CN108707762A - A method of removing arsenic antimony during copper matte regulus is bessemerized - Google Patents
A method of removing arsenic antimony during copper matte regulus is bessemerized Download PDFInfo
- Publication number
- CN108707762A CN108707762A CN201810411282.2A CN201810411282A CN108707762A CN 108707762 A CN108707762 A CN 108707762A CN 201810411282 A CN201810411282 A CN 201810411282A CN 108707762 A CN108707762 A CN 108707762A
- Authority
- CN
- China
- Prior art keywords
- copper
- matte regulus
- bessemerized
- sodium sulphate
- arsenic antimony
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 116
- 239000010949 copper Substances 0.000 title claims abstract description 109
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 89
- DLISVFCFLGSHAB-UHFFFAOYSA-N antimony arsenic Chemical compound [As].[Sb] DLISVFCFLGSHAB-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 241000722270 Regulus Species 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 27
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 112
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 69
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 48
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 29
- 229910001361 White metal Inorganic materials 0.000 claims abstract description 16
- 239000002893 slag Substances 0.000 claims abstract description 16
- 239000010969 white metal Substances 0.000 claims abstract description 16
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 239000007832 Na2SO4 Substances 0.000 claims description 21
- PANBYUAFMMOFOV-UHFFFAOYSA-N sodium;sulfuric acid Chemical compound [Na].OS(O)(=O)=O PANBYUAFMMOFOV-UHFFFAOYSA-N 0.000 claims description 5
- GYZGFUUDAQXRBT-UHFFFAOYSA-J calcium;disodium;disulfate Chemical compound [Na+].[Na+].[Ca+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GYZGFUUDAQXRBT-UHFFFAOYSA-J 0.000 claims description 4
- 239000010446 mirabilite Substances 0.000 claims description 4
- RSIJVJUOQBWMIM-UHFFFAOYSA-L sodium sulfate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-]S([O-])(=O)=O RSIJVJUOQBWMIM-UHFFFAOYSA-L 0.000 claims description 2
- 238000007664 blowing Methods 0.000 abstract description 18
- 230000008859 change Effects 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 230000001360 synchronised effect Effects 0.000 abstract description 2
- 229910052785 arsenic Inorganic materials 0.000 description 27
- 239000012535 impurity Substances 0.000 description 13
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- 230000004907 flux Effects 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 11
- 239000001301 oxygen Substances 0.000 description 11
- 238000007670 refining Methods 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 238000012946 outsourcing Methods 0.000 description 10
- 238000001125 extrusion Methods 0.000 description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 239000011449 brick Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 241001124569 Lycaenidae Species 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 235000014987 copper Nutrition 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 238000003723 Smelting Methods 0.000 description 6
- 238000005868 electrolysis reaction Methods 0.000 description 6
- 229910052681 coesite Inorganic materials 0.000 description 5
- 229910052906 cristobalite Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 229910052682 stishovite Inorganic materials 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229910052905 tridymite Inorganic materials 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- PTLRDCMBXHILCL-UHFFFAOYSA-M sodium arsenite Chemical compound [Na+].[O-][As]=O PTLRDCMBXHILCL-UHFFFAOYSA-M 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 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 3
- GOLCXWYRSKYTSP-UHFFFAOYSA-N arsenic trioxide Inorganic materials O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- NSBGJRFJIJFMGW-UHFFFAOYSA-N trisodium;stiborate Chemical compound [Na+].[Na+].[Na+].[O-][Sb]([O-])([O-])=O NSBGJRFJIJFMGW-UHFFFAOYSA-N 0.000 description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- 235000019738 Limestone Nutrition 0.000 description 2
