CA1040866A - Refining of chloride salts - Google Patents
Refining of chloride saltsInfo
- Publication number
- CA1040866A CA1040866A CA224,068A CA224068A CA1040866A CA 1040866 A CA1040866 A CA 1040866A CA 224068 A CA224068 A CA 224068A CA 1040866 A CA1040866 A CA 1040866A
- Authority
- CA
- Canada
- Prior art keywords
- salt
- impurity
- organic liquid
- loaded
- chlorides
- 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
Links
- 238000007670 refining Methods 0.000 title claims description 10
- 150000003841 chloride salts Chemical class 0.000 title abstract description 3
- 239000012535 impurity Substances 0.000 claims abstract description 35
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 30
- 230000008569 process Effects 0.000 claims abstract description 26
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 17
- 239000012634 fragment Substances 0.000 claims abstract description 9
- 150000003839 salts Chemical class 0.000 claims description 64
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 32
- 239000010949 copper Substances 0.000 claims description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 16
- 229910017052 cobalt Inorganic materials 0.000 claims description 16
- 239000010941 cobalt Substances 0.000 claims description 16
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 16
- 229910052802 copper Inorganic materials 0.000 claims description 16
- 229910052742 iron Inorganic materials 0.000 claims description 16
- 239000003153 chemical reaction reagent Substances 0.000 claims description 14
- 150000001805 chlorine compounds Chemical class 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 238000002386 leaching Methods 0.000 claims description 11
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 10
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 10
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 10
- 229910001510 metal chloride Inorganic materials 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 5
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052785 arsenic Inorganic materials 0.000 claims description 4
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052797 bismuth Inorganic materials 0.000 claims description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 4
- 229910052793 cadmium Inorganic materials 0.000 claims description 4
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000011133 lead Substances 0.000 claims description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 4
- 150000003141 primary amines Chemical class 0.000 claims description 4
- 239000011135 tin Substances 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- 150000003335 secondary amines Chemical class 0.000 claims description 3
- -1 tertiary amine hydrochlorides Chemical class 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 230000006872 improvement Effects 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 claims 2
- 150000001298 alcohols Chemical class 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 229930195733 hydrocarbon Natural products 0.000 claims 1
- 150000002430 hydrocarbons Chemical class 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 6
- 238000005660 chlorination reaction Methods 0.000 abstract description 3
- 235000002639 sodium chloride Nutrition 0.000 description 61
- 239000000203 mixture Substances 0.000 description 14
- 238000000605 extraction Methods 0.000 description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 10
- 238000000746 purification Methods 0.000 description 6
- 239000011780 sodium chloride Substances 0.000 description 6
- 230000000536 complexating effect Effects 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000007792 addition Methods 0.000 description 4
- 239000008346 aqueous phase Substances 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000011833 salt mixture Substances 0.000 description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical class [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000003350 kerosene Substances 0.000 description 3
- PLLBRTOLHQQAQQ-UHFFFAOYSA-N 8-methylnonan-1-ol Chemical compound CC(C)CCCCCCCO PLLBRTOLHQQAQQ-UHFFFAOYSA-N 0.000 description 2
- 229940123150 Chelating agent Drugs 0.000 description 2
- 229910020598 Co Fe Inorganic materials 0.000 description 2
- 229910017521 Cu Ni Co Fe Inorganic materials 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 102000018361 Contactin Human genes 0.000 description 1
- 108060003955 Contactin Proteins 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 101100059652 Mus musculus Cetn1 gene Proteins 0.000 description 1
- 101100059655 Mus musculus Cetn2 gene Proteins 0.000 description 1
- 229910017709 Ni Co Inorganic materials 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 229940083124 ganglion-blocking antiadrenergic secondary and tertiary amines Drugs 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000000622 liquid--liquid extraction Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000010310 metallurgical process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- BUKHSQBUKZIMLB-UHFFFAOYSA-L potassium;sodium;dichloride Chemical compound [Na+].[Cl-].[Cl-].[K+] BUKHSQBUKZIMLB-UHFFFAOYSA-L 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- C22B23/02—Obtaining nickel or cobalt by dry processes
- C22B23/025—Obtaining nickel or cobalt by dry processes with formation of a matte or by matte refining or converting into nickel or cobalt, e.g. by the Oxford process
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G1/00—Methods of preparing compounds of metals not covered by subclasses C01B, C01C, C01D, or C01F, in general
- C01G1/06—Halides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/08—Halides
- C01G53/09—Chlorides
-
- 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/16—Extraction of metal compounds from ores or concentrates by wet processes by leaching in organic solutions
- C22B3/1608—Leaching with acyclic or carbocyclic agents
- C22B3/1616—Leaching with acyclic or carbocyclic agents of a single type
- C22B3/1625—Leaching with acyclic or carbocyclic agents of a single type with amines
-
- 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
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Proteomics, Peptides & Aminoacids (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
A chloride salt, in particular one used as impurity solvent in a nickel matte chlorination process, is fragmented and leached with an organic liquid effective to extract chloride impurities from the fragments.
