CN115821056A - Method for co-processing zinc-containing ash and zinc-containing paint slag in steel plant - Google Patents
Method for co-processing zinc-containing ash and zinc-containing paint slag in steel plant Download PDFInfo
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- CN115821056A CN115821056A CN202211113939.XA CN202211113939A CN115821056A CN 115821056 A CN115821056 A CN 115821056A CN 202211113939 A CN202211113939 A CN 202211113939A CN 115821056 A CN115821056 A CN 115821056A
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- zinc
- slag
- flue gas
- iron
- paint slag
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 214
- 239000011701 zinc Substances 0.000 title claims abstract description 213
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 202
- 239000002893 slag Substances 0.000 title claims abstract description 92
- 239000003973 paint Substances 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 34
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 31
- 239000010959 steel Substances 0.000 title claims abstract description 31
- 238000012545 processing Methods 0.000 title description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 138
- 229910052742 iron Inorganic materials 0.000 claims abstract description 62
- 238000003723 Smelting Methods 0.000 claims abstract description 46
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000003546 flue gas Substances 0.000 claims abstract description 37
- 239000000203 mixture Substances 0.000 claims abstract description 33
- 239000004071 soot Substances 0.000 claims abstract description 18
- 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
- 238000002156 mixing Methods 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
- 239000000463 material Substances 0.000 claims abstract description 10
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims abstract description 10
- 239000002699 waste material Substances 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 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 21
- 229910052799 carbon Inorganic materials 0.000 claims description 17
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 13
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 12
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 12
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 12
- 238000002844 melting Methods 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 8
- 239000003245 coal Substances 0.000 claims description 6
- 230000002195 synergetic effect Effects 0.000 claims description 6
- 125000001153 fluoro group Chemical class F* 0.000 claims description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 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
- 239000010881 fly ash Substances 0.000 claims description 2
- 239000006028 limestone Substances 0.000 claims description 2
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 claims description 2
- 229910001635 magnesium fluoride Inorganic materials 0.000 claims description 2
- 239000011698 potassium fluoride Substances 0.000 claims description 2
- 235000003270 potassium fluoride Nutrition 0.000 claims description 2
- 239000010453 quartz Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 239000011775 sodium fluoride Substances 0.000 claims description 2
- 235000013024 sodium fluoride Nutrition 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 6
- 239000012141 concentrate Substances 0.000 claims 2
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 4
- 239000000047 product Substances 0.000 description 26
- 238000011084 recovery Methods 0.000 description 18
- 229910000805 Pig iron Inorganic materials 0.000 description 16
- 239000002956 ash Substances 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 230000008569 process Effects 0.000 description 13
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 12
- 238000004017 vitrification Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 238000010791 quenching Methods 0.000 description 10
- 239000000428 dust Substances 0.000 description 9
- 239000011734 sodium Substances 0.000 description 9
- 230000000171 quenching effect Effects 0.000 description 8
- 229910004298 SiO 2 Inorganic materials 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 239000011575 calcium Substances 0.000 description 4
- 239000003034 coal gas Substances 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229910004261 CaF 2 Inorganic materials 0.000 description 3
- 239000011449 brick Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 239000000779 smoke 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
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical group [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- 229910001308 Zinc ferrite Inorganic materials 0.000 description 1
- LAZOHFXCELVBBV-UHFFFAOYSA-N [Mg].[Ca].[Si] Chemical compound [Mg].[Ca].[Si] LAZOHFXCELVBBV-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- 239000000470 constituent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000003631 expected effect Effects 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000010309 melting process Methods 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
- 238000010587 phase diagram Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001698 pyrogenic 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
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- WGEATSXPYVGFCC-UHFFFAOYSA-N zinc ferrite Chemical compound O=[Zn].O=[Fe]O[Fe]=O WGEATSXPYVGFCC-UHFFFAOYSA-N 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 relates to a method for the cooperative treatment of zinc-containing soot and zinc-containing paint slag in a steel mill, which comprises the following steps: uniformly mixing the zinc-containing mixture, a reducing agent, a slagging agent, sodium salt and villiaumite 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-enriched flue gas, molten slag and molten iron which are layered up and down; and condensing the zinc-rich flue gas to obtain metal zinc and residual flue gas. The method provided by the invention has the advantages that the zinc-containing paint slag and the zinc-containing ash in a steel mill are subjected to cooperative treatment in a waste-to-waste treatment mode, and zinc and iron in the zinc-containing paint slag are recovered while the high calorific value attached to the zinc-containing paint slag is fully utilized. And through proper proportion, heat sources can be provided only by paint slag, only a small amount of anthracite and other substances are required to be added as reducing agents of zinc and iron, and energy consumption is greatly reduced.
