CN113862473A - Hydrogen metallurgy fuming zinc extraction method for zinc-containing material - Google Patents
Hydrogen metallurgy fuming zinc extraction method for zinc-containing material Download PDFInfo
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- CN113862473A CN113862473A CN202110953749.8A CN202110953749A CN113862473A CN 113862473 A CN113862473 A CN 113862473A CN 202110953749 A CN202110953749 A CN 202110953749A CN 113862473 A CN113862473 A CN 113862473A
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- zinc
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 122
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 122
- 239000011701 zinc Substances 0.000 title claims abstract description 122
- 239000000463 material Substances 0.000 title claims abstract description 94
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 239000001257 hydrogen Substances 0.000 title claims abstract description 77
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 77
- 238000005272 metallurgy Methods 0.000 title claims abstract description 26
- 238000000605 extraction Methods 0.000 title claims description 19
- 239000002893 slag Substances 0.000 claims abstract description 80
- 238000000034 method Methods 0.000 claims abstract description 78
- 239000007789 gas Substances 0.000 claims abstract description 55
- 229910052751 metal Inorganic materials 0.000 claims abstract description 38
- 239000002184 metal Substances 0.000 claims abstract description 38
- 238000003723 Smelting Methods 0.000 claims abstract description 30
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000003546 flue gas Substances 0.000 claims abstract description 29
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002699 waste material Substances 0.000 claims abstract description 21
- 239000011787 zinc oxide Substances 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 238000007599 discharging Methods 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 230000001590 oxidative effect Effects 0.000 claims abstract description 6
- 238000010791 quenching Methods 0.000 claims abstract description 6
- 230000000171 quenching effect Effects 0.000 claims abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 46
- 239000001301 oxygen Substances 0.000 claims description 46
- 229910052760 oxygen Inorganic materials 0.000 claims description 46
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 24
- 230000002829 reductive effect Effects 0.000 claims description 15
- 239000000428 dust Substances 0.000 claims description 14
- 238000002844 melting Methods 0.000 claims description 14
- 230000008018 melting Effects 0.000 claims description 14
- 229910052742 iron Inorganic materials 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 10
- 229910052791 calcium Inorganic materials 0.000 claims description 10
- 239000011575 calcium Substances 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- 229910052710 silicon Inorganic materials 0.000 claims description 10
- 239000010703 silicon Substances 0.000 claims description 10
- 238000009854 hydrometallurgy Methods 0.000 claims description 8
- 238000011084 recovery Methods 0.000 claims description 8
- 238000002386 leaching Methods 0.000 claims description 6
- 239000007921 spray Substances 0.000 claims description 5
- 238000011272 standard treatment Methods 0.000 claims description 5
- 239000002918 waste heat Substances 0.000 claims description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052799 carbon Inorganic materials 0.000 abstract description 9
- 239000003245 coal Substances 0.000 abstract description 8
- 239000002803 fossil fuel Substances 0.000 abstract description 4
- 238000003763 carbonization Methods 0.000 abstract 1
- 150000002431 hydrogen Chemical class 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 238000004519 manufacturing process Methods 0.000 description 10
- 230000002159 abnormal effect Effects 0.000 description 8
- 239000011261 inert gas Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000004575 stone Substances 0.000 description 7
- 238000007664 blowing Methods 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000009856 non-ferrous metallurgy Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000000126 substance Substances 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
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
- C22B5/12—Dry methods smelting of sulfides or formation of mattes by gases
-
- 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
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/34—Obtaining zinc oxide
-
- 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
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
- C22B5/16—Dry methods smelting of sulfides or formation of mattes with volatilisation or condensation of the metal being produced
-
- 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
Abstract
The invention discloses a method for extracting zinc by fuming in hydrogen metallurgy of a zinc-containing material. Adding a zinc-containing material or a zinc-containing material and an auxiliary material into a fuming furnace, and introducing hydrogen and combustion-supporting gas for heating and temperature raising; when the temperature of the molten pool reaches 1000-1300 ℃; increasing the introduction amount of hydrogen gas entering the furnace, carrying out reduction converting reaction at the temperature, reducing zinc oxide into elemental metal in the reduction converting reaction, volatilizing the elemental metal in the form of metal steam, oxidizing the metal steam again in the upper space of the furnace chamber, entering a flue gas pipeline along with process flue gas, and treating and recovering to obtain a finished product zinc oxide; discharging the generated smelting waste slag through a slag hole, and piling or externally selling the slag after water quenching; and the generated process flue gas is treated and then is emptied. The invention replaces fossil fuel pulverized coal with clean and efficient hydrogen, and replaces the traditional carbon metallurgy process with the hydrogen metallurgy concept, thereby realizing the non-carbonization fire method smelting of zinc-containing materials.