A chloride salt, in particular one used as impurity solvent in a nickel matte chlorination process, is fragmented and leached with an organic liquid effective to extract chloride impurities from the fragments.
Description
Pc-~125 104~8~
The present invention relates to processes for purifying chlorides of alkali or alkaline earth metals, and is particularly applicable to the cleaning of chloride salts used in processes for purifying nickel mattes by chlorination.
The selective chlorination of impurities present in a nickel matte has been the subject of much recent study. In Canadian Patent No. 955,756, assigned in common with the present invention, there is described the process wherein nickel chloride dissolved in a fused chloride solvent is used to chlorinate impurities such as iron, copper and cobalt for removal thereof from a nickel matte. In this process the molten matte to be chlorinated is contacted with a molten salt mixture con-sisting of a solvent salt, such as common salt or a mixture of sodium and potassium chlorides, and nickel chloride.
Thus at the end of the purification process, the supernatant salt mixture consists of the solvent salt loaded with the chlorides of the impurities removed from the nickel matte as well as unreacted nickel chloride.
This loaded salt must be treated to remove, and if desired recover, the impurity chlorides so that the salt can be re-cycled. In such a salt-cleaning treatment it is highly desirable not to remove any nickel chloride present in the loaded salt since this is required upon subsequent recycling of the salt.
In the process described in the aforementioned Canadian Patent, the salt is cleaned by electrolyzing it in the molten state. Fused salt electrolysis is, of course, a complex technology and is predicated on the local availa-bility of electrical power. Moreover such a cleaning process ,, ''' ,:' .:
~)4~)8t;6 also removes nickel chloride from the salt. Alternative salt cleanin~ methods suggested hy other workers in the field have been far less attractive in that they involve the energy intensive cycle of dissolving the salt in water, purifying the solution and then evaporating to dryness to regenerate to solvent chlorides.
It is an object of the present invention to provide an improved, convenient process for the regeneration of solvent salts used in matte purification processes.
` 10 It is a further and important object of the in-vention to provide a process of low energy consumption which does not involve the solution of the salt and subsequent evaporation.
~ccording to the invention a process for refining a salt comprisinq at least one of the chlorides of alkali and alkaline earth metals, to remove therefrom at least one im-purity selected from the group consisting of the chlorides of iron, nickel, cobalt, copper, lead, arsenic, zinc, manga-nese, cadmium, silver, bismuth, gold, tin, tungsten and titanium, comprises producing fragments of the salt, leaching the fragments with an organic liquid comprising a reagent which is effective to form with said at least one impurity an addi-tion complex soluble in the organic liquid, and separating the impurity loaded organic liquid from the refined salt.
The invention is particularly applicable to the refining of a loaded salt which has been used as impurity sol-vent in a nickel matte refining process, and which contains,in the form of chloride impurities, at least about 0.5% by weight of nickel and at least about 0.1~ by weight of one or more of:
iron, cobalt and copper.
The present invention further provides a process of refining a nickel matte to remove therefrom at least 1~)4(~86~
one impurity metal, selected from the group consisting of iron, cobalt, copper, lead, arsenic, zinc, manganese, cadmium, bismuth, tin, tungsten and titanium, by selec-tively chlorinating the impurity metal(s), dissolving the im-purity metal chloride(s) in a molten salt comprising at least one chloride of an alkali or alkaline earth metal, and separat-ing the impurity-loaded salt from the refined matte, wherein the improvement comprises producing fragments of the loaded salt, leaching the fragments with an organic liquid comprising a reagent effective to form with at least one impurity metal chloride in the loaded salt an addition complex soluble in the organic liquid, and separating the impurity loaded organic liquid from the purified salt.
