CN115869938B - Treatment method of waste denitration catalyst, preparation method of denitration catalyst and application of denitration catalyst - Google Patents
Treatment method of waste denitration catalyst, preparation method of denitration catalyst and application of denitration catalyst Download PDFInfo
- Publication number
- CN115869938B CN115869938B CN202310214591.1A CN202310214591A CN115869938B CN 115869938 B CN115869938 B CN 115869938B CN 202310214591 A CN202310214591 A CN 202310214591A CN 115869938 B CN115869938 B CN 115869938B
- Authority
- CN
- China
- Prior art keywords
- solution
- denitration catalyst
- soaking
- concentration
- source
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention relates to the field of solid waste treatment, and discloses a treatment method of a waste denitration catalyst, a preparation method of the denitration catalyst and application of the denitration catalyst. The method comprises the following steps: (1) Soaking the waste denitration catalyst in hydrogen peroxide, and adding Na into the hydrogen peroxide 2 S 2 O 3 Then, continuously soaking to obtain a material a; (2) Soaking the material a in an alkaline solution, taking out, and soaking in an acidic solution to obtain a material b; (3) Immersing material b in potassium iodide solution, EDTA solution, phosphate solution and chloride solutionSoaking, and taking out to obtain a material c; (4) pulverizing the material c to obtain a pulverized material d; (5) Carrying out the steps (1) to (3) on the crushed material d to obtain a material e; (6) Mixing the material e, the surfactant and the ethanol, ball milling, filtering, and drying filter residues to obtain a reclaimed material. The method removes harmful substances in the waste denitration catalyst, and the obtained reclaimed material is used for preparing the denitration catalyst, so that the method has a great application prospect.
Description
Technical Field
The invention relates to the field of solid waste treatment, in particular to a treatment method of a waste denitration catalyst, a preparation method of the denitration catalyst and application of the denitration catalyst.
Background
NH 3 SCR is an important denitration technology in the field of coal burning at present, and the denitration catalyst is NH 3 -a critical part of the SCR. However, the denitration catalyst is deactivated after long-term use, and the deactivated denitration catalyst cannot be put into use any more and needs to be disposed of by a proper method. The inactivated denitration catalyst contains a large amount of harmful heavy metal elements and some harmful substances for inactivating the catalyst, and has great harm to human body health and environment. In addition, the waste denitration catalyst also contains a large amount of valuable components such as titanium dioxide, tungsten trioxide and the like, and if the valuable components can be reused, the cost is necessarily greatly saved.
In the prior art, the waste denitration catalyst is used for preparing titanium dioxide or titanium tungsten powder, and the processes of high-temperature roasting or high-temperature high-pressure leaching and the like exist, so that pollutants are inevitably discharged in the recovery process, and the recovery condition is harsh. In addition, the problems of large raw material consumption, high price and the like are faced when the fresh denitration catalyst is prepared.
Disclosure of Invention
The invention aims to solve the problems of recycling of waste denitration catalysts, expensive raw materials for preparing the denitration catalysts and the like in the prior art, and provides a treatment method of the waste denitration catalysts, a preparation method of the denitration catalysts and application thereof.
In order to achieve the above object, an aspect of the present invention provides a method for treating a waste denitration catalyst, comprising the steps of:
(1) Placing the waste denitration catalyst into hydrogen peroxide solution for first-stage soaking, and then adding Na into the hydrogen peroxide solution 2 S 2 O 3 Soaking the aqueous solution in the second stage, and performing solid-liquid separation after the soaking is finished to obtain a material a;
(2) Placing the material a in an alkaline solution for a third stage of soaking, then performing solid-liquid separation, placing the obtained solid phase in an acidic solution for a fourth stage of soaking, and then performing solid-liquid separation to obtain a material b;
(3) Sequentially soaking the material b in a potassium iodide solution, an EDTA solution, a phosphate solution and a hydrochloride solution, and then carrying out solid-liquid separation to obtain a material c;
(4) Drying and crushing the material c to obtain a crushed material d;
(5) Subjecting the crushed material d to the operations from step (1) to step (3) to obtain a treated material e;
(6) Mixing the material e, the surfactant and the ethanol, performing ball milling, filtering, washing filter residues, and drying to obtain a reclaimed material.
