CN101757984B - Beneficiation reagent and method for separating scheelite from complex tungsten ore - Google Patents
Beneficiation reagent and method for separating scheelite from complex tungsten ore Download PDFInfo
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Abstract
The invention relates to a beneficiation reagent and a method for separating scheelite from complex tungsten ore; the beneficiation reagent adopts oxidized paraffin soap, kerosene, butyl xanthate, dithiophosphate BA as collectors, adopts sodium carbonate as modifier and terpenic oil as foaming agent, and also adopts one or the combination of Sodium silicate and ferrous sulfate or aluminum sulfate as inhibitor; the method employing the beneficiation reagent for separating scheelite from complex tungsten ore includes: desliming in normal temperature, carbon-sulfide bulk rough floatation, secondary tungsten rough floatation and quintic tungsten concentration, so tailings and tungsten concentrate product are obtained; besides, the invention has the advantages of high sorting efficiency, high yield rate, wide reagent resource, low price, low cost and dosage, simple and reliable process, easy operation and normal temperature working, and is particularly applicable to the beneficiation application of complex tungsten ores.
Description
One. technical field
The present invention relates to a kind of beneficiation reagent and method of separating white tungsten from complicated tungsten ore, the ore dressing that is particularly suitable for complicated tungsten ore is used.
Two. background technology
Complicated tungsten ore typically refers to the ore that comprises pyrite, stibnite, Fe-Ti oxides particulate, quartz, calcite, sericite, shale thing, cryptocrystalline carbon etc.Isolating cryptocrystalline carbon, calcite and scheelite and be acknowledged as one of ore dressing difficult problem always from complicated tungsten ore, is also the main cause that this class tungsten ore is difficult to utilize.Trace it to its cause: the one, exist in ore with the similar calcium mineral of scheelite floatability such as calcite, fluorite and apatite etc. to cause the process of swimming complicated, the FLOTATION SEPARATION of scheelite and calcium mineral is the key factor that affects the scheelite sorting index; The 2nd, a large amount of carbonate minerals that complicated tungsten ore exists, the CO of its generation
3 2-Also there is very large impact in flotation on carbonaceous, sulfide.Technique that someone attempts adopting " desulfurization and decarburization-Bai tungsten heat flotation ", but fail to solve the separation problem of carbon sulphur-scheelite, scheelite-calcite.
The conventional method that scheelite separates with calcite has gravity separation method and floatation.The ratio of equilibrium settling velocity e=2.08 of gangue mineral～2.78 in scheelite and ore belong to the ore of easier gravity treatment, but because the scheelite disseminated grain size is thinner, is milled to 0.2mm ability basic monomer and dissociates, thereby increase the gravity treatment recovery difficult.Press the characteristic of milling ore fine size, can only be with the gravitational separation equipment that is suitable for sorting fine, spiral chute, fine sand or thin mud grooved table etc.Because scheelite is crisp, the easy mistake pulverized, therefore should in time with the scheelite discharge of monomer dissociation, prevent overground in grinding process; Because the rate of recovery of scheelite gravity treatment is lower, concentrate grade is not high simultaneously, therefore use seldom separately in production practices.The most typical flow process of Scheelite Flotation is as adjusting agent with sodium carbonate or NaOH and sodium metasilicate, come the Scheelite Flotation ore deposit with aliphatic acid as collecting agent, the method that often adopts has sodium metasilicate-enuatrol method, sodium metasilicate-slaine-enuatrol method, sodium carbonate-sodium metasilicate-enuatrol method, waterglass-NaOH-enuatrol and lime method.The characteristics of these methods are all to suppress fluorite and calcite under the high alkalinity condition, the Scheelite Flotation ore deposit, and due to the enuatrol poor selectivity, more difficult to the separation of calcic gangue mineral, therefore the separation for the calcic gangue mineral is generally the low-grade rough concentrate that first obtains tungstenic.At present, adopting more is that the Dinko Petrov method is the underflow high temperature method, and its mineral processing index is more stable, and is stronger to the adaptability of ore, but the ore pulp of need to heating, beneficiation cost is high.External generally remove calcite and apatite in bulk concentrate with the acid-hatching of young eggs, then desulfurization and decarburization fubai tungsten ore again.
