CN115703090A - Tungsten ore flotation method - Google Patents
Tungsten ore flotation method Download PDFInfo
- Publication number
- CN115703090A CN115703090A CN202110887073.7A CN202110887073A CN115703090A CN 115703090 A CN115703090 A CN 115703090A CN 202110887073 A CN202110887073 A CN 202110887073A CN 115703090 A CN115703090 A CN 115703090A
- Authority
- CN
- China
- Prior art keywords
- flotation
- tungsten ore
- tungsten
- hydroximic acid
- acid
- 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.)
- Pending
Links
- 238000005188 flotation Methods 0.000 title claims abstract description 177
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 229910052721 tungsten Inorganic materials 0.000 title claims abstract description 87
- 239000010937 tungsten Substances 0.000 title claims abstract description 87
- 238000000034 method Methods 0.000 title claims abstract description 59
- 239000002253 acid Substances 0.000 claims abstract description 101
- ZXOKVTWPEIAYAB-UHFFFAOYSA-N dioxido(oxo)tungsten Chemical compound [O-][W]([O-])=O ZXOKVTWPEIAYAB-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000002500 ions Chemical class 0.000 claims abstract description 4
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 claims description 68
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 43
- 239000011591 potassium Substances 0.000 claims description 43
- 229910052700 potassium Inorganic materials 0.000 claims description 43
- 230000008569 process Effects 0.000 claims description 22
- 239000003153 chemical reaction reagent Substances 0.000 claims description 16
- 239000012190 activator Substances 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- -1 n-octyl Chemical group 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 8
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000012141 concentrate Substances 0.000 claims description 5
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- 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 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 4
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims 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 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 229940046892 lead acetate Drugs 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000002002 slurry Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 238000011084 recovery Methods 0.000 abstract description 55
- VDEUYMSGMPQMIK-UHFFFAOYSA-N benzhydroxamic acid Chemical compound ONC(=O)C1=CC=CC=C1 VDEUYMSGMPQMIK-UHFFFAOYSA-N 0.000 abstract description 24
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 9
- 239000011707 mineral Substances 0.000 abstract description 9
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical group [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 abstract description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 6
- 239000011593 sulfur Substances 0.000 abstract description 6
- 229910052717 sulfur Inorganic materials 0.000 abstract description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 5
- 239000011575 calcium Substances 0.000 abstract description 5
- 229910052791 calcium Inorganic materials 0.000 abstract description 5
- 230000000536 complexating effect Effects 0.000 abstract description 5
- 230000003213 activating effect Effects 0.000 abstract description 4
- 230000004913 activation Effects 0.000 abstract description 4
- 125000000524 functional group Chemical group 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 230000009920 chelation Effects 0.000 abstract description 2
- WVYWICLMDOOCFB-UHFFFAOYSA-N 4-methyl-2-pentanol Chemical compound CC(C)CC(C)O WVYWICLMDOOCFB-UHFFFAOYSA-N 0.000 description 58
- 239000004088 foaming agent Substances 0.000 description 33
- 230000000052 comparative effect Effects 0.000 description 17
- 229910021532 Calcite Inorganic materials 0.000 description 15
- 239000002245 particle Substances 0.000 description 13
- IOEJYZSZYUROLN-UHFFFAOYSA-M Sodium diethyldithiocarbamate Chemical compound [Na+].CCN(CC)C([S-])=S IOEJYZSZYUROLN-UHFFFAOYSA-M 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 239000012990 dithiocarbamate Substances 0.000 description 9
- 238000000926 separation method Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 4
- NEAQRZUHTPSBBM-UHFFFAOYSA-N 2-hydroxy-3,3-dimethyl-7-nitro-4h-isoquinolin-1-one Chemical compound C1=C([N+]([O-])=O)C=C2C(=O)N(O)C(C)(C)CC2=C1 NEAQRZUHTPSBBM-UHFFFAOYSA-N 0.000 description 3
- JZRWCGZRTZMZEH-UHFFFAOYSA-N Thiamine Natural products CC1=C(CCO)SC=[N+]1CC1=CN=C(C)N=C1N JZRWCGZRTZMZEH-UHFFFAOYSA-N 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 235000019353 potassium silicate Nutrition 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- KYMBYSLLVAOCFI-UHFFFAOYSA-N thiamine Chemical compound CC1=C(CCO)SCN1CC1=CN=C(C)N=C1N KYMBYSLLVAOCFI-UHFFFAOYSA-N 0.000 description 3
- 229960003495 thiamine Drugs 0.000 description 3
- 235000019157 thiamine Nutrition 0.000 description 3
- 239000011721 thiamine Substances 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 235000003140 Panax quinquefolius Nutrition 0.000 description 2
- 240000005373 Panax quinquefolius Species 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 125000001033 ether group Chemical group 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- ICRPZKBRYZRHLB-UHFFFAOYSA-N 4-methylpentan-2-ol Chemical compound CC(C)CC(C)O.CC(C)CC(C)O ICRPZKBRYZRHLB-UHFFFAOYSA-N 0.000 description 1
- 241001251371 Betula chinensis Species 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000008396 flotation agent Substances 0.000 description 1
- 239000010436 fluorite Substances 0.000 description 1
- 238000009291 froth flotation Methods 0.000 description 1
- 239000002223 garnet Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 125000001990 thiamine group Chemical group 0.000 description 1
Classifications
-
- 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
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a tungsten ore flotation method, and belongs to the technical field of ore dressing. The method takes lead ions as an activating agent and azote-hydroximic acid or azoxystrobin-hydroximic acid as a collecting agent, and recycles wolframite and scheelite by flotation. The sulfur nitrogen functional group has strong complexing ability with Pb (II), and the hydroximic acid functional group also has complexing effect with Pb (II), so that the sulfur nitrogen-hydroximic acid and the sulfur nitrogen ester-hydroximic acid have double-site chelation effect on Pb (II), and can strengthen the activated flotation of tungsten ore. The tungsten ore flotation method has the characteristics of strong collecting capability and good selectivity, and particularly has excellent selectivity on calcium-containing gangue minerals. Compared with the prior lead ion activation and benzohydroxamic acid flotation or the single use of the azote-hydroximic acid or the azote-hydroximic acid, the tungsten ore flotation method can greatly improve the tungsten ore flotation recovery rate, has obvious economic benefit and has good industrial application prospect.
