CN115821056B - Cooperative treatment method for zinc-containing soot and zinc-containing paint slag of steel mill - Google Patents
Cooperative treatment method for zinc-containing soot and zinc-containing paint slag of steel mill Download PDFInfo
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- CN115821056B CN115821056B CN202211113939.XA CN202211113939A CN115821056B CN 115821056 B CN115821056 B CN 115821056B CN 202211113939 A CN202211113939 A CN 202211113939A CN 115821056 B CN115821056 B CN 115821056B
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- zinc
- slag
- flue gas
- iron
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 209
- 239000011701 zinc Substances 0.000 title claims abstract description 208
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 199
- 239000002893 slag Substances 0.000 title claims abstract description 96
- 239000003973 paint Substances 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 36
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 27
- 239000010959 steel Substances 0.000 title claims abstract description 27
- 239000004071 soot Substances 0.000 title claims abstract description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 134
- 229910052742 iron Inorganic materials 0.000 claims abstract description 63
- 238000003723 Smelting Methods 0.000 claims abstract description 50
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000003546 flue gas Substances 0.000 claims abstract description 36
- 239000000203 mixture Substances 0.000 claims abstract description 34
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 13
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 11
- 239000001301 oxygen Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 9
- 150000004673 fluoride salts Chemical class 0.000 claims abstract description 7
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000003830 anthracite Substances 0.000 claims abstract description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 20
- 229910052799 carbon Inorganic materials 0.000 claims description 16
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 13
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical group [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 12
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 12
- 239000003245 coal Substances 0.000 claims description 6
- 125000001153 fluoro group Chemical class F* 0.000 claims description 5
- 230000002195 synergetic effect Effects 0.000 claims description 4
- 239000000571 coke Substances 0.000 claims description 3
- 235000019738 Limestone Nutrition 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- 238000004939 coking Methods 0.000 claims description 2
- 239000010459 dolomite Substances 0.000 claims description 2
- 229910000514 dolomite Inorganic materials 0.000 claims description 2
- 239000006028 limestone Substances 0.000 claims description 2
- 239000010453 quartz Substances 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 239000004575 stone Substances 0.000 claims description 2
- 238000003672 processing method Methods 0.000 claims 4
- 239000002699 waste material Substances 0.000 abstract description 8
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 238000011084 recovery Methods 0.000 description 18
- 229910000805 Pig iron Inorganic materials 0.000 description 16
- 238000010791 quenching Methods 0.000 description 14
- 230000000171 quenching effect Effects 0.000 description 13
- 238000004017 vitrification Methods 0.000 description 11
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000428 dust Substances 0.000 description 10
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical group [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 229910052681 coesite Inorganic materials 0.000 description 6
- 229910052906 cristobalite Inorganic materials 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 229910052682 stishovite Inorganic materials 0.000 description 6
- 229910052905 tridymite Inorganic materials 0.000 description 6
- 239000011575 calcium Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000000779 smoke Substances 0.000 description 4
- 235000014692 zinc oxide Nutrition 0.000 description 4
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 239000011449 brick Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052911 sodium silicate Inorganic materials 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 229910001308 Zinc ferrite Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000003034 coal gas Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 235000013980 iron oxide Nutrition 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- WGEATSXPYVGFCC-UHFFFAOYSA-N zinc ferrite Chemical compound O=[Zn].O=[Fe]O[Fe]=O WGEATSXPYVGFCC-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical group [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910001567 cementite Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000007596 consolidation process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000010405 reoxidation reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 229910052844 willemite Inorganic materials 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Classifications
-
- 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
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to a cooperative treatment method of zinc-containing soot and zinc-containing paint slag in a steel mill, which comprises the following steps: uniformly mixing a zinc-containing mixture, a reducing agent, a slag former, sodium salt and fluoride salt to obtain a mixed material; adding the mixed material into a smelting furnace, and introducing oxygen-enriched air for smelting at 1300-1500 ℃ to obtain zinc-rich flue gas, upper and lower layered molten slag and molten iron; condensing the zinc-rich flue gas to obtain metallic zinc and residual flue gas. According to the invention, the zinc-containing paint slag and the zinc-containing ash of a steel mill are cooperatively treated in a waste treatment mode, and zinc and iron in the zinc-containing paint slag are recovered while the high heat value attached to the zinc-containing paint slag is fully utilized. And through proper proportion, the heat source can be provided by only paint slag, and only a small amount of anthracite and other substances are added to serve as reducing agents of zinc and iron, so that the energy consumption is greatly reduced.
