CN106861919A - A kind of tin-lead soldering collecting agent and its application - Google Patents
A kind of tin-lead soldering collecting agent and its application Download PDFInfo
- Publication number
- CN106861919A CN106861919A CN201710297019.0A CN201710297019A CN106861919A CN 106861919 A CN106861919 A CN 106861919A CN 201710297019 A CN201710297019 A CN 201710297019A CN 106861919 A CN106861919 A CN 106861919A
- Authority
- CN
- China
- Prior art keywords
- tin
- cassiterite
- phosphoric acid
- collecting agent
- lead soldering
- 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
- 238000005476 soldering Methods 0.000 title claims abstract description 27
- LQBJWKCYZGMFEV-UHFFFAOYSA-N lead tin Chemical compound [Sn].[Pb] LQBJWKCYZGMFEV-UHFFFAOYSA-N 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 132
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 52
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 50
- 238000005188 flotation Methods 0.000 claims abstract description 39
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 27
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims abstract description 20
- 229910021532 Calcite Inorganic materials 0.000 claims abstract description 19
- AVXXOYCGDFNFRX-UHFFFAOYSA-N phenylmethoxy dihydrogen phosphate Chemical compound C(C1=CC=CC=C1)OOP(O)(O)=O AVXXOYCGDFNFRX-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000012141 concentrate Substances 0.000 claims description 27
- MPPQGYCZBNURDG-UHFFFAOYSA-N 2-propionyl-6-dimethylaminonaphthalene Chemical compound C1=C(N(C)C)C=CC2=CC(C(=O)CC)=CC=C21 MPPQGYCZBNURDG-UHFFFAOYSA-N 0.000 claims description 20
- 229940084030 carboxymethylcellulose calcium Drugs 0.000 claims description 20
- RBNWAMSGVWEHFP-UHFFFAOYSA-N trans-p-Menthane-1,8-diol Chemical compound CC(C)(O)C1CCC(C)(O)CC1 RBNWAMSGVWEHFP-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 16
- 239000010453 quartz Substances 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- 239000003112 inhibitor Substances 0.000 claims description 13
- 239000004088 foaming agent Substances 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 10
- 239000012190 activator Substances 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 claims description 4
- 238000007670 refining Methods 0.000 claims description 2
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 claims 1
- 229920002134 Carboxymethyl cellulose Polymers 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
- 235000008331 Pinus X rigitaeda Nutrition 0.000 claims 1
- 235000011613 Pinus brutia Nutrition 0.000 claims 1
- 241000018646 Pinus brutia Species 0.000 claims 1
- 239000001768 carboxy methyl cellulose Substances 0.000 claims 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims 1
- 229940105329 carboxymethylcellulose Drugs 0.000 claims 1
- 229940055577 oleyl alcohol Drugs 0.000 claims 1
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 231100000252 nontoxic Toxicity 0.000 abstract description 4
- 230000003000 nontoxic effect Effects 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 25
- 239000011707 mineral Substances 0.000 description 25
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 22
- -1 alkyl sulfosuccinamate Chemical compound 0.000 description 15
- 238000011084 recovery Methods 0.000 description 13
- 238000007667 floating Methods 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 8
- 229910052698 phosphorus Inorganic materials 0.000 description 8
- 239000011574 phosphorus Substances 0.000 description 8
- 239000003814 drug Substances 0.000 description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 7
- 238000000227 grinding Methods 0.000 description 6
- WRKCIHRWQZQBOL-UHFFFAOYSA-N octyl dihydrogen phosphate Chemical compound CCCCCCCCOP(O)(O)=O WRKCIHRWQZQBOL-UHFFFAOYSA-N 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000004575 stone Substances 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 5
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 4
- 229910001431 copper ion Inorganic materials 0.000 description 4
- 238000010494 dissociation reaction Methods 0.000 description 4
- 230000005593 dissociations Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 238000011017 operating method Methods 0.000 description 4
- 239000002516 radical scavenger Substances 0.000 description 4
- 210000003462 vein Anatomy 0.000 description 4
- QZRMKGRPCTVXBS-UHFFFAOYSA-N 2,6,8-trimethylnonan-4-yl dihydrogen phosphate Chemical compound CC(C)CC(C)CC(CC(C)C)OP(O)(O)=O QZRMKGRPCTVXBS-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 150000003016 phosphoric acids Chemical class 0.000 description 3
