CN102643998B - Method for processing molybdenite - Google Patents
Method for processing molybdenite Download PDFInfo
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- CN102643998B CN102643998B CN2012101318313A CN201210131831A CN102643998B CN 102643998 B CN102643998 B CN 102643998B CN 2012101318313 A CN2012101318313 A CN 2012101318313A CN 201210131831 A CN201210131831 A CN 201210131831A CN 102643998 B CN102643998 B CN 102643998B
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- Prior art keywords
- molybdenum
- copper
- matte
- sulfonium
- slag
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- 238000000034 method Methods 0.000 title claims abstract description 65
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title abstract description 9
- 229910052961 molybdenite Inorganic materials 0.000 title abstract description 7
- 238000012545 processing Methods 0.000 title abstract description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 81
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 81
- 239000011733 molybdenum Substances 0.000 claims abstract description 81
- 230000008569 process Effects 0.000 claims abstract description 37
- 239000010949 copper Substances 0.000 claims abstract description 31
- 229910052802 copper Inorganic materials 0.000 claims abstract description 30
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 29
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 20
- 239000001301 oxygen Substances 0.000 claims abstract description 20
- 230000003647 oxidation Effects 0.000 claims abstract description 15
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 15
- 238000007664 blowing Methods 0.000 claims abstract description 11
- 239000000428 dust Substances 0.000 claims abstract description 8
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 5
- 239000002893 slag Substances 0.000 claims description 45
- 241000722270 Regulus Species 0.000 claims description 32
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 25
- WJCGQGXVDQBQIX-UHFFFAOYSA-N S.[Cu+2].[Mo+4] Chemical compound S.[Cu+2].[Mo+4] WJCGQGXVDQBQIX-UHFFFAOYSA-N 0.000 claims description 25
- 239000003546 flue gas Substances 0.000 claims description 18
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 17
- 229910052742 iron Inorganic materials 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000003500 flue dust Substances 0.000 claims description 8
- 238000003723 Smelting Methods 0.000 claims description 7
- 239000006004 Quartz sand Substances 0.000 claims description 6
- 230000004907 flux Effects 0.000 claims description 6
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 229910052728 basic metal Inorganic materials 0.000 claims description 4
- 150000003818 basic metals Chemical class 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 238000011084 recovery Methods 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 230000004927 fusion Effects 0.000 claims description 3
- 238000007499 fusion processing Methods 0.000 claims description 2
- WUUZKBJEUBFVMV-UHFFFAOYSA-N copper molybdenum Chemical compound [Cu].[Mo] WUUZKBJEUBFVMV-UHFFFAOYSA-N 0.000 abstract description 14
- 238000002386 leaching Methods 0.000 abstract description 5
- 238000012546 transfer Methods 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 238000005272 metallurgy Methods 0.000 abstract description 4
- -1 alkaline-earth metal salts Chemical class 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 abstract 4
- 239000000779 smoke Substances 0.000 abstract 3
- 229910052783 alkali metal Inorganic materials 0.000 abstract 1
- 150000001340 alkali metals Chemical class 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 239000011734 sodium Substances 0.000 description 18
- 150000003839 salts Chemical class 0.000 description 8
- 229910004298 SiO 2 Inorganic materials 0.000 description 7
- 229910052593 corundum Inorganic materials 0.000 description 7
- 239000010431 corundum Substances 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000001590 oxidative effect Effects 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- ULPSLEOUCXNSAE-UHFFFAOYSA-N S.[Mo+4] Chemical compound S.[Mo+4] ULPSLEOUCXNSAE-UHFFFAOYSA-N 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 238000005422 blasting Methods 0.000 description 3
- 230000001698 pyrogenic effect Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000009854 hydrometallurgy Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910000570 Cupronickel Inorganic materials 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 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 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 235000019082 Osmanthus Nutrition 0.000 description 1
- 241000333181 Osmanthus Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 1