Where, as is common, the salt contains significant amounts of nickel chloride, which may have been added as an anhydrous reaqent or formed in situ as a result of bub-bling chlorine through the matte to be refined, it is a particular advantage of the process of the present invention that the complexing reagent chosen for the salt cleaning reaction may be one which reacts selectively or preferentially with the impurity metal chlorides rather than with the nickel chloride present in the salt.
It is of course essential that the complexing reagent used be inert with respect to the solvent salt which is to be cleaned, and that it be effective for forming an addition complex with the impurity metal chloride in the absence of an aqueous phase. Thus the many chelating agents -which are effective only in liquid-liquid ion exchange re-actions, would not be effective for leaching the impurities from the solid salt in the present process. Reagents which l~U408ti6 are known to be capable of forming addition complexes with, for example, chlorides of iron, cobalt or copper and which can therefore be used in the present process include primary, secondary and tertiary amine hydrochlo-rides as well as quaternarv ammonium chlorides.
In practice the complexing reagent is used in the form of a solution, the solvent being an aliphatic or aromatic hydrocarbon or an alcohol or a mixture thereof.
Numerous commercially available solvents may be used, the only essential requirement being the insolubility of the salt to be refined in the solvent used to dissolve the complexing reagent. Preferred solvents include kerosene, xylene, isodecanol or mixtures thereof.
It is important that the loaded salt to be puri-fied be in the form of particles sufficiently small to enable the extraction of impurities to proceed rapidly to a high degree of completion. Such particles could be obtained by granulation of the molten salt, or by cooling to solidify the salt and subsequently grinding it. It is preferred that the loaded salt be ground to particles smaller than about 200 microns, and preferably smaller than about 50 microns. Such a particle size enables satisfactory extraction results to be obtained when the residence time of the salt in the extractant is of the order of one hour for each stage of extraction. In general more than one stage of extraction will be needed according to the initial composition of the salt. The purified salt is finally recovered by filtration, and after rinsing thereof with organic solvent and drying,it can be reused in the metal purification process. The organic extractant used 1~4V8tj6 for purification of the salt can be recycled after appro-priate purification, for example by contact with an aqueous phase which dissolves the impurities.
The invention will be more readily understood from the following specific description of examples of salt purification in accordance with the invention.
EXAMPLE
An organic extraction solution was prepared in the following manner. A mixture was made up which comprised, by volume, 68 parts of kerosene, 12 parts of isodecanol and 20 parts of a reagent made by General Mills, Inc. and known by the trade name Alamine 336, which is a tri-alkyl amine with the alkyl chains containing 8-10 carbon atoms. The mixture was reacted with 4.5 N hydrochloric acid, after which the aqueous phase was separated from the organic phase which was then used for leaching impurities from a loaded salt in the following manner.
An impure sodium chloride was synthesized in order to simulate a loaded salt which might be obtained when one type of nickel sulfide is refined in the presence of molten sodium chloride. The synthetic mixture was prepared by melting sodium chloride together with chlorides of nickel, copper, cobalt and iron and cooling to obtain a solid containing the following metal values:
Copper: 4.15 weight percent Nickel: 4.55 weight percent Cobalt: 0.50 weight percent Iron: 0.22 weight percent This synthetic loaded salt was ground to -100 mesh, Tyler Screen Size (TSS) and was leached by the 104t~866 organic liquid described above using a two stage leaching procedure. The first stage leach consisted of contacting lon grams of the salt with 250 mls of the organic liquid at 25C for one hour. At the end of this time the partially purified salt was separated by filtration, washed with 130 mls of kerosene and then filtered and dried. This dried salt was then suhjected to a second stage of leaching by contactin~ it with 200 mls of the organic liquid at 25C
for one hour, at the end of which it was again separated, washed, iltered and dried. The metal values present in the salt before and after each of the leaching stages are given in Table 1 below:
TABLE
SALT
Weight Composition ~ ~t. ~) .