Preferably, the concentration of the hydrogen peroxide solution is 5-20%.
Preferably, the Na 2 S 2 O 3 Na in aqueous solution 2 S 2 O 3 The concentration of (C) is 0.2-0.5mol/L.
Preferably, the conditions of the first stage soaking include: the temperature is 60-90deg.C, and the time is 60-120min.
Preferably, the conditions of the second stage soaking include: the temperature is 60-90deg.C, and the time is 60-120min.
Preferably, the alkaline solution is a NaOH solution and/or a KOH solution; the acidic solution is selected from one or more than two of sulfuric acid solution, oxalic acid solution, hydrochloric acid solution and phosphoric acid solution;
preferably, OH in the alkaline solution - The concentration of (C) is 0.02-0.2mol/L.
Preferably, the concentration of solute in the acidic solution is 0.01-0.1mol/L.
Preferably, the conditions of the third stage soaking include: the temperature is 60-90deg.C, and the time is 60-200min.
Preferably, the conditions of the fourth stage soaking include: the temperature is 60-90 ℃ and the time is 1-5h.
Preferably, the concentration of potassium iodide in the potassium iodide solution is 0.05-0.5mol/L, the concentration of EDTA in the EDTA solution is 0.1-0.3g/L, the concentration of phosphate in the phosphate solution is 0.02-0.2mol/L, and the concentration of hydrochloride in the hydrochloride solution is 0.05-5mol/L.
Preferably, the soaking temperature in the potassium iodide solution, EDTA solution, phosphate solution and hydrochloride solution is 60-90 ℃, and the soaking time is 1-10h.
Preferably, the surfactant is selected from one or more of sodium hard fatty acid, sodium dodecyl sulfonate and cetyltrimethylammonium bromide.
Preferably, the weight ratio of the surfactant to the amount of material e is 0.03-0.1:1.
Preferably, the solid to liquid ratio when soaking in step (5) is 1g:5-30mL.
The second aspect of the invention provides an application of the treatment method of the waste denitration catalyst in preparation of the denitration catalyst.
The third aspect of the present invention provides a method for preparing a denitration catalyst, the method comprising the steps of:
(1) Mixing a tungsten source with an ammonia water solution to obtain a mixed solution A, and then mixing the mixed solution A with a titanium source to obtain a titanium-tungsten mixture;
(2) Mixing a vanadium source, an ammonia water solution and monoethanolamine to obtain a mixed solution B, and then mixing the mixed solution B with a titanium tungsten powder mixture to obtain a mixture C;
(3) Mixing the mixture C with a lubricant, a binder, a plasticizer and glass fibers, and then mixing and ageing;
(4) Extruding and molding the stale material, and then drying and calcining;
the tungsten source is ammonium metatungstate, and the vanadium source is ammonium metavanadate;
The content of the tungsten source is 1.8-2.6wt% based on 100wt% of the total weight of the tungsten source and the titanium source, and the content of the vanadium source is 0.5-0.9wt% based on 100wt% of the total weight of the vanadium source and the titanium source, wherein the tungsten source is WO 3 Calculated by V as the vanadium source 2 O 5 Counting;
the titanium source comprises TiO 2 And a reclaimed material obtained by the treatment method of the waste denitration catalyst;
the content of the reclaimed materials is 10-30 wt% based on the total weight of the titanium source as 100 wt%.
The fourth aspect of the invention provides an application of the denitration catalyst obtained by the preparation method of the denitration catalyst in removing nitrogen oxides in industrial boiler tail gas.
