CN108187917A - A kind of aromatic radical phosphonic acids and its esters collecting agent and its application - Google Patents
A kind of aromatic radical phosphonic acids and its esters collecting agent and its application Download PDFInfo
- Publication number
- CN108187917A CN108187917A CN201810029330.1A CN201810029330A CN108187917A CN 108187917 A CN108187917 A CN 108187917A CN 201810029330 A CN201810029330 A CN 201810029330A CN 108187917 A CN108187917 A CN 108187917A
- Authority
- CN
- China
- Prior art keywords
- esters
- phenyl
- phosphonic acid
- cassiterite
- aromatic radical
- 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.)
- Granted
Links
- 150000002148 esters Chemical class 0.000 title claims abstract description 46
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 29
- -1 aromatic radical phosphonic acids Chemical class 0.000 title claims abstract description 25
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 92
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical compound OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000005188 flotation Methods 0.000 claims abstract description 29
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 21
- 239000011707 mineral Substances 0.000 claims abstract description 21
- 229910021532 Calcite Inorganic materials 0.000 claims abstract description 7
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims abstract description 7
- 239000010436 fluorite Substances 0.000 claims abstract description 7
- 239000010453 quartz Substances 0.000 claims abstract description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000000926 separation method Methods 0.000 claims abstract description 4
- 239000004115 Sodium Silicate Substances 0.000 claims description 21
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 21
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 21
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 21
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 19
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 19
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 19
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 19
- WVYWICLMDOOCFB-UHFFFAOYSA-N 4-methyl-2-pentanol Chemical compound CC(C)CC(C)O WVYWICLMDOOCFB-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- 239000012141 concentrate Substances 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- 239000004088 foaming agent Substances 0.000 claims description 12
- 239000003112 inhibitor Substances 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 239000002516 radical scavenger Substances 0.000 claims description 8
- 150000003009 phosphonic acids Chemical class 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000007670 refining Methods 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000004575 stone Substances 0.000 claims description 4
- 150000001768 cations Chemical class 0.000 claims description 2
- 229920000609 methyl cellulose Polymers 0.000 claims 2
- 239000001923 methylcellulose Substances 0.000 claims 2
- PODHJIQSMSGBRQ-UHFFFAOYSA-N C1=CC=CC=C1.P(O)(O)=O Chemical class C1=CC=CC=C1.P(O)(O)=O PODHJIQSMSGBRQ-UHFFFAOYSA-N 0.000 claims 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 1
- 210000001367 artery Anatomy 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 210000003462 vein Anatomy 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 7
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 238000007667 floating Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- LQBJWKCYZGMFEV-UHFFFAOYSA-N lead tin Chemical compound [Sn].[Pb] LQBJWKCYZGMFEV-UHFFFAOYSA-N 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000005476 soldering Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- DJHGAFSJWGLOIV-UHFFFAOYSA-N Arsenic acid Chemical compound O[As](O)(O)=O DJHGAFSJWGLOIV-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 229940000488 arsenic acid Drugs 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/018—Mixtures of inorganic and organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/02—Collectors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/04—Frothers
-
- 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
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Paper (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a kind of aromatic radical phosphonic acids and its esters collecting agent and its applications, belong to flotation technology field.The aromatic radical phosphonic acids and its esters collecting agent include phenyl-phosphonic acid and/or phenyl-phosphonic acid and its esters, are applied in the FLOTATION SEPARATION of cassiterite and gangue mineral.The present invention is using aromatic radical phosphonic acids and its esters as collectors for cassiterite, not only increase the water solubility of collecting agent, and with preferable selectivity, the gangue minerals such as cassiterite and quartz, fluorite, calcite can be efficiently separated, and the flotation of cassiterite can be realized under the conditions of more wide in range pH values of pulp.
Description
Technical field
The present invention relates to tin-lead soldering technical field, more particularly to a kind of aromatic radical phosphonic acids and its esters collecting agent and its
Using.