Stage 1 (g) Cu Ni Co Fe_ Initial 100 4.15 4.55 0.50 0.22 Final 94 1.15 4.85 0.10 0.07 Stage 2 Initial 88 1.15 4.85 0.10 0.07 Final 88 0 80 4 55 0 06 0.05 ~ .:
' ' ' ~, '; ' ;
86~i Whereas the extraction of copper from the salt was less efficient in this test than the extraction of either cobalt or iron, it will be seen that the organic reagent used achieved the desired effect of extracting a large part of the copper, cobalt and iron but very little of the nickel.
This is most readily apparent from the comparison of the percentage extraction of each of the metal values in each stage of the process, which are shown in Table 2 below:
_ METAL EXT~A~TION (%) Cu N r Co Fe Stage 1 74 0 81 7 d Stage 2 30 6 40 29 Overall 82 6 89 79 EXAMPLE II
The organic solution for this test was prepared by reacting 4.5 N hydrochloric acid with a mixture compris-ing, by volume, 20 parts of the tertiary amine: Alamine 336, with 80 parts of xylene, and separating the aqueous phase from the mixture.
A sample of the synthetic calt described in Example I was ground to -325 mesh (TSS) and leached con-secutively with 250 mls and 225 mls of the organic solution, ~-following the same two stage leach procedure as described in Example I. Tables 3 and 4 below show the satisfactory results obtained in this refining test.
-~4~8t~6 SALT
Weight Composition (wt. ~) (~) Cu Ni Co Fe Stage 1 Initial100 4.154.55 0.50 0.22 Final 95 1.444.55 0.07 0.03 Initial89 1.444.55 0.07 0.03 Final 88 0.984.30 0.03 0.03 _ - .
. , . METAL EXTRACTION (~
Cu Ni Co Fe :
Stage 1 67 5 87 87 Stage 2 33 7 57 1 . Overall 78 12 94 87 ;~
, . , . ,. . ., . . :
1~40866 EXAMPLE III
For this test, the organic solution used was identical to that described in Example II above. In this case however the impure salt was synthesized so as to simulate the type of composition obtained when nickel sulfide is refined by chloridization in the presence of a sodium chloride-potassium chloride mixture. Thus the impure salt was prepared by melting 7 parts by weight of sodium chloride with 3 parts by weight of potassium chloride and small amounts of the chlorides of copper, nickel, cobalt and iron so as to give a metal content of:
Copper: 1.50 weight percent Nickel: 1.52 weight percent Cobalt: 1.80 weight percent Iron: ~.80 weight percent.
A 100 gram sample of this synthetic salt was leached in turn with 300 mls and 250 mls of the organic solution following the same procedure described in connection with Example I. Table 5 below shows the composition of the salt during the extraction, while Table 6 shows that after the second stage of leaching only lq% of th~ nickel chloride had been extracted from the salt while between 93 and 98% of the chlorides of iron, copper and cobalt had been eliminated.
104~866 . . . . _ __ SALT
Wei~ht Co~ ?Sitio~ I (wt- %?
Stage 1 ~g?_ Cu ~i Co Fe_ Initial 100.0 1.50 1.52 1.80 2.80 ¦Final ¦93 6 10.36 ¦ 1.52 ¦ 0. 7 ¦ 0.94 Initial 86.2 0.36 1.52 0.37 0.94 Final 81 1 0.06 1 42 0.03 0.-l .
P~ETAL EXTRACTION ( % ) _ Cu N~l Co Fe ¦
Stage 1 78 6 81 69 Stage 2 84 12 92 79 Overall 96 17 98 93 -10- -:~
~t)40866 It will be readily understood by those skilled in the art that the benefits of the present invention, i.e. the convenient removal of chloride impurities from a salt mixture without the need to dissolve the salt and thereafter reevaporate the solution, can be realized with the aid of many organic reagents other than those specified in the preceding examples. Thus use can be made of any of the various primary, secondary and tertiary amines known to be effective for complexing cobalt, copper and iron.
Although in general such extractants have been advocated for use in liquid-liquid extraction processes, they are in fact effective in the non-aqueous extraction involved in the process of the present invention because, unlike chelat-ing agents, they do not rely on an ion-exchange mechanism.
It will be further understood that while the salt refining process of the invention is particularly applicable to the regeneration of the solvent salt mixtures described, it is also useful in other metallurgical processes. For example, in the process of electrorefining with the aid of a fused chloride electrolyte, it is necessary from time to time to remove impurities which have accumulated in the electrolyte. The process of the present invention can be used effectively for refining such electrolytes.
