CN102643998A - Method for processing molybdenite - Google Patents
Method for processing molybdenite Download PDFInfo
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- CN102643998A CN102643998A CN2012101318313A CN201210131831A CN102643998A CN 102643998 A CN102643998 A CN 102643998A CN 2012101318313 A CN2012101318313 A CN 2012101318313A CN 201210131831 A CN201210131831 A CN 201210131831A CN 102643998 A CN102643998 A CN 102643998A
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- China
- Prior art keywords
- molybdenum
- copper
- matte
- sulfonium
- slag
- Prior art date
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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 80
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 80
- 239000011733 molybdenum Substances 0.000 claims abstract description 80
- 239000010949 copper Substances 0.000 claims abstract description 47
- 229910052802 copper Inorganic materials 0.000 claims abstract description 38
- 230000008569 process Effects 0.000 claims abstract description 37
- 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 13
- 239000000428 dust Substances 0.000 claims abstract description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 5
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 4
- 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 31
- 229910052717 sulfur Inorganic materials 0.000 claims description 27
- WJCGQGXVDQBQIX-UHFFFAOYSA-N S.[Cu+2].[Mo+4] Chemical compound S.[Cu+2].[Mo+4] WJCGQGXVDQBQIX-UHFFFAOYSA-N 0.000 claims description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- 239000003546 flue gas Substances 0.000 claims description 18
- 229910052742 iron Inorganic materials 0.000 claims description 18
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 9
- 239000003500 flue dust Substances 0.000 claims description 8
- 238000003723 Smelting Methods 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 230000004907 flux Effects 0.000 claims description 6
- 239000004576 sand Substances 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
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000011084 recovery Methods 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
- 239000000463 material Substances 0.000 abstract description 4
- -1 alkaline-earth metal salts Chemical class 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000005272 metallurgy 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
- 229910052784 alkaline earth metal Inorganic materials 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
- 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
- 229910004298 SiO 2 Inorganic materials 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
- 238000011160 research Methods 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
- 208000012839 conversion disease Diseases 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
- 230000036632 reaction speed Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 239000003870 refractory metal Substances 0.000 description 1
- 230000002787 reinforcement 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
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 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
Images
Classifications
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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 two types of pyrogenic process and wet methods
[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 be prone to cause the material local melting influence desulfurization with the molybdate congruent melting, the baking operation temperature can not surpass 600 ℃, thereby needs strict controls reaction speed 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 again to keep required temperature of reaction; 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 in acidity or alkaline environment, to work, and 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, Youxiaolin also to have environmental protection or techno-economic question
[7,8,9]
In a word, the problem in the face of when the pre-treatment molybdenum glance, existing remains through theoretic innovation, develops the metallurgical method of new energy-saving and emission-reduction.
Receive 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]Adopt yellow soda ash or sodium sulfate fused salt as reaction medium, molybdenum glance that discovery adds and fused salt reaction conversion blast air then oxidation generation Sodium orthomolybdate and SO for the low price Thiomolybdate dissolves
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.Indissoluble is separated the melt of 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 valuable metal from copper slag research shows
[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 is contained 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], find that even if molybdenum is also optionally oxidized to be enriched in the slag when the grade of copper matte regulus is hanged down, obviously a small amount of molybdenum glance of association is oxidized more easily 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: with copper matte regulus (matte) is flux, molybdenum glance is dissolved in wherein forms copper molybdenum sulfonium, and gangue content slag making such as the silicon-dioxide of association discard, and this is equivalent to a matte smelting process; Then through in copper molybdenum sulfonium, blasting air or oxygen enrichment makes the molybdenum oxidation, with MoO
3The form volatilization, and then use for reference MoO
3Distillation purified mature technology is collected through the bag filter, thereby or adds slag former and make the molybdenum oxidation products combine with basic metal, earth alkali metal molybdate to be separated with sulfonium in the entering slag), this is equivalent to a converting process; Blowing back produce low molybdenum copper matte regulus return again and be used to dissolve 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 is metallurgical. 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.
12?Ammann?P?R.Process?for?recovering?non-ferrous?metal?values?from?reverberatory?furnace?slags：US?PAT.3857699.1974.
13?Kim?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, and productivity is high, and heat utilization efficiency is high, SO in the flue gas
2Concentration is high, to advantages such as the flexibility of raw material are strong.
The present invention realizes through following steps.
A kind of method of handling molybdenum glance may further comprise the steps:
A) matte smelting process: with fused copper matte regulus (being matte) is flux, adds the molybdenum glance melting and makes it to form liquid copper molybdenum sulfonium and primary slag, makes (generally through 1～10h), primary slag to be discarded after sulfonium is accomplished;
B) the molybdenum process is put forward in oxidation: in the liquid copper molybdenum sulfonium that step a) obtains, blast air or oxygen-rich air blows, from flue dust, reclaim MoO through gathering dust then
3, perhaps earlier in the liquid copper molybdenum sulfonium that step a) obtains, add slag former, and then blast air or oxygen-rich air, make molybdenum oxidation products and slag former generate the secondary slag, then through the molybdenum in the hydrometallurgical recovery secondary slag.
