CN116116422A - Preparation process and application of flue gas denitration catalyst - Google Patents

Preparation process and application of flue gas denitration catalyst Download PDF

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CN116116422A
CN116116422A CN202310054611.3A CN202310054611A CN116116422A CN 116116422 A CN116116422 A CN 116116422A CN 202310054611 A CN202310054611 A CN 202310054611A CN 116116422 A CN116116422 A CN 116116422A
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flue gas
denitration catalyst
acid
gas denitration
peroxycarbonate
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CN116116422B (en
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张玉斌
张星
蒋海涛
林科
彭爽
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Shandong Boran Power Technology Co ltd
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Shandong Boran Power Technology Co ltd
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/847—Vanadium, niobium or tantalum or polonium
    • B01J23/8472—Vanadium
    • 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
    • B01D53/54—Nitrogen compounds
    • B01D53/56—Nitrogen oxides
    • 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
    • B01D53/8621—Removing nitrogen compounds
    • B01D53/8625—Nitrogen oxides
    • B01D53/8628—Processes characterised by a specific catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0283—Flue gases
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • 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

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Abstract

The invention relates to the technical field of flue gas denitration, and particularly discloses a preparation process and application of a flue gas denitration catalyst. The preparation process comprises the following steps: (1) Acid leaching the copper slag with acid liquor, then carrying out solid-liquid separation, and respectively collecting acid leaching liquor and solid slag. (2) Firstly adding a thickening agent into the acid leaching solution to form slurry, then adding ammonium metavanadate powder to stir and react, and adding peroxycarbonate to stir and react under the heating condition after the reaction is completed to obtain precursor slurry for later use. (3) And mixing the solid slag with the precursor slurry, uniformly stirring, drying, calcining in air, and crushing the calcined product to obtain the denitration catalyst particles. Compared with the method which adopts commercial titanium dioxide as a carrier, the method has the advantages that the production cost of the catalyst is effectively reduced, and the catalyst with good catalytic effect is obtained.

Description

Preparation process and application of flue gas denitration catalyst
Technical Field
The invention relates to the technical field of flue gas denitration, in particular to a preparation process and application of a flue gas denitration catalyst.
Background
The flue gas generated after the combustion of fossil fuel contains pollutants such as nitrogen oxides and sulfur oxides, which may not only cause the formation of acid rain after entering the air, but also induce photochemical smog and destroy one of the main substances of ozone layer. Therefore, the flue gas can be discharged after the purification procedures such as desulfurization, denitration and the like. At present, flue gas denitration mainly comprises a selective catalytic reduction flue gas denitration (SCR) technology, a selective non-catalytic reduction denitration (SNCR) technology, a polymer denitration (HNCR) technology, a dry denitration technology such as a combined flue gas denitration technology and a wet denitration technology, and the wet denitration technology mainly utilizes an oxidant (such as O 3 、ClO 2 Etc.) to oxidize poorly water-soluble NO in flue gas to readily water-soluble NO 2 And then absorbing by utilizing water and cargo alkali liquor so as to separate out nitrogen oxides in the flue gas. However, the wet denitration technology has disadvantages in that a large amount of waste liquid generated is not easy to treat, has corrosiveness to equipment, has high running cost and the like.
In contrast, the dry denitration technology does not produce waste liquid, does not treat waste water and waste, and is not easy to cause secondary pollution. For example, the main principle of denitration by SCR technology is to convert nitrogen oxides in flue gas into pollution-free substances such as nitrogen and water by using a catalyst which is mainly composed of a carrier and a catalytic active component, such as common V 2 O 5 /TiO 2 、V 2 O 5 -WO 3 (MoO 3 )/TiO 2 Etc., such catalysts are mainly composed of titanium dioxide (TiO 2 ) Is a carrier, resulting in higher catalyst costs. Therefore, there is an important real demand for developing a catalyst which is low in cost and good in denitration effect.
