CA2525466A1 - Re-activation of de-activated nickel for nickel carbonyl production - Google Patents
Re-activation of de-activated nickel for nickel carbonyl production Download PDFInfo
- Publication number
- CA2525466A1 CA2525466A1 CA002525466A CA2525466A CA2525466A1 CA 2525466 A1 CA2525466 A1 CA 2525466A1 CA 002525466 A CA002525466 A CA 002525466A CA 2525466 A CA2525466 A CA 2525466A CA 2525466 A1 CA2525466 A1 CA 2525466A1
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- Prior art keywords
- nickel
- carbon monoxide
- carbonyl
- hydrogen
- gaseous mixture
- Prior art date
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 127
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 69
- 150000002815 nickel Chemical class 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 230000007420 reactivation Effects 0.000 title claims abstract description 9
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 54
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 54
- 238000000034 method Methods 0.000 claims abstract description 41
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 35
- 239000001257 hydrogen Substances 0.000 claims abstract description 35
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000008246 gaseous mixture Substances 0.000 claims abstract description 30
- 230000004913 activation Effects 0.000 claims abstract description 14
- 230000006315 carbonylation Effects 0.000 claims abstract description 12
- 238000005810 carbonylation reaction Methods 0.000 claims abstract description 12
- 230000000694 effects Effects 0.000 claims abstract description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 229910052742 iron Inorganic materials 0.000 claims description 11
- 230000008021 deposition Effects 0.000 claims description 9
- 229940087654 iron carbonyl Drugs 0.000 claims description 9
- 150000002505 iron Chemical class 0.000 claims description 6
- 229910000863 Ferronickel Inorganic materials 0.000 claims description 5
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- 238000004891 communication Methods 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 abstract description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 2
- 238000001994 activation Methods 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000005137 deposition process Methods 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- 229910017147 Fe(CO)5 Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000010960 commercial process Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/06—Refining
- C22B23/065—Refining carbonyl methods
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Vapour Deposition (AREA)
Abstract
A process and apparatus for the production of a deposited metallic nickel product from an inactivated, pre-activated metallic nickel source, the process including treating the nickel source with hydrogen at a nickel activation temperature selected from 150-350°C, preferably, 150°C to effect re-activation of the nickel source;
treating the re-activated nickel with carbonylation carbon monoxide to produce a gaseous mixture containing nickel carbonyl and carbon monoxide; collecting the nickel carbonyl gaseous mixture;
and decomposing the nickel carbonyl in the gaseous mixture to produce the nickel product, and a resultant carbon monoxide gaseous mixture which is most preferably recycled back to treat the nickel source. The process provides efficacious re-activation of the de-activated nickel without the need for hydrogen sulfide or chloride anion.
treating the re-activated nickel with carbonylation carbon monoxide to produce a gaseous mixture containing nickel carbonyl and carbon monoxide; collecting the nickel carbonyl gaseous mixture;
and decomposing the nickel carbonyl in the gaseous mixture to produce the nickel product, and a resultant carbon monoxide gaseous mixture which is most preferably recycled back to treat the nickel source. The process provides efficacious re-activation of the de-activated nickel without the need for hydrogen sulfide or chloride anion.
Description
RE-ACTNATION OF DE-ACTIVATED NICKEL FOR
NICKEL CARBONYL PRODUCTION
FIELD OF THE INVENTION
This invention relates to a process for the re-activation of de-activated metallic nickel in the production of nickel carbonyl and subsequent deposition of metallic nickel product, therefrom; and apparatus of use in said process. The process, optionally, includes the 10 analogous process for the re-activation of de-activated iron to produce a ferronickel product.
BACKGROUND OF THE INVENTION
Nickel carbonyl, Ni(CO)4, was first produced by the reaction of metallic nickel with carbon monoxide by Mond in the early part of the 19th century. Today, one of the major industrial processes for making metallic nickel is based on the production of Ni(CO)4 and subsequent thermal decomposition thereof to Ni and CO. One known commercial process operates at about 180 C and a CO pressure of about 70 atm. It is known that the CO pressure may be reduced when the reactant nickel is catalytically activated.