Description
The technical field is as follows:
the invention relates to a pyrometallurgical method in the field of nonferrous metal metallurgy, in particular to a zinc extracting method by fuming in hydrogen metallurgy of zinc-containing materials.
Secondly, background art:
the common zinc-containing materials in the heavy nonferrous metallurgy industry include zinc-containing intermediate slag produced in the lead smelting process, leaching slag produced in the zinc hydrometallurgy process or other zinc-containing metallurgical slag materials, including partial zinc oxide raw ore and the like.
The fuming furnace is a common technical device for non-ferrous metal smelting. At present, the recovery of zinc in heavy metal metallurgy intermediate slag at home and abroad is mostly realized by adopting a fuming furnace to realize reduction fuming recovery. The essence of the general fuming recovery process is a reduction volatilization process, namely, air and pulverized coal are blown into slag in a fuming furnace, the pulverized coal generates heat and carbon monoxide after being combusted, the slag is kept at high temperature, compounds in the slag, free metal oxides mainly comprising lead and zinc, and the like are reduced into steam of simple substance metal, the metal steam rises to the upper space of the furnace and meets CO in process flue gas2Or the air sucked by the upper tertiary air port is oxidized into metal oxide again and is captured and recovered in a dust collecting system in a smoke state.
The addition amount of the pulverized coal in the prior art process is high, and CO is finally added after the pulverized coal is combusted2And is discharged to the atmosphere. Meanwhile, the reduction of the carbon emission amount for reducing the use of industrial internalized fossil fuels is a problem to be urgently faced in the future.
Third, the invention
The technical problem to be solved by the invention is as follows: according to the problems which need to be solved urgently for reducing the use of fossil fuels in the industry and reducing the carbon emission at home and abroad at present, the clean and efficient hydrogen replaces fossil fuel pulverized coal, and the hydrogen metallurgy concept replaces the traditional carbon metallurgy process at present, so that the non-carbon fire method smelting of zinc-containing materials is realized; namely, the invention provides a method for extracting zinc by fuming in hydrogen metallurgy of a zinc-containing material.