- 229910003328 NaAsO2 Inorganic materials 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- NACUKFIFISCLOQ-UHFFFAOYSA-N [Mg].[Cr] Chemical compound [Mg].[Cr] NACUKFIFISCLOQ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- COHDHYZHOPQOFD-UHFFFAOYSA-N arsenic pentoxide Chemical compound O=[As](=O)O[As](=O)=O COHDHYZHOPQOFD-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical class [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- PTVDYARBVCBHSL-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu] PTVDYARBVCBHSL-UHFFFAOYSA-N 0.000 description 2
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 229910052840 fayalite Inorganic materials 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 239000006028 limestone Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical compound [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RMBBSOLAGVEUSI-UHFFFAOYSA-H Calcium arsenate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-][As]([O-])([O-])=O.[O-][As]([O-])([O-])=O RMBBSOLAGVEUSI-UHFFFAOYSA-H 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 241001062472 Stokellia anisodon Species 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Inorganic materials O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 1
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 1
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 description 1
- 229940000489 arsenate Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- LGRDPUAPARTXMG-UHFFFAOYSA-N bismuth nickel Chemical compound [Ni].[Bi] LGRDPUAPARTXMG-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229940103357 calcium arsenate Drugs 0.000 description 1
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- XBBFPHLRACEUEX-UHFFFAOYSA-L calcium;dihydroxy(dioxo)chromium Chemical compound [Ca].O[Cr](O)(=O)=O XBBFPHLRACEUEX-UHFFFAOYSA-L 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000009853 pyrometallurgy Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- YEAUATLBSVJFOY-UHFFFAOYSA-N tetraantimony hexaoxide Chemical compound O1[Sb](O2)O[Sb]3O[Sb]1O[Sb]2O3 YEAUATLBSVJFOY-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0026—Pyrometallurgy
- C22B15/0028—Smelting or converting
- C22B15/003—Bath smelting or converting
- C22B15/0041—Bath smelting or converting in converters
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0026—Pyrometallurgy
- C22B15/0054—Slag, slime, speiss, or dross treating
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The method that the present invention relates to a kind of to remove arsenic antimony during copper matte regulus is bessemerized, belongs to Copper making technical field.Copper matte regulus bessemerizes the period 1, and routinely operation obtains white metal, sodium sulphate slag making dearsenification antimony is added during second round white metal and cold burden being blown out blister copper, the addition total amount of sodium sulphate is 1% ~ 3% of metal copper mass in furnace charge.This method implements the synchronous abjection of arsenic antimony during the second round bessemerized making copper, hardly increases equipment, does not change blowing system, and energy consumption increases unobvious；Copper making period terminal has arrived arsenic antimony slag without special discharge, enters subsequent processing with blister copper and carries out refinement oxide, does not reduce the blowing direct yield of copper.
Description
Technical field
The method that the present invention relates to a kind of to remove arsenic antimony during copper matte regulus is bessemerized belongs to Copper making technology neck
Domain.
Background technology
Global Copper making is quickly grown, and the continuous exploitation of copper mine causes high-quality copper raw material fewer and fewer, in addition other coloured
The cupric intermediate material of metal smelt process output hands over copper work processing, cause copper raw material impurity content to increase and fluctuate it is larger, this
It is to cause the main reason for arsenic impurities antimony is high in blister copper.Existing copper smelting by pyrometallurgy flow usually matches fayalite slag in melting process
Type, main the completing abjection gangue and part iron of the task, apportionment ratio of the arsenic antimony in copper matte regulus are higher.It is main bessemerizing process
It is that deferrization sulphur makes blister copper, there is no the abjections specifically for arsenic antimony to carry out process optimization, the result is that arsenic antimony content is high in copper matte regulus, blows
Arsenic antimony affirmative height in obtained blister copper is refined, transfers to pyro-refining to undertake the task of arsenic antimony in abjection blister copper and lead bismuth nickel.State