The invention provides a treatment method of a waste denitration catalyst with milder conditions, which aims at the high heavy metal removal rate and sulfate removal rate of the waste denitration catalyst, the recovery rate of valuable components in the waste denitration catalyst is high, and the method does not need to adopt methods such as high-temperature treatment, high-pressure treatment and the like, and the recovery condition is mild, but the method still has excellent removal rate for harmful substances influencing the recycling utilization of the waste denitration catalyst. The reclaimed materials obtained by the method can be successfully applied to the preparation of the denitration catalyst, the dosage of a titanium source, a tungsten source and a vanadium source in the raw material of the denitration catalyst can be reduced, and more importantly, the prepared denitration catalyst still has excellent performance, and the preparation cost of the denitration catalyst is further saved.
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 treatment method of a waste denitration catalyst, which comprises the following steps:
(1) Placing the waste denitration catalyst into hydrogen peroxide solution for first-stage soaking, and then adding Na into the hydrogen peroxide solution 2 S 2 O 3 Soaking the aqueous solution in the second stage, and performing solid-liquid separation after the soaking is finished to obtain a material a;
(2) Placing the material a in an alkaline solution for a third stage of soaking, then performing solid-liquid separation, placing the obtained solid phase in an acidic solution for a fourth stage of soaking, and then performing solid-liquid separation to obtain a material b;
(3) Sequentially soaking the material b in a potassium iodide solution, an EDTA solution, a phosphate solution and a hydrochloride solution, and then carrying out solid-liquid separation to obtain a material c;
(4) Drying and crushing the material c to obtain a crushed material d;
(5) Subjecting the crushed material d to the operations from step (1) to step (3) to obtain a treated material e;
(6) Mixing the material e, the surfactant and the ethanol, performing ball milling, filtering, washing filter residues, and drying to obtain a reclaimed material.
In the method of the present invention, the shape of the waste denitration catalyst is not limited, and may be a shape well known to those skilled in the art, for example, a honeycomb shape or a plate shape. In a specific embodiment, the waste denitration catalyst is a vanadium-titanium denitration catalyst used by a coal-fired boiler, and the waste denitration catalyst contains 65-85wt% of titanium dioxide, 2-6wt% of tungsten trioxide and 0.2-1.5wt% of V based on 100wt% of the total weight of the waste denitration catalyst 2 O 5 。
In the method of the present invention, when the waste denitration catalyst is directly removed from the immersion solution in the "solid-liquid separation" operation described in the steps (1) to (3) before the pulverization operation described in the step (4), the "solid-liquid separation" operation is filtration or centrifugal separation when the pulverized material d is subjected to the operation described in the steps (1) to (3) in the step (5) after the pulverized material c is pulverized to obtain the pulverized material d.
In the method of the present invention, in the steps (1) to (3), the waste denitration catalyst is in a block shape, and the size thereof is close to the size of the waste denitration catalyst used in the SCR denitration reaction.
In a specific embodiment, in the step (1), the waste denitration catalyst is further required to be pretreated before being soaked in the first stage, and the pretreatment process is to simply purge the surface and pore channels of the waste denitration catalyst to remove floating dust and physically attached pollutants on the surface of the waste denitration catalyst.
In the method, the waste denitration catalyst is placed in the hydrogen peroxide solution for first-stage soaking, as element on the surface of the waste denitration catalyst is oxidized in the hydrogen peroxide solution, subsequent further removal is facilitated, and meanwhile, pollutants attached to the surface of the waste denitration catalyst and in a pore canal in a physical mode can be further removed by the hydrogen peroxide solution. After the first stage soaking is finished, na is added into the hydrogen peroxide solution 2 S 2 O 3 The aqueous solution is soaked in the second stage to further remove As element.
In a specific embodiment, in order to further improve the removal rate of heavy metals in the waste denitration catalyst, the concentration of the hydrogen peroxide solution is controlled to be 5-20%, preferably 6-15%. Specifically, the concentration of the hydrogen peroxide solution may be 6%, 8%, 10%, 12%, 14% or 15%.
