U.S. patent number 3,688,474 [Application Number 05/155,532] was granted by the patent office on 1972-09-05 for collection of metal carbonyls.
This patent grant is currently assigned to The International Nickel Company. Invention is credited to John Robert Michael Thompson, Oakville, Michael David Head, Copper Cliff.
United States Patent |
3,688,474 |
|
September 5, 1972 |
COLLECTION OF METAL CARBONYLS
Abstract
Gaseous streams of carbon monoxide containing nickel and iron
carbonyls are contacted with cooled liquid iron pentacarbonyl to
dissolve the carbonyls and to provide purified carbon monoxide.
When the liquid iron pentacarbonyl has dissolved controlled amounts
of nickel carbonyl, the solution is fractionally distilled to
recover nickel carbonyl and liquid iron pentacarbonyl which can be
recycled. The process can also be conducted under pressure and in
conjunction with intermediate pressure carbonyl processes for
recovering nickel.
Inventors: |
Michael David Head, Copper
Cliff (Ontario, CA), John Robert Michael Thompson,
Oakville (Ontario, CA) |
Assignee: |
The International Nickel
Company (Inc., New York)
|
Family
ID: |
4087154 |
Appl.
No.: |
05/155,532 |
Filed: |
June 22, 1971 |
Foreign Application Priority Data
Current U.S.
Class: |
95/193; 95/234;
75/413 |
Current CPC
Class: |
C01G
49/16 (20130101); C01G 53/02 (20130101) |
Current International
Class: |
C01G
53/00 (20060101); C01G 53/02 (20060101); C01G
49/16 (20060101); B01d 003/14 (); C22b
023/00 () |
Field of
Search: |
;55/48,68,72,84,50,228
;23/2R,203C ;75/0.5AA,82 |
References Cited
[Referenced By]
U.S. Patent Documents
|
|
|
2985509 |
May 1961 |
Breining et al. |
3342587 |
September 1967 |
Goodrich et al. |
|
Primary Examiner: Charles N. Hart
Attorney, Agent or Firm: Maurice L. Pinel
Claims
We claim:
1. A process for separating nickel carbonyl from other gases that
are substantially insoluble in liquid iron pentacarbonyl which
comprises: contacting a gaseous stream containing nickel carbonyl
with liquid iron carbonyl containing less than about 1 percent
nickel carbonyl to scrub nickel carbonyl from the gaseous stream
and to produce a carbonyl solution of nickel carbonyl dissolved in
liquid iron pentacarbonyl, and treating the carbonyl solution to
recover substantially pure nickel carbonyl.
2. The process as described in claim 1 wherein the dissolved nickel
carbonyl is recovered from the carbonyl solution by fractional
distillation and liquid iron pentacarbonyl is recycled to scrub
more nickel carbonyl from the gaseous stream.
3. A process for separating nickel carbonyl from other gases that
are substantially insoluble in liquid iron pentacarbonyl which
comprises: contacting a gaseous stream containing nickel carbonyl
with liquid iron pentacarbonyl containing less than about 1 percent
nickel carbonyl to scrub nickel carbonyl from the gaseous stream
and to produce a carbonyl solution of nickel carbonyl dissolved in
liquid iron pentacarbonyl, and fractionally distilling
substantially pure nickel carbonyl from the carbonyl solution by
passing a stream of carbon monoxide through the carbonyl
solution.
4. The process as described in claim 3 wherein the gaseous stream
contains nickel carbonyl, iron pentacarbonyl and carbon
monoxide.
5. The process as described in claim 3 wherein the gaseous stream
is maintained at a temperature below about 80.degree. C. and at a
pressure of more than about 2 psig.
6. The process as described in claim 5 wherein the liquid iron
pentacarbonyl is maintained at a temperature below about 25.degree.
C. and at a pressure of more than about 2 psig.
7. The process as described in claim 6 wherein the liquid iron
pentacarbonyl is maintained at a temperature below about 20.degree.
C.
8. The process as described in claim 7 wherein the liquid iron
pentacarbonyl is maintained at a temperature below about 5.degree.
C.
9. The process as described in claim 8 wherein the liquid iron
pentacarbonyl is maintained at a pressure between about 2 and 150
psig.
10. The process as described in claim 9 wherein the gaseous stream
is maintained at a pressure between about 2 and 150 psig.
