U.S. patent number 3,839,011 [Application Number 05/384,200] was granted by the patent office on 1974-10-01 for nickel-aluminum particle with improved grindability.
This patent grant is currently assigned to The International Nickel Company, Inc.. Invention is credited to Floyd Gotthard Larson, Jr..
United States Patent |
3,839,011 |
Larson, Jr. |
October 1, 1974 |
NICKEL-ALUMINUM PARTICLE WITH IMPROVED GRINDABILITY
Abstract
A water shattered Raney alloy characterized by a readily
crushable mechanical structure comprising for the most part loosely
agregated lamenae, convoluted and folded to irregularly shaped
masses.
Inventors: |
Larson, Jr.; Floyd Gotthard
(Ringwood, NJ) |
Assignee: |
The International Nickel Company,
Inc. (New York, NY)
|
Family
ID: |
23516428 |
Appl.
No.: |
05/384,200 |
Filed: |
July 31, 1973 |
Current U.S.
Class: |
502/301;
502/527.16 |
Current CPC
Class: |
C22C
5/06 (20130101); B22F 9/082 (20130101); C22C
9/00 (20130101); C22C 19/007 (20130101); B22F
2009/0812 (20130101) |
Current International
Class: |
C22C
5/06 (20060101); C22C 9/00 (20060101); B22F
9/08 (20060101); C22C 19/00 (20060101); B22f
009/100 () |
Field of
Search: |
;75/.5C,.5B,.5BA,.5BB
;264/11 ;252/477Q |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Rutledge; L. Dewayne
Assistant Examiner: Steiner; Arthur J.
Claims
I claim:
1. A Raney metal alloy product comprising water shattered particles
each consisting essentially of thin, convoluted and folded laminae
having internal voids in communication with the particle surface
said particles being characterized by a tapped bulk density of
about 0.3 to about 1.2 grams per cubic centimeter "and consisting
of about 25 percent to about 65 percent by weight of a catalytic
metal from the group consisting of iron, nickel, cobalt copper,
silver and mixtures thereof with the balance, apart from
impurities, incidental elements and promoting ingredients, being an
alkali-soluble metal selected from the group consisting of
aluminum, zinc, silicon and mixtures thereof".
2. A Raney metal alloy product as in claim 1 wherein the
alkali-soluble metal is aluminum.
3. A Raney metal alloy product as in claim 1 wherein the catalytic
metal is nickel.
4. A Raney metal alloy product as in claim 1 wherein the alloy
contains about 50 percent by weight of nickel and about 50 percent
by weight of aluminum.
Description
The present invention is concerned with Raney metal and, more
particularly, with Raney nickel alloy.
It is known that nickel alloys containing nickel in the range of
about 25 percent to about 70 percent by weight with the balance
being essentially aluminum or other alkali soluble metal can be
leached with caustic solutions, e.g., aqueous solutions of sodium
hydroxide to provide masses of highly catalytically reactive
nickelferrous material. Other catalytically active metals can be
produced by essentially the same process. For example,
aluminum-rich binary alloys of silver, iron, cobalt, copper as well
as more complex alloys, e.g., aluminum-iron-nickel or
aluminum-cobalt nickel rich in aluminum can be leached with caustic
to give catalytically active metal masses. For purposes of this
specification and claims all such alloys will be called "Raney
alloys" and the present invention is pertinent to all of them even
though particular reference will be with respect to "Raney nickel
alloy." The residue after caustic leaching will be identified as
"Raney metal" e.g., "Raney nickel."
In industrial use, Raney metal is often required to be in a form of
a coating on small particles of Raney metal alloy so that it can be
used as a catalyst in either a fixed or a fluid bed. Heretofore
Raney nickel has been cast in massive form and has been broken up
and ground to a desired particle size. This prior process has two
disadvantages. The metals of the Raney alloy can segregate during
casting and thus give non-uniformity in the casting. Secondly,
substantial power is required to break up and grind the cast
alloy.
It is an object of the present invention to provide Raney metal
alloy in a form which can immediately be leached to provide a
useful catalyst product and which if necessary, can be ground to
any required fineness.
Other objects and advantages will become apparent from the
following description taken in conjunction with the drawing which
depicts the product of the present invention.
Generally speaking the present invention contemplates
water-shattered Raney metal alloy having a mechanical structure
comprising for the most part loosely agregated laminae (layers)
less than about 0.2 centimeters (cm) thick, folded and convoluted
to irregularly shaped masses having a high proportion of internal
voids in communication with the exterior surfaces and having, in a
fraction screened to pass through a 2 cm mesh and to be retained on
a 0.3 cm mesh, a tapped bulk density of about 0.3 to about 1.2
grams per cubic centimeter (g/cc). This product is characterized by
extreme ease of fragmentation (i.e., it is extremely friable) and
by good catalytic activity when leached with aqueous caustics.
In manufacturing the product of the present invention the Raney
metal alloy is melted and is poured at a superheat of at least
about 50.degree. in centigrade units in a molten stream through an
essentially horizontally flowing stream of water. It is essential
that the water be flowing at a minimum velocity to shatter the
Raney metal alloy because mere quenching from the liquid state is
reported to result in a product which is very hard and difficult to
break up. Assuming a metal pouring rate of about 1.5 kg/second in a
thin stream and a roughly rectangular stream 1.6 cm thick by 6.35
cm wide a minimum water flow rate of 350 liters per minute is
necessary to provide the shattered, fragmented structure of the
present invention.
