AU2005234712B1 - Re-activation of de-activated nickel for nickel carbonyl production - Google Patents

Description

P/00/011 Regulation 3.2

AUSTRALIA

Patents Act 1990 COMPLETE SPECIFICATION STANDARD PATENT Invention Title: Re-activation of de-activated nickel for nickel carbonyl production The following statement is a full description of this invention, including the best method of performing it known to us: RE-ACTIVATION OF DE-ACTIVATED NICKEL FOR O NICKEL CARBONYL PRODUCTION z C 5 FIELD OF THE INVENTION C-K, 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 tj 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 191 h 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 0 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 H 2 S, 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 ,004958189 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.

SThere 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 04 hydrochloric acid.

0 10 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 HCI, H 2 S or H 2 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 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; 004958189 collecting said nickel carbonyl gaseous mixture; and

O

,i decomposing said nickel carbonyl in said gaseous mixture to produce said nickel product, and a resultant carbon monoxide gaseous mixture.

s) Preferably, the temperature is selected from 150-200 0 C. Most preferably and, surprisingly, the temperature can be as low as about 150 0

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 0 C, and, preferably, about 50 0

C.

cN 10 The process as hereinabove defined may be modified to produce a deposited ferronickel alloy by incorporating an analogous process with iron carbonyl, Fe(CO)s, 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 0 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.

0 Preferably, the iron activation temperature is selected from 150-200°C, and more Z preferably, about C 5 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 Cnickel 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 t 10 comprising Streating said nickel source with hydrogen at a nickel activation temperature selected from 150-350 0 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 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 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 In order that the invention may be better understood, preferred embodiments will now Sbe described, by way of example only, with reference to the accompanying drawing, 0 wherein:- Z Fig. 1 is a diagrammatic flow diagram of a self-contained, closed-loop process and apparatus, according to the invention.

C DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS C€ With reference to Fig. 1, this shows generally as 10, a closed-loop apparatus t' 10 comprising a reactor 12 linked to decomposition chamber 14 by conduits 16 and 18.

SReactor 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 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.

Reactor 12 is subsequently cooled to about 500 by cooling coils 50. Gases are forced through the apparatus 10 by a blower 52, when required. A plurality of appropriate valves 0 54, are located and utilized where and when necessary. Gas flow is measured by flow meter Z 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 150C by heater 48. Hydrogen is passed into C1 reactor 12 at atmospheric pressure for 2 hours from cylinder 22 through conduits 18 and and passed out of outlet 36 and part of conduit 16 to exit apparatus 10 under direction of C€ valve 38.

t' 10 Reactor 12 is cooled to about 50'C, and the remaining hydrogen displaced by initial Scarbon 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 175-200C 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.

004958189 As used herein, except where the context requires otherwise, the term "comprise" and variations of the term, such as "comprising", "comprises" and "comprised", are not intended to exclude other additives, components, integers or steps.

Reference to any prior art in the specification is not, and should not be taken as, an acknowledgment or any form of suggestion that this prior art forms part of the common general knowledge in Australia or any other jurisdiction or that this prior art could reasonably be expected to be ascertained, understood and regarded as relevant by a person skilled in the art.

Claims (2)

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 0 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. 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 150 0 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. 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 7. A process as defined in any one of claim 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. 004958189 8. A process as defined in claim 7 wherein said iron activation temperature is selected from 150-200 0 C. S 9. A process as defined in claim 8 wherein said iron activation temperature is about 150'C. 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 Cc a metallic nickel source and carbon monoxide and decomposing said nickel carbonyl to a t metal nickel product; said apparatus comprising N 10 a nickel carbonyl carbonylation reactor for containing said nickel source, and having 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 cooling means for cooling said chamber; a nickel carbonyl deposition chamber comprising 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; means for feeding hydrogen to said reactor inlet conduit means; and 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 reaction chamber outlet hydrogen conduit means; (ii) reaction chamber outlet carbon monoxide conduit means; and 004958189 (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 reactor inlet hydrogen conduit means; C (ii) reactor inlet carbon monoxide conduit means; and t (iii) selective inlet valve means separating said inlet hydrogen conduit means from r 'said inlet carbon monoxide conduit means. 14. Apparatus as defined in any one of claims 11 to 13 wherein said means for feeding cNI 10 carbon monoxide to said reactor is in communication with said deposition chamber outlet means and said reactor inlet means. A process for the production of a deposited metallic nickel product from an inactivated, pre-activated metallic nickel source having the steps substantially as hereinbefore described.