U.S. patent number 3,709,664 [Application Number 05/070,623] was granted by the patent office on 1973-01-09 for high shear mixing apparatus for making silica gels.
This patent grant is currently assigned to National Petro-Chemicals Corporation. Invention is credited to Henri A. Aboutboul, Jerome H. Krekeler, Charles H. Wehr.
United States Patent |
3,709,664 |
Krekeler , et al. |
January 9, 1973 |
HIGH SHEAR MIXING APPARATUS FOR MAKING SILICA GELS
Abstract
Apparatus comprising a rotary agitator possessing movable sets
of flat blades interspersed with stationary sets of flat blades,
the pitch and clearances of the blades being such that high shear
agitation is obtained. This apparatus is suitable for use in the
carrying out of any process requiring high shear mixing. It has
been found to be particularly useful in the preparation of silica
gels of high quality.
Inventors: |
Krekeler; Jerome H.
(Cincinnati, OH), Wehr; Charles H. (Butler, OH),
Aboutboul; Henri A. (Byram, CT) |
Assignee: |
National Petro-Chemicals
Corporation (New York, NY)
|
Family
ID: |
22096418 |
Appl.
No.: |
05/070,623 |
Filed: |
August 14, 1970 |
Current U.S.
Class: |
422/225;
366/181.4; 261/84; 366/192; 366/307; 366/149; 366/303; 423/338;
366/327.3; 516/82; 516/85; 516/930 |
Current CPC
Class: |
B01F
15/065 (20130101); B01F 7/183 (20130101); C01B
33/154 (20130101); Y10S 516/93 (20130101) |
Current International
Class: |
B01F
15/06 (20060101); B01F 15/00 (20060101); B01F
7/18 (20060101); C01B 33/154 (20060101); C01B
33/00 (20060101); C01b 033/16 (); B01j 001/04 ();
B01f 007/20 () |
Field of
Search: |
;23/283,285,252,182R,270.5 ;261/84 ;259/7,8,23,24,43,44,107,108
;252/359R,359C,314 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Tayman, Jr.; James H.
Claims
We claim:
1. High-shear mixing apparatus comprising:
a vertically disposed cylindrical vessel provided with a centrally
located rotatable driven shaft having a plurality of sets of
horizontally disposed and pitched flat blades extending radially
outwardly from said shaft toward the interior surface of said
vessel, the end of each blade being fixedly attached to said shaft
and thereby rotatable with said shaft, the blades of each set of
rotatable blades being positioned equidistant around said
shaft;
a plurality of sets of stationary, horizontally disposed and
uniformly pitched flat blades extending radially inwardly from the
interior surface of said vessel toward said shaft, the end of each
stationary blade being secured to said interior surface of said
vessel, each set of stationary blades comprising at least two
blades positioned equidistant around the interior surface of said
vessel;
said sets of rotatable blades alternating with said sets of
stationary blades along the length of said shaft, with the
lowermost set of blades being rotatable, the clearance between each
vertically adjacent set of rotatable and stationary blades and
between the free ends of the rotatable blades and the interior
surface of the vessel varying from one-eighth to 2 inches;
wherein the blades of each rotatable set are uniformly angularly
offset in the same circumferential direction from the blades of the
next vertically adjacent set of rotatable blades with the angle of
offset being such that the blades of the lowermost and uppermost
set of rotatable blades are offset by the same increment as the
blades of the vertically adjacent sets of rotatable blades; and
wherein the blades of selected sets of rotatable blades are pitched
opposite to the pitch of the blades of other selected sets of
rotatable blades and to the pitch of the stationary blades.
2. The apparatus of claim 1, wherein each of said blades is pitched
at an angle of 45.degree. .
3. The apparatus of claim 1, wherein each of said sets of rotatable
blades contains four blades.
4. The apparatus of claim 1, which contains five rotatable sets of
blades and four stationary sets of blades, each stationary set
containing two blades.
5. The apparatus of claim 1 comprising, in addition, a jacket
disposed around said vessel.
6. The apparatus of claim 1 wherein said angular offset is about
18.degree..
