstream in an inert
atmosphere to produce a calcined material. The term inert
atmosphere refers to any atmosphere which is less oxidizing than
air. For example, an inert atmosphere can be an atmosphere of
carbon dioxide. Alternatively, the carbon dioxide can also include
water vapor and/or air. As discussed in more detail below, some
gaseous by-products of calcination, such as carbon dioxide and
water vapor generated as part of a calcining gas in some processes
can be recycled and used as a fluidizing gas in a fluidized bed
calciner.
[0025] The calcining step is preferably performed utilizing an
indirect heating process in a calcining vessel such as a fluidized
bed reactor. In the indirect heating process, the combustion gases
from the heat source are not in direct fluid communication with the
material being calcined, but rather provide heat to the material by
conduction through, for example, heating coils, as described in
more detail below.
[0026] The step of indirectly heating material for calcining
comprises the steps of heating a fluid and bringing the heated
fluid into thermal communication with material in the calcining
vessel. As used in this invention, a "fluid" refers to a gas or a
liquid medium. This step can be accomplished utilizing a heat
source which provides the heated fluid to coils positioned within
the interior of the calcining vessel. In one embodiment, the heat
source is a steam boiler and the fluid is steam. Alternatively, the
fluid may comprise oil or any other appropriate medium. The step of
heating the fluid can comprise the steps of combusting an energy
source to produce heat and combustion gas, transferring at least a
portion of the heat to the fluid, and directing at least a portion
of the combustion gas through a combustion gas outlet which is not
in direct fluid communication with the calcining vessel.
[0027] Referring to FIG. 5 there is shown one embodiment of an
indirect heat calcination apparatus of the present invention. The
indirect heat calcination apparatus 10 includes an indirect heating
element 14 located within the calcining chamber 16 for providing
indirect heat to the material. The indirect heating element 14 can
be any conduit that allows a fluid to flow within its walls while
facilitating the transfer of heat from the fluid to the material.
As described above, the fluid is heated to a desired temperature
and enters the indirect heating element 14 at an inlet port 18 and
travels through the entire length of the indirect heating element
14 and exits through the outlet port 22. As the fluid travels
through the indirect heating element 14, heat is transferred from
the fluid to the indirect heating element 14 and ultimately to the
material to be calcined. In this manner, the material is calcined
without being exposed to a direct flame or heating fluid.
Typically, a sufficient amount of material is added to the indirect
heat calcination apparatus 10 to cover the entire indirect heating
element 14 within the calcining chamber 16. However, a smaller
amount of the material can be calcined using the apparatus of the
present invention.
[0028] In order for an efficient heat transfer to occur, it is
preferred that the indirect heating element 14 be made from a
material which is a good heat conductor. Preferably, the material
of indirect heating element 14 is selected from the group
consisting of a metal such as copper, steel, iron, nickel, zinc,
stainless steel and mixtures thereof; ceramics; and composites.
More preferably, the material of indirect heating element 14 is
selected from the group consisting of steel and stainless steel and
most preferably, is stainless steel.
[0029] As described above, the fluid for providing the heat for
calcination can be any liquid or gas which can be heated to a
sufficiently high temperature required for calcination. Such fluids
include water, steam, oil, and gases, including air. For calcining
trona, preferably the fluid is steam.
[0030] Again referring to FIG. 5, it is preferred that the fluid
inlet port 18 is located above the fluid outlet port 22. This
arrangement ensures that a lower amount of energy is required to
operate the indirect heating element 14 because gravity aids in
removing fluid from the indirect heating element 14. Moreover, when
a gas such as steam is used, it is possible that some of it may
condense to a liquid form as the heat is transferred to the
indirect heating element. The presence of a condensed liquid within
the indirect heating element 14 reduces the amount of heat
transferred to the indirect heating element 14 because some of the
energy will be used to heat the condensed liquid. In order to
reduce this problem, the inlet port 18 is located above the outlet
port 22 to facilitate the removal of any condensed liquid.
[0031] The indirect heating element 14 can be positioned within the
apparatus 10 such that the indirect heating element 14 traverses
back and forth across the apparatus and from top to bottom. This
arrangement provides a large indirect heating element surface area.
