US3425550A - Flotation separation of metallic sulfide ores - Google Patents
Flotation separation of metallic sulfide ores Download PDFInfo
- Publication number
- US3425550A US3425550A US567088A US3425550DA US3425550A US 3425550 A US3425550 A US 3425550A US 567088 A US567088 A US 567088A US 3425550D A US3425550D A US 3425550DA US 3425550 A US3425550 A US 3425550A
- Authority
- US
- United States
- Prior art keywords
- flotation
- sulfide ores
- metallic sulfide
- dithiocarbamate
- collector
- 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 - Lifetime
Links
- 238000005188 flotation Methods 0.000 title description 19
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 title description 14
- 238000000926 separation method Methods 0.000 title description 7
- 238000000034 method Methods 0.000 description 24
- -1 Alkali metal salts Chemical class 0.000 description 15
- 239000012990 dithiocarbamate Substances 0.000 description 14
- 159000000000 sodium salts Chemical class 0.000 description 11
- 229910052500 inorganic mineral Inorganic materials 0.000 description 9
- 239000011707 mineral Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 229910052783 alkali metal Inorganic materials 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 239000012141 concentrate Substances 0.000 description 6
- 150000004659 dithiocarbamates Chemical class 0.000 description 6
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000010665 pine oil Substances 0.000 description 5
- 239000003760 tallow Substances 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 239000007900 aqueous suspension Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000009291 froth flotation Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 235000010469 Glycine max Nutrition 0.000 description 3
- 244000068988 Glycine max Species 0.000 description 3
- 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 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 230000001143 conditioned effect Effects 0.000 description 3
- 230000003750 conditioning effect Effects 0.000 description 3
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- RZFBEFUNINJXRQ-UHFFFAOYSA-M sodium ethyl xanthate Chemical compound [Na+].CCOC([S-])=S RZFBEFUNINJXRQ-UHFFFAOYSA-M 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000003240 coconut oil Substances 0.000 description 2
- 235000019864 coconut oil Nutrition 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920001281 polyalkylene Polymers 0.000 description 2
- 239000003549 soybean oil Substances 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052569 sulfide mineral Inorganic materials 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- HTJDQJBWANPRPF-UHFFFAOYSA-N Cyclopropylamine Chemical group NC1CC1 HTJDQJBWANPRPF-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000005263 alkylenediamine group Chemical group 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- TYUWIWBZXGOFHY-UHFFFAOYSA-N carbamodithioic acid;prop-1-ene Chemical compound CC=C.NC(S)=S TYUWIWBZXGOFHY-UHFFFAOYSA-N 0.000 description 1
- 150000001723 carbon free-radicals Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910001779 copper mineral Inorganic materials 0.000 description 1
- 239000013058 crude material Substances 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005064 octadecenyl group Chemical group C(=CCCCCCCCCCCCCCCCC)* 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- YIBBMDDEXKBIAM-UHFFFAOYSA-M potassium;pentoxymethanedithioate Chemical compound [K+].CCCCCOC([S-])=S YIBBMDDEXKBIAM-UHFFFAOYSA-M 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- ICNCMCHAPLUNBG-UHFFFAOYSA-N propyl carbamodithioate Chemical compound CCCSC(N)=S ICNCMCHAPLUNBG-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 150000005619 secondary aliphatic amines Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 150000003558 thiocarbamic acid derivatives Chemical class 0.000 description 1
- UMFCIIBZHQXRCJ-NSCUHMNNSA-N trans-anol Chemical compound C\C=C\C1=CC=C(O)C=C1 UMFCIIBZHQXRCJ-NSCUHMNNSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/004—Organic compounds
- B03D1/012—Organic compounds containing sulfur
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/02—Collectors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2203/00—Specified materials treated by the flotation agents; Specified applications
- B03D2203/02—Ores
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2203/00—Specified materials treated by the flotation agents; Specified applications
- B03D2203/02—Ores
- B03D2203/04—Non-sulfide ores
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S209/00—Classifying, separating, and assorting solids
- Y10S209/901—Froth flotation; copper
Definitions
- This invention relates to a process for froth flotation separation of metallic sulfide ores, and more particularly to the use of dithiocarbamate compounds as flotation collectors for metallic sulfide mineralization, especially of oxidized sulfide ores.