Thus although the present invention has been described in conjunction with preferred embodiments, various modifications of the reagents and conditions described may be resorted to without departing from the scope of the in-vention which is defined by the appended claims.
. .,
The present invention relates to processes for purifying chlorides of alkali or alkaline earth metals, and is particularly applicable to the cleaning of chloride salts used in processes for purifying nickel mattes by chlorination.
The selective chlorination of impurities present in a nickel matte has been the subject of much recent study. In Canadian Patent No. 955,756, assigned in common with the present invention, there is described the process wherein nickel chloride dissolved in a fused chloride solvent is used to chlorinate impurities such as iron, copper and cobalt for removal thereof from a nickel matte. In this process the molten matte to be chlorinated is contacted with a molten salt mixture con-sisting of a solvent salt, such as common salt or a mixture of sodium and potassium chlorides, and nickel chloride.
Thus at the end of the purification process, the supernatant salt mixture consists of the solvent salt loaded with the chlorides of the impurities removed from the nickel matte as well as unreacted nickel chloride.
This loaded salt must be treated to remove, and if desired recover, the impurity chlorides so that the salt can be re-cycled. In such a salt-cleaning treatment it is highly desirable not to remove any nickel chloride present in the loaded salt since this is required upon subsequent recycling of the salt.
In the process described in the aforementioned Canadian Patent, the salt is cleaned by electrolyzing it in the molten state. Fused salt electrolysis is, of course, a complex technology and is predicated on the local availa-bility of electrical power. Moreover such a cleaning process ,, ''' ,:' .:
~)4~)8t;6 also removes nickel chloride from the salt. Alternative salt cleanin~ methods suggested hy other workers in the field have been far less attractive in that they involve the energy intensive cycle of dissolving the salt in water, purifying the solution and then evaporating to dryness to regenerate to solvent chlorides.
It is an object of the present invention to provide an improved, convenient process for the regeneration of solvent salts used in matte purification processes.
` 10 It is a further and important object of the in-vention to provide a process of low energy consumption which does not involve the solution of the salt and subsequent evaporation.
~ccording to the invention a process for refining a salt comprisinq at least one of the chlorides of alkali and alkaline earth metals, to remove therefrom at least one im-purity selected from the group consisting of the chlorides of iron, nickel, cobalt, copper, lead, arsenic, zinc, manga-nese, cadmium, silver, bismuth, gold, tin, tungsten and titanium, comprises producing fragments of the salt, leaching the fragments with an organic liquid comprising a reagent which is effective to form with said at least one impurity an addi-tion complex soluble in the organic liquid, and separating the impurity loaded organic liquid from the refined salt.
The invention is particularly applicable to the refining of a loaded salt which has been used as impurity sol-vent in a nickel matte refining process, and which contains,in the form of chloride impurities, at least about 0.5% by weight of nickel and at least about 0.1~ by weight of one or more of:
iron, cobalt and copper.
The present invention further provides a process of refining a nickel matte to remove therefrom at least 1~)4(~86~
one impurity metal, selected from the group consisting of iron, cobalt, copper, lead, arsenic, zinc, manganese, cadmium, bismuth, tin, tungsten and titanium, by selec-tively chlorinating the impurity metal(s), dissolving the im-purity metal chloride(s) in a molten salt comprising at least one chloride of an alkali or alkaline earth metal, and separat-ing the impurity-loaded salt from the refined matte, wherein the improvement comprises producing fragments of the loaded salt, leaching the fragments with an organic liquid comprising a reagent effective to form with at least one impurity metal chloride in the loaded salt an addition complex soluble in the organic liquid, and separating the impurity loaded organic liquid from the purified salt.
Where, as is common, the salt contains significant amounts of nickel chloride, which may have been added as an anhydrous reaqent or formed in situ as a result of bub-bling chlorine through the matte to be refined, it is a particular advantage of the process of the present invention that the complexing reagent chosen for the salt cleaning reaction may be one which reacts selectively or preferentially with the impurity metal chlorides rather than with the nickel chloride present in the salt.
It is of course essential that the complexing reagent used be inert with respect to the solvent salt which is to be cleaned, and that it be effective for forming an addition complex with the impurity metal chloride in the absence of an aqueous phase. Thus the many chelating agents -which are effective only in liquid-liquid ion exchange re-actions, would not be effective for leaching the impurities from the solid salt in the present process. Reagents which l~U408ti6 are known to be capable of forming addition complexes with, for example, chlorides of iron, cobalt or copper and which can therefore be used in the present process include primary, secondary and tertiary amine hydrochlo-rides as well as quaternarv ammonium chlorides.