Disclosure of Invention
The invention aims to solve the technical problem of providing a novel flue gas denitration catalyst for replacing the existing titanium dioxide (TiO) 2 ) Is a denitration catalyst of a carrier. Therefore, the invention provides a process for preparing a flue gas denitration catalyst by taking solid waste copper slag as a main raw material, which comprises the following steps ofThe modification of copper slag and the preparation of the copper slag into a denitration catalyst not only effectively reduces the production cost of the catalyst, but also obtains the catalyst with good catalytic effect. In order to achieve the above purpose, the present invention discloses the following technical solutions.
In a first aspect, the invention discloses a preparation process of a flue gas denitration catalyst, which comprises the following steps:
(1) Acid leaching the copper slag with acid liquor, then carrying out solid-liquid separation, and respectively collecting acid leaching liquor and solid slag for later use.
(2) Firstly adding a thickening agent into the acid leaching solution to form slurry, then adding ammonium metavanadate powder to stir and react, and adding peroxycarbonate to stir and react under the heating condition after the reaction is completed to obtain precursor slurry.
(3) And mixing the solid slag with the precursor slurry, uniformly stirring, drying, calcining in air, and crushing the calcined product to obtain the denitration catalyst particles.
Further, in step (1), the acid solution includes: any one of hydrochloric acid, sulfuric acid, nitric acid and the like, wherein copper slag contains iron element with higher content, the iron element is extracted through acid leaching, and is further processed to be converted into ferric oxide as an active ingredient of the catalyst.
Further, in the step (1), the proportion of the copper slag to the acid liquid is 1g: 30-50 ml. Optionally, the acid liquor is 20-30% by mass, and the particle size of the copper slag is 400-600 meshes.
Further, in the step (1), the acid leaching time is 10-24 hours. Preferably, the acid leaching is carried out under the heating condition of 40-70 ℃ so as to accelerate the dissolution of iron element in the copper slag.
Further, in step (2), the ratio of the leaching solution to the thickener is 1.5ml:0.11 to 0.14g. The thickening agent is added into the leaching liquor to form slurry with certain viscosity, so that the vanadium pentoxide and ferric hydroxide/ferrous iron formed after the peroxycarbonate is added are suspended and dispersed, and the sedimentation of the vanadium pentoxide and the ferric hydroxide/ferrous iron is prevented.
Further, in the step (2), the thickener includes any one of starch, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, and the like.
Further, in the step (2), the molar ratio of the ammonium metavanadate to the hydrogen ions in the acidic leaching solution is 2.5-3.2: 1.0, wherein the molar ratio of the peroxycarbonate to the iron ions in the acid leaching solution is 1.5-1.7: 1.0. optionally, the peroxycarbonate comprises at least one of sodium peroxycarbonate, potassium peroxycarbonate and the like, which releases hydrogen peroxide and carbonate ions after entering the solution, thereby simultaneously converting metavanadate and iron element in the solution into vanadium pentoxide colloid and ferric hydroxide/ferrous colloid.
Further, in the step (2), the ammonium metavanadate powder is added and stirred for reaction for 10-20 min. Preferably, the reaction is carried out under the heating condition of 45-60 ℃. In this process, the ammonium metavanadate reacts with hydrogen ions in the acidic leach solution to form metavanadate, which further reacts with hydrogen peroxide released by the peroxycarbonate to form vanadium pentoxide, thereby yielding the active component of the catalyst.
Further, in the step (2), the heating temperature is 50-75 ℃, and the stirring reaction time is 20-35 min. In this process, iron/ferrous ions in the solution and carbonate ions released by the peroxycarbonate are double hydrolyzed to form iron hydroxide/ferrous colloid, which together with the vanadium pentoxide form the active component of the catalyst, improving the catalytic performance of the catalyst.
Further, in step (3), the ratio of the solid slag to the precursor slurry is 1.0g: 5-8 ml. Optionally, mixing the two materials, and stirring for 10-15 min to fully mix the two materials.
