US20030228244A1 - Inhibition of the depletion of metal values from pregnant lixiviant solutions - Google Patents
Inhibition of the depletion of metal values from pregnant lixiviant solutions Download PDFInfo
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- US20030228244A1 US20030228244A1 US10/163,700 US16370002A US2003228244A1 US 20030228244 A1 US20030228244 A1 US 20030228244A1 US 16370002 A US16370002 A US 16370002A US 2003228244 A1 US2003228244 A1 US 2003228244A1
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- gold
- metal ore
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- metal
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- 239000002184 metal Substances 0.000 title claims abstract description 50
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 50
- 230000005764 inhibitory process Effects 0.000 title claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 37
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 16
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 239000004094 surface-active agent Substances 0.000 claims abstract description 11
- 238000007037 hydroformylation reaction Methods 0.000 claims abstract description 8
- 239000002280 amphoteric surfactant Substances 0.000 claims abstract description 6
- 230000002401 inhibitory effect Effects 0.000 claims abstract description 6
- 229910052737 gold Inorganic materials 0.000 claims description 43
- 239000010931 gold Substances 0.000 claims description 43
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 40
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 20
- 239000003350 kerosene Substances 0.000 claims description 16
- 238000000605 extraction Methods 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 claims description 8
- 238000002386 leaching Methods 0.000 claims description 7
- 239000010970 precious metal Substances 0.000 claims description 7
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 150000001336 alkenes Chemical class 0.000 claims description 5
- WSJWDSLADWXTMK-UHFFFAOYSA-L disodium;2-[2-(carboxylatomethoxy)ethyl-[2-(octanoylamino)ethyl]amino]acetate Chemical compound [Na+].[Na+].CCCCCCCC(=O)NCCN(CC([O-])=O)CCOCC([O-])=O WSJWDSLADWXTMK-UHFFFAOYSA-L 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- LCFKURIJYIJNRU-UHFFFAOYSA-N 2-methylhexan-1-ol Chemical compound CCCCC(C)CO LCFKURIJYIJNRU-UHFFFAOYSA-N 0.000 claims description 4
- WOFVPNPAVMKHCX-UHFFFAOYSA-N N#C[Au](C#N)C#N Chemical class N#C[Au](C#N)C#N WOFVPNPAVMKHCX-UHFFFAOYSA-N 0.000 claims description 4
- 229940079857 disodium cocoamphodipropionate Drugs 0.000 claims description 4
- KJDVLQDNIBGVMR-UHFFFAOYSA-L disodium;3-[2-aminoethyl-[2-(2-carboxylatoethoxy)ethyl]amino]propanoate Chemical compound [Na+].[Na+].[O-]C(=O)CCN(CCN)CCOCCC([O-])=O KJDVLQDNIBGVMR-UHFFFAOYSA-L 0.000 claims description 4
- 238000001179 sorption measurement Methods 0.000 claims description 4
- LGYNIFWIKSEESD-UHFFFAOYSA-N 2-ethylhexanal Chemical compound CCCCC(CC)C=O LGYNIFWIKSEESD-UHFFFAOYSA-N 0.000 claims description 3
- PFNHSEQQEPMLNI-UHFFFAOYSA-N 2-methyl-1-pentanol Chemical compound CCCC(C)CO PFNHSEQQEPMLNI-UHFFFAOYSA-N 0.000 claims description 3
- 150000001299 aldehydes Chemical class 0.000 claims description 3
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 claims description 3
- 230000006872 improvement Effects 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 4
- 239000011707 mineral Substances 0.000 abstract description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 abstract 1
- 239000003960 organic solvent Substances 0.000 abstract 1
- 238000011282 treatment Methods 0.000 description 12
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 6
- -1 gold cation Chemical class 0.000 description 6
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 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 4
- 238000005065 mining Methods 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- NKJOXAZJBOMXID-UHFFFAOYSA-N 1,1'-Oxybisoctane Chemical class CCCCCCCCOCCCCCCCC NKJOXAZJBOMXID-UHFFFAOYSA-N 0.000 description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 3
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 241000549435 Pria Species 0.000 description 3
- 235000011941 Tilia x europaea Nutrition 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000003556 assay Methods 0.000 description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 3
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 3
- 239000004571 lime Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 230000001143 conditioned effect Effects 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- QVYIAHOSBDIXIQ-UHFFFAOYSA-M sodium;2-chloroacetic acid;2-(2-heptyl-4,5-dihydroimidazol-1-yl)ethanol;hydroxide Chemical compound [OH-].[Na+].OC(=O)CCl.CCCCCCCC1=NCCN1CCO QVYIAHOSBDIXIQ-UHFFFAOYSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- PCWGTDULNUVNBN-UHFFFAOYSA-N 4-methylpentan-1-ol Chemical compound CC(C)CCCO PCWGTDULNUVNBN-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 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
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000004103 aminoalkyl group Chemical group 0.000 description 1