Description
Technical Field
The invention relates to a flotation and mineral separation method, and belongs to the technical field of mineral flotation.
Background
The tungsten ore mainly comprises wolframite and scheelite, wherein the scheelite is a main tungsten mineral and accounts for about 70% of tungsten ore resources, the wolframite accounts for about 20%, and the mixed wolframite and scheelite accounts for about 10%. Flotation is the main beneficiation method for separating and enriching tungsten ores.
There are currently two main processes for tungsten ore flotation (Wei Zhao, sun Wei, han Haisheng, wang Jianjun, wang Relin, kang Jianhua. Tungsten ore flotation process advances and practices metal mines 2021, 540 (06): 60-72), a flotation process based on fatty acid collectors, which is divided into normal temperature flotation and "bedloff" warming flotation, mainly used for scheelite flotation recovery, where warming flotation helps flotation separation of scheelite and calcium-containing gangue minerals. The other flotation process mainly comprises a GY (hydroximic acid and fatty acid) method and a benzohydroximic acid method, wherein the GY method uses lead nitrate as an activating agent and utilizes the synergy of the benzohydroximic acid and the fatty acid to realize the mixed flotation of the black and white tungsten ores. The benzohydroxamic acid method uses lead nitrate as an activator and benzohydroxamic acid as a collector to float the wolframite, can realize normal-temperature high-efficiency short-flow flotation separation of the wolframite, and can improve the flotation index of the wolframite by mixing the lead nitrate and the benzohydroxamic acid in advance (lead complexes or complex ions of the benzohydroxamic acid can be generated).
Meanwhile, chinese patent (Liu Anyi, quiet paint, van hong Li, liu Sheng. A collector with double functional groups of the sulfur nitrogen-hydroximic acid and application thereof, ZL2018111291418, 2018-9-26) discloses that a collector of the sulfur nitrogen-hydroximic acid is applied to tungsten ore flotation; chinese patents (Liu Anyi, liu Sheng, zhong Hong, cao Zhanfang, wang Shuai. An N-alkyl hydroximic acid-dithiocarbamate collector and a preparation and flotation method thereof, ZL201710230937.1, 2017-4-10) disclose a thiamine ester-hydroximic acid collector applied to tungsten ore flotation. Because of the weak reactivity of the thioacid and thioacid functional groups to calcium ions (hanging Qi, guangyi Liu, yan Dong. Binding the hydronic mechanism of N- [ (3-hydroxyamino) -proxy ] -N-octyl dithiocarbamate hydration by in situ AFM, FTIR and XPS. Journal of colloid and Interface Science 572 (2020) 179-189), the thioacid or thioacid ester-hydroximic acid functions primarily to adjust the solubility or hydrophobicity of the collector when it is flotated in tungsten ore, especially in scheelite. However, the existing tungsten ore flotation method has the problem of unsatisfactory flotation performance.
Disclosure of Invention
In order to solve the problem of unsatisfactory flotation performance of the existing tungsten ore flotation method, the invention aims to provide a brand-new tungsten ore flotation method, and aims to improve the flotation effect of tungsten ore and improve the separation selectivity of tungsten ore and gangue.
A tungsten ore flotation method comprises the steps of carrying out flotation on ore pulp containing tungsten ore and a flotation reagent to obtain tungsten concentrate; wherein the flotation reagent at least comprises a lead ion activator and a collector;
the collecting agent comprises at least one of a azote-hydroximic acid collecting agent shown in a formula I and an azote-hydroximic acid collecting agent shown in a formula II;
M 1 is sodium, potassium or hydrogen; m 2 Is sodium or potassium;
R 1 is C 2 ～C 16 A hydrocarbon group or oxygen-containing hydrocarbon group of (a);
R 2 and R 3 Independently of hydrogen, C 1 ～C 16 A hydrocarbon group or oxygen-containing hydrocarbon group of (II), but R 2 And R 3 Is not hydrogen at the same time; n is 1 to 4.
The research of the invention finds that the sulfur nitrogen functional group has strong complexing ability with Pb (II), and the hydroximic acid functional group also has complexing effect with Pb (II), so that the sulfur nitrogen-hydroximic acid and the sulfur nitrogen ester-hydroximic acid have double-site chelation effect on Pb (II), and can enhance the activated flotation of tungsten ore. The tungsten ore flotation method has the characteristics of strong collecting capability and good selectivity, and particularly has excellent selectivity on calcium-containing gangue minerals. Compared with the prior lead ion activation and benzohydroxamic acid flotation or the single use of the azote-hydroximic acid or the azote-hydroximic acid, the tungsten ore flotation method can greatly improve the tungsten ore flotation recovery rate, has obvious economic benefit and has good industrial application prospect.
In the invention, the coordination of the intramolecular double chelating mechanism of lead, sulfur nitrogen (azothionate) and hydroximic acid is the key to improve the tungsten ore collecting performance.
The above tungsten ore flotation process, R 1 Is C 2 ～C 16 An alkyl group or an oxaalkyl group (ether group); preferably butyl, isobutyl, pentyl, isopentyl, n-hexyl, n-octyl or isooctyl.
The above tungsten ore flotation method, R 2 And R 3 Independently of one another are H or hydrogen, C 1 ～C 16 Alkyl or oxaalkyl (ether) groups.
The above tungsten ore flotation process, R 3 Preferably hydrogen, R 2 Preferably butyl, isobutyl, pentyl, isopentyl, n-hexyl, n-octyl, isooctyl or dodecyl. Or, R 2 And R 3 Likewise, ethyl, propyl, ethylpropyl or butyl are preferred.
In the tungsten ore flotation method, n is preferably 2.
In the invention, the lead ion activator can ionize Pb in water 2+ The water-soluble salt of (1); preferably at least one of lead nitrate and lead acetate;
preferably, the addition molar ratio of the lead ions in the collecting agent and the lead ion activating agent is 1:1-10; more preferably 1:2 to 4.