In practice the complexing reagent is used in the form of a solution, the solvent being an aliphatic or aromatic hydrocarbon or an alcohol or a mixture thereof.
Numerous commercially available solvents may be used, the only essential requirement being the insolubility of the salt to be refined in the solvent used to dissolve the complexing reagent. Preferred solvents include kerosene, xylene, isodecanol or mixtures thereof.
It is important that the loaded salt to be puri-fied be in the form of particles sufficiently small to enable the extraction of impurities to proceed rapidly to a high degree of completion. Such particles could be obtained by granulation of the molten salt, or by cooling to solidify the salt and subsequently grinding it. It is preferred that the loaded salt be ground to particles smaller than about 200 microns, and preferably smaller than about 50 microns. Such a particle size enables satisfactory extraction results to be obtained when the residence time of the salt in the extractant is of the order of one hour for each stage of extraction. In general more than one stage of extraction will be needed according to the initial composition of the salt. The purified salt is finally recovered by filtration, and after rinsing thereof with organic solvent and drying,it can be reused in the metal purification process. The organic extractant used 1~4V8tj6 for purification of the salt can be recycled after appro-priate purification, for example by contact with an aqueous phase which dissolves the impurities.
The invention will be more readily understood from the following specific description of examples of salt purification in accordance with the invention.
EXAMPLE
An organic extraction solution was prepared in the following manner. A mixture was made up which comprised, by volume, 68 parts of kerosene, 12 parts of isodecanol and 20 parts of a reagent made by General Mills, Inc. and known by the trade name Alamine 336, which is a tri-alkyl amine with the alkyl chains containing 8-10 carbon atoms. The mixture was reacted with 4.5 N hydrochloric acid, after which the aqueous phase was separated from the organic phase which was then used for leaching impurities from a loaded salt in the following manner.
An impure sodium chloride was synthesized in order to simulate a loaded salt which might be obtained when one type of nickel sulfide is refined in the presence of molten sodium chloride. The synthetic mixture was prepared by melting sodium chloride together with chlorides of nickel, copper, cobalt and iron and cooling to obtain a solid containing the following metal values:
Copper: 4.15 weight percent Nickel: 4.55 weight percent Cobalt: 0.50 weight percent Iron: 0.22 weight percent This synthetic loaded salt was ground to -100 mesh, Tyler Screen Size (TSS) and was leached by the 104t~866 organic liquid described above using a two stage leaching procedure. The first stage leach consisted of contacting lon grams of the salt with 250 mls of the organic liquid at 25C for one hour. At the end of this time the partially purified salt was separated by filtration, washed with 130 mls of kerosene and then filtered and dried. This dried salt was then suhjected to a second stage of leaching by contactin~ it with 200 mls of the organic liquid at 25C
for one hour, at the end of which it was again separated, washed, iltered and dried. The metal values present in the salt before and after each of the leaching stages are given in Table 1 below:
TABLE
SALT
Weight Composition ~ ~t. ~) .
Stage 1 (g) Cu Ni Co Fe_ Initial 100 4.15 4.55 0.50 0.22 Final 94 1.15 4.85 0.10 0.07 Stage 2 Initial 88 1.15 4.85 0.10 0.07 Final 88 0 80 4 55 0 06 0.05 ~ .:
' ' ' ~, '; ' ;
86~i Whereas the extraction of copper from the salt was less efficient in this test than the extraction of either cobalt or iron, it will be seen that the organic reagent used achieved the desired effect of extracting a large part of the copper, cobalt and iron but very little of the nickel.
This is most readily apparent from the comparison of the percentage extraction of each of the metal values in each stage of the process, which are shown in Table 2 below:
_ METAL EXT~A~TION (%) Cu N r Co Fe Stage 1 74 0 81 7 d Stage 2 30 6 40 29 Overall 82 6 89 79 EXAMPLE II
The organic solution for this test was prepared by reacting 4.5 N hydrochloric acid with a mixture compris-ing, by volume, 20 parts of the tertiary amine: Alamine 336, with 80 parts of xylene, and separating the aqueous phase from the mixture.