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- GSPKZYJPUDYKPI-UHFFFAOYSA-N diethoxy sulfate Chemical compound CCOOS(=O)(=O)OOCC GSPKZYJPUDYKPI-UHFFFAOYSA-N 0.000 description 1
- 229940047642 disodium cocoamphodiacetate Drugs 0.000 description 1
- 229940079881 disodium lauroamphodiacetate Drugs 0.000 description 1
- ZPRZNBBBOYYGJI-UHFFFAOYSA-L disodium;2-[1-[2-(carboxylatomethoxy)ethyl]-2-undecyl-4,5-dihydroimidazol-1-ium-1-yl]acetate;hydroxide Chemical compound [OH-].[Na+].[Na+].CCCCCCCCCCCC1=NCC[N+]1(CCOCC([O-])=O)CC([O-])=O ZPRZNBBBOYYGJI-UHFFFAOYSA-L 0.000 description 1
- HQYLVDYBSIUTBB-UHFFFAOYSA-L disodium;3-[2-(2-carboxylatoethoxy)ethyl-[2-(dodecanoylamino)ethyl]amino]propanoate Chemical compound [Na+].[Na+].CCCCCCCCCCCC(=O)NCCN(CCC([O-])=O)CCOCCC([O-])=O HQYLVDYBSIUTBB-UHFFFAOYSA-L 0.000 description 1
- GEGKMYLSPGGTQM-UHFFFAOYSA-L disodium;3-[2-(2-carboxylatoethoxy)ethyl-[2-(octanoylamino)ethyl]amino]propanoate Chemical compound [Na+].[Na+].CCCCCCCC(=O)NCCN(CCC([O-])=O)CCOCCC([O-])=O GEGKMYLSPGGTQM-UHFFFAOYSA-L 0.000 description 1
- SFNALCNOMXIBKG-UHFFFAOYSA-N ethylene glycol monododecyl ether Chemical compound CCCCCCCCCCCCOCCO SFNALCNOMXIBKG-UHFFFAOYSA-N 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000002462 imidazolines Chemical class 0.000 description 1
- 239000002736 nonionic surfactant Substances 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
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000005325 percolation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229940114536 sodium capryloamphopropionate Drugs 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- WMLIJOUAGPIENT-UHFFFAOYSA-M sodium;3-[2-hydroxyethyl-[2-(octanoylamino)ethyl]amino]propanoate Chemical compound [Na+].CCCCCCCC(=O)NCCN(CCO)CCC([O-])=O WMLIJOUAGPIENT-UHFFFAOYSA-M 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000002195 synergetic effect Effects 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
- 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
-
- 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
- C22B11/00—Obtaining noble metals
- C22B11/08—Obtaining noble metals by cyaniding
-
- 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
Definitions
- the present invention relates to methods for inhibiting the “robbing” or depletion of metal values from “pregnant” lixiviant solutions that have extracted the desired metal value from the requisite ore.
- Leaching is a cost effective method for recovering precious metals such as gold or silver from ores.
- a lixiviant system comprising a ligant and an oxidant is used to dissolve out the desired precious metal from the ore.
- the metal bearing ore may be obtained from an open pit mine or the like and is crushed to produce an aggregate that is coarse enough to expose the desired mineral values but fine enough to allow intimate contact of the lixiviant system or solution therewith.
- the lixiviant solution may be distributed over the top of the metal ore heap via sprinklers, wobblers, or other similar equipment.
- the barren lixiviant “percolates” through the heap to perform its desired function with the metal and the resulting “pregnant” solution is then collected by an impervious leach pad or the like located at the bottom of the heap.
- the pregnant solution is then subjected to conventional mineral recovery techniques to obtain the desired precious metal.
- a lixiviant system comprising cyanide, air and lime is commonly used under highly alkaline conditions (pH 9-11.5) to form the pregnant solution, (i.e., a complex or ligand coordinated with a gold cation).
- the gold cation complex or ligand leaches from the ore heap and is recovered.
- the gold is then separated from the lixiviant complex via conventional separation techniques such as the conventional method of adsorption on an activated carbon column or bed.
- the present invention is directed toward methods for inhibiting the depletion of metal values from pregnant lixiviant solutions in which certain preg-robbing inhibition agents are brought into contact with the metal ore.
- the preg-robbing inhibition agent may, for example, be applied by itself to the heaped metal ore either before or after the heap is formed.
- the preg-robbing inhibition agents may be combined directly with the lixiviant for concurrent percolation of the combined lixiviant/PRIA throughout the heaped mass.
- the PRIAs may be brought into contact with the crushed metal ore via drip or spray application or may be applied as a foam to the ore. Generally from about 0.024 kg to about 6.0 kg of the PRIA are applied to the metal ore based upon 1 ton of the ore. More preferably, about 0.5 kg to about 2.0 kg of PRIA are applied per ton of ore. Also, the PRIAs may be used in combination with other conventional treatments.
- the preg-robbing inhibition agents in accordance with the invention can be chosen from the groups I-III as explained hereinafter.
- Group I comprises non-ionic surfactants that are members of the alkyl polyglucoside class. These are the mono and oligomeric alkyl polyglucosides having alkyl groups of about 4-20 carbon atoms, preferably about 8 to about 16 carbon atoms and from about 1-4 glucose units. Preferred alkyl polyglucosides are alkyl and (+ ⁇ ) mono and oligo glucopyranoside (CASRN 110615-47-9); D-Glucose, decyl, octyl ethers, oligomeric (CAS No.
