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Patent 2213738 Summary

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(12) Patent: (11) CA 2213738
(54) English Title: PROCESS FOR THE PREPARATION OF GRANULATED POTASSIUM CHLORIDE
(54) French Title: PROCEDE DE PRODUCTION DE CHLORURE DE POTASSIUM GRANULE
Status: Expired
Bibliographic Data
(51) International Patent Classification (IPC):
  • C01D 3/22 (2006.01)
  • B01J 2/00 (2006.01)
  • B01J 2/22 (2006.01)
  • C05D 1/02 (2006.01)
(72) Inventors :
  • FEINBLUM, EPHRAIM (Israel)
(73) Owners :
  • ASHLI CHEMICALS (HOLLAND) B.V. (Netherlands (Kingdom of the))
  • DEAD SEA WORKS LTD. (Israel)
(71) Applicants :
  • DEAD SEA WORKS LTD. (Israel)
  • ASHLI CHEMICALS (HOLLAND) B.V. (Netherlands (Kingdom of the))
(74) Agent: LAVERY, DE BILLY, LLP
(74) Associate agent:
(45) Issued: 2006-11-07
(86) PCT Filing Date: 1996-03-21
(87) Open to Public Inspection: 1996-09-26
Examination requested: 2003-03-06
Availability of licence: N/A
(25) Language of filing: English

Patent Cooperation Treaty (PCT): Yes
(86) PCT Filing Number: PCT/EP1996/001214
(87) International Publication Number: WO1996/029287
(85) National Entry: 1997-09-19

(30) Application Priority Data:
Application No. Country/Territory Date
113104 Israel 1995-03-23

Abstracts

English Abstract





A process for producing granulated potassium chloride, comprising: forming a
mixture of potassium sulfate and potassium chloride;
melting said mixture (5); bringing said molten mixture into physical contact
with a cooling surface provided with recesses (16), said recesses
being substantially of dimension and shape of the granules to be produced,
said surface being cooled, whereby solidification of the molten
mixture is obtained; and collecting the solid granules from the said surface.


French Abstract

Ce procédé de production de chlorure de potassium granulé comprend les étapes consistant à: former un mélange de sulfate de potassium et de chlorure de potassium; faire fondre ce mélange (5); porter ce mélange en fusion en contact physique avec une surface de refroidissement (16) pourvue d'évidements, lesquels possèdent sensiblement la dimension et la forme des granules à produire, cette surface étant refroidie, ce qui permet d'obtenir la solidification du mélange en fusion; et enfin, recueillir les granules solides à partir de cette surface.

Claims

Note: Claims are shown in the official language in which they were submitted.





10
Claims
1. A process for producing granules of potassium
chloride, comprising the steps of
- forming a mixture of potassium sulfate and
potassium chloride;
- melting the mixture into a molten mixture;
- bringing the molten mixture into physical contact
with a cooling surface provided with recesses, the
recesses being substantially of dimension and shape
of the granules to be produced, the cooling surface
being cooled, whereby solidification of the molten
mixture is obtained; and
- collecting solid granules from the cooling
surface.
2. The process according to claim 1, wherein said step
of melting the mixture is carried out in an oven.
3. The process according to claim 1, wherein said step
of melting the mixture is carried out in a cyclone oven.
4. The process according to claim 1, wherein the
cooling surface is made of material possessing high
thermal conductivity.
5. The process according to claim 1, wherein the
cooling surface is cooled by a cooling fluid.




11
6. The process according to claim 5, wherein the
cooling fluid is water.
7. The process according to claim 1, wherein the
granules are further cooled, heat removed therefrom being
recycled.
8. The process according to any one of claims 1 to 7,
wherein the mixture contains about 1 to 5% by weight K2SO4
and 99 to 95% by weight KCl.
9. The process according to any one of claims 1 to 7,
wherein the solid granules are obtained from
solidification of molten drops, the solid granules having
a size comprised between 1.5 and 6 mm.
10. The process according to any one of claims 1 to 7,
wherein the solid granules are obtained from
solidification of molten drops, the solid granules having
a compressive strength in a range between 3 and 7 kg when
dimensions thereof are in a range between 2.0 and 4.5 mm.
11. The process according to claim 1, wherein the
cooling surface is provided on a drum capable of making
rotational movement.
12. The process according to claim 11, wherein the drum
is made of iron.
13. The process according to claim 12, the drum being
coated with a removable porous coating.
14. The process according to any one of claims 11 to 13,
wherein the drum is coupled to a roller to break salt