11. The process as described in claim 3 wherein the gaseous stream
contains between about 20 grams per cubic meter and 250 grams per
cubic meter of nickel as nickel carbonyl and between about 20 grams
per cubic meter and 250 grams per cubic meter of iron as iron
pentacarbonyl.
12. The process as described in claim 11 wherein the liquid iron
pentacarbonyl is maintained at a temperature below about minus
10.degree. C.
13. The process as described in claim 3 wherein fractional
distillation is conducted in a column which contains a solution of
carbonyls that is substantially pure liquid nickel carbonyl at the
top of the column and substantially pure liquid iron pentacarbonyl
at the bottom of the column and is maintained at a temperature
range between about 0.degree. C. and 85.degree. C. with the
solution at the top of the column being maintained at the lower end
of the temperature range and the solution at the bottom of the
column being maintained at the upper end of the temperature range
and carbon monoxide is introduced at the bottom of the column so
that the carbon monoxide and carbonyl vapors are progressively
cooled to condense iron pentacarbonyl therefrom and to provide a
gaseous stream of carbon monoxide containing substantially pure
nickel carbonyl at the top of the column.
Description
The present invention relates to the treatment of gases containing
carbonyls of iron and nickel, and more particularly, to the
separation of nickel carbonyl and iron carbonyl from carbon
monoxide. The process is also useful when recovering nickel
carbonyl under elevated pressures.
Nickel and iron carbonyls are frequently produced under dynamic
conditions, i.e., carbon monoxide is continuously flowed over or
through metals containing nickel and iron to react therewith. Under
such dynamic conditions, nickel and iron are more rapidly
carbonylated since flowing carbon monoxide continually removes
products of reaction from the reaction site thereby speeding up the
overall reaction rate. Although this procedure increases the
overall reaction rate, it has the distinct disadvantage of
producing a dilute off-gas so that the ultimate recovery of metal
carbonyls is difficult and expensive. In most instances, the
off-gas must be refrigerated to about 0.degree. C. and the gas
volume reduced to about 1percent of its original volume in order to
condense the highly volatile metal carbonyls. Refrigerating a
dilute off-gas which may contain less than about 30percent metal
carbonyls is inefficient, particularly when large volumes of
off-gas are treated. Compressing the off-gas in order to condense
the metal carbonyls is expensive, particularly when only about
90percent of the carbonyls in the off-gases are recovered by
condensation, and, in addition, such compression increases the
temperature of the gases being compressed thereby increasing the
refrigeration required.
In order to overcome the foregoing problems, it has been suggested
that off-gases containing carbonyls of nickel and iron be collected
in organic solvents which have boiling points higher than either of
the carbonyls. This approach works reasonably well but it involves
additional reagent expense and can complicate subsequent separation
of nickel and iron carbonyl from the organic solvent and from each
other.
After separation from carbon monoxide, nickel and iron carbonyls
are most often separated from each other for individual use. After
separation, most frequently by distillation, nickel carbonyl is
thermally decomposed to carbonyl nickel, which carbonyl nickel is
characterized by high purity. Therefore, so carbonyl nickel will
not be contaminated with iron or with other impurities resulting
from iron carbonyl co-decomposition,nickel carbonyl must be
separated from iron carbonyl. The separation of carbonyls of iron
and nickel can be effected by chemical processes, but often the
cost of such chemical processes far outweighs their results. In
industrial practice, nickel carbonyl is most frequently separated
from iron carbonyl by fractional distillation. Since fractional
distillation depends upon one component in a solution of two or
more components having a vapor pressure greater than the vapor
pressure of the other components and since the vapor pressure of
the component being volatilized is directly proportional to its
concentration in the solution from which it is being distilled,
care is exercised in the industrial treatment of gases containing
carbonyls to provide solutions concentrated in nickel carbonyl.
Thus, most industrial processes for producing and separately
recovering iron and nickel carbonyls are specially designed, some
successfully and others not, to intermediately produce, when
separating metal carbonyls from carbon monoxide, carbonyl solutions
rich in nickel carbonyl to expedite the recovery of pure nickel
carbonyl. In so designing such processes, highly inefficient and
expensive refrigeration and compression operations are resorted to.
Although attempts have been made to avoid the foregoing problems
and disadvantages, none, as far as we are aware, has been entirely
successful when carried into commercial practice on an industrial
scale.