In order to solve the problems, the invention adopts the technical scheme that:
the invention provides a zinc extraction method by hydrogen metallurgy fuming of a zinc-containing material, which comprises the following steps:
a. taking a zinc-containing material or the zinc-containing material and an auxiliary material as raw materials, wherein the zinc-containing material is crude lead pyrometallurgical reduced slag, leaching slag produced in a zinc hydrometallurgy process or zinc-containing oxidized ore raw ore, and the auxiliary material is at least one of iron ore, quartz and pebbles;
when the raw material is a zinc-containing material, the charging amount of the material is based on that the upper surface of a molten pool formed after melting is 700-1500 mm above the tuyere area of the fuming furnace, and the weight ratio of the iron, silicon and calcium in the smelting waste slag produced by reduction smelting in the fuming furnace reaches FeO: SiO 22：CaO＝(25～35)：(25～35)：(0～30)；
When the raw materials are zinc-containing materials and auxiliary materials, the proportion of the auxiliary materials is that the weight ratio of iron, silicon and calcium in smelting waste slag produced by reduction smelting in a fuming furnace reaches FeO: SiO 22: CaO (25-35): (25-35): (0-30), wherein the total material charging amount is 700-1500 mm above the tuyere area of the upper surface of a molten pool formed after melting;
b. adding a zinc-containing material or a zinc-containing material and an auxiliary material into a fuming furnace, starting to introduce hydrogen and combustion-supporting gas for heating and temperature raising when the total material addition amount reaches the tuyere area of the fuming furnace to be less than or equal to 200mm, controlling the pressure of gas entering the furnace to be 0.01-0.4 MPa (the gas entering the furnace is continuously increased along with the continuous rise of the liquid level of the material in the furnace entering process), controlling the time to be 60-100 min to complete the material entering the furnace, and controlling the temperature of a molten pool to be 1000-1300 ℃;
in the process of the operation, if the furnace temperature is too high or other abnormal production conditions occur, inert gases (such as nitrogen and argon) are introduced to dilute the oxygen concentration for treatment;
c. when the charging is finished and the temperature of a molten pool reaches 1000-1300 ℃, increasing the introduction amount of hydrogen entering the furnace, controlling the gas pressure to be 0.01-0.4 MPa, carrying out reduction converting reaction for 90-180 min, reducing oxides of zinc in a high-temperature molten pool into elemental metal and volatilizing the elemental metal in the form of metal steam in the reduction converting process, separating the elemental metal from the molten pool, oxidizing the metal steam again in the upper space of the furnace chamber, then entering a flue gas pipeline along with process flue gas, collecting and recovering the metal steam from a dust collecting system in the form of flue gas, and collecting and recovering the flue gas which is finished zinc oxide;
in the process of the operation, if the furnace temperature is too high or other abnormal production conditions occur, inert gases (such as nitrogen and argon) are introduced to dilute the oxygen concentration for treatment;
d. the smelting waste slag reaching the fuming converting end point is discharged through a slag hole, and is stacked or sold outside after water quenching;
e. in the slag discharging process, the amount of gas fed into the furnace is gradually reduced according to the reduction of the liquid level of the molten hot slag in the furnace, and the gas supply is stopped until the discharge of the molten hot slag in the furnace is finished;
f. the generated process flue gas is subjected to waste heat recovery and dust collection, and the harmful gas in the tail gas is subjected to standard treatment and reuse treatment without utilizing hydrogen and then is exhausted.
According to the above-mentioned method for extracting zinc by means of hydrometallurgical fuming of zinc-containing material, the zinc-containing material is added into a fuming furnace in the form of one or both of high-temperature molten liquid and cold material in step a; the cold material is a blocky cold material or a granular cold material.
According to the above-mentioned method for extracting zinc by fuming in hydrometallurgy of the zinc-containing material, the weight percentage content of zinc element in the zinc-containing material in step a is 5-40%.
According to the method for extracting zinc by fuming in the hydrometallurgy of the zinc-containing material, the combustion-supporting gas in the step b and the step c is oxygen, compressed air or oxygen-enriched compressed air, and the oxygen concentration in the combustion-supporting gas is 5-100%.
According to the above method for extracting zinc by hydrogen metallurgy fuming of zinc-containing materials, the molar ratio of hydrogen in the furnace gas to oxygen in the combustion-supporting gas in the step b is 2-4: 1.
according to the above method for extracting zinc by hydrogen metallurgy fuming of zinc-containing materials, the molar ratio of hydrogen in hydrogen gas in the furnace gas to oxygen in the combustion-supporting gas in the step c is 3-5: 1.
according to the above-mentioned zinc extraction method by hydrogen metallurgy fuming of zinc-containing materials, the introduction modes of hydrogen and combustion-supporting gas in the steps b and c both adopt a multi-channel tuyere mode or a gas spray gun mode.