12
solidified out of the recesses and thus to level an upper
face of the granules.
15. The process according to any one of claims 11 to 14,
wherein the solid granules are dropped, during the
rotational movement of the drum, to a container, and
further cooled by means of heat exchanger, heat being
recycled.
16. The process according to any one of claims 2 to 15,
wherein the mixture is fed to the oven by gases that are
produced during a combustion of hot fuel and hot air.
17. The process according to claim 16, wherein the gases
that flow out of the oven have a temperature in a range
between 900°C and 950°C.
18. The process according to claim 16, wherein the fuel
is one of mazout and gas.
19. The process according to claim 17, wherein the fuel
is sulfur rich.
20. The process according to claim 18, wherein the fuel
is vanadium rich.
21. The process according to any one of claims 16 to 20,
further comprising using energy of the gases after said
step of melting, the gases being finally brought to a
lower temperature, in a range between 200°C and 250°C.
22. The process according to any one of claims 16 to 19,
the gases, when leaving the oven, being mostly free from
oxides of sulfur and vanadium.




13
23. The process according to claim 1, wherein said step
of melting is carried out at a temperature of about
850°C.
24. The process according to any one of claims 9 to 11,
further comprising using means for improving the process
efficacy, whereby gases used to drive the mixture to the
oven leave the oven and are brought into contact with
heat exchangers, KCl-K2SO4 particles that were carried
over by the gases being formed as a result of a cooling
of suspension and being collected and transferred to a
granulation system.
25. The process according to any one of claims 9 to 11,
further comprising using means for improving the process
efficacy, whereby gases used to drive the mixture to the
oven leave the oven and are brought into contact with
heat exchangers, KCl-K2SO4 particles that were carried
over by the gases being formed as a result of a cooling
and being collected and transferred to a granulation
system, whereby heat transferred from the gases is used
to heat air from ambient temperature to about 450°C, the
air being used as hot air needed for a combustion that
produces the gases.
26. The process according to any one of claims 9 to 11,
further comprising using means for improving the process
efficacy, whereby gases used to drive the mixture to the
oven leave the oven and are brought into contact with
heat exchangers, KCl-K2SO4 particles that were carried
over by the gases being formed as a result of a cooling
and being collected and transferred to a granulation
system, whereby heat transferred from the gases is used




14
to heat air from ambient temperature to about 450°C, the
air being used as hot air needed for a combustion that
produces the gases, whereby the gases are further passed
through filters, to collect salt that remained therein,
the salt being then melted and transferred to a
granulation system.
27. An apparatus for producing granulated potassium
chloride, comprising:
- means for forming a mixture of potassium sulfate
and potassium chloride:
- means for bringing said mixture to an oven;
- means for melting the mixture in said oven;
- means for obtaining crystals by bringing the
molten mixture into a physical contact with a
cooling surface provided with recesses, said
recesses being substantially of dimension and shape
of granules to be produced, said cooling surface
being cooled obtain solidification of the molten
mixture; and
- means for collecting solidified granules from the
cooling surface and further cooling them.
28. The apparatus according to claim 27, wherein the
oven is a cyclone oven.
29. The apparatus according to any of claims 27 and 28
comprising means for recovering heat from hot gases, said
means including heat exchangers.




15
30. The apparatus according to claim 27, comprising a
cyclone heat exchanger.

Description

Note: Descriptions are shown in the official language in which they were submitted.