- the process of froth flotation depends for its eflicacy on the ability of the collector to wet selectively some mineral particles while other desirable constituents remain unwetted and adhere to air bubbles which float to the surface of the mixture and are removed as a concentrate in the froth.
- Coating finely iground mineral particles is accomplished by agitating a mixture of ore, water, and a suitable chemical collector such as sodium ethylxanthate in a conditioner for a short time during which the chemical attaches to the surface of the mineral particles to form a new surface which is more water repellent than the original surface and which is therefore air avid.
- Minerals that naturally tend to resist wetting may be treated so that their surfaces will be wetted and they will sink in the water and thereby not be floated 'with the concentrates containing desired mineral particles.
- An object of the invention is to provide a process in which dithiocarbamate compounds are employed as flotation collectors in the separation of metallic sulfide ores, and particularly oxidized ores.
- a further object is to provide a process in (which dialkali metal and amine salts of dithiocarbarnates prepared from N-aliphatic substituted poly alkylene diamines in which the aliphatic hydrocarbon has from '8 to 22 carbon atoms or mixtures thereof.
- an excess of CS is dissolved in an NaOI-I alcohol solution of a primary or secondary aliphatic amine, or a N-aliphatic substituted polyalkylene diamine.
- the reaction can then be evaporated to give the sodium salt.
- the amine salt can be prepared by omitting the NaOH.
- dithiocarbamates of diamines either a monodithiocarbamate can be prepared, or if both amino nitrogens are substituted with CS a di-dithiocarbamate will result.
- Other methods known to those skilled in the art may be employed.
- Typical compounds which may be used in the practice of our process include:
- H2501 S Sodium salt of N,N-dodecyl ll dithiocarbamate.
- R is coco Sodium salt of N-(3-cocoamino) propylene dithiocarbamate.
- Preferred dithiocarbamate salts useful in the process of this invention have the formula:
- R is selected from the group consisting of hydrogen and S Bra-llradical
- x is an integer from 2 to 4
- M represents an alkali metal radical.
- long chain aliphatic hydrocarbon radicals having from 6 to 22 carbon atoms coming within the definition of R described hereinabove include octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, octadecenyl, octadecadienyl, octadecatrienyl, docosy, eicosy, and mixtures of the foregoing carbon radicals as contained in naturally occurring glycerides such as coconut oil, tallow, soybean oil, and the like.
- These long chain aliphatic hydrocarbon radicals may either be straight or branched chain.
- Collectors containing diamines particularly useful in the practice of this invention are those with the trade name Duomeen by Armour and Company, having the letter C for the symbol Coco indicating that the long chain aliphatic hydrocarbon radicals in the compound are mixtures derived from coconut oil, the letter S for the symbol soya indicating mixtures derived from soybean oil, and the letter T for the symbol tallow indicating mixtures derived from tallow.
- Alkali metal radicals coming within the definition of M described hereinabove include the monovalent metals lithium, sodium, potassium, rubidium and cessium. However, in the practice of this invention We prefer to employ sodium as the alkali metal radical contained in the collectors of our process.
- Short chain hydrocarbon radicals coming within the definition of (CH wherein at is an integer from 2 to 4 as described hereinabove include ethylene, propylene and butylene; however, in the practice of our invention, we prefer to employ propylene in our collectors.
- suitable mineral containing sulfide ores may be comminutated to a suitable size for flotation by any 0 fthe methods known such as crushing and then grinding in a ball mill at 50% solids in a water suspension (pulp).
- the ground ore may be directly charged to a flotation cell and the pulp diluted to about 16% solids.
- the water suspension of finely-divided metallic sulfide ores is then conditioned after adding our alkali metal salt of dithiocarbamate collector. Rates of collector addition to the cell may vary directly proportional to the amount of ore present.
- rate of collector addition may be from 0.005 to 0.5#/t. (pounds per ton), although we prefer a rate of from 0.03 to 0.10#/t.
- the pH of the pulp may be adjusted to the alkaline range, and we prefer a pH of from 10.5 to 13.
- the dithiocarbamates desirable in our invention may be synthesized at various concentrations with isopropanol or other suitable alcohols as solvents in order to facilitate their addition to the cell as a liquid, although the collector may be added in solid form.