- Group II comprises the imidazoline based amphoteric surfactants such as the amphopropionate, amphodipropionate, amphoacetate, and amphodiacetate surfactants.
- These are reported in U.S. Pat. No. 5,744,063, and as stated in that patent, they are prepared by reacting an aminoalkyl alkanol amine or an ethylene or propylene alkylene triamine with a fatty acid to form the desired substituted imidazoline. The so formed imidazoline is then hydrolyzed to an amido amine followed by alkylation of the product with a monohaloacetic acid or its sodium salt.
- the preferred imidazoline amphoteric surfactants are the amphopropionates, amphodipropionates, amphoacetates and amphodiacetates.
- Exemplary members of this class include:
- the preferred composition III is 5-15% 2-ethylhexanol (000104-76-7) 1-5% 2-methylpentanol (000105-30-6) 1-5% 2-ethylhexanal (000123-05-7) 1-5% 2-methylhexanol (000624-22-6) 10-20% ester alcohol and isomers 60-80% others
- the PRIAs preferred for use are the family III hydroformylation products provided in a C 3 -C 24 solvent medium.
- the ore sample is staged crushed to minus 10 mesh.
- a head sample is riffled out for analysis of Au, C(total) and C(graphitic).
- the remainder is riffled into test charges (500 g and/or 1000 g). These charges are then ground in a laboratory ball mill to achieve optimum size for extraction. The optimum size is determined by a series of grinding tests.
- activated carbon typically 20 g fresh, preattritioned, +16 mesh GRC-22 carbon presoaked in water for 24 hours is added to 500 g of the conditioned pulp.
- the required amount of sodium cyanide (1 g/L NaCN) is added, and the bottle is rolled for 48 hours.
- the cyanide and the pH are maintained at the desired levels (1 g/L NaCN and pH 11) during the leach.
- the loaded carbon is recovered by screening on a 20 mesh screen.
- the carbon is washed and dried.
- the dry carbon is weighed and prepared for gold assay.
- the barren pulp is filtered, and the filter cake is washed with water.
- the filtrate and the wash are combined for gold analysis. Owing to the low concentration of gold in solution ( ⁇ 0.05 mg/L), 40 mL of solution is fire assayed.
- the precious metal bead is dissolved in aqua regia to 10 mL for gold reading on an atomic adsorption spectrometer (AA).
- the combined barren wash solution is analyzed for residual NaCN and lime.
- the leach residue is dried, and a sample is riffled out for fire assay for gold using a 30-g sample.
- the pulp is filtered and the filter cake is washed with water. The filtrate and the wash are combined for gold analysis. The leach residue is dried, and a sample is riffled out for fire assay for gold using 30-g sample.
- Table 1 illustrates the efficacy of the treatments by themselves: TABLE 1 Gold Preg-Robbing Tests Dosage Treatment Percent of Gold Treatment kg/ton Time Extraction after Chemical Name of ore (hours) 48 hours None 0 0 14.6 Kerosene 2.0 24 34.1 Kerosene 4.0 24 35.8 Alkyl ⁇ (+ ⁇ )-Mono and oligo Ex. 1 4.0 24 29.5 glucopyranoside (CASRN 110615-47-9) D-Glucose, decyl, octyl ethers, Ex. 2 4.0 24 41.3 oligomeric (CAS No. 68515-73-1) Mixture of ammonium laureth Ex. 3 4.0 24 33.9 (CAS No.
- Table 2 illustrates the increase in efficacy when the treatments are blended with kerosene. TABLE 2 Synergistic effect of treatments when blended with kerosene to a total dosage of 4 kg/t. Percent Gold of Gold Treatment Ratio Extraction after 48 hours Ex. 2/Kerosene 2/2 47.0 Ex. 3/Kerosene 2/2 43.7 Ex. 1/Kerosene 2/2 43.3 Ex. 6/Kerosene 2/2 45.2 Ex. 2/Kerosene 1/3 36.8 Ex. 3/Kerosene 1/3 43.3 Ex. 1/Kerosene 1/3 38.3 Ex. 6/Kerosene 1/3 43.9 Kerosene * — 35.8
- Table 3 illustrates the increase in gold recovery when the treatment is used with activated carbon. TABLE 3 Increase in Gold recovery when treatment is used with activated carbon.
- the invention finds specific utility in the field of inhibiting the depletion of gold from cyanide based lixiviants by heaped gold metal ore, it is also applicable to other mining environments such as precious metal heap mining in general.
- the invention is generally applicable to methods of leaching metals from metal ores in which a lixiviant solution is placed in contact with the metal ore to extract the metal therefrom in the form of a pregnant lixiviant solution.
- the desired metal value is depleted from the pregnant lixiviant solution by contact of the pregnant lixiviant solution with the metal ore.
- the improvement comprises contacting the metal ore with an effective amount of a preg-robbing inhibition agent comprising a member or members selected from the groups consisting of I, II, and III as previously identified.
- the invention may be further viewed as being useful in a metal pulp environment comprising a gold metal ore and a pregnant lixiviant solution containing gold cyanide complexes.