However, even with this arrangement, the amount of surface area of
the indirect heating element 14 is limited; therefore, not all of
the material particles will come in direct contact with the
indirect heating element 14 when the material is stationary within
the apparatus. Although all of the particles can be heated to a
desired calcination temperature by prolonged exposure to the
indirect heating element 14-and allowing the heat to transfer from
one particle to another and eventually reaching an equilibrium,
this method of stationary indirect heat calcination requires a
large amount of energy and time rendering the apparatus rather
inefficient. To expedite the calcination process and/or to reduce
the amount of energy required, substantially all of the particles
within the calcining chamber 16 can be made to be dynamic, i.e.,
non-stationary within the calcining chamber 16, during at least a
portion of the calcination process. Any method of creating a
dynamic motion of the particles can be used such as stirring,
shaking and agitating.
[0032] In one particular embodiment, the particles are placed on
top of the bed plate 26 and are fluidized by a fluidizing gas which
is introduced into the calcining chamber through a plurality of bed
plate holes 30. This fluidization process causes a juggling effect
of the particles and allows more particles to come in a direct
contact with the indirect heating element 14, resulting in a
relatively even distribution of heat among the material particles.
In addition, this fluidization process can be used to separate the
particles based on the difference in density. The juggling effect
provided by the fluidizing gas allows relatively heavy particles to
settle to the bottom of the pile while allowing relatively light
particles to "float", i.e., concentrate, to the top of the
pile.
[0033] The primary heat transfer mechanism is the material to coil
contact and not the material to fluidizing gas contact. Therefore,
the fluidization gas velocity and volume has to be low or kept to a
minimum to maximize the contact of the material to the indirect
heating coils. This concept is contrary to current technology where
the coils in a fluid bed calciner are used to heat the fluidizing
gas which in turn is used to heat the material. In such a process,
large volumes of fluidizing gas is required for the heat transfer
to the material to take place.
[0034] The indirect heat calcination apparatus of the present
invention can also include a gas plenum 34. The gas plenum 34 may
be located underneath the bed plate 26 to provide a substantially
equal gas pressure throughout the bed plate holes 30. These holes
can be angled, vertical or perpendicular to the direction of gas
from the plenum to the calcination bed. Angled holes will aid in
the direction of flow of material through the calcining zone. In
this embodiment, the angle of the hole must be greater than the
angle of repose of the material being calcined to prevent material
from falling into the hole. Moreover, the presence of a gas plenum
34 in the apparatus 10 also reduces a possibility of particles
falling through the bed plate holes 30 and blocking the flow of
fluidizing gas into the apparatus. In operation, the fluidizing gas
is introduced into the apparatus 10 through a gas inlet 38 into the
gas plenum 34. As some materials are calcined, the density of the
material decreases. With the lower density, the amount of
fluidization gas needed decreases. Therefore, individual flow
controls for the fluidizing gas to each calcining zone is
preferred. In one particular embodiment, fluidizing gas is heated
to about the same temperature as the temperature of the heating
coils to prevent cooling of material particles and/or to maintain
the temperature above the dew point. In this manner, condensation
of water in the fluidizing gas is avoided.
[0035] The indirect heat calcination apparatus 10 of the present
invention can also include an exhaust port 42 to prevent excess
pressure build-up within the apparatus or to remove any volatile
compounds which are released or generated from the material during
the calcination process. The exhaust port is located above the
material level to allow the fluidizing gas to fluidize the material
particles. Since the particles are not all identical size, it is
expected that some of the lighter particles, e.g., smaller
particles or the material dust, will be carried into the exhaust
port 42.
[0036] In order to reduce the amount of particles removed from the
apparatus by the action of the fluidizing gas, the indirect heat
calcination apparatus 10 of the present invention can also include
an expansion chamber 46 which is located below or near the exhaust
port 42. The cross-sectional area of the expansion chamber 46 is
larger than the cross-sectional area of the calcining chamber 16,
and as a result the velocity of gas, i.e., the flow rate, decreases
as the fluidizing gas flows from the calcining chamber 16 into the
expansion chamber 46. This decrease in the fluidizing gas flow rate
results in some of the solids carried upward into the expansion
chamber 46 by the fluidizing gas to settle and drop back down into
the calcining chamber 16, thus reducing the particulate emission
from the calcination apparatus. The expansion chamber is even more
important in a case where the material releases vapor upon during
calcining. This is the case with trona, where carbon dioxide and
water vapor are released. This release of vapors increases the
volume of fluidizing gas in the calciner bed and therefore
increases the velocity of the fluidizing gas. This effect further
entrains particles that can be returned to the calciner bed with
the use of an expansion zone. Moreover, the exhaust port 42 can be
fitted with other apparatus to collect any material that is
released through the exhaust port 42. For example, a condenser can
be fitted to the exhaust port 42 to condense and collect water
vapor or other useful materials, a filter can be fitted to further
reduce the amount of particulate matter that is released into the
environment, or a gas collector can be fitted to collect or recycle
the fluidizing gas or other gases which may be released through the
exhaust port 42. Alternatively, the exhaust port 42 and the
expansion chamber 46 can be a single unit piece, i.e, the expansion
chamber 46 can be an integral part of the exhaust port 42 as shown
in FIG. 5A.