7. The apparatus of claim 1, wherein said clearance is about
one-half inch.
8. The apparatus of claim 4, wherein the second and fifth rotatable
sets of blades, the first set being the lowermost set in the
vessel, are pitched in a direction opposite to the pitch of the
other rotatable sets of blades.
9. The apparatus of claim 1 wherein at least five sets of said
rotatable blades are provided and wherein at least four sets of
said stationary blades are provided.
10. The apparatus of claim 1 wherein the number of sets of said
stationary blades is equal to one less than the number of sets of
said rotatable blades.
11. The apparatus of claim 10 wherein the uppermost set of blades
is rotatable, the blades of said uppermost set being pitched
downwardly, and wherein the blades of the lowermost set of
rotatable blades are pitched upwardly.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a novel, internally baffled and agitated
high shear mixing apparatus.
2. Description of the Prior Art
The provision of apparatus which can be employed to obtain thorough
and complete mixing of various ingredients or chemical reactants
has been a long sought-after goal. Various solutions to the problem
of obtaining thorough and uniform admixture of various materials
have been proposed. Many of the proposed solutions relate to the
use of some combination of baffles and rotating agitating means or
blades within a confined mixing zone.
This type of mixing apparatus is illustrated by the disclosures of
U.S. Pat. Nos. 634,093, 1,138,201, 1,520,375, 1,854,732 and
3,063,815. Each of these disclosures relate to the use of some
combination of baffles and agitator blades in order to obtain
improved mixing and illustrate the variety of different, although
similar, arrangements of such means which have been brought to bear
on the problem.
However, the degree of uniform, high shear mixing obtainable with
apparatus presently available leaves something to be desired.
Although presently available apparatus is perfectly suitable for
applications which do not require extremely uniform high shear
forces, the effectiveness of such apparatus has left something to
be desired in the case of certain processes in which highly uniform
application of the shearing forces is particularly
advantageous.
One such process is the large scale production of silica gel,
particularly the production of silica gel in accordance with the
method set forth in copending application Ser. No. 750,734, filed
on Aug. 6, 1968, now U.S. Pat. No. 3,652,215. For convenience, the
apparatus of the present invention will be described and
exemplified by reference to this specific process, although it will
be understood that the present apparatus is particularly applicable
to any mixing process in which the application of highly uniform
shearing forces is desired.
In addition to the afore-mentioned application which describes a
method of preparing a xerogel-type silica gel, copending
applications Ser. Nos. 750,733 and 766,693, now U.S. Pat. Nos.
3,652,214 and 3,652,216, respectively also describe similar
processes. Each of the three applications describe a method which
comprises critically controlled steps of precipitation of a sodium
silicate solution to form a hydrogel; heat-aging the hydrogel under
specific temperature, time and pH limitations; reducing the sodium
ion concentration of the hydrogel below a certain point; reducing
the gel particle size by high shear mixing; and removing
substantially all the water from the gel by a drying step.
In Ser. No. 750,734, a drying step is disclosed which comprises
displacing the water from the gel by use of a suitable organic
solvent (e.g., a surfactant, an alcohol, acetone, etc.) which can
displace the water and reduce the surface tension of the wetting
agent in the pores of the gel, followed by drying the gel.
Ser. No. 750,733, discloses a method of drying the gel which
comprises a vacuum freeze-drying process to remove essentially all
the water, wherein the gel is frozen at a temperature between
-100.degree.C and -10.degree.C and the water is then vacuum
sublimed from the gel.
Lastly, in Ser. No. 766,693 there is disclosed a drying procedure
which comprises adding a non-water miscible solvent which forms an
azeotrope with water when distilled and distilling the azeotrope so
as to remove substantially all the water under specified
conditions.
In the aforesaid method for the production of silica gel, the
reagents are admixed in a suitable reaction vessel and subjected to
agitation in order to obtain as thorough a mixing of the reactants
as possible. As it has been found that non-specific agitation tends
to produce a gel which varies in particle size and other physical
properties from batch to batch the reactions are usually subjected
to high shear mixing before the drying of the gel in order to
obtain uniformity in particle size between various lots of silica
gel produced.
