CN108311292A - A kind of sulfide flotation activator and preparation method thereof - Google Patents
A kind of sulfide flotation activator and preparation method thereof Download PDFInfo
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- CN108311292A CN108311292A CN201810130300.XA CN201810130300A CN108311292A CN 108311292 A CN108311292 A CN 108311292A CN 201810130300 A CN201810130300 A CN 201810130300A CN 108311292 A CN108311292 A CN 108311292A
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- ammonium
- flotation
- copper sulphate
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- 238000005188 flotation Methods 0.000 title claims abstract description 65
- 239000012190 activator Substances 0.000 title claims abstract description 49
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims description 10
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 34
- 230000023556 desulfurization Effects 0.000 claims abstract description 34
- 230000004913 activation Effects 0.000 claims abstract description 27
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 23
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims abstract description 21
- AJGPQPPJQDDCDA-UHFFFAOYSA-N azanium;hydron;oxalate Chemical compound N.OC(=O)C(O)=O AJGPQPPJQDDCDA-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 238000000926 separation method Methods 0.000 claims abstract description 8
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 20
- 239000011707 mineral Substances 0.000 claims description 20
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 239000002002 slurry Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 8
- 238000009291 froth flotation Methods 0.000 claims description 5
- 238000001802 infusion Methods 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 244000025254 Cannabis sativa Species 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 285
- 229910052742 iron Inorganic materials 0.000 abstract description 141
- 239000012141 concentrate Substances 0.000 abstract description 55
- 238000011084 recovery Methods 0.000 abstract description 27
- 230000000694 effects Effects 0.000 abstract description 20
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 abstract description 14
- 239000003814 drug Substances 0.000 abstract description 11
- 239000012991 xanthate Substances 0.000 abstract description 11
- 239000002253 acid Substances 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 230000007935 neutral effect Effects 0.000 abstract description 4
- 230000007420 reactivation Effects 0.000 abstract description 3
- 235000013399 edible fruits Nutrition 0.000 abstract description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 68
- 229910052717 sulfur Inorganic materials 0.000 description 53
- 239000011593 sulfur Substances 0.000 description 53
- 238000000034 method Methods 0.000 description 31
- 239000005864 Sulphur Substances 0.000 description 18
- 239000011028 pyrite Substances 0.000 description 18
- 229910052683 pyrite Inorganic materials 0.000 description 18
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 18
- 229910052952 pyrrhotite Inorganic materials 0.000 description 15
- 238000007885 magnetic separation Methods 0.000 description 14
- 230000008569 process Effects 0.000 description 14
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- 238000011160 research Methods 0.000 description 10
- 239000010949 copper Substances 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 7
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 7
- 238000000227 grinding Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 230000007246 mechanism Effects 0.000 description 6
- 238000005457 optimization Methods 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 5
- 229910052737 gold Inorganic materials 0.000 description 5
- 239000010931 gold Substances 0.000 description 5
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 4
- 235000011130 ammonium sulphate Nutrition 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000007667 floating Methods 0.000 description 4
- 235000006408 oxalic acid Nutrition 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- 102000005298 Iron-Sulfur Proteins Human genes 0.000 description 3
- 108010081409 Iron-Sulfur Proteins Proteins 0.000 description 3
- 230000003213 activating effect Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- TUZCOAQWCRRVIP-UHFFFAOYSA-N butoxymethanedithioic acid Chemical compound CCCCOC(S)=S TUZCOAQWCRRVIP-UHFFFAOYSA-N 0.000 description 3
- 230000003009 desulfurizing effect Effects 0.000 description 3
- 230000008676 import Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-O butylazanium Chemical compound CCCC[NH3+] HQABUPZFAYXKJW-UHFFFAOYSA-O 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 229940116901 diethyldithiocarbamate Drugs 0.000 description 2
- LMBWSYZSUOEYSN-UHFFFAOYSA-N diethyldithiocarbamic acid Chemical compound CCN(CC)C(S)=S LMBWSYZSUOEYSN-UHFFFAOYSA-N 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000008235 industrial water Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 229910001608 iron mineral Inorganic materials 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- KOVPITHBHSZRLT-UHFFFAOYSA-N 2-methylpropoxymethanedithioic acid Chemical compound CC(C)COC(S)=S KOVPITHBHSZRLT-UHFFFAOYSA-N 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003818 cinder Substances 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 230000009429 distress Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000005307 ferromagnetism Effects 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- -1 iron ion Chemical class 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910021646 siderite Inorganic materials 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 230000031068 symbiosis, encompassing mutualism through parasitism Effects 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
- B03D2203/00—Specified materials treated by the flotation agents; Specified applications
- B03D2203/02—Ores
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a kind of sulfide flotation activators, are made of the raw material of following parts by weight:04 parts of ammonium oxalate, ammonium binoxalate 04,0 10 parts of copper sulphate;The present invention relates to sulfide flotation technical fields.The present invention is environmentally friendly, and water recycles, and without outer row, long-time service will not increase pulp viscosity so that is separated by solid-liquid separation difficult.Activation effect of the present invention is more preferable, and hardly possible selects sulphide ore that can select difficulty by common xanthate and is not necessarily to special collecting agent, it is lower that medicament derives from a wealth of sources desulphurization cost in sulphide ore collecting.Iron concentrate desulfurization rate of recovery higher, Iron concentrate grade can be improved 2% 3%, and iron ore desulfurization effect is more preferable;Neutral flotation (can also carry out flotation under acid or alkaline conditions) can be used, it is corrosion-free to equipment;This product is not necessarily to carry out re-activation to target minreal, only needs one stage activation of roughing that can reach the difficult active fruit for selecting sulphide ore.