Further, in step (3), the drying mode includes: naturally airing for 1-3 days or drying for 2-3 hours at 65-80 ℃ to reduce the moisture in the mixture formed by the solid slag and the precursor slurry, so that the subsequent calcination treatment is facilitated.
Further, in the step (3), the calcination temperature is 1320-1450 ℃, the heat preservation time is 30-50 min, and the heating rate is 10-15 ℃/min. The ferric hydroxide/ferrous hydroxide is converted into ferric oxide and the vanadium pentoxide jointly form an active component of the catalyst after calcination, and meanwhile, the thickener is carbonized and removed at high temperature to form a large number of pores in the catalyst, so that the specific surface area of the catalyst is effectively improved, and the flue gas is better contacted with the catalyst.
Optionally, in the step (3), the particle size of the denitration catalyst particles is optionally 1.0-10 mm, and the appropriate particle size can be selected according to the requirement.
In a second aspect, the invention discloses application of the catalyst obtained by the preparation process of the flue gas denitration catalyst in thermal power generation, chemical engineering field, environmental engineering field and the like.
Compared with the prior art, the invention has the beneficial effects that: the copper slag contains higher iron element, and the invention takes the iron element as a main raw material and prepares the denitration catalyst by modifying the iron element. In order to achieve the above purpose, the invention firstly carries out soaking extraction on copper slag by acid liquor to obtain acid leaching liquor containing iron ions and ferrous ions, then the invention adds thickener to prepare the acid leaching liquor into slurry with certain viscosity, thereby dispersing and suspending ferric hydroxide/ferrous colloid and vanadium pentoxide generated in the subsequent steps in the liquid phase, so as to enable the colloid to be more uniformly dispersed in the solid slag after being mixed with the solid slag, and obtaining the catalyst with more uniform load. Meanwhile, the thickener is used as a carbon source to form a large number of pores in the catalyst after being carbonized and removed in the subsequent calcination process, so that the specific surface area of the catalyst is effectively increased, the better contact between the flue gas and the catalyst is facilitated, and the catalysis effect on nitrogen oxides in the flue gas is improved. Furthermore, ammonium metavanadate is added into the slurry, and the slurry contains acid liquor/hydrogen ions remained after iron elements in copper slag are leached, so that the hydrogen ions can be eliminated after the ammonium metavanadate is added, carbonate ions in peroxycarbonate added later are prevented from being converted into carbon dioxide, and the ammonium metavanadate is converted into metavanadate by utilizing the hydrogen ions to serve as a raw material for preparing the active ingredient vanadium pentoxide of the catalyst. Furthermore, the invention utilizes the characteristic that the peroxycarbonate can release carbonate ions and hydrogen peroxide simultaneously after being dissolved in water, after the peroxycarbonate is added into the slurry, the iron/ferrous ions and the carbonate ions in the slurry undergo double hydrolysis reaction to form ferric hydroxide/ferrous colloid, and the ferrous hydroxide is further converted into ferric hydroxide under the action of the hydrogen peroxide so as to form the catalytic active component ferric oxide after subsequent calcination treatment. And the metavanadate formed by ammonium metavanadate is converted into vanadium pentoxide under the action of hydrogen peroxide, and the vanadium pentoxide and ferric oxide formed by ferric hydroxide decomposition form an active component of the catalyst together, so that the catalytic performance of the catalyst is improved. In addition, the formation of the vanadium pentoxide and the formation of the ferric hydroxide are synchronously carried out, so that the two substances are combined and separated out, a synergistic catalytic site is formed after calcination treatment, the catalytic performance is improved more favorably than that of the independently distributed vanadium pentoxide and ferric oxide, and the solid slag obtained after copper slag leaching is used as a carrier of the active component, so that the production cost of the catalyst is reduced relatively to that of the catalyst by using commercial titanium dioxide, and the recycling of the copper slag is realized.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the invention. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the present invention. As used herein, the singular is also intended to include the plural unless the context clearly indicates otherwise, and furthermore, it is to be understood that the terms "comprises" and/or "comprising" when used in this specification are taken to specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof. The invention will now be further illustrated by means of a specific implementation.