In a specific embodiment, the Na is controlled 2 S 2 O 3 Na in aqueous solution 2 S 2 O 3 The concentration of (C) is 0.2-0.5mol/L, preferably 0.25-0.4mol/L. Specifically, the Na 2 S 2 O 3 Na in aqueous solution 2 S 2 O 3 The concentration of (C) may be 0.25mol/L, 0.3mol/L, 0.35mol/L or 0.4mol/L.
In the method of the invention, in order to further improve the removal rate of heavy metals in the waste denitration catalyst, the conditions of the first stage soaking and the second stage soaking need to be reasonably controlled.
In a specific embodiment, the conditions of the first stage soaking include: the temperature is 60-90deg.C, and the time is 60-120min. Specifically, the temperature of the first stage soaking may be 60 ℃, 70 ℃, 80 ℃ or 90 ℃; the first stage soaking time may be 60min, 70min, 80min, 90min, 100min, 110min or 120min.
In a specific embodiment, the conditions of the second stage soaking include: the temperature is 60-90deg.C, and the time is 60-120min. Specifically, the temperature of the second stage soaking may be 60 ℃, 70 ℃, 80 ℃ or 90 ℃; the second stage soaking time can be 60min, 70min, 80min, 90min, 100min, 110min or 120min.
In a specific embodiment, step (1) further includes: and after the second stage of soaking is finished, taking out the soaked material, and washing the material with clear water for 4-5 times to obtain a material a.
In the method, the material a is soaked in alkaline solution and acidic solution to remove sulfate, water-soluble vanadium, ammonium salt and the like on the surface of the waste denitration catalyst. In order to further improve the removal rate of heavy metals and harmful substances in the waste denitration catalyst, the concentrations of the alkaline solution and the acidic solution need to be controlled.
In a preferred embodiment, the alkaline solution is a NaOH solution and/or a KOH solution; the acidic solution is one or more selected from sulfuric acid solution, oxalic acid solution, hydrochloric acid solution and phosphoric acid solution.
In a specific embodiment, OH in the alkaline solution - The concentration of (C) is 0.02-0.2mol/L, preferably 0.04-0.15mol/L; the concentration of the solute in the acidic solution is 0.01 to 0.1mol/L, preferably 0.02 to 0.06mol/L. Specifically, OH in the alkaline solution - The concentration of (C) may be 0.04mol/L, 0.06mol/L, 0.08mol/L, 0.1mol/L, 0.12mol/L or 0.15mol/L; the concentration of solute in the acidic solution may be 0.02mol/L, 0.03mol/L, 0.04mol/L, 0.05mol/L or 0.06mol/L.
In the method of the present invention, in order to further ensure that heavy metals and harmful substances in the waste denitration catalyst are removed as much as possible, conditions of the third stage soaking and the fourth stage soaking need to be reasonably controlled.
In a specific embodiment, the conditions of the third stage soaking include: the temperature is 60-90deg.C, and the time is 60-200min, preferably 80-150min. Specifically, the temperature of the third stage soaking may be 60 ℃, 70 ℃, 80 ℃, 90 ℃; the third stage soaking time may be 80min, 100min, 120min, 140min or 150min. The conditions of the fourth stage soaking include: the temperature is 60-90 ℃, and the time is 1-5 hours, preferably 2-4 hours. Specifically, the temperature of the fourth stage soaking may be 60 ℃, 70 ℃, 80 ℃, 90 ℃; the fourth stage soaking time can be 2 hours, 2.5 hours, 3 hours, 3.5 hours or 4 hours.
In a specific embodiment, in the step (2), after the second stage soaking and the fourth stage soaking are finished, the soaked materials are taken out and washed for 4-5 times by adopting clear water, and then the subsequent recovery process is carried out.