In the preparation of high pore volume silica gel, it has been
found to be necessary to conduct the polymerization with thorough
and extremely turbulent agitation This violent gitation is
necessary for a variety of reasons.
Unless the agitation is thorough and extremely turbulent at the
time of gelation, there is a tendency to form agglomerates of the
gel which tend to separate from the bulk of the gel suspension
until dissipated by the lowering of the pH of the reaction mixture.
The delay in disintegration of such agglomerates causes the gel
contained therein to be neutralized at a slower rate than the
remainder of the gel formed, which results in the production of a
product possessing non-uniform pore volumes.
After gelation, the product is heat aged while maintaining the pH
within a specified narrow range. Inadequate agitation tends to
cause a non-uniform pH level, resulting in a pH gradient across the
gel particles. Such gradients tend to result in undesirable
variations in physical properties of the final silica gel
product.
In order to insure efficient leaching of alkali from the gel during
the subsequent washing operations, it is necessary that the gel
possess a uniform, fine particle size. Variations in particle size
will result in uneven leaching of the alkali during the washing
operations which, again, would result in uneven product properties.
The application of uniform shearing forces throughout the reactant
mixture would result in a product possessing uniform particle sizes
and thus overcome this problem.
Further, the thorough and efficient agitation of the reactants and
gelled products avoids the necessity of a separate homogenization
step before the drying of the gel, which step has heretofore been
normally required in this art in order to insure uniform particle
size. The elimination of such a step results in self-evident
economies.
SUMMARY OF THE INVENTION
Applicants have discovered that very high shear mixing can be
obtained by the use of a particular apparatus of the
agitator-baffle type, in which stationary and movable sets of
blades are arranged in a specific configuration with respect to
each other. The specific design of the mixing apparatus of the
present invention permits the obtaining of uniform and controlled
application of high shear forces which result in extremely thorough
and efficient agitation of ingredients or reactants with which the
apparatus may be charged.
Essentially the mixing apparatus of the present invention comprises
a vertical vessel having cylindrical walls, a vertical driven shaft
disposed centrally therein, a plurality of movable sets of flat
blades secured to said shaft for rotation therewith, each of said
movable sets being spaced equidistant from each other along the
length of said shaft with the blades in each set extending radially
outwardly from said shaft in equally spaced relation and pitched at
an angle with respect to the axis of said shaft, a plurality of
sets of stationary flat blades secured to said cylindrical wall of
said vessel, each of said stationary sets being spaced equidistant
from each other along the length of said shaft with the blades in
each set extending radially inwardly from said wall toward said
shaft in equally spaced relation and disposed at an acute angle
with respect to the axis of said shaft, said stationary sets being
located in alternate relation with said movable sets with
substantially identical clearances therebetween and with the blades
in selected sets being pitched in the opposite direction with
respect to the pitched blades in other selected sets, the blades of
each movable set being offset in the same circumferential direction
from the blades of the adjacent movable set thereabove by equal
angular increments.
DESCRIPTION OF THE DRAWINGS
FIG. 1 is a plan view of one embodiment of the apparatus of the
present invention, illustrating the arrangement of the stationary
and movable sets of blades therein.
FIG. 2 is a side elevation of the apparatus of FIG. 1, modified as
explained below for purposes of illustration.
FIG. 3 is a sectional view taken along line A -- A of FIG. 2,
illustrating the pitched configuration of the various blades.
FIG. 4 is a graphic illustration of the particle size distribution
of silica gels produced in the apparatus of the present
invention.
The apparatus consists of a vertical, cylindrical tank with a flat
top and bottom. The top lid 6 contains a partial hinged door 6a,
which may be used for inspection and cleaning. The sides and bottom
of the apparatus may be jacketed as shown at 7 and provision made
for the introduction and removal of heating or cooling fluid to the
jacketed portion at 7a and 7b. Insulation, for example foam or
glass fiber, (not illustrated) may be applied to the exterior of
this jacket.