The method that inside and outside copper smelting plant deviates from arsenic antimony in pyro-refining：
（1）Using oxidation-reduction-oxidation-reduction, operation is repeated, the readily volatilized characteristic of the low oxide of arsenic antimony is utilized
The two is set to deviate from；
（2）Basic solvent is added（Soda or lime）, the natrium arsenicum insoluble in copper can be generated（Or calcium arsenate）And sodium antimonate（Or antimony
Sour calcium）, float to bath surface and be removed.Since existing blister copper pyro-refining stove reacting dynamics condition is weaker, both
Method is all difficult to increase substantially the extrusion rate of arsenic antimony.Existing copper matte regulus bessemerizes output blister copper and is divided into two periods, and first
Period is slag-formation period, quartzy flux effect under ferrous sulfide air oxidation make fayalite (2FeOSiO2) slag：
FeS + 1.5O2 = FeO + SO2
FeO + SiO2 = 2FeO·SiO2
White metal (Cu is obtained after sieving stove2S) enter second round.Second round is copper making period, is not added with flux and vulcanizes by dioxygen oxidation
It is cuprous to make blister copper：
Cu2S +1.5O2 = Cu2O + SO2
2Cu2O + Cu2S = 6Cu + SO2
Copper making period oxygen gesture is high, and arsenic antimony is easy to be oxidized to high oxide and Cu2O generates arsenate and stibate.When containing in copper liquid
When arsenic antimony is higher, nickel mica is generated with the oxide of nickel（6Cu2O·8NiO·2As2O5And 6Cu2O·8NiO·2Sb2O5）, easily
It is dissolved in copper.
It is difficult to slagging in copper making period arsenic antimony and floats abjection from copper liquid, it is also difficult to which the object for controlling arsenic antimony is mutually volatile
As2O3And Sb2O3, so copper making period has a single function, the abjection of impurity is contributed little.Traditional copper matte regulus bessemerizes process
The extrusion rate of arsenic is less than 52% less than the extrusion rate of 60%, antimony.
Invention content
Existing traditional copper matte regulus bessemerizes the low problem of process arsenic, antimony extrusion rate and not for the above-mentioned prior art
Foot, the present invention provide a kind of method removing arsenic antimony during copper matte regulus is bessemerized.The present invention is according in copper making period melt
In impurity sulphur removal outside other accountings it is few, if removing impurities agent dearsenification antimony is added during making blister copper, just have reagent consumption few
The good advantage of reaction condition efficiently deviates from arsenic antimony while obtaining blister copper.Therefore, the technology of the present invention is by the abjection of arsenic antimony, by passing
The anode furnace pyro-refining process of system advances to the completion of Copper Matte Converting process, i.e., quartzy flux is added in the period 1（SiO2) de-
After iron, air is blown into second round（Or oxygen-enriched air）When making copper, removing impurities agent, which is added, makes arsenic antimony slag making deviate from.The present invention passes through
Following technical scheme is realized.
A method of removing arsenic antimony during copper matte regulus is bessemerized, specific steps include：
Copper matte regulus bessemerizes the period 1, and routinely operation obtains white metal, and white metal and cold burden are blown out to the mistake of blister copper in second round
Sodium sulphate slag making dearsenification antimony is added in journey, the addition total amount of sodium sulphate is 1% ~ 3% of metal copper mass in furnace charge.
The sodium sulphate is natural mirabilite, glauberite or artificial synthesized Na2SO4。
The artificial synthesized Na2SO4It is artificial synthesized for anhydrous sodium sulfate, seven hydrated sulfuric acid sodium or Disodium sulfate decahydrate
Na2SO4For granular, blocky or powdery.
The artificial synthesized Na2SO4Powdery granularity is 60 ~ 270 mesh.
It can be that be added at one time can also be according to the practical dispensing of each factory that sodium sulphate is added in above-mentioned second round
And it is added in batches.
Can also be added sodium sulphate and sodium carbonate, sodium sulphate and lime in above-mentioned second round, sodium sulphate and lime stone with
A mixture of arbitrary proportions.