Raney metal alloy suitable for use in providing the structure of
the present invention advantageously, contains about 25 percent to
about 65 percent by weight of catalytic metal from the group of
nickel, cobalt, iron, copper, silver and mixtures thereof with the
balance apart from impurities, incidental elements and promotors
and promotor precursors being aluminum. Normally, it is
advantageous to use about equal parts by weight of catalytic metal
and aluminum with impurities, incidental elements and promoting
ingredients, if any, being limited in total to, at most, about 5
percent by weight of the composition. Table I contains melting
point and pouring temperature data as to examples of Raney metal
alloy amenable to being produced as the product of the present
invention.
TABLE I ______________________________________ Alkali Pouring
Example Catalytic % by Sol. % by MP Temp. No. Metal Wt. Met. Wt.
(.degree.C) (.degree.C) ______________________________________ 1 Ni
42 Al 58 1080 1200 2 Fe 55 Al 45 1230 1350 3 Co 50 Al 50 1400 1500
4 Ag 35 Al 65 620 750 5 Ni 50 Al 50 1310 1480 6 Ni 60 Al 40 1570
1650 7 Co 40 Si 60 1140 1300 8 Ni 50 Zn* 40 -- 1300 9 Cu 55 Al 45
600 800 ______________________________________ *Alloy includes 10%
aluminum
Any of the exemplifying alloys of Table I can be modified by
inclusion of catalyst promoters or modifiers. For example, small
amounts of alkaline earth metals, e.g., calcium, barium or the
like, thorium vanadium, chromium, molybdenum or similar elements
known in the metallic or oxidic forms to promote particular
catalytic activity can be included in the Raney metal alloys useful
as the product of the present invention. Likewise, small amounts of
inert metal, e.g., copper in nickel catalysts or nickel in silver
catalysts can be used either alone or in combination with promoters
to appropriately modify the Raney catalyst produced by leaching the
product of the present invention.
In manufacturing the product of the present invention the catalytic
metal, e.g., nickel, is melted and the alkali soluble metal, e.g.,
aluminum is added, due care being taken in view of exothermic
reaction of the metals. Alternatively, the alkali soluble metal is
melted and the catalytic metal is added and dissolved in the melt.
Any modifying ingredient can then be added. The molten alloy is
then poured in a thin stream into a flowing stream of water. Using
the rectangular, essentially horizontally flowing water stream
described hereinbefore and a flow of molten metal of about 1.5
kg/sec a water flow rate of about 850 liters per minute produces
excellent product. Slower flow of water is not desirable because
under those conditions water is likely to be entrapped in
bubble-like particles rendering drying difficult. At water flow
rates below about 350 liters per minute effective metal shattering
is not readily achieved. The water temperature is not critical, no
effect being noticed because of water temperature variation in the
range of about 27.degree.C. to about 65.degree.C.
In order to give those skilled in the art a better understanding of
the invention the following specific description is given. A 24
kilogram heat of the alloy of Example 5 was made by melting nickel,
pouring the molten nickel into a ladle and adding aluminum. The
molten alloy was then poured into a preheated tundish which
directed the metal stream into a horizontally flowing water stream
about 1.6 cm thick by about 6.4 cm wide flowing at a rate of about
750 to about 950 liters per minute. The metal passed through the
tundish nozzle at a rate of about 1.5 kilogram/second. Metal
temperature was approximately 1,480.degree.C. and the water
temperature was about 40.degree.C. The product produced is depicted
in the drawing which shows a water fragmented, highly friable alloy
of high surface area of low bulk density. The individual particles
of the alloy are composed essentially of laminae convoluted and
folded to provide a high specific surface area. Upon leaching with
aqueous alkali, the Raney metal produced from the Raney metal alloy
product of the present invention exhibits high catalytic activity
for hydrogenation and other reactions. The product is also readily
ground to whatever size is required.
Five samples of the water-shattered Raney metal alloy of the
present invention screened to pass through a 3/4 inch (about 1.9
cm) mesh screen with about 30 percent to 80 percent of the material
passing through a 1/4 inch (about 0.635 cm) mesh screen exhibited
tapped bulk densities of about 0.7 to 1.0 g/cc. A relatively coarse
fraction passing through a 3/4 inch mesh screen and retained on a
1/2 inch (about 1.27 cm) mesh screen exhibited a tapped bulk
density of about 0.6 g/cc whereas a fraction passing through a 1/4
inch mesh screen gave a tapped bulk density of 1.0 Raney catalyst
made by leaching Raney metal alloy of the present invention with
caustic was tested for activity in the hydrogenation of 2,
4-dinitrotoluene and was found to have commercially satisfactory
activity.
Although the present invention has been described in conjunction
with preferred embodiments, it is to be understood that
modifications and variations may be resorted to without departing
from the spirit and scope of the invention, as those skilled in the
art will readily understand. Such modifications and variations are
considered to be within the purview and scope of the invention and
appended claims.
* * * * *