- a frother such as pine oil is added to the cell and the total mixture in the flotation cell may be conditioned about one minute before the introduction of air. Flotation may be conducted for from 3 minutes to about 15 minutes.
- the sample is ground to flotation size in a ball mill at about 50% solids in a water suspension with CaO and the ground ore is charged directly to a flotation cell where the pulp is diluted to about 16% solids by the addition of water.
- a fifty percent solution of the sodium salt of Duomeen C mono-dithiocarbamate is added as collector at the rate of about 0.1#/t. (about 0.05#/t. isopropanol being present therein) and increments of about 0.04# /t. of pine oil are added at the beginning and again after 4 minutes of froth time.
- Conditioning time is about one minute before introduction of air and froth is removed for nine minutes.
- the pH is maintained at 12.0 to 12.3.
- the copper is floated and only one rougher concentrate containing floated copper mineral particles is collected, although further concentrates may be collected.
- flotation collectors were tested, the collectors being identified by reference numbers as set out in the following list:
- EXAMPLE I In each test a 500 gram sample of fresh copper sulfide ore analyzing 4.5% Cu was ground to flotation size in a laboratory ball mill at 50% solids with 13 grams CaO. The ground ore was charged directly to a Fagergren laboratory flotation cell without desliming, where the pulp was diluted to about 16% solids. Collector addition rates in each test are shown in the results. Conditioning time was one minute before introduction of air. Pine oil was added at 0.04#/t. at the beginning of each test and again after four minutes float time. The pH was maintained at 12.0-12.3. Froth was removed for nine minutes. Only one rougher concentrate was collected in each test.
- Mincree 27 a xanthogen sulfate.
- Example II Test procedure and conditions are the same as for Example I, except that increments of 0.04#/t. of pine oil were added. The same ore as used in Example I was used except that it had been subject to atmospheric oxidation in storage for up to two years. No artificial sulfidization was used in the referenced tests.
- EXAMPLE IV A 500 gram sample of a complex sulfide ore analyzing 1.6% Cu and 22% Fe was ground to flotation size in a laboratory rod mill at 50% solids. Sutficient lime was used in the grind to obtain a subsequent flotation pH of 11.6-11.8. Sodium-(3-coco amino) propyl dithiocarbamate was added at 0.05 #/t. and Dowfroth 250 was added as frother at 0.08 #/t. The pulp was conditioned 1 minute before flotation. Flotation was conducted for 10 minutes. One rougher concentrate was obtained. A standard test was conducted under identical conditions except potassium amyl xanthate was used at 0.10 #/t.
- Example I testing the thiocarbamates on fresh copper sulfide ore did not show the grade and recovery as did Example II testing the same ore subjected to atmospheric oxidation. Further, in Example IH, the collector obtained slightly higher zinc grade and 18.3% higher zinc recovery at only one-third of the collector addition rate of sodium ethyl xanthate used as a standard collector.
- x is an integer from 2 to 4
- M represents an alkali metal radical
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Description
United States Patent 3,425,550 FLOTATION SEPARATION OF METALLIC SULFIDE ORES Robert E. Baarson, La Grange, Paul L. Du Brow, Chicago,
and Charles L. Ray, Wheaton, Ill., assignors, by mesne assignments, to Armour Industrial Chemical Company,
a corporation of Delaware No Drawing. Filed July 22, 1966, Ser. No. 567,088 US. Cl. 209-166 11 Claims Int. Cl. B0311 1/00 ABSTRACT OF THE DISCLOSURE Alkali metal salts of dithiocarbamates and di-dithiocarbamates are disclosed as collectors in froth flotation separation of sulfide minerals from metallic sulfide ores, particularly oxidized metallic sulfide ores.
This invention relates to a process for froth flotation separation of metallic sulfide ores, and more particularly to the use of dithiocarbamate compounds as flotation collectors for metallic sulfide mineralization, especially of oxidized sulfide ores.