In the method, the material b is sequentially soaked in potassium iodide solution, EDTA solution, phosphate solution and hydrochloride solution, so that metal elements such as calcium element, vanadium element and the like in the waste denitration catalyst can be further removed.
In a specific embodiment, the concentration of potassium iodide in the potassium iodide solution is 0.05 to 0.5mol/L, preferably 0.2 to 0.4mol/L; the concentration of EDTA in the EDTA solution is 0.1-0.3g/L, preferably 0.15-0.25g/L; the concentration of phosphate in the phosphate solution is 0.02-0.2mol/L, preferably 0.1-0.15mol/L; the concentration of the hydrochloride in the hydrochloride solution is 0.05-5mol/L, preferably 2-4mol/L.
In the method of the present invention, the kinds of the phosphate and hydrochloride are not particularly limited herein, and may be water-soluble substances common in the art. In particular, the phosphate may be sodium phosphate or potassium phosphate; the hydrochloride may be sodium chloride, potassium chloride or ammonia chloride.
In the method, in the step (3), the material b is sequentially placed in a potassium iodide solution, an EDTA solution, a phosphate solution and a hydrochloride solution, the soaking temperature is 60-90 ℃, and the soaking time is 1-10h. In a specific embodiment, the temperature and time of soaking the material b in any one solution may be the same or different, and the relationship between the temperature and time of soaking in each stage is not limited in the method of the present invention.
In specific embodiments, the material b is soaked in potassium iodide solution, EDTA solution, phosphate solution and chloride solution at a temperature of 60 ℃, 70 ℃, 80 ℃ or 90 ℃ for a time of 1h, 3h, 5h, 8h or 10h.
In a specific embodiment, in the step (3), the material b is sequentially placed in a potassium iodide solution, an EDTA solution, a phosphate solution and a chloride solution for soaking, and after each soaking, the soaked material is washed for 4-5 times by adopting clear water, and then is continuously placed in a subsequent solution for soaking.
In a specific embodiment, in step (1) to step (3), the amount of the soaking solution is such that the spent denitration catalyst is completely immersed.
In the process according to the invention, in step (3) the mass c is crushed to less than 100 mesh to give crushed mass d, preferably 100-120 mesh.
In the method of the invention, the heavy metal elements and the harmful substances in the waste denitration catalyst can be further removed by treating the crushed material d according to the operations in the steps (1) to (3), so that the removal rate of the heavy metal elements and the harmful substances is further improved.
In the method of the present invention, in step (5), when the pulverized material d is treated in accordance with the operations of step (1) to step (3), the solid-to-liquid ratio at the time of soaking is controlled to be 1g:5-30ml, preferably 1g:10-20ml.
In a specific embodiment, the crushed material d is sequentially placed in hydrogen peroxide solution and added with Na 2 S 2 O 3 When the aqueous solution is soaked in hydrogen peroxide solution, alkaline solution, acid solution, potassium iodide solution, EDTA solution, phosphate solution and hydrochloride solution, the solid-liquid ratio in each stage of soaking is controlled to be 1g:5-30mL. Specifically, the solid to liquid ratio may be 1g:10mL, 1g:12mL, 1g:14mL, 1g:16mL, 1g:18mL, or 1g:20mL.
In a specific embodiment, the specific steps of the step (5) are as follows: soaking the crushed material d in hydrogen peroxide solution, and adding Na into the hydrogen peroxide solution after the soaking is finished 2 S 2 O 3 Continuously soaking in water solution, filtering to obtain residue, soaking the residue in alkaline solution again, filtering to obtain residue, soaking in acidic solution, and filtering to obtain filtrateAnd (3) sequentially soaking the obtained filter residues in a potassium iodide solution, an EDTA solution, a phosphate solution and a hydrochloride solution, and filtering after the completion of the soaking to obtain a material e.
In the method of the present invention, in the step (5), when the crushed material d is subjected to the operations of the steps (1) to (3), the concentration of the solution and the soaking conditions during the operations are the same as those in the previous steps (1) and (3).
