CN107213774B - Flue gas desulfurization and resource utilization method based on smelting tailing slag - Google Patents
Flue gas desulfurization and resource utilization method based on smelting tailing slag Download PDFInfo
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Abstract
The invention discloses a flue gas desulfurization and resource utilization method based on smelting tailing slag, and belongs to the field of comprehensive utilization of waste slag and the technical field of industrial waste gas purification. Mixing smelting tailing slag containing iron, zinc, manganese, aluminum and other metals with water to prepare desulfurization slurry, and performing countercurrent contact reaction on the desulfurization slurry and flue gas to absorb SO in the flue gas2And catalytically oxidizing into sulfuric acid, leaching iron, zinc, manganese, aluminum and other elements in the slag by using the sulfuric acid, then adding an oxidizing solution to perform oxidation, hydrolysis and polymerization reactions, and performing resource production to obtain the polyferric flocculant. The flocculant can be used for treating enterprise wastewater. The method has the advantages of simple operation and low cost, not only has better flue gas desulfurization effect, but also can produce the polyferric flocculant in a recycling manner and improve the high-value recycling utilization level of the slag materials.
Description
Technical Field
The invention relates to a flue gas desulfurization and resource utilization method based on smelting tailing slag, belonging to the field of comprehensive utilization of waste slag and the technical field of industrial waste gas purification.
Technical Field
As mineral resources in China are rich, and as far as 2014, the resource reserves of copper ores are found out to be 9689.6 ten thousand in China, and the copper ores are widely distributed in China and relatively concentrated in provinces such as Tibet, Yunnan and Jiangxi. In recent years, the mining usage amount of mineral products in China is large, the copper-containing slag is produced by 958-1437 thousands of tons each year, and the red mud slag is 3000 thousands of tons. These slags are complex in composition, with copper-containing slags often containing valuable metals such as Fe, Zn, Ca, Mg, Mn, Al and small amounts of noble metals such as Ag, Au, with Fe content around 40%, much higher than the average industrial grade of iron ore of 29.1%, mainly fayalite (Fe)2SiO4) Fayalite (MgFeSiO)4) Magnetite (Fe)3O4) Etc., Al exists mainly in the form of aluminosilicate, and Cu exists mainly in the form of copper matte (CuFeS)2) The form exists; the red mud residue mainly contains Al, Fe, Ca, Si and the like, wherein Al in the red mud residue is mainly hydrated garnet (3 CaO. Al)2O3·SiO2·4H2O), calcium aluminosilicate (CaO. Al)2O3·2SiO2) In the form of Ca, in addition to the above two forms, mainly calcite (CaCO)3) Perovskite (CaTiO)3) In the form of a salt with small amounts of impurities, e.g. Fe2O3、SiO2. The slag is not effectively recycled, has potential harm to the environment due to improper treatment and causes huge resourcesIs wasted. Meanwhile, a large amount of sulfur-containing smelting flue gas is generated in the smelting process and is commonly used for industrial acid production, but a large amount of sulfur dioxide with low concentration is still contained after the acid production tail gas process, and the traditional process mainly uses alkaline solution containing metal oxides, carbonates or hydroxides such as Na, Ca, Al and the like for absorption, but has higher cost and difficult resource utilization, and brings heavy environmental protection burden to enterprises.
In recent years, the wet flue gas desulfurization and resource production byproduct process represented by lean ore slag slurry of manganese ore, red mud ore, magnesite, zinc dust and the like is popularized and applied, the method provides a new idea for industries such as electrolytic manganese, lead and zinc smelting plants and the like, coupling of flue gas desulfurization and resource recovery can be realized, and the operation cost is reduced, but the lean ore distribution and the like are limited by the industries. At the same time, with Fe: (
)、Fe(
) When the transition metal ion additive is used as a catalyst and a desulfurizer for flue gas desulfurization, the attention is widely paid, but the process needs to consume a large amount of additive, the operation cost is high, and the popularization is difficult. Chinese patent (application No. 201210580849.1) uses acidic ferric iron solution as desulfurizer to absorb sulfur dioxide in flue gas, and uses liquid phase catalytic oxidation principle to realize iron circulation under oxygen or ozone oxidation condition, and finally obtains ferric sulfate or ferric chloride through separation, purification and crystallization when sulfate radical concentration reaches higher concentration. Chinese patent (application No. 201610019014.1) discloses a formula of red mud slurry for flue gas desulfurization and a preparation method thereof. The concentration of the red mud slurry in the formula is 4-10%, and the red mud slurry can be used in thermal power plants around the red mud. Chinese patent (application No. 201510959956.9) discloses a method for preparing a Fenton catalyst by adding magnetite into a nano titanium dioxide solution after roasting and cooling, standing and roasting again, wherein the catalyst can effectively catalyze hydrogen peroxide for flue gas desulfurization and denitration. However, the Fenton catalyst required by the invention needs to be calcined under high temperature, the steps are complicated, and hydrogen peroxide is consumed, so that the catalyst is desulfurized intoThe cost is higher.