Description
Technical Field
The invention relates to a cooperative treatment method of zinc-containing soot and zinc-containing paint slag in a steel mill, belonging to the technical field of comprehensive recovery of nonferrous metals.
Background
Zinc-containing ash in steel mills mainly comprises blast furnace gas ash (mud) and electric furnace ash, wherein zinc in the gas ash (mud) is mainly obtained by continuously enriching low-grade zinc in the large and small circulation processes, and the electric furnace ash mainly comprises higher zinc in the raw materials in the scrap steel smelting process, so that the smoke dust has higher zinc content.
At present, the fire process for disposing zinc-containing soot mainly comprises a rotary kiln reduction method and a rotary hearth furnace method, wherein the product mainly comprises direct reduced iron, and zinc mainly enters smoke for reoxidation and then enters smoke dust to obtain a secondary zinc oxide product. The direct reduced iron still needs to be matched into a blast furnace for smelting, and cannot be directly used for steelmaking.
The hazardous waste class of zinc-containing paint slag is HW12 fuel and paint waste. Wherein, the slag-forming agent contains valuable components such as zinc, iron, organic matters and the like, and slag-forming components such as silicon, calcium and the like. The traditional paint slag treatment method is to treat the paint slag by a low-temperature incineration or pyrolysis method, but only organic matters in the paint slag can be utilized, and the metal recovery rate in the paint slag is low. Therefore, it is necessary to develop a process capable of effectively treating the waste paint slag, clean the production environment and high in metal recovery rate so as to meet the actual requirements of dangerous waste treatment of the waste paint slag.
Chinese patent application CN103740939a discloses a method for producing molten iron and recovering zinc from zinc-containing dust mud of iron and steel works. The method comprises the following steps: uniformly mixing the dried zinc-containing dust mud of the iron and steel plant with a binder and water to obtain a mixed raw material; cold consolidation molding is carried out on the mixed raw materials to obtain pellets or bricks; the cold solidified pellets or bricks are sent to a dryer or a grate machine to be dried until the water content is less than or equal to 1wt%; mixing the dried pellets or bricks with coke and flux for reduction smelting to obtain molten iron and zinc steam; extracting gas containing zinc steam, removing coarse dust by using a hot cyclone dust collector, recovering sensible heat of the gas by using a waste heat boiler, exchanging heat by using a heat exchanger, and finely removing dust by using a cloth bag dust collector to obtain high zinc dust. The method can be carried out at a higher temperature (> 1500 ℃), which is no different from the conventional iron-making process.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a cooperative treatment method of zinc-containing soot and zinc-containing paint slag of a steelworks with low energy consumption.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a cooperative treatment method of zinc-containing soot and zinc-containing paint slag in a steel mill comprises the following steps:
s1, uniformly mixing a zinc-containing mixture, a reducing agent, a slag former, sodium salt and fluoride salt to obtain a mixed material;
The zinc-containing mixture is formed by mixing zinc-containing soot and zinc-containing paint slag of a steel mill; the addition amount of the reducing agent is 10-30wt% of the zinc-containing mixture, the addition amount of the slag former is 0-20wt% of the zinc-containing mixture, the addition amount of the sodium salt is 1-10wt% of the zinc-containing mixture, and the addition amount of the fluorine salt is 1-10wt% of the zinc-containing mixture;
S2, adding the mixed material into a smelting furnace, and introducing oxygen-enriched air for smelting at 1300-1500 ℃ to obtain zinc-rich flue gas, upper and lower layered molten slag and molten iron;
Wherein, during smelting, the molar ratio of CO and CO 2 in the smelting furnace is controlled to be more than 1.2; generally, the molar ratio of CO and CO 2 can be regulated and controlled to be more than 1.2 by controlling the addition amount of the reducing agent in the mixed material and the ventilation amount and concentration of oxygen-enriched air in the smelting process;
and S3, condensing the zinc-rich flue gas to obtain metal zinc and residual flue gas.
