CN108525513B - Removing agent for simultaneous desulfurization and denitrification and preparation method thereof - Google Patents
Removing agent for simultaneous desulfurization and denitrification and preparation method thereof Download PDFInfo
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- CN108525513B CN108525513B CN201810320627.3A CN201810320627A CN108525513B CN 108525513 B CN108525513 B CN 108525513B CN 201810320627 A CN201810320627 A CN 201810320627A CN 108525513 B CN108525513 B CN 108525513B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8637—Simultaneously removing sulfur oxides and nitrogen oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/60—Simultaneously removing sulfur oxides and nitrogen oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
- B01D53/78—Liquid phase processes with gas-liquid contact
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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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
The invention discloses a removing agent for simultaneous desulfurization and denitrification and a preparation method thereof, belonging to the fields of comprehensive utilization of waste residues and purification of industrial waste gas; the remover is prepared from the following components: the slag-smelting furnace comprises non-ferrous metal slag, water, an oxygen transfer agent and a dispersing agent, wherein the addition amount of the oxygen transfer agent is 0.1-1% of the mass of the non-ferrous metal slag, and the addition amount of the dispersing agent is 1-10% of the mass of the non-ferrous metal slag; the invention has simple process flow, safe and simple operation and SO2High NO removing efficiency and can remove SO in gas2And NO is removed simultaneously, a catalyst is not needed, the operation cost is low, and the method is suitable for market popularization and application.
Description
Technical Field
The invention discloses a removing agent for simultaneous desulfurization and denitrification and a preparation method thereof, belonging to the technical field of environmental engineering.
Background
Non-ferrous metal smelting belongs to the typical industries with high pollution, high energy consumption and resources, enterprises are located in ecological fragile areas, the problem of environmental deterioration caused by smoke emission is prominent, and the non-ferrous metal smelting is an important factor for restricting the sustainable development of the enterprises; the nonferrous smelting flue gas is one of the industrial waste gases with the greatest treatment difficulty, and SO in the flue gas2And NOxUltra-low emission of pollutants has been difficult to economically and effectively meet increasingly stringent environmental requirements.
The research on the simultaneous flue gas desulfurization and denitration technology is active at home and abroad, and the simultaneous flue gas desulfurization and denitration technology can be divided into a wet method, a semi-dry method and a dry method according to different working media for absorbing flue gas. The technology for simultaneously desulfurizing and denitrating the flue gas by the dry method and the semi-dry method mainly has the problems of high economic cost, easy generation of secondary pollution, multiple operation condition limiting factors and the like. The technology of wet-process simultaneous desulfurization and denitrification has attracted extensive attention because of its advantages of simple equipment, small floor area, low capital investment, high desulfurization efficiency and the like.
The traditional wet-process simultaneous desulfurization and denitrification technology is characterized in that Nitric Oxide (NO) is oxidized into nitrogen dioxide (NO) with higher solubility by utilizing an oxidant on the basis of the classic wet-process desulfurization technology2) Then using alkali liquor to treat SO2And NO2Absorption is carried out. The absorption liquid can be divided into: limestone method, ammonia method, complexation method, etc. The limestone method has a high treatment cost,a large amount of by-product gypsum and acidic waste liquid are generated, which easily causes secondary pollutants and corrosion of equipment; the ammonia method and the desulfurization and denitrification technology are easy to generate aerosol which is difficult to remove such as ammonium sulfite, ammonium sulfate, ammonium nitrate and the like, and the problems of ammonia loss, smoke emission and the like are caused. The complexing method has the problems of difficult regeneration, secondary pollution and the like, and a part of complexing agents need to be added with high-toxicity medicines, so that great risk exists in use.
The ore pulp desulfurization and denitrification is a new resource flue gas removal technology developed in China in recent years, and the ore pulp is slurry formed by adding water and other auxiliary agents in a certain proportion into solid raw materials such as ore, ore soil and the like and residues after mineral separation or smelting in the mining process. In the non-ferrous metallurgy and phosphorus chemical industry, the flue gas contains a large amount of SO2The flue gas is purified to prepare acid, and a large amount of sulfuric acid is consumed in typical technological processes of ore dressing, mineral processing and utilization, solid tailing treatment and the like. For example, mineral separation of metals such as copper oxide ore and manganese oxide ore often requires sulfuric acid pickling treatment of refractory minerals to meet hydrometallurgy requirements; in the wet-process phosphoric acid production in the phosphorus chemical industry, phosphate ore is decomposed by sulfuric acid to obtain phosphoric acid; nonferrous smelting often employs acid treatment to recover the valuable metals in the tailings. Therefore, the ore pulp desulfurization and denitrification has the characteristics of low desulfurization raw material cost, short flow and the like. The existing ore pulp desulfurization and denitrification technologies mainly comprise: a phosphorite slurry desulfurization technology, a pyrolusite desulfurization and denitrification technology and the like.