In a more specific embodiment, in the step (4), the filter residue obtained by filtering after the soaking in each stage is washed with water for 4-5 times, and then the next operation is performed.
In the method of the invention, the material e is mixed with the surfactant, so that the dispersibility among powder particles can be improved, the powder is not easy to agglomerate, and the method is convenient for later application.
In a specific embodiment, the surfactant is selected from one or more of sodium hard fatty acid, sodium dodecyl sulfate and cetyltrimethylammonium bromide.
In a specific embodiment, the weight ratio of the surfactant to the amount of material e is controlled to be 0.03-0.1:1, preferably 0.05-0.08:1. Specifically, the weight ratio of the surfactant to the amount of material e may be 0.05:1, 0.06:1, 0.07:1 or 0.08:1.
In the method, in order to facilitate the recovery of the recovered material to be better applied to the preparation of the denitration catalyst, the particle size of the recovered material obtained by ball milling and drying is controlled to be less than or equal to 100 meshes, preferably 200-300 meshes.
In the method of the invention, the reclaimed material contains 85 to 93 weight percent of TiO based on 100 weight percent of the total weight of the reclaimed material 2 WO 2.2-6wt% 3 0.1-1.2wt% of V 2 O 5 。
In the method, in order to remove heavy metal elements and harmful substances in the waste denitration catalyst As much As possible, any step in the method cannot be lacked, mutual synergistic effect exists between any treatment steps, the heavy metal elements (Ni, pb, cr, zn, cu) in the waste denitration catalyst can be removed in percentage through the treatment processes of the steps (1) to (5), and the attached As elements can be removed, so that the activity of the reclaimed materials is improved.
The invention further provides an application of the treatment method of the waste denitration catalyst in preparation of the denitration catalyst.
In the method, heavy metals and harmful substances which deactivate the catalyst in the waste denitration catalyst are removed through a proper treatment mode, the recycled material obtained through recycling can be applied to the preparation of the denitration catalyst again, the addition of the recycled material does not have adverse effect on the performance of the prepared denitration catalyst, the recycling of the waste denitration catalyst is realized, and the raw material cost of the denitration catalyst is further reduced. In addition, the reclaimed material contains a large amount of Ti element, part of W element and V element, and can be used for preparing denitration catalysts. Thereby saving the preparation cost of the denitration catalyst.
The invention also provides a preparation method of the denitration catalyst, which comprises the following steps:
(1) Mixing a tungsten source with an ammonia water solution to obtain a mixed solution A, and then mixing the mixed solution A with a titanium source to obtain a titanium-tungsten mixture;
(2) Mixing a vanadium source with an ammonia water solution and monoethanolamine to obtain a mixed solution B, and then mixing the mixed solution B with a titanium-tungsten mixture to obtain a mixture C;
(3) Mixing the mixture C with a lubricant, a binder, a plasticizer and glass fibers, and then mixing and ageing;
(4) And extruding and molding the stale material, and then drying and calcining.
In a specific embodiment, the tungsten source is ammonium metatungstate and the vanadium source is ammonium metavanadate.
In the method of the present invention, the content of the tungsten source is 1.8 to 2.6wt% based on 100wt% of the total weight of the tungsten source and the titanium source, and the total weight of the vanadium source and the titanium source is 100wt%The vanadium source is contained in an amount of 0.5 to 0.9wt%, wherein the tungsten source is WO 3 Calculated by V as the vanadium source 2 O 5 And (5) counting.
In a preferred embodiment, the tungsten source is present in an amount of 2 to 2.3wt% based on 100wt% of the total weight of the tungsten source and the titanium source; the vanadium source is present in an amount of 0.6 to 0.8wt% based on 100wt% of the total weight of the tungsten source and the titanium source.
In a specific embodiment, the liquid to solid ratio of the amount of monoethanolamine to the amount of ammonium metavanadate is 1-4ml:1g.