Background technology
Tin is one of metal material that the mankind develop and use earliest, in the medical instrument of today, chemical industry, national defence, electronics electricity
The fields such as device, ocean engineering have irreplaceable role.Cassiterite is can be uniquely used for metal smelting tin existing for nature
Mineral, so cassiterite mineral flotation recycle for ensureing that the national economic development is of great significance.Because cassiterite proportion compared with
Greatly, coarse grain cassiterite can be recycled effectively using reselection technique；But cassiterite is crisp, is easily produced in broken grinding process
Raw a large amount of thin mud, when the granularity of cassiterite is less than 20 μm, gravity separation method recycles the rate of recovery wretched insufficiency of cassiterite, causes a large amount of
Micro fine particle is lost in tailing, only takes flotation technology that can ensure efficiently separating back for micro fine particle at this time
It receives.
So rational collectors application is the successful key point of flotation, the collecting agent type available for tin-lead soldering
Very much, including fatty acid, alkyl sulfosuccinate, hydroximic acid, arsenic acid, phosphonic acids etc..But aliphatic acid, alkyl sulfosuccinate
Acid collector is selectively very poor, and the collecting ability of hydroximic acid is insufficient, and arsenic acid collecting agent has toxicity and is prohibited from using, only
Phosphonic acid collecting agent is able to extensive use in the industry, and in phosphonic acid collecting agent, although short-chain alkyl phosphonic acids can be used for floating
Choosing recycling cassiterite, but collecting ability is insufficient, needs to act synergistically using heavy metal salt (such as plumbi nitras) activator, can cause
The problems such as cost increase, pollution of waterhead；The alkyl phosphonic acid collecting ability of long-chain is strong, but poorly water-soluble, and selectivity also can be significantly
It reduces, limits its application in the industry.Therefore, in order to solve the above technical problems, needing to provide a kind of new tin-lead soldering
Collecting agent.
Invention content
The object of the present invention is to provide one kind to enhance cassiterite surface hydrophobic, and can answer with cassiterite surface action
The collecting agent that cassiterite is selectively isolated from gangue mineral is realized in flotation, it is above-mentioned of the existing technology to solve
Problem.
To achieve the above object, the present invention provides following schemes：
The present invention provides a kind of aromatic radical phosphonic acids and its esters collecting agent, it is characterised in that：Including phenyl-phosphonic acid and/or phenyl
Shown in the structural formula such as formula (I) of phosphonic acids and its esters, the phenyl-phosphonic acid and its esters；The structure of the phenyl-phosphonic acid and its esters
Shown in formula such as formula (II),
Wherein, M1And M2Respectively monovalence or bivalent cation.
Preferably, the M1And M2Respectively H+、NH4+、Na+、Li+、K+、Rb+、Cs+、1/2Sr2+、1/2Be2+、1/2Mg2+、
1/2Ca2+、1/2Ba2+、1/2Zn2+And 1/2Mn2+In one kind.
The present invention also provides the applications of a kind of aromatic radical phosphonic acids and its esters collecting agent, it is characterised in that：Applied to tin
The FLOTATION SEPARATION of stone and gangue mineral.
Preferably, the gangue mineral is quartz, fluorite and calcite.
Preferably, using phenyl-phosphonic acid and/or phenyl-phosphonic acid and its esters as collectors for cassiterite, methyl isobutyl carbinol is made
For foaming agent, carboxymethyl cellulose and sodium metasilicate carry out flotation to cassiterite ore pulp, obtain cassiterite essence as gangue mineral inhibitor
Ore deposit.
Preferably, floatation process includes 1 rougher process, scans process and 3 refining process for 2~3 times.