The invention processes zinc-containing ash and zinc-containing paint slag in the steel mill in a synergistic way, and can fully utilize the heat value of the zinc-containing paint slag and slag-forming components such as calcium, silicon and the like, thereby efficiently recovering valuable components of zinc and iron. Meanwhile, the CaO-SiO 2-MgO-Na2O-CaF2 pentad slag system is constructed by adding sodium salt and fluoride salt, so that the melting point and viscosity of the whole smelting system can be effectively reduced, zinc-containing ash and zinc-containing paint slag of a steel mill can be treated at low temperature, and the product metallic zinc and pig iron can be obtained through smelting and condensing treatment, so that the treatment flow is short, and the energy conservation and consumption reduction are facilitated.
In the present invention, the ph value (cao+mgo)/(SiO 2) =0.6 to 1.4 (i.e., the ratio of the total mass of CaO and MgO to the mass of SiO 2) of the reaction system in the melting furnace can be preferably controlled to 0.6 to 1.0.
Further, in S1, the sodium salt is one or more of sodium sulfate, sodium carbonate and sodium chloride, preferably sodium carbonate; the fluoride salt is one or more of sodium fluoride, potassium fluoride, magnesium fluoride and calcium fluoride, preferably calcium fluoride.
Further, in S1, the addition amount of the reducing agent is 15-35wt% of the zinc-containing mixture, and further 20-30wt%; the addition amount of the slag former is 5-15wt% of the zinc-containing mixture, and further 8-12wt%.
Further, in S2, the concentration of the oxygen-enriched air is more than 40vol percent, preferably 50-80 vol percent, so that the smoke generation amount is effectively reduced to increase the zinc steam concentration and reduce the operation pressure of the subsequent condensation process.
Further, in S2, the flue gas temperature at the flue gas outlet of the smelting furnace is controlled to be more than 1000 ℃, preferably 1050-1150 ℃, so that oxidation of zinc in the flue gas can be further prevented.
Optionally, the concentration of zinc vapor in the zinc-rich flue gas is more than or equal to 5vol%.
Further, in S2, during smelting, the molar ratio of CO to CO 2 in the smelting furnace is controlled to be 1.4-1.8, preferably 1.5-1.7.
Therefore, by controlling the mole ratio of CO and CO 2 in the smelting furnace and controlling the reducing atmosphere, the full reduction of iron and zinc is ensured, and the zinc is prevented from being secondarily oxidized in the condensation process.
Optionally, in S2, the smelting temperature is 1350-1450 ℃.
Optionally, water quenching is carried out on the molten slag to obtain water quenched slag. The water quenched slag can be sold.
The main reactions in the smelting process are as follows:
(1) Oxidation-reduction reaction:
2C+O2＝2CO
ZnFe2O4+C＝ZnO+2FeO+CO(g)
ZnO+CO＝Zn+CO2
2Zn+O2＝2ZnO
2Fe2O3+C＝4FeO+CO2
FeO+C＝2Fe+CO2
Fe2O3+CO＝2FeO+CO2
FeO+CO＝Fe+CO2
Zn2SiO4+Na2O＝2ZnO+Na2SiO3
*2FeO*SiO2+Na2O＝2FeO+Na2SiO3
Fe+C＝Fe3C
(2) Slag-making reaction
Na2O+SiO2＝Na2SiO3
MgO+SiO2＝MgO·SiO2
CaO+SiO2＝CaO·SiO2
Further, in S3, condensing the zinc-rich flue gas by adopting a lead rain condenser, so that the temperature of the zinc-rich flue gas is reduced to below 500 ℃. Zinc steam has lower saturated vapor pressure at about 500 ℃, so that the high-efficiency recovery of zinc is ensured, the zinc steam is condensed into a lead rain pool in the form of zinc liquid, and zinc ingots are obtained by precipitation and layered discharge.