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000021321 essential mineral Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229940062044 oxygen 40 % Drugs 0.000 description 1
- 229940103067 oxygen 60 % Drugs 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- 238000009527 percussion Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000009853 pyrometallurgy Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000003870 refractory metal Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- CXVCSRUYMINUSF-UHFFFAOYSA-N tetrathiomolybdate(2-) Chemical compound [S-][Mo]([S-])(=S)=S CXVCSRUYMINUSF-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for processing molybdenite and belongs to the molybdenum metallurgy field. According to the method for processing molybdenite, molten copper matte (matte) serves as fusing agents to fuse the molybdenite, after copper molybdenum matte is generated, air or oxygen-enriched air is pumped into the copper molybdenum matte to conduct blowing, so that the molybdenite in the copper molybdenum matte is oxidized to be MoO3 to be volatilized, then the volatilized MoO3 in smoke dust is recycled through dust collection, and the smoke after dust removing is sent to prepare acid. Or alkali metals or alkaline-earth metal salts are added into the copper molybdenum matte before blowing so that molybdenum oxidation product enters residues, and the molybdenum is recycled from the residues through alkaline leaching. Low copper molybdenum matte is returned to next round matte preparing process after blowing. The method has the advantages that the technological process is short, heat transfer conditions of mass transfer are good, the production rate and the heat utilization rate are high, the concentration of SO2 in smoke is high, the adaptability to materials is high, and the like.
Description
Technical field
The invention belongs to the molybdenum field of metallurgy, relate to a kind of method of from molybdenum glance, carrying molybdenum.
Background technology
Molybdenum is a kind of important strategic reserve metal air, is widely used in fields such as iron and steel, petrochemical industry, aerospace, defence and military.The essential mineral of molybdenum is molybdenum glance (MoS
2), molybdenum glance at first will be converted into molybdenum oxide to moly-sulfide when smelting, and separates with main accompanying impurities
[1]For this reason, the processing molybdenum glance technology of domestic and foreign current mainly contains pyrogenic process and wet method two classes
[2]
Pyrogenic process mainly contains external general multiple hearth furnace, boiling roaster
[3,4]With China's general rotary kiln, reverberatory furnace roasting at present
[5,6]Product of roasting MoO
3Because the saturation vapour pressure height very easily causes damage, and easily cause the material local melting influence desulfurization with the molybdate congruent melting, the baking operation temperature can not surpass 600 ℃, thereby needs strict control speed of response and reinforcement to dispel the heat.Correspondingly, the shortcoming of roasting method is: 1) productivity is low, even if also 1.2～1.3t/ (m only of fluidizing furnace
2.d), multiple hearth furnace 0.08～0.12t/ (m only
2.d); 2) heat utilization efficiency is low, and original oxidizing reaction heat release is enough to keep self-heating, but for the multiple hearth furnace roasting, needs to feed excessive air to take away unnecessary heat in early stage for avoiding overheated, and the later stage need heat to keep required temperature of reaction again; 3) flue gas SO
2Concentration is low, SO in the fluidizing furnace flue gas
2About 3%, multiple hearth furnace 0.8～3%, rotary kiln 0.8～2% or even lower, be difficult to produce sulfuric acid and maybe can only prepare low-quality sulfuric acid.Many factories discharge after processing even directly discharge and cause atmospheric pollution; 4) equipment life short, rotary kiln can only use about 60 days, the multiple hearth furnace renewal part (mainly being rake teeth) that also will often stop production.
The throughput of wet method is also little; The oxygen lixiviation process requires equipment to work in acidity or alkaline environment, equipment material is required harsh; Cost is higher, and only comprehensive benefit just equals to roasting method when molybdenum glance rhenium-containing amount is higher; In addition, adopt the wet processing of strong oxidizers such as chlorine, nitric acid, clorox also to have environmental protection or techno-economic question
[7,8,9]
In a word, the problem in the face of existing when the pre-treatment molybdenum glance remains by theoretic innovation, develops the metallurgical method of new energy-saving and emission-reduction.