Description
Technical Field
The invention relates to a method for the cooperative treatment of zinc-containing ash and zinc-containing paint slag in a steel plant, belonging to the technical field of comprehensive recovery of nonferrous metals.
Background
The zinc-containing ash of a steel mill 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 of raw materials in a large and small circulation process, and the electric furnace ash mainly comprises high zinc content of the raw materials in a waste steel smelting process, so that the smoke has high zinc content.
At present, the pyrogenic process for treating the 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 flue gas for reoxidation and then enters smoke dust to obtain a zinc hypoxide product. The direct reduced iron still needs to be added into a blast furnace for smelting and cannot be directly used for steelmaking.
The zinc-containing paint slag dangerous waste category is HW12 fuel and paint waste. Wherein the slag-forming agent contains valuable components such as zinc, iron and organic matters, and also contains slag-forming components such as silicon and calcium. The traditional paint slag treatment method is to treat by using a low-temperature incineration or pyrolysis method, but only utilizes organic matters in the paint slag, and has low metal recovery rate. Therefore, it is necessary to research and develop a process capable of effectively treating waste paint slag, clean production environment and high metal recovery rate, so as to meet the practical requirement of dangerous waste treatment of waste paint slag.
The chinese patent application CN103740939A discloses a method for producing molten iron and recovering zinc by using zinc-containing dust and mud of steel and iron works. The method comprises the following steps: uniformly mixing dry zinc-containing dust mud of a steel plant with a binder and water to obtain a mixed raw material; carrying out cold consolidation molding on the mixed raw materials to obtain pellets or bricks; sending the cold-bonded pellets or bricks into a dryer or a chain grate to be dried until the water content is less than or equal to 1wt%; mixing the dried pellets or bricks with coke and a flux for reduction smelting to obtain molten iron and zinc steam; and (2) leading out the coal gas containing zinc steam, removing coarse-grained dust by using a hot cyclone dust collector, recovering sensible heat of the coal gas by using a waste heat boiler, exchanging heat by using a heat exchanger, and finely removing dust by using a bag-type dust collector to obtain high-zinc dust. The method can be carried out only at a higher temperature (1500 ℃), and is not different from the conventional iron-making process.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for the synergistic treatment of zinc-containing soot and zinc-containing paint slag in a steel mill with low energy consumption.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a method for the cooperative treatment 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 villiaumite 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; the addition amount of the reducing agent is 10-30wt% of the zinc-containing mixture, the addition amount of the slagging agent 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-enriched flue gas, upper and lower layered molten slag and molten iron;
wherein during smelting, controlling CO and CO in the smelting furnace 2 The molar ratio of (A) is more than 1.2; generally, the addition amount of the reducing agent in the mixed material and the introduction amount and concentration of the oxygen-enriched air in the smelting process are controlled, so that the CO and the CO can be regulated and controlled 2 The molar ratio of (A) is more than 1.2;
s3, condensing the zinc-rich flue gas to obtain metal zinc and residual flue gas.
