CN116060425B - Method for removing Hg on surface of waste denitration catalyst - Google Patents
Method for removing Hg on surface of waste denitration catalyst Download PDFInfo
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- CN116060425B CN116060425B CN202310214598.3A CN202310214598A CN116060425B CN 116060425 B CN116060425 B CN 116060425B CN 202310214598 A CN202310214598 A CN 202310214598A CN 116060425 B CN116060425 B CN 116060425B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/70—Chemical treatment, e.g. pH adjustment or oxidation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
- B08B3/04—Cleaning involving contact with liquid
- B08B3/08—Cleaning involving contact with liquid the liquid having chemical or dissolving effect
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
- B08B3/04—Cleaning involving contact with liquid
- B08B3/10—Cleaning involving contact with liquid with additional treatment of the liquid or of the object being cleaned, e.g. by heat, by electricity or by vibration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B5/00—Cleaning by methods involving the use of air flow or gas flow
- B08B5/02—Cleaning by the force of jets, e.g. blowing-out cavities
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B2101/00—Type of solid waste
- B09B2101/95—Waste catalysts; Waste ion exchange materials; Waste adsorbents
Abstract
The invention relates to the technical field of solid waste treatment, and discloses a method for removing Hg on the surface of a waste denitration catalyst. The method comprises the following steps: pretreating the waste denitration catalyst, soaking in water, aerating, and taking out; soaking the taken-out waste denitration catalyst in an acidic solution containing chloride ions, taking out and washing; soaking the washed waste denitration catalyst in a solution containing iodide ions, taking out and washing; placing the washed waste denitration catalyst in a catalyst containing Na 2 S 2 O 3 And alkali metal hydroxide, taking out and washing; and (3) soaking the washed waste denitration catalyst in an organic acid aqueous solution, taking out, washing and drying. By the method, hg on the surface of the waste denitration catalyst can be effectively removed, and the subsequent recycling of the waste denitration catalyst is facilitated.
Description
Technical Field
The invention relates to the technical field of solid waste treatment, in particular to a method for removing Hg on the surface of a waste denitration catalyst.
Background
NH 3 SCR is an important denitration technology in the field of coal burning at present, and the catalyst is NH 3 The key to SCR. After the denitration catalyst is used for a long time, deactivation can occur, a large amount of harmful elements are filled in the deactivated denitration catalyst, hg in coal can be attached to the surface of the catalyst along with flue gas after combustion, and certain Hg poisoning of the catalyst can occur. Because of the coal types in part of power plants, the coal contains a considerable amount of Hg, the Hg has great harm to human beings and the environment, and has very little harm to the recycling of the follow-up denitration catalystA favorable effect.
Hg attached to the surface of the catalyst is not removed, and the quality of the subsequent recovery product and the leaching toxicity of waste water, waste residue and the like generated in the middle of recovery are affected. If Hg on the surface of the denitration catalyst can be removed, the method has a very positive effect on subsequent product recovery. Meanwhile, hg is not in the internal structure of the catalyst along with the flue gas, if the catalyst is crushed to remove Hg, reagent and equipment are wasted, and the influence on the components of the catalyst is large.
Disclosure of Invention
The invention aims to remove Hg on the surface of a waste denitration catalyst and reduce the influence of Hg on the subsequent product recovery of the waste denitration catalyst, and provides a method for removing Hg on the surface of the waste denitration catalyst.
In order to achieve the above object, the present invention provides a method for removing Hg on the surface of a waste denitration catalyst, the method comprising:
(1) Pretreating the waste denitration catalyst, soaking in water, aerating, and taking out;
(2) Soaking the waste denitration catalyst taken out in the step (1) in an acidic solution containing chloride ions, taking out, and then washing;
(3) Soaking the waste denitration catalyst washed in the step (2) in a solution containing iodide ions, taking out, and then washing;
(4) Placing the waste denitration catalyst washed in the step (3) in a catalyst containing Na 2 S 2 O 3 And alkali metal hydroxide, then taking out, and then washing;
(5) And (3) soaking the waste denitration catalyst washed in the step (4) in an organic acid aqueous solution, taking out, and then washing and drying.