Description
Technical field
The present invention relates to sulfide flotation technical field, specially a kind of sulfide flotation activator and its preparation side
Method.
Background technology
Iron ore desulfurization iron selection technique:
The influence of stage grinding, stage grading desulfurization iron selection technique mog to mineral processing index is very big, and different ore grindings is thin
Spending its product has different granularmetric composition, and to influence the liberation degree of minerals and washability of mineral, the iron ore of fine-grained disseminated grain needs
Want fine grinding that can just mineral monomer be made to dissociate.The iron relatively thin for disseminated grain size, sulfur-bearing type (pyrite and magnetic iron ore) is single
Ore, generally use stage grinding, stage grading technique are to realize the purpose for putting forward iron sulfur reduction.Iron ore owner in the iron ore of Anhui
To exist in the form of magnetic iron ore, sulphur mainly in the form of pyrite exist, use stage grinding, stage low intensity magnetic separation can be obtained grade for
65.25%, the iron ore concentrate that the rate of recovery is 80.33%.Certain iron ore of staff containing TFe 42.86%, sulfur-bearing 1.69%
It is successfully transported by stage grinding, stage grading, rationally the control means such as magnetic field intensity and concentration times as research object
The iron ore concentrate that Iron grade is 66.97% is obtained with full magnetic separation process, iron recovery reaches 80.3l%.Staff is ground using the stage
Mine, stage grading technique have carried out the experimental study of system, as a result show:Iron recovery is increased to by 86.43% before
90.38%, sulfur content significantly reduces in iron.Iron mineral disseminated grain size is thinner in Iron Ore in Yunnan Province stone, and Iron grade is relatively low, is
20.18%, harmful element sulphur is exceeded, belongs to compared with refractory ore.Using stage grinding, the stage grading process ore, product are obtained
Position is the iron ore concentrate of 63.98%, the rate of recovery 71.55%, sulfur-bearing 0.48%.
The flotation combined desulfurization iron selection technique of magnetic separation-:
The magnetic iron ore that China is selected at present contains a large amount of magnetic iron ore and pyrite due to fine size so that magnetic coagulation is sorting
In negative effect clearly, improve concentrate grade by single magnetic method and be increasingly difficult to.Magnetic method is anti-with anion
Flotation combines, and realizes the mutual supplement with each other's advantages during magnetic iron ore sorts, and is conducive to raising magnetic iron ore and sorts concentrate grade.