Activation of the metal has been observed in the presence of mercury, sulfur in the form of H2S, hydrogen or carbon. It has been suggested that the high initial rate of formation of Ni(CO)4 and the subsequent decline to a steady state value is the result of a rapid decrease in the number of activated reaction sites which are produced upon heat treatment of the sample. A study of surface changes during carbonyl synthesis suggests that the maximum rate is associated with fundamental changes in the defect structure. All of the above methods use catalytic activation of nickel in the presence of CO.
However, it can be readily appreciated that processes that at atmospheric pressure can produce nickel, particularly, activated nickel for subsequent reaction with CO
at atmospheric pressure would provide significant capital and operating cost advantages.
Further, it can also be appreciated that processes that enable Ni(CO)4 to be manufactured at a sufficient rate as to obviate the need for storage in order to build up a sufficient supply for practical, efficient use in a subsequent nickel deposition process, would also offer significant capital and operating cost savings. To-date, in commercial operations rate limitations on the production of Ni(CO)4 require such storage facilities and operations.
There is, thus, a desire for an improved method of Ni(CO)4 production which is operable at atmospheric pressure and which is of a sufficient rate as to negate the need for storage of the Ni(CO)4 prior to use in a subsequent decomposition and/or deposition process.
Canadian Patent No. 2,461,624, published 27 September 2004 to Chemical Vapour Metal Refining Inc., describes a process for producing activated nickel for subsequent carbonylation at an efficacious rate using hydrogen in the presence of a chloride anion, preferably gaseous hydrochloric acid.
One of the disadvantages of activated nickel is that it is readily de-activated in the presence of air and moisture, and, therefore, should be utilized in the manufacture of nickel carbonyl as soon as practicable. However, de-activation of freshly prepared activated nickel inevitably occurs during transfer or storage unless stringent precautions are taken. Thus, there is a need for a means of readily re-activating de-activated nickel to a sufficient degree to facilitate the production of nickel carbonyl therefrom.
Although it is possible to use the aforesaid nickel activation processes according to the prior art, namely, gaseous HC1, H2S or H2/CI-, such entities do not also provide ready and convenient methods of re-activation.
Accordingly, there is a need for an improved process for re-activating nickel which has been allowed to become de-activated.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide an improved, convenient and efficacious process for re-activating deactivated nickel.
It is a further object to, preferably, provide said process as part of a nickel carbonyl production and deposition process for the production of pure nickel product.
It is a further object to provide an aforesaid process incorporating a carbon monoxide closed-loop arrangement.
It is a further object to provide said aforesaid processes modified to provide a ferronickel material .
NICKEL CARBONYL PRODUCTION
FIELD OF THE INVENTION
This invention relates to a process for the re-activation of de-activated metallic nickel in the production of nickel carbonyl and subsequent deposition of metallic nickel product, therefrom; and apparatus of use in said process. The process, optionally, includes the 10 analogous process for the re-activation of de-activated iron to produce a ferronickel product.
BACKGROUND OF THE INVENTION
Nickel carbonyl, Ni(CO)4, was first produced by the reaction of metallic nickel with carbon monoxide by Mond in the early part of the 19th century. Today, one of the major industrial processes for making metallic nickel is based on the production of Ni(CO)4 and subsequent thermal decomposition thereof to Ni and CO. One known commercial process operates at about 180 C and a CO pressure of about 70 atm. It is known that the CO pressure may be reduced when the reactant nickel is catalytically activated.
Activation of the metal has been observed in the presence of mercury, sulfur in the form of H2S, hydrogen or carbon. It has been suggested that the high initial rate of formation of Ni(CO)4 and the subsequent decline to a steady state value is the result of a rapid decrease in the number of activated reaction sites which are produced upon heat treatment of the sample. A study of surface changes during carbonyl synthesis suggests that the maximum rate is associated with fundamental changes in the defect structure. All of the above methods use catalytic activation of nickel in the presence of CO.
However, it can be readily appreciated that processes that at atmospheric pressure can produce nickel, particularly, activated nickel for subsequent reaction with CO
at atmospheric pressure would provide significant capital and operating cost advantages.