Preferably, in step (1), the soaking conditions include: the temperature is 30-90deg.C, and the time is 30-300min.
Preferably, in the step (2), the concentration of hydrogen ions in the acidic solution containing chloride ions is more than or equal to 0.5mol/L;
and/or the concentration of chloride ions in the acidic solution containing chloride ions is more than or equal to 0.5mol/L.
Preferably, in step (2), the soaking conditions include: the temperature is 30-60deg.C, and the time is 30-200min.
Preferably, in the step (3), the concentration of iodide ions in the solution containing iodide ions is more than or equal to 0.05mol/L.
Preferably, in the step (3), the soaking time is 4-20 hours.
Preferably, in step (4), na is contained 2 S 2 O 3 And alkali metal hydroxide, na 2 S 2 O 3 The concentration of (2) is 0.1-0.8mol/L, and the concentration of alkali metal hydroxide is 0.05-1mol/L.
Preferably, in the step (4), the soaking time is 1-10 hours.
Preferably, in the step (5), the concentration of the organic acid in the organic acid aqueous solution is 0.1-2mol/L.
Preferably, in the step (5), the soaking time is 0.5-10h.
By the method, hg on the surface of the waste denitration catalyst can be effectively removed, and the subsequent recycling of the waste denitration catalyst is facilitated.
Detailed Description
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The invention provides a method for removing Hg on the surface of a waste denitration catalyst, which comprises the following steps:
(1) Pretreating the waste denitration catalyst, soaking in water, aerating, and taking out;
(2) Soaking the waste denitration catalyst taken out in the step (1) in an acidic solution containing chloride ions, taking out, and then washing;
(3) Soaking the waste denitration catalyst washed in the step (2) in a solution containing iodide ions, taking out, and then washing;
(4) Placing the waste denitration catalyst washed in the step (3) in a catalyst containing Na 2 S 2 O 3 And alkali metal hydroxide, then taking out, and then washing;
(5) And (3) soaking the waste denitration catalyst washed in the step (4) in an organic acid aqueous solution, taking out, and then washing and drying.
In the invention, the waste denitration catalyst is a waste SCR catalyst.
In a preferred embodiment, the Hg content of the spent SCR catalyst is from 0.001 to 1.5 μg/g.
In a preferred embodiment, in step (1), the pretreatment is performed by purging. The blowing process can remove the waste denitration catalyst pore canal and the fly ash on the surface.
In the present invention, there is no particular requirement for the selection of the purge apparatus, and various purge instruments conventionally used in the art may be used for purging.
In the method, in the step (1), aeration is carried out in the soaking process, so that the contact between water and the surface of the waste denitration catalyst is accelerated.
In a specific embodiment, the aeration mode may be bottom aeration.
In a preferred embodiment, in step (1), the soaking conditions include: the temperature is 30-90 ℃, more preferably 50-80 ℃; the time is 30-300min, more preferably 60-120min. Specifically, the temperature may be 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃ or 80 ℃; the time may be 60min, 70min, 80min, 90min, 100min, 110min or 120min.
In the invention, in the step (2), the waste denitration catalyst is placed in an acid solution containing chloride ions for soaking, and Cl - The catalyst is a group with strong affinity, and the acid has strong permeation, so that part of insoluble HgO can be converted into soluble chloride, and part of Hg compound and the adsorption adhesion of the catalyst surface can be broken.
In a preferred embodiment, in the step (2), the acidic solution containing chloride ions may be directly an aqueous hydrochloric acid solution or may be obtained by mixing chloride salt, inorganic acid and water. The inorganic acid may be sulfuric acid or nitric acid, and the chloride salt may be sodium chloride.