On the other hand, a large amount of acid-containing wastewater is generated in the smelting process, and the components of the acid-containing wastewater are complex and contain suspended matters, various high-concentration heavy metals and the like; meanwhile, other wastewater discharge sources exist around the smelting industry. In the traditional method, reagents such as lime neutralization and ferrous sulfate are mainly used for coagulating and precipitating heavy metals in the solution, but the process causes the problems of large consumption of the reagents, excessive hardness and salinity of effluent and the like. Therefore, how to treat the wastewater economically and efficiently needs to be solved urgently, and the poly-composite polymeric flocculant represented by polymeric ferric sulfate has a remarkable effect on the wastewater with heavy industrial pollution, so that the poly-composite polymeric flocculant is concerned highly. Chinese patent (application No. 201410713473.6) discloses a preparation method and application of modified polymeric ferric sulfate for treating industrial wastewater. The modified polyferric sulfate mainly utilizes ferrous sulfate heptahydrate and sulfuric acid solution to prepare polyferric sulfate under the oxidation of sodium chlorate, and the obtained polyferric sulfate is modified by kaolin and talc, so that the removal rate of COD, SS and chromaticity in waste paper papermaking wastewater by a polyferric flocculant is improved, the use amount of the flocculant can be reduced, the generation amount of chemical sludge is reduced, and the purposes of saving cost and simplifying process are achieved. Chinese patent (application No. 201310653910.5) uses ferrous sulfate as flue gas desulfurizing agent and KClO3/NaClO3As an oxidant, flue gas desulfurization is realized in a jet bubble reactor while liquid polymeric ferric sulfate is synthesized, but the desulfurization of the invention needs to consume a large amount of ferrous sulfate. Chinese patent (application No. 201610045097.7) proposes that ferric salt components such as ferrous sulfate and the like, polymeric aluminum sulfate and the like are used as raw materials, and magnesium chloride, zinc chloride and the like are used as coagulant aids to produce the high-efficiency water treatment composite flocculant in a combined manner. The invention effectively exerts the synergistic effect of aluminum salt and ferric salt, has excellent flocculation effect, but has higher medicament cost.
At present, no method for producing the polyferric flocculant based on flue gas desulfurization and resource utilization of smelting tailing slag exists.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a method for producing a polyferric flocculant based on flue gas desulfurization and resource utilization of smelting tailing slag, valuable metals such as iron, manganese, zinc, aluminum and the like in the tailing slag have better catalytic oxidation capability, low-concentration sulfur dioxide in flue gas can be catalytically oxidized in a liquid phase to generate sulfuric acid, meanwhile, the sulfuric acid can further leach out metal elements in the slag, the concentration of the metals such as iron, manganese, aluminum and the like in absorption liquid is continuously increased along with the reaction, and the polyferric flocculant can be generated in a desulfurizing tower by adding an oxidant to obtain resource byproducts, so that the flue gas desulfurization operation cost is reduced, and the economic benefit is increased.
The invention is realized by the following technical scheme: a flue gas desulfurization and resource utilization method based on smelting tailing slag comprises the following specific steps:
(1) performing dust removal and temperature reduction pretreatment on the smelting flue gas to obtain pretreated flue gas A;
(2) adding water into copper tailings and/or red mud waste residue powder to prepare flue gas desulfurization slurry A;
(3) in a reaction vessel, under the condition of stirring, carrying out countercurrent contact reaction on the pretreated flue gas A obtained in the step (1) and the flue gas desulfurization slurry A obtained in the step (2) until the pH value of the desulfurization slurry is 1-4, adding an oxidizing solution at a constant speed, and continuously reacting to obtain reaction slurry B and desulfurization gas B, wherein SO in the desulfurization gas B2Is not higher than 200mg/m3The mixture is emptied;
(4) filtering the reaction slurry B obtained in the step (3) to obtain filtrate and filter residue, concentrating the filtrate until the mass concentration of iron is not lower than 11% to obtain a liquid polyferric flocculant, and dehydrating the filter residue;
further, the method comprises the step of spray drying the liquid polyferric flocculant at the temperature of 60-80 ℃ to obtain the solid polyferric flocculant.
The particle size of the smelting tailing slag powder in the step (2) is 200-300 meshes, and the solid-liquid mass ratio of the smelting tailing slag powder to water is 1 (3-10).