CA 02213738 1997-08-19
- 1 -
PROCESS FOR THE PRODUCTION OF
GRANULATED POTASSIUM CHLORIDE
This invention relates to the manufacture of inorganic
fertilizers, and more particularly to the production of
granulated potassium chloride.
Potassium chloride is an inorganic fertilizer component.
It is used in granulated form and various processes are
known in the art for preparing it in such a form. One
such process consists in feeding particulate potassium
chloride to calendering rollers, whereby to produce a
sheet which is then ground to granules. However, this
process has a low efficiency and only about 300 of the
prcduct is satisfactc=ily granulated by passage between
calendering rollers. Further, a significant amount of
the material (3-So) is lost and t~;e resistance of the
granules to compressicn is relati~.re~y low, specifically
they have a crushing load - the ccmpression load which
destroys the granules by crushing them - of about 2-
2.5 kg.
Another method of prcducing potassium chloride granules
involves preparing a mixture of the raw material with 3-
i0 a of ammonium chloride, humidifying the mixture by the
addition of water, passing it through a sieve and drying
the resulting granules. This process, however, is
relatively expensive, and does not permit the use of
high temperatures and therefore necessarily comprises a
relatively long drying phase.
CA-A-212650 discloses a process for producing granulated
potassium chloride from powdered KC1 salt by melting
said powdered salt in a melting furnace, and solidifying
the liquified salt into granules by spraying said
liquified salt into a cooling chamber.
ANIEI~I~t~ SHEET
IPEA~~Q

CA 02213738 1997-08-19
WO 96/Z9287 PCT/EP96/01214
_9_
It is also been attempted to increase the strength of the potassium chloride
granules by the addition of secondary products formed in the manufacture of '
said chloride, particularly magnesium chloride in the amount of about 3.~%
and calcium chloride in the amount of about 1.5%. In this way, however, a
more by groscopic material is produced and the necessity of using a relatively
low drying temperatures (e.g., about 200°C) increases the duration of
the
drying and the expense of energy.
It is particularly difficult to obtain hCl granules having dimensions of about
3-
4 mm and adequate compression strength, e.g. of 3 to 7 kg and such production
is not possible by the methods and apparatus of the prior art.
It is a purpose of this invention to overcome the defects of the known
processes
and to provide a process for the production of granulated potassium chloride
which produces the desired product in granulated form, without substantially
increasing manufacturing costs.
It is another purpose of this invention to provide such a process w hick
produces potassium chloride granules having a high resistance, in particular a
resistance to compression or crushing load of 3 to 7 kg.
It is a further purpose of this invention to provide such a process which
permits to produce granules having dimensions of 1.5 mm and more. ,
a
It is a further purpose of this invention to provide Such a process «-hich
reduces the by groscopicity of the final product.

CA 02213738 1997-08-19
WO 96/29287 PCTlEP96/01214
-3-
It is a still further purpose of this invention to provide such a process
which
' affords a saving in the energy required for carrying it out.
These and other purposes and advantages of the invention will appear as the
description proceeds.
The process according to the invention comprises the steps of
- forming a mixture of potassium sulfate and potassium chloride;
- melting said mixture;
- bringing said molten mixture into physical contact with a cooling surface
provided with recesses, said recesses being substantially of dimension and
shape of the granules to be produced. said surface being cooled, whereby
solidification of the molten mi.Yture is obtained: and
-collecting the solid granules from the said surface.
T'refer< <~ly, the amount of h,~SO~ used is about 1 to ~% by weight of the hCl-

Ii.,SO~ mi.~ture.
Generally, the granules obtained from the solidification of the molten drops
have sizes comprised between 1.o and 6 mm.
The granulation process is characterized by a cooling method which was
discovered to be very efficient. according to said method, the molten mi.Yture
is poured on a cooling surface having recesses thereon, the recesses
substantially of dimension and shape of the granules to be produced.
according to a preferred embodiment of the invention, said surface is provided
SUBSTITUTE SHEET (RULE 26)

CA 02213738 1997-08-19
WO 96/29287 PCTlEP96/01214
by a drum capable of rotational movement. Heat is transferred from the
molten drops collected in the recesses to the substance of which the drum is
made of (preferably iron), while the drum being continuously cooled by water.
Granules are therefore obtained in the recesses, and may then be collected in
a
container wherein heat exchanger is placed to complete the cooling procedure,
while the heat is recycled.
Preferably, the drum makes a continuous rotational movement, through which
the granules obtained in the recesses fall to a container for collection,
because
due to the cooling process their dimensions become smaller than these of the
recesses. Of course, any other convenient procedure which allows cycling
process, such as conveyer belt, may be adapted, and further means to allow the
falling of said granules from said recesses to said container may be added.
~s stated, the surface provided with recesses thereon mad- be of any desired
structure: the recesses. for example, may have a rectam ular or hexagonal
cross section, and their bottom is usually rounded. _' ccording to one
embodiment of the invention, the drum is coated with a porous coating to
provide a protection for the drum. . according to another embodiment of the
invention, a second roller may be coupled to the drum to break the material
crvstalized outside the recesses. By the use of said second roller, eYCess of
material is removed from the recesses, leveling the upper face of the granules
produced, and thus obtaining well defined shapes of the granules.
a
The apparatus according to the invention comprises
- means for forming a mi.Yture of potassium sulfate and potassium chloride:
- means for bringing said mi.Yture to an oven;
SUBSTITUTE SHEET (RULE 26)