- the method is directed toward inhibition of the adsorption of the gold cyanide complexes by the gold metal ore and comprises contacting the gold metal ore with an effective preg-robbing inhibition agent comprising a member selected from the groups consisting of I, II, and III and mixtures, as described above.
- the invention serves to improve gold extraction in gold refining processes in which activated carbon solutions are used to extract gold from pregnant lixiviant solutions.
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Abstract
Methods for inhibiting depletion of mineral values from pregnant lixiviant solutions comprise contacting the requisite metal ore with a preg-robbing inhibition agent (PRIA) comprising (I) alkyl polyglucoside surfactants; (II) imidazoline based amphoteric surfactants; and (III) hydroformylation products of lower (C2-C8) alkanes in an organic solvent medium.
Description
- The present invention relates to methods for inhibiting the “robbing” or depletion of metal values from “pregnant” lixiviant solutions that have extracted the desired metal value from the requisite ore.
- Leaching is a cost effective method for recovering precious metals such as gold or silver from ores. In the process, a lixiviant system, comprising a ligant and an oxidant is used to dissolve out the desired precious metal from the ore. As used herein, the phrases “lixiviant system” and “lixiviant solution” will be used interchangeably and do not imply a true chemical solution—only a chemical combination adapted to extract the mineral value in the ore.
- In heap leaching, the metal bearing ore may be obtained from an open pit mine or the like and is crushed to produce an aggregate that is coarse enough to expose the desired mineral values but fine enough to allow intimate contact of the lixiviant system or solution therewith. The lixiviant solution may be distributed over the top of the metal ore heap via sprinklers, wobblers, or other similar equipment. The barren lixiviant “percolates” through the heap to perform its desired function with the metal and the resulting “pregnant” solution is then collected by an impervious leach pad or the like located at the bottom of the heap. The pregnant solution is then subjected to conventional mineral recovery techniques to obtain the desired precious metal.
- In gold heap mining operations, a lixiviant system comprising cyanide, air and lime is commonly used under highly alkaline conditions (pH 9-11.5) to form the pregnant solution, (i.e., a complex or ligand coordinated with a gold cation). The gold cation complex or ligand leaches from the ore heap and is recovered. The gold is then separated from the lixiviant complex via conventional separation techniques such as the conventional method of adsorption on an activated carbon column or bed.
- It has been discovered that in some leach mining operations, the metal ore itself can rob or adsorb the metal value that is complexed with the lixiviant in the pregnant lixiviant solution. That is, the amount of metal contained within the pregnant lixiviant solution is depleted by the metal ore itself. This undesirable action is referred to as “preg-robbing” since the pregnant lixiviant solution is robbed or depleted of the desired solubilized metal. Although applicants are not to be bound to any scientific explanation as to the reason for this phenomenon, it is thought that the problem may be caused by presence of graphite or other carbonaceous matter in the raw metal ore.
- Presently, preg-robbing is inhibited by the addition of kerosene, which is highly flammable. In other cases, the ore is roasted or treated in autoclaves at high temperatures. These latter two alternatives are energy intensive, resulting in overall high metal recovery costs.
- It is therefore an object to provide an effective alternative to present day preg-robbing inhibition treatments and methods.
- The present invention is directed toward methods for inhibiting the depletion of metal values from pregnant lixiviant solutions in which certain preg-robbing inhibition agents are brought into contact with the metal ore. The preg-robbing inhibition agent (PRIA) may, for example, be applied by itself to the heaped metal ore either before or after the heap is formed. Also, the preg-robbing inhibition agents may be combined directly with the lixiviant for concurrent percolation of the combined lixiviant/PRIA throughout the heaped mass.
- The PRIAs may be brought into contact with the crushed metal ore via drip or spray application or may be applied as a foam to the ore. Generally from about 0.024 kg to about 6.0 kg of the PRIA are applied to the metal ore based upon 1 ton of the ore. More preferably, about 0.5 kg to about 2.0 kg of PRIA are applied per ton of ore. Also, the PRIAs may be used in combination with other conventional treatments.
- Other objects and advantages of the invention will be apparent from the following description and the appended claims.
- The preg-robbing inhibition agents in accordance with the invention can be chosen from the groups I-III as explained hereinafter.
- I.
- Group I comprises non-ionic surfactants that are members of the alkyl polyglucoside class. These are the mono and oligomeric alkyl polyglucosides having alkyl groups of about 4-20 carbon atoms, preferably about 8 to about 16 carbon atoms and from about 1-4 glucose units. Preferred alkyl polyglucosides are alkyl and (+β) mono and oligo glucopyranoside (CASRN 110615-47-9); D-Glucose, decyl, octyl ethers, oligomeric (CAS No. 68515-73-1); and mixtures of an alcohol ethoxysulfate (ammonium salt) poly (oxy-1,2-ethanediyl), alpha-sulfa-omega-hydroxy-C 10-C16 alkyl ethers, ammonium salts, (CAS No. 67762-19-0), D-Glucose, decyl, octyl ethers oligomerics (CAS No. 68515-73-1) and D-glucopyranoside, C10-C16 alkyl oligomerics (110615-47-9).
