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Патент USA US3060016

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Oct. 23, 1962
Filed May 24, 1960
tent O
Patented‘ Oct. 23, 1962
is shown in more detail in copending Serial No. 786,758
?led 1-13-59, owned by the same assignee and now
Calvin J. Benning, Clarksville, Md., assignor to W. R.
Grace & Co., New York, N.Y., a corporation of Con
To carry out this activation, a 750 ml. stainless steel
mill 3 containing 75 %-inch stainless steel balls and a
charge of 173 g. TiClz was connected through two needle
valves 4 and 6 to ethylene cylinder 7 having a capacity
of 75 ml. and which contained ethylene under a pressure
The device of this invention is a means for ball milling
catalysts or the like under pressure of a reactive gas. 10 of 200 p.s.i.g. Both valves 4 and 6 were opened for a
few minutes to equalize the pressure between the mill
In brief, the invention contemplates the addition of an
3 and the ethylene cylinder 7. This gave a pressure
auxiliary gas cylinder connected to the ball mill and
of about 50 p.s.i.g. in the mill 3. The valves 4 and 6
adapted to roll with the mill on the same rollers during
were then closed and milling was begun. About every
the milling operation. In normal operation, the connec
tion between the gas cylinder and the ball mill is opened 15 4 to 6 hours the assemblage was removed from the rolls
and the valves ‘4 and '6 opened to admit more ethylene
from time to time to maintain the gas pressures in the
to the mill 3 and then closed and milling resumed. This
mill at a predetermined level. If the mill is small the
procedure ‘was continued for three days, after which the
assemblage of mill and auxiliary pressure vessel can be
Filed May 24, 1960, Ser. No. 31,481
1 Claim. (Cl. 23—289)
nearly empty cylinder 7 was replaced by another (pres
lifted manually off the rolls, gas admitted through the
cut-off valve linking the gas cylinder and the mill, and 20 sured at 3010 p.s.i.g. of ethylene) and the procedure re
peated for another day of milling. An additional cyl
the assemblage then returned to the rolls. If the mill
inder charge of 400 p.s.i.g. ethylene was added intermit
is large, the rolls can be stopped to permit opening the
tently on the beginning of the ?fth day of milling, and
valve. Under certain reaction conditions, it may be
the milling was ?nally stopped at the end of the fifth day.
found desirable to leave the connecting valve open slightly
At this point the mill was disconnected from the cylinder
during the milling operation so that admission of gas
by uncoupling the connector 5 (both valves 4 and 6
will be continuous during the milling operation.
closed) and then opened in a nitrogen atmosphere to
The drawing shows a perspective view of the milling
vent o? a slight pressure of residual ethylene. The ethyl
assembly. 1 and 2 are the rolls. The means for driv
ene-activated TiClz catalyst was then removed and
ing them is not shown. The mill is shown at 3; under
normal operation it may be about 1/3 full of stainless 30 weighed. It showed a gain of 6.3 grams.
There are several advantages in the apparatus used as
steel balls. The mill 3 is provided with shut-o? valve,
described. The ?rst and perhaps main advantage
4, connected through the coupling 5 to the adjacent cut
is the saving of time in pressuring the mill with active
o? valve 6 of the gas cylinder 7. If the diameter of
gas. In the old way, the mill had to be taken from the
the gas cylinder is smaller than that of the mill, an
brought to the gas cylinder, connected to it, pres
adapter ring 8 may be ?tted around it. Conversely, an 35
sured, disconnected, and returned to the rolls, and this
adapter ring may be ?tted around the mill if its diameter
had to be done many times. In the new way as provided
is smaller than that of the gas cylinder. If desired,
by my invention, the connection to the gas cylinder is
the gas cylinder may also be ?tted with charging or
semi-permanent, and very little time is lost. Even the
venting valve 9. It is not absolutely necesary to have
both cut-off valves 4 and 6, but if both are present 40 act of replacing the cylinder 7 is less time consuming
than one repressuring by the old technique.
it is possible to seal o?” both the mill and the gas cyl
inder at the end of the run and disconnect and store
Example 2
both separately without loss of material.
It is "known to treat material being ground with a gas.