The mass percentage concentration of the oxidizing solution is 25-40%, the adding amount of the oxidizing solution is 0.2-10% of the volume of the flue gas desulfurization slurry, and the oxidizing solution is one or more of hydrogen peroxide, sodium chlorate and sodium hypochlorite in any ratio.
And (4) concentrating the filtrate at 50-70 ℃.
The temperature of the pretreated mixed gas A is lower than 45 ℃, and the volume concentration of oxygen is 8.0-19.5%;
in the reaction vessel, the gas retention time is 4-20 s;
the smelting flue gas can be a mixed gas of smelting tail gas and environment smoke collection flue gas;
the smelting tail gas is SO-containing gas released in the non-ferrous metal smelting process2A tail gas of the gas;
the environment smoke collection flue gas refers to flue gas collected by a large smoke collection system formed by connecting all smoke hoods in a smelting workshop in a smelting plant by pipelines;
the main chemical reactions involved in the invention are as follows:
(1) flue gas desulfurization principle of ore pulp
Flue gas desulfurization of red mud: na (Na)2O+SO2=Na2SO3
4SO2+4Na2O=3Na2SO4+Na2S
4.5SO2+Al2O3=Al2(SO4)3+1.5S
4CaO+4SO2=3CaSO4+CaS
2Fe2++SO2+O2=2Fe3++SO4 2-
2Fe3++SO2+2H2O=2Fe3++SO4 2-+4H+
And (3) flue gas desulfurization of copper ore pulp:
SO2+H2O
H2SO3 
H++HSO3 -
2Fe2++SO2+O2=2Fe3++SO4 2-
2Fe3++SO2+2H2O=2Fe3++SO4 2-+4H+
Fe2SiO4+2SO2+O2= 2FeSO4+ SiO2↓
FeSO4+SO2+O2=Fe2(SO4)3
Fe2(SO4)3+SO2+2H2O=2FeSO4+2H2SO4
the reaction formula can be summarized as
2SO2+2H2O+O2 
H2SO4
(2) Production principle of polyferric flocculant
And (3) oxidation: 2FeSO4+H2O2+H2SO4=Fe2(SO4)3+2H2O
Hydrolysis: fe2(SO4)3+nH2O=Fe2(OH)n(SO4)3-n/2+n/2H2SO4
Polymerization reaction: mFe2(OH)n(SO4)3-n/2=[Fe2(OH)n(SO4)3-n/2]m
The invention has the beneficial effects that:
(1) the invention uses the smelting tailing slag for smelting flue gas desulfurization, the removal rate of sulfur dioxide is more than 90 percent, and the purpose of treating wastes with processes of wastes against one another is realized;
(2) according to the invention, the catalytic oxidation capacity of valuable metals such as iron, manganese, zinc, copper and the like in the tailing slag is utilized, low-concentration sulfur dioxide in the flue gas is catalytically oxidized in a liquid phase to generate sulfuric acid, the sulfuric acid leaches out metal elements in the slag, the concentration of metals such as iron, manganese, aluminum and the like in the absorption liquid is continuously increased along with the reaction, and a recycling byproduct, namely a polyferric flocculant, is generated in a desulfurization tower by adding an oxidant, so that the flue gas desulfurization operation cost is reduced, and the economic benefit is increased;
(3) the water obtained by the filter residue dehydration treatment can be used as industrial water, so that the treatment load of flue gas desulfurization sewage of enterprises is reduced;
(4) the polyferric flocculant prepared by resource utilization of the invention can be suitable for wastewater treatment.
Detailed Description
The present invention will be described in detail with reference to the following embodiments.