According to the above-mentioned zinc-containing material hydrogen metallurgy fuming zinc extraction method, in the step b and the step c, the hydrogen gas introduction amount of the single tuyere of the fuming furnace is 0-1500 Nm3/h。
According to the above-mentioned hydrometallurgical fuming zinc extraction method of the zinc-containing material, the weight percentage content of zinc in the finished zinc oxide in step c is 60-75%.
According to the above-mentioned method for extracting zinc by fuming in hydrometallurgy of zinc-containing materials, the weight percentage content of zinc in the smelting waste slag in the step d is less than or equal to 2%.
The technical scheme of the invention is that hydrogen and combustion-supporting gas are introduced into the fuming furnace, and the furnace is responsible for providing and creating a reductive chemical reaction atmosphere required by reduction and fuming of materials in a molten pool besides combustion heat supply; the fuming zinc extraction process operation is divided furnace periodic intermittent operation, namely feeding, fuming, deslagging, slag re-feeding, fuming again, deslagging again, and periodic repeated operation.
The invention has the following positive beneficial effects:
1. in the technical scheme of the invention, the heating melting and the reduction of the zinc-containing material are both H2The realization that the carbon emission is greatly reduced:
according to the technical scheme, the traditional process of carbon metallurgy is changed into hydrogen metallurgy, hydrogen is adopted for combustion heat supply for heating and melting and heat preservation of furnace burden, hydrogen is adopted for material reduction as a reducing agent, carbon is not newly introduced in the process, and emission of greenhouse gas in the process is greatly reduced. Therefore, the method for reducing and fuming the zinc-containing material greatly reduces the carbon emission, belongs to clean metallurgy in the true sense, is beneficial to environmental protection, and has remarkable social benefit.
2. In the technical scheme of the invention, the hydrogen metallurgy has high heat utilization rate, high heat transfer efficiency, high reduction speed and high productivity:
in the technical scheme of the invention, the reaction temperature point of hydrogen metallurgy is lower, more heat can be transmitted into a material layer or a molten pool under the same combustion space temperature, so that the heating melting and reduction speed of the zinc-containing material is accelerated, the process energy consumption is reduced, and the productivity can be greatly improved on the premise of the same heat transfer quantity.
3. In the technical scheme of the invention, the hydrogen metallurgy reduction fuming product of the zinc-containing material has high quality and good production stability:
the heat supply fuel and the reducing agent for reducing and fuming the zinc-containing material by the traditional process both adopt pulverized coal, and cheap pulverized coal is introduced10-30% of impurity components, wherein the impurity components can not avoid generating certain negative effects on the product quality and also have certain effects on the thermal stability of a molten pool. The process of the invention adopts pure H2As fuel and reducing agent, the method achieves the technical purposes of high quality and good production stability of the reduction fuming product.
The fifth embodiment is as follows:
the invention is further illustrated by the following examples, which do not limit the scope of the invention.
Example 1:
the invention relates to a zinc extraction method by hydrogen metallurgy fuming of zinc-containing materials, which comprises the following detailed steps:
a. taking the crude lead pyrometallurgical reduced slag as a raw material (the weight percentage of zinc in the crude lead pyrometallurgical reduced slag is 12 percent), and stones as auxiliary materials;
the stone addition amount is that the weight ratio of the iron, silicon and calcium in the smelting waste slag produced by reduction smelting in the fuming furnace reaches FeO: SiO 22: CaO 30: 28: 14, taking the total material addition as the standard, and taking the upper surface of a molten pool formed after melting to be 1000mm above a tuyere zone as the standard;