In the tungsten ore flotation method, the amount of the flotation reagent is not particularly required, for example, the amount of the collector is 10 to 1200g/t, preferably 50 to 500g/t, based on the weight of the metal ore (tungsten ore); more preferably 150 to 350g/t.
The tungsten ore flotation method is not particularly limited as to the pH of the slurry during flotation, and may be, for example, 6.0 to 10.0, preferably 7.5 to 8.5.
In the tungsten ore flotation method, the tungsten ore comprises at least one of scheelite and wolframite.
The flotation reagent is added in the tungsten ore grinding process, the size mixing process or the size mixed slurry.
Preferably, in the flotation reagent, the lead ion activator and the collector are added respectively, or are added after being mixed and reacted in advance; it is preferable to add the reaction mixture after the preliminary reaction. Research finds that the lead ion activating agent and the collecting agent are mixed and reacted in advance and then participate in the flotation of tungsten ores, so that the flotation performance of the tungsten ores can be further improved.
In the present invention, the flotation is, for example, froth flotation.
In the invention, the flotation reagent also allows other reagents which are helpful for flotation, such as foaming agents, pH regulators, water glass dispersants and the like.
The invention discloses a preferable tungsten ore flotation method, which comprises the following steps of:
step (1): crushing and pulp mixing the tungsten ore to obtain ore pulp;
step (2): adding a flotation reagent into the ore pulp obtained in the step (1) for flotation, and collecting flotation concentrate; the flotation reagent at least comprises the lead ion activator and a sulfur nitrogen-hydroximic acid (formula I) collecting agent or the lead ion activator and a sulfur nitrogen ester-hydroximic acid (formula II) collecting agent; other flotation agents may also include frothers, pH adjusters, water glass dispersants, and the like; the lead ion activator is mainly lead nitrate.
Compared with the prior art, the invention has the advantages that:
1. the tungsten ore flotation method provided by the invention has the advantages of low dosage of the flotation reagent and high tungsten ore recovery rate, and compared with benzohydroxamic acid, the tungsten flotation recovery rate can be improved by more than 40 percent; compared with lead nitrate activation and benzohydroxamic acid collection, the tungsten flotation recovery rate can be improved by more than 20 percent; compared with the single use of the azothiohydroxamic acid (formula I) or the azothiohydroxamic acid (formula II), the tungsten flotation recovery rate can be improved by more than 20 percent. Lead nitrate in combination with a thiamine-hydroxamic acid (formula I) or a thiamine ester-hydroxamic acid (formula II), both the thiamine or thiamine functionality and the hydroxamic acid functionality being able to react with Pb 2+ Complexing to form a double-site action mechanism, strengthening the activated flotation of tungsten ore and reducing the dosage of the medicament.
2. The tungsten ore flotation method provided by the invention has good selectivity on calcium/magnesium-containing gangue minerals (such as calcite and dolomite), and can realize efficient flotation separation of the tungsten ore and the calcium/magnesium-containing gangue minerals.
3. The tungsten ore flotation method provided by the invention has the advantages of simple process and high flotation efficiency. The method takes the azote-hydroximic acid or azote-hydroximic acid and lead nitrate as main flotation reagents, has high flotation speed and high efficiency, does not need to change field process equipment and flow, and is easy for industrial application.
Detailed Description
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein, but rather should be construed as broadly as the present invention is capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Comparative example 1: benzohydroxamic acid flotation scheelite
The concentration of benzohydroxamic acid is 4.0 × 10 -5 mol/L, pH of ore pulp of 8.0, concentration of foaming agent methyl isobutyl carbinol (MIBC) of 1.0 × 10 -4 mol/L, floating scheelite with the particle size of 0.037-0.074 mm, and the floating recovery rate of the scheelite is 7.2%.
Comparative example 2: flotation of scheelite with lead nitrate and benzohydroxamic acid
The concentration of lead nitrate is 1.0X 10 -4 mol/L, benzohydroxamic acid concentration of 4.0X 10 -5 mol/L, pH of ore pulp of 8.0, concentration of foaming agent methyl isobutyl carbinol (MIBC) of 1.0 × 10 -4 mol/L, the scheelite with the grain diameter of 0.037 mm-0.074 mm is subjected to activated flotation, and the recovery rate of the scheelite is 53.3 percent
Comparative example 3: flotation of scheelite with potassium N- [ (3-hydroximic acid) -propyl ] -N-N-butyldithiocarbamate
N-[ (3-hydroximic acid) -propyl]Potassium (E) -N-butyldithiocarbamate concentration 4.0X 10 -5 mol/L, pH of the ore pulp is 8.0, and the concentration of a foaming agent methyl isobutyl carbinol (MIBC) is 1.0 multiplied by 10 -4 And mol/L, directly floating the scheelite with the grain diameter of 0.037 mm-0.074 mm, wherein the flotation recovery rate of the scheelite is 21.1%.
Example 1: flotation of scheelite with lead nitrate and potassium N- [ (3-hydroximic acid) -propyl ] -N-N-butyldithiocarbamate
The concentration of lead nitrate is 1.0 × 10 -4 mol/L, N- [ (3-hydroximic acid) -propyl]Potassium (E) -N-N-butyldithiocarbamate in a concentration of 4X 10 -5 mol/L, pH of ore pulp of 8.0, concentration of foaming agent methyl isobutyl carbinol (MIBC) of 1.0 × 10 -4 And mol/L, performing activated flotation on the scheelite with the particle size of 0.037 mm-0.074 mm, wherein the flotation recovery rate of the scheelite reaches 79.3%.
Thus, the combined use of lead nitrate and potassium N- [ (3-hydroxamic acid) -propyl ] -N-N-butyldithiocarbamate significantly improves the flotation recovery of scheelite as compared to the addition of potassium N- [ (3-hydroxamic acid) -propyl ] -N-N-butyldithiocarbamate alone or in combination with lead nitrate and hydroxamic acid.