Magnetic separation-joint flotation technology is that China's high sulfide pyrite puies forward one of more effective technique of iron sulfur reduction.Staff is high for certain import
Sulphur magnetic iron ore (wherein sulphide ore is mainly magnetic iron ore and pyrite), using magnetic separation process flow after first reverse flotation to this
Ore carries out sulfur reduction and carries iron beneficiation test, iron ore concentrate sulfur grade by raw ore sulfur-bearing 6.14% be down to 0.30% hereinafter, achieve compared with
Good test index.Staff studies Yunnan mine, under conditions of sulfur-bearing 5.71%, iron content 31.52%, adopts
With the technological process of magnetic separation after first flotation, iron ore concentrate iron content 65.36%, sulfur-bearing 0.171%, iron recovery 81.67% are obtained
Be satisfied with index.Staff carries out synthetical recovery to sulphur, the iron resource in certain tailing, selects magnetic iron ore containing in distress in ore,
Using the flotation combined recovery process of flotation-magnetic separation-, successfully obtain high-quality iron concentrate that sulfur grade is 38.77% and
The qualified iron ore concentrate of iron content 58.04%, sulfur-bearing 0.547%.Staff studies white tone pile of stones high-sulfur magnetic iron ore, former
Containing 1.98% sulphur in mine, which part exists in the form of magnetic iron ore, using magnetic separation-joint flotation technology, effectively drops
The content of sulphur, is finally obtained the fine quality iron concentrate of full Iron grade 65.20%, sulfur-bearing 0.22% in low iron ore concentrate, is difficult
On Iron Ore Resource Exploitation utilizes and proposes new thinking.So-and-so iron ore property is more complex, and the presence of magnetic iron ore disturbs iron ore
Middle valuable mineral sorts and influences final sorting index, and staff with magnetic separation by first removing most of gangue and one
Divide sulphur (pyrite), then uses the sulphur (magnetic iron ore) in flotation removing magnetic separation rough concentrate, obtain preferable index.Work people
Member has carried out ore elemental analysis to certain iron ore, and iron ore sulfur-bearing is high, iron mineral in ore mainly with magnetic iron ore and
Two kinds of forms of magnetic iron ore exist, and use the flotation combined sorting process of magnetic separation-and have carried out experimental study.The result shows that first
The available TFe grades 64.97% of the technique of flotation after magnetic separation, the qualified iron ore concentrate of sulfur-bearing 0.16%, iron overall recovery are reachable
To 71.21%.
The flotation combined sulfur removal technology of roasting-magnetic separation-:
The reduction roasting magnetic separation process of country's iron ore fails extensive use because of its factor such as low with iron concentrate grade of high cost at present,
The technique is mainly suitable for the larger iron ore of the scaling loss such as limonite and siderite.Relatively low for theoretical grade, sulfur-bearing type is various
Weak-magnetic iron ore, the iron ore concentrate of low impurity content can be obtained by roasting-magnetic separation-joint flotation technology, significantly
Improve product quality.Staff is high for so-and-so western ore sulfur content, it is determined that roasting scheme and roasting condition, to roasting
Mine carries out magnetic separation-cation reverse flotation experiment.Experiments have shown that TFe grades can be obtained and be by carrying out cation reverse flotation
63.67%, the iron ore concentrate that the rate of recovery is 50.82%, sulfur content drop to 0.31% by 2.74%, realize upgrading and drop miscellaneous target.
The magnetizing roast of staff's rotary kiln baking pyrite cinder is tested, effectively by weak magnetic Fe in slag2O3It is reduced into
Ferromagnetism Fe3O4, magnetic susceptibility is up to 2.38%.By ball milling, magnetic separation process, concentrate grade and metal can be significantly increased
The rate of recovery, while slag desulfurization effect in rotary kiln is apparent, desulfurization degree may be up to 85% or more.Staff is directed to through flotation
Flow generate Iron grade be 17.75%, the high pyrite tailing that sulfur content is 5.87%, using direct-reduction roasting-magnetic separation side
Method, the direct reduced iron production that available Iron grade is 93.57%, sulfur content 0.39%, the inferior fine magnetite concentrate rate of recovery are 82.01%
Product provide new approach to effectively improve comprehensive resource utilization rate;A large amount of sulfur dioxide gas are released in roasting method desulfurization, dirty
Air is contaminated, and floatation desulfurization, existing floating agent desulfurization can only largely be directed to part magnetic iron ore, using with limitation
Property.
Invention content
In view of the deficiencies of the prior art, the present invention provides a kind of sulfide flotation activator and preparation method thereof, solutions
The difficult problem proposed in background technology of having determined.
Realize that object above, the present invention are achieved by the following technical programs:A kind of sulfide flotation activator, by
The raw material of following parts by weight forms:0-4 parts of ammonium oxalate, 0-4 parts of ammonium binoxalate, 0-10 parts of copper sulphate.
As present invention further optimization technical solution, it is made of the raw material of following parts by weight:1 part of ammonium oxalate, oxalic acid
1 part of hydrogen ammonium, 4 parts of copper sulphate.
As present invention further optimization technical solution, it is made of the raw material of following parts by weight:2 parts of ammonium binoxalate, sulphur
4 parts of sour copper.
As present invention further optimization technical solution, it is made of the raw material of following parts by weight:2 parts of ammonium binoxalate, sulphur
4 parts of sour copper.
As present invention further optimization technical solution, it is made of the raw material of following parts by weight:3 parts of ammonium oxalate, oxalic acid
3 parts of hydrogen ammonium, 8 parts of copper sulphate.