Preferably, a kind of aromatic radical phosphonic acids and its esters collecting agent and its application, include the following steps：
(1) in rougher process, the pH value of cassiterite ore pulp is adjusted to 4~7, gangue mineral is sequentially added and inhibits agent carboxymethyl fine
Dimension element and sodium metasilicate, collectors for cassiterite phenyl-phosphonic acid and/or phenyl-phosphonic acid and its esters, foaming agent methyl isobutyl carbinol carry out
Roughing obtains rougher concentration and rougher tailings；Carboxymethyl cellulose and sodium metasilicate are 300~500g/ relative to the dosage of raw ore
T, phenyl-phosphonic acid and/or phenyl-phosphonic acid and its esters are 1200~1500g/t relative to the dosage of raw ore, methyl isobutyl carbinol phase
Dosage for raw ore is 120g/t；
(2) during scanning, collectors for cassiterite phenyl-phosphonic acid and/or phenyl-phosphonic acid and its salt are added in gained rougher tailings
Class, foaming agent methyl isobutyl carbinol, is scanned, and is scanned 2~3 times, is obtained scavenger concentrate；Scavenger concentrate sequence is back to
Flotation operation；Phenyl-phosphonic acid and/or phenyl-phosphonic acid and its esters are 600~750g/t relative to the dosage of raw ore, and methyl is different
Butyl carbinol is 80g/t relative to the dosage of raw ore；
(3) in refining process, gangue mineral inhibitor carboxymethyl cellulose and sodium metasilicate are added in gained rougher concentration,
Selected 3 times, selected concentrate and selected chats are obtained, selected chats sequence is back to last flotation operation；Carboxymethyl cellulose
With sodium metasilicate relative to raw ore dosage be 150~250g/t.
Preferably, the mass ratio of the carboxymethyl cellulose and sodium metasilicate is 1:1.
Preferably, the carboxymethyl cellulose and sodium metasilicate be configured to mass percent concentration be 20%~25% it is water-soluble
Liquid, the phenyl-phosphonic acid and/or phenyl-phosphonic acid and its esters are configured to the aqueous solution that mass percent concentration is 10%~15%, institute
It states methyl isobutyl carbinol and is configured to the aqueous solution that mass percent concentration is 20%.
The invention discloses following technique effects：
1. phenyl-phosphonic acid provided by the invention and/or phenyl-phosphonic acid and its esters are the phosphonic acid collectings containing benzene ring structure
Agent, the polar group in phenyl-phosphonic acid and phenyl-phosphonic acid are phosphinic acids base and phosphonic acid base respectively, and phosphorus atoms and oxygen atom therein can be with
It is chemically reacted with the tin metal atom on cassiterite surface, so as to adsorb on cassiterite surface；In phenyl-phosphonic acid and phenyl-phosphonic acid
Nonpolar base is benzene ring structure, and introducings of phenyl ring can improve the selectivity of phosphonic acids collecting agent, collecting ability, hydrophobicity by force and
Water solubility can efficiently separate the gangue minerals such as cassiterite and quartz, fluorite, calcite, and can be in more wide in range ore pulp
The flotation of cassiterite is realized under the conditions of pH.
2. collecting agent provided by the invention is environmentally protective, nontoxic, water-soluble strong, suitable for large-scale industrial application.
Specific embodiment
It is clearly and completely described below in conjunction with the technical solution in the embodiment of the present invention, it is clear that described reality
It is only part of the embodiment of the present invention to apply example, instead of all the embodiments.Based on the embodiments of the present invention, this field is general
Logical technical staff all other embodiments obtained without making creative work belong to what the present invention protected
Range.
In order to make the foregoing objectives, features and advantages of the present invention clearer and more comprehensible, With reference to embodiment
The present invention is described in further detail.