It has now been discovered that carbonyls of iron and/or nickel can
be separated from carbon monoxide in a more efficient manner,
particularly when such a process is conducted in conjunction with
the recovery of nickel and iron from materials containing the same
by atmospheric or pressure carbonylation techniques, without unduly
affecting the separation of nickel carbonyl from iron carbonyl.
The principal object of the present invention is to separate
carbonyls of nickel and/or iron from each other and from carbon
monoxide.
Another object of the present invention is to minimize the
inefficient steps of refrigeration and compression of gases
containing carbonyls of nickel and/or iron in order to recover the
carbonyls as liquids.
Other objects and advantages will become apparent from the
following description taken in conjunction with the drawings in
which:
FIG. 1 is a general flowsheet including the process in accordance
with the present invention; and
FIG. 2 is a schematic diagram of carbonyl manufacture, collection,
separation and decomposition operations of the process depicted in
FIG. 1.
Generally speaking, the present invention involves a process for
separating nickel carbonyl from other gases which are nearly
insoluble in liquid iron pentacarbonyl. Gases, containing nickel
carbonyl, are contacted with liquid iron pentacarbonyl containing
less than about 1.0 percent nickel carbonyl to dissolve nickel
carbonyl in the liquid iron pentacarbonyl, thereby separating
nickel carbonyl from the gases. The liquid iron pentacarbonyl with
nickel carbonyl dissolved therein is treated to separately recover
pure nickel carbonyl.
Advantageously, the nickel-carbonyl-containing gases are maintained
at a temperature below about 80.degree. C. and at a pressure of
more than about 2 pounds per square inch gauge (psig), and the
liquid iron pentacarbonyl is maintained at a temperature below
about 25.degree. C., e.g., less than about 20.degree. C. and even
lower, and at a pressure of more than about 2 psig. The
nickel-carbonyl-containing gas and the liquid iron pentacarbonyl
are advantageously maintained at a pressure between about 2 psig
and 150 psig.
FIG. 1 is a general flowsheet showing the use of the process in
accordance with the present invention in conjunction with the
treatment of nickeliferous material to recover nickel as nickel
carbonyl. A mixture of nickel and iron carbonyls in a stream of
carbon monoxide is produced in step A by treating nickeliferous
material (e.g., a nickeliferous lateritic ore that has been
selectively reduced) with carbon monoxide. The gaseous stream
produced in step A is scrubbed with liquid iron pentacarbonyl in
step B to collect substantially all of the metal carbonyls and to
provide a gas stream of carbon monoxide which contains only minor
amounts of iron carbonyl which is recycled to step A. The solution
of nickel carbonyl and iron pentacarbonyl is treated in step C to
separate carbonyls with a portion of nickel carbonyl being
thermally decomposed to metallic nickel in step E and a portion of
iron pentacarbonyl being decomposed in step D. Appropriate amounts
of purified carbon monoxide are recycled to steps A and C.
The process in accordance with the present invention will most
frequently be employed to separate nickel carbonyl from carbon
monoxide or gases containing large quantities of carbon monoxide.
Generally, the gases being so treated will not contain oxidizing
constituents, such as oxygen or chlorine, in amounts that will
cause undue oxidation. Advantageously, the gases are substantially
free of oxidizing constituents. Although gases containing only
nickel carbonyl can be treated in accordance with the present
invention, gases containing carbonyls of nickel and iron are
advantageously treated since the use of liquid iron pentacarbonyl
requires eventual separation of nickel from iron while gases
containing only nickel carbonyl may be treated more economically by
other methods. Nickel carbonyl will generally be present in the
gases being treated in amounts between about 250 grams of nickel
per standard cubic meter (gmsNi/Sm.sup.3) and 20 gmsNi/Sm.sup.3,
i.e., between about 40 and 5percent, advantageously between about
80 gmsNi/SM.sup.3 and 120 gmsNi/SM.sup.3, i.e., about 18and
25percent. Higher and lower concentrations of nickel carbonyl can
be treated but concentrations in the foregoing ranges are most
effectively treated. Likewise, the gases will generally contain
between about 250 grams of iron per standard cubic meter (gms
Fe/SM.sup.3) and 20 gmsFe/SM.sup.3, i.e., about 45 and 5percent
iron pentacarbonyl. It will be noted that all compositions given
herein are on a weight basis unless otherwise expressly stated.
Volumetric units are on a standard basis of 15.5.degree. C. and
14.7 pounds per square inch absolute (psia).