The invention carries out the synergistic treatment of the zinc-containing ash and the zinc-containing paint slag in the steel plant, can fully utilize the heat value of the zinc-containing paint slag and slagging components such as calcium, silicon and the like, and efficiently recover the valuable components of zinc and iron. Meanwhile, the invention constructs CaO-SiO by adding sodium salt and villiaumite 2 -MgO-Na 2 O-CaF 2 The quinary slag system can effectively reduce the melting point and viscosity of the whole smelting system, thereby realizing the low-temperature treatment of zinc-containing soot and zinc-containing paint slag in a steel mill, obtaining the products of metallic zinc and pig iron through smelting and condensation treatment, having short treatment flow and being beneficial to energy conservation and consumption reduction.
In the invention, the pH value of the reaction system in the smelting furnace is (CaO + MgO)/(SiO) 2 ) = 0.6-1.4 (i.e. total mass of CaO and MgO and SiO) 2 The mass ratio of (b) 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, and preferably sodium carbonate; the fluoride salt is one or more of sodium fluoride, potassium fluoride, magnesium fluoride and calcium fluoride, and is 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 slagging constituent is 5-15wt% of the zinc-containing mixture, and further 8-12wt%.
Furthermore, in S2, the concentration of the oxygen-enriched air is more than 40vol%, and preferably 50-80 vol%, so that the smoke gas generation amount is effectively reduced, the zinc steam concentration is increased, and the working pressure of a subsequent condensation process is reduced.
Further, in S2, the temperature of the flue gas at the flue gas outlet of the smelting furnace is controlled to be more than 1000 ℃, and 1050-1150 ℃ is preferred, so that the oxidation of zinc in the flue gas can be further prevented.
Optionally, the concentration of the zinc steam in the zinc-rich flue gas is more than or equal to 5vol%.
Further, in S2, during the smelting, controlling CO and CO in the smelting furnace 2 Is 1.4 to 1.8, preferably 1.5 to 1.7.
Thereby controlling CO and CO in the smelting furnace 2 The molar ratio of the zinc and the reducing atmosphere is controlled, so that the full reduction of the iron and the zinc is ensured, and the secondary oxidation of the zinc in the condensation process is prevented.
Optionally, in S2, the smelting temperature is 1350-1450 ℃.
Optionally, the molten slag is water quenched to obtain water-quenched slag. The water-quenched slag can be sold externally.
The main reactions in the smelting process are as follows:
(1) Oxidation-reduction reaction:
2C+O 2 ＝2CO
ZnFe 2 O 4 +C＝ZnO+2FeO+CO(g)
ZnO+CO＝Zn+CO 2
2Zn+O 2 ＝2ZnO
2Fe 2 O 3 +C＝4FeO+CO 2
FeO+C＝2Fe+CO 2
Fe 2 O 3 +CO＝2FeO+CO 2
FeO+CO＝Fe+CO 2
Zn 2 SiO 4 +Na 2 O＝2ZnO+Na 2 SiO 3
*2FeO*SiO 2 +Na 2 O＝2FeO+Na 2 SiO 3
Fe+C＝Fe 3 C
(2) Slagging reaction
Na 2 O+SiO 2 ＝Na 2 SiO 3
MgO+SiO 2 ＝MgO·SiO 2
CaO+SiO 2 ＝CaO·SiO 2
Further, in S3, a lead rain condenser is adopted to condense the zinc-rich flue gas, so that the temperature of the zinc-rich flue gas is reduced to be below 500 ℃. The zinc vapor has lower saturated vapor pressure at about 500 ℃ so as to ensure the high-efficiency recovery of zinc, and the zinc vapor is condensed to a lead rain tank in the form of zinc liquid and is discharged by precipitation and delamination to obtain a zinc ingot.