Optionally, cooling, dedusting, SCR denitration and gas purification are sequentially carried out on the residual flue gas to obtain clean gas. Optionally, cooling by a quench tower; optionally, wet dust removal is performed. Specifically, the rest flue gas after lead rain condensation is sprayed and cooled by an alkali liquor quenching tower, the cooling interval is 500-200 ℃, so that a dioxin synthesis interval is avoided, the chlorine-containing flue gas possibly generated after zinc-containing paint slag is combusted is prevented from synthesizing dioxin again, and sulfur dioxide possibly existing in the flue gas is removed. And then clean coal gas is obtained through wet dust removal, coal gas purification and other processes.
Further, in S1, the reducing agent is one or more of carbon, waste activated carbon, coking coal, anthracite, carbon and coke; the slag former is one or more of quartz stone, limestone and dolomite.
Further, in S1, the addition amount of the reducing agent is 15-25wt% of the zinc-containing mixture, further 18-22wt%, and the addition amount of the slag former is 2-18wt% of the zinc-containing mixture, further 5-15wt%.
Further, in S1, in the zinc-containing soot of the steel mill, the Zn content is 10-50wt% and the Fe content is 20-50wt%.
Optionally, in the zinc-containing soot of the steel mill, the Zn content is 15-30 wt%, the Fe content is 22-35 wt%, the Si content is 0.5-3.5wt%, the Ca content is 0.5-3wt%, the Mg content is 0-1wt%, the Mn content is 0-1.5wt%, and the Cu content is 0-0.8wt%.
Further, in the zinc-containing paint slag, the Zn content is 1-50wt% and the Fe content is 1-20wt%. Alternatively, the heating value (lower heating value) of the zinc-containing paint slag is 2000 to 4000kcal, further 25000 to 3500kcal.
Optionally, in the zinc-containing paint slag, the Zn content is 5-20wt%, the Fe content is 5-20wt%, the Si content is 0.5-5wt%, the Ca content is 0-1.5wt%, the Mg content is 0-1wt%, the C content is 15-45wt%, and the H content is 1-8wt%.
Further, the sodium salt is added in an amount of 2 to 8wt%, preferably 4 to 6wt%, of the zinc-containing mixture.
Further, the addition amount of the fluorine salt is 2 to 8wt%, preferably 4 to 6wt%, of the zinc-containing mixture.
Further, in S1, the zinc-containing mixture is formed by mixing zinc-containing soot and zinc-containing paint slag of a steelworks in a mass ratio of 1-5:1 (preferably 1-3:1).
Further, in S2, the melting time is 0.5 to 2 hours, more preferably 0.75 to 1.5 hours, and still more preferably 1 to 1.25 hours.
The zinc-containing paint slag has higher heat value, and the ratio of the zinc-containing ash and the zinc-containing paint slag in a steel mill can ensure that the reducing agent is only used for reducing zinc and iron oxides without adding extra coal as fuel. Meanwhile, organic matters in the zinc-containing paint slag can be fully combusted through smelting, and the slag is subjected to water quenching to obtain harmless water quenching slag, so that the aim of harmlessness is achieved.
The applicant researches find that slag formation is carried out by sodium salt and fluoride salt together, so that slag with low melting point and low viscosity can be obtained, and low-temperature smelting of zinc-containing soot is realized; however, the addition of a sodium salt or a fluorine salt alone does not provide the desired effect.
Compared with the prior art, the invention has the following beneficial effects:
1) According to the invention, the zinc-containing paint slag and the zinc-containing ash of a steel mill are cooperatively treated in a waste treatment mode, and zinc and iron in the zinc-containing paint slag are recovered while the high heat value attached to the zinc-containing paint slag is fully utilized. And through proper proportion, the heat source can be provided by only paint slag, and only a small amount of anthracite and other substances are added to serve as reducing agents of zinc and iron, so that the energy consumption is greatly reduced. In general, the coal consumption of the direct zinc and iron smelting process for zinc-containing soot in a steel mill is about 650-800 kg/t-zinc-containing soot, and the smelting temperature is required to be 1600 ℃; the invention can reduce the coal consumption to 200 kg-400 kg/t-zinc-containing ash through adding zinc-containing paint slag with high heat value and developing slag with low melting point and oxygen-enriched smelting.