Example 1: this example is at 10000 mg/m3Sulfur dioxide steel cylinder gas with the purity of 99.5 percent and nitrogen steel cylinder gas are precisely mixed by an air pump to prepare mixed gas A simulation smelting flue gas, wherein the gas flow rate of the mixed gas A is 1.2L/min, and the mixed gas A contains 19.5 percent of oxygen and SO by mass fraction2Has a concentration of 1500mg/m3；
A flue gas desulfurization and resource utilization method based on smelting tailing slag comprises the following specific steps:
(1) adding water into the copper tailing waste residue powder to prepare flue gas desulfurization slurry A, wherein the particle size of the smelting tailing powder is 200 meshes, and the solid-liquid mass ratio of the smelting tailing powder to the water is 1: 4;
(2) conveying the flue gas desulfurization slurry A obtained in the step (1) into a spraying device at the top end of an ore pulp desulfurization bubbling reactor through a slurry pump;
(3) introducing the mixed gas A into the bottom of the ore pulp desulfurization bubbling reactor, under the stirring condition, enabling the mixed gas A and the flue gas desulfurization slurry obtained in the step (2) to form a countercurrent contact reaction in the ore pulp desulfurization bubbling reactor until the pH value of the desulfurization slurry is 1, adding an oxidizing solution at a constant speed, and continuously reacting to obtain reaction slurry B and desulfurization gas B, wherein SO in the desulfurization gas B2In a concentration of less than 150mg/m3Directly emptying, wherein the oxidizing solution is hydrogen peroxide solution with the mass fraction of 30%, oxidizing solution (hydrogen peroxide solution)The adding amount of (A) is 4% of the volume of the flue gas desulfurization slurry;
(4) when SO is present in the desulfurized gas B2Has a concentration of 150mg/m3Filtering the reaction slurry B obtained in the step (3) to obtain filtrate and filter residues, concentrating the filtrate by a rotary evaporator at the temperature of 60 ℃ until the mass concentration of iron is 12.8% to obtain a liquid polyferric flocculant, and dehydrating the filter residues;
in the embodiment, the concentration of sulfur dioxide at an inlet and an outlet is detected by an HC-6 sulfur-phosphorus analyzer, and the temperature and the stirring speed of the desulfurization slurry are controlled by a constant-temperature magnetic stirrer; indexes such as total iron, reducing substances, basicity and the like of the polyferric flocculant are measured by a GB 14591-2006 polyferric sulfate detection method;
SO in the desulfurization gas B of this example2Has a concentration of 150mg/m3The desulfurization efficiency of the mixed gas A is 90 percent, the mass fraction of total iron in the liquid polyferric flocculant is 12.8 percent, and reducing substances (Fe is used)2+Calculated) the mass fraction is 0.12 percent, the basicity is 14.2 percent, and the requirements of national standard GB 14591 and 2006 are met.
Example 2: the smelting flue gas in this embodiment is a mixed gas of flue gas generated in the copper smelting acid making process and environment smoke collecting flue gas, and the flue gas amount of the mixed gas is 100000Nm3H, SO in flue gas2At a concentration of 1200 mg/Nm3，O2The volume concentration is 19.5%;
a flue gas desulfurization and resource utilization method based on smelting tailing slag comprises the following specific steps:
(1) performing dust removal and temperature reduction pretreatment on the smelting flue gas to obtain pretreated flue gas A, wherein the temperature of the pretreated flue gas A is 25 ℃, and the temperature of the pretreated flue gas A is O2The volume concentration is 19.5%;
(2) adding water into the copper tailing waste residue powder to prepare flue gas desulfurization slurry A, wherein the particle size of the smelting tailing powder is 200 meshes, and the solid-liquid mass ratio of the smelting tailing powder to the water is 1: 5; conveying the flue gas desulfurization slurry A into a spraying device at the top end of a desulfurization tower through a slurry pump;
(3) pressurizing the pretreated flue gas A obtained in the step (1) to 0.20-0.25 Kpa by using a blower, introducing the flue gas A into the bottom end of a desulfurizing tower, and stirring the flue gas A by using a stirring barUnder the condition, the mixed gas A and the flue gas desulfurization slurry obtained in the step (2) form a countercurrent contact reaction in a desulfurization tower until the pH value of the desulfurization slurry is 1, an oxidizing solution is added at a constant speed to continue the reaction to obtain reaction slurry B and desulfurization gas B, and SO in the desulfurization gas B2In a concentration of less than 100mg/m3Directly emptying, wherein the oxidizing solution is 35 percent of hydrogen peroxide solution by mass, the adding amount of the oxidizing solution (hydrogen peroxide solution) is 1.5 percent of the volume of the flue gas desulfurization slurry, so that part of Fe in the slurry is2+Is oxidized into Fe3+The oxidation of sulfur dioxide is promoted;
(4) when SO is present in the desulfurized gas B2Has a concentration of 100mg/m3Filtering the reaction slurry B obtained in the step (3) to obtain filtrate and filter residues (the filter residues are copper tailing residues), concentrating the filtrate by a rotary evaporator at the temperature of 70 ℃ until the mass concentration of iron is 11.20% to obtain a liquid polyferric flocculant, dehydrating the filter residues, stacking and recycling the filter residues as building materials or further dissolving and recycling silicon in the residues by hot alkali;
(5) spray drying the liquid polyferric flocculant at the temperature of 70 ℃ to obtain a solid polyferric flocculant;
in the embodiment, the concentration of sulfur dioxide at an inlet and an outlet is detected by an HC-6 sulfur-phosphorus analyzer, and the temperature and the stirring speed of the desulfurization slurry are controlled by a constant-temperature magnetic stirrer; indexes such as total iron, reducing substances, basicity and the like of the polyferric-based flocculant are measured by a GB 14591-2006 polyferric sulfate detection method;
SO in the desulfurization gas B of this example2Has a concentration of 100mg/m3The desulfurization efficiency of the mixed gas A is 91.6 percent, the mass fraction of total iron in the liquid polyferric flocculant is 11.20 percent, and reducing substances (Fe is used)2+Calculated) the mass fraction is 0.042 percent, the basicity is 12.45 percent, and the requirements of national standard GB 14591 and 2006 are met.