In the following examples, the main chemical composition of the copper slag is (in mass percent): 41.4% of silicon dioxide, 31.7% of iron phase, 6.2% of calcium oxide, 4.9% of magnesium oxide, 2.2% of aluminum oxide and the balance of other inorganic minerals and unavoidable impurities.
Example 1
A preparation process of a flue gas denitration catalyst comprises the following steps:
(1) Crushing copper slag, sieving with a 500-mesh sieve, and mixing the obtained copper slag powder with 25% hydrochloric acid according to the mass fraction of 1g:40ml of the mixture was stirred uniformly and then allowed to stand for 12 hours. Filtering after completion, carrying out solid-liquid separation, and respectively collecting the obtained acid leaching liquor and solid slag for later use.
(2) The acid leaching solution and the thickener are 1.5ml: and (3) adding hydroxyethyl cellulose into the acidic leaching solution at a ratio of 0.12g, and stirring for 5min to form uniform slurry. Then ammonium metavanadate powder (the molar ratio of ammonium metavanadate to hydrogen ions in the slurry is 3:1) was added to the slurry, and then the reaction was carried out for 15min with magnetic stirring. After completion, sodium peroxycarbonate powder is continuously added, and the molar ratio of the sodium peroxycarbonate to the iron ions in the acid leaching solution is 1.65:1.0, and then magnetically stirring and reacting for 30min at the heating temperature of 60 ℃ to obtain precursor slurry for later use.
(3) Mixing the solid slag obtained in the step (1) with the precursor slurry obtained in the step (2) according to the weight ratio of 1.0g: after mixing in a proportion of 7ml, the mixture was mechanically stirred for 15min and then dried at 80℃for 2 hours. Calcining the obtained dried product in air atmosphere, wherein the process comprises the steps of heating to 1350 ℃ at a speed of 15 ℃/min, preserving heat for 40min, cooling to room temperature along with a furnace, and crushing the obtained calcined product to obtain the denitration catalyst particles.
Example 2
A preparation process of a flue gas denitration catalyst comprises the following steps:
(1) Crushing copper slag, sieving the crushed copper slag with a 600-mesh sieve, and mixing the obtained copper slag powder with sulfuric acid with the mass fraction of 30% according to 1g:30ml of the mixture is stirred uniformly, and then the mixture is leached at 70 ℃ for 15 hours. Filtering after completion, carrying out solid-liquid separation, and respectively collecting the obtained acid leaching liquor and solid slag for later use.
(2) The acid leaching solution and the thickener are 1.5ml: a proportion of 0.14g is that wheat starch is added into the acid leaching solution firstly and then stirred for 5min to form uniform slurry. Then, ammonium metavanadate powder (the molar ratio of ammonium metavanadate to hydrogen ions in the slurry is 3.2:1) was added to the slurry, and then the reaction was magnetically stirred at a heating temperature of 60 ℃ for 10min. After completion, sodium peroxycarbonate powder is continuously added, and the molar ratio of the sodium peroxycarbonate to the iron ions in the acid leaching solution is 1.6:1.0, and then magnetically stirring and reacting for 20min at the heating temperature of 75 ℃ to obtain precursor slurry for later use.
(3) Mixing the solid slag obtained in the step (1) with the precursor slurry obtained in the step (2) according to the weight ratio of 1.0g: after mixing in a proportion of 5ml, the mixture was mechanically stirred for 10min and then dried at 65℃for 3 hours. Calcining the obtained dried product in air atmosphere, wherein the process comprises the steps of heating to 1450 ℃ at a speed of 15 ℃/min, then preserving heat for 30min, cooling to room temperature along with a furnace, and crushing the obtained calcined product to obtain the denitration catalyst particles.