As illustrated, the agitator consists of at least 5 rows of
4-bladed movable sets 1, 2, 3, 4 and 5, mounted on a vertical shaft
8, each blade being pitched at an angle of 45.degree.. However, the
pitch of the blades can be varied from the disclosed
45.degree.pitch, although a 45.degree. pitch provides the advantage
of being able to reverse the direction of agitation for another
application of the apparatus; for example, when working with a
suspension where the solid is lighter than the medium. A pitch
greater than 45.degree. (e.g., 60.degree.) would result in more
agitation but would require more power and would not necessarily
provide more shear; while a pitch lower than 45.degree. (e.g.,
30.degree.) would give less mixing and require more, or larger,
blades to fill the tank.
Between these movable blades in the vertical direction are mounted
4 (or more) rows of horizontal stationary sets of blades 14
positioned 180.degree. apart and also pitched at an angle of
45.degree.. These horizontal stationary blades are mounted to the
vertical walls of the vessel. As illustrated, each such stationary
set contains two blades, although as will readily occur to one
skilled in the art, additional blades could be employed in such
sets, although additional blades would necessarily increase the
power required to turn the agitator blades. In addition, the number
of rows of blades is not limited so long as the apparatus remains a
"vessel" instead of a "column."
The stationary paddles should not be positioned at the bottom of
the vessel since this would inhibit the complete and thorough
agitation required by the process for producing the silica gel
product described herein.
It should be noted that agitator blade sets 1 to 5 are staggered
with respect to each other, each at an angle of 18.degree., as
shown in the plan view of FIG. 1. In the side elevational view of
FIG. 2, however, the agitator blades are shown aligned vertically
instead of being staggered. This method of illustrating the
apparatus has been employed in order to more clearly illustrate the
pitched configuration of the various blades, clearly shown in
Section 3--3 of FIG. 2, and should not be construed as an
illustration of the actual positions of the movable sets of blades,
which are, in reality, staggered as shown in FIG. 1.
It should be noted that any arrangement of the rotating blades and
stationary paddles is possible, as long as the arrangement selected
provides the intimate and thorough mixing required to minimize the
concentration gradients in the system equivalent to the preferred
design shown above.
The agitator, comprising blade sets 1 to 5 and vertical shaft 8, is
driven by a suitable motor, preferably combined with a variable
speed drive and reduction gear coupled to the vertical agitator
shaft. Various combinations of motor and gears can be employed in
order to obtain any desired range of speed and/or power. In the
apparatus used in the following specific examples, the vessel
possessed a 6-foot diameter and the agitator possessed a speed
range of 5 to 50 RPM. It will be understood, however, that the
vessel size and speed range can be varied at will and the present
invention will not be limited by the above.
The blades of the present apparatus preferably have square edges
and the horizontal edges of the blades and paddles are preferably
parallel to each other and spaced as set forth below.
The ends of the agitator blades are illustrated as being square,
but can be slightly rounded if desired. The shear action occurs
along the front (i.e., leading) edge of the blades as they rotate
and little, if any, takes place along the end of the blades as they
travel through the liquid along the wall of the vessel. The
configuration of the ends of the blades should be such that there
is a minimum clearance between the blade ends and the vessel wall
to prevent a buildup of solids in this space.
The tapered ends of the stationary paddles is desirable since the
hub end of the rotating blades should not touch the ends of the
paddles when the former are slipped into position along shaft
8.
A flanged ball bearing 9 at the top of the unit supports the drive
shaft and a bushing 10 stabilizes the lower end of the shaft.
Spacers 15 between the rotating horizontal paddles maintain the
proper spacing.
A quick opening valve 11 may be located at the bottom in order to
drain the tank.
Reactants or the ingredients to be mixed may be added at inlets 12
and 13.
Various additional instrumentation may be employed, as is well
known and conventional in the art. For example, a direct and
continuous reading temperature gauge and pH meter may be installed.
The temperature may be automatically controlled for both cooling
and heating cycles and, in addition, automatic control of the
addition of reactants may also be achieved, as by control of the
addition of an acid in response to the pH of the mixture.