Optionally, after the remaining flue gas is sequentially subjected to cooling, dust removal, SCR denitration, and gas purification, clean gas is obtained. Optionally, cooling by a quench tower; optionally, wet dedusting is performed. Specifically, the residual flue gas after lead rain condensation is sprayed and cooled by an alkali liquor quench tower, wherein the cooling interval is 500-200 ℃, so that a dioxin synthesis interval is avoided, 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. Then the 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 extract, waste activated carbon, coking coal, anthracite, carbon extract and coke; the slagging agent 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, and further 18-22wt%, and the addition amount of the slagging agent is 2-18wt% of the zinc-containing mixture, and further 5-15wt%.
Further, in S1, the zinc-containing soot of the steel mill contains 10-50 wt% of Zn and 20-50 wt% of Fe.
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%.
Furthermore, in the zinc-containing paint slag, the Zn content is 1-50 wt%, and the Fe content is 1-20 wt%. Optionally, the calorific value (lower calorific 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 5-20 wt%, the Fe content is 5-20 wt%, 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 addition amount of the sodium salt is 2-8wt% of the zinc-containing mixture, and is preferably 4-6wt%.
Further, the addition amount of the fluorine salt is 2-8wt% of the zinc-containing mixture, and is preferably 4-6wt%.
Further, in S1, the zinc-containing mixture is formed by mixing the zinc-containing ash and the zinc-containing paint slag of a steel mill according to the mass ratio of 1-5 (preferably 1-3).
Further, in S2, the melting time is 0.5 to 2 hours, further 0.75 to 1.5 hours, and preferably 1 to 1.25 hours.
The zinc-containing paint slag has higher heat value, and the zinc-containing ash and the zinc-containing paint slag in a steel mill are proportioned, so that the reducing agent can be only used for reducing zinc and iron oxide, and extra coal is not required to be added as fuel. Meanwhile, through smelting, organic matters in the zinc-containing paint slag can be fully combusted, and the slag is water-quenched to obtain harmless water-quenched slag, so that the aim of harmlessness is fulfilled.
The applicant researches and discovers that the low-melting-point low-viscosity slag form can be obtained by slagging with sodium salt and villiaumite together, so that the low-temperature smelting of the zinc-containing soot is realized; however, the expected effect cannot be obtained by adding only sodium salt or fluorine salt.
Compared with the prior art, the invention has the following beneficial effects:
1) The method provided by the invention has the advantages that the zinc-containing paint slag and the zinc-containing ash in a steel mill are subjected to cooperative treatment in a waste-to-waste treatment mode, and zinc and iron in the zinc-containing paint slag are recovered while the high calorific value attached to the zinc-containing paint slag is fully utilized. And through proper proportion, heat sources can be provided only by paint slag, only a small amount of anthracite and other substances are required to be added as reducing agents of zinc and iron, and energy consumption is greatly reduced. Generally, for the direct zinc and iron smelting process of zinc-containing soot in a steel plant, the coal consumption is about 650-800 kg/t-zinc-containing soot, and the smelting temperature needs 1600 ℃; the invention develops a low-melting-point slag type by adding the high-heat-value zinc-containing paint slag, and can reduce the coal consumption to 200 kg-400 kg/t-zinc-containing soot by oxygen-enriched smelting.
2) The invention solves the problem that valuable metals in zinc-containing paint slag and zinc-containing ash in steel plants cannot be efficiently recycled in one step, and simultaneously, the zinc ingot and pig iron products are directly obtained by separating and purifying zinc-containing and iron-containing hazardous waste in one step through oxygen-enriched smelting, thereby greatly shortening the existing process flow, increasing the energy utilization rate and reducing the carbon emission. Meanwhile, the harmless treatment of the zinc-containing paint slag and the zinc-containing soot of a steel mill can be realized.
3) The conventional process adopts a silicon-calcium-magnesium ternary slag form which has high melting point, so that sufficient coal needs to be added to ensure the melting temperature, and the invention constructs CaO-SiO in the melting process 2 -MgO-Na 2 O-CaF 2 The five-element slag type can obtain better fluidity while reducing the melting point of the slag phase, thereby realizing the aim of smelting the zinc-containing soot at low temperature.