Further, it can also be appreciated that processes that enable Ni(CO)4 to be manufactured at a sufficient rate as to obviate the need for storage in order to build up a sufficient supply for practical, efficient use in a subsequent nickel deposition process, would also offer significant capital and operating cost savings. To-date, in commercial operations rate limitations on the production of Ni(CO)4 require such storage facilities and operations.
There is, thus, a desire for an improved method of Ni(CO)4 production which is operable at atmospheric pressure and which is of a sufficient rate as to negate the need for storage of the Ni(CO)4 prior to use in a subsequent decomposition and/or deposition process.
Canadian Patent No. 2,461,624, published 27 September 2004 to Chemical Vapour Metal Refining Inc., describes a process for producing activated nickel for subsequent carbonylation at an efficacious rate using hydrogen in the presence of a chloride anion, preferably gaseous hydrochloric acid.
One of the disadvantages of activated nickel is that it is readily de-activated in the presence of air and moisture, and, therefore, should be utilized in the manufacture of nickel carbonyl as soon as practicable. However, de-activation of freshly prepared activated nickel inevitably occurs during transfer or storage unless stringent precautions are taken. Thus, there is a need for a means of readily re-activating de-activated nickel to a sufficient degree to facilitate the production of nickel carbonyl therefrom.
Although it is possible to use the aforesaid nickel activation processes according to the prior art, namely, gaseous HC1, H2S or H2/CI-, such entities do not also provide ready and convenient methods of re-activation.
Accordingly, there is a need for an improved process for re-activating nickel which has been allowed to become de-activated.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide an improved, convenient and efficacious process for re-activating deactivated nickel.
It is a further object to, preferably, provide said process as part of a nickel carbonyl production and deposition process for the production of pure nickel product.
It is a further object to provide an aforesaid process incorporating a carbon monoxide closed-loop arrangement.
It is a further object to provide said aforesaid processes modified to provide a ferronickel material .
2 It is a further object of the invention to provide apparatus of use in the aforesaid processes.
We have surprisingly discovered that hydrogen can efficaciously re-activate de-activated nickel to enable the resultant activated nickel to react with carbon monoxide to produce nickel carbonyl at a satisfactory rate.
Accordingly, in one aspect the invention provide a process for the production of a deposited metallic nickel product from an inactivated, pre-activated metallic nickel source, said process comprising treating said nickel source with hydrogen at a nickel activation temperature selected from 150-350 C to effect re-activation of said nickel source;
treating said re-activated nickel with carbonylation carbon monoxide to produce a gaseous mixture comprising nickel carbonyl and carbon monoxide;
collecting said nickel carbonyl gaseous mixture; and decomposing said nickel carbonyl in said gaseous mixture to produce said nickel product, and a resultant carbon monoxide gaseous mixture.
Preferably, the temperature is selected from 150-200 C. Most preferably and, surprisingly, the temperature can be as low as about 150 C.
The resultant carbon monoxide gaseous mixture is, preferably, recycled to treat the nickel source to constitute in whole or in part the carbonylation carbon monoxide.
The subsequent carbonylation temperature is selected from 40-80 C, and, preferably, about 50 C.
The process as hereinabove defined may be modified to produce a deposited ferronickel alloy by incorporating an analogous process with iron carbonyl, Fe(CO)5, preferably, but not limited to Fe(CO)5 made from re-activated, de-activated iron.
Accordingly, in a further aspect, the invention provides a process as hereinabove defined further comprising treating a metallic iron source with hydrogen at an iron activation temperature selected from 150-350 C to produce activated iron;
treating said activated iron with carbonylation carbon monoxide to produce a gaseous mixture comprising iron carbonyl and carbon monoxide;
collecting said iron carbonyl gaseous mixture;
combining said nickel carbonyl gaseous mixture and said iron carbonyl gaseous mixture to produce a combiried gaseous mixture; and
We have surprisingly discovered that hydrogen can efficaciously re-activate de-activated nickel to enable the resultant activated nickel to react with carbon monoxide to produce nickel carbonyl at a satisfactory rate.