A sample of the synthetic calt described in Example I was ground to -325 mesh (TSS) and leached con-secutively with 250 mls and 225 mls of the organic solution, ~-following the same two stage leach procedure as described in Example I. Tables 3 and 4 below show the satisfactory results obtained in this refining test.
-~4~8t~6 SALT
Weight Composition (wt. ~) (~) Cu Ni Co Fe Stage 1 Initial100 4.154.55 0.50 0.22 Final 95 1.444.55 0.07 0.03 Initial89 1.444.55 0.07 0.03 Final 88 0.984.30 0.03 0.03 _ - .
. , . METAL EXTRACTION (~
Cu Ni Co Fe :
Stage 1 67 5 87 87 Stage 2 33 7 57 1 . Overall 78 12 94 87 ;~
, . , . ,. . ., . . :
1~40866 EXAMPLE III
For this test, the organic solution used was identical to that described in Example II above. In this case however the impure salt was synthesized so as to simulate the type of composition obtained when nickel sulfide is refined by chloridization in the presence of a sodium chloride-potassium chloride mixture. Thus the impure salt was prepared by melting 7 parts by weight of sodium chloride with 3 parts by weight of potassium chloride and small amounts of the chlorides of copper, nickel, cobalt and iron so as to give a metal content of:
Copper: 1.50 weight percent Nickel: 1.52 weight percent Cobalt: 1.80 weight percent Iron: ~.80 weight percent.
A 100 gram sample of this synthetic salt was leached in turn with 300 mls and 250 mls of the organic solution following the same procedure described in connection with Example I. Table 5 below shows the composition of the salt during the extraction, while Table 6 shows that after the second stage of leaching only lq% of th~ nickel chloride had been extracted from the salt while between 93 and 98% of the chlorides of iron, copper and cobalt had been eliminated.
104~866 . . . . _ __ SALT
Wei~ht Co~ ?Sitio~ I (wt- %?
Stage 1 ~g?_ Cu ~i Co Fe_ Initial 100.0 1.50 1.52 1.80 2.80 ¦Final ¦93 6 10.36 ¦ 1.52 ¦ 0. 7 ¦ 0.94 Initial 86.2 0.36 1.52 0.37 0.94 Final 81 1 0.06 1 42 0.03 0.-l .
P~ETAL EXTRACTION ( % ) _ Cu N~l Co Fe ¦
Stage 1 78 6 81 69 Stage 2 84 12 92 79 Overall 96 17 98 93 -10- -:~
~t)40866 It will be readily understood by those skilled in the art that the benefits of the present invention, i.e. the convenient removal of chloride impurities from a salt mixture without the need to dissolve the salt and thereafter reevaporate the solution, can be realized with the aid of many organic reagents other than those specified in the preceding examples. Thus use can be made of any of the various primary, secondary and tertiary amines known to be effective for complexing cobalt, copper and iron.
Although in general such extractants have been advocated for use in liquid-liquid extraction processes, they are in fact effective in the non-aqueous extraction involved in the process of the present invention because, unlike chelat-ing agents, they do not rely on an ion-exchange mechanism.
It will be further understood that while the salt refining process of the invention is particularly applicable to the regeneration of the solvent salt mixtures described, it is also useful in other metallurgical processes. For example, in the process of electrorefining with the aid of a fused chloride electrolyte, it is necessary from time to time to remove impurities which have accumulated in the electrolyte. The process of the present invention can be used effectively for refining such electrolytes.
Thus although the present invention has been described in conjunction with preferred embodiments, various modifications of the reagents and conditions described may be resorted to without departing from the scope of the in-vention which is defined by the appended claims.
. .,
Claims (5)
1. A process for refining a salt comprising at least one of the chlorides of alkali and alkaline earth metals, to remove therefrom at least one impurity selected from the group consisting of the chlorides of iron, nickel, cobalt, copper, lead, arsenic, zinc, manganese, cadmium, silver, bismuth, gold, tin, tungsten and titanium, comprises produc-ing fragments of the salt, leaching the fragments with an organic liquid comprising a reagent selected from the group consisting of primary, secondary and tertiary amine hydrochlorides and quaternary ammonium chlorides, to form with said at least one impurity an addition complex soluble in the organic liquid, and separating the impurity loaded organic liquid from the refined salt.