The slag-formation period that copper matte regulus is bessemerized routinely operation adds quartzy flux to remove iron, and white metal is left in molten bath after sieving stove, into
Enter copper making period and sodium sulphate is added into molten bath, the reaction step of sodium sulphate and arsenic impurities antimony is：
4As+3O2+2Na2SO4=4NaAsO2+ 2SO3（1）
4As+5O2+2Na2SO4=4NaAsO3+ 2SO3 （2）
4Sb+3O2+2Na2SO4=4NaSbO2+ 2SO3 （3）
4Sb+5O2+2Na2SO4=4NaSbO3+ 2SO3（4）
In melt with arsenic, antimony existing for simple substance oxygen effect under with Na2SO4Reaction generates sodium arsenite（NaAsO2）, natrium arsenicum
（NaAsO3）, antimonious acid sodium（NaSbO2）And sodium antimonate（NaSbO3）；
As2O3+Na2SO4=2NaAsO2+ SO3（5）
As2O5+Na2SO4=2NaAsO3+ SO3 （6）
Sb2O3+Na2SO4=2NaSbO2+ SO3（7）
Sb2O5+Na2SO4=2NaSbO3+ SO3 （8）
In melt directly and Na with arsenic sb oxide existing for trivalent and pentavalent2SO4Reaction generates sodium arsenite（NaAsO2）, arsenic
Sour sodium（NaAsO3）, antimonious acid sodium（NaSbO2）And sodium antimonate（NaSbO3）.Under 1200 DEG C ~ 1300 DEG C of blowing temperature these
The sodium salt of arsenic antimony different valence state is insoluble in copper water, light specific gravity, is easy to swim in the exclusion of copper water surface.
The addition of sodium sulphate can be according to the purity of arsenic antimony content, sodium sulphate in copper matte regulus amount, copper matte regulus in stove by reaction（1）With
Reaction（3）Theoretical addition is calculated, then coefficient of excess is taken to determine the amount of being actually added into.Complexity, scene in view of reaction system
The uncertainty of material impurity grade is added and there is the sieve halfway situation of stove, also for tissue easy to produce, sodium sulphate
Addition calculated by 1% ~ 3% of metal amount of copper in stove.
The arsenic in converter blister copper can be controlled 0.06% hereinafter, antimony is controlled 0.08% hereinafter, reaching using the above method
The Con trolling index of arsenic antimony in pyro-refining anode copper.
Compared with prior art, the invention has the advantages that：
（1）Sodium sulphate price is low, source is wide, and blowing cost, copper making period arsenic antimony extrusion rate can be reduced compared with using soda ash reagent
It is high.
（2）The liner of Copper Matte Converting converter uses magnesium chromium matter refractory brick, since blowing operation is not easy that liner is allowed to hang
Flux shielding, magnesium chromium firebrick inner wall working environment are severe.Judged with thermodynamic data, the sodium sulphate that copper making period is added is in blowing temperature
Degree is lower to be reacted with the magnesium chromated oxide in refractory brick, and sodium sulphate will not chemical erosion refractory brick.
If using overbasic Na2CO3As removing impurities agent, it is easy to occur to react as follows under blowing temperature：
Cr2O3+Na2CO3=Na2O·Cr2O3+CO2
Make chemical erosion of the magnesite-chrome brick by alkali.Using CaCO3Also there is larger harm to refractory brick to deviate from arsenic antimony, because blowing
The calcium oxide of decomposition of limestone output can be reacted with the chromated oxide in refractory brick at a temperature of refining, generate CaCr2O4Although chromic acid
Calcium is high-melting-point substances, but its formation can destroy the original spinel structure of magnesite-chrome brick working face, and reduce refractory brick uses the longevity
Life.
（3）The synchronous abjection for implementing arsenic antimony during the second round bessemerized making copper, hardly increases equipment,
Blowing system is not changed, energy consumption increases unobvious；Copper making period terminal has arrived arsenic antimony slag without special discharge, is entered with blister copper next
Process carries out refinement oxide, does not reduce the blowing direct yield of copper.