Comparative example 4: flotation of wolframite with benzohydroxamic acid
The concentration of benzohydroxamic acid is 4.0 × 10 -5 mol/L, pH of ore pulp of 8.0, concentration of foaming agent methyl isobutyl carbinol (MIBC) of 1.0 × 10 -4 And (2) mol/L, directly floating the wolframite with the grain size of 0.037-0.074 mm, wherein the flotation recovery rate of the wolframite is 2.6%.
Comparative example 5: lead nitrate and benzohydroxamic acid flotation wolframite
The concentration of lead nitrate is 1.0X 10 -4 mol/L, benzohydroxamic acid concentration of 4.0X 10 -5 mol/L, pH of ore pulp of 8.0, concentration of foaming agent methyl isobutyl carbinol (MIBC) of 1.0 × 10 -4 And mol/L, carrying out activated flotation on the wolframite with the grain diameter of 0.037-0.074 mm, wherein the flotation recovery rate of the wolframite is 23.8%.
Comparative example 6: flotation of wolframite with potassium N- [ (3-hydroximic acid) -propyl ] -N-N-butyldithiocarbamate
N- [ (3-hydroximic acid) -propaneBase of]Potassium (E) -N-butyldithiocarbamate concentration 4.0X 10 -5 mol/L, pH of ore pulp of 8.0, concentration of foaming agent methyl isobutyl carbinol (MIBC) of 1.0 × 10 -4 And (2) mol/L, directly floating the wolframite with the grain diameter of 0.037-0.074 mm, wherein the flotation recovery rate of the wolframite is 25.2%.
Example 2: flotation of wolframite with lead nitrate and potassium N- [ (3-hydroximic acid) -propyl ] -N-N-butyldithiocarbamate
The concentration of lead nitrate is 1.0 × 10 -4 mol/L, N- [ (3-hydroximic acid) -propyl]Potassium (E) -N-butyldithiocarbamate concentration 4.0X 10 -5 mol/L, pH of ore pulp of 8.0, concentration of foaming agent methyl isobutyl carbinol (MIBC) of 1.0 × 10 - 4 And mol/L, carrying out activated flotation on the wolframite with the grain diameter of 0.037-0.074 mm, wherein the flotation recovery rate of the wolframite is 75.9%.
Thus, the combined use of lead nitrate and potassium N- [ (3-hydroxamic acid) -propyl ] -N-butyldithiocarbamate significantly improves the flotation recovery of wolframite as compared to the addition of potassium N- [ (3-hydroxamic acid) -propyl ] -N-butyldithiocarbamate alone or in combination with lead nitrate and hydroxamic acid.
Comparative example 7: flotation of scheelite with sodium N, N-diethyldithiocarbamate
The concentration of sodium N, N-diethyldithiocarbamate is 4.0X 10 -5 mol/L, pH of the ore pulp is 8.0, and the concentration of a foaming agent methyl isobutyl carbinol (MIBC) is 1.0 multiplied by 10 -4 And mol/L, directly floating the scheelite with the grain diameter of 0.037 mm-0.074 mm, wherein the flotation recovery rate of the scheelite is 9.9%.
Comparative example 8: flotation of scheelite by lead nitrate and sodium N, N-diethyldithiocarbamate
The concentration of sodium N, N-diethyldithiocarbamate is 4.0X 10 -5 mol/L, lead nitrate concentration of 1.0X 10 - 4 mol/L, pH of ore pulp of 8.0, concentration of foaming agent methyl isobutyl carbinol (MIBC) of 1.0 × 10 -4 And mol/L, performing activated flotation on the scheelite with the particle size of 0.037 mm-0.074 mm, wherein the flotation recovery rate of the scheelite is 20.6%.
Comparative example 9: flotation of scheelite with potassium N- [ (3-hydroximic acid) -propyl ] -N-N-hexyldithiocarbamate
N- [ (3-hydroximic acid) -propyl]potassium-N-N-hexyldithiocarbamate concentration 4.0X 10 -5 mol/L, pH of ore pulp of 8.0, concentration of foaming agent methyl isobutyl carbinol (MIBC) of 1.0 × 10 -4 And mol/L, directly floating the scheelite with the grain diameter of 0.037 mm-0.074 mm, wherein the flotation recovery rate of the scheelite is 22.3%.
Example 3: flotation of scheelite with lead nitrate and potassium N- [ (3-hydroximic acid) -propyl ] -N-N-hexyldithiocarbamate
The concentration of lead nitrate is 1.0X 10 -4 mol/L, N- [ (3-hydroximic acid) -propyl]potassium-N-N-hexyldithiocarbamate concentration 4.0X 10 -5 mol/L, pH of ore pulp of 8.0, concentration of foaming agent methyl isobutyl carbinol (MIBC) of 1.0 × 10 - 4 mol/L, carrying out activated flotation on the scheelite with the particle size of 0.037-0.074 mm, wherein the recovery rate of the scheelite is 88.7%.
Thus, the combined use of lead nitrate and potassium N- [ (3-hydroxamic acid) -propyl ] -N-N-hexyl dithiocarbamate significantly improves the flotation recovery of scheelite as compared to the addition of sodium N, N-diethyldithiocarbamate alone or potassium N- [ (3-hydroximic acid) -propyl ] -N-N-hexyl dithiocarbamate in combination with lead nitrate and sodium N, N-diethyldithiocarbamate.
Comparative example 10: flotation of wolframite by sodium N, N-diethyldithiocarbamate
The concentration of sodium N, N-diethyldithiocarbamate is 3.0X 10 -5 mol/L, pH of the ore pulp is 8.0, and the concentration of a foaming agent methyl isobutyl carbinol (MIBC) is 1.0 multiplied by 10 -4 And (3) mol/L, directly floating the wolframite with the grain diameter of 0.037-0.074 mm, wherein the floating recovery rate of the wolframite is 1.6%.
Comparative example 11: flotation of wolframite with lead nitrate and sodium N, N-diethyldithiocarbamate
The concentration of sodium N, N-diethyldithiocarbamate is 3.0X 10 -5 mol/L, lead nitrate concentration of 1.0X 10 - 4 mol/L, pH of ore pulp of 8.0, concentration of foaming agent methyl isobutyl carbinol (MIBC) of 1.0 × 10 -4 mol/L of black tungsten with the grain diameter of 0.037 mm-0.074 mmThe ore is subjected to activated flotation, and the flotation recovery rate of the wolframite is 7.7%.