Example 3
A preparation process of a flue gas denitration catalyst comprises the following steps:
(1) Crushing copper slag, sieving with a 450-mesh sieve, and mixing the obtained copper slag powder with sulfuric acid with the mass fraction of 20% according to 1g:45ml of the mixture was stirred uniformly and then leached at 40℃for 24 hours. Filtering after completion, carrying out solid-liquid separation, and respectively collecting the obtained acid leaching liquor and solid slag for later use.
(2) The acid leaching solution and the thickener are 1.5ml:0.13g, and stirring for 5min to form uniform slurry after adding hydroxypropyl cellulose into the acidic leaching solution. Then, ammonium metavanadate powder (the molar ratio of ammonium metavanadate to hydrogen ions in the slurry is 2.8:1) was added to the slurry, and then the reaction was magnetically stirred at a heating temperature of 45 ℃ for 20min. After completion, sodium peroxycarbonate powder is continuously added, and the molar ratio of the sodium peroxycarbonate to the iron ions in the acid leaching solution is 1.5:1.0, and then magnetically stirring and reacting for 30min at the heating temperature of 60 ℃ to obtain precursor slurry for later use.
(3) Mixing the solid slag obtained in the step (1) with the precursor slurry obtained in the step (2) according to the weight ratio of 1.0g:8ml of the materials are mixed, mechanically stirred for 15min and then naturally dried for 3 days. Calcining the obtained mixture in air atmosphere, wherein the process is that the temperature is firstly increased to 1400 ℃ at the speed of 15 ℃/min, then the temperature is kept for 40min, the mixture is cooled to room temperature along with a furnace, and the obtained calcined product is crushed to obtain the denitration catalyst particles.
Example 4
A preparation process of a flue gas denitration catalyst comprises the following steps:
(1) Crushing copper slag, sieving the crushed copper slag with a 400-mesh sieve, and mixing the obtained copper slag powder with 30% nitric acid according to the mass fraction of 1g:50ml of the mixture was stirred uniformly and then leached at 70℃for 10 hours. Filtering after completion, carrying out solid-liquid separation, and respectively collecting the obtained acid leaching liquor and solid slag for later use.
(2) The acid leaching solution and the thickener are 1.5ml: and (3) adding carboxymethyl cellulose into the acid leaching solution at a ratio of 0.11g, and stirring for 5min to form uniform slurry. Then, ammonium metavanadate powder (the molar ratio of ammonium metavanadate to hydrogen ions in the slurry is 2.5:1) was added to the slurry, and then the reaction was magnetically stirred at a heating temperature of 60 ℃ for 15min. After completion, continuously adding potassium peroxycarbonate powder, wherein the molar ratio of the potassium peroxycarbonate to the iron ions in the acid leaching solution is 1.7:1.0, and then magnetically stirring and reacting for 35min at the heating temperature of 50 ℃ to obtain precursor slurry for later use.
(3) Mixing the solid slag obtained in the step (1) with the precursor slurry obtained in the step (2) according to the weight ratio of 1.0g:6.5ml, and mechanically stirring for 15min, and naturally airing for 1 day. The obtained mixture is calcined in air atmosphere, the process is that the temperature is firstly increased to 1320 ℃ at the speed of 10 ℃/min, then the temperature is kept for 50min, the obtained mixture is cooled to room temperature along with the furnace, and the obtained calcined product is crushed to obtain the denitration catalyst particles.
Comparative example 1
A preparation process of a flue gas denitration catalyst comprises the following steps:
(1) Crushing copper slag, sieving with a 500-mesh sieve, and mixing the obtained copper slag powder with 25% hydrochloric acid according to the mass fraction of 1g:40ml of the mixture was stirred uniformly and then allowed to stand for 12 hours. Filtering after completion, carrying out solid-liquid separation, and respectively collecting the obtained acid leaching liquor and solid slag for later use.