- 230000031068 symbiosis, encompassing mutualism through parasitism Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- DJHGAFSJWGLOIV-UHFFFAOYSA-N Arsenic acid Chemical compound O[As](O)(O)=O DJHGAFSJWGLOIV-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229940000488 arsenic acid Drugs 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- QWUWMCYKGHVNAV-UHFFFAOYSA-N 1,2-dihydrostilbene Chemical group C=1C=CC=CC=1CCC1=CC=CC=C1 QWUWMCYKGHVNAV-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052614 beryl Inorganic materials 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- ZXOKVTWPEIAYAB-UHFFFAOYSA-N dioxido(oxo)tungsten Chemical compound [O-][W]([O-])=O ZXOKVTWPEIAYAB-UHFFFAOYSA-N 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 150000002148 esters Chemical class 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
- 239000006260 foam Substances 0.000 description 1
- 229910052949 galena Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- XCAUINMIESBTBL-UHFFFAOYSA-N lead(ii) sulfide Chemical compound [Pb]=S XCAUINMIESBTBL-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 235000012054 meals Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052592 oxide mineral Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
- 229910052683 pyrite Inorganic materials 0.000 description 1
- 239000011028 pyrite Substances 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 229910001662 tin mineral Inorganic materials 0.000 description 1
- IVIIAEVMQHEPAY-UHFFFAOYSA-N tridodecyl phosphite Chemical compound CCCCCCCCCCCCOP(OCCCCCCCCCCCC)OCCCCCCCCCCCC IVIIAEVMQHEPAY-UHFFFAOYSA-N 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
- B03D1/004—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
- B03D2201/02—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
- B03D2203/00—Specified materials treated by the flotation agents; Specified applications
- B03D2203/02—Ores
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Abstract
It is used for tin-lead soldering collecting agent and its application the invention discloses one kind, belongs to flotation technology field.Tin-lead soldering collecting agent includes two phenoxy group phosphoric acid and/or benzyloxy phosphoric acid, is applied to the FLOTATION SEPARATION of cassiterite and gangue, and compared with the existing collectors for cassiterite for commonly using, two phenoxy group phosphoric acid and benzyloxy phosphoric acid are obvious as collectors for cassiterite advantage：Normal temperature is solvable, nontoxic, consumption is low, collecting ability is strong, selectivity is strong, and efficiently separating for cassiterite and quartzy, calcite is capable of achieving in the case where pH is neutrallty condition.
Description
Technical field
The present invention relates to a kind of mineral floating collecting agent, and in particular to a kind of collecting agent for for tin-lead soldering separate, category
In cassiterite mineral floating technical field.
Background technology
Tin is human being's production and a kind of indispensable important meals of life, is also to find and use earliest in human history
One of metal, because it has the advantages that fusing point is low, corrosion-resistant and malleable other metallicities, in all fields of national economy
It is widely used；Current countries in the world constantly increase to the demand of tin, and the level of consumption of tin has turned into one National Industrial hair of measurement
One of index of exhibition level.Cassiterite stanniferous 78.6%, is most common tin mineral, is also the topmost ore mineral of tin.I
State's Tin Resources enrich, and distributed areas are wide.Mainly based on primary deposit, wherein Associated Constituents are more.The main work of cassiterite preservation
Industry type：In cassiterite-Rare Metal Deposit, cassiterite is close with columbite, tantalite, beryl, calcite, quartzy symbiosis；
In residual slide rock sandy cofferdam, the densification symbiosis of cassiterite and oxide mineral；In cassiterite-Sulphide Ore, cassiterite and calcite, stone
The symbiosis such as English, wolframite, galena, pyrite, disseminated grain size is thin.Therefore, cassiterite is difficult with other mineral disaggregations, in technique often
Need fine grinding.Meanwhile, cassiterite density is big, and gravity treatment is traditional ore-dressing technique that cassiterite is reclaimed, the method low cost, environmentally friendly.