Be subjected to the inspiration of the fused salt chlorimation process of titanium, Sun Peimei etc. once carried out molybdenum glance fused salt oxidation Study on new method
[10,11]Employing yellow soda ash or sodium sulfate fused salt are as reaction medium, and the molybdenum glance that discovery adds and fused salt reaction are converted into the low price Thiomolybdate and dissolve, and blast air then oxidation generation Sodium orthomolybdate and SO
2Gas.Oxidising process only 10min just reacts completely.Yet, because the Na that generates
2MoO
4Be melted in the reaction medium Na after the water logging
2CO
3And Na
2SO
4Be dissolved in the water therewith, and the solubleness of three kinds of compounds in water is all very high.As in 20 ℃ water, Na
2MoO
4, Na
2CO
3And Na
2SO
4Solubleness be respectively 55.6,21.5 and 19.5g/(100g water).Therefore, be difficult in the water they separation.
Trace it to its cause, yellow soda ash and sodium sulfate fused salt belong to oxide melt, and resultant is the oxysalt of sodium, owing to similar mixing is difficult to separate.The melt of indissoluble solution molybdenum oxygen compound if can find the solubilized molybdenum glance then is expected to overcome the difficult separated shortcoming of molybdenum after the above-mentioned fused salt oxidation.And the easy dissolution of metals sulfide of sulfide melt, the molybdenum oxidation products that can not dissolving properties differs greatly most possibly meets this requirement.If molybdenum glance can be dissolved in the metallic sulfide really, then can form a kind of intermediate product---copper matte regulus (matte) that heavy metal copper nickel etc. is smelted that is similar to, this dissolution process just is equivalent to the matte smelting process, and the oxidation sweetening process is then actual just to be equivalent to the blowing of sulfonium.
Kennecott company reclaims studies show that of valuable metal from copper slag
[12], the copper in the slag can change the iron sulphide melt over to and form low copper matte regulus under reductive condition, and the molybdenum that contains in the slag also can change in the lump.In addition, the behavior of impurity element in the copper flash has been studied by Outokumpu company
[13]Even if when finding that grade at copper matte regulus is low, molybdenum is oxidized being enriched in the slag optionally also, obviously a small amount of molybdenum glance of association is easier to be oxidized in the copper ore concentrates.
The research of this two company linked together sees:
1) if use molybdenum glance and metallic sulfide effect instead, might realize the matte smelting of molybdenum glance, obtain the molybdenum sulfonium;
2) this molybdenum sulfonium of expection is when blasting oxygen, and moly-sulfide will be oxidized prior to cupric sulfide, realizes the blowing of molybdenum sulfonium.
Therefore, the applicant proposes the pyrometallurgy new approaches of molybdenum.Specifically: be flux with copper matte regulus (matte), molybdenum glance be dissolved in wherein form copper molybdenum sulfonium that gangue content slag making such as the silicon-dioxide of association discard, this is equivalent to a matte smelting process; Then by in copper molybdenum sulfonium, blasting air or oxygen enrichment makes the molybdenum oxidation, with MoO
3The form volatilization, and then use for reference MoO
3The mature technology of distillation refining is collected by bag filter, thereby or adds slag former and make the molybdenum oxidation products be combined to enter in the slag with basic metal, alkaline-earth metal molybdate to be separated with sulfonium), this is equivalent to a converting process; Blowing back produce low molybdenum copper matte regulus return again for the dissolving molybdenum glance; What produce in the converting process contains SO
2Flue gas is then sent to relieving haperacidity or is produced liquid sulfur dioxide.
Reference
1. Li Hong osmanthus. the metallurgical handbook of coloured extraction---rare refractory metal (on). Beijing: the .1999:271-273. of metallurgical industry press
2.Dorfler?R.,Laferty?J.Review?of?molybdenum?recovery?process.Journal?of?metals.1981,33(5):48-54.