In treating crude ores and mineral products to separate the valuable minerals, such as copper, lead and zinc, from the crude material, the process of froth flotation depends for its eflicacy on the ability of the collector to wet selectively some mineral particles while other desirable constituents remain unwetted and adhere to air bubbles which float to the surface of the mixture and are removed as a concentrate in the froth. Coating finely iground mineral particles is accomplished by agitating a mixture of ore, water, and a suitable chemical collector such as sodium ethylxanthate in a conditioner for a short time during which the chemical attaches to the surface of the mineral particles to form a new surface which is more water repellent than the original surface and which is therefore air avid. Minerals that naturally tend to resist wetting may be treated so that their surfaces will be wetted and they will sink in the water and thereby not be floated 'with the concentrates containing desired mineral particles.
An object of the invention is to provide a process in which dithiocarbamate compounds are employed as flotation collectors in the separation of metallic sulfide ores, and particularly oxidized ores.
A further object is to provide a process in (which dialkali metal and amine salts of dithiocarbarnates prepared from N-aliphatic substituted poly alkylene diamines in which the aliphatic hydrocarbon has from '8 to 22 carbon atoms or mixtures thereof.
Other specific objects and advantages will appear as the specification proceeds.
In the synthesis of the compounds useful in our process, an excess of CS is dissolved in an NaOI-I alcohol solution of a primary or secondary aliphatic amine, or a N-aliphatic substituted polyalkylene diamine. The reaction can then be evaporated to give the sodium salt. If desired, the amine salt can be prepared by omitting the NaOH. In the case of dithiocarbamates of diamines, either a monodithiocarbamate can be prepared, or if both amino nitrogens are substituted with CS a di-dithiocarbamate will result. Other methods known to those skilled in the art may be employed.
Typical compounds which may be used in the practice of our process include:
H2501: S Sodium salt of N,N-dodecyl ll dithiocarbamate.
N S-Na HisCu RRNCSSH-RNHQ where R is a long chain aliphatic hydrocarbon.
Amine salt of N,N-dialiphatic dithiooarbamate.
[I I I ll amino trimethylene di- Na-SC N(O Hz) aN-C S -N a dithiocarbamate.
where R is coco Sodium salt of N-(3-cocoamino) propylene dithiocarbamate.
Preferred dithiocarbamate salts useful in the process of this invention have the formula:
from 6 to 22 carbon atoms, R is selected from the group consisting of hydrogen and S Bra-llradical, x is an integer from 2 to 4, and M represents an alkali metal radical.
Examples of long chain aliphatic hydrocarbon radicals having from 6 to 22 carbon atoms coming within the definition of R described hereinabove include octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, octadecenyl, octadecadienyl, octadecatrienyl, docosy, eicosy, and mixtures of the foregoing carbon radicals as contained in naturally occurring glycerides such as coconut oil, tallow, soybean oil, and the like. These long chain aliphatic hydrocarbon radicals may either be straight or branched chain. Collectors containing diamines particularly useful in the practice of this invention are those with the trade name Duomeen by Armour and Company, having the letter C for the symbol Coco indicating that the long chain aliphatic hydrocarbon radicals in the compound are mixtures derived from coconut oil, the letter S for the symbol soya indicating mixtures derived from soybean oil, and the letter T for the symbol tallow indicating mixtures derived from tallow.
Alkali metal radicals coming within the definition of M described hereinabove include the monovalent metals lithium, sodium, potassium, rubidium and cessium. However, in the practice of this invention We prefer to employ sodium as the alkali metal radical contained in the collectors of our process. Short chain hydrocarbon radicals coming within the definition of (CH wherein at is an integer from 2 to 4 as described hereinabove include ethylene, propylene and butylene; however, in the practice of our invention, we prefer to employ propylene in our collectors.
In the practice of the process of this invention, suitable mineral containing sulfide ores may be comminutated to a suitable size for flotation by any 0 fthe methods known such as crushing and then grinding in a ball mill at 50% solids in a water suspension (pulp). The ground ore may be directly charged to a flotation cell and the pulp diluted to about 16% solids. The water suspension of finely-divided metallic sulfide ores is then conditioned after adding our alkali metal salt of dithiocarbamate collector. Rates of collector addition to the cell may vary directly proportional to the amount of ore present. Our
rate of collector addition may be from 0.005 to 0.5#/t. (pounds per ton), although we prefer a rate of from 0.03 to 0.10#/t. The pH of the pulp may be adjusted to the alkaline range, and we prefer a pH of from 10.5 to 13. The dithiocarbamates desirable in our invention may be synthesized at various concentrations with isopropanol or other suitable alcohols as solvents in order to facilitate their addition to the cell as a liquid, although the collector may be added in solid form. A frother such as pine oil is added to the cell and the total mixture in the flotation cell may be conditioned about one minute before the introduction of air. Flotation may be conducted for from 3 minutes to about 15 minutes.