(2) The acid leaching solution and the thickener are 1.5ml: and (3) adding hydroxyethyl cellulose into the acidic leaching solution at a ratio of 0.12g, and stirring for 5min to form uniform slurry. Then ammonium metavanadate powder (the molar ratio of ammonium metavanadate to hydrogen ions in the slurry is 3:1) was added to the slurry, and then the reaction was carried out for 15min with magnetic stirring. After completion, sodium carbonate is continuously added, and the molar ratio of the sodium carbonate to the iron ions in the acid leaching solution is 1.65:1.0, and then magnetically stirring and reacting for 30min at the heating temperature of 60 ℃ to obtain precursor slurry for later use.
(3) Mixing the solid slag obtained in the step (1) with the precursor slurry obtained in the step (2) according to the weight ratio of 1.0g: after mixing in a proportion of 7ml, the mixture was mechanically stirred for 15min and then dried at 80℃for 2 hours. Calcining the obtained dried product in air atmosphere, wherein the process comprises the steps of heating to 1350 ℃ at a speed of 15 ℃/min, preserving heat for 40min, cooling to room temperature along with a furnace, crushing the calcined product, and sieving with a 30-mesh sieve to obtain the denitration catalyst particles.
Comparative example 2
A preparation process of a flue gas denitration catalyst comprises the following steps:
(1) Crushing copper slag, sieving the crushed copper slag with a 600-mesh sieve, and mixing the obtained copper slag powder with sulfuric acid with the mass fraction of 30% according to 1g:30ml of the mixture is stirred uniformly, and then the mixture is leached at 70 ℃ for 15 hours. Filtering after completion, carrying out solid-liquid separation, and respectively collecting the obtained acid leaching liquor and solid slag for later use.
(2) Ammonium metavanadate powder (the molar ratio of ammonium metavanadate to hydrogen ions in the slurry is 3.2:1) is added into the acidic leaching solution, and then the reaction is carried out for 10min under magnetic stirring at the heating temperature of 60 ℃. After completion, sodium peroxycarbonate powder is continuously added, and the molar ratio of the sodium peroxycarbonate to the iron ions in the acid leaching solution is 1.6:1.0, and then magnetically stirring and reacting for 20min at the heating temperature of 75 ℃ to obtain precursor slurry for later use.
(3) Mixing the solid slag obtained in the step (1) with the precursor slurry obtained in the step (2) according to the weight ratio of 1.0g: after mixing in a proportion of 5ml, the mixture was mechanically stirred for 10min and then dried at 65℃for 3 hours. Calcining the obtained dried product in air atmosphere, wherein the process comprises the steps of heating to 1450 ℃ at a speed of 15 ℃/min, then preserving heat for 30min, cooling to room temperature along with a furnace, and crushing the obtained calcined product to obtain the denitration catalyst particles.
Comparative example 3
A preparation process of a flue gas denitration catalyst comprises the following steps:
(1) Crushing copper slag, sieving with a 450-mesh sieve, and mixing the obtained copper slag powder with water according to the weight ratio of 1g:45ml of the mixture was stirred uniformly and then leached at 40℃for 24 hours. Filtering after completion, carrying out solid-liquid separation, and respectively collecting the obtained leaching liquor and solid slag for later use.
(2) The leaching solution and the thickener are 1.5ml:0.13g of hydroxypropyl cellulose is added into the leaching solution, and then the solution is stirred for 5min to form uniform slurry. Then, ammonium metavanadate powder (the molar ratio of ammonium metavanadate to hydrogen ions in the slurry is 2.8:1) was added to the slurry, and then the reaction was magnetically stirred at a heating temperature of 45 ℃ for 20min. After completion, sodium peroxycarbonate powder is continuously added, and the molar ratio of the sodium peroxycarbonate to the iron ions in the acid leaching solution is 1.5:1.0, and then magnetically stirring and reacting for 30min at the heating temperature of 60 ℃ to obtain precursor slurry for later use.