2) The method solves the problem that zinc paint slag and zinc-containing soot of a steel mill cannot be efficiently recycled in one step, and simultaneously carries out one-step separation and purification on dangerous wastes containing zinc and iron through oxygen-enriched smelting to directly obtain zinc ingots and pig iron, thereby greatly shortening the existing process flow, increasing the energy utilization rate and reducing the carbon emission. Meanwhile, harmless treatment of zinc-containing paint slag and zinc-containing ash of a steel mill can be realized.
3) The conventional process adopts a ternary slag type of Si-Ca-Mg, which has high melting point, so that enough coal is needed to be matched for ensuring the smelting temperature, and the smelting process can reduce the melting point of slag phase and obtain better fluidity by constructing a five-membered slag type of CaO-SiO 2-MgO-Na2O-CaF2 in the smelting process, thereby realizing the purpose of smelting zinc-containing soot at low temperature.
4) According to the invention, the silicate structure is destroyed by adding the sodium salt, so that the release and reduction of zinc are promoted, the smelting efficiency is improved, and zinc is reduced into flue gas as much as possible. Meanwhile, fe-O bonds in FeO can be weakened, so that iron oxide is easier to reduce by carbon, thereby promoting iron-oxygen separation, further releasing zinc in zinc ferrite, accelerating reduction rate and increasing recovery rate of zinc;
5) The invention can reduce the melting point and viscosity of slag by the synergistic effect of the fluorine salt and the sodium salt, and realize low-temperature smelting.
Drawings
FIG. 1 is a flow chart of a method for treating zinc-containing soot and zinc-containing paint slag in a steelworks in accordance with the present invention.
FIG. 2 is a five-membered slag phase diagram of CaO-SiO 2-MgO-Na2O-CaF2 in example 1.
Detailed Description
The present invention will be described in detail with reference to examples. It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other. The relevant percentages refer to mass percentages unless otherwise indicated.
Example 1
TABLE 1 composition of zinc-containing soot in Steel works
| Element(s) | Fe | Zn | Si | Ca | Mg | Mn | Cu |
| Content/wt% | 26.3 | 24.8 | 1.4 | 2.6 | 0.6 | 0.8 | 0.2 |
TABLE 2 composition of main chemical components of zinc-containing paint slag
| Element(s) | Fe | Zn | Si | Ca | Mg | C | H | Low heat value |
| Content/wt% | 13.6 | 12.7 | 2.4 | 0.8 | 0.4 | 34.2 | 3.52 | 3100kcal/kg |
In this example, the compositions of the zinc-containing soot and the zinc-containing paint slag of the steel mill are shown in tables 1 and 2, respectively, and referring to fig. 1, the specific treatment method is as follows:
(1) Mixing zinc-containing ash of a steel mill with zinc-containing paint slag according to the proportion of 2:1 to obtain a mixture;
(2) Uniformly mixing the mixture, anthracite, sodium carbonate and calcium fluoride to obtain a mixture;
Wherein, the adding amount of sodium carbonate is 3% of the mixture, and the adding amount of calcium fluoride is 1% of the mixture; the addition amount of anthracite is 15% of the mixture; the natural alkalinity (CaO+MgO)/(SiO 2) of the material ratio is 0.8, and is within the optimal range, so that no additional slag former is needed.
(3) Adding the mixed material into a smelting furnace, and introducing oxygen-enriched air for smelting to obtain zinc-enriched flue gas, and molten slag and molten iron distributed vertically;
Wherein the smelting temperature is 1400 ℃, the smelting time is 60min, the reducing atmosphere is CO/CO 2 =1.6 (namely the molar ratio of CO and CO 2), the oxygen concentration of the oxygen-enriched air is 80vol%, and the introducing amount is used for meeting the requirement of the reducing atmosphere; the temperature of the zinc-rich flue gas at the outlet of the furnace top is 1300 ℃, and the concentration of zinc steam is 12vol%.