- II.
- Group II comprises the imidazoline based amphoteric surfactants such as the amphopropionate, amphodipropionate, amphoacetate, and amphodiacetate surfactants. These are reported in U.S. Pat. No. 5,744,063, and as stated in that patent, they are prepared by reacting an aminoalkyl alkanol amine or an ethylene or propylene alkylene triamine with a fatty acid to form the desired substituted imidazoline. The so formed imidazoline is then hydrolyzed to an amido amine followed by alkylation of the product with a monohaloacetic acid or its sodium salt.
- The preferred imidazoline amphoteric surfactants are the amphopropionates, amphodipropionates, amphoacetates and amphodiacetates. Exemplary members of this class include:
- disodium cocoamphodipropionate
- disodium capryloamphodipropionate
- disodium lauroamphodipropionate
- cocoamphodipropionic acid
- sodium cocoamphopropionate
- sodium capryloamphopropionate
- alkyl imidazoline propionate ester
- alkyl imidazoline propionate salt
- oleoamphopropionic acid
- disodium cocoamphodiacetate
- disodium capryloamphodiacetate
- disodium lauroamphodiacetate
- disodium soyamphodiacetate
- disodium wheat germ amphodiacetate
- Especially preferred members of Group II are:
- disodium capryloamphodiacetate
- CAS 68608-64-0 and
- disodium cocoamphodipropionate
- CAS 68604-71-7
- III.
- As to the third group of compounds that may be used as preg-robbing inhibition agents, these may be described as hydroformylation products of lower alkenes (C 2-C8; C2-C4 preferred) in a C3-C24 solvent medium.
- The preferred composition III is
5-15% 2-ethylhexanol (000104-76-7) 1-5% 2-methylpentanol (000105-30-6) 1-5% 2-ethylhexanal (000123-05-7) 1-5% 2-methylhexanol (000624-22-6) 10-20% ester alcohol and isomers 60-80% others - Based upon presently available data, the PRIAs preferred for use are the family III hydroformylation products provided in a C 3-C24 solvent medium.
- The invention will be further explained in conjunction with the following examples which are included for illustrative purposes only and are not to be construed as limitations to the invention.
- Procedures for Cyanide Leaching of Preg-Robbing Ores
- Procedure
- Feed Sample Preparation
- The ore sample is staged crushed to minus 10 mesh. A head sample is riffled out for analysis of Au, C(total) and C(graphitic). The remainder is riffled into test charges (500 g and/or 1000 g). These charges are then ground in a laboratory ball mill to achieve optimum size for extraction. The optimum size is determined by a series of grinding tests.
- Cyanidation
- a) Carbon-in-Leach Cyanidation
- In order to simulate carbon-in-leach (CIL) extraction, activated carbon (typically 20 g fresh, preattritioned, +16 mesh GRC-22 carbon presoaked in water for 24 hours is added to 500 g of the conditioned pulp. The required amount of sodium cyanide (1 g/L NaCN) is added, and the bottle is rolled for 48 hours. The cyanide and the pH are maintained at the desired levels (1 g/L NaCN and pH 11) during the leach.
- Following CIL, the loaded carbon is recovered by screening on a 20 mesh screen. The carbon is washed and dried. The dry carbon is weighed and prepared for gold assay. The barren pulp is filtered, and the filter cake is washed with water. The filtrate and the wash are combined for gold analysis. Owing to the low concentration of gold in solution (<0.05 mg/L), 40 mL of solution is fire assayed. Following cupelling, the precious metal bead is dissolved in aqua regia to 10 mL for gold reading on an atomic adsorption spectrometer (AA). The combined barren wash solution is analyzed for residual NaCN and lime. The leach residue is dried, and a sample is riffled out for fire assay for gold using a 30-g sample.
- b) Standard Cyanidation
- The required amount of sodium cyanide (1 g/L NaCN) is added to the conditioned pulp, and the bottle is rolled for 48 hours. The cyanide and the pH are maintained at the desired levels (1 g/L NaCN and pH 11) during leaching. Solution samples (30-40 mL) are taken at 6, 24, and 32 hours into the leach for gold analysis. The bottle is weighed before each sampling time to determine the actual volume of solution in the bottle for calculation of the intermediate gold extraction.
- Following leaching, the pulp is filtered and the filter cake is washed with water. The filtrate and the wash are combined for gold analysis. The leach residue is dried, and a sample is riffled out for fire assay for gold using 30-g sample.
- Gold Extraction and Reagent Consumption
- Gold extractions and sodium cyanide and lime (calculated a CaO) consumption are calculated from the analytical results and reported.