But cassiterite is crisp frangible, and grinding process was susceptible to crushing, while with the passage of recovery time, the tin in milling ore
Stone granularity constantly attenuates, and when micro fine particle is reclaimed using reselecting method, the tin rate of recovery is low, and effective recovery lower limit of flotation grain
Spend, important method for as micro fine particle effectively reclaiming one of low compared with gravity treatment.Additionally, often containing various oxidations in tin ore
Mineral, the presence of such as quartz and calcite mineral directly affects the raising of Tin concentrate quality, can effectively be realized using flotation
Cassiterite separation therewith.
The development of Flotation of Cassiterite collecting agent is the key for promoting micro fine particle flotation development.Tin-lead soldering collecting agent amounts to
Up to as many as over one hundred kind, aliphatic acid, arsenic acid, alkyl sulfate, alkyl sulfosuccinamate and alkyl phosphorous acid can be divided into
Several major classes such as ester (alkyl phosphoric acid).Fatty acid collecting agent collecting is cheap, nontoxic, collecting ability strong, but to association gangue
Mineral quartz, calcite poor selectivity；Arsenic acid selectivity is strong, but environmental pollution is serious, be detrimental to health；Alkylsurfuric acid
Salt is stronger to the collecting ability of cassiterite mineral, but such collecting agent is to Ca2+、Fe2+Sensitivity, and it is just effective only under acid condition,
It is difficult to industrial applications；Alkyl sulfosuccinamate collecting ability very strong, consumption is less, cheap, nontoxic nothing
Evil, it is short with mineral action time, and to coarse grain tin-lead soldering effect preferably, but equally exist to quartz, calcite poor selectivity
Shortcoming；It is worth it is emphasized that short-chain alkyl phosphite ester and short-chain alkyl phosphoric acid are isomers, existing report two
Person may be used to tin-lead soldering collecting, but both are weaker, it is necessary to add substantial amounts of activator to the collecting ability of cassiterite
(heavy metal ion) is used cooperatively, and not only increased industrial cost but also has been caused environmental disruption.Although sub- by increasing short-chain alkyl
The carbochain of phosphate and short-chain alkyl phosphoric acid, can to a certain extent strengthen the collecting ability of collecting agent, but its dissolubility
Can be substantially reduced again with selectivity, and alkyl phosphite and alkyl phosphoric acid are all in the presence of extremely quick to iron, copper ion in ore pulp
The problem of sense, causes its collecting ability to cassiterite and selectivity cannot be guaranteed.
The content of the invention
For in the prior art, short-chain alkyl phosphite ester and short-chain alkyl phosphoric acid class tin-lead soldering collecting agent are in flotation
Technical problem present in journey, it is to provide a kind of adsorption capacity that can strengthen to cassiterite mineral surfaces that the purpose of the present invention is,
Cassiterite surface hydrophobic is improved, to realize that the phosphoric acid class tin-lead soldering that cassiterite is efficiently separated with gangue mineral quartz and calcite is caught
Receive agent.
It is to provide a kind of application of the tin-lead soldering collecting agent that another object of the present invention is, be applied to
Cassiterite mineral and quartz and the gangue mineral FLOTATION SEPARATION such as calcite, not only can be to the collecting ability of cassiterite and selectively can
It is guaranteed, and solves again to iron, copper ion sensitive issue in ore pulp.
In order to realize above-mentioned technical purpose, the invention provides a kind of tin-lead soldering collecting agent, it includes two phenoxy group phosphorus
Acid and/or benzyloxy phosphoric acid.