Example 3: the smelting flue gas of the embodiment is a mixed gas of flue gas generated in the copper smelting acid making process and environment smoke collecting flue gas, and the flue gas amount of the mixed gas is 200000Nm3H, SO in flue gas2Concentration 1400 mg/Nm3，O2The volume concentration is 19.0 percent;
a flue gas desulfurization and resource utilization method based on smelting tailing slag comprises the following specific steps:
(1) performing dust removal and temperature reduction pretreatment on the smelting flue gas to obtain pretreated flue gas A, wherein the temperature of the pretreated flue gas A is 30 ℃, and the temperature of the pretreated flue gas A is O2The volume concentration is 19.0 percent;
(2) adding water into the copper tailing waste residue powder to prepare flue gas desulfurization slurry A, wherein the particle size of the smelting tailing powder is 200 meshes, and the solid-liquid mass ratio of the smelting tailing powder to the water is 1: 5; conveying the flue gas desulfurization slurry A into a spraying device at the top end of a desulfurization tower through a slurry pump;
(3) pressurizing the pretreated flue gas A obtained in the step (1) to 0.20-0.30 Kpa by a blower, introducing the pretreated flue gas A into the bottom end of a desulfurization tower, forming a countercurrent contact reaction between the mixed gas A and the flue gas desulfurization slurry obtained in the step (2) in the desulfurization tower under the stirring condition until the pH value of the desulfurization slurry is 1.5, adding an oxidizing solution at a constant speed, and continuously reacting to obtain reaction slurry B and desulfurization gas B, wherein SO in the desulfurization gas B2In a concentration of less than 100mg/m3Directly emptying, wherein the oxidizing solution is a hydrogen peroxide solution with the mass fraction of 40 percent, and the adding amount of the oxidizing solution (the hydrogen peroxide solution) is 2.5 percent of the volume of the flue gas desulfurization slurry, so that part of Fe in the slurry is2+Is oxidized into Fe3+The oxidation of sulfur dioxide is promoted;
(4) when SO is present in the desulfurized gas B2Has a concentration of 100mg/m3Filtering the reaction slurry B obtained in the step (3) to obtain filtrate and filter residues (the filter residues are copper tailing residues), concentrating the filtrate by a rotary evaporator at the temperature of 70 ℃ until the mass concentration of iron is 11.02 percent to obtain a liquid polyferric flocculant, dehydrating the filter residues, stacking and recycling the filter residues as building materials or further dissolving and recycling silicon in the residues by hot alkali;
(5) spray drying the liquid polyferric flocculant at the temperature of 70 ℃ to obtain a solid polyferric flocculant;
in the embodiment, the concentration of sulfur dioxide at an inlet and an outlet is detected by an HC-6 sulfur-phosphorus analyzer, and the temperature and the stirring speed of the desulfurization slurry are controlled by a constant-temperature magnetic stirrer; indexes such as total iron, reducing substances, basicity and the like of the polyferric-based flocculant are measured by a GB 14591-2006 polyferric sulfate detection method;
SO in the desulfurization gas B of this example2Has a concentration of 100mg/m3The desulfurization efficiency of the mixed gas A is 91.6 percent, the mass fraction of total iron in the liquid polyferric flocculant is 11.02 percent, and reducing substances (Fe is used)2+Calculated) the mass fraction is 0.01 percent, the basicity is 14.56 percent, and the requirements of national standard GB 14591 and 2006 are met.