[0037] A process for indirect heat calcination of a material using
the apparatus of the present invention will now be described in
reference to FIG. 6 which illustrates the indirect heat calcination
apparatus having four different calcining zones 54, 58, 62 and 66,
that are separated by three compartmental walls 70, 74 and 78. The
material can be pretreated, e.g., comminuted, size separated and/or
dried, prior to being calcined using the indirect heat calcining
apparatus of the present invention. In a typical operation, a
feedstream of comminuted material is introduced into the apparatus
10 through a feed inlet 50. In order to reduce the amount of
agglomeration of particles due to the moisture that is present in
the calcining atmosphere, the indirect heat calcining apparatus 10
can also include a predried-gas inlet (not shown) near the feed
inlet 50 for reducing the moisture level of the particles or
moisture in the atmosphere from coming in contact with particles.
Alternatively, the first calcining zone 54 can be used as both a
pre-drying region as well as the first calcining zone. However, if
a separate predried-gas inlet is used, the diameter of the
predried-gas inlet is selected to ensure that a sufficient gas flow
rate is maintained to provide a sufficient level of pre-drying.
Factors influencing the diameter of the predrying-gas inlet include
the particle size of the material, the moisture level of the
calcining atmosphere, density of the material, and the desired gas
flow rate. Pre-heating with dry fluidization gas is used to allow
material of a lower temperature to enter the calciner and mix into
the material bed before condensation can occur on the entering
material. Condensation on the material can cause agglomerates to
form or caking. The temperature of this gas is less than the
calcining temperature, but above the dew point for the material's
moisture content. It is also important not to let the material
reach a temperature above the calcination temperature before it is
fluidized, otherwise moisture released during calcination can cause
the particle to cake. To limit the temperature in the first
calcining zone to prevent condensation and caking of material, the
amount of heating element, such as coils, for conducting heating
fluid in the first calcining zone can be less than in other zones.
In addition, the first calcining zone can also include already
calcined material to reduce the amount of gas released from
calcination in the first zone.
[0038] The primary purpose of heating the material with the
predrying gas is to reduce the amount of moisture present where the
ore enters the calciner. Thus, although some of the material may be
calcined during this pre-drying process, the majority of the
material is not calcined by this pre-drying process. Drying the
material reduces the agglomeration, thus maintaining the high
surface area of the particles which is desired for indirect heat
calcination. Particles having a high surface area to volume ratio
can be calcined more quickly and/or more efficiently than the
particles having a low surface area to volume ratio.
[0039] The rate of pre-dried gas flow depends on a variety of
factors including the feed rate, the particle size and the density
of impurities and/or the material being calcined.
[0040] As the materials are introduced into the first calcining
zone 54, they are fluidized by a fluidizing gas and are heated by
the indirect heating element 14. The materials then flow to the
second calcining zone 58, the third calcining zone 62 and the
fourth calcining zone 66, in a successive manner. Although FIG. 6
shows each calcining zones having its own gas inlet 38 and flow
control (not shown), the apparatus can have less than one gas inlet
per calcining zone for providing the fluidizing gas to the entire
bed plate 26 of the apparatus 10. As more material is fed to the
first zone 54, at least a portion of the materials in the first
zone 54 flows in to the second zone 58 through the opening 82. As
the height of the feedstream in the second zone 58 reaches the top
of the compartment wall 74, the material overflows into the third
calcination zone 62. At least a portion of the material in the
third calcination zone 62 then flows into the fourth calcination
zone 66 through the opening 86. The calcined material then
overflows into the product collection chute 90 where it is
collected.
[0041] Having a multiple calcination zone provides a longer average
residence time for material within the indirect heat calcination
apparatus 10. The desired average residence time depends on a
variety of factors including the temperature of the indirect
heating element 14, the feed rate, the particle size of the feed,
the completeness of calcination of the feedstream and the amount of
time required to calcine the material. The underflow/overflow
design forces contact of the material being calcined with the
coils.