In a preferred embodiment of our process for the flotation separation of a sample of oxidized copper sulfide ore, the sample is ground to flotation size in a ball mill at about 50% solids in a water suspension with CaO and the ground ore is charged directly to a flotation cell where the pulp is diluted to about 16% solids by the addition of water. A fifty percent solution of the sodium salt of Duomeen C mono-dithiocarbamate is added as collector at the rate of about 0.1#/t. (about 0.05#/t. isopropanol being present therein) and increments of about 0.04# /t. of pine oil are added at the beginning and again after 4 minutes of froth time. Conditioning time is about one minute before introduction of air and froth is removed for nine minutes. The pH is maintained at 12.0 to 12.3. The copper is floated and only one rougher concentrate containing floated copper mineral particles is collected, although further concentrates may be collected.
In the following specific examples, flotation collectors were tested, the collectors being identified by reference numbers as set out in the following list:
RF No.:
1 Sodium salt of Duomeen S mono-dithiocarbamate.
2 Sodium salt of N-tallow (B-cyanoethyl) dithiocarbamate.
3 Sodium salt of Duomeen S didithiocarbamate.
4 Sodium salt of Duomeen C didithiocarbamate.
5 Sodium salt of Duomeen T didithiocarbamate.
6 Sodium salt of Duomeen C mono-dithiocarbamate.
7 Sodium salt of Duomeen T mono-dithiocarbamate.
The procedures are outlined in the following specific examples in testing the above-referenced compounds as flotation collectors, with typical results as shown:
EXAMPLE I In each test a 500 gram sample of fresh copper sulfide ore analyzing 4.5% Cu was ground to flotation size in a laboratory ball mill at 50% solids with 13 grams CaO. The ground ore was charged directly to a Fagergren laboratory flotation cell without desliming, where the pulp was diluted to about 16% solids. Collector addition rates in each test are shown in the results. Conditioning time was one minute before introduction of air. Pine oil was added at 0.04#/t. at the beginning of each test and again after four minutes float time. The pH was maintained at 12.0-12.3. Froth was removed for nine minutes. Only one rougher concentrate was collected in each test.
Mincree 27, a xanthogen sulfate.
4 EXAMPLE II Test procedure and conditions are the same as for Example I, except that increments of 0.04#/t. of pine oil were added. The same ore as used in Example I was used except that it had been subject to atmospheric oxidation in storage for up to two years. No artificial sulfidization was used in the referenced tests.
Collector Isopro- Pine oil, Analyses,
panol, #/I percent Cu Percent RF #/1 #/1 added added rougher tails recovery N 0. added 4 0. 056 0 2 0. 05 16. 67 1. 12 76. 29 5 0. 05 0 069 0. 05 14. 84 1. 16 77. 91 6 0. 05 0 053 0. 05 20. 50 0. 72 85. 22 7 0. 051 0 054 0. 05 15. 2.08 58. 73 Std. 0. 054 0. 05 7. 42 3.08 29. 30
1 Minerec 27.
EXAMPLE III Collector Weight percent Analyses, percent Percent Zn recgvery 11 RF No. #IT Cone. Tails Cone. Tails added Std. 0.058 18. 4 81. 6 4. 1 0. 49 65. 3 .018 18. 8 81. 2 4. 4 0.20 83.6
I Sodium ethyl xanthate.
EXAMPLE IV A 500 gram sample of a complex sulfide ore analyzing 1.6% Cu and 22% Fe was ground to flotation size in a laboratory rod mill at 50% solids. Sutficient lime was used in the grind to obtain a subsequent flotation pH of 11.6-11.8. Sodium-(3-coco amino) propyl dithiocarbamate was added at 0.05 #/t. and Dowfroth 250 was added as frother at 0.08 #/t. The pulp was conditioned 1 minute before flotation. Flotation was conducted for 10 minutes. One rougher concentrate was obtained. A standard test was conducted under identical conditions except potassium amyl xanthate was used at 0.10 #/t.