Accordingly, in one aspect the invention provide a process for the production of a deposited metallic nickel product from an inactivated, pre-activated metallic nickel source, said process comprising treating said nickel source with hydrogen at a nickel activation temperature selected from 150-350 C to effect re-activation of said nickel source;
treating said re-activated nickel with carbonylation carbon monoxide to produce a gaseous mixture comprising nickel carbonyl and carbon monoxide;
collecting said nickel carbonyl gaseous mixture; and decomposing said nickel carbonyl in said gaseous mixture to produce said nickel product, and a resultant carbon monoxide gaseous mixture.
Preferably, the temperature is selected from 150-200 C. Most preferably and, surprisingly, the temperature can be as low as about 150 C.
The resultant carbon monoxide gaseous mixture is, preferably, recycled to treat the nickel source to constitute in whole or in part the carbonylation carbon monoxide.
The subsequent carbonylation temperature is selected from 40-80 C, and, preferably, about 50 C.
The process as hereinabove defined may be modified to produce a deposited ferronickel alloy by incorporating an analogous process with iron carbonyl, Fe(CO)5, preferably, but not limited to Fe(CO)5 made from re-activated, de-activated iron.
Accordingly, in a further aspect, the invention provides a process as hereinabove defined further comprising treating a metallic iron source with hydrogen at an iron activation temperature selected from 150-350 C to produce activated iron;
treating said activated iron with carbonylation carbon monoxide to produce a gaseous mixture comprising iron carbonyl and carbon monoxide;
collecting said iron carbonyl gaseous mixture;
combining said nickel carbonyl gaseous mixture and said iron carbonyl gaseous mixture to produce a combiried gaseous mixture; and
3 decomposing said nickel carbonyl and said iron carbonyl in said combined mixture to produce a ferronickel product and a resultant carbon monoxide combined gaseous mixture.
Preferably, the iron activation temperature is selected from 150-200 C, and more preferably, about 50 C..
Most preferably, the invention provides a process, as hereinabove defined, wherein the metallic iron source is in admixture with the metallic nickel source when the metallic nickel source and the metallic iron source are treated with the hydrogen.
In a further aspect, the invention provides a process for the production of a deposited metallic nickel product from an inactivated, pre-activated metallic nickel source, said process 10 comprising treating said nickel source with hydrogen at a nickel activation temperature selected from 150-350 C to effect re-activation of said nickel source;
treating said re-activated nickel with carbonylation carbon monoxide to produce a gaseous mixture comprising nickel carbonyl and carbon monoxide;
collecting said nickel carbonyl gaseous mixture; and decomposing said nickel carbonyl in said gaseous mixture to produce said nickel product, and a resultant carbon monoxide gaseous mixture.
Preferably, the reaction chamber outlet conduit means comprises (i) reaction chamber outlet hydrogen conduit means;
(ii) reaction chamber outlet carbon monoxide conduit means; and (iii) hydrogen selective outlet valve means separating said outlet hydrogen conduit means from said outlet carbon monoxide conduit means.
More preferably, the reactor inlet conduit means comprises (i) reactor inlet hydrogen conduit means;
(ii) reactor inlet carbon monoxide conduit means; and (iii) selective inlet valve means separating said inlet hydrogen conduit means from said inlet carbon monoxide conduit means.
Further, preferably the means for feeding carbon monoxide to the reactor is in communication with the deposition chamber outlet means and the reactor inlet means.
BRIEF DESCRIPTION OF THE DRAWINGS
Preferably, the iron activation temperature is selected from 150-200 C, and more preferably, about 50 C..
Most preferably, the invention provides a process, as hereinabove defined, wherein the metallic iron source is in admixture with the metallic nickel source when the metallic nickel source and the metallic iron source are treated with the hydrogen.
In a further aspect, the invention provides a process for the production of a deposited metallic nickel product from an inactivated, pre-activated metallic nickel source, said process 10 comprising treating said nickel source with hydrogen at a nickel activation temperature selected from 150-350 C to effect re-activation of said nickel source;
treating said re-activated nickel with carbonylation carbon monoxide to produce a gaseous mixture comprising nickel carbonyl and carbon monoxide;
collecting said nickel carbonyl gaseous mixture; and decomposing said nickel carbonyl in said gaseous mixture to produce said nickel product, and a resultant carbon monoxide gaseous mixture.