Mass ratio by molybdenum glance and copper matte regulus in the step a) is 0.05～10 adding molybdenum glance.
The temperature of copper matte regulus is controlled 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 silica sand one or more and confirm its add-ons.
Said copper matte regulus comprises the composition of following mass content: Cu 60～83%, and S 14～30%, Fe≤10%, and described molybdenum glance comprises the composition of following mass content: Mo 7～58%, S 18～40%.
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.
Blowing completion when molybdenum content is lower than 2wt.% in the copper matte regulus in the step b), the copper matte regulus after blowing is accomplished directly returns step a) and recycles.
Slag former described in the step b) is the carbonate or the vitriol of basic metal or earth alkali 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 following
With the fused copper matte regulus is flux, and the composition of copper matte regulus is Cu 60～83%, and S 14～30%; Fe≤10%; Temperature is controlled at 1150～1400 ℃, adds molybdenum glance (Mo 7～58%, and S 18～40%) and makes it to be dissolved in the liquid copper molybdenum sulfonium of formation in the copper matte regulus; Gangue content forms primary slag simultaneously, and the mass ratio of molybdenum glance and copper matte regulus is between 0.05～10.The fusing point (being lower than 1150 ℃), density of considering 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, silica 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 need not add flux such as Wingdale, silica sand or iron ore, but gangue content more for a long time, need to add these flux).Through 1～10h make the sulfonium process after, remove primary slag.In liquid copper molybdenum sulfonium, blast air then or oxygen-rich air (oxygen content 22～60%) blows, make molybdenum be oxidized to MoO
3, distillation back and SO
2Get into 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 oxygen too high levels or over-blowing in the converting process, when making sulfonium, metallic copper also can be vulcanized the generation matte by molybdenum glance again next time.The flue gas that generates in the converting process passes through the MoO that gathers dust wherein through dust collecting system
3Form with pressed powder reclaims.Flue gas after gathering dust contains 8～15% SO
2, can sulfuric acid be processed in its absorption with existing maturation process.
Perhaps the carbonate of adding basic metal or earth alkali metal or vitriol get in the secondary slag molybdenum oxidation products as slag former in blasting air or oxygen-rich air forward direction copper molybdenum sulfonium, reclaim the molybdenum in the secondary slag through the hydrometallurgy flow process then.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) technical scheme procedure for preparation of the present invention is simple, the mass-and heat-transfer condition is good, the siege ability high; 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 of the present invention is high, energy consumption is 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 make full use 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 flexibility 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 the schema that the present invention handles molybdenum glance;
Figure a and b represent two technological line schemas of the present invention respectively.
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 2.400kg matte (contain Cu 60.00%, S 29.30%, and Fe 9.1%) and 0.60kg Wingdale (containing CaO 48.33%), 0.149kg iron ore (containing FeO 70.87%) mixes, and is placed in the corundum crucible, is heated to 1400 ℃.(contain Mo 58.00%, S 36.00%, SiO to add the 1.600kg molybdenum glance then
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 Mo 1.53%, Cu 76.76%, and S 19.20%; Obtain flue dust 1.202kg, contain MoO
396.70%, direct yield 83.50%; Obtain SO in the flue gas
214.5%.
Embodiment 2
2.500kg matte (contain Cu 65.00%, S 21.30%, and Fe 8.9%) is placed in the corundum crucible, is heated to 1350 ℃.(contain Mo 50.00%, S 36.00%, SiO to add the 0.125kg molybdenum glance then
26.40%, CaO 2.00%).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 Mo 0.70%, Cu 77.89%, and S 19.20%; Obtain flue dust 0.072kg, contain MoO
397.40%, direct yield 74.80%; Obtain SO in the flue gas
212.4%.
Embodiment 3
2.000kg matte (contain Cu 75.00%, S 19.40%, and Fe 1.28%) and 0.155kg silica sand (are contained SiO
298.00%), 1.058kg iron ore (containing 70.87%) mixes, and is placed in the corundum crucible, is heated to 1250 ℃.(contain Mo 22.00%, S 23.10%, SiO to add the 2.500kg molybdenum glance
216.40%, CaO 3.00%).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 Mo 1.72%, Cu 77.14%, and S 20.06%; Obtain flue dust 0.759kg, contain MoO
396.10%, direct yield 8841%; Obtain SO in the flue gas
211.1%.