Comparative example 12: flotation of wolframite using potassium N- [ (3-hydroximic acid) -propyl ] -N-N-hexyl dithiocarbamate
N- [ (3-hydroximic acid) -propyl]potassium-N-N-hexyldithiocarbamate concentration 3.0X 10 -5 mol/L, pH of ore pulp of 8.0, concentration of foaming agent methyl isobutyl carbinol (MIBC) of 1.0 × 10 -4 And (2) mol/L, directly floating the wolframite with the grain diameter of 0.037-0.074 mm, wherein the flotation recovery rate of the wolframite is 51.9%.
Example 4: flotation of wolframite with lead nitrate and potassium N- [ (3-hydroximic acid) -propyl ] -N-N-hexyldithiocarbamate
The concentration of lead nitrate is 1.0X 10 -4 mol/L, N- [ (3-hydroximic acid) -propyl]potassium-N-N-hexyldithiocarbamate concentration 3.0X 10 -5 mol/L, pH of ore pulp of 8.0, concentration of foaming agent methyl isobutyl carbinol (MIBC) of 1.0 × 10 - 4 And (3) mol/L, carrying out flotation on the wolframite with the particle size of 0.037-0.074 mm, wherein the flotation recovery rate of the wolframite is 89.5%.
Thus, the combined use of lead nitrate and potassium N- [ (3-hydroxamic acid) -propyl ] -N-N-hexyl dithiocarbamate significantly improves the flotation recovery of wolframite as compared to the addition of sodium N, N-diethyldithiocarbamate alone or potassium N- [ (3-hydroxamic acid) -propyl ] -N-N-hexyl dithiocarbamate and the combined use of lead nitrate and sodium N, N-diethyldithiocarbamate.
Example 5: flotation of calcite from lead nitrate and potassium N- [ (3-hydroximic acid) -propyl ] -N-N-hexyldithiocarbamate
The concentration of lead nitrate is 1.0X 10 -4 mol/L, pH of the pulp 8.0, N- [ (3-hydroximic acid) -propyl group]potassium-N-N-hexyldithiocarbamate concentration 4.0X 10 -5 mol/L, concentration of foaming agent methyl isobutyl carbinol (MIBC) is 1.0X 10 - 4 And (3) mol/L, carrying out flotation on calcite with the particle size of 0.037-0.074 mm, wherein the flotation recovery rate of the calcite is 36.5%.
This shows that the combined agent of lead nitrate and potassium N- [ (3-hydroximic acid) -propyl ] -N-hexyldithiocarbamate has significantly better capacity for collecting wolframite and scheelite than calcite, and the flotation recovery of wolframite or scheelite is more than 50% higher than calcite, compared to calcite, indicating that the combined agent of lead nitrate and potassium N- [ (3-hydroximic acid) -propyl ] -N-hexyldithiocarbamate has excellent selectivity for wolframite and scheelite.
Comparative example 13: flotation of scheelite with potassium N- [ (3-hydroximic acid) -propyl ] -N-octyl dithiocarbamate
N- [ (3-hydroximic acid) -propyl]potassium-N-N-octyldithiocarbamate concentration 1.0X 10 -5 mol/L, pH of the ore pulp is 8.0, and the concentration of a foaming agent methyl isobutyl carbinol (MIBC) is 1.0 multiplied by 10 -4 And mol/L, directly floating the scheelite with the grain diameter of 0.037 mm-0.074 mm, wherein the flotation recovery rate of the scheelite is 35.4%.
Example 6: scheelite flotation using lead nitrate and potassium N- [ (3-hydroximic acid) -propyl ] -N-N-octyldithiocarbamate
The concentration of lead nitrate is 1.0X 10 -4 mol/L, N- [ (3-hydroximic acid) -propyl]potassium-N-N-octyldithiocarbamate concentration 1.0X 10 -5 mol/L, pH of the ore pulp is 8.0, and the concentration of a foaming agent methyl isobutyl carbinol (MIBC) is 1.0 multiplied by 10 - 4 And (3) mol/L, performing flotation on the scheelite with the particle size of 0.037 mm-0.074 mm, wherein the flotation recovery rate of the scheelite is 71.9%.
Thus, the combined use of lead nitrate and potassium N- [ (3-hydroxamic acid) -propyl ] -N-octyl dithiocarbamate significantly improves the flotation recovery of scheelite as compared to the addition of potassium N- [ (3-hydroxamic acid) -propyl ] -N-octyl dithiocarbamate alone.
Comparative example 14: s- [ (3-hydroximic acid) -propyl]Flotation of scheelite S- [ (3-hydroximic acid) -propyl group using (E) -N, N-dipropyl dithiocarbamate]The concentration of the (E) -N, N-dipropyldithiocarbamate was 4.0X 10 -5 mol/L, pH of ore pulp of 8.0, concentration of foaming agent methyl isobutyl carbinol (MIBC) of 1.0 × 10 -4 And mol/L, performing flotation on the scheelite with the particle size of 0.037 mm-0.074 mm, wherein the flotation recovery rate of the scheelite is 20.1%.
Example 7: flotation of scheelite with lead nitrate and S- [ (3-hydroximic acid) -propyl ] -N, N-dipropyl dithiocarbamate
The concentration of lead nitrate is 1.0X 10 -4 mol/L, S- [ (3-hydroximic acid) -propyl]The concentration of the (E) -N, N-dipropyldithiocarbamate was 4.0X 10 -5 mol/L, pH of ore pulp of 8.0, concentration of foaming agent methyl isobutyl carbinol (MIBC) of 1.0 × 10 - 4 And (3) mol/L, performing flotation on the scheelite with the particle size of 0.037 mm-0.074 mm, wherein the flotation recovery rate of the scheelite is 85.7%.