(3) Mixing the solid slag obtained in the step (1) with the precursor slurry obtained in the step (2) according to the weight ratio of 1.0g:8ml of the materials are mixed, mechanically stirred for 15min and then naturally dried for 3 days. Calcining the obtained mixture in air atmosphere, wherein the process is that the temperature is firstly increased to 1400 ℃ at the speed of 15 ℃/min, then the temperature is kept for 40min, the mixture is cooled to room temperature along with a furnace, and the obtained calcined product is crushed to obtain the denitration catalyst particles.
Comparative example 4
A preparation process of a flue gas denitration catalyst comprises the following steps:
(1) Crushing copper slag, sieving the crushed copper slag with a 400-mesh sieve, and mixing the obtained copper slag powder with 30% nitric acid according to the mass fraction of 1g:50ml of the mixture was stirred uniformly and then leached at 70℃for 10 hours. Filtering after completion, carrying out solid-liquid separation, respectively collecting the obtained acid leaching liquor and solid slag, adding sodium hydroxide into the acid leaching liquor to neutralize and obtain neutral leaching liquor for later use.
(2) According to the neutral leaching solution and the thickener, 1.5ml: and (3) adding carboxymethyl cellulose into the neutral leaching solution at a ratio of 0.11g, and stirring for 5min to form uniform slurry. Then, ammonium metavanadate powder (the molar ratio of ammonium metavanadate to hydrogen ions in the slurry is 2.5:1) was added to the slurry, and then the reaction was magnetically stirred at a heating temperature of 60 ℃ for 15min. After completion, continuously adding potassium peroxycarbonate powder, wherein the molar ratio of the potassium peroxycarbonate to the iron ions in the acid leaching solution is 1.7:1.0, and then magnetically stirring and reacting for 35min at the heating temperature of 50 ℃ to obtain precursor slurry for later use.
(3) Mixing the solid slag obtained in the step (1) with the precursor slurry obtained in the step (2) according to the weight ratio of 1.0g:6.5ml, and mechanically stirring for 15min, and naturally airing for 1 day. The obtained mixture is calcined in air atmosphere, the process is that the temperature is firstly increased to 1320 ℃ at the speed of 10 ℃/min, then the temperature is kept for 50min, the obtained mixture is cooled to room temperature along with the furnace, and the obtained calcined product is crushed to obtain the denitration catalyst particles.
Performance testing
The denitration catalyst particles prepared in each of the above examples and a certain commercial catalyst (titanium dioxide is used as a carrier, vanadium pentoxide is used as a catalytic active ingredient, namely, comparative example 5) were tested for the denitration rate of nitrogen oxides in flue gas, wherein the denitration rate= (a-B) ×100%/a, wherein: the A is the concentration of nitrogen oxides in the flue gas which is not subjected to denitration treatment, the B is the concentration of nitrogen oxides in the flue gas which is subjected to denitration catalyst particle treatment, and the unit of A, B is mg/Nm 3 . At the time of the test, the denitration catalyst particles were packed in a reactor, and the temperature was set to 280℃to contain NO (concentration 400 mg/Nm 3 ) Is simulated flue gas, is fed into the reactor at a rate of 4.5L/min, and is provided with a flue gas analyzer at the exhaust port of the reactor to test the concentration of NO in the treated gas, and then the denitration rate is calculated according to the above formula, and the result is shown in the following Table 1.