Preferably, the reaction chamber outlet conduit means comprises (i) reaction chamber outlet hydrogen conduit means;
(ii) reaction chamber outlet carbon monoxide conduit means; and (iii) hydrogen selective outlet valve means separating said outlet hydrogen conduit means from said outlet carbon monoxide conduit means.
More preferably, the reactor inlet conduit means comprises (i) reactor inlet hydrogen conduit means;
(ii) reactor inlet carbon monoxide conduit means; and (iii) selective inlet valve means separating said inlet hydrogen conduit means from said inlet carbon monoxide conduit means.
Further, preferably the means for feeding carbon monoxide to the reactor is in communication with the deposition chamber outlet means and the reactor inlet means.
BRIEF DESCRIPTION OF THE DRAWINGS
4 In order that the invention may be better understood, preferred embodiments will now be described, by way of example only, with reference to the accompanying drawing, wherein:-Fig. I is a diagrammatic flow diagram of a self-contained, closed-loop process and apparatus, according to the invention.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
With reference to Fig. 1, this shows generally as 10, a closed-loop apparatus comprising a reactor 12 linked to decomposition chamber 14 by conduits 16 and 18.
Reactor 12 has an inlet conduit 20 whereby hydrogen and carbon monoxide are alternatively fed, when desired, into reactor 12. Conduit 18 has connectors to hydrogen source 22 and initial carbon monoxide source 24 for passage to inlet conduit 20 through conduits 26,28 respectively when required as hereinafter described. Conduit 18 has a selector valve 30 and an initial source valve 32 for controlling the passage of carbon monoxide from chamber 14 or initial source 24 when desired, to inlet conduit 20. Control of hydrogen to inlet conduit 20, via conduit 18, for the initial activation reaction is by selection valve 34.
Reactor 12 has outlet conduit 36 through which, initially, exits spent hydrogen, to part of conduit 16, and, alternatively, spent carbon monoxide/nickel carbonyl gaseous mixture through the full length of conduit 16 to deposition chamber 14.
Conduit 18 has a selection valve 38 which directs the flow of hydrogen or carbon monoxide/nickel carbonyl, alternatively, when desired to the respective locations. The hydrogen may be collected and re-used or burnt.
Trace amounts of gaseous nickel carbonyl in apparatus 10 at the termination of the process, may be subsequently decomposed in decomposition tube 40 and carbon monoxide recycled, through conduit 42, when desired. Unwanted carbon monoxide of system 10 can be sent for incineration through conduit 44.
In operation, bubble-bed reactor 12 is filled with de-activated nickel 46 and with hydrogen from source 22, via conduits 26, 18 and 20 when valve 34 is open, and valves 30 and 32 closed. Valve 38 is open in the mode to allow hydrogen to continuously pass through and exit from system 10. The temperature of reactor 12 is maintained at about 150 C by heater 48, for about 2 hours.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
With reference to Fig. 1, this shows generally as 10, a closed-loop apparatus comprising a reactor 12 linked to decomposition chamber 14 by conduits 16 and 18.
Reactor 12 has an inlet conduit 20 whereby hydrogen and carbon monoxide are alternatively fed, when desired, into reactor 12. Conduit 18 has connectors to hydrogen source 22 and initial carbon monoxide source 24 for passage to inlet conduit 20 through conduits 26,28 respectively when required as hereinafter described. Conduit 18 has a selector valve 30 and an initial source valve 32 for controlling the passage of carbon monoxide from chamber 14 or initial source 24 when desired, to inlet conduit 20. Control of hydrogen to inlet conduit 20, via conduit 18, for the initial activation reaction is by selection valve 34.
Reactor 12 has outlet conduit 36 through which, initially, exits spent hydrogen, to part of conduit 16, and, alternatively, spent carbon monoxide/nickel carbonyl gaseous mixture through the full length of conduit 16 to deposition chamber 14.
Conduit 18 has a selection valve 38 which directs the flow of hydrogen or carbon monoxide/nickel carbonyl, alternatively, when desired to the respective locations. The hydrogen may be collected and re-used or burnt.