(4) The zinc-rich flue gas is input into a lead rain condenser from the top of the furnace to be condensed to 500 ℃ to obtain a zinc ingot product with zinc direct yield of 99.2% and zinc grade of 99.6%;
And (3) discharging molten iron to obtain a pig iron product containing 95% of iron and 2.5% of carbon, wherein the iron recovery rate reaches 97%.
Carrying out water quenching treatment on the molten slag to obtain water quenched slag; wherein the incineration rate of organic matters in the zinc-containing paint slag is more than 99.9%, the vitrification rate is more than 97%, the iron content is 2.48%, and the zinc content is 0.6%.
Comparative example 1
Example 1 was repeated, with the only difference that: sodium carbonate was not added.
The results show that: the temperature of the zinc-rich flue gas at the outlet of the furnace top is 1300 ℃, and the concentration of zinc steam is 12vol%. Zinc ingot products with zinc direct yield of 95% and zinc grade of 99.5%; but the molten slag is not completely melted, slag-iron separation cannot be realized, the natural gas is adopted to supplement heat, the smelting temperature is further increased to 1550 ℃, the slag-iron separation can be realized, and the molten iron is discharged, so that a pig iron product containing 93% of iron and 3.5% of carbon is obtained, and the iron recovery rate reaches 94%. Carrying out water quenching treatment on the molten slag to obtain water quenched slag; wherein the incineration rate of organic matters in the zinc-containing paint slag is more than 99.9%, the vitrification rate is more than 98%, the iron content is 4.96%, and the zinc content is 3.89%.
Comparative example 2
Example 1 was repeated, with the only difference that: no calcium fluoride was added.
The results show that: the temperature of the zinc-rich flue gas at the outlet of the furnace top is 1300 ℃, and the concentration of zinc steam is 12vol%; zinc ingot products with zinc direct yield of 98.5% and zinc grade of 99.4%; and (3) discharging molten iron to obtain a pig iron product containing 91% of iron and 4.5% of carbon, wherein the iron recovery rate is up to 85%.
Carrying out water quenching treatment on the molten slag to obtain water quenched slag; wherein the incineration rate of organic matters in the zinc-containing paint slag is more than 99.9%, the vitrification rate is more than 97%, the iron content is 9,46%, and the zinc content is 1.16%. The production status shows that the slag has high viscosity, is not easy to discharge and has higher iron content.
Comparative example 3
Example 1 was repeated, with the only difference that: sodium carbonate is not added, and the addition amount of calcium fluoride is controlled to be 4% of the mixture.
The results show that: the temperature of the zinc-rich flue gas at the outlet of the furnace top is 1300 ℃, and the concentration of zinc steam is 12vol%; zinc ingot products with zinc direct yield of 96% and zinc grade of 99.2%; the slag is not completely melted, slag-iron separation cannot be realized, natural gas is adopted to supplement heat, the smelting temperature is further increased to 1500 ℃, slag-iron separation can be realized, molten iron is discharged, and a pig iron product containing 95% of iron and 1.5% of carbon is obtained, and the iron recovery rate reaches 98%. Carrying out water quenching treatment on the molten slag to obtain water quenched slag; wherein the incineration rate of organic matters in the zinc-containing paint slag is more than 99.9%, the vitrification rate is more than 98%, the iron content is 0.8%, and the zinc content is 3.1%.
Comparative example 4
Example 1 was repeated, with the only difference that: the addition amount of sodium carbonate is controlled to be 10% of the mixture without adding calcium fluoride.
The result shows that the temperature of the zinc-rich flue gas at the outlet of the furnace top is 1300 ℃, and the concentration of zinc steam is 12vol%; zinc ingot product with zinc direct yield 78% and zinc grade 96.5%; the pig iron product contains 89% of iron, 4.3% of carbon and the iron recovery rate reaches 87%. Carrying out water quenching treatment on the molten slag to obtain water quenched slag; wherein the incineration rate of organic matters in the water quenching slag is more than 99.9%, the vitrification rate is more than 97%, the iron content is 8.43%, and the zinc content is 14.22%. The test results show that the furnace conditions are seriously deteriorated due to excessive addition of sodium carbonate, and the recovery rate of zinc is remarkably reduced due to the weakening of the reducing atmosphere.
