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AU612528B2 - Two phase oxime synthesis - Google Patents
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AU612528B2 - Two phase oxime synthesis - Google Patents

Two phase oxime synthesis Download PDF

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Publication number
AU612528B2
AU612528B2 AU44515/89A AU4451589A AU612528B2 AU 612528 B2 AU612528 B2 AU 612528B2 AU 44515/89 A AU44515/89 A AU 44515/89A AU 4451589 A AU4451589 A AU 4451589A AU 612528 B2 AU612528 B2 AU 612528B2
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AU
Australia
Prior art keywords
oxime
ketone
aldehyde
phase
conversion
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
AU44515/89A
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AU4451589A (en
Inventor
Edward Stanley Ferguson
Malcolm John Price
John Graham Reid
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Queensland Nickel Pty Ltd
Original Assignee
MEQ Nickel Pty Ltd
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Filing date
Publication date
Application filed by MEQ Nickel Pty Ltd filed Critical MEQ Nickel Pty Ltd
Priority to AU44515/89A priority Critical patent/AU612528B2/en
Publication of AU4451589A publication Critical patent/AU4451589A/en
Application granted granted Critical
Publication of AU612528B2 publication Critical patent/AU612528B2/en
Assigned to QUEENSLAND NICKEL PTY LTD reassignment QUEENSLAND NICKEL PTY LTD Alteration of Name(s) in Register under S187 Assignors: MEQ NICKEL PTY. LTD.
Anticipated expiration legal-status Critical
Expired legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C249/00Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C249/04Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
    • C07C249/08Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes by reaction of hydroxylamines with carbonyl compounds
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/32Oximes
    • C07C251/34Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
    • C07C251/48Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with the carbon atom of at least one of the oxyimino groups bound to a carbon atom of a six-membered aromatic ring