b. after the crude lead pyrometallurgical reduced slag is produced, preserving heat through an electric heating front bed, then discharging the slag into a molten hot liquid slag bag, lifting the slag bag to a fuming furnace workshop through a crane, adding hot slag into the fuming furnace from a fuming furnace charging port, starting a gas supply valve of hydrogen and oxygen-enriched compressed air when the hot slag enters a fuming furnace tuyere zone below 100mm, starting to introduce the hydrogen and the oxygen-enriched compressed air for heating (the introduction modes of the hydrogen and the oxygen-enriched compressed air both adopt a multi-channel tuyere mode), controlling the gas pressure of the hydrogen and the oxygen-enriched compressed air to be 0.06MPa, and simultaneously controlling the molar ratio of hydrogen in the hydrogen and oxygen in the oxygen-enriched compressed air to be 2: 1; when the adding amount of the slag in the fuming furnace reaches 1000mm in the tuyere area, stopping adding hot slag in the crude lead pyrometallurgical reduction furnace, adding 120Kg of pebbles into each furnace, and adding the pebbles into the fuming furnace; the hydrogen is soaked in the molten pool, burned and heated for 90min, and the temperature of the molten pool, namely the furnace temperature, reaches 1100 ℃;
(in the process of the operation, if the furnace temperature is too high or other abnormal production conditions occur, inert gas nitrogen is introduced to dilute the oxygen concentration for treatment);
c. when the charging is finished and the temperature of a molten pool reaches 1100 ℃, continuously introducing hydrogen and oxygen-enriched compressed air, controlling the gas pressure of the hydrogen and the oxygen-enriched compressed air to be 0.06MPa, increasing the molar ratio of hydrogen in the hydrogen to oxygen in the oxygen-enriched compressed air to be 4:1, reducing fuming blowing for 120min under the condition, reducing zinc into elemental metal in a high-temperature molten pool in the reducing blowing process, volatilizing the elemental metal in the form of metal steam, separating the elemental metal steam from the molten pool, oxidizing the metal steam again in the upper space of a furnace chamber, then introducing the metal steam into a flue gas pipeline along with process flue gas, and carrying out sectional cooling and dust collection on the flue gas by the process flue gas pipeline respectively provided with a water spray tower, a surface cooler and a bag dust collector to recover the zinc oxide product (the weight percentage content of zinc in the zinc oxide product is 66% on average);
(in the process of the operation, if the furnace temperature is too high or other abnormal production conditions occur, inert gas nitrogen is introduced to dilute the oxygen concentration for treatment);
d. the smelting waste slag reaching the fuming converting end point is discharged through a slag hole, and is stacked or sold outside after water quenching (the weight ratio of the iron, the silicon and the calcium in the smelting waste slag is FeO to SiO)2: CaO 30: 28: 14, the weight percentage content of zinc in the waste slag is 0.8 percent);
e. in the slag discharging process, the amount of gas fed into the furnace is gradually reduced according to the reduction of the liquid level of the molten hot slag in the furnace, and the gas supply is stopped until the discharge of the molten hot slag in the furnace is finished;
f. the generated process flue gas is subjected to waste heat recovery and dust collection, and the harmful gas in the tail gas is subjected to standard treatment and reuse treatment without utilizing hydrogen and then is exhausted.
Example 2:
the invention relates to a zinc extraction method by hydrogen metallurgy fuming of zinc-containing materials, which comprises the following detailed steps:
a. leaching residues produced in the zinc hydrometallurgy process are used as raw materials (the weight percentage content of zinc in the leaching residues produced in the zinc hydrometallurgy process is 25 percent), and stones are used as auxiliary materials;
the stone addition amount is that the weight ratio of the iron, silicon and calcium in the smelting waste slag produced by reduction smelting in the fuming furnace reaches FeO: SiO 22: CaO 28: 28: 14, taking the total material addition as the standard, and taking the upper surface of a molten pool formed after melting to be 900mm above a tuyere zone as the standard;