3.Wilkomirsky?I.Production?of?molybdenum?trioxide?from?molybdenite?in?a?fluidized?bed.US?PAT.3941867.1976.
4.Gupta?C?K.Extractive?Metallurgy?of?Molybdenum.CRC?Press.1992:225-251.
5. Yu ancestor weighs. rotary kiln baking molybdenum glance industrial practice. and the metallurgical .1995 in Jiangsu, (4): 28-30,39.
6. to the iron root. molybdenum metallurgy. Changsha: the .2002:35-56. of press of Central South University
7. open civilian bell-shaped percussion instrument, used in ancient time by troops on march, Kang Taicheng, yellow constitution. molybdenum is smelted. the .1991:103-148. of press of Xi'an Communications University
8.Vizsolyi?A.,Peters?E.Nitric?acid?leaching?of?molybdenite?concentrate.Hydrometallurgy.1980,6(1-2):103-119.
9. big among Zhao. the superficial view of some theoretical question of molybdenum glance wet method leaching process. rare metal and Wimet .1995, (2): 1-3.
10. Sun Pei plum, Liu Maosheng, Shen Hui, Li Yunjiao. molybdenum glance fused salt oxidizing process research---Na
2MoO
4-Na
2SO
4System. the journal .2001 of Zhongnan Polytechnic Univ, 32 (5): 487-490.
11. the Sun Pei plum, Liu Maosheng, Huang Yongzhong, Li Honggui, Li Yunjiao. molybdenum glance fused salt oxidizing process: Na
2CO
3-Na
2MoO
4-Na
2SO
4System. the journal .2001 of Zhongnan Polytechnic Univ, 31 (5): 407-410.
12Ammann?P?R.Process?for?recovering?non-ferrous?metal?values?from?reverberatory?furnace?slags:US?PAT.3857699.1974.
13Kim?J?J.Pyrometallurgical?oxidation?of?molybdenum?rich?matte:US?PAT.4334924.1983.
Summary of the invention
The object of the present invention is to provide a kind of method of handling molybdenum glance, it is short that this method has flow process, and the mass-and heat-transfer condition is good, productivity height, heat utilization efficiency height, SO in the flue gas
2The concentration height is to advantage such as the adaptability of raw material is strong.
The present invention realizes as follows.
A kind of method of handling molybdenum glance may further comprise the steps:
A) matte smelting process: the copper matte regulus (being matte) with fusion is flux, adds the molybdenum glance melting and makes it to form liquid copper molybdenum sulfonium and primary slag, (generally through 1～10h), primary slag is discarded after making sulfonium and finishing;
B) the molybdenum process is put forward in oxidation: blast air in the liquid copper molybdenum sulfonium that obtains to step a) or oxygen-rich air blows, reclaim MoO through gathering dust from flue dust then
3, perhaps add slag former in the liquid copper molybdenum sulfonium that obtains to step a) earlier, and then blast air or oxygen-rich air, make molybdenum oxidation products and slag former generate the secondary slag, pass through the molybdenum in the hydrometallurgical recovery secondary slag then.
Mass ratio by molybdenum glance and copper matte regulus in the step a) is 0.05～10 adding molybdenum glance.
The control of the temperature of copper matte regulus is at 1150～1400 ℃ in the step a).
According to CaO, SiO in the primary slag of step a) formation
2With the mass ratio of FeO be (5～15): (30～40): (45～60), in fusion process, allocate in Wingdale, iron ore and the quartz sand one or more and determine its add-ons.
Described copper matte regulus comprises the composition of following mass content: Cu60～83%, S14～30%, and Fe≤10%, described molybdenum glance comprises the composition of following mass content: Mo7～58%, S18～40%.
The oxygen content of the oxygen-rich air that blasts in the step b) is 22～60%.
Step b) keeps the temperature of copper molybdenum sulfonium in the process of blowing between 1150～1400 ℃.
Flue gas in the step b) after the dedusting is sent to relieving haperacidity.