In a preferred embodiment, in the step (2), the concentration of hydrogen ions in the acidic solution containing chloride ions is not less than 0.5mol/L; more preferably 0.5 to 2mol/L. Specifically, it may be 0.5mol/L, 1mol/L, 1.5mol/L or 2mol/L.
In a preferred embodiment, in step (2), the concentration of chloride ions in the acidic solution containing chloride ions is not less than 0.5mol/L, more preferably 0.5 to 2mol/L. Specifically, it may be 0.5mol/L, 1mol/L, 1.5mol/L or 2mol/L.
In a preferred embodiment, in step (2), the soaking conditions include: the temperature is 30-60deg.C, and the time is 30-200min. Specifically, the soaking temperature can be 30deg.C, 35deg.C, 40deg.C, 45deg.C, 50deg.C, 55deg.C or 60deg.C; the soaking time can be 30min, 40min, 50min, 60min, 70min, 80min, 90min, 100min, 110min, 120min, 140min, 160min, 180min or 200min.
In a preferred embodiment, in the step (3), the concentration of iodide ions in the solution containing iodide ions is not less than 0.05mol/L, more preferably 0.05 to 1mol/L, still more preferably 0.1 to 0.5mol/L. Specifically, it may be 0.05mol/L, 0.1mol/L, 0.2mol/L, 0.3mol/L, 0.4mol/L, 0.5mol/L, 0.6mol/L, 0.8mol/L or 1mol/L.
In the method disclosed by the invention, in the step (3), the waste denitration catalyst is placed in an aqueous solution containing iodide ions for soaking, so that part of Hg compounds can be subjected to complexation with the iodide ions in the solution, and further Hg removal is facilitated.
In a specific embodiment, the solution containing iodide ions may be an aqueous solution of potassium iodide or an aqueous solution of sodium iodide.
In a preferred embodiment, in step (3), the soaking time is 4 to 20 hours, more preferably 5 to 10 hours. Specifically, it may be 5h, 6h, 7h, 8h, 9h or 10h.
In a preferred embodiment, in step (4), na is contained 2 S 2 O 3 And alkali metal hydroxide, na 2 S 2 O 3 The concentration of (2) is 0.1-0.8mol/L, and the concentration of alkali metal hydroxide is 0.05-1mol/L. Specifically, na 2 S 2 O 3 The concentration of (C) may be 0.1mol/L, 0.2mol/L, 0.3mol/L, 0.4mol/L, 0.5mol/L, 0.6mol/L, 0.7mol/L or 0.8mol/L; the concentration of the alkali metal hydroxide may be 0.05mol/L, 0.1mol/L, 0.2mol/L, 0.3mol/L, 0.4mol/L, 0.5mol/L, 0.6mol/L, 0.7mol/L, 0.8mol/L, 0.9mol/L or 1mol/L.
In particular embodiments, the alkali metal hydroxide may be sodium hydroxide and/or potassium hydroxide.
In the method of the present invention, in the step (4), the waste denitration catalyst is placed in a reactor containing Na 2 S 2 O 3 And alkali metal hydroxide solution, the alkaline environment can promote the dissociation of Hg adsorbate, and thiosulfate can be in certain complexation with Hg compounds, so that Hg removal is promoted.
In a preferred embodiment, in step (4), the soaking time is 1 to 10 hours, more preferably 2 to 6 hours. Specifically, the time period may be 2h, 3h, 4h, 5h or 6h.
In the invention, in the step (5), the waste denitration catalyst is placed in an organic acid aqueous solution for soaking, so that the waste denitration catalyst can be subjected to acidolysis and complexation with Hg to promote removal of Hg.
In a preferred embodiment, in step (5), the concentration of the organic acid in the aqueous organic acid solution is 0.1 to 2mol/L, more preferably 0.1 to 0.5mol/L. Specifically, it may be 0.1mol/L, 0.2mol/L, 0.3mol/L, 0.4mol/L or 0.5mol/L.
In a preferred embodiment, in step (5), the organic acid is oxalic acid or tartaric acid.