Thus, the combination of lead nitrate and S- [ (3-hydroxamic acid) -propyl ] -N, N-dipropyl dithiocarbamate significantly improved the flotation recovery of scheelite compared to the single addition of S- [ (3-hydroxamic acid) -propyl ] -N, N-dipropyl dithiocarbamate.
Comparative example 15: s- [ (3-hydroximic acid) -propyl]Flotation of wolframite S- [ (3-hydroximic acid) -propyl ] -N, N-dipropyl dithiocarbamate]The concentration of the (E) -N, N-dipropyldithiocarbamate was 4.0X 10 -5 mol/L, pH of ore pulp of 8.0, concentration of foaming agent methyl isobutyl carbinol (MIBC) of 1.0 × 10 -4 And (3) mol/L, directly floating the black tungsten with the grain size of 0.037-0.074 mm, wherein the floating recovery rate of the black tungsten is 30.7%.
Example 8: flotation of wolframite with lead nitrate and S- [ (3-hydroximic acid) -propyl ] -N, N-dipropyl dithiocarbamate
The concentration of lead nitrate is 1.0X 10 -4 mol/L, S- [ (3-hydroximic acid) -propyl]The concentration of (E) -N, N-dipropyldithiocarbamate was 4.0X 10 -5 mol/L, pH of the ore pulp is 8.0, and the concentration of a foaming agent methyl isobutyl carbinol (MIBC) is 1.0 multiplied by 10 - 4 And (3) mol/L, carrying out flotation on the wolframite with the particle size of 0.037-0.074 mm, wherein the flotation recovery rate of the wolframite is 87.1%.
Thus, the combined use of lead nitrate and S- [ (3-hydroxamic acid) -propyl ] -N, N-dipropyl dithiocarbamate significantly improves the flotation recovery of wolframite as compared to the addition of S- [ (3-hydroxamic acid) -propyl ] -N, N-dipropyl dithiocarbamate alone.
Example 9: lead nitrate and potassium N- [ (3-hydroxamic acid) -propyl ] -N-N-hexyldithiocarbamate were mixed with addition of scheelite
Lead nitrate concentration of 1.0×10 -4 mol/L, N- [ (3-hydroximic acid) -propyl]potassium-N-N-hexyldithiocarbamate concentration 4.0X 10 -5 mol/L, pH of ore pulp of 8.0, concentration of foaming agent methyl isobutyl carbinol (MIBC) of 1.0 × 10 - 4 mol/L, the particle diameter of the white tungsten is 0.037 mm-0.074 mm. During flotation, N- [ (3-hydroximic acid) -propyl group is firstly used]And (3) mixing and stirring potassium-N-N-hexyl dithiocarbamate and lead nitrate for 20s, adding the mixture into ore pulp, and then adding a foaming agent for flotation, wherein the recovery rate of scheelite is 91.9%.
Compared with the method of adding lead nitrate and then adding potassium N- [ (3-hydroximic acid) -propyl ] -N-N-hexyl dithiocarbamate in example 3, the beneficiation method of adding the potassium N- [ (3-hydroximic acid) -propyl ] -N-N-hexyl dithiocarbamate and the lead nitrate into the ore pulp after mixing and stirring the mixture in the embodiment of the invention improves the flotation recovery rate of the scheelite in a small range.
Example 10: lead nitrate and potassium N- [ (3-hydroximic acid) -propyl ] -N-N-hexyldithiocarbamate were mixed with addition of wolframite
The concentration of lead nitrate is 1.0 × 10 -4 mol/L, N- [ (3-hydroximic acid) -propyl]potassium-N-N-hexyldithiocarbamate concentration 3.0X 10 -5 mol/L, pH of ore pulp of 8.0, concentration of foaming agent methyl isobutyl carbinol (MIBC) of 1.0 × 10 - 4 mol/L, the particle diameter of the black tungsten is 0.037 mm-0.074 mm. During flotation, N- [ (3-hydroximic acid) -propyl group is firstly used]And (3) mixing potassium-N-N-hexyl dithiocarbamate and lead nitrate for 20s, adding the mixture into ore pulp, and then adding a foaming agent for flotation, wherein the recovery rate of the wolframium nigrum is 92.8%.
Compared with the method of adding lead nitrate and then adding potassium N- [ (3-hydroximic acid) -propyl ] -N-N-hexyl dithiocarbamate in example 4, the beneficiation method of adding the potassium N- [ (3-hydroximic acid) -propyl ] -N-N-hexyl dithiocarbamate and the lead nitrate into the ore pulp after mixing and stirring the mixture in the embodiment of the invention improves the flotation recovery rate of the wolframite in a small range.
Comparative example 16: lead nitrate and benzohydroxamic acid flotation scheelite-calcite artificial mixed ore (mass ratio 1:1)
The concentration of benzohydroxamic acid is 4.0X 10 -5 mol/L, lead nitrate concentration of 1.0X 10 -4 mol/L, pH of ore pulp of 8.0, concentration of foaming agent methyl isobutyl carbinol (MIBC) of 1.0 × 10 -4 And (3) performing activated flotation separation on the scheelite-calcite artificial mixed ore with the grain size of 0.037-0.074 mm by mol/L, wherein the scheelite recovery rate is 46.4% and the calcite recovery rate is 11.3%.
Example 11: flotation of scheelite-calcite artificial mixed ore (mass ratio 1:1) by lead nitrate and potassium N- [ (3-hydroximic acid) -propyl ] -N-N-hexyl dithiocarbamate
N- [ (3-hydroximic acid) -propyl]potassium-N-N-hexyldithiocarbamate concentration 4.0X 10 -5 mol/L, lead nitrate concentration of 1.0X 10 -4 mol/L, pH of ore pulp of 8.0, concentration of foaming agent methyl isobutyl carbinol (MIBC) of 1.0 × 10 - 4 And (3) performing activated flotation separation on the scheelite-calcite artificial mixed ore with the particle size of 0.037-0.074 mm in mol/L, wherein the scheelite recovery rate is 83.2 percent, and the calcite recovery rate is 28.4 percent.
Thus, the combination of lead nitrate and potassium N- [ (3-hydroximic) -propyl ] -N-N-hexyldithiocarbamate, in combination with the ratio of lead nitrate to benzohydroxamic acid, effectively separates scheelite from its artificially mixed ore with calcite.