Blow when molybdenum content is lower than 2wt.% in the copper matte regulus in the step b) and finish, the copper matte regulus after blowing is finished directly returns step a) and recycles.
Slag former described in the step b) is carbonate or the vitriol of basic metal or alkaline-earth metal, comprises Na
2CO
3, K
2CO
3, MgCO
3, Na
2SO
4, K
2SO
4And MgSO
4In one or more, the mass ratio that its consumption satisfies Mo in slag former and the copper molybdenum sulfonium is 0.45～1.80.
The detail operations process is as follows
Copper matte regulus with fusion is flux, the composition of copper matte regulus is Cu60～83%, S14～30%, Fe≤10%, temperature control adds molybdenum glance (Mo7～58%, S18～40%) and makes it to be dissolved in the liquid copper molybdenum sulfonium of formation in the copper matte regulus at 1150～1400 ℃, gangue content forms primary slag simultaneously, and the mass ratio of molybdenum glance and copper matte regulus is between 0.05～10.Consider that the fusing point (being lower than 1150 ℃), density of a slag system are (less than 3.9g/cm
3) and the requirement of viscosity aspects such as (less than 1Pas), being dispensed in Wingdale, quartz sand or the iron ore one or more according to the one-tenth of gangue, their add-on satisfies CaO, SiO in the primary slag that forms
2With the mass ratio of FeO be (5～15): (30～40): (45～60), final slag type be among Fig. 1 shown in the dotted ellipse zone (generally speaking, if gangue content is less in the molybdenum glance known in this field, be not need to add flux such as Wingdale, quartz sand or iron ore, but gangue content more for a long time, needs to add these flux).Through 1～10h make the sulfonium process after, remove primary slag.Blast air in the liquid copper molybdenum sulfonium then or oxygen-rich air (oxygen content 22～60%) blows, make molybdenum be oxidized to MoO
3, distillation back and SO
2Enter flue gas together, the temperature of copper molybdenum sulfonium remains on 1150～1400 ℃ during blowing.When molybdenum content is lower than 2wt.% in the copper molybdenum sulfonium, can return next round matte smelting process, even the part copper matte regulus is oxidized to metallic copper because of local too high oxygen level or over-blowing in the converting process, when making sulfonium, metallic copper also can be vulcanized the generation matte again by molybdenum glance next time.The flue gas that generates in the converting process passes through the MoO that gathers dust wherein by dust collecting system
3Form with pressed powder reclaims.Flue gas after gathering dust contains 8～15% SO
2, can sulfuric acid be made in its absorption with existing maturation process.
Perhaps the carbonate of adding basic metal or alkaline-earth metal or vitriol enter in the secondary slag molybdenum oxidation products as slag former in blasting air or oxygen-rich air forward direction copper molybdenum sulfonium, then by the molybdenum in the hydrometallurgy flow process recovery secondary slag.Slag former can use Na
2CO
3, K
2CO
3, MgCO
3, Na
2SO
4, K
2SO
4And MgSO
4In one or more, the mass ratio of Mo is 0.45～1.80 in slag former and the copper molybdenum sulfonium.
Beneficial effect of the present invention has:
1) the present invention reclaims MoO from flue dust
3The technical scheme flow process short, can directly obtain MoO
3And in traditional technology molybdenum glance soak-purify through passing through ammonia after the oxidizing roasting-evaporative crystallization-calcining just can obtain pure MoO
3
2) simple, good, the siege ability height of mass-and heat-transfer condition of technical scheme procedure for preparation of the present invention; The similar process of implementation method of the present invention and bath smelting-fuming process, its specific productivity are 8～40 times of roasting molybdenum glances such as multiple hearth furnace, fluidizing furnace, rotary kiln even higher.
3) heat utilization efficiency height of the present invention, energy consumption are low; Because the molybdenum glance pyrogenic process is oxidized to strong exothermic process, the unit thermal value surpasses FeS
2, NiS etc., technical scheme of the present invention can take full advantage of the molybdenum glance oxidation heat liberation, and heat-transfer effect is good, so energy consumption is low.