Embodiment 4
1.500kg matte (contain Cu 78.00%, S 18.60%, and Fe 0.12%) and 6.105kg silica sand (are contained SiO
298.00%), 12.150kg iron ore (containing Fe 70.87%) mixes, and is placed in the corundum crucible, is heated to 1150 ℃.(contain Mo 7.00%, S 15.60%, SiO to add the 15.000kg molybdenum glance
216.00%, CaO 24.30%).At 1150 ℃ of insulation 1h.Skim the upper strata primary slag, amount to 24.100kg.Then with 2.5m
3The flow velocity of/h is bubbling air 20min in copper molybdenum sulfonium.Obtain low molybdenum copper matte regulus 1.700kg, contain Mo 1.50%, Cu 79.14%, and S 17.06%; Obtain flue dust 1.070kg, contain MoO
395.40%, direct yield 64.80%; Obtain SO in the flue gas
28.3%.
Embodiment 5
With 5.600kg matte (contain Cu 83.00%, S 15.10%) and 0.070kg Wingdale (containing CaO 48.33%), 0.285kg iron ore (containing FeO 70.87%) mixes, and is placed in the corundum crucible, is heated to 1200 ℃.(contain Mo 38.00%, S 30.60%, SiO to add the 1.800kg molybdenum glance then
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 Mo 1.86%, Cu 77.24%, and S 17.55%; Obtain secondary slag 1.263kg, wherein contain Mo 45.60%, alkali soaks the back leaching yield and reaches 96.32%; Obtain SO in the flue gas
29.1%.
Embodiment 6
2.900kg matte (contain Cu 75.00%, S 19.40%, and Fe 1.28%) and 0.140kg iron ore (containing FeO 70.87%) are mixed, be placed in the corundum crucible, be heated to 1300 ℃.(contain Mo 50.00%, S 36.00%, SiO to add the 1.000kg molybdenum glance then
26.40%, CaO 1.20%).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 Mo 0.72%, Cu 76.16%, and S 17.56%; Obtain secondary slag 0.985kg, wherein contain Mo 47.70%, alkali soaks the back leaching yield and reaches 97.90%; Obtain SO in the flue gas
214.7%.
Embodiment 7
The low molybdenum copper matte regulus (contain Mo 1.72%, Cu 77.14%, and S 20.06%) that embodiment 3 is obtained is got 2.000kg and is placed in the corundum crucible, is heated to 1200 ℃.Add 0.400kg molybdenum glance (contain Mo 51.00%, S 35.30%) then.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 Mo 1.66%, Cu 75.06%, and S 16.20%; 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: with the fused copper matte regulus is flux, adds the molybdenum glance melting and makes it to form liquid copper molybdenum sulfonium and primary slag, after making sulfonium and accomplishing, primary slag is discarded;
B) the molybdenum process is put forward in oxidation: in the liquid copper molybdenum sulfonium that step a) obtains, blast air or oxygen-rich air blows, from flue dust, reclaim MoO through gathering dust then
3, perhaps earlier in the liquid copper molybdenum sulfonium that step a) obtains, add slag former, and then blast air or oxygen-rich air, make molybdenum oxidation products and slag former generate the secondary slag, then through the molybdenum in the hydrometallurgical recovery secondary slag.
2. method according to claim 1 is characterized in that: the mass ratio by molybdenum glance and copper matte regulus in the step a) is 0.05～10 adding molybdenum glance.
3. method according to claim 1 and 2 is characterized in that: molybdenum glance and copper matte regulus temperature of reaction are controlled 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 silica sand one or more and confirm its add-ons.
5. method according to claim 1; It is characterized in that: said 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 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: the temperature that keeps copper molybdenum sulfonium in the step b) converting process is between 1150～1400 ℃.
8. method according to claim 1 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: blowing completion when molybdenum content is lower than 2wt.% in the copper matte regulus in the step b), the copper matte regulus after blowing is accomplished directly returns step a) and recycles.
10. method according to claim 1 is characterized in that: the slag former described in the step b) is the carbonate or the vitriol of basic metal or earth alkali 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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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106148676A (en) * | 2015-03-27 | 2016-11-23 | 中南大学 | A kind of ore phase reconstruction that carries out molybdenite processes to improve its method leaching activity |
| CN106148732A (en) * | 2015-03-27 | 2016-11-23 | 中南大学 | A kind of process molybdenite and the method for bidery metal simultaneously |
| CN106756122A (en) * | 2016-11-25 | 2017-05-31 | 桂林理工大学 | A kind of method that caustic fusion decomposes molybdenite |
| CN108707762A (en) * | 2018-05-02 | 2018-10-26 | 昆明理工大学 | A method of removing arsenic antimony during copper matte regulus is bessemerized |
| CN111979473A (en) * | 2020-07-14 | 2020-11-24 | 河南豫中新材料有限公司 | Preparation method of high-purity ferrophosphorus |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106756122A (en) * | 2016-11-25 | 2017-05-31 | 桂林理工大学 | A kind of method that caustic fusion decomposes molybdenite |
| CN108707762A (en) * | 2018-05-02 | 2018-10-26 | 昆明理工大学 | A method of removing arsenic antimony during copper matte regulus is bessemerized |
| CN111979473A (en) * | 2020-07-14 | 2020-11-24 | 河南豫中新材料有限公司 | Preparation method of high-purity ferrophosphorus |
| 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 |
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