As present invention further optimization technical solution, it is made of the raw material of following parts by weight:3 parts of ammonium oxalate, sulfuric acid
4 parts of copper.
As present invention further optimization technical solution, it is made of the raw material of following parts by weight:3 parts of ammonium binoxalate, sulphur
4 parts of sour copper.
A kind of sulfide flotation activator preparation method, specifically comprises the following steps:
Step 1, first, staff chooses a certain amount of ammonium oxalate, ammonium binoxalate and copper sulphate, as spare;
The ammonium oxalate chosen in step 1, ammonium binoxalate and copper sulphate are poured into blender and are uniformly mixed by step 2, are configured
At desulfurization activator;
Step 3, staff adjust liquid pH value, PH according to different minerals demand by the way that sulfuric acid is added into ore pulp<7;
Desulfurization activator after regulating slurry pH, is reconfigured to certain proportion solution, is added in raw ore slurry and carries out by step 4
Activation;
Sodium hydroxide or sodium carbonate adjustment pH=3-10 are added into the ore pulp after activation for step 5, and collecting agent is then added and rises
Infusion.
Step 6 completes minerals separation by froth flotation.
Advantageous effect
The present invention provides a kind of sulfide flotation activators and preparation method thereof.Has following advantageous effect:
1, the method for existing magnetic separation, which can only detach, does not have magnetic sulphide ore.Magnetic magnetic iron ore is difficult to the side by magnetic separation
Formula is detached with other iron ores.
2, a large amount of sulfur dioxide gas are released in roasting method desulfurization, pollute air.
3, floatation desulfurization, existing floating agent desulfurization can only largely be directed to part magnetic iron ore, and the present invention can be directed to
High-content magnetic iron ore Iron concentrate, there is good desulfurization effect.
4, the present invention is environmentally friendly, and water recycles, and without outer row, long-time service will not increase pulp viscosity so that Gu
Liquid separation is difficult.Activation effect of the present invention is more preferable, and hardly possible selects sulphide ore that can select difficulty in sulphide ore collecting by common xanthate
Come, is not necessarily to special collecting agent, it is lower that medicament derives from a wealth of sources desulphurization cost.Iron concentrate desulfurization rate of recovery higher, Iron concentrate grade can
2%-3% is improved, iron ore desulfurization effect is more preferable.It is corrosion-free to equipment using neutral flotation.This product is not necessarily to carry out target minreal
Re-activation only needs one section of roughing that can reach the difficult active fruit for selecting sulphide ore.Sulfur recovery rate is 90% or more, useful mine
The object rate of recovery illustrates that hybrid activator of the present invention has good selectivity activation effect 90% or more;Refractory gold ore,
On the basis of original medicament, activator of the present invention is added, the grade and the rate of recovery of gold and silver concentrate can be effectively improved.
Specific implementation mode
The present invention provides three kinds of embodiments:
A kind of sulfide flotation activator, is made of the raw material of following parts by weight:3 parts of ammonium oxalate, 3 parts of ammonium binoxalate, sulfuric acid
8 parts of copper.
A kind of sulfide flotation activator preparation method, specifically comprises the following steps:
Step 1, first, staff chooses a certain amount of ammonium oxalate, ammonium binoxalate and copper sulphate, as spare;
The ammonium oxalate chosen in step 1, ammonium binoxalate and copper sulphate are poured into blender and are uniformly mixed by step 2, are configured
At desulfurization activator;
Step 3, staff adjust liquid pH value, PH according to different minerals demand by the way that sulfuric acid is added into ore pulp<7;
Desulfurization activator after regulating slurry pH, is reconfigured to certain proportion solution, is added in raw ore slurry and carries out by step 4
Activation;
Sodium carbonate or sodium hydroxide adjustment pH=3-10 are added into the ore pulp after activation for step 5, and collecting agent is then added and rises
Infusion.
Step 6 completes minerals separation by froth flotation.
Embodiment two
A kind of sulfide flotation activator, is made of the raw material of following parts by weight:3 parts of ammonium oxalate, 4 parts of copper sulphate.
A kind of sulfide flotation activator preparation method, specifically comprises the following steps:
Step 1, first, staff chooses a certain amount of ammonium oxalate and copper sulphate, as spare;
The ammonium oxalate chosen in step 1 and copper sulphate are poured into blender and are mixed by step 2, are configured to desulfurization work
Agent;
Step 3, staff adjust liquid pH value, PH according to different minerals demand by the way that sulfuric acid is added into ore pulp<7;
Desulfurization activator after regulating slurry pH, is reconfigured to a certain proportion of solution by step 4, be added in raw ore slurry into
Row activation;
Sodium carbonate or sodium hydroxide adjustment pH=3-10 are added into the ore pulp after activation for step 5, and collecting agent is then added and rises
Infusion.