[0042] Referring again to FIG. 6, as the material flows into the
second calcining zone 58, the fluidizing gas can be used to provide
a density separation as described above. In this manner, the
lighter materials will be concentrated on the top portion and the
denser materials will be concentrated on the bottom portion. In the
case of trona ore being calcined, this means that the lighter
anhydrous sodium carbonate and/or trona will be on the top portion
and the heavier impurities such as shortite, shale and/or pyrite
will be concentrated in the bottom portion. A similar density
separation can be achieved in the fourth calcining zone 66. By
allowing a means for removing the bottom impurity concentrated
portion in the second and/or the fourth calcination zones, a
substantially purified calcined material can be collected through
the product collection chute 90.
[0043] Alternatively, all the flow of the material from one
calcining zone to another calcining zone can be made to proceed
over the compartmental walls, thus eliminating a need for openings
82 and 86. One way this can be accomplished is by increasing the
fluidizing gas flow directly adjacent to the compartment wall to
the point where all material including high density material is
forced to overflow the compartmental wall. In order to prevent
back-flow of the materials, the successive compartment walls can be
lower in height than the previous compartment wall. In this manner,
each successive calcining zone will contain less amount of heavier
impurities.
[0044] As shown in FIG. 7A, the bed plate holes 30 can simply be an
opening, in which case the direction of the gas flow is
substantially perpendicular to the opening of the bed plate holes
30 or can be determined by the direction of gas-flow prior to
entering the bed plate holes 30.
[0045] Alternatively, as shown in FIG. 7B, the bed plate holes 12
can also include a gas flow deflector 94 which is placed above the
bed plate holes 30. The deflector 94 can serve a multiple purposes.
For example, it can be designed to prevent any particles from
entering, or falling through, the bed plate holes 30. Another way
to achieve this result is to punch holes in the plate at an angle.
In addition, the movement of the particles towards the product
collection chute 90 can be facilitated by using the gas flow
deflector 94 to introduce the fluidizing gas in the direction
towards the product collection chute 90. Thus, the average
residence time of the particles can be controlled by using the
fluidizing gas and the gas flow deflector 94.
[0046] The materials calcined using the indirect heat calcination
apparatus of the present invention have unique product
characteristics because of the use of low heat and relatively even
heating of the particles during the calcination process. In
addition, the materials can be further processed, including dry
separation such as density separation, electrostatic separation,
magnetic separation, calorimetric separation; and wet separation
such as recrystallization methods and evaporative crystallization
methods.
[0047] The utilization of indirect heating for calcining material
provides significant benefits in that it significantly reduces the
amount of gas flowing through the fluidized bed because no
combustion gas flows through the bed. In this manner, a
significantly lower amount of particulates from the material are
entrained and need to be removed from exhaust gas from the
calcining operation. More specifically, the amount of gas required
for fluidization is typically about 80% less than the amount of gas
produced during the combustion necessary to produce sufficient heat
for the calcining process (e.g., utilizing natural gas in a steam
boiler). Accordingly, by utilizing a source of gas for fluidization
which is different than the combustion gases, a smaller amount of
fluidizing gas can be used. Further, the smaller amount means that
the fluidizing gas will flow at lower velocities, thereby
potentially reducing particulate entrainment even further. In
addition, less fluidizing gas means that less gas needs to be
scrubbed for particulates before emission, thereby reducing the
costs of the calcining process.
[0048] It is well known that some calcining processes produce
calcining gas having a significant amount of water vapor. For
example, in the instance of calcining trona to produce anhydrous
sodium carbonate, calcining three moles of trona produces five
moles of water and one mole of carbon dioxide. In order to reduce
the amount of calcining gas exiting the system, the process may
further comprise the step of condensing at least a portion of the
water vapor from the calcining gas by, for example, cooling the
calcining gas. Such condensation step will reduce the calcining gas
volume by as much as 5/6ths, thereby reducing the amount of
calcining gas which must be treated. In addition to reducing the
volume of gas exiting the system, the condensing step also has a
scrubbing effect on the calcining gas by removing particulates from
the calcining gas. It is believed that the amount of particulates
removed is proportional to the amount of gas removed (i.e., as much
as 5/6ths or more in the case of trona). It is estimated that the
particulate emission from a process for calcining trona ore in a
direct-fired rotary calciner is typically about 6 lbs/ton of feed.