Table 1 denitration rate test results of the above examples and comparative examples
Performance index Example 1 Example 2 Example 3 Example 4 Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5
NO denitration rate/% 95.33 93.71 92.46 93.28 80.19 84.41 71.62 78.35 86.54
It can be seen that the denitration catalyst prepared in examples 1 to 4 can better realize the denitration effect on flue gas compared with comparative examples 1 to 5, and the denitration catalyst uses the solid slag obtained by leaching copper slag as a carrier of a catalytic active component, so that compared with the catalyst using commercial titanium dioxide as a carrier, the denitration catalyst is beneficial to reducing the production cost of the catalyst, and has higher catalytic performance, and one of the reasons is that the catalyst components prepared in examples 1 to 4 are composed of vanadium pentoxide and ferric oxide together, so that a synergistic catalytic site is formed, the denitration catalyst is more beneficial to improving the catalytic performance compared with the independently distributed vanadium pentoxide and ferric oxide, and the recycling utilization of the copper slag is realized.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. The preparation process of the flue gas denitration catalyst is characterized by comprising the following steps of:
(1) Acid leaching the copper slag with acid liquor, then carrying out solid-liquid separation, and respectively collecting acid leaching liquor and solid slag for later use;
(2) Firstly adding a thickening agent into the acid leaching solution to form slurry, then adding ammonium metavanadate powder to stir and react, and adding peroxycarbonate to stir and react under the heating condition after the reaction is completed to obtain precursor slurry;
(3) And mixing the solid slag with the precursor slurry, uniformly stirring, drying, calcining in air, and crushing the calcined product to obtain the denitration catalyst particles.
2. The process for preparing the flue gas denitration catalyst according to claim 1, wherein in the step (1), the ratio of the copper slag to the acid liquid is 1g: 30-50 ml;
or the grain size of the copper slag is 400-600 meshes;
or, the mass fraction of the acid liquor is 20-30%;
alternatively, the acid solution includes any one of hydrochloric acid, sulfuric acid and nitric acid.
3. The process for preparing the flue gas denitration catalyst according to claim 1, wherein in the step (1), the acid leaching time is 10-24 hours; and (3) carrying out acid leaching under the heating condition of 40-70 ℃.
4. The process for preparing a flue gas denitration catalyst according to claim 1, wherein in the step (2), the ratio of the leaching solution to the thickener is 1.5ml: 0.11-0.14 g;
or in the step (2), the thickener comprises any one of starch, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose and carboxymethyl cellulose.
5. The process for preparing a flue gas denitration catalyst according to claim 1, wherein in the step (2), the molar ratio of ammonium metavanadate to hydrogen ions in the acidic leaching solution is 2.5-3.2: 1.0; the molar ratio of the peroxycarbonate to the iron ions in the acid leaching solution is 1.5-1.7: 1.0;
alternatively, in the step (2), the peroxycarbonate includes at least one of sodium peroxycarbonate and potassium peroxycarbonate.
6. The process for preparing the flue gas denitration catalyst according to claim 1, wherein in the step (2), the ammonium metavanadate powder is added and stirred for reaction for 10-20 min; carrying out the reaction under the heating condition of 45-60 ℃;
or in the step (2), adding peroxycarbonate, heating to 50-75 ℃, and stirring for 20-35 min.
7. The process for preparing a flue gas denitration catalyst according to claim 1, wherein in the step (3), the ratio of the solid slag to the precursor slurry is 1.0g: 5-8 ml; and mixing the solid slag with the precursor slurry, and stirring for 10-15 min.
8. The process for preparing the flue gas denitration catalyst according to claim 1, wherein in the step (3), the calcination temperature is 1320-1450 ℃, and the heat preservation time is 30-50 min;
or in the step (3), the particle size of the denitration catalyst particles is 1.0-10 mm.
9. The process for preparing a flue gas denitration catalyst according to any one of claims 1 to 8, wherein in the step (3), the drying mode comprises natural drying for 1 to 3 days or drying at 65 to 80 ℃ for 2 to 3 hours.
10. The use of the catalyst obtained by the preparation process of the flue gas denitration catalyst as claimed in any one of claims 1 to 9 in the fields of thermal power generation, chemical industry and environmental engineering.
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