Step 6 completes minerals separation by froth flotation.
Embodiment three
A kind of sulfide flotation activator, is made of the raw material of following parts by weight:3 parts of ammonium binoxalate, 4 parts of copper sulphate.
A kind of sulfide flotation activator preparation method, specifically comprises the following steps:
Step 1, first, staff chooses a certain amount of ammonium binoxalate and copper sulphate, as spare;
The ammonium binoxalate chosen in step 1 and copper sulphate are poured into blender and are mixed by step 2, are configured to desulfurization
Activator;
Step 3, staff adjust liquid pH value, PH according to different minerals demand by the way that sulfuric acid is added into ore pulp<7;
Desulfurization activator after regulating slurry pH, is reconfigured to certain proportion solution, is added in raw ore slurry and carries out by step 4
Activation;
Sodium hydroxide or sodium carbonate adjustment pH=3-10 are added into the ore pulp after activation for step 5, and collecting agent is then added and rises
Infusion, so as to complete the whole process of flotation of ore pulp.
Step 6 completes minerals separation by froth flotation.
Staff is directed to certain import high-sulfur magnetic iron ore (wherein sulphide ore is mainly magnetic iron ore and pyrite), adopts
Desulfurization test research is carried out with new and effective floating sulphur MHH-1 activators, iron ore concentrate sulfur grade is down to by raw ore sulfur-bearing 6.14%
0.30% hereinafter, achieve preferable test index.Iron ore concentrate desulfurization special efficacy activator MHH-1 is to the sulphur in removing iron ore concentrate
Changing the mine especially poor magnetic iron ore of relatively high magnetism, floatability has positive effect.Compared with other activators, MHH-1 is used
Amount is few, and at low cost, desulfurization effect is apparent, and the development of the product puies forward iron sulfur reduction for iron ore concentrate and provides new way.
Staff is directed to the feature that magnetic iron ore content is high in so-and-so mining industry Co., Ltd sulfur-containing magnetite, uses
HH-1 efficient activators carry out desulfurization test, obtain iron ore concentrate sulfur-bearing 0.319%, TFe grades 66.99%, the TFe rate of recovery
47.68% reaches requirement with iron concentrate sulphur 34.59%, the sorting index of the sulfur content rate of recovery 99.23%, indices.
Staff is higher for so-and-so iron ore lower part ore body raw ore sulfur content, and especially wherein magnetic iron ore content is big,
The actual conditions for causing magnetite concentrate sulfur-bearing exceeded by intensified Daqu process, increase xanthate dosage, using composite activating agent
The means such as MS-1 make iron ore concentrate sulfur content be down to 0.4% by 0.8%, have reached sale and have required.
Gangue entrainment is serious in the research of troilite new collector and application so-and-so copper mine magnetic concentrate, affects iron essence
The raising of mine grade;Its industrial water largely uses return water, and high ph-values return water inhibits magnetic iron ore, seriously reduces flotation
Desulfurization degree;Magnetic iron ore floatability is poor, it is necessary to can just obtain satisfactory result with strength collecting agent.The yellow peace of so-and-so copper mine uses
Mog is improved, improvement selects iron industrial water water quality, adjustment collecting agent medicament kind (to become bavin from previous single xanthate
Oil is combined with xanthate), desulfurization effect is apparent, obtains great economic benefit.
Staff is directed to the high-sulfur iron resource in certain factory's tailing, using QY-309 hybrid collectors, to inferior fine magnetite concentrate
Direct reverse flotation desulfurizing removal of impurities, it is the index that 67.56%, sulfur content is only 0.13% to obtain flotation concentrate Iron grade.
Staff has carried out proposing sulfur test research for certain low-grade carbonaceous sulfur-containing magnetite stone, and test result shows
Using new medicament 402 as sulphur collecting agent is carried, the iron concentrate that sulfur grade is 42.25%, the rate of recovery is 92.96% has been obtained.
Based on magnetic iron ore, staff passes through to sulfide in so-and-so ore dressing plant time iron ore concentrate sulfide in so-and-so ore dressing plant ore
Process mineralogy and ore properties analysis, propose in acid condition, magnetic iron ore is caught to realize using advanced xanthate
It receives, to achieve the purpose that iron ore concentrate sulfur reduction, sulfur content reduces by 0.2% ~ 0.3% in final iron ore concentrate, and grade also has centainly
The raising of amplitude.