Two phenoxy groups phosphoric acid of the invention and benzyloxy phosphoric acid belong to the phosphate compound containing aromatic hydrocarbon.It is to cassiterite
The surface of mineral has stronger activation, is on the one hand lived by phosphorus, oxygen atom isopolarity functional group and cassiterite mineral surfaces
Property point-metallic element reacts, so as to adsorb on mineral surfaces；And the organic group of nonpolar moiety mainly rise it is thin
Water is acted on.The species of organic group plays an important role to the dissolubility of collecting agent, the selectivity of polar functional group.Such as use short carbon
When chain phosphoric acid is as collectors for cassiterite, poor selectivity, while needing addition plurality of heavy metal activator to use cooperatively；Using carbon long
When chain phosphoric acid is as collectors for cassiterite, polar functional group phosphorus, the enhancing of oxygen atom electron supplying capacity cause the selectivity of collecting agent to drop
It is low, while medicament dissolubility in the solution is deteriorated.And the present patent application technical scheme preferably phosphorus containing phenyl ring (or benzyloxy)
Acid as collectors for cassiterite, compared to carbochain, phenyl ring due to there is π keys, phosphorus, oxygen atom electron supplying capacity to polar functional group
It is weak, collecting agent had not only been ensure that to the selectivity of target minreal cassiterite but also had been solved to iron, copper ion sensitive issue；Phenyl ring (or
Benzyloxy) introducing can't substantially reduce the dissolubility of medicament, so allow to introduce more phenyl ring (or benzyloxy) strengthening
The collecting ability of medicament, brings unexpected effect during tin-lead soldering.
The two phenoxy groups phosphoric acid has the structure of formula 1：
The benzyloxy phosphoric acid has the structure of formula 2：
Present invention also offers a kind of application of described tin-lead soldering collecting agent, it is applied to cassiterite floating with gangue
Choosing is separated.
Preferred scheme, the gangue includes calcite and/or quartz.
More preferably scheme, is made using two phenoxy group phosphoric acid and/or benzyloxy phosphoric acid as collectors for cassiterite, terpinol
Be foaming agent, plumbi nitras as activator, carboxymethylcellulose calcium and prodan as gangue inhibitor, to cassiterite crude ore pulp
Flotation is carried out, cassiterite concentrate is obtained.
Further preferred scheme, described flotation include roughing, scan with it is selected.
Preferred scheme, in rougher process, the pH for adjusting cassiterite crude ore pulp is 6~8, and plumbi nitras adds with respect to raw ore
Enter amount for 50~100g/t, carboxymethylcellulose calcium and prodan are 200~400g/t, two phenoxy groups with respect to the addition of raw ore
Phosphoric acid and/or benzyloxy phosphoric acid are 600~1000g/t with respect to the addition of raw ore, and terpinol is with respect to the addition of raw ore
50~100g/t.
Preferred scheme, during scanning, the addition of two phenoxy group phosphoric acid and/or benzyloxy phosphoric acid with respect to raw ore
It is 300~500g/t, terpinol is 25~50g/t with respect to the addition of raw ore.
Preferred scheme, in refining process, carboxymethylcellulose calcium and prodan with respect to the addition of raw ore be 100~
200g/t。
The mass ratio of preferred scheme, carboxymethylcellulose calcium and prodan is 1:0.5~1.5.
Preferred scheme, the flotation includes one roughing, scans selected with 2~3 times for 2~3 times.
Two phenoxy groups phosphoric acid of the invention and benzyloxy phosphoric acid are applied to the method tool of cassiterite and the FLOTATION SEPARATION of gangue
Body is comprised the following steps：
1) regulation tin-lead soldering slurry pH adds activator, inhibitor, collecting agent and foaming agent, often successively to 6~8
Stirring 3min adds down a kind of medicament again after planting medicament addition；Activator is 50~100g/t with respect to the addition of raw ore, is suppressed
Agent is 100~200g/t with respect to the addition of raw ore, and collecting agent is 600~1000g/t, foaming agent phase with respect to the addition of raw ore
Addition to raw ore is 50~100g/t；After the addition of whole medicaments is finished, flotation of ventilating carries out roughing, obtain rough concentrate and
Thick mine tailing；
2) collecting agent and foaming agent are added in the thick mine tailing of gained, is scanned, obtain sweeping concentrate；Collecting agent is with respect to raw ore
Addition is 300~500g/t, and foaming agent is 25~50g/t with respect to the addition of raw ore；Number of times is scanned to be generally 2~3 times；
3) inhibitor is added in gained rough concentrate, carries out selected, obtain Tin concentrate；Inhibitor is with respect to the addition of raw ore
50~100g/t；Concentration times are 2~3 times.