CA 02213738 1997-08-19
WO 96/29287 PCTIEP96/01214
_a_
means for melting said mixture in the oven:
- means for obtaining the crystals by bringing said molten mixture into a
physical contact with a cooling surface provided with recesses, said recesses
being substantially of dimension and shape of the granules to be produced,
said surface being cooled, whereby solidification of the molten mixture is
obtained; and
means for collecting the solidified granules from the surface and further
cooling them, and for recy cling the heat.
In a preferred embodiment of the invention, means for improving the energt-
use are provided. in order to make the process more industrially attracti~-e.
~s may be clear to one skilled in the art, several ways for improving the
consumption of energy may be applied in the above described process and
apparatus, two of which are exemplified in the drawings.
In the drawings:
Fig. 1 illustrates one preferred embodiment of the invention.
Fig.2 illustrates another preferred embodiment of the invention based on the
use of cyclone heat exchanger.
Fig. 3 shows a preferred embodiment of the drum and its cooling sy stem.
Fig. ~ shows another preferred embodiment of the drum, when coupled to a
second roller ( a view of the rotary axis).

CA 02213738 2005-09-07
Detai end Description of Preferred embodiments
Referring to Fig. 1, the solid material to be treated, comprising a mixture of
about 95 to 9996 0~ KCl and 1 to 6°6 of K.zS04, indicated at (1), is
chargred into a
container or like apparatus ~. By any coxtvenient feeder (3), such as screw-
feeder, the mixture is fed, ~ a controlled manner, to conduit (4). Numeral
(4a)
indicates a reservoir containing a fuel, such as mazout. A different fuel
could,
of course, be usEd. The pxeb~eated fuel is fed, together with preheated air
(according to one embodiment of the invention, the loot six is obtained from
heat exchanger (10), to be described hereinafter) to a burner, whiclx is
schematically indicated as 4b. The product of the burning of the fuel and the
hot air, i.e., combustion gases, flow through conduit (4) and drive the salt
mixture to melting oven (5), which is a cyclone oven. The salt mixture
completely melts in oven (5) ( at about 8$0-8b0 °C). Numeral (6)
indicates a
container in which the melted salt mixture is collected, and numeral (6a)
stands for the Ievel of the molten salt in said cox~taxner. This mixture is
now
brought into contact with the granulation system. The granulation system is
composed of a drum, (16), made of a material which is a good heat conductor,
such as iron., capable of making a rotational movement. V~ater (20) is pumped
by a pump (7.9), in order to cool the sotating drum, in a manner specifically
shown in figure 3. The surface of said drum has recesses on, and the molten
mixture is poured from, container ~ to the recesses of said surface. Due to
the
rotational movement of the drum, crystals obtai~aed in the recesses fall,
being
collected in a container (17a), in which heat exchanger (1'~ is placed, to
further
carry out the cooling process of the granules anal to recycle the heat
absorbed.
As stated, the apparatus described above may be further modified, in order to
make it more attractive from the economical and i,xxdustrial points of view,
For