The scheelite sorting has entered new medicament, parallel epoch of new technology, the emphasis of research has been transferred to by original separation index and has been paid attention in cost and environmental protection, therefore seek and develop a kind of low pollution, low cost and efficient tungsten ore recovery process and floating agent, become domestic and international tungsten mine worker's operative orientation, it has been broken through tool be of great significance.
Three. summary of the invention
The object of the present invention is to provide a kind of beneficiation reagent and method of separating white tungsten from complicated tungsten ore, it can have good sorting result, can make again work simplification, and reagent cost reduces.
For completing this task, the present invention carries out in the following way:
A kind of beneficiation reagent that separates white tungsten from complicated tungsten ore, this beneficiation reagent comprises that adopting oxidized paraffin wax soap, kerosene, butyl xanthate, butyl ammonium aerofloat is collecting agent, employing sodium carbonate is adjusting agent, the employing terpenic oil is foaming agent, also comprises adopting selecting of sodium metasilicate and ferrous sulfate or aluminum sulfate one to be combined as inhibitor.
Sodium metasilicate molecular formula: Na
2SiO
3
Ferrous sulfate molecular formula: FeSO
4
Aluminum sulfate molecular formula: Al
2(SO
4)
3
Sodium metasilicate is widely used inhibitor in the flotation of oxide ore, nonmetallic ore, and being used in conjunction with of it and slaine can form close colloidal sol, strengthens the inhibition of gangue mineral, mixes with inorganic acid, can be made into acidified sodium silicate, the strong inhibition silicate mineral.
The described beneficiation reagent that separates white tungsten from complicated tungsten ore, this beneficiation reagent is add 470～1350 gram oxidized paraffin wax soaps, add 30～150 gram kerosene, add 150～550 gram butyl xanthates, add 30～150 gram butyl ammonium aerofloats, add 2000～4500 gram sodium carbonate, add 10～60 gram terpenic oils, add 3050～7000 gram sodium metasilicate and add 400～1300 gram ferrous sulfate or add 65～160 gram aluminum sulfate by raw ore per ton.
Separating the method for white tungsten from complicated tungsten ore with described beneficiation reagent, is to be undertaken by following process sequence step and condition at normal temperatures:
(a) desliming drops into the raw ore after fragmentation, rod milling in hydrocyclone or desliming bucket, adds 300～1000 gram sodium metasilicate 6 to carry out desliming by raw ore per ton, removes mud;
(b) mixed floating the roughly selecting of carbon sulphur, raw ore after desliming enters the flotation unit, add 20～100 gram kerosene, add 150～550 gram butyl xanthates, add 30～150 gram butyl ammonium aerofloats, add 5～40 gram terpenic oils to carry out mixed floating the roughly selecting of carbon sulphur by raw ore per ton, select mixed floating ore deposit, the mixed floating rougher tailings of carbon sulphur roughly selected of carbon sulphur, remove sulfide and carbonaceous;
(c) tungsten roughly selects one, add 1500～3500 gram sodium carbonate, add 1500～3500 gram sodium metasilicate, add 300～1000 gram ferrous sulfate, add 300～1000 gram oxidized paraffin wax soaps to carry out for the first time tungsten to roughly select, select a tungsten rougher tailings and a tungsten and roughly select the ore deposit by raw ore per ton in roughly selecting the ore deposit carbon sulphur is mixed floating;
(d) tungsten roughly selects two, add 500～1000 gram sodium carbonate, add 500～1000 gram sodium metasilicate, add 100～300 gram ferrous sulfate, add 100～200 gram oxidized paraffin wax soaps to carry out for the second time tungsten to roughly select by raw ore per ton in a tungsten is roughly selected the ore deposit, select secondary tungsten rougher tailings and secondary tungsten is roughly selected the ore deposit;
(e) tungsten is selected one, adds 500～800 gram sodium metasilicate, adds 40～100 gram aluminum sulfate to carry out that tungsten is selected for the first time by raw ore per ton in the ore deposit that twice tungsten is roughly selected, and selects a tungsten cleaner tailings and the selected concentrate of tungsten;
(f) tungsten is selected two, adds 200～400 gram sodium metasilicate, adds 20～50 gram aluminum sulfate by raw ore per ton in selected one concentrate, carries out that tungsten is selected for the second time, selects secondary tungsten cleaner tailings and the selected concentrate of secondary tungsten;
(g) tungsten is selected three, the selected concentrate of secondary tungsten is carried out tungsten is selected for the third time, selects three tungsten cleaner tailings and three selected concentrate of tungsten;
(h) tungsten is selected four, adds 50～100 gram sodium metasilicate, adds 5～10 gram aluminum sulfate by raw ore per ton in three selected concentrate of tungsten, carries out the 4th tungsten selected, selects four tungsten cleaner tailings and four selected concentrate of tungsten;
(i) tungsten is selected five, with four selected concentrate of tungsten carry out the 5th time selected, select five tungsten cleaner tailings and product tungsten concentrate.