In technical scheme, in ore deposit floatation process, scavenger concentrate order is back to last flotation operation；It is selected
Chats order is back to last flotation operation.
In technical scheme, in mineral floating, it is 10~20% that plumbi nitras is made into mass percent concentration in advance
The aqueous solution is added, and carboxymethylcellulose calcium and prodan are made into the aqueous solution that mass percent concentration is 20~30% and enter in advance
Row addition, two phenoxy group phosphoric acid or benzyloxy phosphoric acid are made into the aqueous solution that mass percent concentration is 5~10% and are added in advance
Plus, the direct stoste addition of terpinol.
Compared with the prior art, the Advantageous Effects that technical scheme is brought：
1) technical scheme is caught using the organophosphor acid compounds containing two phenyl ring as the flotation of cassiterite first
Agent, relatively existing short-chain alkyl phosphite ester or short-chain alkyl phosphoric acid class collectors for cassiterite are received, not only to the collecting energy of cassiterite
Power and selectivity all increase, and solve to iron, copper ion sensitive issue in ore pulp.
2) the phosphorus acid collector for containing two phenyl ring of the invention is strong to the collecting ability and selective power of cassiterite, can realize
Cassiterite is efficiently separated with quartz, calcite in composite ore flotation, and to the iron in ore pulp, copper insensitive.
3) the phosphorus acid collector for containing two phenyl ring of the invention is nontoxic, environmental protection, with it is fabulous it is water-soluble, have
Dissolving beneficial to medicament in ore pulp, uses in neutral environment, is suitable for commercial Application,
Specific embodiment
Following examples are intended to further illustrate present invention, but the protection domain of the claims in the present invention does not receive these
The limitation of embodiment.
Embodiment 1
A kind of application of the phosphoric acid class tin-lead soldering collecting agent of the present embodiment in tin-lead soldering, specifically includes following steps：
(1) the preparation of cassiterite ore pulp：By composite ore that granularity is -74~+38 μm, (mass ratio of cassiterite, quartz and calcite is 1:2:2)
The distilled water 40mL of 2g sums is added in the hanging trough flotator of 60mL, is stirred under 1600r/min rotating speeds and sized mixing, and obtains cassiterite ore deposit
Slurry；(2) by the control of cassiterite ore pulp 7, collecting agent (respectively two phenoxy group phosphoric acid and benzyloxy phosphoric acid) is firstly added, controlled
Collecting agent concentration processed is respectively 20mg/L, 40mg/L, 60mg/L, 80mg/L, 100mg/L), stir 3min；Add terpinol
Foaming agent (concentration is 15mg/L), stirs 3min；After whole floating agents are added, ventilate flotation, after flotation terminates, the bubble for obtaining
Mine tailing in foam product and flotation cell；(3) froth pulp and mine tailing are respectively dried, the calculating yield i.e. rate of recovery of weighing.Minal
Flotation results are as shown in table 1 below.From result, two kinds of phosphorus acid collectors separate equal to cassiterite from quartz and Calcite by Flotation
Can have effect, and index is similar.When the concentration of collecting agent in ore pulp is in the range of 60~80mg/L, the rate of recovery 84% of cassiterite
Left and right, cassiterite grade is more than 62%.Concentration is too low will to cause the tin-lead soldering rate of recovery relatively low；Excessive concentration causes insignificant
Reagent consumption and quartz, the calcite rate of recovery are too high.
The minal flotation experiments analysis result of table 1.