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

I
17.1:-rllili e~L~ YC r -~ar;deD-L- e i
~Y
6125 2 8
AUSTRALIA
Patents Act COMPLETE SPECIFICATION
(ORIGINAL)
Class Application Number: Lodged: Complete Specification Lodged: Accepted: Published: Priority: Related Art: Int. Class APPLICANT'S REF.: 04/TEC/AVO/MJP/BC Name(s) of Applicant(s): MEQ NICKEL PTY. LTD.
Address(es) of Applicant(s): Bentley Co., 23rd Floor, 127 Creek Street, Brisbane, Queensland 4000, Australia Actual Inventor(s): EDWARD STANLEY FERGUSSON MALCOLM JOHN PRICE JOHN GRAHAM REID Address for Service is: PHILLIPS, ORMONDE FITZPATRICK Patent and Trade Mark Attorneys 367. Collins Street Melbourne, Australia, 3000 Complete Specification for the invention entitled: TWO PHASE OXIME SYNTHESIS The following statement is a full description of this invention, including the best method of performing it known to applicant(s): P 19/11/77 vu 1%s J *r raten ana iraae MarK Attorneys 367 Collins Street Melbourne, Australia P17/2/83 2 TWO PHASE OXIME SYNTHESIS The present invention relates to an organic reagent synthesis procedure which enables organic reagent degradation products to be converted back to the parent compound. More specifically it relates to the conversion of ketones and aldehydes to oximes.
The use of organic reagents for the isolation and purification of metals in the mineral industry is widespread. Oxime type compounds in particular have been used for a number of years in the copper industry and also So in the nickel and cobalt industries.
o 0o o During the course of use of an oxime reagent in an industrial situation it may be subjected to both low and 0 0 high pH solutions. These extremes of pH may be encountered a o 0 during the extraction and stripping cycles of a continuously o.o operating solvent extraction plant. Continued exposure to either high or low pH solutions, particularly at higher than ambient temperatures, will result in degradation or hydrolysis of the oxime resulting in the formation of a 00oooo °oo° ketone or aldehyde product. These ketone and aldehyde o°o°o degradation products accumulate in the organic phase and do not take part in the recovery of metals since they have no o.o0- metal complexing ability.
0The various oxime type reagents used in solvent extraction systems are relatively expensive. Consequently, any procedure to convert the degradation product back to the parent oxime should result in reduced operating costs in the solvent extraction circuit.
The continued accumulation of the organic reagent degradation products in the solvent phase may impair the 1 physical properties of the reagent mixture. As the degradation products cannot extract metals, new oxime reagent has to be added to the organic phase to maintain the design metal loading power of the organic reagent mixture,, This continued addition of reagent concentrate will result in viscosity and density changes which may have a significant deleterious effect on metal transfer kinetics
AP
I
Melbourne, Australia 3 and phase separation.
Commercial solvent extraction plants are designed using both metal transfer kinetic data and phase separation rate information. It is important that the properties of the organic phase are maintained as similar as possible to those of the mixture used for design purposes. Clearly, if metal transfer kinetics are slowed due to the development of a more viscous organic phase because of the accumulation of unwanted degradation products then the throughput for a given design will decrease. The same. end result will occur if the phase separation rate decreases.
oo The present invention enables both physical and chemical properties of the organic reaction mixture to be S controlled and maintained in a condition similar to that used for design purposes, It will be recognised by those skilled in the art of 4 solvent extraction that the above physical problems, associated with the accumulation of degradation products, would be corrected if the specific degradation product could be isolated and removed from the mixture. However, there is S no simple economically feasible procedure for the isolation of closely related organic compounds.
Accordingly, the present invention provides a method 4 fol the conversion of ketones and aldehydes to corresponding oximes wherein a ketone or aldehyde is dissolved in a substantially water immiscible organic solvent and reacted with a hydroxylamine acid addition salt and aqueous ammonia to form the corresponding oxime from the ketone or aldehyde, water, and the ammonium salt of the acid.
The method of the invention is thus an organic reaction procedure that enables "in situ" conversion of the ketone or aldehyde degradation product back to its parent oxime. The reaction may be carried out on batches of organic phase material removed from the main metal extraction system or on a proportion of the organic phase continuously removed from and returned to the main system.
The reaction used in the present invention is specific to the reactants concerned. The only products of the reaction
AP
apart from the desired oxime are ammonium salts and water which contribute to the aqueous phase, not the organic phase.
Oxime regeneration in accordance with the present invention is achieved by reacting a ketone or aldehyde with hydroxylamine in the presence of aqueous ammonia. In the two phase liquid system where the invention is particularly useful, a water-soluble hydroxylamine salt is used to form corresponding ammonium salts which are taken up by solution in the aqueous phase. The oxime product dissolves in the organic phase for re-use in the metal extraction system.
The reaction as applied to commercially available o materials encountered in metal extraction systems is illustrated by the following equation: 0 0 o oo 0 0 Q 00) 0
Y
0000 X C=0 oo c=o .oo0 NH2 OH.HC1 NH OH 0 00 o a -CN
OH
oo000 o0 0 0 0 4 f orooo o+
NH
4 C1 2 ooooo OH 0 C t where X CH 3
(CH
2 7
CH
2
CH
3
(CH
2 1 0
CH
2 or branched isomers Y H, CH 3 The above equation shows phenolic materials because the phenolic hydrogen is the leaving group in the metal chelation reaction. However, the presence of the phenolic hydroxyl group is not essential to the present invention.
~I I;ii_ /_iiij __II_~LIY~_I 5 Similarly, the X groups illustrated are present in the commercially used materials to confer appropriate solvent solubility on the oxime molecule. A hydrophobic side chain will decrease the aqueous phase solubility of the molecule which is desirable to prevent loss of the oxime into the aqueous phase. However, inappropriate side chains, such as longer or more complex alkyl groups, could undesirably affect the viscosity of the organic phase. The nature of the X group, or indeed the presence or absence of this group, is not a critical feature of this invention.
SAgain, the Y groups illustrated are used and chosen o commercially because of their effect on metal extraction o strength and surface properties. In relation to the present 0 a 0 0 invention, the nature of the Y group will affect the oxime O0 O 0o0 O regeneration rate. Thus, for example, ketones in which Y is o phenyl have a slower regeneration rate to the corresponding S oxime than ketones in which Y is methyl. Alkyl groups other than methyl or substituted phenyl groups could be used but with probable slowing of the regeneration rate.
The ketone or aldehyde is dissolved in a substantially ooo 0 0 water immiscible organic solvent before the reaction is o0 0 0 carried out. The solvent used may be mainly aliphatic or 0 0), aromatic hydrocarbon. Kerosene is a preferred solvent.
o,00 Where a particular water immiscible organic solvent is used 000 in a metal extraction process, the same solvent forms the o 0 organic phase in the reaction of the present invention.