Trace amounts of gaseous nickel carbonyl in apparatus 10 at the termination of the process, may be subsequently decomposed in decomposition tube 40 and carbon monoxide recycled, through conduit 42, when desired. Unwanted carbon monoxide of system 10 can be sent for incineration through conduit 44.
In operation, bubble-bed reactor 12 is filled with de-activated nickel 46 and with hydrogen from source 22, via conduits 26, 18 and 20 when valve 34 is open, and valves 30 and 32 closed. Valve 38 is open in the mode to allow hydrogen to continuously pass through and exit from system 10. The temperature of reactor 12 is maintained at about 150 C by heater 48, for about 2 hours.
5 Reactor 12 is subsequently cooled to about 50 by cooling coils 50. Gases are forced through the apparatus 10 by a blower 52, when required. A plurality of appropriate valves 54, are located and utilized where and when necessary. Gas flow is measured by flow meter 56.
In operation, de-activated nickel 46 is placed in reactor 12, which is purged with argon inert gas from cylinder 58 and heated to 150 C by heater 48. Hydrogen is passed into reactor 12 at atmospheric pressure for 2 hours from cylinder 22 through conduits 18 and 20, and passed out of outlet 36 and part of conduit 16 to exit apparatus 10 under direction of valve 38.
Reactor 12 is cooled to about 50 C, and the remaining hydrogen displaced by initial carbon monoxide stream from cylinder 24 fed through valve 32 conduits 18, 20 and its flow rate measured by meter 56.
Nickel carbonyl is formed from the hydrogen re-activated nickel in reactor 12 and carried to deposition chamber 14 with the excess carbon monoxide through conduit 36 and 16 after selection valve 38 and regular valves 54 suitably opened or closed as appropriate.
Chamber 14 contains a substrate 60 at a temperature of about 175-200 C which effects deposition of nickel by the thermal decomposition of the nickel carbonyl, as known in the art, to produce a nickel mold. The carbon monoxide produced by the thermal decomposition and that carried through conduit 18 to chamber 16 is now recycled back to reactor 12 under the direction of the plurality of valves suitably opened/closed.
The carbon monoxide recycle process to and from reactor 12 and chamber 14 is continued in this closed-loop arrangement until the desired amount of nickel carbonyl has been formed and decomposed.
Upon termination of the operation, the apparatus is purged with argon, trace amounts of nickel carbonyl is decomposed in copper tube 40 at about 200 C and unwanted carbon monoxide is incinerated. Finally, the nickel mold is removed from chamber 14.
Although this disclosure has described and illustrated certain preferred embodiments of the invention, it is to be understood that the invention is not restricted to those particular embodiments. Rather, the invention includes all embodiments which are functional or mechanical equivalence of the specific embodiments and features that have been described and illustrated.
In operation, de-activated nickel 46 is placed in reactor 12, which is purged with argon inert gas from cylinder 58 and heated to 150 C by heater 48. Hydrogen is passed into reactor 12 at atmospheric pressure for 2 hours from cylinder 22 through conduits 18 and 20, and passed out of outlet 36 and part of conduit 16 to exit apparatus 10 under direction of valve 38.
Reactor 12 is cooled to about 50 C, and the remaining hydrogen displaced by initial carbon monoxide stream from cylinder 24 fed through valve 32 conduits 18, 20 and its flow rate measured by meter 56.
Nickel carbonyl is formed from the hydrogen re-activated nickel in reactor 12 and carried to deposition chamber 14 with the excess carbon monoxide through conduit 36 and 16 after selection valve 38 and regular valves 54 suitably opened or closed as appropriate.
Chamber 14 contains a substrate 60 at a temperature of about 175-200 C which effects deposition of nickel by the thermal decomposition of the nickel carbonyl, as known in the art, to produce a nickel mold. The carbon monoxide produced by the thermal decomposition and that carried through conduit 18 to chamber 16 is now recycled back to reactor 12 under the direction of the plurality of valves suitably opened/closed.
The carbon monoxide recycle process to and from reactor 12 and chamber 14 is continued in this closed-loop arrangement until the desired amount of nickel carbonyl has been formed and decomposed.