b. dehydrating and drying leached slag produced in the wet-process zinc smelting process, adding the leached slag into a pyrometallurgical electric furnace for heating and melting, discharging the molten slag into a molten hot liquid slag bag after melting, lifting the slag bag to a fuming furnace workshop through a crane, adding hot slag into the furnace from a fuming furnace charging port, opening a gas supply valve of hydrogen and oxygen-enriched compressed air when the hot slag enters a fuming furnace tuyere zone to be 150mm below, starting introducing the hydrogen and the oxygen-enriched compressed air for heating (the introduction modes of the hydrogen and the oxygen-enriched compressed air both adopt a multi-channel tuyere mode), controlling the gas pressure of the hydrogen and the oxygen-enriched compressed air to be 0.06MPa, and simultaneously controlling the molar ratio of hydrogen in the hydrogen to oxygen in the oxygen-enriched compressed air to be 2: 1; when the addition amount of the slag in the fuming furnace reaches 900mm of the tuyere area, stopping adding the hot slag of the leaching slag, and adding 200kg of stones into each furnace into the fuming furnace; the hydrogen is soaked in the molten pool, burned and heated for 90min, and the temperature of the molten pool, namely the furnace temperature, reaches 1000 ℃;
(in the process of the operation, if the furnace temperature is too high or other abnormal production conditions occur, inert gas nitrogen is introduced to dilute the oxygen concentration for treatment);
c. when the charging is finished and the temperature of a molten pool reaches 1000 ℃, continuously introducing hydrogen and oxygen-enriched compressed air, controlling the gas pressure of the hydrogen and the oxygen-enriched compressed air to be 0.06MPa, increasing the molar ratio of hydrogen in the hydrogen to oxygen in the oxygen-enriched compressed air to be 4:1, reducing fuming blowing for 180min under the condition, reducing zinc into elemental metal in a high-temperature molten pool in the reducing blowing process, volatilizing the elemental metal in the form of metal steam, separating the elemental metal steam from the molten pool, oxidizing the metal steam again in the upper space of a furnace chamber, then introducing the metal steam into a flue gas pipeline along with process flue gas, and carrying out sectional cooling and dust collection on the flue gas by the process flue gas pipeline respectively provided with a water spray tower, a surface cooler and a bag dust collector to recover the zinc oxide product (the weight percentage content of zinc in the zinc oxide product is 68% on average);
(in the process of the operation, if the furnace temperature is too high or other abnormal production conditions occur, inert gas nitrogen is introduced to dilute the oxygen concentration for treatment);
d. the smelting waste slag reaching the fuming converting end point is discharged through a slag hole, and is stacked or sold outside after water quenching (the weight ratio of the iron, the silicon and the calcium in the smelting waste slag is FeO to SiO)2: CaO 28: 28: 14, the weight percentage content of zinc in the waste slag is 1.6 percent);
e. in the slag discharging process, the amount of gas fed into the furnace is gradually reduced according to the reduction of the liquid level of the molten hot slag in the furnace, and the gas supply is stopped until the discharge of the molten hot slag in the furnace is finished;
f. the generated process flue gas is subjected to waste heat recovery and dust collection, and the harmful gas in the tail gas is subjected to standard treatment and reuse treatment without utilizing hydrogen and then is exhausted.
Example 3:
the invention relates to a zinc extraction method by hydrogen metallurgy fuming of zinc-containing materials, which comprises the following detailed steps:
a. taking zinc-containing oxidized ore raw ore as a raw material (the weight percentage content of zinc in the zinc-containing oxidized ore raw ore is 30 percent) and pebbles as an auxiliary material;
the stone addition amount is that the weight ratio of the iron, silicon and calcium in the smelting waste slag produced by reduction smelting in the fuming furnace reaches FeO: SiO 22: CaO 30: 28: 15, taking the total material addition as the standard, and taking the upper surface of a molten pool formed after melting to be positioned 800mm above the tuyere zone as the standard;