Both nickel and iron carbonyls are highly volatile so that in order
to effect an acceptable separation of the carbonyls from the other
gases the temperatures of the gases being treated and of the liquid
iron pentacarbonyl must be carefully controlled. For example, if
only a small quantity of liquid iron pentacarbonyl is employed and
the temperature and the volume of the gases being treated are high
and large, it is possible that liquid iron pentacarbonyl will be
volatilized rather than scrubbing the carbonyls from the gases
being treated. Thus, for the sake of efficiency and control, the
liquid iron pentacarbonyl preferably is maintained at a temperature
below about 5.degree. C., advantageously at a temperature lower
than about minus 10.degree. C., while the gases being treated are
maintained at a temperature below about 80.degree. C., e.g., about
minus 10.degree. C. or lower. When the nickel carbonyl-containing
gas is derived from extractive metallurgical operations which
produce gases rich in nickel carbonyl,e.g.,up to 250
gmsNi/SM.sup.3, cooling the effluent gases to below about 5.degree.
C. by passage through heat exchangers is highly advantageous in
that a portion of the gaseous nickel carbonyl is thereby condensed
as liquid from the gases and smaller amounts of iron pentacarbonyl
can be employed for scrubbing in a more efficient manner. The
liquid iron pentacarbonyl and the gases being treated can be
maintained at even lower temperatures with the absolute minimum
being that temperature at which iron pentacarbonyl, nickel carbonyl
and solutions thereof begin to freeze or solidify. Although such
lower temperatures provide a better separation of the carbonyls
from other gases, at temperatures substantially below minus
10.degree. C. the overall efficiency of the process begins to
suffer.
Overall efficiency of the process can be increased by subjecting
both the gases being treated and the liquid iron pentacarbonyl to
superatmospheric pressures, i.e., pressures of at least about 30
psig preferably are employed to increase processing efficiency. The
greater efficiencies realized when conducting the process at
superatmospheric pressures can, at least in part, be attributed to
the lower volumes of gases that have to be treated. Cooling of the
gases being treated is also rendered more efficient at
superatmospheric pressures since (1) smaller volumes of gases must
be cooled, (2) the thermal conductivity of compressed gases is
greater and (3) the gases do not have to be refrigerated to such
low temperatures as when superatmospheric pressures are not
employed. For reasons of efficiency and economy, the liquid iron
pentacarbonyl and the gases being treated are maintained at
superatmospheric pressures between about 80 psig and 100 psig.
Lower pressures can be employed, but the process is less efficient;
higher pressures are less economical but they too can be
employed.
Another important aspect of the present invention is the
concentration of nickel carbonyl in liquid iron pentacarbonyl.
Nickel carbonyl boils at 42.5.degree. C. and has a vapor pressure
substantially higher than iron pentacarbonyl at all temperatures
employed in the present invention. Therefore, to insure recovery of
at least about 99percent of the nickel carbonyl in the gases being
scrubbed, fresh or recycled liquid iron pentacarbonyl employed for
scrubbing should not contain more than about 0.01 percent nickel
carbonyl. When liquid pentacarbonyl has dissolved sufficient nickel
carbonyl to have a concentration thereof of up to about 25percent
e.g., about 10percent or even less, the liquid iron pentacarbonyl
is removed and treated to separately recover nickel tetracarbonyl
and iron pentacarbonyl.
Gases containing metal carbonyls and liquid iron pentacarbonyl are
contacted in any manner which provides good gas-liquid contact. For
example, a bath of liquid iron pentacarbonyl can be established and
gases containing metal carbonyls passed therethrough to collect the
metal carbonyls. When the latter procedure is employed,
countercurrent principles are advantageously employed. Fresh or
recycled iron pentacarbonyl containing less than about 0.01 percent
nickel carbonyl is continuously added to the top of the bath and is
recovered from the bottom of the bath containing up to about
25percent nickel carbonyl. In practice, it is advantageous to use a
packed or tray-type column with cold iron pentacarbonyl being
continuously added to the top and the gas to be treated being
precooled and added at the bottom. Provision can be made for
intercoolers between trays to remove the heat released by the
condensation of the metal carbonyls.