Embodiment 1
The flotation of artificial mixed ore
(1) by cassiterite minal respectively with quartzy minal, fluorite minal, calcite minal according to mass ratio be 1:
1 ratio is configured to artificial mixed ore, and the granularity of all minals is -45 μm；
(2) artificial mixed ore 2g and 20mL distilled water is taken to be placed in the hanging trough flotator of 30mL, in the stirring of 1992r/min
Size mixing 3min under rotating speed, obtains cassiterite ore pulp；
(3) pH value of cassiterite ore pulp is adjusted with sodium hydroxide and sulfuric acid to 7, adds in collectors for cassiterite (phenyl-phosphonic acid and/or benzene
Base phosphonic acids and its esters), a concentration of 60mg/L of collectors for cassiterite after stirring 3min, adds in foaming agent (methyl isobutyl carbinol),
Foaming agent concentration is 100mg/L, stirs air flotation after 3min, obtains remaining tailing in froth pulp and slot；
(4) froth pulp and tailing be respectively dried, weighed, the grade of wherein tin is chemically examined after sample preparation, calculate yield and returned
Yield.
The flotation results of artificial mixed ore are as shown in table 1 below.The result shows that phenyl-phosphonic acid and its esters and phenyl-phosphonic acid and its
Salt collecting agent effectively can separate cassiterite and quartz, fluorite, calcite, and floatation indicators are not much different.
1 artificial mixed ore flotation results of table
Embodiment 2
Selection Inner Mongol cassiterite green ore is raw material, and the tin grade in raw ore is 0.37%, and gangue mineral is quartz, long
Stone, mica, calcite and kaolin.
Floatation process Chinese medicine dosage is：In rougher process, carboxymethyl cellulose is 250g/ relative to the addition of raw ore
T, it relative to the addition of raw ore is 1500g/t that sodium metasilicate, which relative to the addition of raw ore is 250g/t, phenyl-phosphonic acid and its esters,
Methyl isobutyl carbinol is 120g/t relative to the addition of raw ore；During scanning, phenyl-phosphonic acid and its esters are relative to raw ore
Addition for 750g/t, methyl isobutyl carbinol is 80g/t relative to the dosage of raw ore；In refining process, carboxymethyl cellulose
Element is 100g/t relative to the addition of raw ore, and sodium metasilicate is 100g/t relative to the addition of raw ore.
Floating operation step is：
(1) tcrude ore reaches monomer dissociation after broken, ore grinding, be configured in flotation cell ore pulp and with sodium hydroxide with
Sulphur acid for adjusting pH value sequentially adds gangue mineral inhibitor (carboxymethyl cellulose and sodium metasilicate), collectors for cassiterite (benzene to 4~7
Phosphonic acids and its esters), foaming agent (methyl isobutyl carbinol), carry out roughing, obtain rougher concentration and rougher tailings；
(2) collectors for cassiterite (phenyl-phosphonic acid and its esters), foaming agent (methyl-isobutyl first are added in gained rougher tailings
Alcohol), it is scanned, scans progress 3 times, obtain scavenger concentrate, scavenger concentrate sequence is back to last flotation operation；
(3) the addition gangue mineral inhibitor (carboxymethyl cellulose and sodium metasilicate) in gained rougher concentration, selected 3 times,
Selected concentrate and selected chats are obtained, selected chats sequence is back to last flotation operation.
By raw ore that grade is 0.37% after one thick three sweeps three cleaner flotations, grade is obtained as 38.03%, the rate of recovery is
73.15% cassiterite concentrate.
Embodiment 3
Selection Jiangxi Province's cassiterite green ore is raw material, and the tin grade in raw ore is 0.34%, and gangue mineral is quartz, long
Stone, mica and fluorite.
Floatation process Chinese medicine dosage is：In rougher process, carboxymethyl cellulose is 200g/ relative to the addition of raw ore
T, it relative to the addition of raw ore is 1200g/ that sodium metasilicate, which relative to the addition of raw ore is 200g/t, phenyl-phosphonic acid and its esters,
T, methyl isobutyl carbinol are 120g/t relative to the addition of raw ore；During scanning, phenyl-phosphonic acid and its esters relative to
The addition of raw ore is 600g/t, and methyl isobutyl carbinol is 80g/t relative to the dosage of raw ore；In refining process, carboxymethyl
Cellulose is 100g/t relative to the addition of raw ore, and sodium metasilicate is 100g/t relative to the addition of raw ore.