Advantage of the present invention:
1. compare with gravity separation method or heating method, method of the present invention sorts that efficient is high, yield is large.
2. the medicament that adopts is the production domesticization raw material, and low price, cost is low, consumption is little.
3. simple and reliable, the easy operating of technological process.
4. carry out under normal temperature, need not heat.
Four. description of drawings
Concrete grammar and the equipment of invention are provided by the following drawings.
Fig. 1 Fig. 1 is that a kind of normal temperature method that proposes according to the present invention separates the beneficiation method process chart of scheelite from the tungsten ore that is rich in carbonaceous, calcite.
Each sign expression in accompanying drawing:
1. kerosene 2. butyl xanthate 3. butyl ammonium aerofloat 4. terpenic oil 5. sodium carbonate 6. sodium metasilicate 7. ferrous sulfate 8. oxidized paraffin wax soap 9. aluminum sulfate
Below in conjunction with accompanying drawing, the embodiment of the present invention is described in further detail.
Five. the specific embodiment
A kind of beneficiation reagent that separates white tungsten from complicated tungsten ore, this beneficiation reagent comprises that adopting oxidized paraffin wax soap 8, kerosene 1, butyl xanthate 2, butyl ammonium aerofloat 3 is collecting agent, adopting sodium carbonate 5 is adjusting agent, adopting terpenic oil 4 be foaming agent, comprises that also selecting of employing sodium metasilicate 6 and ferrous sulfate 7 or aluminum sulfate 9 one is combined as inhibitor.
The described beneficiation reagent that separates white tungsten from complicated tungsten ore, this beneficiation reagent is add 470～1350 gram oxidized paraffin wax soaps 8, add 30～150 gram kerosene 1, add 150～550 gram butyl xanthates 2, add 30～150 gram butyl ammonium aerofloats 3, add 2000～4500 gram sodium carbonate 5, add 10～60 gram terpenic oils 4, add 3050～7000 gram sodium metasilicate 6 and add 400～1300 gram ferrous sulfate 7 or add 65～160 gram aluminum sulfate 9 by raw ore per ton.
As shown in Figure 1, the described beneficiation reagent of a kind of use separates the method for white tungsten from complicated tungsten ore, is to be undertaken by following process sequence step and condition at normal temperatures:
(a) desliming drops into the raw ore after fragmentation, rod milling in hydrocyclone or desliming bucket, adds 300～1000 gram sodium metasilicate 6 to carry out desliming by raw ore per ton, removes mud;
(b) mixed floating the roughly selecting of carbon sulphur, raw ore after desliming enters the flotation unit, add 20～100 gram kerosene 1, add 150～550 gram butyl xanthates 2, add 30～150 gram butyl ammonium aerofloats 3, add 5～40 gram terpenic oils 4 to carry out mixed floating the roughly selecting of carbon sulphur by raw ore per ton, select mixed floating ore deposit, the mixed floating rougher tailings of carbon sulphur roughly selected of carbon sulphur, remove sulfide and carbonaceous;
(c) tungsten roughly selects one, add 1500～3500 gram sodium carbonate 5, add 1500～3500 gram sodium metasilicate 6, add 300～1000 gram ferrous sulfate 7, add 300～1000 gram oxidized paraffin wax soaps 8 to carry out for the first time tungsten to roughly select, select a tungsten rougher tailings and a tungsten and roughly select the ore deposit by raw ore per ton in roughly selecting the ore deposit carbon sulphur is mixed floating;
(d) tungsten roughly selects two, add 500～1000 gram sodium carbonate 5, add 500～1000 gram sodium metasilicate 6, add 100～300 gram ferrous sulfate 7, add 100～200 gram oxidized paraffin wax soaps 8 to carry out for the second time tungsten to roughly select by raw ore per ton in a tungsten is roughly selected the ore deposit, select secondary tungsten rougher tailings and secondary tungsten is roughly selected the ore deposit;
(e) tungsten is selected one, adds 500～800 gram sodium metasilicate 6, adds 40～100 gram aluminum sulfate 9 to carry out that tungsten is selected for the first time by raw ore per ton in the ore deposit that twice tungsten is roughly selected, and selects a tungsten cleaner tailings and the selected concentrate of tungsten;
(f) tungsten is selected two, adds 200～400 gram sodium metasilicate 6, adds 20～50 gram aluminum sulfate 9 by raw ore per ton in selected one concentrate, carries out that tungsten is selected for the second time, selects secondary tungsten cleaner tailings and the selected concentrate of secondary tungsten;
(g) tungsten is selected three, the selected concentrate of secondary tungsten is carried out tungsten is selected for the third time, selects three tungsten cleaner tailings and three selected concentrate of tungsten;
(h) tungsten is selected four, adds 50～100 gram sodium metasilicate 6, adds 5～10 gram aluminum sulfate 9 by raw ore per ton in three selected concentrate of tungsten, carries out the 4th tungsten selected, selects four tungsten cleaner tailings and four selected concentrate of tungsten;
(i) tungsten is selected five, with four selected concentrate of tungsten carry out the 5th time selected, select five tungsten cleaner tailings and product tungsten concentrate.
Described method of separating white tungsten from complicated tungsten ore, as shown in dotted arrow in figure, the method further comprises following process sequence step and condition:
(b1) mixed the floating of carbon sulphur scanned, and adds 10～50 gram kerosene 1, adds 5～20 gram terpenic oils 4 by raw ore per ton in the mixed floating rougher tailings of carbon sulphur, carries out mixed floating the scanning of carbon sulphur, and carbon sulphur mixes the floating ore deposit of scanning and returns to the mixed floating operation of roughly selecting of (b) carbon sulphur;
(c1) tungsten roughly selects one, a tungsten cleaner tailings is returned to (c) tungsten roughly select a step, carries out tungsten and roughly selects one and subsequent step;
(d1) tungsten scans one, adding 50～100 gram oxidized paraffin wax soaps 8 to carry out a tungsten by raw ore per ton in secondary tungsten rougher tailings scans, tell that tungsten is scanned mine tailing and a tungsten is scanned the ore deposit, tungsten is scanned the ore deposit and is returned to (d) tungsten and roughly select two operations and subsequent step thereof;
(d2) tungsten scans two, add 20～50 gram oxidized paraffin wax soaps 8 by raw ore per ton in a tungsten is scanned mine tailing, carry out secondary tungsten and scan, tell mine tailing and secondary tungsten is scanned the ore deposit, secondary tungsten is scanned the ore deposit and is returned to (d1) tungsten and scan an operation, and remaining mine tailing is selected in circulation.
(e1) tungsten is selected one, and secondary tungsten cleaner tailings is returned to the selected step of (e) tungsten, carries out tungsten selected one and subsequent step thereof;
(f1) tungsten is selected two, and three tungsten cleaner tailings are returned to selected two steps of (f) tungsten, carries out tungsten selected two and subsequent step thereof;
(g1) tungsten is selected three, and four tungsten cleaner tailings are returned to selected three steps of (g) tungsten, carries out tungsten selected three and subsequent step thereof;
(h1) tungsten is selected four, and five tungsten cleaner tailings are returned to selected four steps of (h) tungsten, carries out tungsten selected four and subsequent step thereof, and remaining tungsten concentrate is selected in circulation.
The selected medicament of the present invention and method and prior art are carried out the flotation contrast with the fatty acid collecting agent tungsten ore that method for floating is rich in carbonaceous, calcite to same of heating, through appropriate authority testing result such as following table:
As seen from the table, use the white tungsten fine ore WO of the selected medicament of the present invention and method flotation
3Grade reaches 70.86%, WO
3The rate of recovery 66.82% is with the white tungsten fine ore WO of the floatation of heating with fatty acid collecting agent
3Grade 11.25%, WO
3The rate of recovery 64.64% has been compared significantly and has been improved.
Claims (4)
1. beneficiation reagent that separates white tungsten from complicated tungsten ore, this beneficiation reagent comprises that adopting oxidized paraffin wax soap (8), kerosene (1), butyl xanthate (2), butyl ammonium aerofloat (3) is collecting agent, adopting sodium carbonate (5) is adjusting agent, adopting terpenic oil (4) be foaming agent, characterized by further comprising selecting of employing sodium metasilicate (6) and ferrous sulfate (7) or aluminum sulfate (9) and one is combined as inhibitor.
2. the beneficiation reagent that separates white tungsten from complicated tungsten ore according to claim 1, this beneficiation reagent is to add 470～1350 gram oxidized paraffin wax soaps (8) by raw ore per ton, add 30～150 gram kerosene (1), add 150～550 gram butyl xanthates (2), add 30～150 gram butyl ammonium aerofloats (3), add 2000～4500 gram sodium carbonate (5), add 10～60 gram terpenic oils (4), add 3050～7000 gram sodium metasilicate (6) and add 400～1300 gram ferrous sulfate (7) or add 65～160 gram aluminum sulfate (9).
3. one kind is separated the method for white tungsten from complicated tungsten ore with beneficiation reagent claimed in claim 1, is to be undertaken by following process sequence step and condition at normal temperatures:
(a) desliming drops into the raw ore after fragmentation, rod milling in hydrocyclone or desliming bucket, adds 300～1000 gram sodium metasilicate (6) to carry out desliming by raw ore per ton, removes mud;
(b) mixed floating the roughly selecting of carbon sulphur, raw ore after desliming enters the flotation unit, add 20～100 gram kerosene (1), add 150～550 gram butyl xanthates (2), add 30～150 gram butyl ammonium aerofloats (3), add 5～40 gram terpenic oils (4) to carry out mixed floating the roughly selecting of carbon sulphur by raw ore per ton, select mixed floating ore deposit, the mixed floating rougher tailings of carbon sulphur roughly selected of carbon sulphur, remove sulfide and carbonaceous;
(c) tungsten roughly selects one, add 1500～3500 gram sodium carbonate (5), add 1500～3500 gram sodium metasilicate (6), add 300～1000 gram ferrous sulfate (7), add 300～1000 gram oxidized paraffin wax soaps (8) to carry out for the first time tungsten to roughly select, select a tungsten rougher tailings and a tungsten and roughly select the ore deposit by raw ore per ton in roughly selecting the ore deposit carbon sulphur is mixed floating;
(d) tungsten roughly selects two, add 500～1000 gram sodium carbonate (5), add 500～1000 gram sodium metasilicate (6), add 100～300 gram ferrous sulfate (7), add 100～200 gram oxidized paraffin wax soaps (8) to carry out for the second time tungsten to roughly select, select secondary tungsten and roughly select concentrate and secondary tungsten rougher tailings by raw ore per ton in tungsten rougher tailings;
(e) tungsten is selected one, adds 500～800 gram sodium metasilicate (6) by raw ore per ton or add 40～100 gram aluminum sulfate (9) to carry out that tungsten is selected for the first time in a tungsten is roughly selected concentrate, selects a tungsten cleaner tailings and the selected concentrate of tungsten;
(f) tungsten is selected two, adds 200～400 gram sodium metasilicate (6) by raw ore per ton or add 20～50 gram aluminum sulfate (9) to carry out that tungsten is selected for the second time in selected concentrate of tungsten, selects secondary tungsten cleaner tailings and the selected concentrate of secondary tungsten;
(g) tungsten is selected three, the selected concentrate of secondary tungsten is carried out tungsten is selected for the third time, selects three tungsten cleaner tailings and three selected concentrate of tungsten;
(h) tungsten is selected four, adds 50～100 gram sodium metasilicate (6) or adds 5～10 gram aluminum sulfate (9) by raw ore per ton in three selected concentrate of tungsten, carries out the 4th tungsten selected, selects four tungsten cleaner tailings and four selected concentrate of tungsten;
(i) tungsten is selected five, with four selected concentrate of tungsten carry out the 5th time selected, select five tungsten cleaner tailings and product tungsten concentrate.