See for example, U.S. 1,453,057, disclosing grinding iron
The apparatus was used in such a way to provide a
45 predetermined weight of active gas (in this case, hydro
gen) to the catalyst being milled, but at a pressure not
oxide in the presence of a stream of hydrogen to make
exceeding substantially atmospheric pressure, and by use
of a technique not requiring removal of the mill from
metallic iron.
It is also known to rotate together two or more inter
connected mills in a ball-milling operation, as taught,
for example, in U.S. 1,435,930, for grinding mixtures of 50
salt and nitre cake, or U.S. 42,257, for grinding coal.
It is also known to ball mill catalysts under pressure
in a single milling vessel. See U.S. 2,891,043. Further,
the rolls except at the end of the run.
In this particular run it was desired to add 0.3 g. (0.115
mole) of hydrogen to a mixture of aluminum turnings
(16 g.) and TiCls (30 g.) at a uniform rate over a
120 hour period of uninterrupted ball milling, so as to
in U.S. 2,856,272, polymer is made in situ by ball-milling
prepare a highly active polyethylene catalyst. (The prep
generally provide elaborate cooling means to dissipate the
frictional heat generated around the seal, and the prob
lems of excluding ground material and vapor from the
was then placed in a pneumatic trough and the valve 6
55 aration and use of this catalyst is described in more detail
the catalyst and monomer together under pressure.
in copending Serial No. 825,410, ?led July 7, 1959, owned
It is also known to charge ?uid material (liquid or
by the same assignee.)
vapor) through a stationary tube into a rotating ball mill,
To accomplish this, the gas cylinder 7 was ?rst pres
as shown in U.S. 955,814. However, such devices must
sured with hydrogen to about 60 p.s.i.g. This cylinder
opened slightly. The bubbles coming oil were collected
and measured. The valve was adjusted until the hydro
seal are dif?cult to deal with in practice.
The following examples illustrate the use of the in
gen ?ow rate was 0.5 ml. per minute (equal to 0.3 g. over
the projected 5 day run).
The mill 3, containing the A1—-TiC13 mixture and about
1/3 its volume of steel balls, was ?ushed with nitrogen
and connected to the gas cylinder 7, with valve 4 fully
open and ‘valve 6 adjusted as above described. The
Here the apparatus is used to increase the activity of
thus-assembled mill and cylinder were then placed on
TiClz for use as a polyethylene catalyst. This is done
by ball-milling the TiClz for a prolonged period under 70 the rolls, and the milling operation was begun and con
tinued without interruption for 5 days. At the end of
a predetermined pressure of ethylene gas. (This feature
this time, the run was stopped and the catalyst recovered
Example 1
ring resting upon and being rotatable by said rolls, a
as above described. The hydrogen pick-up was very
nearly 0.3 g.
For situations in which moisture or foreign liquids
cannot be tolerated near the mill, or if it be desired to,
conduit extending between the mill and the gas cylinder
centered on the longitudinal axis and providing a gas
passage interconnecting the interior of the mill with that
of the cylinder, and valve means in the conduit adapted
to control the volume of ‘gas supplied to the mill, whereby
keep the mill asesmbly completely ‘intact, the center con
necting tube or coupling 5 can be replaced by a small
gas regulator (not shown) of any well known design.
both cylinders may rotate as a completely sealed unit
about a common axis and pre-determined gaseous condi
Such gas regulator (calibrated before installation) will
deliver a steady stream of any gaseous product and there
by avoid the calibration step and associated technique
in Example 2.
tions may be uninterruptedly maintained in the mill
10 throughout the duration of a mill run.
I claim:
References Cited in the ?le of this patent
In apparatus for milling catalysts and the like under
pressure of a reactive gas, the combination consisting
of a set of parallel mill-driving rolls, power means to 15
rotate the rolls, a pressure-resistant ball-‘mill having a
cylindrical body, a container for compressed, reactive
gas comprising a cylinder having a diameter other than
that of the mill, an adaptor ring ?tted about the smaller
of the cylindrical bodies to increase its effective diameter
to that of the larger cylinder, the cylindrical wall of one
of said cylinders and the cylindrical wall of the adaptor
Heylingstaedt ________ __ May 22, 1894
Leet ________________ __ Apr. 19,
Laury ______________ .__ Nov. 21,
Williams ____________ __ Apr. 24,
Wendler ____________ __ June 14,
Punnett ______________ __ Sept. 27,
Baeyaert _____________ __ Oct. 14,
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