Example 4: the smelting flue gas in the embodiment is a mixed gas of a thermal power plant matched with alumina smelting and environmental smoke collection flue gas, and the flue gas amount of the mixed gas is 100000Nm3H, SO in flue gas2Concentration 2000mg/Nm3，O2The volume concentration is 8.0 percent;
a flue gas desulfurization and resource utilization method based on smelting tailing slag comprises the following specific steps:
(1) performing dust removal and temperature reduction pretreatment on the smelting flue gas to obtain pretreated flue gas A, wherein the temperature of the pretreated flue gas A is 44.8 ℃, and the temperature of O is2The volume concentration is 8.0 percent;
(2) adding water into the red mud waste residue powder to prepare flue gas desulfurization slurry A, wherein the particle size of the smelting waste residue powder is 300 meshes, and the solid-liquid mass ratio of the smelting tail slag powder to the water is 1: 3; conveying the flue gas desulfurization slurry A into a spraying device at the top end of a desulfurization tower through a slurry pump;
(3) pressurizing the pretreated flue gas A obtained in the step (1) to 0.20-0.30 Kpa by a blower, introducing the pretreated flue gas A into the bottom end of a desulfurization tower, forming a countercurrent contact reaction between the mixed gas A and the flue gas desulfurization slurry obtained in the step (2) in the desulfurization tower under the stirring condition until the pH value of the desulfurization slurry is 4, adding an oxidizing solution at a constant speed, and continuously reacting to obtain reaction slurry B and desulfurization gas B, wherein SO in the desulfurization gas B2In a concentration of less than 200mg/m3Directly emptying, wherein the oxidizing solution is a sodium chlorate solution with the mass fraction of 40 percent, the adding amount of the oxidizing solution (the sodium chlorate solution) is 10 percent of the volume of the flue gas desulfurization slurry, and part of Fe in the slurry is caused to be in2+Is oxidized into Fe3+The oxidation of sulfur dioxide is promoted;
(4) when SO is present in the desulfurized gas B2At a concentration of 200mg/m3Filtering the reaction slurry B obtained in the step (3) to obtain filtrate and filter residues (the filter residues are red mud residues), concentrating the filtrate by a rotary evaporator at the temperature of 50 ℃ until the mass concentration of iron is 11.01% to obtain a liquid polyferric flocculant, and dehydrating the filter residues;
(5) spray drying the liquid polyferric flocculant at the temperature of 60 ℃ to obtain a solid polyferric flocculant;
in the embodiment, the concentration of sulfur dioxide at an inlet and an outlet is detected by an HC-6 sulfur-phosphorus analyzer, and the temperature and the stirring speed of the desulfurization slurry are controlled by a constant-temperature magnetic stirrer; indexes such as total iron, reducing substances, basicity and the like of the polyferric-based flocculant are measured by a GB 14591-2006 polyferric sulfate detection method;
SO in the desulfurization gas B of this example2At a concentration of 200mg/m3The desulfurization efficiency of the mixed gas A is 90 percent, the mass fraction of total iron in the liquid polyferric flocculant is 11.01 percent, and reducing substances (Fe is used)2+Calculated) the mass fraction is 0.01 percent, the basicity is 14.2 percent, and the requirements of national standard GB 14591 and 2006 are met.
Example 5: the smelting flue gas of the embodiment is mixed gas of aluminum oxide smelting matched thermal power plant and environment smoke collection flue gas, and the flue gas amount of the mixed gas is 150000Nm3H, SO in flue gas2The concentration is 1800mg/Nm3，O2The volume concentration is 16.0 percent;
a flue gas desulfurization and resource utilization method based on smelting tailing slag comprises the following specific steps:
(1) performing dust removal and temperature reduction pretreatment on the smelting flue gas to obtain pretreated flue gas A, wherein the temperature of the pretreated flue gas A is 35 ℃, and the temperature of the pretreated flue gas A is O2The volume concentration is 16.0 percent;
(2) adding water into waste residue powder of the red mud to prepare flue gas desulfurization slurry A, wherein the particle size of smelting tailing residue powder is 220 meshes, and the solid-liquid mass ratio of the smelting tailing residue powder to the water is 1: 10; conveying the flue gas desulfurization slurry A into a spraying device at the top end of a desulfurization tower through a slurry pump;
(3) subjecting the product obtained in step (1)Pressurizing the pretreated flue gas A to 0.20-0.30 Kpa by using an air blower, introducing the pretreated flue gas A into the bottom end of a desulfurization tower, enabling the mixed gas A and the flue gas desulfurization slurry obtained in the step (2) to form a countercurrent contact reaction in the desulfurization tower under the stirring condition until the pH value of the desulfurization slurry is 2.5, adding an oxidizing solution at a constant speed, and continuously reacting to obtain reaction slurry B and desulfurization gas B, wherein SO in the desulfurization gas B2Is less than 120mg/m3Directly emptying, wherein the oxidizing solution is a mixed oxidizing solution prepared by a hydrogen peroxide solution with the mass fraction of 28% and a sodium hypochlorite solution with the mass fraction of 30% according to the volume ratio of the hydrogen peroxide solution to the sodium hypochlorite solution of 2:1, the adding amount of the mixed oxidizing solution is 5.6% of the volume of the flue gas desulfurization slurry, and part of Fe in the slurry is enabled to be2+Is oxidized into Fe3+The oxidation of sulfur dioxide is promoted;