By practice of the present process, including indirect calcination
and condensing water from calcining gas, the particulate emissions
from calcination of trona ore can be less than about 3 lbs/ton of
feed, more preferably less than about 1.5 lbs/ton of feed and most
preferably less than about 1 lbs/ton of feed.
[0049] In a preferred embodiment, the condensing step for
condensing water from gas produced during calcining comprises two
stages. In the first stage, a small amount (e.g., less than about
5%) of the water vapor within the calcining gas is condensed to
significantly reduce the particulate content of the gas. The first
stage can be performed utilizing a water-cooled condenser, such as
a tubed condenser. In the second stage, as much as 80% of the water
vapor is condensed. Because of the reduction in particulate content
resulting from the first stage, the water condensed from the second
stage is essentially distilled water grade. A third stage may be
added to further scrub particulates from the gas. For example, a
high-efficiency venturi scrubber or electrostatic precipitator may
be used.
[0050] The water which is removed during the condensing steps can
be utilized for other processes. For example, the condensed water
may be cooled (e.g., using air coolers) and then recycled and used
as the cooling medium to condense further water vapor from the
calcining gas by bringing the cooled water into thermal
communication with the pre-condensed calcining gas. Further, the
condensed water could be utilized for processes in other areas of a
facility which involve the use of water. The condensed water may
also be treated and utilized for almost any other appropriate
purpose, such as for general water usage in the facility (e.g., for
cleaning, drinking water, etc.).
[0051] Calcining gas which is produced during the calcining process
may be removed from the calcining vessel through a calcining gas
outlet, and at least a portion of the calcining gas (proportional
to the amount of CO.sub.2 produced in the calcining process) may be
expelled through a stack. The expelled gas is preferably heated
prior to exiting through the stack to inhibit condensation and
plume formation at the stack outlet. For example, the expelled gas
can be mixed with hot combustion gas from heating fluid for
indirect calcination.
[0052] Another portion of the calcining gas may be recycled back to
the inlet of the calcining vessel and utilized for heating and
fluidizing additional material for calcining. Preferably, this gas
is recycled and/or heated after the above-noted condensation step,
thereby resulting in dry gas as the heating and fluidizing medium.
The recycled gas may be heated (e.g., by steam coils) in order to
bring the gas up to a temperature prior to entry into the calcining
vessel. In one embodiment, the recycled gas temperature is between
about 120.degree. C. and about 200.degree. C., and is preferably
about 140.degree. C. This recycling of gas is beneficial in that it
utilizes latent heat within the calcining gas as part of the energy
required for calcining, rather than heating ambient temperature gas
up to calcining temperature. Further, such recycling reduces the
gas requirements and emissions of the process by eliminating the
need for fresh gas.
[0053] In a further embodiment of the present invention, a density
separation is conducted in the calcining vessel. As some materials
are calcined, they lose mass while impurities in the material do
not. In this manner, the apparent density of the calcined material
is less compared to the impurities and can, therefore, be separated
on a density separation basis. For example, as trona, containing
impurities such as shale, pyrite and/or shortite, is calcined, the
sodium carbonate particles lose mass and become less dense, thereby
creating a significant density difference between the anhydrous
sodium carbonate and the impurities. Thus, in a fluidized bed, the
anhydrous sodium carbonate will migrate to the top of the bed and
the denser impurities will migrate to the bottom. For example, an
average apparent density of calcined trona is less than about 1.6.
An average density of a bottom impurity stream in this embodiment
is greater than about 2.1, more preferably greater than 2.3, and
most preferably greater than about 2.5. Thus, a further aspect of
the present invention is to calcine trona and remove a particle
stream comprising impurities from the bottom of the calciner bed.
As will be appreciated, depending on how much of an impurity stream
is taken, the impurity stream may include some sodium carbonate.
However, a bottom stream will contain primarily impurities, such as
shale, pyrite and/or shortite, and the concentration of sodium
carbonate in top stream is greater than in the bottom stream. More
particularly, the concentration of sodium carbonate in the top
stream will be at least about 96 wt. %, more preferably at least
about 98 wt. %, and most preferably at least about 99 wt. %.
[0054] After calcination of materials, subsequent processing of
some sort is typically conducted on the material. Often, such
subsequent processing involves purification. In a preferred
embodiment of the present invention, the material being calcined is
a saline mineral, and the calcined saline mineral is subsequently
processed by purification in a crystallization process. In a
further preferred embodiment, the saline mineral is trona. By way
of example, a particular crystallization process for purification
of saline minerals will be described in detail. Use of the present
calcination process and apparatus (specifically, low temperature
calcination) provides significant benefits in terms of
crystallization processes for saline minerals, including among
other things, larger crystals.