When liquid iron pentacarbonyl dissolves sufficient nickel carbonyl
to contain between about 5 and 25percent thereof, the iron
pentacarbonyl is removed from the absorber and is heated to
fractionally distill nickel carbonyl. The solution of nickel and
iron carbonyls is preheated to a temperature between about
10.degree. C. and 25.degree. C. under pressures between about 2 and
10 psig. Nickel carbonyl is distilled in a distillation column or
tower from the preheated solution of carbonyls with a carrier gas,
such as carbon monoxide, at a temperature below the boiling point
of iron pentacarbonyl, e.g., 85.degree. C. The carbonyl solution is
maintained at temperatures between about 0.degree.and 85.degree.
C.; and, more specifically, when a distillation column is employed
so that the carbonyl solution at the top of the column is
substantially pure nickel carbonyl and the bottom of the column is
substantially pure iron pentacarbonyl, the top of the column is
maintained at the lower end of the temperature range and the bottom
of the column is maintained at the higher part of the temperature
range. Again, any multi-stage apparatus and mode of operation which
provides good gas-liquid contact between the carrier gas and the
liquid carbonyls can be employed. Fractional distillation is
conducted in such a manner that the carbonyl vapors and carrier gas
are progressively cooled and passed through carbonyl solutions
progressively enriched in nickel carbonyl so that any gaseous iron
pentacarbonyl is dissolved in the cooler carbonyl solutions
enriched with nickel and the carrier gas vaporizes progressively
more nickel carbonyl by passing through carbonyl solutions enriched
with nickel carbonyl. The distilled nickel carbonyl can be heated
to decompose and provide a purified nickel product. The nickel
carbonyl-depleted liquid iron pentacarbonyl can be cooled and
transferred to the absorber for further use. If the gas being
purified also contains iron pentacarbonyl, some of the nickel
carbonyl-depleted liquid iron pentacarbonyl can be bled off and
decomposed to iron product in order to maintain a constant
circulating load of liquid iron pentacarbonyl.
The present invention is best carried into practice as shown in
FIG. 2. Referring now to FIG. 2 which is a schematic diagram
showing in greater detail operations depicted in FIG. 1,
nickeliferous material is carbonylated at A to produce a mixture of
nickel and iron carbonyls which is collected at B, separated at C
and then thermally decomposed into iron and nickel metals at D and
E.
The gaseous stream of metal carbonyls in carbon monoxide exiting
from apparatus 1 is passed through conduit 2 to heat exchanger 3 to
partially cool the carbonyl-containing stream and to preheat
stripped carbon monoxide before it is reintroduced into apparatus 1
via conduit 4. The partially cooled carbonyl-containing stream is
then passed through pipe 5 to glycol-cooled heat exchanger 6 to
further cool the gaseous stream. Portions of the carbonyls passing
through heat exchangers 3 and 6 are condensed to the liquid state
which condensed carbonyls are sent to carbonyl separation unit 7
via conduit 8.
The cooled carbonyl-containing stream exiting from heat exchanger 6
is then fed to carbonyl absorption unit 9 to strip substantially
all the nickel carbonyl from the carbon monoxide stream. Carbonyl
absorption unit 9 can be either a packed column or a tray-type
column which may have separate coolers below all or some of the
trays to compensate for the heat released by condensation of the
carbonyls. Liquid iron pentacarbonyl at a temperature below about
5.degree. C., e.g., below about 0.degree. C. or even below about
minus 10.degree. C., is fed to the top of carbonyl absorption unit
9 through pipe 10 while the carbon monoxide stream to be treated is
fed to the bottom of the unit whereby countercurrent flow between
the carbon monoxide stream and the liquid iron pentacarbonyl is
established. Additional liquid iron pentacarbonyl containing
dissolved nickel carbonyl from a secondary carbonyl absorption unit
11 is fed via conduit 12 to absorption tower 9 to establish a
reservoir of liquid iron pentacarbonyl having dissolved therein
controlled amounts of nickel carbonyl. Liquid iron pentacarbonyl
collected in a reservoir of carbonyl absorption unit 9 is conveyed
to carbonyl separation unit 7 through pipe 13. The carbon monoxide
stream scrubbed of its nickel carbonyl content and having its iron
carbonyl content lowered to less than about 10 grams of iron per
standard cubic meter, e.g., about 5 grams of iron per standard
cubic meter or lower, is passed through heat exchanger 3 via pipe
14 for recycle to apparatus 1. In heat exchanger 3, the stripped
carbon monoxide is heated and then recompressed before being
reintroduced into apparatus 1 along with makeup carbon monoxide via
pipe 15 from gas storage.