0000 S0 The temperature at which the regeneration reaction will be conducted will depend both cn the reagents and their concentration as well as on the choice of batch or continuous reaction. Other factors such as the desired rate of reaction and the extent to which the reaction is to be completed will also influence the choice of reaction temperature.
The use of temperatures over 60 0 C greatly increases the reaction rate and therefore decreases the size of the vessel required to process the reagent to be regenerated.
However, higher temperatures such as 70°C enhance corrosion and allow loss of the ammonia compound of the i. 6 reaction mixture.
If batch regeneration is to be used with a continuous extraction process, the quantity of reagent to be regenerated and the time taken to proceed to the desired level of regeneration will determine the size of the reaction vessel. On the other hand, the regeneration procedure of the invention may be used to treat stored batches of degraded reagent where prompt return to the extraction process is not critical. In this case, vessel size is not as important.
The invention is illustrated by the following ii.n-limiting examples of oxime regeneration.
EXAMPLE 1 o 0 0 0 0 0 00 0 0 0 1 0 *0 0 0 0 0 1 A sample of a commercially available oxime was mixed 0ooo with kerosene and was used continuously in a solvent extraction plant for a period of 5 months. The organic phase containing the oxime when analysed was found to contain 2.8% w/w of a ketone resulting from oxime 000oooo 00 0 degradation.
o°o One hundred ml of the organic phase was contacted with an equal volume of aqueous phase containing 8 g NH 3 and 2.0 g hydroxylamine hydrochloride dissolved therein.
o0-o ooS After stirring the mixture for approximately 20 hours 0 0 at higher than ambient temperature the phases were allowed 00O o0° 0 to separate and on analysis greater than 80 percent of the initial degradation product was found to have been converted to the parent oxime.
In addition when the organic phase recovered from the above "in situ" two phase oxime regeneration was contacted with a suitable solution containing nickel it was found that the increased nickel loading ability of the organic phase was exactly proportional to the percentage of ketone (the degradation product) converted to oxime.
Modifiers are frequently incorporated into the organic phase and these reagents, of which tridecylalcohol is an example, have been shown to have no effect on the above 7 reaction. An "in situ" two phase oxime synthesis in the presence of tridecylalcohol is given in Example No. 2.
EXAMPLE 2 One hundred ml of the organic phase consisting of 2.8% w/w ketone (the degradation product) and 17% w/w tridecylalcohol together with undegraded oxime and kerosene was contacted with an equal volume of aqueous phase containing 8 g of NH 3 and 2 g of hydroxylamine hydrochloride dissolved therein. After stirring the mixture o O 0O o o for approximately 20 hours at 60 C the phases were allowed oocoo to separate. The organic phase was recovered and analysed 0 0 o o wherein it was found that in excess of 80% of the o000 degradation product, 2-hydroxy-5-nonylacetophenone, had been 0000 0 00oo converted to the oxime, 0000 ooo It will be recognised by those familiar with organic reactions that both the quantities of hydroxylamine hydrochloride and ammonia used in examples 1 and 2 above are in excess of that stoichiometrically required to achieve 0000 oo0 0 complete conversion of ketone to oxime. Losser quantities of hydroxylamine reagent reduce the reaction rate and make the reaction less economically attractive.
0 oo0oo In the above described two phase reaction system the ooooon unreacted reagents hydroxylamine hydrochloride and ammonia S 0 0 are not lost as they remain in the aqueous phase. In 0000oooo I 00o o addition any ketone or aldehyde degradation product that is not converted to oxime is also not lost as it remains in the organic phase.
The same aqueous phase with additions of ammonia and hydroxylamine salt as required may be used repeatedly to contact different batches of organic reagent containing degradation product.
Results from this multiple contact system are presented in Example No. 3.
AP
.i 8 EXAMPLE 3 One hundred and fifty ml of the organic phase consisting of 2,8% w/w ketone (the degradation product) and 17% w/w tridecylalcohol together with undegraded oxime and kerosene was contacted with an equal volume of aqueous phase containing 12 g of NH 3 and 20 g of hydroxylamine hydrochloride dissolved therein. After stirring the mixture for approximately 24 hours at 25 C the phases were allowed to separate.
It was found that the ketone concentration in the 0oo 00 organic phase had been reduced to 1% w/w.
oooooo Without changing the composition of the aqueous phase, o o o co a second sample of 150 ml of organic mixture of identical 0000 composition to that described above was added and agitation o00o at 38 C was carried out for 24 hours. Analyses of the 000o ooo organic phase showed that the ketone concentration had been reduced to 0.5% w/w.
The above procedure was repeated (24 hours at 38 C) with a third 150 ml increment of organic reagent mixture and 0000 o00 o again the analysis of the organic phase showed that the 0 00 o0 oo ketone concentration had been reduced to 0.5 w/w.
In addition to the reduction of ketone concentration 0 0oo0oo by conversion to the oxime, it was also found that the ooooo nickel loading capacity of the organic mixture increased.
If either a batch system or a continuous system of "in 0000 0oo 0 situ" two phase oxime synthesis is incorporated into a plant it is necessary to carry out the reaction in as short a time as possible. This will have an important economic bearing on the size of the tankage required.
Experiments were carried out at different temperatures to determine the optimum conditions for the reaction. The results are given in Example 4.
EXAMPLE 4 One hundred and fifty ml of the organic phase consisting of 2.8% w/w ketone (the degradation product) and 17% w/w tridecylalcohol together with undegraded oxime and kerosene was contacted with an equal volume of aqueous phase
AP
i j3 :!i ii 9 containing 12 g of NH 3 and 2 g of hydroxylamine sulphate.
The above phases were agitated for 12 hours at and the experiment was repeated with new phases at 70 0
C.
Analysis of the organic phases from each experiment at 6 and 12 hour intervals gave the following results:- At 70 C, 80% of the ketone had been converted to oxime within 6 hours.
At 60 C, 80% of the ketone had been converted to oxime within 12 hours.
Thus the reaction should proceed at 60-70 C for 6-12 hours to enable acceptable conversion of the degradation product to oxime.
sooeo As the above example illustrates the reaction system o oo will proceed equally well if hydroxylamine sulphate is used 0o 0 instead of hydroxylamine chloride. Where the corrosive 00 ,o nature of the chloride ion may present a problem, it would 0000 000o be preferable to use hydroxylamine sulphate.
The invention as described above can be readily incorporated into the flow streams of operating solvent extraction plants using oxime type metal extracting 0000 oo0 I reagents. The choice of either a continuous or a batch 0 00 o'o 0 o system of "in situ" two phase oxime synthesis will depend primarily on the rate of degradation of the oxime to the 0 o0 oo ketone or aldehyde. The rate of carbonyl conversion back to Coog oxime for a particular reaction system will also be a factor in this choice.
0000 0oo° It will be obvious to those experienced in the commercial utilisation of solvent extraction that a percentage of the oxime reagent always remains complexed with the metal species being extracted. The stripping systems used do not completely remove all of the metal from the organic reagent. The presence of a metal organic complex has no effect on the efficiency of the "in situ" two phase oxime synthesis.