Comparative example 17: flotation of scheelite and scheelite mixed ore (the mass ratio of scheelite to scheelite 7:3) by using potassium N- [ (3-hydroximic acid) -propyl ] -N-N-hexyl dithiocarbamate
N- [ (3-hydroximic acid) -propyl]potassium-N-N-hexyldithiocarbamate concentration 4.0X 10 -5 mol/L, pH of ore pulp of 8.0, concentration of foaming agent methyl isobutyl carbinol (MIBC) of 1.0 × 10 -4 And mol/L, carrying out activated flotation on the black and white tungsten mixed ore with the grain size of 0.037-0.074 mm, wherein the comprehensive recovery rate of the tungsten ore is 33.3%.
Example 12: flotation of scheelite and scheelite mixed ore (the mass ratio of scheelite to scheelite 7:3) by lead nitrate and potassium N- [ (3-hydroximic acid) -propyl ] -N-N-hexyldithiocarbamate
N- [ (3-hydroximic acid) -propyl]potassium-N-N-hexyldithiocarbamate concentration 4.0X 10 -5 mol/L, lead nitrate concentration of 1.0X 10 -4 mol/L, pH of ore pulp is 8.0, foaming agent methyl isobutyl carbinol (methyl isobutyl carbinol) ((methyl isobutyl carbinol))MIBC) concentration of 1.0X 10 - 4 And mol/L, carrying out activated flotation on the black and white tungsten mixed ore with the grain size of 0.037-0.074 mm, wherein the comprehensive recovery rate of the tungsten ore is 85.5%.
Thus, the combination of lead nitrate and potassium N- [ (3-hydroxamate) -propyl ] -N-N-hexyldithiocarbamate significantly improved the overall recovery of tungsten ore compared to the single addition of potassium N- [ (3-hydroxamate) -propyl ] -N-N-hexyldithiocarbamate.
Example 13: actual ore flotation test
A scheelite ore containing WO 3 0.26 percent, the main minerals comprise scheelite, calcite (about 8 percent), fluorite (about 2 percent), garnet (about 60 percent), grinding fineness of-200 meshes and 50 percent, flotation concentration is 40 percent, and the flotation process is primary roughing: 750g/t of sodium carbonate, 1500g/t of water glass and 250g/t of lead nitrate, and N- [ (3-hydroximic acid) -propyl]The using amount of the potassium-N-N-hexyl dithiocarbamate is 100g/t, the using amount of the foaming agent No. 2 oil is 20g/t, and the tungsten rough concentrate is obtained by flotation for 4 minutes, wherein WO 3 The grade is 3.46 percent, and the tungsten recovery rate is 76.2 percent. If the same amount of benzohydroxamic acid is used in place of the N- [ (3-hydroxamic acid) -propyl group]potassium-N-N-hexyl dithiocarbamate, under otherwise identical conditions, in the tungsten rough concentrate obtained, in which WO is contained 3 Grade is 2.64%, and tungsten recovery rate is 50.3%.
In conclusion, the method for flotation of tungsten ore by combining lead nitrate and sulfur nitrogen-hydroximic acid (formula I) or sulfur nitrogen ester-hydroximic acid (formula II) has the advantages of low dosage of flotation reagents and high tungsten ore recovery rate, and compared with benzohydroxamic acid, the tungsten flotation recovery rate can be improved by more than 40 percent; compared with lead nitrate activation and benzohydroxamic acid collection, the tungsten flotation recovery rate can be improved by more than 20 percent; compared with the single use of the azothiohydroxamic acid (formula I) or the azothiohydroxamic acid (formula II), the tungsten flotation recovery rate can be improved by more than 20 percent.
Claims (10)
1. A tungsten ore flotation method comprises the steps of carrying out flotation on ore pulp containing tungsten ore and a flotation reagent to obtain tungsten concentrate; the method is characterized in that the flotation reagent at least comprises a lead ion activator and a collector;
the collecting agent comprises at least one of a azote-hydroximic acid collecting agent shown in a formula I and an azote-hydroximic acid collecting agent shown in a formula II;
M 1 is sodium, potassium or hydrogen; m 2 Is sodium or potassium;
R 1 is C 2 ～C 16 A hydrocarbon group or oxygen-containing hydrocarbon group of (a);
R 2 and R 3 Independently of hydrogen, C 1 ～C 16 A hydrocarbon group or oxygen-containing hydrocarbon group, except that R 2 And R 3 Not hydrogen at the same time; n is 1 to 4.
2. The tungsten ore flotation process of claim 1, wherein R is 1 Is C 2 ～C 16 An alkyl or oxaalkyl group of (a); preferably butyl, isobutyl, pentyl, isopentyl, n-hexyl, n-octyl or isooctyl.
3. The tungsten ore flotation process of claim 1, wherein R is 2 And R 3 Independently of one another are H or hydrogen, C 1 ～C 16 Alkyl or oxaalkyl of (a).
4. The tungsten ore flotation process of claim 1, wherein R is 3 Is hydrogen; r 2 Is butyl, isobutyl, pentyl, isopentyl, n-hexyl, n-octyl, isooctyl or dodecyl;
or, R 2 And R 3 Together are ethyl, propyl, ethylpropyl or butyl.
5. The tungsten ore flotation process of claim 1, wherein n is 2.
6. The tungsten ore flotation process of claim 1 whereinCharacterized in that the lead ion activator is capable of ionizing Pb in water 2 + Water-soluble salts of (a); preferably at least one of lead nitrate and lead acetate;
preferably, the molar ratio of the lead ions added in the collector and the lead ion activator is 1:1-10.
7. The tungsten ore flotation method according to claim 1, wherein the amount of the collector is 10 to 1200g/t, preferably 50 to 500g/t, based on the weight of the tungsten ore.
8. The tungsten ore flotation process according to claim 1, wherein the pulp pH during flotation is 6.0 to 10.0.
9. The tungsten ore flotation process of claim 1, wherein the tungsten ore comprises at least one of scheelite and wolframite.