Comparative example 1
The present embodiment JG-12 (dodecyl phosphite ester), JG-8 (octyl group phosphite ester) collecting agent are in tin-lead soldering
Application, specifically include following steps：(1) the preparation of cassiterite ore pulp：By composite ore (cassiterite, quartz that granularity is -74~+38 μm
It is 1 with the mass ratio of calcite:2:2) the distilled water 40mL of 2g sums is added in the hanging trough flotator of 60mL, in 1600r/min
Stirring is sized mixing under rotating speed, obtains cassiterite ore pulp；(2) by the control of cassiterite ore pulp 7, collecting agent is firstly added, control collecting agent is dense
Degree is respectively 20mg/L, 40mg/L, 60mg/L, 80mg/L, 100mg/L, stirs 3min；Add terpinol foaming agent (concentration
It is 15mg/L), stir 3min；After whole floating agents are added, flotation of ventilating, after flotation terminates, the froth pulp that obtains and floating
Select the mine tailing in groove；(3) froth pulp and mine tailing are respectively dried, the calculating yield i.e. rate of recovery of weighing.Minal flotation results are such as
Shown in table 2 below.From result, alkyl phosphoric acid esters collecting agent to cassiterite collecting performance and selection poor performance, both with
Floatation indicators all reach stabilization when measuring as 80mg/L, and grade is about 50%, and the rate of recovery is only or less than 70% or so, much low
In two phenoxy group phosphoric acid and the floatation indicators of benzyloxy phosphoric acid.
The minal flotation experiments analysis result of table 2.
Embodiment 2
Raw mineral materials
Guangxi province cassiterite mountain plateau ore is taken, stanniferous amount is 0.35%
The total consumption of floating agent is：
Plumbi nitras：60g/t
Carboxymethylcellulose calcium：The selected 50g/t of roughing 100g/t
Prodan：The selected 50g/t of roughing 100g/t
Two phenoxy group phosphoric acid：Roughing 600g/t scans 300g/t
Terpinol：Roughing 50g/t scans 25g/t
Operating procedure and technical conditions are as follows：
In floatation process, after ore is added into ore mill ore grinding to mineral monomer dissociation, in slurry pH in 6~8 scopes
It is interior, sequentially add plumbi nitras and make activator, carboxymethylcellulose calcium and the prodan of cassiterite as calcite and quartz vein stone ore
The inhibitor of thing, two phenoxy group phosphoric acid make collecting agent and terpinol carries out roughing operation as foaming agent, obtains rough concentrate and thick tail
Ore deposit, thick mine tailing adds two phenoxy group phosphoric acid and terpinol to be scanned, and it is 2 times to scan number of times, and scavenger concentrate order is back to
Flotation operation.Rough concentrate adds inhibitor carboxymethylcellulose calcium and prodan, and concentration times are 2 times, obtain Tin concentrate,
Selected chats order is back to last flotation operation.Under conditions of being 0.35% to ore deposit tin grade, by one roughing two
It is secondary it is selected scan twice after, can obtain stanniferous 24.17%, the rate of recovery is 74.36% Tin concentrate.
Comparative example 2
Raw mineral materials
Guangxi province cassiterite mountain plateau ore is taken, stanniferous amount is 0.35%
The total consumption of floating agent is：
Plumbi nitras：60g/t
Carboxymethylcellulose calcium：The selected 50g/t of roughing 100g/t
Prodan：The selected 50g/t of roughing 100g/t
JG-12 (1-isobutyl-3,5-dimethylhexylphosphoric acid)：Roughing 600g/t scans 300g/t
Terpinol：Roughing 50g/t scans 25g/t
Operating procedure and technical conditions are as follows：
In floatation process, after ore is added into ore mill ore grinding to mineral monomer dissociation, in slurry pH in 6~8 scopes
It is interior, sequentially add plumbi nitras and make activator, carboxymethylcellulose calcium and the prodan of cassiterite as calcite and quartz vein stone ore
The inhibitor of thing, JG-12 (1-isobutyl-3,5-dimethylhexylphosphoric acid) make collecting agent and terpinol carries out roughing operation as foaming agent, obtains coarse-fine
Ore deposit and thick mine tailing, thick mine tailing add JG-12 (1-isobutyl-3,5-dimethylhexylphosphoric acid) and terpinol to be scanned, and scan number of times for 2 times, scan
Concentrate order is back to last flotation operation.Rough concentrate adds inhibitor carboxymethylcellulose calcium and prodan, concentration times
It is 2 times, obtains Tin concentrate, selected chats order is back to last flotation operation.To the condition that ore deposit tin grade is 0.35%
Under, by one roughing is selected twice scan twice after, can obtain stanniferous 16.48%, the rate of recovery is 62.70% Tin concentrate,
Far below two phenoxy group phosphoric acid collecting agent floatation indicators.