Sulphur iron ore crystal structure present Research obtains effective richness by magnetic separation process flow, the not magnetic iron ore of the isomorphous system
Collection, wherein most pyrite enter tailing, and the pyrite of incomplete monomer dissociation then enters flotation with magnetic iron ore on a small quantity;
In flotation process, the magnetic iron ore floatability difference of the isomorphous system is not larger, and the pyrite of different crystal structure floats
Property has no apparent difference.Therefore the crystal structure present Research of magnetic iron ore is set forth as follows, magnetic iron ore (Fe1-xS, 0
< x <0.223) often there is monocline, six sides and three kinds of rectangle polymorph with a variety of sulphide ore symbiosis, it is common to be
Monocline and hexa-pyrrhotite.The floatability of the magnetic iron ore of different crystal structures (monocline and six sides) is ground
Study carefully, shows that the floatability of monocline and six sides have apparent difference.
The floatability that staff demonstrates monocrystalline system magnetic iron ore by float test is better than hexagonal crystal system magnetic iron ore,
As the ratio between S contents and Fe contents increase, the crystal structure of magnetic iron ore becomes monoclinic system from hexagonal crystal system, it is magnetic by
Weak to become strong, floatability is improved by difference.Staff is by butyl ammonium aerofloat dosing to six unactivated and activated side's magnetic Huang iron
Mine carries out float test and surface potential ε, has studied under butyl ammonium aerofloat system, the flotation behavior of hexa-pyrrhotite and its surface
Adsorption mechanism, the results showed that, floatability is best in neutral conditions on hexa-pyrrhotite surface.
Staff's Within Monominerals are tested, and the flotation behavior of monocline pyrrhotine is had studied, the results showed that:Monocline pyrrhotine
Floatability in butyl xanthate or diethyldithiocarbamate system is almost the same, and pulp potential influences its flotation behavior little;Alkaline condition
Under, diethyldithiocarbamate is stronger than butyl xanthate to the collecting ability of monocline pyrrhotine.Chemical composition, physical property and the crystal of magnetic iron ore
The characteristics such as structure determines the oxidizable degree of its floatability, surface and property is crisp.It is tried using X lines diffraction, electron probe and flotation
It tests, has investigated the constituent and floatability difference of monocline pyrrhotine and hexa-pyrrhotite, the results showed that:Monocline is than six sides
Magnetic iron ore is rich in sulphur;Monocline is similar with the rule that the flotation recovery rate of hexa-pyrrhotite changes with pH values of pulp, but single
The rate of recovery of oblique magnetic iron ore is higher than hexa-pyrrhotite, and floatability is better than hexa-pyrrhotite;Under acid condition, six side's magnetic are yellow
Iron ore is easier than monocline pyrrhotine by Cu2+Activation.
In recent years, domestic and international ore dressing worker is to selecting sulphur medicament and sulphur iron for the Study on mechanism present situation of troilite and medicament
The reaction mechanism of mine has carried out a large amount of research, and result of study is achieved considerable applied to the production practices for instructing mine
Economic benefit.
Staff has studied sulfuric acid and oxalic acid activation effect and activating mechanism to the magnetic iron ore after being inhibited by lime.
Experiment confirms that sulfuric acid shows both ways the activating mechanism of magnetic iron ore with oxalic acid:First, improving Surface of Pyrrhotite itself oxygen
Change current potential, hydrophilic substance is hindered further to generate;Second is that removal is adsorbed on the hydrophilic substance of Surface of Pyrrhotite, it is allowed to expose new
Fresh surface.The electrochemical research of magnetic iron ore mainly has the electricity of surface oxidation, collecting agent and the mineral effect of magnetic iron ore at present
The activation etc. of chemical research and copper ion to magnetic iron ore.