4) According to the invention, the silicate structure is destroyed by adding the sodium salt, the release and reduction of zinc are promoted, the smelting efficiency is improved, and the zinc is reduced into the flue gas as much as possible. Meanwhile, fe-O bonds in FeO can be weakened, so that iron oxide is more easily reduced by carbon, the iron oxide separation is promoted, the zinc in the zinc ferrite is further released, the reduction rate is accelerated, and the recovery rate of the zinc is increased;
5) The invention can reduce the melting point and viscosity of the slag and realize low-temperature smelting through the synergistic action of the villiaumite and the sodium salt.
Drawings
FIG. 1 is a flow chart of the treatment method of zinc-containing soot and zinc-containing paint slag in a steel mill.
FIG. 2 shows CaO-SiO of example 1 2 -MgO-Na 2 O-CaF 2 Five-element slag phase diagram.
Detailed Description
The present invention will be described in detail with reference to examples. It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict. The percentages referred to are percentages by mass, unless otherwise specified.
Example 1
TABLE 1 Main chemical composition of zinc-containing fly ash of 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 main chemical composition of zinc-containing paint slag
| Element(s) | Fe | Zn | Si | Ca | Mg | C | H | Lower calorific value |
| Content/wt% | 13.6 | 12.7 | 2.4 | 0.8 | 0.4 | 34.2 | 3.52 | 3100kcal/kg |
In this example, the composition of the zinc-containing soot and the zinc-containing paint slag in the steel plant are shown in tables 1 and 2, respectively, and referring to fig. 1, the specific treatment method is as follows:
(1) Mixing the zinc-containing ash and the zinc-containing paint slag in a steel mill according to the proportion of 2;
(2) Uniformly mixing the mixture, anthracite, sodium carbonate and calcium fluoride to obtain a mixed material;
wherein the addition amount of sodium carbonate is 3% of the mixture, and the addition amount of calcium fluoride is 1% of the mixture; the addition amount of the anthracite is 15 percent of the mixture; the material is prepared by natural alkalinity (CaO + MgO)/(SiO) 2 ) I.e., 0.8, is within the optimum range, so no additional slag former is required.
(3) Adding the mixed material into a smelting furnace, introducing oxygen-enriched air, and smelting to obtain zinc-enriched flue gas and molten slag and molten iron which are distributed up and down;
wherein the smelting temperature is 1400 ℃, the smelting time is 60min, and the reducing atmosphere is CO/CO 2 =1.6 (i.e. CO, CO) 2 The molar ratio of (b), the oxygen concentration of the oxygen-enriched air is 80vol%, and the introduction amount is based on 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 the zinc vapor is 12vol%.
(4) Inputting the zinc-rich flue gas from the top of the furnace into a lead-rain condenser to be condensed to 500 ℃ to obtain a zinc ingot product with the direct zinc yield of 99.2 percent and the zinc grade of 99.6 percent;
the molten iron is discharged to obtain a pig iron product containing 95 percent of iron and 2.5 percent of carbon, and the iron recovery rate reaches 97 percent.
Carrying out water quenching treatment on the molten slag to obtain water quenched slag; wherein, the burning rate of organic matters in the zinc-containing paint slag is more than 99.9 percent, the vitrification rate is more than 97 percent, the iron content is 2.48 percent, and the zinc content is 0.6 percent.
Comparative example 1
Example 1 was repeated with the only difference that: no sodium carbonate 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 the zinc vapor is 12vol%. A zinc ingot product with a direct zinc yield of 95% and a zinc grade of 99.5%; however, the molten slag is not completely molten, slag and iron separation cannot be realized, natural gas is adopted for heat supplement, the smelting temperature is further increased to 1550 ℃, slag and iron separation can be realized, molten iron is discharged, 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 burning rate of organic matters in the zinc-containing paint slag is more than 99.9 percent, the vitrification rate is more than 98 percent, the iron content is 4.96 percent, and the zinc content is 3.89 percent.