DETAILED DESCRIPTION OF THE INVENTION
In operation, agitator blades of sets 1, 3 and 4 are angled so that
they tend to lift the ingredients in the mixer, while the blades of
sets 2 and 5 are angled so that they tend to push the ingredients
being mixed in a downward direction. The rotating sets of blades
are keyed to the drive shaft, the keyways being successively
18.degree. apart, which configuration assists in decreasing the
magnitude of the power impulses required.
The clearance employed between the movable sets of blades and the
stationary sets of blades, as well as between the ends of the
rotating blades and the vertical mixer wall may vary between
one-eighth inch and 2 inches, a spacing of one-half inch being
preferred. The aforementioned clearances are the preferred
dimensions for the production of the uniform silica gel product
described herein. The spacing which is chosen is as small as is
commercially practicable but sufficient to maintain suitable
spacing between the various components to prevent accidental
collisions due to vibration or wear of the components.
The clearance may be increased for products other than the silica
gel described herein, bearing in mind that larger clearances result
in less shear action and would necessitate greater rotational speed
to compensate therefor.
The superior high shear mixing which may be achieved as a result of
the improved reactor design of the present invention will be
illustrated in the following examples by the affect upon a silica
gel product prepared in accordance with the aforesaid application
Ser. No. 750,734. The silica gel product obtained in accordance
with the process of this application possesses a narrow pore
diameter distribution primarily in the range of from 300 to 600 A.,
a surface area in the range of from 200 to 500 m.sup.2 /g and
stability at temperatures of up to 2,000.degree.F, even when
subjected to fluidized processing.
The terminology "narrow pore diameter distribution" indicates that
70 percent, or more, of the cumulative pore volume is in the pore
diameter range of 300-600A. when measured by N.sub.2 adsorption by
the B.E.T. Method. In addition, the poor volume of the xerogel-type
silica gel product varies from 2.0 to 3.5 cc/gr. when measured by
N.sub.2 adsorption by the B.E.T. Method.
The properties of the silica gel obtained, particularly the
porosity characteristics, are discussed in terms of pore volume
(PV), surface area (SA), and average pore diameter (PD), where PD =
4PV/SA . Determinations of the values for the various properties
are made by nitrogen absorption-desorption techniques well known in
the art and described in detail in the Journal of the American
Chemical Society, Volume 60, Page 309 (1938), "Journal of
Catalysis," Volume 2, Page 111 (1955).
The first example describes a preferred method for carrying out the
preparation of the silica gel employing the apparatus of the
present invention, to obtain a silica gel with the desired physical
properties and illustrates the consistency of the results obtained.
The remainder of the examples illustrate trials with other types of
mixers and agitators.
EXAMPLE I
2,090 pounds of sodium silicate solution containing 28.7% SiO.sub.2
and 8.9% Na.sub.2 O were added to 387 gallons of deionized water in
the reactor illustrated in FIGS. 1 and 2 and described above and
cooled to 5.degree.C with agitation of 20 RPM.
Approximately 250 gallons of 12.75 weight percent sulfuric acid
were added at the following rates:
a. 40 percent of the acid was added at a constant rate over a
period of 1 hour, with the agitator at 20 RPM.
b. the remainder was added over a period of 45 minutes with
agitation at 28 RPM.
The final pH of the gel was adjusted to 5.0 to 5.5 and the
SiO.sub.2 content was approximately 8.5 percent.
The pore volume of the silica gel made as described in this example
as well as others made in subsequent runs are listed in Table I.
The reproducibility from batch to batch as a result of the specific
design of the reaction of the present invention can be seen.
The consistency of the results after heat aging is also shown in
the appropriate column of Table I.
TABLE I
After Polymerization After Heat Aging Pore Surface Pore Surface
Volume Area Volume Area cm.sup.3 /g m.sup.2 /g cm.sup.3 /g m.sup.2
/g 1 3.12 760 2.63 337 2 2.56 775 2.77 370 3 2.67 897 2.74 363 4
2.88 558 2.74 346 5 2.72 661 2.95 376 6 2.72 473 3.01 366
In addition, the first silica gel product was coated with catalyst
which reduced the PV to 2.43 and then was heated to 1,800.degree.F
with only a slight change in values:
PV = 2.28 cm.sup.3 /g, SA = 315 m.sup.2 /g
The particle size distribution curve of the material produced in
Example I is shown in FIG. 4. This shows a narrow distribution of
the particles between 90 and 140 microns.