Staff detects that there are hydrophobic for the Surface of Pyrrhotite after butyl xanthate effect by ultraviolet spectral analysis
Double xanthate.Staff is tested and analyzed by magnetic iron ore infrared spectrum, and inference ethyl xanthogenate generates double yellow in Surface of Pyrrhotite
Medicine.Staff examines the infrared spectrum for the magnetic iron ore for being adsorbed with Isobutylxanthic acid, also turns out the double Huangs of its Surface Creation
Medicine.Staff observes under nitrogen atmosphere that magnetic iron ore is seldom to the adsorbance of xanthate, this may be since xanthate is oxidized to
Double xanthate needs higher current potential, and the current potential of nitrogen atmosphere it is apparent it is too low caused by.It can be seen that the flotation row of magnetic iron ore
To be closely related with the redox environment of ore pulp, i.e., pulp potential is the decision of the PYRRHOTITE BY FLOTATION rate of recovery and flotation rate
One of factor.Staff passes through ethyl xanthogenate and the magnetic iron ore mechanism of action in a concentration of 1 × 10-4 mol/L of ethyl xanthogenate
Research has obtained the floatability of magnetic iron ore and pH values and pulp potential, and there is matching relationships, under a certain pH values, only
In suitable pulp potential region, magnetic iron ore can just float.Staff improves pulp potential by being inflated in advance into ore pulp,
Magnetic iron ore can be effectively inhibited, conversely, not inflating in advance, then there is certain activation.Under acid condition, copper ion
It is exchanged with the iron ion of Surface of Pyrrhotite, to activate mineral surfaces.Surface of Pyrrhotite oxidation rate is fast, it was reported that
Under the same conditions, the oxidation rate of magnetic iron ore is 20~100 times of pyrite.Magnetic iron ore aoxidizes within certain limits
Generate FeSO4 and Fe2 (SO) 3, when have elemental sulfur generation, but its large specific surface area after argillization, easy severe oxidation, on surface
Fe (OH) 3 and FeO (OH) hydrophilic layer are generated, floatability declines.
Staff by Within Monominerals and live ore pulp sample experiments have shown that, ammonium sulfate and ammonium hydrogen carbonate by lime to being pressed down
The pyrite of system has good activation, and can make pyrite activation floating under high alkalinity (pH up to 11 ~ 12)
Trip.Ammonium sulfate includes to pyrite activation mechanism:
(1) Ca in ore pulp is precipitated2+, low ph value suitably drops;
(2) Ca of mineral surfaces is desorbed2+, and ratio is more thoroughly;
(3) activation of ammonia and mineral surfaces adsorb a small amount of ammonium sulfate, it is possible to Cu be complexed by it2+;
(4) when ammonium sulfate activation pyrite, concentrate grade is high, sludge flocculation can be kept not enter concentrate with it related.
The present invention is environmentally friendly, and water recycles, and without outer row, long-time service will not increase pulp viscosity so that solid-liquid
Separation is difficult.Activation effect of the present invention is more preferable, hardly possible select sulphide ore by common xanthate difficulty can be selected in sulphide ore collecting come,
Without special collecting agent, it is lower that medicament derives from a wealth of sources desulphurization cost.Iron concentrate desulfurization rate of recovery higher, Iron concentrate grade can be improved
2%-3%, iron ore desulfurization effect are more preferable.It is right using neutral flotation (can also carry out flotation in acid condition or under alkaline condition)
Equipment is corrosion-free.This product is not necessarily to carry out re-activation to target minreal, only needs roughing activation that can reach difficult and selects sulphide ore
Activation effect.For sulfur recovery rate 90% or more, the valuable mineral rate of recovery 90% or more, illustrates hybrid activator tool of the present invention
There is good Selective activation effect;Refractory gold ore is added activator of the present invention, can effectively carry on the basis of original medicament
The grade and the rate of recovery of high gold and silver concentrate.
Successful case:
1. Hebei company Iron concentrate desulfurizing item, steady production 3 months, Iron concentrate sulfur content 1.8-2% are reduced to 0.28%,
Achieve preferable effect;The said firm is just establishing 10000 ton days and is selecting factory at present, for handling high sulfide pyrite.
2. it is de- to have carried out flotation for the magnetic separation Iron concentrate of 2% or more sulfur content for Inner Mongol high-sulfur Iron concentrate desulfurizing item
Sulphur commerical test, final iron ore concentrate sulfur content drop to 0.5% or less.
3. before the activator that the present invention is not added, the work of the present invention is added in Shanxi Iron concentrate sulfur content 1.3-1.8%
Sulfide flotation is carried out after agent, final fine powder sulfur content is reduced to 0.28-0.32%.
4. before the activator that the present invention is not added, it is laggard that activator of the invention is added in Jiangsu Iron concentrate sulfur-bearing 2%
After row sulfide flotation, sulfur content is reduced to 0.28%.
5. before the activator that the present invention is not added, Hubei Iron concentrate sulfur-bearing 1.8%, after the activator of the present invention is added
After carrying out sulfide flotation, sulfur content is reduced to 0.26%.
6. before the activator that the present invention is not added, Daye, hubei Province company Iron concentrate sulfur-bearing 4%, by the way that this hair is added
After carrying out sulfide flotation after bright activator, sulfur content is reduced to 0.52%.