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 the zinc steam is 12vol%; a zinc ingot product with a direct zinc yield of 98.5% and a zinc grade of 99.4%; and discharging the molten iron to obtain a pig iron product containing 91% of iron and 4.5% of carbon, wherein the iron recovery rate reaches 85%.
Carrying out water quenching treatment on the molten slag to obtain water quenched slag; wherein, the burning rate of organic matters in the zinc-containing paint slag is more than 99.9 percent, the vitrification rate is more than 97 percent, the iron content is 9,46 percent, and the zinc content is 1.16 percent. The production status indicates that the slag has too high viscosity and is difficult to discharge, and the iron content of the slag is higher.
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 the zinc steam is 12vol%; a zinc ingot product with a zinc direct yield of 96% and a zinc grade of 99.2%; slag is not completely melted, slag and iron separation cannot be realized, natural gas is adopted for supplementing heat, the melting temperature is further increased to 1500 ℃, slag and iron separation can be realized, molten iron is discharged, 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 burning rate of organic matters in the zinc-containing paint slag is more than 99.9 percent, the vitrification rate is more than 98 percent, the iron content is 0.8 percent, and the zinc content is 3.1 percent.
Comparative example 4
Example 1 was repeated with the only difference that: calcium fluoride is not added, and the adding amount of sodium carbonate is controlled to be 10 percent of the mixture.
The results show that the temperature of the zinc-rich flue gas at the furnace top outlet is 1300 ℃, and the concentration of the zinc vapor is 12vol%; a zinc ingot product with a direct zinc yield of 78% and a zinc grade of 96.5%; the pig iron product contains 89% of iron and 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 percent, the vitrification rate is more than 97 percent, the iron content is 8.43 percent, and the zinc content is 14.22 percent. The test results show that the furnace condition is seriously deteriorated due to the excessive addition of sodium carbonate, and the zinc recovery rate is remarkably reduced due to the weakening of the reducing atmosphere.
Comparative example 5
Example 1 was repeated with the only difference that: calcium fluoride is not added, and the smelting time is 90min.
The results show that the temperature of the zinc rich flue gas at the furnace top outlet is 1300 ℃ and the concentration of zinc vapour is 12vol%.
A zinc ingot product with a direct zinc yield of 99.2% and a 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 burning rate of organic matters in the zinc-containing paint slag is more than 99.9 percent, the vitrification rate is more than 97 percent, the iron content is 3.87 percent, and the zinc content is 0.62 percent. 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: no sodium carbonate or calcium fluoride is added, and the smelting temperature is 1550 ℃.
The results show that the temperature of the zinc rich flue gas at the furnace top outlet is 1300 ℃ and the concentration of zinc vapour is 12vol%.
A zinc ingot product with the direct zinc yield of 97.4 percent and the zinc grade of 98.3 percent;
the pig iron product contains 93% of iron and 3.1% of carbon, and the iron recovery rate reaches 82%.
The burning rate of organic matters in the zinc-containing paint slag is more than 99.9 percent, the vitrification rate is more than 97 percent, the iron content is 10.4 percent, and the zinc content is 2.1 percent.
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 the zinc vapor is 12vol%.
A zinc ingot product with the direct zinc yield of 97.6 percent and the zinc grade of 98.7 percent;
the pig iron product contains 94% of iron and 2.8% of carbon, and the iron recovery rate reaches 95%.
The burning rate of organic matters in the zinc-containing paint slag is more than 99.9 percent, the vitrification rate is more than 97 percent, the iron content is 3.82 percent, and the zinc content is 1.75 percent.
Comparative example 8
Comparative example 5 was repeated with the only difference that: and raising the smelting temperature to 1550 ℃.