(4) when SO is present in the desulfurized gas B2Has a concentration of 120mg/m3Filtering the reaction slurry B obtained in the step (3) to obtain filtrate and filter residues (the filter residues are red mud residues), concentrating the filtrate by a rotary evaporator at the temperature of 60 ℃ until the mass concentration of iron is 11.05 percent to obtain a liquid polyferric flocculant, dehydrating the filter residues, stacking and recycling the filter residues as building materials or further recycling silicon in the residues by hot alkali dissolution;
(5) spray drying the liquid polyferric flocculant at the temperature of 80 ℃ to obtain a solid polyferric flocculant;
in the embodiment, the concentration of sulfur dioxide at an inlet and an outlet is detected by an HC-6 sulfur-phosphorus analyzer, and the temperature and the stirring speed of the desulfurization slurry are controlled by a constant-temperature magnetic stirrer; indexes such as total iron, reducing substances, basicity and the like of the polyferric-based flocculant are measured by a GB 14591-2006 polyferric sulfate detection method;
SO in the desulfurization gas B of this example2Has a concentration of 120mg/m3The desulfurization efficiency of the mixed gas A is 93.3 percent, the mass fraction of total iron in the liquid polyferric flocculant is 11.05 percent, and reducing substances (Fe is used)2+Calculated) the mass fraction is 0.04 percent, the basicity is 15.8 percent, and the requirements of national standard GB 14591 and 2006 are met.
Example 6: smelting smoke of the embodimentThe gas is the mixed gas of copper smelting acid making flue gas and environment smoke collecting flue gas, and the flue gas amount of the mixed gas is 120000Nm3H, SO in flue gas2Concentration 1000mg/Nm3，O2The volume concentration is 12.0 percent;
a flue gas desulfurization and resource utilization method based on smelting tailing slag comprises the following specific steps:
(1) performing dust removal and temperature reduction pretreatment on the smelting flue gas to obtain pretreated flue gas A, wherein the temperature of the pretreated flue gas A is 35 ℃, and the temperature of the pretreated flue gas A is O2The volume concentration is 12.0 percent;
(2) adding water into copper tailings and red mud waste residue powder to prepare flue gas desulfurization slurry A, wherein the particle size of smelting tailing residue powder is 260 meshes, and the solid-liquid mass ratio of the smelting tailing residue powder to the water is 1: 8; conveying the flue gas desulfurization slurry A into a spraying device at the top end of a desulfurization tower through a slurry pump;
(3) pressurizing the pretreated flue gas A obtained in the step (1) to 0.20-0.30 Kpa by a blower, introducing the pretreated flue gas A into the bottom end of a desulfurization tower, forming a countercurrent contact reaction between the mixed gas A and the flue gas desulfurization slurry obtained in the step (2) in the desulfurization tower under the stirring condition until the pH value of the desulfurization slurry is 2.0, adding an oxidizing solution at a constant speed, and continuously reacting to obtain reaction slurry B and desulfurization gas B, wherein SO in the desulfurization gas B2Is less than 90mg/m3Directly emptying, wherein the oxidizing solution is 35% by mass of sodium hypochlorite, the adding amount of the oxidizing solution (sodium hypochlorite solution) is 3.8% of the volume of the flue gas desulfurization slurry, and part of Fe in the slurry is enabled to be2+Is oxidized into Fe3+The oxidation of sulfur dioxide is promoted;
(4) when SO is present in the desulfurized gas B2Has a concentration of 90mg/m3Filtering the reaction slurry B obtained in the step (3) to obtain filtrate and filter residues (the filter residues are copper tailing residues), concentrating the filtrate by a rotary evaporator at the temperature of 65 ℃ until the mass concentration of iron is 11.02 percent to obtain a liquid polyferric flocculant, dehydrating the filter residues, stacking and recycling the filter residues as building materials or further dissolving and recycling silicon in the residues by hot alkali;
(5) spray drying the liquid polyferric flocculant at the temperature of 70 ℃ to obtain a solid polyferric flocculant;
in the embodiment, the concentration of sulfur dioxide at an inlet and an outlet is detected by an HC-6 sulfur-phosphorus analyzer, and the temperature and the stirring speed of the desulfurization slurry are controlled by a constant-temperature magnetic stirrer; indexes such as total iron, reducing substances, basicity and the like of the polyferric-based flocculant are measured by a GB 14591-2006 polyferric sulfate detection method;
SO in the desulfurization gas B of this example2Has a concentration of 90mg/m3The desulfurization efficiency of the mixed gas A is 91 percent, the mass fraction of total iron in the liquid polyferric flocculant is 11.01 percent, and reducing substances (Fe is used)2+Calculated) the mass fraction is 0.067 percent, the basicity is 14.28 percent, and the requirements of national standard GB 14591 and 2006 are met.