The key of the present invention is：This method reduces the arsenic antimony content in blister copper.This method is bessemerized in copper matte regulus
Period 1 terminates（After stove is sieved in deferrization）, to sodium sulphate is added in melt during making copper into second round desulfurization, realize
Arsenic antimony is removed while copper matte regulus is bessemerized and makes blister copper.The fusing point of removing impurities agent sodium sulphate is 884 DEG C, is melted rapidly in copper liquid
Change, the viscosity of sodium sulphate melt is small under 1200 DEG C ~ 1300 DEG C of blowing temperature, the arsenic antimony substances of various object phases and removing impurities agent into
Row reactive liquid solution improves reaction rate.The factor for influencing arsenic antimony removal effect is mainly the feed postition of sodium sulphate, quantity is added
And action time.
Specific implementation mode
With reference to embodiment, the invention will be further described.
Embodiment 1
Equipment：100 tons of PS converters（Φ4×10.7m）；
Raw material：（1）Hot copper matte regulus（Cu 57.95wt%,As 0.20wt%,Sb 0.18wt%）；（2）Self-produced cold charge（Cu
30.00wt%, As 0.17wt%, Sb 0.18wt%）；（3）Quartzy flux（SiO2 86.00wt%）；（4）Outsourcing blister copper（Cu
97.20wt%,As 0.40wt%,Sb 0.25wt%）；（5）Adopting electrolysis residual pole（Cu 99.10wt%, As 0.15wt%, Sb
0.08wt%）；（6）Sodium sulphate（Na2SO4Purity 93.50%）
The method that Yunnan copper smelting plant removes arsenic antimony during copper matte regulus is bessemerized, specific steps include：
Step 1, by 160 tons of hot copper matte regulus（Cu 57.95wt%,As 0.20wt%,Sb 0.18wt%）, 45 tons of self-produced cold charges（Cu
30.00wt%, As 0.17wt%, Sb 0.18wt%）, 14 tons of quartzy flux are added in 100 tons of PS converters and carry out PS and bessemerize
One period routine operation, 1150 DEG C ~ 1250 DEG C of furnace temperature, air quantity 32000Nm3Slag making deferrization in 120 minutes is blown in/h, air blast oxygen-containing 25%
After obtain white metal and be transferred to two cycles；
After step 2, two cycles start, 20 tons of outsourcing blister coppers are added according to the conventional formulations of the smeltery in white metal（Cu97.20wt%,
As0.40wt%,Sb0.25wt%）And 1.4 tons of sodium sulphate are added（Sodium sulphate is artificial synthesized Na2SO4, powdered anhydrous sulfuric acid
Sodium, artificial synthesized Na2SO4Powdery granularity is 60 ~ 270 mesh）, blowing routinely 20 tons of second batch outsourcings of addition again after twenty minutes
Blister copper and 1 ton of sodium sulphate（Sodium sulphate is artificial synthesized Na2SO4, powdered anhydrous sodium sulphate, artificial synthesized Na2SO4Powdery
Granularity is 60 ~ 270 mesh）, it blows and 50 tons of adopting electrolysis residual poles is added in five batches after twenty minutes, i.e., be added 10 tons every 10 ~ 15 minutes,
Until blowing end point, copper making period terminates not deslagging, and blister copper pours into copper matte regulus packet from converter mouth together with drift slag and send refining furnace.Two cycles are blown
The refining time is 150 minutes total, 1200 DEG C ~ 1280 DEG C of furnace temperature, air quantity 33000Nm3/ h, oxygen-rich concentration 24%.
Creation data counts：184 tons of output blister copper（Cu 98.wt7%, As 0.05wt%, Sb 0.07wt%）.Enter in furnace charge
Metal amount of copper is 195 tons, adds 2.4 tons of sodium sulphate, the addition of removing impurities agent sodium sulphate is into the 1.2% of stove metal amount of copper.Blow copper
Direct yield 93.34%, arsenic extrusion rate 85.68%, antimony extrusion rate 74.15%.