EXAMPLE II
Three different types of commercially available mixers were used
for preliminary silica gel polymerizations. They were studied and
modified when necessary to obtain the best design for the reactor.
The data obtained demonstrates the superiority of the reactor of
the present invention. The amount of reagents used in each
experiment were less then in Example I but were used in the same
proportions and with the same technique as described in Example I
so that the results, as listed in Table II, are comparable with
those of Example I.
The turbine reactor consisted of a small vertical tank having an
approximate capacity of 15 gallons with provisions for various
types of agitator and baffle arrangements as noted in Table II. The
agitator speed was varied during the experiments from 160 to 260
RPM.
The Kettle mixer was round bottomed, cylindrical 60-gallon tank
similar to those used in restaurants and bakeries for food
preparation. Several impeller designs were used: agitators with
scraper, paddle blades, and beaters which were geared for dual
rotation so that as each agitator rotated in the usual way, the set
of beaters also revolved in a circular manner. This method was used
to assure uniform agitation of the entire contents of the kettle.
The rate of agitation was controlled throughout the experiment
(i.e., the RPM varied from 68 to 160).
The shear bar reactor experiments were conducted in 18-gallon size
batches. The four impeller blades were elliptically shaped and
staggered so as not to pass the opposing stationary blades at the
same instant. The agitator was driven at a RPM which varied from 50
to 90 throughout the experiments.
In all three of the above experiments, the agitation rate was
varied to give what visually looked to be adequate agitation for
each stage of the polymerization. The rate was varied within the
above-defined limits during each run, and the same applies to the
remaining examples.
Column 4 of Table II lists the pore volume and surface area for
representative runs after gellation in the above three reactors.
Variation in the results between similar runs are evident.
EXAMPLE III
This example illustrates that even when a precipitated gel which
has the desired properties after gellation is obtained without
using the reactor of the present invention, those properties can be
destroyed during heat aging.
A further and necessary step in silica gel manufacture is heat
aging of the gel after formation. At the proper pH, the slurry of
silica gel in its mother liquor is aged so as to obtain the desired
properties. This is achieved by raising the temperature at a
predetermined rate and holding the suspension at the desired
minimum temperature for the necessary length of time. This
time-temperature relationship is set forth in the above-identified
applications. An important part of such heat aging is the control
of the pH of the suspension within a narrow range during the
heating. Inadequate agitation, as indicated above, will result in a
non-uniform pH level through the particle and variation in the
physical properties of the finished silica gel.
Table II indicates that for runs SS-16, SS-27, SS-29, KM-1, KM-2,
KM-3, BM-1 and BM-10, even when properties of the polymerized gel
obtained are as desired as shown by the Example II results, these
properties can be destroyed during the heat aging step, even though
proper overall heat aging conditions are respected.
EXAMPLE IV
This example illustrates the effect of reactor design in the
washing step of the silica gel. Subsequent to the polymerization
and heat aging of the silica gel, a washing operation is carried
out to remove sodium from the gel as disclosed in the
afore-mentioned applications. As pointed out previously, if the
silica gel particles are too large or have been allowed to
agglomerate during polymerization due to inadequate agitation, then
the washing operation will be ineffective for the efficient removal
of the sodium ions and large amounts of sodium will remain in the
interior of the gel particles even though the content of sodium in
the effluent water indicates that the product has been thoroughly
washed (i.e., contains less than 20 ppm of sodium).
Table II lists the physical properties of silica gels produced in
each of the three experimental reactors. The presence of high
concentrations of sodium is revealed by a significant lowering of
the pore volume of the gel when heated to 1800.degree.F. Test runs
SS-12, SS-18 and BM-4 show that they have shrunk, whereas the gel
obtained in accordance with Example I diminished much less in pore
volume. ##SPC1##
* * * * *