It is clear from the foregoing examples that the referenced compound or collector is unusually and surprisingly effective on oxidized ore. Example I testing the thiocarbamates on fresh copper sulfide ore did not show the grade and recovery as did Example II testing the same ore subjected to atmospheric oxidation. Further, in Example IH, the collector obtained slightly higher zinc grade and 18.3% higher zinc recovery at only one-third of the collector addition rate of sodium ethyl xanthate used as a standard collector.
While in the foregoing specification, we have set forth specific process steps and collector compounds in considerable detatil for the purpose of illustrating embodiments of the invention, it will be understood that such embodiments may be varied by those skilled in the art without departing from the spirit of our invention.
We claim:
1. In a process for the separation of metallic sulfide minerals from metallic sulfide ores by froth flotation, wherein said minerals are floated, the step of conditioning a water suspension of finely-divided metallic sulfide ores with an alkali metal salt of dithiocarbamate having the formula:
radical, x is an integer from 2 to 4, and M represents an alkali metal radical.
2. The process of claim 1 in which the ores are oxidized metallic sulfide ores.
3. The process of claim 1 in which the ores are zinc sulfide ores.
4. The process of claim 1 in which R is coco and R is hydrogen.
5. The process of claim 4 in which M is sodium and x is 3.
6. The process of claim 1 in which R is soya and R is hydrogen.
is hydrogen.
6 8. The process of claim 1 in which R is coco and R is 9. The process of claim 1 in which R is soya and R is 10. The process of claim 1 in which R is tallow and R is s M.S.( i
11. The process of claim 1 in which R is dodecyl.
References Cited UNITED STATES PATENTS 1,879,871 9/1932 Gaudin 209166 3,298,520 1/1967 Bikales 209166 FOREIGN PATENTS 871,132 2/1953 Germany.
OTHER REFERENCES US. Bureau of Mines, RI6092 (1962), pp. 1-15.
HARRY B. THORNTON, Primary Examiner.
R. HALPER, Assistant Examiner.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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US56708866A | 1966-07-22 | 1966-07-22 |
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US3425550A true US3425550A (en) | 1969-02-04 |
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Application Number | Title | Priority Date | Filing Date |
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US567088A Expired - Lifetime US3425550A (en) | 1966-07-22 | 1966-07-22 | Flotation separation of metallic sulfide ores |
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Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4136020A (en) * | 1976-11-11 | 1979-01-23 | Minerec Corporation | Flotation reagent and process |
US4554108A (en) * | 1983-07-26 | 1985-11-19 | Phillips Petroleum Company | Alkali carboxyalkyl dithiocarbamates and use as ore flotation reagents |
US4554068A (en) * | 1983-07-26 | 1985-11-19 | Phillips Petroleum Company | Ore flotation and flotation agents for use therein |
US4595538A (en) * | 1985-03-04 | 1986-06-17 | Phillips Petroleum Company | Tri-alkali metal-di(carboxyalkyl)dithiocarbamate and triammonium-di(carboxyalkyl)dithiocarbamate flotation agents |
US4702821A (en) * | 1985-02-26 | 1987-10-27 | Phillips Petroleum Company | Ore flotation and di-alkali metal-di(carboxyalkyl)dithiocarbamate and diammonium-di(carboxyalkyl)dithiocarbamate flotation agents for use therein |
US4747940A (en) * | 1985-03-04 | 1988-05-31 | Phillips Petroleum Company | Ore flotation and tri-alkali metal-di(carboxyalkyl) dithiocarbamate and triammonium-di(carboxyalkyl) dithiocarbamate flotation agents for use therein |
US4806234A (en) * | 1987-11-02 | 1989-02-21 | Phillips Petroleum Company | Ore flotation |