4) SO in the flue gas that obtains of the present invention
2The oxidizing roasting flue gas height that concentration ratio is traditional is easy to relieving haperacidity.
5) technical scheme of the present invention is strong to the adaptability of raw material, both can handle pulverulent material, also can handle particulate materials.
Description of drawings
Fig. 1 is CaO-FeO-SiO
2The ternary slag system diagram;
Fig. 2 is that the present invention handles one of schema of molybdenum glance;
Fig. 3 is two of the present invention's schema of handling molybdenum glance.
Embodiment
In order to explain the present invention in more detail, enumerate following examples and describe, but the present invention is not limited to these embodiment.
Embodiment 1
With the 2.400kg matte (contain Cu60.00%, S29.30%, Fe9.1%) and 0.60kg Wingdale (containing CaO48.33%), 0.149kg iron ore (containing FeO70.87%) mixes, and is placed in the corundum crucible, is heated to 1400 ℃.Add the 1.600kg molybdenum glance then and (contain Mo58.00%, S36.00%, SiO
23.60%).Be incubated 10h down at 1400 ℃.Skim the primary slag on upper strata, amount to 0.236kg.Then with 2.5m
3The flow velocity of/h blasts air 100min in copper molybdenum sulfonium.Obtain low molybdenum copper matte regulus 1.842kg, contain Mo1.53%, Cu76.76%, S19.20%; Obtain flue dust 1.202kg, contain MoO
396.70%, direct yield 83.50%; Obtain SO in the flue gas
214.5%.
Embodiment 2
(contain Cu65.00%, S21.30% Fe8.9%) is placed in the corundum crucible, is heated to 1350 ℃ with the 2.500kg matte.Add the 0.125kg molybdenum glance then and (contain Mo50.00%, S36.00%, SiO
26.40%, CaO2.00%).Be incubated 9h down at 1350 ℃.Skim the primary slag on upper strata, amount to 0.025kg.Then with 2.5m
3The flow velocity of/h blasts oxygen-rich air (containing oxygen 26%) 70min in copper molybdenum sulfonium.Obtain low molybdenum copper matte regulus 2.156kg, contain Mo0.70%, Cu77.89%, S19.20%; Obtain flue dust 0.072kg, contain MoO
397.40%, direct yield 74.80%; Obtain SO in the flue gas
212.4%.
Embodiment 3
(contain Cu75.00%, S19.40% Fe1.28%) (contains SiO with 0.155kg quartz sand with the 2.000kg matte
298.00%), 1.058kg iron ore (containing 70.87%) mixes, and is placed in the corundum crucible, is heated to 1250 ℃.Add the 2.500kg molybdenum glance and (contain Mo22.00%, S23.10%, SiO
216.40%, CaO3.00%).Be incubated 7h down at 1250 ℃.Skim the upper strata primary slag, amount to 1.820kg.Then with 2.5m
3The flow velocity of/h feeds oxygen-rich air (containing oxygen 40%) 35min in copper molybdenum sulfonium.Obtain low molybdenum copper matte regulus 2.101kg, contain Mo1.72%, Cu77.14%, S20.06%; Obtain flue dust 0.759kg, contain MoO
396.10%, direct yield 88.41%; Obtain SO in the flue gas
211.1%.
Embodiment 4
(contain Cu78.00%, S18.60% Fe0.12%) (contains SiO with 6.105kg quartz sand with the 1.500kg matte
298.00%), 12.150kg iron ore (containing Fe70.87%) mixes, and is placed in the corundum crucible, is heated to 1150 ℃.Add the 15.000kg molybdenum glance and (contain Mo7.00%, S15.60%, SiO
216.00%, CaO24.30%).At 1150 ℃ of insulation 1h.Skim the upper strata primary slag, amount to 24.100kg.Then with 2.5m
3The flow velocity of/h bubbling air 20min in the copper molybdenum sulfonium.Obtain low molybdenum copper matte regulus 1.700kg, contain Mo1.50%, Cu79.14%, S17.06%; Obtain flue dust 1.070kg, contain MoO
395.40%, direct yield 64.80%; Obtain SO in the flue gas
28.3%.