The concentration of zinc vapor in the flue gas at the outlet of the furnace top is 10.8vol%. And (4) obtaining a zinc ingot product with the direct zinc yield of 99% and the zinc grade of 99.6%. At the same time, iron was tapped off in the form of pig iron, giving 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 percent, the vitrification rate is more than 95 percent, the iron content is 1.66 percent, and the zinc content is 0.39 percent.
The comparison shows that the treatment method of the invention can realize the low energy consumption and high quality treatment of the zinc-containing ash and the zinc-containing paint slag in steel mills.
Example 2
Example 1 was repeated with the only difference that: the addition amount of the sodium carbonate is 5 percent of the mixture, and the addition amount of the calcium fluoride is 2 percent of the mixture.
The concentration of zinc vapor in the flue gas at the outlet of the furnace top is 12.2vol%. In the step (4), the direct zinc yield 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-quenched slag is more than 99.9 percent, the vitrification rate is more than 97 percent, the iron content is 0.8 percent, and the zinc content is 0.1 percent.
Comparative example 9
Example 1 was repeated with the only difference that: the addition amount of sodium carbonate is 12 percent of the mixture.
The concentration of zinc vapor in the flue gas at the outlet of the furnace top 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%. Meanwhile, the iron is discharged in the form of pig iron, so that 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 percent, the vitrification rate is more than 97 percent, the iron content is 10.36 percent, and the zinc content is 7.02 percent.
The above examples are set forth so that this disclosure will be understood in all instances to be considered illustrative and not restrictive, and that various modifications and equivalent arrangements may be devised by those skilled in the art after reading this disclosure and are intended to be included within the scope of the appended claims.
Claims (10)
1. A method for the cooperative treatment 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 villiaumite to obtain a mixed material;
wherein the zinc-containing mixture is formed by mixing steel mill zinc-containing soot and zinc-containing paint slag; the addition amount of the reducing agent is 10-30wt% of the zinc-containing mixture, the addition amount of the slagging agent 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-enriched flue gas, upper and lower layered molten slag and molten iron;
wherein during smelting, controlling CO and CO in the smelting furnace 2 The molar ratio of (A) is more than 1.2;
s3, condensing the zinc-rich flue gas to obtain metal zinc.
2. The synergistic treatment method according to claim 1, wherein in S1, the sodium salt is one or more of sodium sulfate, sodium carbonate and sodium chloride; the fluorine salt is one or more of sodium fluoride, potassium fluoride, magnesium fluoride and calcium fluoride.
3. The co-processing method according to claim 1, wherein the concentration of oxygen-enriched air in S2 is > 40vol%.
4. The co-processing method according to claim 1, characterized in that in S2, the flue gas temperature at the flue gas outlet of the smelting furnace is controlled to be > 1000 ℃.
5. The CO-processing method according to claim 1, wherein in S2, during the smelting, CO and CO in the smelting furnace are controlled 2 Is 1.4 to 1.8.
6. The co-processing method according to claim 1, wherein in S3, a lead rain condenser is used to condense the zinc-rich flue gas, so that the temperature of the zinc-rich flue gas is reduced to below 500 ℃.
7. The cooperative processing method according to any one of claims 1 to 6, wherein in S1, the reducing agent is one or more of carbon concentrate, waste activated carbon, coking coal, anthracite, carbon concentrate and coke; the slagging agent is one or more of quartz stone, limestone and dolomite.
8. The synergistic treatment method according to any one of claims 1 to 6, wherein in S1, in the zinc-containing fly ash of a steel mill, the Zn content is 10 to 50wt%, and the Fe content is 20 to 50wt%; in the zinc-containing paint slag, the Zn content is 1-50 wt%, and the Fe content is 1-20 wt%.
9. The synergistic treatment method according to any one of claims 1 to 6, wherein in S1, the zinc-containing mixture is prepared by mixing steel mill zinc-containing soot and zinc-containing paint slag according to a mass ratio of 1-5.
10. The co-processing method according to any one of claims 1 to 6, wherein in S2, the melting time is 0.5 to 2 hours.
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