[0055] As used herein, the term "saline mineral" refers generally
to any mineral which occurs in evaporite deposits. Saline minerals
that can be beneficiated by the present process include, without
limitation, trona, borates, potash, sulfates, nitrates, sodium
chloride, and preferably, trona.
[0056] The purity of saline minerals within an ore depends on the
deposit location, as well as on the area mined at a particular
deposit. In addition, the mining technique used can significantly
affect the purity of the saline minerals. For example, by selective
mining, higher purities of trona ore can be achieved. Deposits of
trona ore are located at several locations throughout the world,
including Wyoming (Green River Formation), California (Searles
Lake), Egypt, Kenya, Venezuela, Botswana, Tibet and Turkey
(Beypazari Basin). For example, a sample of trona ore from Searles
Lake has been found to have between about 50% and about 90% by
weight (wt. %) trona and a sample taken from the Green River
Formation in Wyoming has been found to have between about 80 and
about 90 wt. % trona. The remaining 10 to 20 wt. % of the ore in
the Green River Formation sample comprised impurities including
shortite (1-5 wt. %) and halite, and the bulk of the remainder
comprises shale consisting predominantly of dolomite, clay, quartz,
kerogen and iron, and traces of other impurities. Other samples of
trona ore can include different percentages of trona and
impurities, as well as include other impurities. The present
process can also be used with feedstreams having lower impurity
contents, including impurity levels as low as 0.1% by weight.
[0057] The crystallization process described herein is particularly
well adapted for use with feedstreams having high contents of
insoluble impurities. For example, the present invention is
suitable for use with feedstreams having greater than about 4% by
weight insoluble impurities, more particularly greater than about
15% by weight insoluble impurities, and even more particularly
greater than about 30% by weight insoluble impurities. The present
process can also be used with feedstreams having lower impurity
contents, including impurity levels as low as 0.1% by weight.
[0058] The sodium carbonate resulting from calcination of trona, as
described above, is treated by purification in a crystallization
process to remove insoluble impurities. A first crystallization
process includes contacting the calcined feedstream comprising
sodium carbonate and insoluble impurities with a saturated sodium
carbonate brine solution, the saturated sodium carbonate brine
solution being maintained at a temperature between about 35.degree.
C. and about 112.degree. C., more preferably between about
85.degree. C. and about 112.degree. C., and most preferably between
about 95.degree. C. and about 112.degree. C., to form sodium
carbonate monohydrate crystals and separating the sodium carbonate
monohydrate crystals from the saturated sodium carbonate brine
solution, preferably on a size separation basis. The sodium
carbonate monohydrate crystals which are removed from the brine
solution can be dewatered, dried and eventually converted to
anhydrous sodium carbonate. Such a process is described generally
in U.S. Pat. No. 3,948,744 to Frint, which is hereby incorporated
by reference.
[0059] In particular, sodium carbonate monohydrate crystals having
a crystal size of greater than about 150 mesh, more preferably
greater than about 100 mesh, and more preferably greater than about
80 mesh, can be obtained by the present process. By forming large
sodium carbonate monohydrate crystals, significant advantages are
obtained. For example, the ability to recover purified crystals on
a size separation basis is enhanced. Larger crystals enable greater
recovery yields when separating crystals from smaller insoluble
impurities, such as in the case of recovering sodium carbonate from
a feedstream of trona ore. Thus, in a further aspect of the
invention, the crystallization process is conducted in the absence
of procedures, such as grinding or shearing, which significantly
reduce crystal size in the crystallization operation.
[0060] As noted, a preferred method of recovery of sodium carbonate
crystals is on a size separation basis. Such a basis involves the
separation of sodium carbonate monohydrate crystals from impurities
based on differences in size between the sodium carbonate
monohydrate crystals and the impurities. Typically, impurities
which can occur in the trona feedstream include iron-bearing
materials, dolomite, shale, shortite, searlesite and northupite. It
will be recognized that the size of insoluble impurities will not
be affected by the recrystallization process. Thus, the initial
particle size of an insoluble impurity will be the minimum particle
size at which size separation of crystals can occur. Moreover, the
particle size of insoluble impurities can be reduced prior to
introduction into the brine solution by grinding the feedstream to
smaller sizes. Typically, the feedstream has a particle size of
minus 100 mesh and more preferably minus 200 mesh. The size
separation is typically conducted at a size from about 80 mesh to
about 150 mesh, and even more particularly at about 100 mesh.