CA 02213738 2005-09-07
_''f
example, it may be coupled to another system, in order to improve the energy
use and to avoid possible loses of heat and material. Particularly, the
combustion gases have a temperature of about 880-950°C at their exit
from
oven ~, az~d in addition they carry some small amounts of the salt mixture in
the form of very small drops or in the dorm of molecules which are in the
gaseous phase. Thus, the suspension of molten salt drops in the combustion
gases flows through gas conduit ('T) into a gas separator ($), walls of which
are
cooled by water. KCl-K~S04 particles, formed as a result of the cooling of the
suspension, fall to the bottom of the separator and therefrom into a vessel
($b).
A pneumatic system (15) is used to transfer it to the container (6), to be
melted therein. and further to be subjected to the granulation procedure, as
described above. The gases are brought into contact with heat exchangers.
Outside air (11) is driven from fan (9) to said heat exchanger, it is heated
therein from ambient temperature to about 450°C. According to one
preferred
embodiment of the invention, this heated air may now be used in the burner
(4b), fox the combustion process, as described above. 'fb~e cooled gases,
together
with the materials that have not separated from them, pass through a
separator (I2), and from it to mechanical filters (13), from which they are
drawn by exhauster fan (14), while the salt granules settle to the bottoux of
said second separator (12) and said filters (13) and reach said pneumatic
system (15), from which they are collected in vessel (8b) and transferred to
Container (6), as described above.
Another important aspect of the it~vention, which is considered to be a great
advantage, is the composition of the gases when they leave the melting oven
(5). Typically, the compositio~a of said gases coptain only small amounts of
oxides of nitrogen, sulfur and vanadium, and therefore fuel which is rich of

CA 02213738 2005-09-07
_8_
sulfur and/or vanadium may be used. As can be appreciated by one skilled in
the art, this comprises both economical and ecological advantages, since these
gases may be further used in other industrial applications.
Referring to Fig.2, According to another embodiment of the invention, the
energy use is improved by using heat exchanger of cyclone type. Numeral 26
indicates a drying oven or the like, wherein said initial salt mixture is
subjected to some small extant of heating to remove humidity. The mixture is
collected ixx a container (2~5 , and is then fed 24 , in a controlled manner,
into
an ejector (~, and then transferred, by the use of an air stream 23a), to the
cyclone heat exchanger. The oven for carrying out the melting is indicated by
numeral 21 , wherein burners 30 are provided. The salt mixture is passing
through the cyclone heat exchanger 22 in the way to the oven, and the gases
produced during the melting axe driven into the heat exchanger, where they
flow in. a direction opposite to that of the air and salt, thus heating said
salt
mixture, in their way to the drying oven and from said drying oven to
mechanical filters (~. Salt that was carried over by the gases is collected at
the filters and transferred 28 to the oven.. The molten salt mixture obtained
at the oven is transferred (~ to the granulation process as described above.
Referring to Fig. 3, the drum is illustrated. The surface o~ the drum U is
provided ~uvith recesses (~, dimension of which is substantially of the
granules
tv be formed. Numeral, 33 indicates the internal water cooling.
Referring to Fig. 4, a preferred embodiment o~ the drum is illustrated
schematically (the view is of the rotary axis). The drum 34 coupled to a
roller
35 , their axes being parallel and they touch each other along a line. When
the

CA 02213738 2005-09-07
-g_
rotational movemex~t of the drum is taking place (36], the roller is
performing
an opposite rotational movement 3? by which material that was solidi~~.ed on
the surface of the drum is removed, the upper face of the granules in the
recesses are leveled and the granules are brought ~,to a uniform shape.
~ a
Table I sum~ztarizes the results of the granulation process according to the
embodiment of Fig. 1, for varaious initial compositions and conditions (i.e,
dimensions of recesses in the drum). Initial KCl and K2S04 were obtained from
Dead Sea Works Ltd., in the form of a powder. The amount of mazout needed
is about 42 kg per tone of salt.
initialinitial total weight dimension of compression load
KCl K2S04 of final granules (kg)
K K final granules mm
K


50.0 1.5 5 i.5 ~.5-~.5 5.0-~.0


50.0 0.75 50.75 S.5-4.5 4.0-6.0


50.0 0.75 50.75 2.0-3.0 3.0-4.5


It will be apparent that the above-described apparatuses show only some
preferred embodiments of the invention and that xt zs possible to carry out
the
invention by using different means for feeding the initial salt mixture,
various
kinds of ovens to melt said mixture, etc. It is surprising that, as long as
the
initial mixture comprises an addition of K~S04, se set forth hereinbefore, and
the cooling of the molten drops is carried out as set forth hereinbEfore, the
granules thus obtained have properties, in particular compressive strength,
not attainable by any weans known in the art.

Representative Drawing
A single figure which represents the drawing illustrating the invention.
Administrative Status

For a clearer understanding of the status of the application/patent presented on this page, the site Disclaimer , as well as the definitions for Patent , Administrative Status , Maintenance Fee  and Payment History  should be consulted.