Claims (5)
1. A flue gas desulfurization and resource utilization method based on smelting tailing slag is characterized by comprising the following specific steps:
(1) performing dust removal and temperature reduction pretreatment on the smelting flue gas to obtain pretreated flue gas A; the temperature of the pretreated mixed gas A is lower than 45 ℃, and the volume concentration of oxygen is 8.0-19.5%;
(2) adding water into copper tailings and/or red mud waste residue powder to prepare flue gas desulfurization slurry A;
(3) in a reaction vessel, under the condition of stirring, carrying out countercurrent contact reaction on the pretreated flue gas A obtained in the step (1) and the flue gas desulfurization slurry A obtained in the step (2) until the pH value of the desulfurization slurry is 1-4, adding an oxidizing solution at a constant speed, and continuously reacting to obtain reaction slurry B and desulfurization gas B, wherein SO in the desulfurization gas B2Is not higher than 200mg/m3The mixture is emptied;
(4) and (4) filtering the reaction slurry B obtained in the step (3) to obtain filtrate and filter residues, concentrating the filtrate until the mass concentration of iron is not lower than 11% to obtain a liquid polyferric flocculant, and dehydrating the filter residues.
2. The flue gas desulfurization and resource utilization method based on smelting tailing slag according to claim 1, characterized in that: and spray drying the liquid polyferric flocculant at the temperature of 60-80 ℃ to obtain the solid polyferric flocculant.
3. The flue gas desulfurization and resource utilization method based on smelting tailing slag according to claim 1 or 2, characterized in that: in the step (2), the particle size of the smelting tailing slag powder is 200-300 meshes, and the solid-liquid mass ratio of the smelting tailing slag powder to water is 1 (3-10).
4. The flue gas desulfurization and resource utilization method based on smelting tailing slag according to claim 1 or 2, characterized in that: the mass percentage concentration of the oxidizing solution is 25-40%, the adding amount of the oxidizing solution is 0.2-10% of the volume of the flue gas desulfurization slurry, and the oxidizing solution is one or more of hydrogen peroxide, sodium chlorate and sodium hypochlorite in any ratio.
5. The flue gas desulfurization and resource utilization method based on smelting tailing slag according to claim 1 or 2, characterized in that: the concentration temperature of the filtrate in the step (4) is 50-70 ℃.
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| CN107899596A (en) * | 2017-10-30 | 2018-04-13 | 昆明理工大学 | A kind of desulfurization denitrification agent and preparation method thereof |
| CN108642948B (en) * | 2018-06-07 | 2023-06-09 | 夹江县天翔纸业有限公司 | Papermaking wastewater treatment process and treatment device |
| CN108926976A (en) * | 2018-07-27 | 2018-12-04 | 昆明冶金研究院 | SO in a kind of stanniferous clinker removing flue gas2The method of resource utilization lead, tin simultaneously |
| CN108905608B (en) * | 2018-07-27 | 2021-02-02 | 昆明冶金研究院 | Smelting furnace slag synergistic purification of SO in tin smelting flue gas2With NOx |
| CN109231258B (en) * | 2018-11-26 | 2020-07-31 | 中国科学院过程工程研究所 | Method for comprehensively treating copper slag tailings and smelting flue gas |
| CN110090548B (en) * | 2019-04-11 | 2021-11-30 | 昆明理工大学 | Method for wet desulphurization and zinc sulfate recovery of copper slag tailings and zinc smelting fly ash |
| CN109971968A (en) * | 2019-04-16 | 2019-07-05 | 昆明理工大学 | A kind of copper ashes tailing prepares the resource utilization method of iron ore concentrate |
| CN110423892A (en) * | 2019-08-19 | 2019-11-08 | 肖功明 | A kind of method of copper ashes Tailings Slurry flue gas desulfurization collaboration copper resource high efficiente callback |
| CN112387106A (en) * | 2020-11-27 | 2021-02-23 | 昆明理工大学 | Method for improving desulfurization efficiency of electrolytic manganese ore/slag slurry |
| CN115043471A (en) * | 2022-06-16 | 2022-09-13 | 白银有色集团股份有限公司 | Method for preparing polysilicate aluminum ferric sulfate flocculant by using copper smelting furnace slag |
| CN115432789A (en) * | 2022-08-31 | 2022-12-06 | 中国矿业大学 | Method for preparing ferrous sulfate flocculating agent from copper smelting tailing slag |
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