Floating operation step is：
(1) tcrude ore reaches monomer dissociation after broken, ore grinding, be configured in flotation cell ore pulp and with sodium hydroxide with
Sulphur acid for adjusting pH value sequentially adds gangue mineral inhibitor (carboxymethyl cellulose and sodium metasilicate), collectors for cassiterite (benzene to 4~7
Base phosphonic acids and its esters), foaming agent (methyl isobutyl carbinol), carry out roughing, obtain rougher concentration and rougher tailings；
(2) collectors for cassiterite (phenyl-phosphonic acid and its esters), foaming agent (methyl-isobutyl are added in gained rougher tailings
Methanol), it is scanned, scans progress 2 times, obtain scavenger concentrate, scavenger concentrate sequence is back to last flotation operation；
(3) the addition gangue mineral inhibitor (carboxymethyl cellulose and sodium metasilicate) in gained rougher concentration, selected 3 times,
Selected concentrate and selected chats are obtained, selected chats sequence is back to last flotation operation.
By raw ore that grade is 0.34% after one thick two sweeps three cleaner flotations, grade is obtained as 34.49%, the rate of recovery is
75.86% cassiterite concentrate.
Embodiment described above is only that the preferred embodiment of the present invention is described, and not the scope of the present invention is carried out
It limits, under the premise of design spirit of the present invention is not departed from, those of ordinary skill in the art make technical scheme of the present invention
Various modifications and improvement, should all fall into the protection domain that claims of the present invention determines.
Claims (9)
1. a kind of aromatic radical phosphonic acids and its esters collecting agent, it is characterised in that：Including phenyl-phosphonic acid and/or phenyl-phosphonic acid and its salt
Shown in the structural formula such as formula (I) of class, the phenyl-phosphonic acid and its esters；The structural formula of the phenyl-phosphonic acid and its esters such as formula (II)
It is shown,
Wherein, M1And M2Respectively monovalence or bivalent cation.
2. a kind of aromatic radical phosphonic acids according to claim 1 and its esters collecting agent, it is characterised in that：The M1And M2Point
It Wei not H+、NH4+、Na+、Li+、K+、Rb+、Cs+、1/2Sr2+、1/2Be2+、1/2Mg2+、1/2Ca2+、1/2Ba2+、1/2Zn2+With 1/
2Mn2+In one kind.
3. the application of a kind of aromatic radical phosphonic acids described in claim 1 and its esters collecting agent, it is characterised in that：Applied to cassiterite
With the FLOTATION SEPARATION of gangue mineral.
4. the application of a kind of aromatic radical phosphonic acids according to claim 3 and its esters collecting agent, it is characterised in that：The arteries and veins
Stone ore object is quartz, fluorite and calcite.
5. the application of a kind of aromatic radical phosphonic acids according to claim 3 and its esters collecting agent, it is characterised in that：Using benzene
Phosphonic acids and/or phenyl-phosphonic acid and its esters are as collectors for cassiterite, and methyl isobutyl carbinol is as foaming agent, carboxymethyl cellulose
With sodium metasilicate as gangue mineral inhibitor, flotation is carried out to cassiterite ore pulp, obtains cassiterite concentrate.
6. the application of a kind of aromatic radical phosphonic acids according to claim 5 and its esters collecting agent, it is characterised in that：Flotation
Journey include 1 roughing, scan for 2~3 times with 3 times it is selected.