2. A process in accordance with claim 1 wherein said at least one impurity in the salt to be refined consists of the chlorides of at least about 0.5% by weight of nickel, and at least about 0.1% by weight of a metal selected from the group consisting of iron, cobalt and copper.
3. A process for refining a nickel matte to remove therefrom at least one impurity metal, selected from the group consisting of iron, cobalt, copper, lead, arsenic, zinc, manganese, cadmium, bismuth, tin, tungsten and titanium, by selectively chlorinating the impurity metal(s),dissolving the impurity metal chloride(s) in a molten salt comprising at least one of the chlorides of alkali and alkaline earth metals, and separating the impurity-loaded salt from the refined matte, the improvement comprising producing frag-ments of the loaded salt, leaching the fragments with an organic liquid comprising a reagent selected from the group consisting of primary, secondary and tertiary amine hydrochlorides and quaternary ammonium chlorides, to form with at least one impurity metal chloride in the loaded salt an addition complex soluble in the organic liquid, and separating the impurity loaded organic liquid from the purified salt.
4. A process in accordance with claim 3 wherein the loaded salt contains nickel chloride in addition to the impurity metal chloride(s), and wherein the reagent is effective to leach the impurity metal chloride(s) without leaching substantial amounts of the nickel chloride.
5. A process in accordance with claim 3 wherein the organic liquid comprises said compound mixed with an organic solvent selected from the group consisting of hydrocarbons and alcohols.
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA224,068A CA1040866A (en) | 1975-04-08 | 1975-04-08 | Refining of chloride salts |
GB11191/76A GB1532514A (en) | 1975-04-08 | 1976-03-19 | Process for refining chloride salts |
ZA761739A ZA761739B (en) | 1975-04-08 | 1976-03-22 | Process for refining chloride salts |
AU12344/76A AU496041B2 (en) | 1975-04-08 | 1976-03-25 | Process for refining chloride salts |
FR7609928A FR2306940A1 (en) | 1975-04-08 | 1976-04-06 | PROCESS FOR PURIFYING CHLORIDES OF ALKALINE OR ALKALINO-TER METALS |
JP51038817A JPS51123799A (en) | 1975-04-08 | 1976-04-08 | Refining process for salt of chloride |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA224,068A CA1040866A (en) | 1975-04-08 | 1975-04-08 | Refining of chloride salts |
Publications (1)
Publication Number | Publication Date |
---|---|
CA1040866A true CA1040866A (en) | 1978-10-24 |
Family
ID=4102750
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA224,068A Expired CA1040866A (en) | 1975-04-08 | 1975-04-08 | Refining of chloride salts |
Country Status (5)
Country | Link |
---|---|
JP (1) | JPS51123799A (en) |
CA (1) | CA1040866A (en) |
FR (1) | FR2306940A1 (en) |
GB (1) | GB1532514A (en) |
ZA (1) | ZA761739B (en) |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CH262267A (en) * | 1947-07-26 | 1949-06-30 | Schweizerhall Saeurefab | Process for cleaning liquid metal chlorides. |
BE758679A (en) * | 1969-11-14 | 1971-04-16 | Nickel Le | PROCESS FOR PURIFYING FERROUS AND COBALTIZING NICKEL MATTS |
FR2210569A1 (en) * | 1972-12-14 | 1974-07-12 | Ugine Kuhlmann | Metal chlorides mfr - by extn into amine solvent from aq soln. contg. metal salt and sol chloride |
-
1975
- 1975-04-08 CA CA224,068A patent/CA1040866A/en not_active Expired
-
1976
- 1976-03-19 GB GB11191/76A patent/GB1532514A/en not_active Expired
- 1976-03-22 ZA ZA761739A patent/ZA761739B/en unknown
- 1976-04-06 FR FR7609928A patent/FR2306940A1/en active Granted
- 1976-04-08 JP JP51038817A patent/JPS51123799A/en active Pending
Also Published As
Publication number | Publication date |
---|---|
FR2306940A1 (en) | 1976-11-05 |
FR2306940B1 (en) | 1981-06-12 |
GB1532514A (en) | 1978-11-15 |
JPS51123799A (en) | 1976-10-28 |
AU1234476A (en) | 1977-09-29 |
ZA761739B (en) | 1977-04-27 |
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