In a preferred embodiment, in step (5), the soaking time is 0.5 to 10 hours. Specifically, it may be 0.5h, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h or 10h.
In a specific embodiment, in the steps (2) - (5), the washing mode may be to soak the material to be washed in water, and the soaking time may be 0.5-2h.
In a preferred embodiment, in step (5), the temperature of the drying is 50-105 ℃, more preferably 80-100 ℃.
The present invention will be described in detail by way of examples, but the scope of the present invention is not limited thereto.
Example 1
(1) Purging the surface and pore canal of a honeycomb waste denitration catalyst of a certain power plant, soaking the whole waste denitration catalyst in clean water and aerating, wherein the soaking temperature is 60 ℃, the soaking time is 80min, the aerating mode is bottom aerating, and then taking out;
(2) Placing the waste denitration catalyst taken out in the step (1) into hydrochloric acid solution (the concentration of hydrogen ions is 0.6mol/L and the concentration of chloride ions is 0.6 mol/L) for soaking, wherein the soaking temperature is 40 ℃ for 80min, then taking out, and then washing (soaking in clear water for 1 h);
(3) Placing the waste denitration catalyst washed in the step (2) into a solution (KI aqueous solution) containing iodide ions for soaking, wherein the concentration of the iodide ions is 0.3mol/L, the soaking time is 8 hours, and then taking out the catalyst, and then washing (soaking in clear water for 1 hour);
(4) Placing the waste denitration catalyst washed in the step (3)In the presence of Na 2 S 2 O 3 Soaking in NaOH solution, na 2 S 2 O 3 The concentration of (2) is 0.5mol/L, the concentration of NaOH is 0.3mol/L, soaking for 5h, then taking out, and then washing (soaking in clear water for 1 h);
(5) And (3) placing the waste denitration catalyst washed in the step (4) into an organic acid (oxalic acid) aqueous solution for soaking, wherein the concentration of oxalic acid is 0.3mol/L, the soaking time is 1h, then taking out, washing (soaking in clear water for 1 h), and then drying at 90 ℃ to constant weight.
Example 2
(1) Purging the surface and pore canal of a honeycomb waste denitration catalyst of a certain power plant, soaking the whole waste denitration catalyst in clean water and aerating, wherein the soaking temperature is 60 ℃, the soaking time is 80min, the aerating mode is bottom aerating, and then taking out;
(2) Placing the waste denitration catalyst taken out in the step (1) into hydrochloric acid solution (the concentration of hydrogen ions is 0.6mol/L and the concentration of chloride ions is 0.6 mol/L) for soaking, wherein the soaking temperature is 40 ℃ for 60min, then taking out, and then washing (soaking in clear water for 1 h);
(3) Placing the waste denitration catalyst washed in the step (2) into a solution (KI aqueous solution) containing iodide ions for soaking, wherein the concentration of the iodide ions is 0.2mol/L, the soaking time is 8 hours, and then taking out the catalyst, and then washing (soaking in clear water for 1 hour);
(4) Placing the waste denitration catalyst washed in the step (3) in a catalyst containing Na 2 S 2 O 3 Soaking in NaOH solution, na 2 S 2 O 3 The concentration of (2) is 0.5mol/L, the concentration of NaOH is 0.4mol/L, soaking for 5h, then taking out, and then washing (soaking in clear water for 1 h);
(5) And (3) placing the waste denitration catalyst washed in the step (4) into an organic acid (oxalic acid) aqueous solution for soaking, wherein the concentration of oxalic acid is 0.3mol/L, the soaking time is 1h, then taking out, washing (soaking in clear water for 1 h), and then drying at 95 ℃ to constant weight.