Upon termination of the operation, the apparatus is purged with argon, trace amounts of nickel carbonyl is decomposed in copper tube 40 at about 200 C and unwanted carbon monoxide is incinerated. Finally, the nickel mold is removed from chamber 14.
Although this disclosure has described and illustrated certain preferred embodiments of the invention, it is to be understood that the invention is not restricted to those particular embodiments. Rather, the invention includes all embodiments which are functional or mechanical equivalence of the specific embodiments and features that have been described and illustrated.
6
Claims (14)
1. A process for the production of a deposited metallic nickel product from an inactivated, pre-activated metallic nickel source, said process comprising treating said nickel source with hydrogen at a nickel activation temperature selected from 150-350°C to effect re-activation of said nickel source;
treating said re-activated nickel with carbonylation carbon monoxide to produce a gaseous mixture comprising nickel carbonyl and carbon monoxide;
collecting said nickel carbonyl gaseous mixture; and decomposing said nickel carbonyl in said gaseous mixture to produce said nickel product, and a resultant carbon monoxide gaseous mixture.
treating said re-activated nickel with carbonylation carbon monoxide to produce a gaseous mixture comprising nickel carbonyl and carbon monoxide;
collecting said nickel carbonyl gaseous mixture; and decomposing said nickel carbonyl in said gaseous mixture to produce said nickel product, and a resultant carbon monoxide gaseous mixture.
2. A process as defined in claim 1 wherein said nickel activation temperature is selected from 150-200°C.
3. A process as defined in claim 2 wherein said nickel activation temperature is about 50°C.
4. A process as defined in any one of claims 1-3 wherein said resultant carbon monoxide mixture is recycled to treat said nickel source to constitute in whole or in part said carbonylation carbon monoxide.
5. A process as defined in any one of claims 1 to 4 wherein said re-activated nickel is treated with said carbonylation carbon monoxide at a temperature selected from 40-80°C.
6. A process as defined in claim 5 wherein said temperature is about 50°C.
7. A process as defined in any one of claims 1 to 6 further comprising treating a metallic iron source with hydrogen at an iron activation temperature selected from 150-350°C to produce activated iron;
treating said activated iron with carbonylation carbon monoxide to produce a gaseous mixture comprising iron carbonyl and carbon monoxide;
collecting said iron carbonyl gaseous mixture;
combining said nickel carbonyl gaseous mixture and said iron carbonyl gaseous mixture to produce a combined gaseous mixture; and decomposing said nickel carbonyl and said iron carbonyl in said combined mixture to produce a ferronickel product and a resultant carbon monoxide combined gaseous mixture.
treating said activated iron with carbonylation carbon monoxide to produce a gaseous mixture comprising iron carbonyl and carbon monoxide;
collecting said iron carbonyl gaseous mixture;
combining said nickel carbonyl gaseous mixture and said iron carbonyl gaseous mixture to produce a combined gaseous mixture; and decomposing said nickel carbonyl and said iron carbonyl in said combined mixture to produce a ferronickel product and a resultant carbon monoxide combined gaseous mixture.
8. A process as defined in claim 7 wherein said iron activation temperature is selected from 150-200°C.
9. A process as defined in claim 8 wherein said iron activation temperature is about 50°C.
10. A process as defined in any one of claims 7 to 9 wherein said metallic iron source is in admixture with said metallic nickel source when said metallic nickel source and said metallic iron source are treated with said hydrogen.
11. A combined carbon monoxide closed-loop apparatus for producing nickel carbonyl from a metallic nickel source and carbon monoxide and decomposing said nickel carbonyl to a metal nickel product; said apparatus comprising (a) a nickel carbonyl carbonylation reactor for containing said nickel source, and having (i) a reaction chamber;
(ii) inlet conduit means for feeding an input gas selected from hydrogen and carbon monoxide to said chamber;
(iii) outlet conduit means for collecting an exit gas selected from hydrogen, carbon monoxide, nickel carbonyl and mixtures thereof from said chamber;
(iv) heating means for heating said chamber; and (v) cooling means for cooling said chamber;
(b) a nickel carbonyl deposition chamber comprising (i) deposition chamber inlet means in communication with said reactor conduit outlet means;
(ii) deposition chamber outlet means in communication with said reactor conduit inlet means;
(c) means for feeding hydrogen to said reactor inlet conduit means; and (d) means for feeding carbon monoxide to said reactor inlet conduit means.