- Test Results
- Table 1 illustrates the efficacy of the treatments by themselves:
TABLE 1 Gold Preg-Robbing Tests Dosage Treatment Percent of Gold Treatment kg/ton Time Extraction after Chemical Name of ore (hours) 48 hours None 0 0 14.6 Kerosene 2.0 24 34.1 Kerosene 4.0 24 35.8 Alkyl α (+β)-Mono and oligo Ex. 1 4.0 24 29.5 glucopyranoside (CASRN 110615-47-9) D-Glucose, decyl, octyl ethers, Ex. 2 4.0 24 41.3 oligomeric (CAS No. 68515-73-1) Mixture of ammonium laureth Ex. 3 4.0 24 33.9 (CAS No. 67762-19-0) D- Glucose, decyl, octyl ethers- oligomeric (CAS No. 68515-73-1) and D-glucopyranoside, C10-C16 alkyl oligomeric (110615-47-9) Disodium capryloamphodiacetate Ex. 4 4.0 24 29.8 (CAS No. 68608-64-0) Mixture of disodium Ex. 5 4.0 24 35.2 cocoamphodiproponate (CAS No. 68604-71-7) Mixture of 2-ethylhexanol; 2- Ex. 6 4.0 24 39.4 methylpentanol; 2-ethylhexanal; 2-methylhexanol; ester alcohol and isomers; C3-C24 alcohols, aldehydes, and esters - Table 2 illustrates the increase in efficacy when the treatments are blended with kerosene.
TABLE 2 Synergistic effect of treatments when blended with kerosene to a total dosage of 4 kg/t. Percent Gold of Gold Treatment Ratio Extraction after 48 hours Ex. 2/Kerosene 2/2 47.0 Ex. 3/Kerosene 2/2 43.7 Ex. 1/Kerosene 2/2 43.3 Ex. 6/Kerosene 2/2 45.2 Ex. 2/Kerosene 1/3 36.8 Ex. 3/Kerosene 1/3 43.3 Ex. 1/Kerosene 1/3 38.3 Ex. 6/Kerosene 1/3 43.9 Kerosene * — 35.8 - Table 3 illustrates the increase in gold recovery when the treatment is used with activated carbon.
TABLE 3 Increase in Gold recovery when treatment is used with activated carbon. Treatment Activated Percent of Gold Dosage Carbon Extraction after Treatment kg/t G/L Solution 48 hours None 0 0 6.8 None 0 20.0 68.2 Ex. 6 0.024 20.0 72.5 Ex. 6 0.050 20.0 73.5 Ex. 6 0.075 20.0 74.9 Ex 6 0.10 20.0 77.6 Ex. 6 0.20 20.0 75.0 Ex. 6 2.0 20.0 75.8 Ex. 6 4.0 20.0 73.2 Ex. 6 0.024 0 11.0 Ex. 6 0.050 0 15.5 Ex. 6 0.075 0 18.3 Ex. 6 0.10 0 20.6 Ex. 6 0.20 0 27.8 Ex. 6 2.0 0 51.6 Ex. 6 4.0 0 57.5 - Although the invention finds specific utility in the field of inhibiting the depletion of gold from cyanide based lixiviants by heaped gold metal ore, it is also applicable to other mining environments such as precious metal heap mining in general.
- The invention is generally applicable to methods of leaching metals from metal ores in which a lixiviant solution is placed in contact with the metal ore to extract the metal therefrom in the form of a pregnant lixiviant solution. As indicated previously, in some cases, the desired metal value is depleted from the pregnant lixiviant solution by contact of the pregnant lixiviant solution with the metal ore. In these methods, the improvement comprises contacting the metal ore with an effective amount of a preg-robbing inhibition agent comprising a member or members selected from the groups consisting of I, II, and III as previously identified.
- The invention may be further viewed as being useful in a metal pulp environment comprising a gold metal ore and a pregnant lixiviant solution containing gold cyanide complexes. The method is directed toward inhibition of the adsorption of the gold cyanide complexes by the gold metal ore and comprises contacting the gold metal ore with an effective preg-robbing inhibition agent comprising a member selected from the groups consisting of I, II, and III and mixtures, as described above.
- Additionally, the invention serves to improve gold extraction in gold refining processes in which activated carbon solutions are used to extract gold from pregnant lixiviant solutions.
- While the present invention has been described with respect to particular embodiments thereof, it is apparent that other forms and modifications of the invention will be obvious to those skilled in the art. The appended claims and this invention generally should be construed to cover all such obvious forms and modifications which are within the true spirit and scope of the present invention.
Claims (24)
1. In the leaching of metals from a metal ore in which a lixiviant solution is placed in contact with said metal ore to extract said metal therefrom in the form of a pregnant lixiviant solution, a method of inhibiting depletion of said extracted metal from said pregnant lixiviant solution, said method comprising contacting said metal ore with an effective amount of a preg-robbing inhibition agent (PRIA) comprising a member selected from the groups consisting of I, II, and III and mixtures of said groups wherein I is an alkyl polyglucoside surfactant, II is an imidazoline based amphoteric surfactant, and III comprises hydroformylation products of C2-C8 alkenes in a C3-C24 medium.
2. Method as recited in claim 1 wherein from about 0.024-about 6 kg of said PRIA is brought into contact with said metal ore based upon 1 ton of said metal ore.
3. Method as recited in claim 2 wherein from about 0.5-about 2.0 kg of said PRIA is brought into contact with said metal ore based upon 1 ton of said metal ore.
4. Method as recited in claim 1 wherein said metal ore comprises a precious metal.
5. Method as recited in claim 4 wherein said precious metal ore comprises gold.
6. Method as recited in claim 5 wherein said pregnant lixiviant solution comprises a cyanide solution.
7. Method as recited in claim 1 wherein I is present and comprises an alkyl group of about 4-20 carbon atoms and about 1-4 glucose units.