Example 3
(1) Purging the surface and pore canal of a plate-shaped waste denitration catalyst of a certain power plant, soaking the whole waste denitration catalyst in clean water and aerating, wherein the soaking temperature is 60 ℃, the soaking time is 70min, the aeration mode is bottom aeration, and then taking out;
(2) Placing the waste denitration catalyst taken out in the step (1) into hydrochloric acid solution (the concentration of hydrogen ions is 0.6mol/L and the concentration of chloride ions is 0.6 mol/L) for soaking, wherein the soaking temperature is 40 ℃ for 60min, then taking out, and then washing (soaking in clear water for 1 h);
(3) Placing the waste denitration catalyst washed in the step (2) into a solution (KI aqueous solution) containing iodide ions for soaking, wherein the concentration of the iodide ions is 0.2mol/L, the soaking time is 7 hours, and then taking out the catalyst, and then washing (soaking in clear water for 1 hour);
(4) Placing the waste denitration catalyst washed in the step (3) in a catalyst containing Na 2 S 2 O 3 Soaking in NaOH solution, na 2 S 2 O 3 The concentration of (2) is 0.5mol/L, the concentration of NaOH is 0.4mol/L, soaking for 5h, then taking out, and then washing (soaking in clear water for 1 h);
(5) And (3) placing the waste denitration catalyst washed in the step (4) into an organic acid (oxalic acid) aqueous solution for soaking, wherein the concentration of oxalic acid is 0.3mol/L, the soaking time is 1h, then taking out, washing (soaking in clear water for 1 h), and then drying at 90 ℃ to constant weight.
Example 4
(1) Purging the surface and pore canal of a plate-shaped waste denitration catalyst of a certain power plant, soaking the whole waste denitration catalyst in clean water and aerating, wherein the soaking temperature is 55 ℃, the soaking time is 80min, the aeration mode is bottom aeration, and then taking out;
(2) Placing the waste denitration catalyst taken out in the step (1) into an acidic solution containing chloride ions (obtained by mixing nitric acid, sodium chloride and water, wherein the concentration of the hydrogen ions is 0.6mol/L and the concentration of the chloride ions is 0.8 mol/L), soaking at the temperature of 40 ℃ for 60min, taking out, and then washing (soaking in clear water for 1 h);
(3) Placing the waste denitration catalyst washed in the step (2) into a solution containing iodide ions (NaI aqueous solution) for soaking, wherein the concentration of the iodide ions is 0.2mol/L, the soaking time is 8 hours, and then taking out the catalyst, and then washing (soaking in clear water for 1 hour);
(4) Placing the waste denitration catalyst washed in the step (3) in a catalyst containing Na 2 S 2 O 3 Soaking in KOH solution, na 2 S 2 O 3 The concentration of (2) is 0.5mol/L, the concentration of KOH is 0.4mol/L, soaking for 5h, then taking out, and then washing (soaking in clear water for 1 h);
(5) And (3) soaking the waste denitration catalyst washed in the step (4) in an organic acid (citric acid) aqueous solution for 1h at a concentration of 0.25mol/L, taking out, washing (soaking in clear water for 1 h), and drying at 100 ℃ to constant weight.
Example 5
(1) Purging the surface and pore canal of a plate-shaped waste denitration catalyst of a certain power plant, soaking the whole waste denitration catalyst in clean water and aerating, wherein the soaking temperature is 55 ℃, the soaking time is 80min, the aeration mode is bottom aeration, and then taking out;
(2) Placing the waste denitration catalyst taken out in the step (1) into an acidic solution containing chloride ions (obtained by mixing sulfuric acid, sodium chloride and water, wherein the concentration of the hydrogen ions is 0.5mol/L and the concentration of the chloride ions is 0.8 mol/L), soaking at 45 ℃ for 50min, taking out, and then washing (soaking in clear water for 1 h);
(3) Placing the waste denitration catalyst washed in the step (2) into a solution containing iodide ions (NaI aqueous solution) for soaking, wherein the concentration of the iodide ions is 0.2mol/L, the soaking time is 7 hours, and then taking out the catalyst, and then washing (soaking in clear water for 1 hour);
(4) Placing the waste denitration catalyst washed in the step (3) in a catalyst containing Na 2 S 2 O 3 Soaking in KOH solution, na 2 S 2 O 3 The concentration of (2) is 0.5mol/L, the concentration of KOH is 0.4mol/L, soaking for 5h, then taking out, and then washing (soaking in clear water for 1 h);
(5) And (3) soaking the waste denitration catalyst washed in the step (4) in an organic acid (tartaric acid) aqueous solution for 1h at a concentration of 0.4mol/L, taking out, washing (soaking in clear water for 1 h), and drying at 100 ℃ to constant weight.