Embodiment 3
Raw mineral materials
Yunnan Province's cassiterite mountain plateau ore is taken, stanniferous amount is 0.36%
The total consumption of floating agent is：
Plumbi nitras：100g/t
Carboxymethylcellulose calcium：The selected 100g/t of roughing 200g/t
Prodan：The selected 100g/t of roughing 200g/t
Benzyloxy phosphoric acid：Roughing 1000g/t scans 500g/t
Terpinol：Roughing 100g/t scans 50g/t
Operating procedure and technical conditions are as follows：
In floatation process, after ore is added into ore mill ore grinding to mineral monomer dissociation, in slurry pH in 6~8 scopes
It is interior, sequentially add plumbi nitras and make activator, carboxymethylcellulose calcium and the prodan of cassiterite as calcite and quartz vein stone ore
The inhibitor of thing, benzyloxy phosphoric acid make collecting agent and terpinol carries out roughing operation as foaming agent, obtains rough concentrate and thick tail
Ore deposit, thick mine tailing adds benzyloxy phosphoric acid and terpinol to be scanned, and it is 3 times to scan number of times, and scavenger concentrate order is back to
Flotation operation.Rough concentrate adds inhibitor carboxymethylcellulose calcium and prodan, and concentration times are 3 times, obtain Tin concentrate,
Selected chats order is back to last flotation operation.Under conditions of being 0.36% to ore deposit tin grade, by one roughing three
After secondary selected three times are scanned, stanniferous 30.18% is can obtain, the rate of recovery is 62.44% Tin concentrate.
Comparative example 3
Raw mineral materials
Guangxi province cassiterite mountain plateau ore is taken, stanniferous amount is 0.35%
The total consumption of floating agent is：
Plumbi nitras：60g/t
Carboxymethylcellulose calcium：The selected 50g/t of roughing 100g/t
Prodan：The selected 50g/t of roughing 100g/t
JG-8 (octyl phosphate)：Roughing 600g/t scans 300g/t
Terpinol：Roughing 50g/t scans 25g/t
Operating procedure and technical conditions are as follows：
In floatation process, after ore is added into ore mill ore grinding to mineral monomer dissociation, in slurry pH in 6~8 scopes
It is interior, sequentially add plumbi nitras and make activator, carboxymethylcellulose calcium and the prodan of cassiterite as calcite and quartz vein stone ore
The inhibitor of thing, JG-8 (octyl phosphate) make collecting agent and terpinol carries out roughing operation as foaming agent, obtain rough concentrate and
Thick mine tailing, thick mine tailing adds JG-8 (octyl phosphate) and terpinol to be scanned, and scans number of times for 2 times, and scavenger concentrate is sequentially
It is back to last flotation operation.Rough concentrate adds inhibitor carboxymethylcellulose calcium and prodan, and concentration times are 2 times, are obtained
Tin concentrate is obtained, selected chats order is back to last flotation operation.Under conditions of being 0.35% to ore deposit tin grade, by one
Secondary roughing is selected twice scan twice after, can obtain stanniferous 10.56%, the rate of recovery is 54.19% Tin concentrate, far below dibenzyl
Epoxide phosphoric acid collecting agent floatation indicators.
Claims (8)
1. a kind of tin-lead soldering collecting agent, it is characterised in that：Including two phenoxy group phosphoric acid and/or benzyloxy phosphoric acid.