Embodiment 5
(contain Cu83.00%, S15.10%) with 0.070kg Wingdale (containing CaO48.33%), 0.285kg iron ore (containing FeO70.87%) mixes, and is placed in the corundum crucible, is heated to 1200 ℃ with the 5.600kg matte.Add the 1.800kg molybdenum glance then and (contain Mo38.00%, S30.60%, SiO
25.60%).Be incubated 2h down at 1200 ℃.Skim the primary slag on upper strata, amount to 0.350kg.In copper matte regulus, add 0.310kg MgCO
3, then with 2.5m
3The flow velocity of/h blasts air 100min in copper molybdenum sulfonium.Obtain low molybdenum copper matte regulus 5.823kg, contain Mo1.86%, Cu77.24%, S17.55%; Obtain secondary slag 1.263kg, wherein contain Mo45.60%, alkali soaks the back leaching yield and reaches 96.32%; Obtain SO in the flue gas
29.1%.
Embodiment 6
(contain Cu75.00%, S19.40% Fe1.28%) mixes with 0.140kg iron ore (containing FeO70.87%), is placed in the corundum crucible, is heated to 1300 ℃ with the 2.900kg matte.Add the 1.000kg molybdenum glance then and (contain Mo50.00%, S36.00%, SiO
26.40%, CaO1.20%).Be incubated 7h down at 1300 ℃.Skim the primary slag on upper strata, amount to 0.200kg.In copper matte regulus, add 0.360kg Na
2CO
3With 0.540g Na
2SO
4, then with 2.5m
3The flow velocity of/h blasts oxygen-rich air (containing oxygen 60%) 20min in copper molybdenum sulfonium.Obtain low molybdenum copper matte regulus 3.011kg, contain Mo0.72%, Cu76.16%, S17.56%; Obtain secondary slag 0.985kg, wherein contain Mo47.70%, alkali soaks the back leaching yield and reaches 97.90%; Obtain SO in the flue gas
214.7%.
Embodiment 7
(contain Mo1.72%, Cu77.14% S20.06%) gets 2.000kg and is placed in the corundum crucible, is heated to 1200 ℃ with low molybdenum copper matte regulus that embodiment 3 obtains.Add the 0.400kg molybdenum glance then and (contain Mo51.00%, S35.30%).Be incubated 3h down at 1200 ℃.Then with 2.5m
3The flow velocity of/h blasts air 30min in copper molybdenum sulfonium.Obtain low molybdenum copper matte regulus 1.740kg, contain Mo1.66%, Cu75.06%, S16.20%; Obtain flue dust 0.225kg, contain MoO
395.1%, direct yield 60.03%; Obtain SO in the flue gas
212.3%.
Claims (10)
1. a method of handling molybdenum glance is characterized in that, may further comprise the steps:
A) matte smelting process: the copper matte regulus with fusion is flux, adds the molybdenum glance melting and makes it to form liquid copper molybdenum sulfonium and primary slag, after making sulfonium and finishing, primary slag is discarded;
B) the molybdenum process is put forward in oxidation: blast air in the liquid copper molybdenum sulfonium that obtains to step a) or oxygen-rich air blows, reclaim MoO through gathering dust from flue dust then
3, perhaps add slag former in the liquid copper molybdenum sulfonium that obtains to step a) earlier, and then blast air or oxygen-rich air, make molybdenum oxidation products and slag former generate the secondary slag, pass through the molybdenum in the hydrometallurgical recovery secondary slag then.
2. method according to claim 1 is characterized in that: be 0.05～10 to add molybdenum glance by the mass ratio of molybdenum glance and copper matte regulus in the step a).