Example 6
(1) Purging the surface and pore canal of a plate-shaped waste denitration catalyst of a certain power plant, soaking the whole waste denitration catalyst in clear water and aerating, wherein the soaking temperature is 70 ℃, the soaking time is 70min, the aeration mode is bottom aeration, and then taking out;
(2) Placing the waste denitration catalyst taken out in the step (1) into an acidic solution containing chloride ions (obtained by mixing sulfuric acid, sodium chloride and water, wherein the concentration of the hydrogen ions is 0.5mol/L and the concentration of the chloride ions is 0.7 mol/L), soaking at 50 ℃ for 60min, taking out, and then washing (soaking in clear water for 1 h);
(3) Placing the waste denitration catalyst washed in the step (2) into a solution containing iodide ions (NaI aqueous solution) for soaking, wherein the concentration of the iodide ions is 0.2mol/L, the soaking time is 8 hours, and then taking out the catalyst, and then washing (soaking in clear water for 1 hour);
(4) Placing the waste denitration catalyst washed in the step (3) in a catalyst containing Na 2 S 2 O 3 Soaking in KOH solution, na 2 S 2 O 3 The concentration of (2) is 0.5mol/L, the concentration of KOH is 0.4mol/L, soaking for 5h, then taking out, and then washing (soaking in clear water for 1 h);
(5) And (3) soaking the waste denitration catalyst washed in the step (4) in an organic acid (tartaric acid) solution for 1h at a concentration of 0.4mol/L, taking out, washing (soaking in clear water for 1 h), and drying at 100 ℃ to constant weight.
Comparative example 1
The surface and pore canal of a honeycomb waste denitration catalyst (the same as in example 1) of a power plant are purged, then the whole waste denitration catalyst is soaked in clean water and aerated, the soaking temperature is 60 ℃, the soaking time is 80min, and then the waste denitration catalyst is taken out and dried to constant weight at 90 ℃.
Comparative example 2
(1) Purging the surface and pore canal of a honeycomb waste denitration catalyst (the same as that of the embodiment 1) of a certain power plant, soaking the whole waste denitration catalyst in clean water and aerating, wherein the soaking temperature is 60 ℃, the soaking time is 80min, the aeration mode is bottom aeration, and then taking out;
(2) Placing the waste denitration catalyst taken out in the step (1) into hydrochloric acid solution (the concentration of hydrogen ions is 0.6mol/L and the concentration of chloride ions is 0.6 mol/L) for soaking, wherein the soaking temperature is 40 ℃ for 80min, then taking out, and then washing (soaking in clear water for 1 h);
(3) And (3) placing the waste denitration catalyst washed in the step (2) into an organic acid (oxalic acid) solution for soaking, wherein the concentration of oxalic acid is 0.3mol/L, the soaking time is 1h, then taking out, washing (soaking in clear water for 1 h), and then drying at 90 ℃ to constant weight.
Comparative example 3
And (3) simply purging the surface and pore canal of a plate-shaped waste denitration catalyst (the same as that of the embodiment 3) of a certain power plant, heating, aerating and soaking the whole honeycomb-shaped catalyst by clear water, heating at 60 ℃ for 80min, taking out the whole denitration catalyst, and drying at 90 ℃ to constant weight after taking out.