The non-ferrous metal smelting slag has complex components, belongs to bulk industrial solid waste, has great harm to the environment, and is one of the key researches on the treatment and disposal of the solid waste by comprehensive utilization. The smelting slag of nonferrous metals such as copper, lead, zinc, tin and the like contains a large amount of transition metals such as Fe, Mn and the like and alkaline oxides, and SO can be catalytically oxidized in a liquid phase2、NOxThe method has the feasibility of desulfurization and denitrification in principle. If the non-ferrous metal smelting slag is prepared into ore pulp to remove SO in the non-ferrous metal smelting flue gas2And NOxThe method can solve the problems of comprehensive utilization, waste gas purification and the like of bulk industrial solid wastes, achieves the aim of treating wastes with wastes, and can realize the integrated treatment of non-ferrous metal smelting waste gas and solid wastes.
The invention content is as follows:
in order to make up for the defects of the prior art, the invention aims to provide a novel desulfurizing and denitrifying remover which is environment-friendly, simple to prepare, less in investment and construction, high in treatment efficiency and prepared from the following components: the slag-smelting furnace comprises non-ferrous metal slag, water, an oxygen transfer agent and a dispersing agent, wherein the addition amount of the oxygen transfer agent is 0.1-1% of the mass of the non-ferrous metal slag, and the addition amount of the dispersing agent is 1-10% of the mass of the non-ferrous metal slag.
The mass volume ratio g: mL of the nonferrous metal slag to the water is 1: 10-100.
The oxygen transfer agent is one of yellow phosphorus and phosphorus sludge.
The dispersing agent is one of monophosphate, starch, sodium hexametaphosphate and animal glue.
The non-ferrous slag is waste slag generated in smelting non-ferrous minerals, and belongs to one kind of metallurgical waste slag.
The invention also aims to provide a preparation method of the remover, which comprises the following steps:
(1) grinding and screening the non-ferrous metal slag to 200-300 meshes;
(2) adding water into the non-ferrous metal slag to prepare non-ferrous metal slag slurry;
(3) adding an oxygen transfer agent into the nonferrous metal slag slurry at 45-60 ℃;
(4) and (4) finally, uniformly dispersing the dispersing agent into the mixture in the step (3) by means of ultrasonic, stirring, dissolved oxygen removal and the like to prepare the remover.
When in use, the flue gas to be treated is introduced into a remover;
the method of the invention adds oxygen transfer substance into the liquid phase oxidation catalytic system to generate O under the action of trace oxygen in the tail gas3Isostrongly oxidizing species and conversion to H3PO4(ii) a SO in tail gas2、NOxAbsorbed into liquid phase and promoted by O under the catalysis of transition metal ions and the catalysis of metal ions from tail gas3、O2Are oxidized to H respectively2SO4And HNO3(ii) a At H3PO4、H2SO4And HNO3Under the formed acidic condition, the heavy metal in the tail gas is efficiently transferred to a liquid phase in the form of metal ions through acid leaching, so that synchronous purification of sulfur and nitrate is realized.
The invention has the advantages that: simple process flow, relatively low operating cost and SO2The removal efficiency of NO and SO in the gas is high, and the SO in the gas can be removed at a certain temperature2And simultaneously removing NO, mainly used for removing sulfur dioxide and nitric oxide in industrial coal-fired tail gas.
Drawings
FIG. 1 is a diagram showing the effect of simultaneous desulfurization and denitrification by a removing agent in example 1 of the present invention;
FIG. 2 is a diagram showing the effect of simultaneous desulfurization and denitrification by the stripping agent of example 2 of the present invention;
FIG. 3 is a diagram showing the effect of simultaneous desulfurization and denitrification by the removing agent in example 3 of the present invention;
FIG. 4 is a diagram showing the effect of simultaneous desulfurization and denitrification by the removing agent of example 4 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to examples, but the scope of the present invention is not limited to the examples.
Example 1: the removing agent for simultaneous desulfurization and denitrification is prepared from the following components: the smelting process comprises copper smelting slag, water, yellow phosphorus and monophosphoric acid, wherein the addition amount of the yellow phosphorus is 0.1% of the mass of the copper smelting slag, and the addition amount of the monophosphoric acid is 2% of the mass of the copper smelting slag; the mass volume ratio g: mL of the copper smelting slag to the water is 1: 10;
grinding and screening the copper smelting slag to 200 meshes; weighing copper smelting slag, adding distilled water to prepare copper smelting slag slurry, heating the copper smelting slag slurry to 60 ℃, adding yellow phosphorus, and ensuring the molten state of the oxygen transfer agent; performing ultrasonic treatment for 10min, stirring at a speed of 80r/min for 20min, and uniformly dispersing the monophosphoric acid in the mixture to obtain a remover;
will contain SO2The gas of NO is introduced into a remover, SO2And the initial concentration of NO was 2075mg/m, respectively3、367mg/m3Within 720min, 95% of desulfurization efficiency and 80% of denitration efficiency can be achieved (fig. 1).