US4883585A (en) * | 1988-10-27 | 1989-11-28 | Phillips Petroleum Company | Ore flotation and sulfenyl dithiocarbamates as agents for use therein |
US4990656A (en) * | 1987-11-02 | 1991-02-05 | Phillips Petroleum Company | Polyamine substituted dithiocarbamate and process for producing the same |
US5015368A (en) * | 1990-06-15 | 1991-05-14 | The Lubrizol Corporation | Ore flotation process using carbamate compounds |
US20040200760A1 (en) * | 2001-05-14 | 2004-10-14 | Theo Rodopoulos | Selective recovery of minerals by flotation |
US9302272B2 (en) | 2011-10-18 | 2016-04-05 | Cytec Technology Corp. | Froth flotation processes |
US9302273B2 (en) | 2011-10-18 | 2016-04-05 | Cytec Technology Corp. | Froth flotation processes |
US9302274B2 (en) | 2011-10-18 | 2016-04-05 | Cytec Technology Corp. | Collector compositions and methods of using the same |
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US1879871A (en) * | 1929-08-01 | 1932-09-27 | Antoine M Gaudin | Method of flotation |
DE871132C (en) * | 1943-01-20 | 1953-03-19 | Aufbereitung M B H In Aufloesu | Process for flotation of ores |
US3298520A (en) * | 1962-12-26 | 1967-01-17 | American Cyanamid Co | Flotation process with cyanovinyl dithiocarbamates |
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Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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US1879871A (en) * | 1929-08-01 | 1932-09-27 | Antoine M Gaudin | Method of flotation |
DE871132C (en) * | 1943-01-20 | 1953-03-19 | Aufbereitung M B H In Aufloesu | Process for flotation of ores |
US3298520A (en) * | 1962-12-26 | 1967-01-17 | American Cyanamid Co | Flotation process with cyanovinyl dithiocarbamates |
Cited By (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4136020A (en) * | 1976-11-11 | 1979-01-23 | Minerec Corporation | Flotation reagent and process |
US4554108A (en) * | 1983-07-26 | 1985-11-19 | Phillips Petroleum Company | Alkali carboxyalkyl dithiocarbamates and use as ore flotation reagents |
US4554068A (en) * | 1983-07-26 | 1985-11-19 | Phillips Petroleum Company | Ore flotation and flotation agents for use therein |
US4702821A (en) * | 1985-02-26 | 1987-10-27 | Phillips Petroleum Company | Ore flotation and di-alkali metal-di(carboxyalkyl)dithiocarbamate and diammonium-di(carboxyalkyl)dithiocarbamate flotation agents for use therein |
US4595538A (en) * | 1985-03-04 | 1986-06-17 | Phillips Petroleum Company | Tri-alkali metal-di(carboxyalkyl)dithiocarbamate and triammonium-di(carboxyalkyl)dithiocarbamate flotation agents |
US4747940A (en) * | 1985-03-04 | 1988-05-31 | Phillips Petroleum Company | Ore flotation and tri-alkali metal-di(carboxyalkyl) dithiocarbamate and triammonium-di(carboxyalkyl) dithiocarbamate flotation agents for use therein |
US4806234A (en) * | 1987-11-02 | 1989-02-21 | Phillips Petroleum Company | Ore flotation |
US4990656A (en) * | 1987-11-02 | 1991-02-05 | Phillips Petroleum Company | Polyamine substituted dithiocarbamate and process for producing the same |
US4883585A (en) * | 1988-10-27 | 1989-11-28 | Phillips Petroleum Company | Ore flotation and sulfenyl dithiocarbamates as agents for use therein |
US5015368A (en) * | 1990-06-15 | 1991-05-14 | The Lubrizol Corporation | Ore flotation process using carbamate compounds |
US20040200760A1 (en) * | 2001-05-14 | 2004-10-14 | Theo Rodopoulos | Selective recovery of minerals by flotation |
US7150357B2 (en) * | 2001-05-14 | 2006-12-19 | Commonwealth Scientific And Industrial Research Organisation | Selective recovery of minerals by flotation |
US9302272B2 (en) | 2011-10-18 | 2016-04-05 | Cytec Technology Corp. | Froth flotation processes |
US9302273B2 (en) | 2011-10-18 | 2016-04-05 | Cytec Technology Corp. | Froth flotation processes |
US9302274B2 (en) | 2011-10-18 | 2016-04-05 | Cytec Technology Corp. | Collector compositions and methods of using the same |
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