Embodiment 2
Equipment：100 tons of PS converters（Φ4×10.7m）；
Raw material：（1）Hot copper matte regulus（Cu 60.20wt%,As 0.22wt%,Sb 0.20wt%）；（2）Self-produced cold charge（Cu30.00wt%,
As0.26wt%, Sb0.14wt%）；（3）Quartzy flux（SiO2 86.00wt%）；（4）Outsourcing blister copper（Cu 97.10wt%,As
0.41wt%,S b0.26wt%）；（5）Adopting electrolysis residual pole（Cu 99.20wt%, As 0.10wt%, Sb 0.08wt%）；（6）Sodium sulphate
（Na2SO4Purity 96.00%）
The method that Yunnan copper smelting plant removes arsenic antimony during copper matte regulus is bessemerized, specific steps include：
Step 1, by 160 tons of hot copper matte regulus（Cu 60.20wt%,As 0.22wt%,Sb 0.20wt%）, 37 tons of self-produced cold charges（Cu
30.00wt%, As 0.26wt%, Sb 0.14wt%）, 13 tons of quartzy flux are added in 100 tons of PS converters and carry out PS and bessemerize
One period routine operation, 1150 DEG C ~ 1250 DEG C of furnace temperature, air quantity 32000Nm3Slag making deferrization in 120 minutes is blown in/h, air blast oxygen-containing 25%
After obtain white metal and be transferred to two cycles；
After step 2, two cycles start, 20 tons of outsourcing blister coppers are added according to the conventional formulations of the smeltery in white metal（Cu
97.10wt%,As 0.41wt%,Sb 0.26wt%）And 2.5 tons of sodium sulphate are added（Sodium sulphate is artificial synthesized Na2SO4, block
Seven hydrated sulfuric acid sodium of shape）, blow and 20 tons of second batch outsourcing blister coppers and 2 tons of sodium sulphate be routinely added again after twenty minutes（Sulfuric acid
Sodium is artificial synthesized Na2SO4, blocky seven hydrated sulfuric acid sodium）, blow and 50 tons of adopting electrolysis residual poles be added in five batches after twenty minutes, i.e.,
10 tons were added every 10 ~ 15 minutes, until blowing end point, copper making period terminates not deslagging, and blister copper is poured into together with drift slag from converter mouth
Copper matte regulus packet send refining furnace.Two cycles duration of blast is 150 minutes total, 1200 DEG C ~ 1280 DEG C of furnace temperature, air quantity 33000Nm3/ h is rich
Oxygen concentration 24%.
Creation data counts：180 tons of output blister copper（Cu98.8wt%, As0.04wt%, Sb0.06wt%）.Enter golden in furnace charge
It is 192 tons to belong to amount of copper, adds 4.5 tons of sodium sulphate, the addition of removing impurities agent sodium sulphate is into the 2.3% of stove metal amount of copper.The copper that blows is straight
Yield 92.8%, arsenic extrusion rate 89.06%, antimony extrusion rate 78.93%.
Embodiment 3
The method that Yunnan copper smelting plant removes arsenic antimony during copper matte regulus is bessemerized, specific steps include：
Step 1, by 160 tons of hot copper matte regulus（Cu 60.20wt%,As 0.22wt%,Sb 0.20wt%）, 37 tons of self-produced cold charges（Cu
30.00wt%, As 0.26wt%, Sb 0.14wt%）, 13 tons of quartzy flux are added in 100 tons of PS converters and carry out PS and bessemerize
One period routine operation, 1150 DEG C ~ 1250 DEG C of furnace temperature, air quantity 32000Nm3Slag making deferrization in 120 minutes is blown in/h, air blast oxygen-containing 25%
After obtain white metal and be transferred to two cycles；
After step 2, two cycles start, 20 tons of outsourcing blister coppers are added according to the conventional formulations of the smeltery in white metal（Cu97.10wt%,
As0.41wt%,Sb0.26wt%）And sodium sulphate is added（Sodium sulphate is blocky natural mirabilite）, blowing is after twenty minutes again routinely
20 tons of second batch outsourcing blister coppers and sodium sulphate is added（Sodium sulphate is blocky natural mirabilite）, blowing is after twenty minutes by 50 tons of electrolysis
Anode scrap is added in five batches, i.e., was added 10 tons every 10 ~ 15 minutes, and until blowing end point, copper making period terminates not deslagging, blister copper together with
Drift slag pours into copper matte regulus packet from converter mouth and send refining furnace.Two cycles duration of blast is 150 minutes total, 1200 DEG C ~ 1280 DEG C of furnace temperature, wind
Measure 33000Nm3The addition total amount of/h, oxygen-rich concentration 24%, wherein sodium sulphate are 3% of metal copper mass in furnace charge.