[0061] A significant advantage of the low temperature calcination
process described above is that subsequent recovery of impurities
is made easier. It has been determined that low temperature
calcination makes the insoluble impurities less likely to break
down into ultrafine particle sizes, such as less than about 500
mesh. Thus, ease of subsequent recovery and denaturing of the
particles is significantly increased.
[0062] Size separation can be affected by any known appropriate
method. For example, screening or elutriation can be used. In the
instance of screening, the oversize material from a first screening
may be transferred to a repulping operation for suspension of
crystals in the oversize fraction by adding clean liquor to a
repulp tank to obtain a more efficient screening in a second size
separation.
[0063] Upon introduction of a feedstream into a saturated brine
solution, a problem which can be encountered is clumping and poor
dispersion of sodium carbonate. In another embodiment of the
invention, in order to avoid clumping and to allow for adequate
dispersion of the sodium carbonate within the brine solution, the
brine solution is agitated during introduction of the feedstream
containing sodium carbonate. In another embodiment, the feedstream
may be preheated to a temperature above about 175.degree. C. and
blown into the brine solution Once sodium carbonate monohydrate
crystals are separated from the saturated brine solution, the
crystals are dewatered, such as by centrifugation. The crystals can
then be converted to the anhydrous form of sodium carbonate after
dewatering for use in industry, such as in the production of glass.
Conversion of sodium carbonate monohydrate to the anhydrous form
after dewatering provides significant advantages over conversion
while in a slurry. To convert to the anhydrous form while in a
slurry, the temperature of the slurry must be above the boiling
point of water. Thus, the process needs to be conducted in a
pressurized system. The equipment necessary for such systems
introduces significant cost and complexity compared to the present
process.
[0064] The size of the monohydrate crystals may be effected by
varying the feed rate and/or temperature of the anhydrous sodium
carbonate introduced to the saturated sodium carbonate brine
solution and by varying the crystal size distribution of the sodium
carbonate monohydrate seed. Furthermore, appropriate residence
times of sodium carbonate monohydrate crystals in the brine
solution for crystallization can be selected by those skilled in
the art. It should be recognized, however, that longer residence
times will result in larger monohydrate crystals which can have
significant advantages with respect to recovery, as discussed
above. It is believed that residence times of the sodium carbonate
monohydrate crystals in the brine solution could be as little as
fifteen minutes, but can be significantly longer as well. In one
preferred embodiment, the residence time of the crystallization can
be greater than about one and a half hours, more preferably greater
than about three hours and more preferably greater than about five
hours. It will be recognized that residence time corresponds to
feed rate into the crystallizer. In a further embodiment, the feed
rate into the crystallizer is less than about 0.4 lbs. of anhydrous
sodium carbonate per minute per gallon, more preferably less than
about 0.3 lbs. per minute per gallon and even more preferably, less
than about 0.2 lbs. per minute per gallon.
[0065] For example, by maintaining a crystal size distribution with
a high degree of uniformity of size, crystals can be efficiently
grown to a large size. That is, if crystal size distribution is
widely spread over a great number of small to large crystals, while
some new crystal growth will be efficiently spent on making large
crystals larger, some such growth will be inefficiently spent on
making small crystals grow to a size that will still not be
recovered because it will be below the size separation cutoff Thus,
a further aspect of the present crystallization process is to
maintain a narrow crystal size distribution of sodium carbonate
monohydrate seed crystals. This aspect of the invention is
particularly important when the feedstream includes insoluble
impurities because adequate crystal growth is necessary to obtain
crystals having a larger size than the insoluble impurities. This
aspect of the invention can be accomplished by a variety of
techniques. For example, by removing small crystals, either
continuously or intermittently, from the crystallization vessel,
the crystal size distribution will be narrowed with the average
crystal size of the remaining crystals being greater than before
removal. More specifically, crystals having a crystal size less
than about 150 mesh, more particularly less than about 200 mesh and
even more particularly less than about 400 mesh can be removed for
this purpose.