10. The tungsten ore flotation method according to any one of claims 1 to 9, wherein the flotation reagent is added to the slurry obtained in the tungsten ore grinding process, the size mixing process or the size mixing process;
preferably, in the flotation reagent, the lead ion activator and the collector are added respectively, or are added after being mixed and reacted in advance; preferably, the reaction is carried out in advance and then added;
preferably, the pulp in the flotation process also contains a frother.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110887073.7A CN115703090A (en) | 2021-08-03 | 2021-08-03 | Tungsten ore flotation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110887073.7A CN115703090A (en) | 2021-08-03 | 2021-08-03 | Tungsten ore flotation method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115703090A true CN115703090A (en) | 2023-02-17 |
Family
ID=85179784
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110887073.7A Pending CN115703090A (en) | 2021-08-03 | 2021-08-03 | Tungsten ore flotation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115703090A (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5126038A (en) * | 1991-08-02 | 1992-06-30 | American Cyanamid Company | Process for improved precious metals recovery from ores with the use of alkylhydroxamate collectors |
| CN102105229A (en) * | 2008-07-25 | 2011-06-22 | 塞特克技术公司 | Flotation reagents and flotation processes utilizing same |
| CN106391321A (en) * | 2016-12-07 | 2017-02-15 | 广西大学 | Flotation separation method of galena and smaltite |
| CN106423573A (en) * | 2016-10-28 | 2017-02-22 | 江西理工大学 | Application method of ester-based hydroximic acid collecting agent to mineral flotation |
| CN106955791A (en) * | 2017-04-10 | 2017-07-18 | 中南大学 | A kind of N alkyl hydroximic acid dithiocarbamate collector, preparation and its application |
| CN106955790A (en) * | 2017-04-10 | 2017-07-18 | 中南大学 | A kind of N alkyl hydroximic acid O alkyl thiourethanes collecting agent, preparation and its application |
| CN110947522A (en) * | 2018-09-26 | 2020-04-03 | 中南大学 | Sulfur nitrogen-hydroximic acid bifunctional collecting agent and application thereof |
-
2021
- 2021-08-03 CN CN202110887073.7A patent/CN115703090A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5126038A (en) * | 1991-08-02 | 1992-06-30 | American Cyanamid Company | Process for improved precious metals recovery from ores with the use of alkylhydroxamate collectors |
| CN102105229A (en) * | 2008-07-25 | 2011-06-22 | 塞特克技术公司 | Flotation reagents and flotation processes utilizing same |
| CN106423573A (en) * | 2016-10-28 | 2017-02-22 | 江西理工大学 | Application method of ester-based hydroximic acid collecting agent to mineral flotation |
| CN106391321A (en) * | 2016-12-07 | 2017-02-15 | 广西大学 | Flotation separation method of galena and smaltite |
| CN106955791A (en) * | 2017-04-10 | 2017-07-18 | 中南大学 | A kind of N alkyl hydroximic acid dithiocarbamate collector, preparation and its application |
| CN106955790A (en) * | 2017-04-10 | 2017-07-18 | 中南大学 | A kind of N alkyl hydroximic acid O alkyl thiourethanes collecting agent, preparation and its application |
| CN110947522A (en) * | 2018-09-26 | 2020-04-03 | 中南大学 | Sulfur nitrogen-hydroximic acid bifunctional collecting agent and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 吴彩斌: "钨资源开发项目驱动实践教学教程", 31 August 2016, 北京冶金工业出版社, pages: 15 - 18 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103691569B (en) | Flotation method for high-sulfur gold-bearing copper ore | |
| CN106423573B (en) | Application method of ester hydroxamic acid collecting agent in mineral flotation | |
| CN101190426B (en) | Vulcanization-oxidization mixing copper ore floatation method | |
| CN109174459B (en) | Beneficiation method for high-sulfur lead-zinc ore in high-temperature environment | |
| CN109530094B (en) | Amido hydroxy carboxylic acid/hydroximic acid compound and application thereof in mineral flotation | |
| CN106423574A (en) | Application method of aliphatics bis-hydroximic acid compound to mineral flotation | |
| CN102423728A (en) | Flotation method for copper-containing nickel sulfide ore | |
| CN105312160A (en) | Novel collecting agent and application thereof to low-alkaline flotation separation beneficiation of lead zinc sulfide minerals | |
| CN109821661A (en) | A kind of low alkali of high sulfur-lead-zinc ore is without sulfuric acid floatation process | |
| CN101134180A (en) | High iron pelitization wulfenite floatation method | |
| CN110292991A (en) | A kind of fluorite method for concentrating | |
| CN107812616A (en) | A kind of difficulty selects the floatation separation process of lead zinc sulphur ore | |
| CN110465411B (en) | Preferential flotation method for copper-lead sulfide minerals | |
| CN111790517A (en) | Method for sorting copper oxide and copper sulfide mixed ore | |
| CN112495590A (en) | Magnesium-containing silicate mineral inhibitor and application thereof | |
| CN111298982A (en) | High-efficiency collecting agent for copper and gold in copper smelting slag by pyrometallurgy and application of high-efficiency collecting agent | |
| CN103041925A (en) | Application method of combined reagent in copper and sulphur separation of ore beneficiation of covellite predominantly copper sulfide ore | |
| CN115703090A (en) | Tungsten ore flotation method | |
| CN113477405A (en) | Beneficiation activator for sphalerite and willemite and method for reducing zinc by flotation of iron ore concentrate | |
| CN114011582B (en) | Flotation method for improving beneficiation index of gold-bearing copper sulfide ore | |
| CN112718252B (en) | Flotation recovery method for high-calcium-magnesium high-argillaceous mixed lead-zinc ore | |
| CN113333177B (en) | Combined inhibitor for separating copper sulfide ore containing secondary copper and separation method | |
| CN112619902A (en) | Efficient combined collecting agent for galena and preparation method | |
| CN106955792A (en) | A kind of antimony sulfide mixed concentrate floatation separation process and composite restrainer | |
| CN110052327B (en) | Method for sorting zinc oxide-containing high-sulfur high-copper zinc concentrate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |