CN114054212B - Composite inhibitor and application thereof - Google Patents
Composite inhibitor and application thereof Download PDFInfo
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- CN114054212B CN114054212B CN202111224878.XA CN202111224878A CN114054212B CN 114054212 B CN114054212 B CN 114054212B CN 202111224878 A CN202111224878 A CN 202111224878A CN 114054212 B CN114054212 B CN 114054212B
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- flotation
- phosphate
- calcium
- sodium
- scheelite
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- 239000003112 inhibitor Substances 0.000 title claims description 44
- 239000002131 composite material Substances 0.000 title claims description 31
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 58
- 239000011707 mineral Substances 0.000 claims abstract description 58
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000011575 calcium Substances 0.000 claims abstract description 42
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 42
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 31
- 229910052816 inorganic phosphate Inorganic materials 0.000 claims abstract description 31
- 239000010452 phosphate Substances 0.000 claims abstract description 29
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 27
- 238000005188 flotation Methods 0.000 claims description 54
- 239000012141 concentrate Substances 0.000 claims description 26
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 12
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 10
- 239000001488 sodium phosphate Substances 0.000 claims description 10
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 10
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 10
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 10
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 10
- 239000008396 flotation agent Substances 0.000 claims description 9
- 239000003153 chemical reaction reagent Substances 0.000 claims description 7
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 7
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 7
- 239000010456 wollastonite Substances 0.000 claims description 7
- 229910052882 wollastonite Inorganic materials 0.000 claims description 7
- 239000010436 fluorite Substances 0.000 claims description 6
- 229910021532 Calcite Inorganic materials 0.000 claims description 5
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 5
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 5
- 229910052586 apatite Inorganic materials 0.000 claims description 4
- 230000000994 depressogenic effect Effects 0.000 claims description 4
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 claims description 4
- 238000011084 recovery Methods 0.000 abstract description 25
- 238000000926 separation method Methods 0.000 abstract description 15
- 238000000034 method Methods 0.000 abstract description 10
- 230000033228 biological regulation Effects 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
- 235000021317 phosphate Nutrition 0.000 description 27
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 24
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- 229910000029 sodium carbonate Inorganic materials 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 230000002829 reductive effect Effects 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 9
- 230000002195 synergetic effect Effects 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 230000001965 increasing effect Effects 0.000 description 7
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 6
- 229910001424 calcium ion Inorganic materials 0.000 description 6
- 239000003814 drug Substances 0.000 description 6
- 230000005764 inhibitory process Effects 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 4
- 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
- 235000019353 potassium silicate Nutrition 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 230000002000 scavenging effect Effects 0.000 description 3
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 3
- 229940048086 sodium pyrophosphate Drugs 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 3
- UXYAJXBVMZFRMS-UHFFFAOYSA-N 2-hydroxy-1,3,2$l^{5}-dioxaphosphepane 2-oxide Chemical compound OP1(=O)OCCCCO1 UXYAJXBVMZFRMS-UHFFFAOYSA-N 0.000 description 2
- FHHPEPGEFKOMOF-UHFFFAOYSA-N 2-hydroxy-1,3,2lambda5-dioxaphosphetane 2-oxide Chemical compound OP1(=O)OCO1 FHHPEPGEFKOMOF-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000006399 behavior Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- BEGBSFPALGFMJI-UHFFFAOYSA-N ethene;sodium Chemical group [Na].C=C BEGBSFPALGFMJI-UHFFFAOYSA-N 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- -1 phosphoric acid compound Chemical class 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 description 2
- 235000011009 potassium phosphates Nutrition 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229920001732 Lignosulfonate Polymers 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- QILXPCHTWXAUHE-UHFFFAOYSA-N [Na].NCCN Chemical compound [Na].NCCN QILXPCHTWXAUHE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910052612 amphibole Inorganic materials 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 229910001919 chlorite Inorganic materials 0.000 description 1
- 229910052619 chlorite group Inorganic materials 0.000 description 1
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- GDEBSAWXIHEMNF-UHFFFAOYSA-O cupferron Chemical compound [NH4+].O=NN([O-])C1=CC=CC=C1 GDEBSAWXIHEMNF-UHFFFAOYSA-O 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000003916 ethylene diamine group Chemical group 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 229940005740 hexametaphosphate Drugs 0.000 description 1
- BMBUUNTZYQWADI-UHFFFAOYSA-N hexane-1,6-diamine;sodium Chemical compound [Na].NCCCCCCN BMBUUNTZYQWADI-UHFFFAOYSA-N 0.000 description 1
- 230000005660 hydrophilic surface Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000009282 microflotation Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 235000007686 potassium Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/004—Organic compounds
- B03D1/014—Organic compounds containing phosphorus
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/06—Depressants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2203/00—Specified materials treated by the flotation agents; Specified applications
- B03D2203/02—Ores
Landscapes
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invention discloses a preparation and application method of a combined regulator for coarse selection of low-grade scheelite, which mainly comprises inorganic phosphate and organic phosphate; the structure of the inorganic phosphate is shown as a formula 1:
wherein X is 2-5; the structure of the organic phosphate is shown as a formula 2:
wherein n is 2 to 8. Under appropriate dosage and usage, the method can realize the high-efficiency separation of the calcium-containing minerals on the premise of ensuring the recovery rate of the target minerals. The combined regulator has strong adaptability and small dosage, and realizes the accurate separation of different calcium-containing minerals through the regulation and control of component proportion.
Description
Technical Field
The invention relates to an application of a composite inhibitor in scheelite flotation, belonging to the technical field of calcium-containing gangue mineral inhibitors.
Background
Due to the similar physicochemical properties of the surfaces of the calcium-containing minerals, the separation of the calcium-containing minerals is always a difficult problem in the mineral separation field. Flotation is a main technical means for recovering calcium-containing minerals, and fatty acid serving as a main collector for flotation of the calcium-containing minerals has good collecting capacity but extremely poor selectivity, so that the separation of the target calcium-containing minerals and the target calcium-containing gangue minerals cannot be realized. Therefore, depressants are often added during the separation of calcium-containing minerals by flotation to enhance the separation. In the case of scheelite, it is usually associated with calcium-containing minerals such as fluorite, calcite, apatite and wollastonite, which are affected by the mineralization process. Water glass is usually added during flotation to suppress the economically less valuable fluorites, calcites, apatites and wollastonite. The water glass has weak inhibition ability, and the recycling of scheelite is influenced by excessive using amount. After silicic acid is circularly enriched in mineral processing water, tailings are difficult to settle, the recycling effect of tailing reservoir water is poor, flotation indexes are rapidly reduced, a large amount of resources are lost, and the economic benefit of an enterprise is greatly reduced.
For a long time, in order to solve the problem of flotation separation of calcium-containing minerals, related technicians take many measures, for example, a chelate collecting agent with better selectivity, such as hydroximic acid, cupferron and the like, is adopted to replace fatty acid. Although the selectivity is greatly improved, the collecting capacity is low, the using amount is large, the unit price is high, the ore dressing cost is increased sharply, the target minerals cannot be recovered fully, and the pollution of the production process of the reagents is large. Still some technicians select micromolecular carboxylic acid, lignosulfonate etc. as the inhibitor of calcium-containing gangue mineral, although certain effect has been obtained in laboratory monomineral flotation process, can't adapt to the complicated ore pulp environment of actual ore flotation, and the production index is still not ideal. Chinese patents CN110773324A, CN111215247A, CN108906335A, CN108654844B and the like all relate to the application of single inorganic phosphate or single organic phosphate in mineral flotation. Although the single inorganic phosphate or organic phosphate disclosed therein has a certain effect in the flotation of relevant ores, when the raw ore grade and the content of the calcium-containing gangue minerals fluctuate, the separation efficiency can be improved only by adjusting the amount of the depressant, but even if the amount of the depressant is greatly increased, the influence of the flotation efficiency is limited. Especially, in the case of low-grade scheelite with large fluctuations in the properties of the raw ore, the adjustability and operability are still lacking. Moreover, the addition of an excessive amount of inhibitor not only increases the cost greatly, but also has considerable negative effects. Meanwhile, the inventions provided by some patents are only implemented in pure mineral tests, and laboratory micro-flotation tests are greatly different from actual ores. The practical effect is far from the ideal state of a laboratory.
Disclosure of Invention
The invention aims to provide a composite inhibitor which can generate positive synergistic effect by adjusting the proportion and the structure of a combined medicament according to the content of calcium-containing gangue minerals in raw ores. Under the condition of not influencing the scheelite roughing recovery rate, the roughing efficiency of the low-grade scheelite is improved to the maximum extent, the rough concentrate with better quality is provided for the subsequent scheelite heating and concentration, and the load and the cost of the scheelite heating and concentration section are reduced.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the composite inhibitor comprises, by weight, 5-95 parts of inorganic phosphate and 5-95 parts of organic phosphate.
The structure of the inorganic phosphate is shown as the formula 1:
wherein X is 2-5;
the structure of the organic phosphate is shown as a formula 2:
wherein n is 2 to 8.
Further preferably, X is 2 or 3.
Further preferably, the inorganic phosphate is one or more of sodium tripolyphosphate, potassium tripolyphosphate, ammonium tripolyphosphate, sodium hexametaphosphate and potassium hexametaphosphate.
Further preferably, n is 2 or 6.
Further preferably, the organic phosphate is one or two of hexamethylene diamine tetramethylene sodium phosphate, hexamethylene diamine tetramethylene potassium phosphate, ethylene diamine tetramethylene sodium phosphate and ethylene diamine tetramethylene potassium phosphate.
Preferably, the composite inhibitor comprises 25-75 parts of sodium tripolyphosphate and 25-75 parts of ethylenediamine tetramethylene sodium phosphate by weight.
Preferably, the composite inhibitor comprises 25-75 parts by weight of sodium hexametaphosphate and 25-75 parts by weight of sodium hexamethylenediamine tetramethylenephosphate.
The invention claims the application of the composite inhibitor in the field of mineral flotation, and researches show that the composite inhibitor has excellent flotation performance in the field of mineral flotation.
The inventor further researches and discovers that the organic phosphoric acid compound with the structure has better selectivity on calcium-containing gangue minerals and good flotation effect, for example, compared with inhibitors such as water glass and the like commonly used in the field, the composite inhibitor can show excellent selectivity and recovery rate under a smaller using amount.
Preferably, the calcium-containing gangue mineral is at least one of calcite, fluorite, apatite and wollastonite.
Preferably, in the application, the flotation reagent of the flotation inhibitor is added into raw ore, and concentrate is obtained through flotation.
Further preferably, the flotation reagent further comprises a collector, the inhibitor is added into raw ore, and then a small amount of the collector is added for flotation to obtain coarse ore.
The collecting agent can be a medicament with collecting performance commonly used in the industry, and special collecting agents such as sodium oleate, sodium carbonate and the like are not needed.
Preferably, the flotation inhibitor is adapted to the flotation pulp environment with the pH value of 2-12.
Further preferably, the flotation depressor is applied to the flotation pulp in an environment of pH 10 +/-0.2.
At the preferred pH, the flotation effect is better, particularly in the scheelite flotation process, and the selectivity, the taste and the recovery rate of flotation concentrate can be further obviously improved when the preferred pH is controlled.
Preferably, the flotation depressor is adapted to the flotation pulp environment at the temperature of 0-100 ℃.
The flotation method can adopt the conventional method.
In the invention, the flotation separation of scheelite and gangue minerals by using the composite inhibitor comprises the following main steps:
a) Grinding raw ore, and adding the ground raw ore into a flotation tank;
b) Sequentially adding sodium carbonate, an inhibitor and sodium oleate into the ore pulp, stirring and mixing for 2-5 min for roughing.
Preferably, the flotation separation of the scheelite and the gangue minerals by using the composite inhibitor comprises the following main steps:
a) Grinding raw ore to the fineness of 55-78% of-0.074 mm, and adding the raw ore into a flotation tank;
b) After adding sodium carbonate into the ore pulp, stirring and mixing the pulp for 2 to 5min
b) Adding inhibitor, stirring and mixing for 2-5 min;
c) And adding sodium oleate, stirring and mixing the slurry for 3 to 4min, and then carrying out flotation for 3 to 6min.
The invention is further explained below:
the components of the composite medicament have good compatibility under the appropriate proportion and dosage, can realize the accurate separation of scheelite, calcite, fluorite, apatite, wollastonite and other calcium-containing gangue minerals, and can ensure the recovery rate of target minerals. The main principle is as follows:
1. the adsorption behavior of the flotation reagent on the surface of calcium-containing minerals occurs mainly between the hydrophilic base of the reagent and the calcium ions. When the combined modifier occupies calcium ion sites on the surface of the mineral, adsorption sites reserved for the fatty acid collecting agent are reduced, and the hydrophilicity of the surface of the mineral is enhanced and inhibited. The inorganic phosphate may also complex free calcium ions and then precipitate on the surface of the calcium-containing gangue minerals, causing the gangue minerals to form a hydrophilic surface.
2. The differences of the calcium ion density on the surfaces of different calcium-containing minerals and the chemical bond energy related to calcium in the crystal lattices of the minerals cause different adsorption behaviors of the same flotation agent on the surfaces of different calcium-containing minerals. The quantity of phosphate radicals and the length of hydrophobic chains in the structures of inorganic phosphate and organic phosphate also influence the matching degree of the inorganic phosphate and the organic phosphate combined with calcium ions on the surface of the mineral. When the inorganic phosphate and the organic phosphate are mixed singly or in a certain ratio, if the inhibition ability is too strong or too weak and exceeds an adjustable threshold, positive synergism cannot be obtained, and the ideal index cannot be achieved. Therefore, the application of the inorganic phosphate and the hydrocarbon chain length of the organic phosphate in the regulator in the flotation separation of different calcium-containing mineral combinations can be adapted by controlling the number of phosphate in the inorganic phosphate and the length of the hydrocarbon chain in the organic phosphate, so that the regulator is more selectively adsorbed on the surface of the calcium-containing gangue mineral.
3. Under the appropriate proportion and dosage, the inorganic phosphate and the organic phosphate show good compatibility, and simultaneously play the role of directly adsorbing or complexing partial calcium ions in ore pulp on the surface of the calcium-containing gangue mineral and precipitating on the surface of the calcium-containing gangue mineral, but have little influence on the surface of scheelite, prevent the adsorption of a subsequent collecting agent, thereby enhancing the inhibition on the calcium-containing gangue mineral.
The invention has the following advantages:
1. the combined regulator is prepared by mixing organic phosphate and inorganic phosphate serving as raw materials, is easy to obtain the raw materials, simple in preparation process, low in cost, environment-friendly and easy to degrade, and has great practical popularization value and market potential.
2. The method can realize the accurate separation of the low-grade scheelite and the calcium-containing gangue minerals without influencing the recovery rate of the target minerals, realizes the efficient recycling of scheelite resources, and has strong adaptability to different ore pulps and wide application range.
3. The method can greatly reduce the content of the calcium-containing gangue in the scheelite rough concentrate, and reduce the energy consumption and the medicament cost of the subsequent scheelite rough concentrate heating flotation section.
Drawings
In order to more clearly illustrate the technical solution in the embodiments of the present invention, the drawings used in the embodiments are briefly described below.
FIG. 1 is a flotation scheme of example 1 of the present invention;
FIG. 2 is a flotation scheme of example 2 of the present invention;
figure 3 is a flotation scheme of example 3 of the present invention.
Detailed Description
In order to facilitate clear understanding of the technical solutions of the present invention, the following examples are further used to illustrate the present invention, and it is obvious that the present invention is not limited by the scope of the claims of the present invention.
Example 1
The composite inhibitor contains 50% of inorganic phosphate and 50% of organic phosphate by weight percentage. The inorganic phosphate is sodium tripolyphosphate, and the organic phosphate is ethylene diamine tetramethylene sodium phosphate. Adding the components into a stirring barrel according to the weight ratio; and then, adding clear water into the stirring barrel, wherein the ratio of the regulator to the clear water in parts by weight is 1.
The application effect of the composite inhibitor in the roughing process of a certain low-grade scheelite with the WO3 content of 0.09 percent is examined. The ore is typically a scheelite-calcite-fluorite type ore, i.e. the gangue minerals are mainly calcite and fluorite, but also feldspar, chlorite, amphibole, mica, quartz, etc. The flotation flow is shown in figure 1. According to the flow of the figure 1, raw ore is ground to the fineness of-0.074 mm which accounts for 55-78%, and then is added into a flotation tank. Flotation agent and depressor are added in the rough concentration stage, and after rough concentration, scavenging is carried out twice. According to the flow of fig. 1, the dosage of sodium carbonate and sodium oleate was examined on the premise of no addition of the medicament, and the specific results are shown in table 1.
TABLE 1 sodium carbonate and sodium oleate test results
As can be known from the flotation reagent dosage test, the grade of the scheelite rough concentrate is in an increasing trend along with the increase of the dosage of the sodium carbonate, the scheelite recovery rate is increased firstly and then decreased, and the appropriate dosage of the sodium carbonate is 1800g/t by comprehensive consideration. Along with the increase of the using amount of the sodium oleate, the grade of the scheelite rough concentrate is gradually reduced, the recovery rate is increased first and then tends to be balanced, and the appropriate using amount of the sodium oleate is 150g/t by comprehensive consideration.
The action of the different inhibitors was investigated on the premise that the amount of fixed sodium carbonate was 1800g/t and the amount of sodium oleate was 150g/t. The types of specific inhibitors and results are shown in table 2.
TABLE 2 Effect of different inhibitors
From the results in table 2, it can be seen that, although the grade of the scheelite rough concentrate can be improved by adding a single inorganic phosphate or organic phosphate, the scheelite rough concentration recovery rate is greatly reduced and the rough concentrate grade is high when sodium tripolyphosphate is used alone, and the scheelite rough concentration recovery rate is not significantly changed when sodium ethylene diamine tetra-methyl phosphate is used alone, but the rough concentrate grade is not as high as that when sodium tripolyphosphate is used alone. The composite inhibitor of the embodiment 1 improves the grade of the scheelite rough concentrate from 1.75 percent to 2.25 percent, and the recovery rate of the scheelite rough concentrate is also improved from 84.12 percent to 87.67 percent. Meanwhile, the inorganic phosphate and the organic phosphonate can only play the optimal synergistic effect under the proper proportion. In a comparative test, when the ratio of the sodium tripolyphosphate to the ethylene diamine tetramethylene sodium phosphate is 25. When the ratio is 75. It is shown that the inhibitor components show the best compatibility only under the proper proportion.
The results of examining the amount of the composite inhibitor of example 1 used, and keeping the amounts of other agents added, are shown in table 3.
Table 3 results of the dose test
The result of the dosage test proves that when 50g/t of the composite inhibitor in the embodiment 1 is added, compared with the condition that no inhibitor is added, the grade and the recovery rate of the scheelite rough concentrate are simultaneously improved, and a good positive synergistic effect is shown.
Example 2
The composite inhibitor of example 2 comprises 5% of inorganic phosphate and 95% of organic phosphate by weight percentage. The inorganic phosphate is sodium hexametaphosphate, and the organic phosphate is hexamethylenediamine tetramethylene sodium phosphate. Adding the components into a stirring barrel according to the weight ratio; and then, adding clear water into the stirring barrel, wherein the ratio of the regulator to the clear water in parts by weight is 15.
The application effect of the composite inhibitor in example 2 in the course of roughing certain ultralow-grade scheelite with the WO3 content of 0.015% is examined. Compared with the raw ore containing the calcium-containing gangue in the example 1, the kind and content of the calcium-containing gangue minerals in the example 2 are changed, and the content of each component in the combined regulator can be adjusted according to the content and type of the calcium-containing gangue minerals, so that the combined regulator generates optimal compatibility, positive synergistic effect is generated, and the precise separation of scheelite and the calcium-containing gangue is realized. According to the flow of figure 2, raw ore is ground to a fineness of 55-78% of-0.074 mm and then added into a flotation tank. Flotation agent and depressor are added in the rough concentration stage, and after rough concentration, scavenging is carried out twice. Similarly, according to the flow chart of FIG. 2, the amounts of sodium carbonate and sodium oleate are examined without adding any other agent, and it is found that the appropriate amount of sodium carbonate is 1200g/t, the amount of the composite inhibitor of example 2 is 30g/t, and the optimal amount of sodium oleate is 180 g/t.
Flotation tests were performed on different flotation agents with the use of fixed amounts of the agents, and the results are shown in table 4.
Table 4 results for different flotation agents
From the second comparative test, it can be seen that when sodium hexametaphosphate or hexamethylenediamine tetramethylenesodium phosphate is added alone, the grade of the scheelite rough concentrate is increased to a certain extent, but the recovery rate is reduced to a large extent. When the second embodiment is used, the inorganic sodium phosphate and the organic sodium phosphate have good compatibility, and under the condition that the recovery rate of the scheelite is improved in a small range, the grade of the rough concentrate is improved to 0.581% from 0.307%, the yield of the rough concentrate is reduced to 1.84% from 3.45%, and the reduction range is over 40%, which means that the quantity of the rough concentrate entering the subsequent heating concentration is also reduced by over 40%, and the corresponding concentration variation cost is also reduced by 40%, so that the economic feasibility of the recovery of the ultralow-grade scheelite is realized.
Example 3
The composite inhibitor of example 3 contains 95% inorganic phosphate and 5% organic phosphate by weight. The inorganic phosphate is sodium tripolyphosphate, and the organic phosphate is sodium ethylene diamine tetramethylphosphate. Adding the components into a stirring barrel according to the weight ratio; and then, adding clear water into the stirring barrel, wherein the ratio of the regulator to the clear water in parts by weight is 15.
The application effect of the composite inhibitor in the embodiment 3 in the roughing process of a certain low-grade high-wollastonite scheelite is examined, and the content of WO3 in the raw ore is 0.15%, and the content of wollastonite is about 30%. According to the content and the type of the calcium-containing gangue minerals, the content of each component in the combined regulator is adjusted, so that the combined regulator generates optimal compatibility, positive synergistic effect is generated, and the scheelite and the calcium-containing gangue are accurately separated. According to the flow of figure 3, raw ore is ground to-0.074 mm, and the ground raw ore is added into a flotation tank after the fineness of the raw ore accounts for 55-78%. Flotation agent and depressor are added in the rough concentration stage, and after rough concentration, scavenging is carried out twice. Similarly, according to the flow chart of FIG. 3, the amounts of sodium carbonate and sodium oleate are examined respectively without adding any other agent, and the preferable amount of sodium carbonate is 2100g/t and the preferable amount of sodium oleate is 120g/t.
The results of examining the amount of the composite inhibitor of example 3 used, and keeping the amount of other drugs added unchanged, are shown in table 5.
Table 5 results of the amount test
The result of the dosage test of the inhibitor in example 3 proves that when the composite inhibitor in example 3 is added under the appropriate dosage of 35g/t, the grade of the scheelite rough concentrate can be improved, the recovery rate of the scheelite can be improved, and a good positive synergistic effect is shown. However, when the amount is too large, the scheelite recovery rate is lowered as compared with the appropriate amount.
Flotation tests were performed on different flotation agents with the use of fixed amounts of chemicals, and the results are shown in table 4.