3. method according to claim 1 and 2 is characterized in that: the control of molybdenum glance and copper matte regulus temperature of reaction is at 1150～1400 ℃ in the step a).
4. method according to claim 1 is characterized in that: according to CaO, SiO in the primary slag of step a) formation
2With the mass ratio of FeO be (5～15): (30～40): (45～60), in fusion process, allocate in Wingdale, iron ore and the quartz sand one or more and determine its add-ons.
5. method according to claim 1, it is characterized in that: described copper matte regulus comprises the composition of following mass content: Cu 60～83%, and S 14～30%, Fe≤10%, described molybdenum glance comprises the composition of following mass content: Mo 7～58%, and S 18～40%.
6. method according to claim 1, it is characterized in that: the oxygen content of the oxygen-rich air that blasts in the step b) is 22～60%.
7. according to claim 1 or 6 described methods, it is characterized in that: keep the temperature of copper molybdenum sulfonium in the step b) converting process between 1150～1400 ℃.
8. method according to claim 1, it is characterized in that: the flue gas in the step b) after the dedusting is sent to relieving haperacidity.
9. method according to claim 1 is characterized in that: blow when molybdenum content is lower than 2wt.% in the copper matte regulus in the step b) and finish, the copper matte regulus after blowing is finished directly returns step a) and recycles.
10. method according to claim 1, it is characterized in that: the slag former described in the step b) is carbonate or the vitriol of basic metal or alkaline-earth metal, comprises Na
2CO
3, K
2CO
3, MgCO
3, Na
2SO
4, K
2SO
4And MgSO
4In one or more, the mass ratio that its consumption satisfies Mo in slag former and the copper molybdenum sulfonium is 0.45～1.80.
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| CN106148676B (en) * | 2015-03-27 | 2017-10-17 | 中南大学 | It is a kind of to carry out ore phase reconstruction processing to molybdenite to improve the method that it leaches activity |
| CN106148732B (en) * | 2015-03-27 | 2018-01-02 | 中南大学 | Method that is a kind of while handling molybdenite and bidery metal |
| CN106756122A (en) * | 2016-11-25 | 2017-05-31 | 桂林理工大学 | A kind of method that caustic fusion decomposes molybdenite |
| CN108707762B (en) * | 2018-05-02 | 2021-04-09 | 昆明理工大学 | Method for removing arsenic and antimony in blowing process of copper matte converter |
| CN111979473B (en) * | 2020-07-14 | 2022-03-18 | 河南豫中新材料有限公司 | Preparation method of high-purity ferrophosphorus |
| CN118206155B (en) * | 2024-05-17 | 2024-07-16 | 辽宁宏拓新材料科技(集团)有限公司 | Method for recovering molybdenum and copper sulfide from molybdenum calcine pickling wastewater to improve purity |
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| US3734715A (en) * | 1970-07-16 | 1973-05-22 | Kennocott Copper Corp | Extraction of metal values from complex ores |
| GB1362815A (en) * | 1971-07-16 | 1974-08-07 | Kennecott Copper Corp | Separation of copper and nickel valves from deep sea manganese nodules |
| US3788841A (en) * | 1971-09-28 | 1974-01-29 | Kennecott Copper Corp | Recovery of metal values from manganese nodules |
| US3857700A (en) * | 1973-03-05 | 1974-12-31 | Kennecott Copper Corp | Pyrometallurgical recovery of copper values from converter slags |
| JPS56175893U (en) * | 1980-05-28 | 1981-12-25 | ||
| US4334924A (en) * | 1980-12-15 | 1982-06-15 | Kennecott Corporation | Pyrometallurgical oxidation of molybdenum rich matte |
| US4334925A (en) * | 1980-12-15 | 1982-06-15 | Kennecott Corporation | Combined carburization and sulfurization/desulfurization of molybdenum-rich matte |
| US8105651B2 (en) * | 2007-12-21 | 2012-01-31 | United Technologies Corp. | Artifacts, methods of creating such artifacts and methods of using such artifacts |
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