Claims (9)

1. A method for the conversion of ketones and aldehydes to corresponding oximes wherein a ketone or aldehyde is dissolved in a substantially water immiscible organic solvent and reacted with a hydroxylamine acid addition salt and aqueous ammonia to form the corresponding oxime from the ketone or aldehyde, water, and the ammonium salt of the acid.
2. A method as claimed in claim 1 wherein the reaction occurs in a two-phase system, the ammonium salt being held substantially by an aqueous phase and the oxime being held Sa by an organic phase.
3. A method as claimed in claim 1 or claim 2 wherein the I; c ketone or aldehyde is a phenolic ketone or aldehyde. 0
4. A method as claimed in claim 3 wherein the phenol ring has a hydrophobic side chain. °o
5. A method as claimed in claim 4 wherein the hydrophobic o o, side chain is a straight or branched chain alkyl group having from 9 to 12 carbon atoms. S
6. A method as claimed in claim 3 wherein a phenolic alkyl ketone is converted to the corresponding oxime. i 00 0
7. A method as claimed in any one of claims 3 to wherein a phenolic optionally substituted aryl ketone is converted to the corresponding oxime.
8. A method as claimed in any preceding claim wherein the substantially water immiscible organic solvent is kerosene.
9. A method for the solvent extraction of metal values using an oxime extraction agent and wherein the oxime is degraded in use by partial conversion to its corresponding ketone or aldehyde, said method including the conversion of XW~ i- i i- i- i 11 said ketone or aldehyde to its corresponding oxime by a method as claimed in any preceding claim. A method as claimed in claim 9 wherein the conversion reaction is carried out on the extraction agent as removed from the metal extraction procedure. DATED: 8 November, 1989 Coi e a 00P PHILLIPS ORMONDE FITZPATRICK Attorneys for: MEQ NICKEL PTY. LTD. t y 00 CC) C) 0 0' u 0 C O 0 e C)' 0 4 4444 O 04P 04i 4
AU44515/89A 1988-11-21 1989-11-09 Two phase oxime synthesis Expired AU612528B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU44515/89A AU612528B2 (en) 1988-11-21 1989-11-09 Two phase oxime synthesis

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
AUPJ1581 1988-11-21
AUPJ158188 1988-11-21
AU44515/89A AU612528B2 (en) 1988-11-21 1989-11-09 Two phase oxime synthesis

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AU612528B2 true AU612528B2 (en) 1991-07-11

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