8. Method as recited in claim 7 wherein in I, said alkyl group has from about 8 to about 16 carbon atoms.
9. Method as recited in claim 1 wherein II is present and said amphoteric imidazoline surfactant comprises i) an amphopropionate compound; ii) an amphodipropionate compound; iii) an amphoacetate compound; or iv) an amphodiacetate compound.
10. Method as recited in claim 9 wherein said amphoteric imidazoline surfactant comprises disodium capryloamphodiacetate.
11. Method as recited in claim 10 wherein said amphoteric imidazoline surfactant comprises disodium cocoamphodipropionate.
12. Method as recited in claim 1 wherein III is present and said C1-C8 alkene hydroformylation products comprise 2-ethylhexanol, 2-methylpentanol, 2-ethylhexanal; 2-methylhexanol in a medium containing C3-C24 alcohols, aldehydes and esters.
13. Method as recited in claim 1 wherein said preg-robbing inhibition agent further comprises kerosene.
14. In a metal pulp comprising a gold metal ore and a pregnant lixiviant solution containing gold cyanide complexes, a method of inhibiting adsorption of said gold cyanide complexes by said gold metal ore comprising contacting said gold metal ore with an effective preg-robbing inhibition agent (PRIA) comprising a member selected from the groups consisting of I, II, and III and mixtures of said groups wherein I is an alkyl polyglucoside surfactant, II is an imidazoline based amphoteric surfactant, and III comprises hydroformylation products of C2-C8 alkenes in a C3-C24 medium.
15. Method as recited in claim 14 wherein from about 0.024-about 6 kg of said PRIA is brought into contact with said gold metal ore based upon 1 ton of said gold metal ore.
16. Method as recited in claim 15 wherein from about 0.5kg -about 2 kg of said PRIA is brought into contact with said gold metal ore based upon 1 ton of said gold metal ore.
17. Method as recited in claim 14 wherein I is present and comprises an alkyl group of about 4-20 carbon atoms and about 1-4 glucose units.
18. Method as recited in claim 17 wherein in I, said alkyl group has from about 8 to about 16 carbon atoms.
19. Method as recited in claim 14 wherein II is present and said amphoteric imidazoline surfactant comprises i) an amphopropionate compound; ii) an amphodipropionate compound; iii) an amphoacetate compound; or iv) an amphodiacetate compound.
20. Method as recited in claim 19 wherein said amphoteric imidazoline surfactant comprises disodium capryloamphodiacetate.
21. Method as recited in claim 20 wherein said amphoteric imidazoline surfactant comprises disodium cocoamphodipropionate.
22. Method as recited in claim 14 wherein III is present and said hydroformylation products comprise 2-ethylhexanol, 2-methylpentanol, 2-ethyhexanal; 2-methylhexanol in a medium containing C3-C24 alcohols, aldehydes and esters.
23. Method as recited in claim 14 wherein said preg-robbing inhibition agent further comprises kerosene.
24. In a gold extraction process in which a lixiviant solution is brought into contact with a gold bearing ore to form a pregnant lixiviant solution, and wherein said pregnant lixiviant solution is contacted with activated carbon to aid in separating said gold from said pregnant lixiviant solution, the improvement comprising contacting said activated carbon with a member selected form the groups consisting of I, II, and III and mixtures of said groups wherein I is an alkyl polyglucoside surfactant, II is an imidazoline based amphoteric surfactant, and III comprises hydroformylation products of C2-C8 alkenes in a C3-C24 medium.