b. firstly, heating and melting zinc-containing oxidized ore raw ore in a pyrogenic process electric melting furnace, discharging the molten zinc-containing oxidized ore raw ore into a molten hot liquid slag ladle, lifting the slag ladle to a fuming furnace workshop by a crane, adding hot slag into the furnace from a fuming furnace charging port, starting a gas supply valve of hydrogen and oxygen-enriched compressed air when the hot slag is below 120mm of a fuming furnace tuyere area, starting to introduce hydrogen and oxygen-enriched compressed air for heating (the introduction modes of the hydrogen and the oxygen-enriched compressed air both adopt a multi-channel tuyere mode), controlling the gas pressure of the hydrogen and the oxygen-enriched compressed air to be 0.06MPa, and simultaneously controlling the molar ratio of hydrogen in the hydrogen and oxygen in the oxygen-enriched compressed air to be 2: 1; when the adding amount of the slag in the fuming furnace reaches 800mm of the tuyere area, stopping adding the raw materials, and adding 150kg of stones into each furnace into the fuming furnace; the hydrogen is soaked in the molten pool, burned and heated for 90min, and the temperature of the molten pool, namely the furnace temperature, reaches 1200 ℃;
(in the process of the operation, if the furnace temperature is too high or other abnormal production conditions occur, inert gas nitrogen is introduced to dilute the oxygen concentration for treatment);
c. when the charging is finished and the temperature of a molten pool reaches 1200 ℃, continuously introducing hydrogen and oxygen-enriched compressed air, controlling the gas pressure of the hydrogen and the oxygen-enriched compressed air to be 0.06MPa, increasing the molar ratio of hydrogen in the hydrogen to oxygen in the oxygen-enriched compressed air to be 4:1, reducing fuming blowing for 180min under the condition, reducing zinc into elemental metal in a high-temperature molten pool in the reducing blowing process, volatilizing the elemental metal in the form of metal steam, separating the elemental metal steam from the molten pool, oxidizing the metal steam again in the upper space of a furnace chamber, then introducing the metal steam into a flue gas pipeline along with process flue gas, and carrying out sectional cooling and dust collection on the flue gas by the process flue gas pipeline respectively provided with a water spray tower, a surface cooler and a bag dust collector so as to recover the zinc (the weight percentage content of zinc in the zinc oxide product is averagely 70%);
(in the process of the operation, if the furnace temperature is too high or other abnormal production conditions occur, inert gas nitrogen is introduced to dilute the oxygen concentration for treatment);
d. the smelting waste slag reaching the fuming converting end point is discharged through a slag hole, and is stacked or sold outside after water quenching (the weight ratio of the iron, the silicon and the calcium in the smelting waste slag is FeO to SiO)2: CaO 30: 28: 15, the weight percentage content of zinc in the waste slag is 1.8 percent);
e. in the slag discharging process, the amount of gas fed into the furnace is gradually reduced according to the reduction of the liquid level of the molten hot slag in the furnace, and the gas supply is stopped until the discharge of the molten hot slag in the furnace is finished;
f. the generated process flue gas is subjected to waste heat recovery and dust collection, and the harmful gas in the tail gas is subjected to standard treatment and reuse treatment without utilizing hydrogen and then is exhausted.
Claims (10)
1. A method for extracting zinc by fuming in hydrogen metallurgy of a zinc-containing material is characterized by comprising the following steps:
a. taking a zinc-containing material or the zinc-containing material and an auxiliary material as raw materials, wherein the zinc-containing material is crude lead pyrometallurgical reduced slag, leaching slag produced in a zinc hydrometallurgy process or zinc-containing oxidized ore raw ore, and the auxiliary material is at least one of iron ore, quartz and pebbles;
when the raw material is a zinc-containing material, the charging amount of the material is based on that the upper surface of a molten pool formed after melting is 700-1500 mm above the tuyere area of the fuming furnace, and the weight ratio of the iron, silicon and calcium in the smelting waste slag produced by reduction smelting in the fuming furnace reaches FeO: SiO 22：CaO＝(25～35)：(25～35)：(0～30)；
When the raw materials are zinc-containing materials and auxiliary materials, the proportion of the auxiliary materials is that the weight ratio of iron, silicon and calcium in smelting waste slag produced by reduction smelting in a fuming furnace reaches FeO: SiO 22: CaO (25-35): (25-35): (0-30), wherein the total material charging amount is 700-1500 mm above the tuyere area of the upper surface of a molten pool formed after melting;