2. the application of the tin-lead soldering collecting agent described in claim 1, it is characterised in that：It is applied to the flotation point of cassiterite and gangue
From.
3. the application of tin-lead soldering collecting agent according to claim 2, it is characterised in that：The gangue includes calcite
And/or quartz.
4. the application of the tin-lead soldering collecting agent according to Claims 2 or 3, it is characterised in that：Using two phenoxy group phosphoric acid
And/or benzyloxy phosphoric acid as collectors for cassiterite, terpinol as foaming agent, plumbi nitras as activator, carboxymethyl cellulose
Element and prodan carry out flotation as gangue inhibitor to cassiterite crude ore pulp, obtain cassiterite concentrate.
5. the application of tin-lead soldering collecting agent according to claim 4, it is characterised in that：Described flotation include roughing,
Scan with it is selected.
6. the application of tin-lead soldering collecting agent according to claim 5, it is characterised in that：
In rougher process, the pH for adjusting cassiterite crude ore pulp is 6~8, and plumbi nitras is 50~100g/t with respect to the addition of raw ore,
Carboxymethylcellulose calcium and prodan are 200~400g/t, two phenoxy group phosphoric acid and/or benzyloxy with respect to the addition of raw ore
Phosphoric acid is 600~1000g/t with respect to the addition of raw ore, and terpinol is 50~100g/t with respect to the addition of raw ore；
During scanning, two phenoxy group phosphoric acid and/or benzyloxy phosphoric acid are 300~500g/t, pine with respect to the addition of raw ore
Oleyl alcohol is 25~50g/t with respect to the addition of raw ore；
In refining process, carboxymethylcellulose calcium and prodan are 100~200g/t with respect to the addition of raw ore.
7. the application of tin-lead soldering collecting agent according to claim 6, it is characterised in that：Carboxymethylcellulose calcium and fluosilicic acid
The mass ratio of sodium is 1:0.5~1.5.
8. the application of the tin-lead soldering collecting agent according to claim 5 or 6, it is characterised in that：Described flotation includes one
Secondary roughing, scan selected with 2~3 times for 2~3 times.
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| CN108554644A (en) * | 2018-01-12 | 2018-09-21 | 东北大学 | A kind of tin-lead soldering collecting agent and preparation method thereof |
| CN108623627A (en) * | 2018-07-03 | 2018-10-09 | 中南大学 | A kind of preparation method and application of styryl phosphonate monoester |
| CN110038727A (en) * | 2019-04-19 | 2019-07-23 | 北京矿冶科技集团有限公司 | A kind of separation method of white tungsten tin bulk concentrate |
| CN114247568A (en) * | 2021-12-20 | 2022-03-29 | 中南大学 | Composite collecting agent for selectively collecting zircon, flotation reagent and flotation method |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108554644A (en) * | 2018-01-12 | 2018-09-21 | 东北大学 | A kind of tin-lead soldering collecting agent and preparation method thereof |
| CN108554644B (en) * | 2018-01-12 | 2019-11-22 | 东北大学 | A kind of tin-lead soldering collecting agent and preparation method thereof |
| CN108623627A (en) * | 2018-07-03 | 2018-10-09 | 中南大学 | A kind of preparation method and application of styryl phosphonate monoester |
| CN108623627B (en) * | 2018-07-03 | 2019-07-09 | 中南大学 | A kind of preparation method and application of styryl phosphonate monoester |
| CN110038727A (en) * | 2019-04-19 | 2019-07-23 | 北京矿冶科技集团有限公司 | A kind of separation method of white tungsten tin bulk concentrate |
| CN110038727B (en) * | 2019-04-19 | 2021-12-17 | 北京矿冶科技集团有限公司 | Separation method of scheelite and stannic oxide bulk concentrates |
| CN114247568A (en) * | 2021-12-20 | 2022-03-29 | 中南大学 | Composite collecting agent for selectively collecting zircon, flotation reagent and flotation method |
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