The solution of liquid carbonyls condensed from the gaseous phase
in heat exchangers 3 and 6 and the solution of carbonyls from
carbonyl absorption unit 9 are conveyed to carbonyl separation unit
7 wherein nickel carbonyl is separated from liquid iron
pentacarbonyl. Carbonyl separation unit 7 is essentially a
conventional distillation column and is constructed to provide good
gas-liquid contact. Advantageously, carbonyl separation unit 7 is
either a packed or a tray-type column. To provide efficient
operation of carbonyl separation unit 7, the solution of carbonyls
condensed in heat exchangers 3 and 6 is introduced at a higher
level than is the solution of carbonyls from carbonyl absorption
unit 9 since the solutions of carbonyls from heat exchangers 3 and
6 are more enriched in nickel than is the solution from carbonyl
absorption unit 9. In actual practice, the solutions of carbonyls
from heat exchangers 3 and 6 are passed through conduits 8 to heat
exchanger 16 to cool liquid iron pentacarbonyl which is ultimately
transferred to carbonyl absorption unit 9 and to partially preheat
the solutions of liquid carbonyls prior to distillation in step C.
The nickel-rich carbonyl solution from heat exchanger 16 is then
conducted to carbonyl separation unit 7 via pipe 17 and is
introduced to the carbonyl separation unit at a higher elevation as
schematically shown in FIG. 2. The solution of carbonyls from
carbonyl absorption unit 9 is conducted to carbonyl separation unit
7 via pipes 13 to heat exchanger 18 and pipe 19. Substantially pure
liquid iron pentacarbonyl is withdrawn from carbonyl separation
unit 7 by pipe 20 and is passed through independently heated heat
exchanger 21.
Carbon monoxide from storage is passed through heat exchanger 21
via pipe 22 to produce a gaseous stream of carbon monoxide and
substantially pure iron pentacarbonyl at a temperature of
85.degree. C. which gaseous mixture is reintroduced to carbonyl
separation unit 7 by conduit 23. Unvaporized substantially pure
iron pentacarbonyl is transferred from heat exchanger 21 to heat
exchangers 16 and 18 by pipes 24. Sufficient liquid iron
pentacarbonyl from heat exchangers 16 and 18 is conveyed by conduit
25 to glycol-cooled heat exchanger 26 to be cooled to a temperature
below about 10.degree. C. before being divided into streams in
conduits 27 for recycle to carbonyl absorption unit 9 and via heat
exchanger 28 to secondary carbonyl absorption unit 11. The
remaining liquid iron pentacarbonyl from heat exchangers 16 and 18
is sent to the iron carbonyl decomposing unit 29 via pipe 30.
Carbon monoxide containing very low amounts of iron pentacarbonyl
and containing nickel carbonyl in amounts between about 700 to 800
grams of nickel per standard cubic meter is withdrawn from the
carbonyl separation unit 7 through pipe 31. The carbon monoxide
stream containing nickel carbonyl is conveyed to glycol-cooled heat
exchanger 32 to produce a gas stream containing a controlled amount
of nickel carbonyl, e.g., about 500 grams of nickel per standard
cubic meter, and to condense liquid nickel carbonyl from the
stream. The nickel carbonyl-containing carbon monoxide is split
into two streams 33 and 34. Stream 33 is conveyed to glycol-cooled
heat exchanger 35 to condense the major portion of the nickel
carbonyl while stream 34 is transferred to nickel carbonyl
decomposing unit 36 to be described hereinafter. Nickel carbonyl
from heat exchangers 32 and 35 is transferred to liquid nickel
carbonyl surge tank 37 through pipes 38. Liquid nickel carbonyl is
introduced into the top of carbonyl separation unit 7 via conduit
39 to provide an effluent carbon monoxide stream substantially free
of iron pentacarbonyl.
Carbon monoxide from heat exchanger 35, which contains residual
amounts of nickel carbonyl, after passing through nickel carbonyl
surge tank 37 is transferred by pipe 40 to secondary carbonyl
absorption unit 11 which, like carbonyl absorption unit 9, can be
either a packed or a tray-type column as long as good gas-liquid
contact is achieved and which is fitted with glycol-cooled heat
exchangers 41 and 42 to remove the heat of condensation of gaseous
carbonyl. Carbon monoxide stream 40 containing residual amounts of
nickel carbonyl is introduced to the bottom of secondary absorption
unit 11 while cold iron pentacarbonyl from glycol-cooled heat
exchangers 26 and 28 via pipes 27 and 43 is introduced to the top
of column 11. Scrubbed carbon monoxide from absorption unit 11 is
sent by pipes 44 to gas storage. Nickel carbonyl-containing stream
34 from glycol-cooled heat exchanger 32 is introduced into nickel
carbonyl decomposer 36. Carbon monoxide is removed from decomposer
36 and transferred to gas storage by conduit 45. The nickel product
resulting from the decomposition of nickel carbonyl is removed from
decomposer 36 at outlet 46.