Comparative example 5
Example 1 was repeated, with the only difference that: no calcium fluoride is added, and the smelting time is 90min.
The results show that the temperature of the zinc-rich flue gas at the outlet of the furnace roof is 1300 ℃ and the zinc steam concentration is 12vol%.
Zinc ingot products with zinc direct yield of 99.2% and zinc grade of 99.4%;
the pig iron product contains 94% of iron and 2.7% of carbon, and the iron recovery rate reaches 95%.
The incineration rate of organic matters in the zinc-containing paint slag is more than 99.9%, the vitrification rate is more than 97%, the iron content is 3.87%, and the zinc content is 0.62%. Test results show that the recovery rate of zinc and iron can be improved by prolonging the smelting time.
Comparative example 6
Example 1 was repeated, with the only difference that: sodium carbonate and calcium fluoride are not added, and the smelting temperature is 1550 ℃.
The results show that the temperature of the zinc-rich flue gas at the outlet of the furnace roof is 1300 ℃ and the zinc steam concentration is 12vol%.
Zinc ingot products with zinc direct yield of 97.4% and zinc grade of 98.3%;
the pig iron product contains 93% of iron and 3.1% of carbon, and the iron recovery rate reaches 82%.
The incineration rate of organic matters in the zinc-containing paint slag is more than 99.9%, the vitrification rate is more than 97%, the iron content is 10.4%, and the zinc content is 2.1%.
Comparative example 7
Example 1 was repeated, with the only difference that: sodium carbonate and calcium fluoride are not added, the smelting temperature is 1550 ℃, and the smelting time is 90min.
The results show that: the temperature of the zinc-rich flue gas at the outlet of the furnace top is 1300 ℃, and the concentration of zinc steam is 12vol%.
Zinc ingot products with zinc direct yield of 97.6% and zinc grade of 98.7%;
The pig iron product contains 94% of iron and 2.8% of carbon, and the iron recovery rate reaches 95%.
The incineration rate of organic matters in the zinc-containing paint slag is more than 99.9%, the vitrification rate is more than 97%, the iron content is 3.82%, and the zinc content is 1.75%.
Comparative example 8
Comparative example 5 was repeated, with the only difference that: the smelting temperature is raised to 1550 ℃.
The concentration of zinc vapor in the flue gas at the top outlet of the furnace is 10.8vol%. And (3) zinc ingot products with zinc direct yield of 99% and zinc grade of 99.6% in the step (4). At the same time, iron was discharged as pig iron to obtain a pig iron product containing 95% iron and 2.2% carbon, with an iron recovery of 96%. The incineration rate of organic matters in the water quenching slag is more than 99.9%, the vitrification rate is more than 95%, the iron content is 1.66%, and the zinc content is 0.39%.
By contrast, the treatment method disclosed by the invention can be used for realizing low-energy-consumption and high-quality treatment of zinc-containing soot and zinc-containing paint slag of a steel mill.
Example 2
Example 1 was repeated, with the only difference that: the addition amount of sodium carbonate is 5% of the mixture, and the addition amount of calcium fluoride is 2% of the mixture.
The concentration of zinc vapor in the flue gas at the top outlet of the furnace is 12.2vol%. In the step (4), the direct yield of zinc is 99.8%, and the zinc grade of the zinc ingot product is 99.6%. Meanwhile, the iron is discharged in the form of pig iron, so that a pig iron product containing 96% of iron and 2.3% of carbon is obtained, and the iron recovery rate reaches 98%. The incineration rate of organic matters in the water quenching slag is more than 99.9%, the vitrification rate is more than 97%, the iron content is 0.8%, and the zinc content is 0.1%.
Comparative example 9
Example 1 was repeated, with the only difference that: the addition amount of sodium carbonate is 12% of the mixture.