Example 2: the removing agent for simultaneous desulfurization and denitrification is prepared from the following components: the phosphorus smelting slag, water, yellow phosphorus and starch, wherein the addition amount of the yellow phosphorus is 0.6 percent of the mass of the phosphorus smelting slag, and the addition amount of the starch is 5 percent of the mass of the phosphorus smelting slag; the mass volume ratio g: mL of the phosphorus smelting slag to the water is 1: 20;
grinding and screening the phosphorus smelting slag to 300 meshes; weighing phosphorus smelting slag, adding distilled water to prepare phosphorus smelting slag slurry, heating the phosphorus smelting slag slurry to 50 ℃, adding yellow phosphorus, and ensuring the molten state of an oxygen transfer agent; uniformly dispersing starch in the mixture by ultrasonic stirring for 20min at a speed of 50r/min for 10min to prepare a remover;
will contain SO2The gas of NO is introduced into a remover, SO2、The initial concentration of NO was 1955mg/m, respectively3、267mg/m3Within 720min, the desulfurization efficiency of 90% and the denitration efficiency of 70% can be achieved (fig. 2).
Example 3: the removing agent for simultaneous desulfurization and denitrification is prepared from the following components: the smelting slag comprises tin smelting slag, water, phosphorus sludge and sodium hexametaphosphate, wherein the addition amount of the phosphorus sludge is 0.9 percent of the mass of the tin smelting slag, and the addition amount of the sodium hexametaphosphate is 5 percent of the mass of the tin smelting slag; the mass volume ratio g: mL of the tin smelting slag to the water is 1: 50;
grinding and screening tin smelting slag to 260 meshes, weighing the tin smelting slag, adding distilled water to prepare tin smelting slag slurry, heating the tin smelting slag slurry to 45 ℃, adding sludge phosphorus to ensure the molten state of an oxygen transfer agent, stirring for 20min through ultrasound for 10min at 60r/min, and uniformly dispersing sodium hexametaphosphate in a mixture to prepare a remover;
will contain SO2The gas of NO is introduced into a remover, SO2、The initial concentration of NO was 1955mg/m, respectively3、267mg/m3Within 480min, the desulfurization efficiency of 80% and the denitration efficiency of 70% can be achieved (fig. 3).
Example 4: the removing agent for simultaneous desulfurization and denitrification is prepared from the following components: lead-zinc smelting slag, water, phosphorus sludge and animal glue, wherein the addition amount of the phosphorus sludge is 0.4 percent of the mass of the lead-zinc smelting slag, and the addition amount of the animal glue is 10 percent of the mass of the lead-zinc smelting slag; the mass volume ratio g: mL of the lead-zinc smelting slag to the water is 1: 90;
grinding lead-zinc smelting slag and screening to 200 meshes, weighing the lead-zinc smelting slag, adding distilled water to prepare lead-zinc smelting slag slurry, heating the lead-zinc smelting slag slurry to 45 ℃, adding sludge phosphorus to ensure the molten state of an oxygen transfer agent, stirring for 20min at 100r/min by ultrasonic for 10min, and uniformly dispersing animal glue in a mixture to prepare a remover;
will contain SO2The gas of NO is introduced into a remover, SO2、The initial concentration of NO was 2000mg/m, respectively3、300 mg/m3Within 480min, 90% desulfurization efficiency and 80% denitration efficiency can be achieved (fig. 4).
Claims (1)
1. The removing agent for simultaneous desulfurization and denitrification is characterized by being prepared from the following components: the slag-smelting furnace comprises non-ferrous metal slag, water, an oxygen transfer agent and a dispersing agent, wherein the addition amount of the oxygen transfer agent is 0.1-1% of the mass of the non-ferrous metal slag, and the addition amount of the dispersing agent is 1-10% of the mass of the non-ferrous metal slag;
the oxygen transfer agent is yellow phosphorus;
the dispersing agent is one of monophosphate, starch, sodium hexametaphosphate and animal glue;
the preparation of the removing agent for simultaneous desulfurization and denitrification comprises the following steps:
(1) grinding and screening the non-ferrous metal slag to 200-300 meshes;
(2) adding water into the non-ferrous metal slag to prepare non-ferrous metal slag slurry;
(3) adding an oxygen transfer agent into the nonferrous metal slag slurry at 45-60 ℃;
(4) finally, dispersing the dispersing agent into the mixture in the step (3) uniformly to prepare a removing agent;
the mass volume ratio g: mL of the nonferrous metal slag to the water is 1: 10-100.
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| US3906079A (en) * | 1972-07-18 | 1975-09-16 | Nippon Steel Corp | Method for desulfurizing a waste gas |
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