Priority Applications (11)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US10/163,700 US20030228244A1 (en) | 2002-06-05 | 2002-06-05 | Inhibition of the depletion of metal values from pregnant lixiviant solutions |
| US10/417,910 US7157062B2 (en) | 2002-06-05 | 2003-04-17 | Inhibition of the depletion of metal values from pregnant lixiviant solutions |
| PCT/US2003/016184 WO2003104503A1 (en) | 2002-06-05 | 2003-05-22 | Inhibition of the depletion of precious metal values from pregnant lixiviant solutions |
| CA2488146A CA2488146C (en) | 2002-06-05 | 2003-05-22 | Inhibition of the depletion of precious metal values from pregnant lixiviant solutions |
| CNB038188945A CN100383263C (en) | 2002-06-05 | 2003-05-22 | Inhibition of the depletion of precious metal values from pregnant lixiviant solutions |
| AU2003237208A AU2003237208B2 (en) | 2002-06-05 | 2003-05-22 | Inhibition of the depletion of precious metal values from pregnant lixiviant solutions |
| NZ537325A NZ537325A (en) | 2002-06-05 | 2003-05-22 | Inhibition of the depletion of precious metal values from pregnant lixiviant solutions |
| AR20030101928A AR040436A1 (en) | 2002-06-05 | 2003-05-30 | METHOD OF INHIBITION OF THE EXHAUSTION OF METAL VALUES OF PRESSED LIXIVING SOLUTIONS |
| PE2003000547A PE20040239A1 (en) | 2002-06-05 | 2003-06-03 | INHIBITION OF THE DEPLETION OF METAL VALUES FROM PREGNANT LEACHING SOLUTIONS |
| MYPI20032085A MY134901A (en) | 2002-06-05 | 2003-06-04 | Inhibition of the depletion of metal values from pregnant lixiviant solutions |
| ZA200410244A ZA200410244B (en) | 2002-06-05 | 2004-12-20 | Inhibition of the depletion of precious metal values from pregnant lixiviant solutions |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US10/163,700 US20030228244A1 (en) | 2002-06-05 | 2002-06-05 | Inhibition of the depletion of metal values from pregnant lixiviant solutions |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US10/417,910 Continuation-In-Part US7157062B2 (en) | 2002-06-05 | 2003-04-17 | Inhibition of the depletion of metal values from pregnant lixiviant solutions |
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| Publication Number | Publication Date |
|---|---|
| US20030228244A1 true US20030228244A1 (en) | 2003-12-11 |
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|---|---|---|---|
| US10/163,700 Abandoned US20030228244A1 (en) | 2002-06-05 | 2002-06-05 | Inhibition of the depletion of metal values from pregnant lixiviant solutions |
| US10/417,910 Expired - Fee Related US7157062B2 (en) | 2002-06-05 | 2003-04-17 | Inhibition of the depletion of metal values from pregnant lixiviant solutions |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
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| US10/417,910 Expired - Fee Related US7157062B2 (en) | 2002-06-05 | 2003-04-17 | Inhibition of the depletion of metal values from pregnant lixiviant solutions |
Country Status (5)
| Country | Link |
|---|---|
| US (2) | US20030228244A1 (en) |
| AR (1) | AR040436A1 (en) |
| MY (1) | MY134901A (en) |
| PE (1) | PE20040239A1 (en) |
| ZA (1) | ZA200410244B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US10611795B2 (en) | 2013-11-15 | 2020-04-07 | Genentech, Inc. | Methods for viral inactivation using eco-friendly detergents |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FI122685B (en) * | 2010-06-09 | 2012-05-31 | Outotec Oyj | A method for recovering gold by liquid-liquid extraction |
| CA2908336A1 (en) * | 2013-04-18 | 2014-10-23 | Akzo Nobel Chemicals International B.V. | Use of cationic surfactants in the cyanidation of refractory carbonaceous ores for recovery of metals |
| GB2551980A (en) * | 2016-06-30 | 2018-01-10 | Commw Scient Ind Res Org | Method and system for low level metal analysis of mineral samples |
| CN106629211B (en) * | 2017-02-24 | 2019-03-15 | 北京小米移动软件有限公司 | Double-sided adhesive separator |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU451756A1 (en) | 1970-12-25 | 1974-11-30 | Московский Ордена Трудового Красного Знамени Институт Стали И Сплавов | The method of extraction of metals ores |
| CA1062918A (en) | 1976-02-09 | 1979-09-25 | Kerr Addison Mines Limited | Milling of graphitic or carbonaceous ores |
| US4110539A (en) | 1977-07-13 | 1978-08-29 | Eastman Kodak Company | Process for the preparation of 2,2,4-trimethyl-1,3-pentanediol diisobutyrate |
| US4269730A (en) | 1978-05-01 | 1981-05-26 | Stepan Chemical Company | Substituted imidazoline reactions with chloroacetate salts |
| US4929274A (en) | 1989-06-07 | 1990-05-29 | Drew Chemical Corporation | Recovery of metal values from ores |
| US5180847A (en) | 1991-02-15 | 1993-01-19 | Basf Corporation | Processes for preparing 2,2,4-trimethyl-1,3-pentanediol derivatives |
| CA2132289A1 (en) | 1993-10-12 | 1995-04-13 | Bharat Desai | Higher purity imidazoline based amphoacetate surfactants and processes for the preparation thereof |
| US6025522A (en) | 1999-04-30 | 2000-02-15 | Clariant Finance (Bvi) Ltd. | Process for making secondary amphoacetates and diacetates |
-
2002
- 2002-06-05 US US10/163,700 patent/US20030228244A1/en not_active Abandoned
-
2003
- 2003-04-17 US US10/417,910 patent/US7157062B2/en not_active Expired - Fee Related
- 2003-05-30 AR AR20030101928A patent/AR040436A1/en active IP Right Grant
- 2003-06-03 PE PE2003000547A patent/PE20040239A1/en not_active Application Discontinuation
- 2003-06-04 MY MYPI20032085A patent/MY134901A/en unknown
-
2004
- 2004-12-20 ZA ZA200410244A patent/ZA200410244B/en unknown
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10611795B2 (en) | 2013-11-15 | 2020-04-07 | Genentech, Inc. | Methods for viral inactivation using eco-friendly detergents |
Also Published As
| Publication number | Publication date |
|---|---|
| US20030228245A1 (en) | 2003-12-11 |
| ZA200410244B (en) | 2006-07-26 |
| MY134901A (en) | 2007-12-31 |
| US7157062B2 (en) | 2007-01-02 |
| AR040436A1 (en) | 2005-04-06 |
| PE20040239A1 (en) | 2004-04-15 |
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