(ii) inlet conduit means for feeding an input gas selected from hydrogen and carbon monoxide to said chamber;
(iii) outlet conduit means for collecting an exit gas selected from hydrogen, carbon monoxide, nickel carbonyl and mixtures thereof from said chamber;
(iv) heating means for heating said chamber; and (v) cooling means for cooling said chamber;
(b) a nickel carbonyl deposition chamber comprising (i) deposition chamber inlet means in communication with said reactor conduit outlet means;
(ii) deposition chamber outlet means in communication with said reactor conduit inlet means;
(c) means for feeding hydrogen to said reactor inlet conduit means; and (d) means for feeding carbon monoxide to said reactor inlet conduit means.
12. Apparatus as defined in claim 11 wherein said reaction chamber outlet conduit means comprises (i) reaction chamber outlet hydrogen conduit means;
(ii) reaction chamber outlet carbon monoxide conduit means; and (iii) hydrogen selective outlet valve means separating said outlet hydrogen conduit means from said outlet carbon monoxide conduit means.
(ii) reaction chamber outlet carbon monoxide conduit means; and (iii) hydrogen selective outlet valve means separating said outlet hydrogen conduit means from said outlet carbon monoxide conduit means.
13. Apparatus as defined in claim 11 or claim 12 wherein said reactor inlet conduit means comprises (i) reactor inlet hydrogen conduit means;
(ii) reactor inlet carbon monoxide conduit means; and (iii) selective inlet valve means separating said inlet hydrogen conduit means from said inlet carbon monoxide conduit means.
(ii) reactor inlet carbon monoxide conduit means; and (iii) selective inlet valve means separating said inlet hydrogen conduit means from said inlet carbon monoxide conduit means.
14. Apparatus as defined in any one of claims 11 to 13 wherein said means for feeding carbon monoxide to said reactor is in communication with said deposition chamber outlet means and said reactor inlet means.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA002525466A CA2525466A1 (en) | 2005-11-07 | 2005-11-07 | Re-activation of de-activated nickel for nickel carbonyl production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA002525466A CA2525466A1 (en) | 2005-11-07 | 2005-11-07 | Re-activation of de-activated nickel for nickel carbonyl production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2525466A1 true CA2525466A1 (en) | 2007-05-07 |
Family
ID=38024453
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002525466A Abandoned CA2525466A1 (en) | 2005-11-07 | 2005-11-07 | Re-activation of de-activated nickel for nickel carbonyl production |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA2525466A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7776129B2 (en) | 2007-04-24 | 2010-08-17 | Chemical Vapour Metal Refining Inc. | Apparatus and process for making high purity nickel |
| GB2449280B (en) * | 2007-05-17 | 2012-12-19 | Cvmr Corp | Apparatus and process for making high purity nickel |
| CN107815556A (en) * | 2017-11-17 | 2018-03-20 | 金川集团股份有限公司 | A kind of activation device and method of water quenching nickel |
-
2005
- 2005-11-07 CA CA002525466A patent/CA2525466A1/en not_active Abandoned
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7776129B2 (en) | 2007-04-24 | 2010-08-17 | Chemical Vapour Metal Refining Inc. | Apparatus and process for making high purity nickel |
| US8852315B2 (en) | 2007-04-24 | 2014-10-07 | Cvmr Corporation | Apparatus and process for making high purity nickel |
| GB2449280B (en) * | 2007-05-17 | 2012-12-19 | Cvmr Corp | Apparatus and process for making high purity nickel |
| CN107815556A (en) * | 2017-11-17 | 2018-03-20 | 金川集团股份有限公司 | A kind of activation device and method of water quenching nickel |
| CN107815556B (en) * | 2017-11-17 | 2019-11-08 | 金川集团股份有限公司 | Activation device and method for water-quenched nickel |
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