7. the application of a kind of aromatic radical phosphonic acids according to claim 6 and its esters collecting agent, it is characterised in that：Including with
Lower step：
(1) in rougher process, the pH value of cassiterite ore pulp is adjusted to 4~7, sequentially adds gangue mineral inhibitor carboxymethyl cellulose
And sodium metasilicate, collectors for cassiterite phenyl-phosphonic acid and/or phenyl-phosphonic acid and its esters, foaming agent methyl isobutyl carbinol carry out roughing,
Obtain rougher concentration and rougher tailings；Carboxymethyl cellulose and sodium metasilicate are 300~500g/t relative to the dosage of raw ore, phosphniline
Acid and/or phenyl-phosphonic acid and its esters are 1200~1500g/t relative to the dosage of raw ore, and methyl isobutyl carbinol is relative to original
The dosage of ore deposit is 120g/t；
(2) during scanning, collectors for cassiterite phenyl-phosphonic acid and/or phenyl-phosphonic acid and its esters are added in gained rougher tailings,
Foaming agent methyl isobutyl carbinol, is scanned, and is scanned 2~3 times, is obtained scavenger concentrate；Scavenger concentrate sequence is back to one
Secondary flotation operation；Phenyl-phosphonic acid and/or phenyl-phosphonic acid and its esters are 600~750g/t relative to the dosage of raw ore, methyl tert-butyl
Base methanol is 80g/t relative to the dosage of raw ore；
(3) in refining process, gangue mineral inhibitor carboxymethyl cellulose and sodium metasilicate are added in gained rougher concentration, it is selected
3 times, selected concentrate and selected chats are obtained, selected chats sequence is back to last flotation operation；Carboxymethyl cellulose and silicon
Sour sodium is 150~250g/t relative to the dosage of raw ore.
8. the application of a kind of aromatic radical phosphonic acids according to claim 7 and its esters collecting agent, it is characterised in that：The carboxylic
The mass ratio of methylcellulose and sodium metasilicate is 1:1.
9. the application of a kind of aromatic radical phosphonic acids according to claim 7 and its esters collecting agent, it is characterised in that：The carboxylic
Methylcellulose and sodium metasilicate are configured to the aqueous solution that mass percent concentration is 20%~25%, the phenyl-phosphonic acid and/or benzene
Base phosphonic acids and its esters are configured to the aqueous solution that mass percent concentration is 10%~15%, and the methyl isobutyl carbinol is prepared
Into the aqueous solution that mass percent concentration is 20%.
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Cited By (5)
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| CN111068926A (en) * | 2019-11-12 | 2020-04-28 | 中南大学 | Hydroximic acid-alkyl sulfuric acid multi-ligand metal complex collecting agent and preparation method and application thereof |
| CN111482278A (en) * | 2020-06-03 | 2020-08-04 | 广东省资源综合利用研究所 | Copper oxide ore flotation method |
| CN117732597A (en) * | 2024-02-21 | 2024-03-22 | 中国矿业大学(北京) | Flotation recovery method and flotation recovery device for micro-fine cassiterite |
| CN117732597B (en) * | 2024-02-21 | 2024-05-31 | 中国矿业大学(北京) | Flotation recovery method and flotation recovery device for micro-fine cassiterite |
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| CN109225649A (en) * | 2018-10-29 | 2019-01-18 | 贵州川恒化工股份有限公司 | A layers of ore inverse flotation composite collector of phosphorus ore and preparation method thereof |
| CN111068926A (en) * | 2019-11-12 | 2020-04-28 | 中南大学 | Hydroximic acid-alkyl sulfuric acid multi-ligand metal complex collecting agent and preparation method and application thereof |
| CN111482278A (en) * | 2020-06-03 | 2020-08-04 | 广东省资源综合利用研究所 | Copper oxide ore flotation method |
| CN111482278B (en) * | 2020-06-03 | 2022-03-22 | 广东省资源综合利用研究所 | Copper oxide ore flotation method |
| CN117732597A (en) * | 2024-02-21 | 2024-03-22 | 中国矿业大学(北京) | Flotation recovery method and flotation recovery device for micro-fine cassiterite |
| CN117732597B (en) * | 2024-02-21 | 2024-05-31 | 中国矿业大学(北京) | Flotation recovery method and flotation recovery device for micro-fine cassiterite |
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