Embodiment 4
The method that Yunnan copper smelting plant removes arsenic antimony during copper matte regulus is bessemerized, specific steps include：
Step 1, by 160 tons of hot copper matte regulus（Cu 60.20wt%,As 0.22wt%,Sb 0.20wt%）, 37 tons of self-produced cold charges（Cu
30.00wt%, As 0.26wt%, Sb 0.14wt%）, 13 tons of quartzy flux are added in 100 tons of PS converters and carry out PS and bessemerize
One period routine operation, 1150 DEG C ~ 1250 DEG C of furnace temperature, air quantity 32000Nm3Slag making deferrization in 120 minutes is blown in/h, air blast oxygen-containing 25%
After obtain white metal and be transferred to two cycles；
After step 2, two cycles start, 20 tons of outsourcing blister coppers are added according to the conventional formulations of the smeltery in white metal（Cu97.10wt%,
As0.41wt%,Sb0.26wt%）And sodium sulphate is added（Sodium sulphate is granular glauberite）, blow and routinely add again after twenty minutes
Enter 20 tons of second batch outsourcing blister coppers and sodium sulphate（Sodium sulphate is granular glauberite）, blow after twenty minutes by 50 tons of adopting electrolysis residual poles
It is added in five batches, i.e., was added 10 tons every 10 ~ 15 minutes, until blowing end point, copper making period terminates not deslagging, and blister copper is together with drift slag
Copper matte regulus packet, which is poured into, from converter mouth send refining furnace.Two cycles duration of blast is 150 minutes total, 1200 DEG C ~ 1280 DEG C of furnace temperature, air quantity
33000Nm3The addition total amount of/h, oxygen-rich concentration 24%, wherein sodium sulphate are 1.8% of metal copper mass in furnace charge.
The specific implementation mode of the present invention is explained in detail above, but the present invention is not limited to above-mentioned embodiment party
Formula can also be made without departing from the purpose of the present invention within the knowledge of a person skilled in the art
Go out various change.
Claims (4)
1. a kind of method removing arsenic antimony during copper matte regulus is bessemerized, it is characterised in that specific steps include：
Copper matte regulus bessemerizes the period 1, and routinely operation obtains white metal, and white metal and cold burden are blown out to the mistake of blister copper in second round
Sodium sulphate slag making dearsenification antimony is added in journey, the addition total amount of sodium sulphate is 1% ~ 3% of metal copper mass in furnace charge.
2. the method according to claim 1 for removing arsenic antimony during copper matte regulus is bessemerized, it is characterised in that：It is described
Sodium sulphate is natural mirabilite, glauberite or artificial synthesized Na2SO4。
3. the method according to claim 2 for removing arsenic antimony during copper matte regulus is bessemerized, it is characterised in that：It is described
Artificial synthesized Na2SO4For anhydrous sodium sulfate, seven hydrated sulfuric acid sodium or Disodium sulfate decahydrate, artificial synthesized Na2SO4For grain
Shape, bulk or powdery.
4. the method according to claim 3 for removing arsenic antimony during copper matte regulus is bessemerized, it is characterised in that：It is described
Artificial synthesized Na2SO4Powdery granularity is 60 ~ 270 mesh.
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