A stream of liquid iron carbonyl, from conduit 30 is conveyed to
the iron carbonyl decomposer unit 29. Carbon monoxide is removed
from the iron carbonyl decomposer 29 and transferred to gas storage
by conduit 47. The iron product resulting from the decomposition of
iron carbonyl is removed from decomposer 29 via outlet 48.
In order to give those skilled in the art a better understanding of
the present invention, the following illustrative examples are
given:
EXAMPLE I
A nickeliferous oxide ore was selectively reduced and then
carbonylated at a temperature of 55.degree. C. and under a pressure
of 2 psig to provide an off-gas of carbon monoxide containing 16.9
percent nickel carbonyl and 20.3 percent iron carbonyl at a
temperature of 25.degree. C. and at a pressure of 2 psig. The
carbon monoxide containing the metal carbonyls was cooled to minus
12.degree. C. and was then transferred to a glycol-cooled packed
tower absorber at 2 psig where nickel carbonyl vapor was scrubbed
out at minus 12.degree. C. by liquid iron pentacarbonyl containing
less than 0.01 percent nickel carbonyl. This treatment lowered the
nickel and iron carbonyl content of the carbon monoxide to 0.03 and
3.2 percent respectively. Before equilibrium between the gas and
liquid carbonyls was reached, liquid iron pentacarbonyl containing
11.6 percent nickel carbonyl, by volume, was withdrawn to
separately recover the carbonyls. The mixed liquid nickel and iron
carbonyls withdrawn from the absorber were delivered, via a heat
exchanger and pump, to a distilation column at a temperature of
28.degree. C. and at a pressure of 5 psig. Carbon monoxide at a
temperature of 60.degree. C. was passed therethrough at a rate such
as to provide an off-gas containing 72.5 percent nickel carbonyl
and only 0.008 percent iron pentacarbonyl at 16.degree. C. and 2
psig. The remaining liquid iron pentacarbonyl was at a temperature
of 82.degree. C. and contained 0.008 percent nickel carbonyl. Part
of the remaining iron carbonyl was decomposed and the remainder was
cooled to minus 12.degree. C. before being returned to the
glycol-cooled absorber.
EXAMPLE II
A nickeliferous oxide ore was selectively reduced and then
carbonylated at a temperature of 65.degree. C. and under a pressure
of 7 atmospheres to provide an off-gas of carbon monoxide
containing 9.8 percent nickel carbonyl and 11.5 percent iron
carbonyl at a temperature of 45.degree. C. and at a pressure of 45
psig. The carbon monoxide containing the metal carbonyls was cooled
to 2.degree. C. and then transferred to a glycol-cooled packed
tower absorber at 44 psig where nickel carbonyl vapor was scrubbed
out at 2.degree. C. by liquid iron pentacarbonyl containing less
than 0.9 percent nickel carbonyl. This treatment lowered the nickel
and iron carbonyl contents of the carbon monoxide to 0.57 and 2.1
percent respectively. Before equilibrium between the gas and liquid
carbonyls was reached, liquid iron pentacarbonyl containing 8.6
percent nickel carbonyl, by volume, was withdrawn to separately
recover the carbonyls. The mixed liquid nickel and iron carbonyls
withdrawn from the absorber were delivered, via a heat exchanger,
to a distillation column at a temperature of 34.degree. C. and at a
pressure of 5 psig. Carbon monoxide at a temperature of 60.degree.
C. was passed therethrough at a rate such as to provide an off-gas
containing 54.9 percent nickel carbonyl and only 0.01 percent iron
pentacarbonyl at 5.degree. C. and 2 psig. The remaining liquid iron
pentacarbonyl was at a temperature of 82.degree. C. and contained
0.84 percent nickel carbonyl. Part of the remaining iron carbonyl
was decomposed and the remainder was cooled to 2.degree. C. before
being returned to the glycol-cooled absorber.
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 scope and purview of the invention and
appended claims.
* * * * *