The concentration of zinc vapor in the flue gas at the top outlet of the furnace is 8.7vol%. In the step (4), the direct zinc yield is 82%, and the zinc grade of the zinc ingot product is 98.5%. At the same time, the iron is discharged in the form of pig iron, and a pig iron product containing 89% of iron and 4.3% of carbon is obtained, and the iron recovery rate reaches 75%. The incineration rate of organic matters in the water quenching slag is more than 99.9%, the vitrification rate is more than 97%, the iron content is 10.36%, and the zinc content is 7.02%.
The foregoing examples are set forth in order to provide a more thorough description of the present application and are not intended to limit the scope of the application, and various modifications of the application, which are equivalent to those skilled in the art upon reading the present application, will fall within the scope of the application as defined in the appended claims.
Claims (8)
1. A cooperative treatment method of zinc-containing soot and zinc-containing paint slag in a steel mill is characterized by comprising the following steps:
s1, uniformly mixing a zinc-containing mixture, a reducing agent, a slag former, sodium salt and fluoride salt to obtain a mixed material;
wherein the zinc-containing mixture is formed by mixing zinc-containing ash and zinc-containing paint slag of a steel mill according to the mass ratio of 2-5:1; the addition amount of the reducing agent is 10-30wt% of the zinc-containing mixture, the addition amount of the slag former is 0-20wt% of the zinc-containing mixture, the addition amount of the sodium salt is 2-6wt% of the zinc-containing mixture, and the addition amount of the fluorine salt is 1-6wt% of the zinc-containing mixture;
wherein the fluoride salt is calcium fluoride; the sodium salt is one or more of sodium sulfate and sodium carbonate;
S2, adding the mixed material into a smelting furnace, and introducing oxygen-enriched air for smelting at 1300-1400 ℃ to obtain zinc-rich flue gas, upper and lower layered molten slag and molten iron;
wherein, during smelting, the molar ratio of CO and CO 2 in the smelting furnace is controlled to be more than 1.2;
And S3, condensing the zinc-rich flue gas to obtain metallic zinc.
2. The co-processing method according to claim 1, wherein in S2 the concentration of oxygen enriched air is > 40vol%.
3. The co-processing method according to claim 1, wherein in S2, the flue gas temperature at the flue gas outlet of the smelting furnace is controlled to be > 1000 ℃.
4. The cooperative processing method according to claim 1, wherein in S2, during smelting, a molar ratio of CO, CO 2 in the smelting furnace is controlled to be 1.4 to 1.8.
5. The collaborative treatment method according to claim 1, wherein in S3, a lead rain condenser is used to condense the zinc rich flue gas such that the temperature of the zinc rich flue gas is reduced to below 500 ℃.
6. The synergistic process as claimed in any one of claims 1 to 5, wherein in S1, the reducing agent is one or more of carbon, spent activated carbon, coking coal, anthracite, coke; the slag former is one or more of quartz stone, limestone and dolomite.
7. The cooperative processing method according to any one of claims 1 to 5, wherein in S1, the zinc-containing soot in the steel mill has a Zn content of 10 to 50wt% and a Fe content of 20 to 50wt%; in the zinc-containing paint slag, the Zn content is 1-50wt% and the Fe content is 1-20wt%.
8. The synergistic process as claimed in any one of claims 1 to 4, wherein in S2 the smelting time is from 0.5 to 2 hours.
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| CN113025824A (en) * | 2021-02-26 | 2021-06-25 | 中南大学 | Method for harmlessly treating waste paint residues |
| CN114807484A (en) * | 2022-05-20 | 2022-07-29 | 中国恩菲工程技术有限公司 | Method and system for recovering iron and zinc from steel mill ash |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE60126526T2 (en) * | 2000-02-17 | 2007-11-22 | John A. Concord Vallomy | Process for the reduction treatment of liquid slag and filter dust of an electric arc furnace |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101139644A (en) * | 2007-10-10 | 2008-03-12 | 攀钢集团攀枝花钢铁研究院 | High-alkalinity refining slag for slag washing of converter steelmaking |
| CN103468961A (en) * | 2013-09-27 | 2013-12-25 | 北京科技大学 | Method for processing dust containing zinc and lead in steel plant through closed cupola furnace |
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