7. before the activator that the present invention is not added, Yunnan import Burma Iron concentrate sulfur-bearing 3-5%, by the way that this hair is added
After carrying out sulfide flotation after bright activator, sulfur content is reduced to 0.3%.
8. after carrying out sulfide flotation after the activator for passing through the addition present invention, Qinghai refractory gold ore, the rate of recovery improves
3%, concentrate grade improves 5 grams of tons.
It should be noted that herein, relational terms such as first and second and the like are used merely to a reality
Body or operation are distinguished with another entity or operation, are deposited without necessarily requiring or implying between these entities or operation
In any actual relationship or order or sequence.Moreover, the terms "include", "comprise" or its any other variant are intended to
Non-exclusive inclusion, so that the process, method, article or equipment including a series of elements is not only wanted including those
Element, but also include other elements that are not explicitly listed, or further include for this process, method, article or equipment
Intrinsic element.
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
Understanding without departing from the principles and spirit of the present invention can carry out these embodiments a variety of variations, modification, replace
And modification, the scope of the present invention is defined by the appended.
Claims (8)
1. a kind of sulfide flotation activator, which is characterized in that be made of the raw material of following parts by weight:0-4 parts of ammonium oxalate, grass
0-4 parts of sour hydrogen ammonium, 0-10 parts of copper sulphate.
2. a kind of sulfide flotation activator according to claim 1, it is characterised in that:By the raw material of following parts by weight
Composition:1 part of ammonium oxalate, 1 part of ammonium binoxalate, 4 parts of copper sulphate.
3. a kind of sulfide flotation activator according to claim 1, it is characterised in that:By the raw material of following parts by weight
Composition:2 parts of ammonium binoxalate, 4 parts of copper sulphate.
4. a kind of sulfide flotation activator according to claim 1, it is characterised in that:By the raw material of following parts by weight
Composition:2 parts of ammonium oxalate, 4 parts of copper sulphate.
5. a kind of sulfide flotation activator according to claim 1, it is characterised in that:By the raw material of following parts by weight
Composition:3 parts of ammonium oxalate, 3 parts of ammonium binoxalate, 8 parts of copper sulphate.
6. a kind of sulfide flotation activator according to claim 1, it is characterised in that:By the raw material of following parts by weight
Composition:3 parts of ammonium oxalate, 4 parts of copper sulphate.
7. a kind of sulfide flotation activator according to claim 1, it is characterised in that:By the raw material of following parts by weight
Composition:3 parts of ammonium oxalate, 4 parts of copper sulphate.
8. a kind of sulfide flotation activator preparation method, which is characterized in that specifically comprise the following steps:
Step 1, first, staff chooses a certain amount of ammonium oxalate, ammonium binoxalate and copper sulphate, as spare;
The ammonium oxalate chosen in step 1, ammonium binoxalate and copper sulphate are poured into blender and are uniformly mixed by step 2, are configured
At desulfurization activator;
Step 3, staff adjust liquid pH value, PH according to different minerals demand by the way that sulfuric acid is added into ore pulp<7;
Desulfurization activator after regulating slurry pH, is reconfigured to certain proportion solution, is added in raw ore slurry and carries out by step 4
Activation;
Sodium carbonate or sodium hydroxide adjustment pH=3-10 are added into the ore pulp after activation for step 5, and collecting agent is then added and rises
Infusion;
Step 6 completes minerals separation by froth flotation.
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CN109261371A (en) * | 2018-08-01 | 2019-01-25 | 昆明理工大学 | A kind of pyritic activation method |
CN110201798A (en) * | 2019-04-19 | 2019-09-06 | 铜陵有色金属集团股份有限公司 | A kind of DC activator and the acidless craft for sorting the sulphur, iron mineral that are inhibited by high-alkali and high calcium |
CN110394238A (en) * | 2019-07-08 | 2019-11-01 | 中国矿业大学(北京) | Copper, lead, zinc polymetal sulphide ore homogeneity active flotation method |
CN112246445A (en) * | 2020-08-27 | 2021-01-22 | 中国恩菲工程技术有限公司 | Foam sorting activator and application thereof |
CN112604816A (en) * | 2020-11-27 | 2021-04-06 | 矿冶科技集团有限公司 | Copper-sulfur separation inhibitor, lime-free copper-sulfur flotation separation method and application |
CN115155821A (en) * | 2022-06-07 | 2022-10-11 | 青岛鑫润矿业科技有限公司 | Sulfide ore activating agent and preparation method thereof |
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