[0066] In a further embodiment of the present invention, after
recovery of sodium carbonate from the saturated brine solution,
sodium carbonate in the non-recovered portion can also be kept in
the system for subsequent recovery. As will be appreciated, the
non-recovered portion comprises insoluble impurities and residual
sodium carbonate monohydrate crystals having a particles size
smaller than the size separation cutoff. For example, when recovery
is made on a size separation basis, the non-recovered portion will
have crystals with a size below the size separation cutoff. In this
instance, the non-recovered portion can be treated to recover
sodium carbonate values from crystals which are smaller than the
size separation cutoff. Such a treatment can include dissolving the
small crystals, such as by the addition of wash water, and then
making a solid/liquid separation to remove solid impurities from
the dissolved crystals. Then, the solution can be recycled to other
points in the process for use in washing, etc., so that the
solution ultimately returns to the crystallization unit for
recovery of dissolved sodium carbonate. Alternatively, the water in
the sodium carbonate solution could be driven off (e.g., by
heating) to recover the sodium carbonate by crystallization.
[0067] When insoluble impurities are removed by a solid/liquid
separation, most typically, the waste stream is sent to a
clarifier, settling tank or other gravity purification apparatus.
As illustrated below in the Example section, calcination in
accordance with the present invention and in particular, in
accordance with temperature constraints results in faster and more
compact settling of insoluble impurities. This result provides
significant cost and operational advantages in the process. Because
the settling of impurities occurs more quickly and thus, is more
efficient, the capital requirements for a plant using this process
are significantly lower. In addition, the resulting muds have a
higher solids content and therefore, can be readily disposed of.
More particularly, insoluble impurities produced by the process of
the present invention, in the absence of a flocculant or other
settling aid, can settle to a final density of at least about 20%
solids, more preferably to a final density of at least about 25%
solids, and most preferably to a final density of at least about
30% solids.
[0068] A second crystallization process includes dissolving the
anhydrous sodium carbonate in solution to form a sodium carbonate
solution. At least a portion of insoluble impurities present in the
calcined sodium carbonate are separated from the sodium carbonate
solution. Sodium carbonate monohydrate crystals are then formed
from the sodium carbonate solution. This process is generally
discussed in U.S. Pat. No. 3,644,331 to Seglin et al., which is
incorporated herein by reference. The sodium carbonate monohydrate
crystals which are produced can be dewatered, and eventually
converted to anhydrous sodium carbonate by drying or calcining.
[0069] Embodiments of the present invention can be conducted in
combination with other processes known for treating saline minerals
and in particular, trona ore. For example, such other processes are
generally described in the published Patent Cooperation Treaty
applications PCT/US96/00700 for METHOD FOR PURIFICATION OF SALINE
MINERALS and in PCT/US94/05918 for BENEFICTATION OF SALINE
MINERALS, the disclosures of which are incorporated herein by
reference in their entirety. More particularly, separation steps,
such as magnetic separation, electrostatic separation, and density
separation, can be conducted in conjunction with processes as
described herein in detail. Similarly, separation steps based on
other properties can be used as well. For example, for ores or
treated ores in which fractions having different colors or sizes
corresponding to differences in purity, separations can be made on
the basis of such properties, as well.
[0070] The following experimental results are provided for purposes
of illustration and are not intended to limit the scope of the
invention.
EXAMPLE
[0071] The following example illustrates the effect of calcining
temperature and atmosphere on the settling of insoluble impurities
in trona ore.
[0072] Trona ore having a particle size of less than 20 mesh was
calcined at 150.degree. C., 300.degree. C., 450.degree. C., or
600.degree. C. in an atmosphere of either CO.sub.2 or air. The ore
was then ground to minus 100 mesh, and water was added to
completely dissolve all soluble components (i.e., sodium carbonate)
of the material. Some of the samples were first treated by magnetic
separation before the settling test. The samples were then allowed
to settle in graduated cylinders. The volume of settled solid
materials was recorded over time to evaluate settling
characteristics of the samples. Observations were made regarding
the color of the liquid. The final solids content of the various
samples, and the sodium carbonate content of the thickened pulp
were determined. The results of the various settling tests are
illustrated in the graphs in FIGS. 1-3 and the chart in FIG. 4.
[0073] The foregoing description of the present invention has been
presented for purposes of illustration and description.
Furthermore, the description is not intended to limit the invention
to the form disclosed herein. Consequently, variations and
modifications commensurate with the above teachings, and the skill
or knowledge of the relevant art, are within the scope of the
present invention. The embodiment described hereinabove is further
intended to explain the best mode known for practicing the
invention and to enable others skilled in the art to utilize the
invention in such, or other, embodiments and with various
modifications required by the particular applications or uses of
the present invention. It is intended that the appended claims be
construed to include alternative embodiments to the extent
permitted by the prior art.
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