b. adding a zinc-containing material or a zinc-containing material and an auxiliary material into a fuming furnace, starting to introduce hydrogen and combustion-supporting gas for heating and temperature raising when the total material addition amount reaches a tuyere area of the fuming furnace of less than or equal to 200mm, controlling the pressure of the gas entering the furnace to be 0.01-0.4 MPa, controlling the gas entering the furnace for 60-100 min to complete material entering, and controlling the temperature of a molten pool to reach 1000-1300 ℃;
c. when the charging is finished and the temperature of a molten pool reaches 1000-1300 ℃, increasing the introduction amount of hydrogen entering the furnace, controlling the gas pressure to be 0.01-0.4 MPa, carrying out reduction converting reaction for 90-180 min, reducing oxides of zinc in a high-temperature molten pool into elemental metal and volatilizing the elemental metal in the form of metal steam in the reduction converting process, separating the elemental metal from the molten pool, oxidizing the metal steam again in the upper space of the furnace chamber, then entering a flue gas pipeline along with process flue gas, collecting and recovering the metal steam from a dust collecting system in the form of flue gas, and collecting and recovering the flue gas which is finished zinc oxide;
d. the smelting waste slag reaching the fuming converting end point is discharged through a slag hole, and is stacked or sold outside after water quenching;
e. in the slag discharging process, the amount of gas fed into the furnace is gradually reduced according to the reduction of the liquid level of the molten hot slag in the furnace, and the gas supply is stopped until the discharge of the molten hot slag in the furnace is finished;
f. the generated process flue gas is subjected to waste heat recovery and dust collection, and the harmful gas in the tail gas is subjected to standard treatment and reuse treatment without utilizing hydrogen and then is exhausted.
2. The process for the hydrometallurgical fuming extraction of zinc from a zinc containing material as claimed in claim 1, further characterized by: in the step a, the zinc-containing material is added into a fuming furnace in the form of one or two of high-temperature molten liquid and cold materials; the cold material is a blocky cold material or a granular cold material.
3. The process for the hydrometallurgical fuming extraction of zinc from a zinc containing material as claimed in claim 1, further characterized by: in the step a, the zinc element in the zinc-containing material accounts for 5-40% by weight.
4. The process for the hydrometallurgical fuming extraction of zinc from a zinc containing material as claimed in claim 1, further characterized by: in the step b and the step c, the combustion-supporting gas is oxygen, compressed air or oxygen-enriched compressed air, and the oxygen concentration in the combustion-supporting gas is 5-100%.
5. The process for the hydrometallurgical fuming extraction of zinc from a zinc containing material as claimed in claim 1, further characterized by: the molar ratio of the hydrogen element in the hydrogen in the furnace gas to the oxygen element in the combustion-supporting gas in the step b is 2-4: 1.
6. the process for the hydrometallurgical fuming extraction of zinc from a zinc containing material as claimed in claim 1, further characterized by: the molar ratio of the hydrogen element in the hydrogen in the furnace gas to the oxygen element in the combustion-supporting gas in the step c is 3-5: 1.
7. the process for the hydrometallurgical fuming extraction of zinc from a zinc containing material as claimed in claim 1, further characterized by: and c, introducing the hydrogen and the combustion-supporting gas in the step b and the step c in a multi-channel tuyere mode or a gas spray gun mode.
8. The process for the hydrometallurgical fuming extraction of zinc from a zinc containing material as claimed in claim 1, further characterized by: the hydrogen introduction amount of a single air inlet of the fuming furnace in the step b and the step c is 0-1500 Nm3/h。
9. The process for the hydrometallurgical fuming extraction of zinc from a zinc containing material as claimed in claim 1, further characterized by: and c, the zinc content of the finished product zinc oxide in percentage by weight is 60-75%.
10. The process for the hydrometallurgical fuming extraction of zinc from a zinc containing material as claimed in claim 1, further characterized by: d, the weight percentage content of zinc in the smelting waste slag is less than or equal to 2 percent.
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