TABLE 6 results for different flotation agents
From the results, it is found that when the inorganic phosphate component is used alone, the grade of the scheelite rough concentrate is 2.316%, and the recovery rate is 76.53%, although the grade of the rough concentrate is improved, the recovery rate loss is large. When sodium tripolyphosphate and amino sodium trimethylphosphate are used in a matched mode, the inhibiting capacity of the two components is high and exceeds the regulation threshold of the optimal condition, the coarse concentrate grade can reach 2.528%, but the recovery loss is increased, and the coarse concentrate grade and the recovery rate cannot be considered at the same time. When the sodium tripolyphosphate is matched with the polyamino polyether methylene phosphate for use, the polyamino polyether methylene phosphate has weak inhibition capacity, although the recovery rate can reach 82.62%, the grade of the rough concentrate is only 1.971%. Similarly, the control threshold of the optimum condition is exceeded when the sodium ethylenediamine tetramethylenephosphate is combined with other inorganic phosphates. For example, when the sodium pyrophosphate is combined with the sodium pyrophosphate, the sodium pyrophosphate has weak inhibition capacity, the loss of the recovery rate is not large, but the concentrate grade is improved to a low extent. When the sodium hexametaphosphate is combined, the sodium hexametaphosphate has too strong inhibition capacity, so that the scheelite recovery rate loss is large. When the combined regulator provided by the patent is used, the components show good compatibility, the grade of the scheelite rough concentrate is 2.535%, and the recovery rate is 85.51%.
Similarly, the composite inhibitors prepared in example 1 and example 2 were paired with different inorganic phosphates and organic phosphates, and as a result, it was found that only the composite inhibitors specified in example 1 and example 2 were most effective against the specific minerals of example 1 and example 2.
In summary, it can be seen that not all inorganic phosphates and organic phosphonates produce a positive synergy. Different inorganic and organic phosphates have different strengths of action with calcium-containing mineral surfaces of different minerals. The inorganic phosphate and organic phosphate have too strong or too weak an inhibiting ability to exceed a controllable threshold, i.e., no optimal effect is achieved in either of those proportions or when used alone. The invention can match the function of calcium-containing mineral according to the specific inorganic phosphate and organic phosphate pairing selected by different minerals. Aiming at ores with different calcium-containing mineral proportions, the positive synergistic effect can be exerted by adjusting the component proportion and combining the regulators, and the synergistic effect of 1+1 >.
The above description is only a preferred embodiment of the present invention, and the scope of the present invention is not limited to the above-described examples. It will be apparent to those skilled in the art that various modifications and variations can be made without departing from the spirit of the invention.
Claims (5)
1. The composite inhibitor applied to the flotation field of calcium-containing gangue minerals is characterized by comprising 5-95 parts by weight of inorganic phosphate and 5-95 parts by weight of organic phosphate;
the structure of the inorganic phosphate is shown as a formula 1:
wherein X is 2-6;
the structure of the organic phosphate is shown as a formula 2:
wherein n is 2-8;
the composite inhibitor comprises, by weight, 25-75 parts of sodium tripolyphosphate and 25-75 parts of ethylene diamine tetramethylene sodium phosphate, or comprises 25-75 parts of sodium hexametaphosphate and 25-75 parts of hexamethylene diamine tetramethylene sodium phosphate.
2. The use of the composite depressant of claim 1 in the flotation of calcium-containing gangue minerals.
3. Use according to claim 2, wherein the calcium containing gangue minerals are at least one of calcite, fluorite, apatite and wollastonite.
4. The use according to claim 3, characterized in that flotation agent containing the composite depressant is added to the raw ore and flotation is carried out to obtain concentrate.
5. The use according to claim 3, wherein the flotation reagent further comprises a collector, and the crude ore is obtained by adding the inhibitor into the crude ore and then adding a small amount of the collector for flotation.
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| CN105478243B (en) * | 2015-11-19 | 2018-05-08 | 中国地质科学院郑州矿产综合利用研究所 | Novel inhibitor for bauxite beneficiation and using method thereof |
| CN105344488B (en) * | 2015-11-19 | 2018-08-03 | 中国地质科学院郑州矿产综合利用研究所 | Novel inhibitor for aluminosilicate minerals and application method thereof |
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| CN108654844B (en) * | 2018-04-28 | 2020-02-28 | 中南大学 | Application of organic phosphoric acid compound in scheelite flotation |
| CN111215247B (en) * | 2020-01-07 | 2021-04-23 | 中南大学 | Inhibitor for high-calcium fluorite direct flotation and flotation method |
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