Administrative Status

Title Date
Forecasted Issue Date 2006-11-07
(86) PCT Filing Date 1996-03-21
(87) PCT Publication Date 1996-09-26
(85) National Entry 1997-09-19
Examination Requested 2003-03-06
(45) Issued 2006-11-07
Expired 2016-03-21

Abandonment History

There is no abandonment history.

Payment History

Fee Type Anniversary Year Due Date Amount Paid Paid Date
Application Fee $300.00 1997-09-19
Registration of a document - section 124 $100.00 1997-10-29
Maintenance Fee - Application - New Act 2 1998-03-23 $100.00 1998-02-25
Maintenance Fee - Application - New Act 3 1999-03-22 $100.00 1999-03-08
Maintenance Fee - Application - New Act 4 2000-03-21 $100.00 2000-03-06
Maintenance Fee - Application - New Act 5 2001-03-21 $150.00 2001-03-07
Maintenance Fee - Application - New Act 6 2002-03-21 $150.00 2002-02-25
Request for Examination $400.00 2003-03-06
Maintenance Fee - Application - New Act 7 2003-03-21 $150.00 2003-03-06
Maintenance Fee - Application - New Act 8 2004-03-22 $200.00 2004-02-18
Maintenance Fee - Application - New Act 9 2005-03-21 $200.00 2005-02-21
Maintenance Fee - Application - New Act 10 2006-03-21 $250.00 2006-02-10
Final Fee $300.00 2006-08-28
Maintenance Fee - Patent - New Act 11 2007-03-21 $250.00 2007-03-21
Maintenance Fee - Patent - New Act 12 2008-03-21 $250.00 2008-02-20
Maintenance Fee - Patent - New Act 13 2009-03-23 $250.00 2009-03-23
Maintenance Fee - Patent - New Act 14 2010-03-22 $250.00 2010-03-18
Maintenance Fee - Patent - New Act 15 2011-03-21 $650.00 2012-02-16
Maintenance Fee - Patent - New Act 16 2012-03-21 $450.00 2012-02-16
Maintenance Fee - Patent - New Act 17 2013-03-21 $450.00 2013-03-19
Maintenance Fee - Patent - New Act 18 2014-03-21 $450.00 2014-02-14
Maintenance Fee - Patent - New Act 19 2015-03-23 $450.00 2015-03-12
Owners on Record

Note: Records showing the ownership history in alphabetical order.

Current Owners on Record
ASHLI CHEMICALS (HOLLAND) B.V.
DEAD SEA WORKS LTD.
Past Owners on Record
FEINBLUM, EPHRAIM
Past Owners that do not appear in the "Owners on Record" listing will appear in other documentation within the application.
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Document
Description 
Date
(yyyy-mm-dd) 
Number of pages   Size of Image (KB) 
Representative Drawing 1997-12-04 1 8
Representative Drawing 2006-10-06 1 12
Cover Page 2006-10-06 1 43
Cover Page 1997-12-04 1 42
Abstract 1997-08-19 1 55
Description 1997-08-19 9 371
Claims 1997-08-19 6 168
Drawings 1997-08-19 3 34
Description 2005-09-07 9 372
Claims 2005-09-07 6 167
Claims 2005-09-20 6 159
Assignment 1997-08-19 6 233
PCT 1997-08-19 12 396
Correspondence 1997-11-04 1 32
Assignment 1997-10-31 1 27
Assignment 1997-10-29 2 98
Assignment 1998-05-06 1 2
Prosecution-Amendment 2003-03-06 1 26
Fees 2003-03-06 1 43
Fees 2002-02-25 1 42
Fees 1999-03-08 1 48
Fees 1998-02-25 1 55
Fees 2000-03-06 1 40
Fees 2001-03-07 1 40
Fees 2004-02-18 1 38
Prosecution-Amendment 2005-03-15 2 44
Fees 2005-02-21 1 37
Prosecution-Amendment 2005-09-07 13 403
Prosecution-Amendment 2005-09-20 8 208
Fees 2006-02-10 1 46
Correspondence 2006-08-28 1 36
Fees 2007-03-21 1 45
Fees 2008-02-20 1 46
Fees 2009-03-23 1 49
Fees 2012-02-16 1 163