4. method of separating white tungsten from complicated tungsten ore according to claim 3, the method further comprises following process sequence step and condition:
(c1) a tungsten cleaner tailings is returned to (c) tungsten and roughly select a step, carry out tungsten and roughly select one and subsequent step;
(d1) tungsten is roughly selected concentrate and returned to (d) tungsten and roughly select two steps, carry out tungsten and roughly select two and subsequent step;
(d2) secondary tungsten is roughly selected concentrate and returned to (d1) tungsten and scan an operation, remaining mine tailing is selected in circulation;
(e1) secondary tungsten cleaner tailings is returned to the selected step of (e) tungsten, carry out tungsten selected one and subsequent step thereof;
(f1) three tungsten cleaner tailings are returned to selected two steps of (f) tungsten, carry out tungsten selected two and subsequent step thereof;
(g1) four tungsten cleaner tailings are returned to selected three steps of (g) tungsten, carry out tungsten selected three and subsequent step thereof;
(h1) five tungsten cleaner tailings are returned to selected four steps of (h) tungsten, carry out tungsten selected four and subsequent step thereof, remaining tungsten concentrate is selected in circulation.
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| CN102357426B (en) * | 2011-08-03 | 2014-10-29 | 西北矿冶研究院 | Inhibitor for fluorite ore siliceous mineral and calcium carbonate mineral |
| CN103736598B (en) * | 2014-01-14 | 2015-01-28 | 会理县鹏晨废渣利用有限公司 | Copper smelting slag copper recovery and flotation technology |
| CN104475264B (en) * | 2014-11-26 | 2017-05-17 | 广东省工业技术研究院(广州有色金属研究院) | Scheelite beneficiation method |
| CN104984832B (en) * | 2015-07-22 | 2018-01-02 | 东北大学 | A kind of the flotation at low temperature combination medicament and its application method of efficiently collecting scheelite |
| CN107583769A (en) * | 2016-07-06 | 2018-01-16 | 长春黄金研究院 | A kind of method that flotation tailing normal temperature selects tungsten |
| CN109078762B (en) * | 2018-08-14 | 2021-01-08 | 河南天鸿选矿科技有限公司 | Oxidized ore mineral flotation collector |
| CN110142135A (en) * | 2019-05-23 | 2019-08-20 | 昆明理工大学 | A kind of recovery method of white tungsten fine ore |
| CN110026294A (en) * | 2019-05-30 | 2019-07-19 | 阳谷祥光铜业有限公司 | A kind of mineral floating method and mineral floating system |
| CN112044603B (en) * | 2019-06-06 | 2022-03-08 | 钟志勇 | Titanium ore flotation pretreatment and titanium separation method |
| CN111266196B (en) * | 2020-03-12 | 2021-08-17 | 江西都昌金鼎钨钼矿业有限公司 | Combined type scheelite collecting agent for sorting ultra-low-grade tungsten and molybdenum ores and sorting and recycling process |
| CN111570081B (en) * | 2020-04-28 | 2021-02-26 | 长沙矿山研究院有限责任公司 | Method for utilizing high-calcite type low-grade scheelite fluorite paragenic ore |
| CN113369005A (en) * | 2021-05-13 | 2021-09-10 | 西北矿冶研究院 | Beneficiation method for mixed type refractory tungsten ore |
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