Comparative example 4
(1) Purging the surface and pore canal of a plate-shaped waste denitration catalyst (the same as that of the embodiment 3) of a certain power plant, soaking the whole waste denitration catalyst in clean water, aerating, wherein the soaking temperature is 60 ℃, the soaking time is 80min, aerating at the bottom in an aeration mode, and taking out;
(2) Placing the waste denitration catalyst taken out in the step (1) into hydrochloric acid solution (the concentration of hydrogen ions is 0.6mol/L and the concentration of chloride ions is 0.6 mol/L) for soaking, wherein the soaking temperature is 40 ℃ for 60min, then taking out, and then washing (soaking in clear water for 1 h);
(3) And (3) placing the waste denitration catalyst washed in the step (2) into an organic acid (oxalic acid) solution for soaking, wherein the concentration of oxalic acid is 0.3mol/L, the soaking time is 1h, then taking out, washing (soaking in clear water for 1 h), and then drying at 90 ℃ to constant weight.
Test case
The testing method comprises the following steps:
(1) Weighing the weight M0 of the waste denitration catalyst before treatment;
(2) Crushing the waste denitration catalyst obtained after the treatment to obtain a crushed material, and then testing the weight M1 of Hg in the crushed material (Hg content in the crushed material is multiplied by the weight of crushed material); detecting Hg concentration and volume in the solution and the washing liquid after soaking in each step in the treatment process, and then calculating the sum M2 of the weights of Hg in the solution; wherein the Hg content in the crushed material and the Hg concentration in the solution are detected by an atomic absorption spectrometer ICETM3500 (AAS);
the Hg removal rate η was calculated according to the following formula:
the Hg content c in the pre-treatment spent denitration catalyst was calculated according to the following formula:
the Hg content and Hg removal rate in the waste denitration catalyst before treatment in examples and comparative examples were measured according to the above test methods, and the results are shown in table 1.
TABLE 1
As can be seen from Table 1, hg on the surface of the waste denitration catalyst can be effectively removed by the method of the present invention.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
1. A method for removing Hg from the surface of a waste denitration catalyst, comprising the steps of:
(1) Pretreating the waste denitration catalyst, soaking in water, aerating, and taking out;
(2) Soaking the waste denitration catalyst taken out in the step (1) in an acidic solution containing chloride ions, taking out, and then washing;
(3) Soaking the waste denitration catalyst washed in the step (2) in a solution containing iodide ions, taking out, and then washing;
(4) Placing the waste denitration catalyst washed in the step (3) in a catalyst containing Na 2 S 2 O 3 And alkali metal hydroxide, then taking out, and then washing;
(5) Soaking the waste denitration catalyst washed in the step (4) in an organic acid aqueous solution, taking out, and then washing and drying;
the pretreatment mode is purging.
2. The method of claim 1, wherein in step (1), the soaking conditions comprise: the temperature is 30-90deg.C, and the time is 30-300min.
3. The method according to claim 1, wherein in the step (2), the concentration of hydrogen ions in the acidic solution containing chlorine ions is not less than 0.5mol/L;
and/or the concentration of chloride ions in the acidic solution containing chloride ions is more than or equal to 0.5mol/L.
4. A method according to claim 1 or 3, wherein in step (2), the conditions of soaking comprise: the temperature is 30-60deg.C, and the time is 30-200min.
5. The method according to claim 1, wherein in the step (3), the concentration of iodide ions in the solution containing iodide ions is not less than 0.05mol/L.
6. The method according to claim 1 or 5, wherein in step (3), the soaking time is 4 to 20 hours.
7. The method according to claim 1, wherein in the step (4), na is contained 2 S 2 O 3 And alkali metal hydroxide, na 2 S 2 O 3 The concentration of (2) is 0.1-0.8mol/L, and the concentration of alkali metal hydroxide is 0.05-1mol/L.
8. The method according to claim 1 or 7, wherein in step (4), the soaking time is 1 to 10 hours.
9. The method according to claim 1, wherein in the step (5), the concentration of the organic acid in the aqueous organic acid solution is 0.1 to 2mol/L.
10. The method according to claim 1 or 9, wherein in step (5), the soaking time is 0.5 to 10 hours.
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