In the method of the invention, the titanium source comprises TiO 2 And a reclaimed material obtained by the treatment method of the waste denitration catalyst.
In the method of the present invention, in order to successfully apply the reclaimed materials to the preparation of the denitration catalyst, it is necessary to strictly control the reclaimed material content in the titanium source, and the reclaimed material content is 10 to 30 wt%, preferably 20 to 30 wt%, based on the total weight of the titanium source as 100 wt%. Specifically, the content of the reclaimed material may be 10 wt%, 15 wt%, 20 wt%, 25 wt%, or 30 wt%.
In a specific embodiment, the lubricant is one or more selected from glycerol, triethanolamine, stearic acid; the plasticizer is selected from phthalic acid and/or dioctyl phthalate; the binder is one or more selected from polyvinyl alcohol, methyl cellulose, hydroxymethyl cellulose, polyacrylamide and polyethylene glycol.
In the method of the present invention, the amounts of the lubricant, the binder, the plasticizer and the glass fiber are not particularly limited, and may be referred to those of ordinary skill in the art.
In a specific embodiment, the titanium source, tungsten source, vanadium source, lubricant, binder, plasticizer and glass fiber are used in a weight ratio of 1 (0.02-0.03): (0.006-0.009): (0.05-0.1): (0.06-0.1): (0.07-0.1): (0.1-0.25).
In the method of the present invention, in the step (3), the conditions of kneading and aging are not particularly limited, and may be carried out according to the kneading and aging conditions common in the art.
In a specific embodiment, in step (3), the mixing conditions include: the temperature is 200-300 ℃ and the time is 5-12h; the conditions of the staling include: the temperature is 20-30 ℃ and the time is 24-72h.
In the method of the present invention, in the step (4), the conditions of the calcination are not additionally limited, and may be carried out according to the conventional conditions in the art.
In a specific embodiment, in step (4), the number of times of calcination may be 1 to 3, preferably 2; the conditions of the calcination include: the temperature is 300-650 ℃ and the time is 1-5h.
In a specific embodiment, step (4) further comprises cutting the calcined product to obtain a denitration catalyst product with a specified size.
The invention also provides a reclaimed material obtained by the treatment method of the waste denitration catalyst and application of the denitration catalyst obtained by the preparation method of the denitration catalyst in removing nitrogen oxides in industrial boiler tail gas.
The present invention will be described in detail by way of examples, but the scope of the present invention is not limited thereto.
The waste denitration catalyst in the following examples and comparative examples was derived from a waste denitration catalyst in a coal-fired power plant in Zhejiang.
In the following examples, the content of the metal element in the waste denitration catalyst and the reclaimed material was tested by ICP-OES.
Example 1
(1) Purging the waste honeycomb denitration catalyst to remove floating ash on the surface and in the pore canal, then placing the catalyst in a hydrogen peroxide solution with the concentration of 10% for first-stage soaking, wherein the first-stage soaking temperature is 70 ℃, the first-stage soaking time is 100min, and adding Na into the hydrogen peroxide solution after the completion of the first-stage soaking 2 S 2 O 3 Soaking in water solution (0.3 mol/L) at 70deg.C for 100minTaking out after soaking, and then washing for 4-5 times to obtain a material a;
(2) The material a was placed in NaOH solution (OH - The concentration is 0.1 mol/L), the third stage soaking is carried out, the third stage soaking temperature is 80 ℃, and the third stage soaking time is 120min; taking out the block after finishing, washing for 4-5 times, then placing the block in oxalic acid solution (the concentration is 0.05 mol/L) for soaking in the fourth stage, wherein the soaking temperature in the fourth stage is 80 ℃, the soaking time in the fourth stage is 4 hours, and then taking out and washing with water for 4-5 times to obtain a material b;
(3) Sequentially soaking the material b in a potassium iodide solution (with the concentration of 0.2 mol/L), an EDTA solution (with the concentration of 0.25 g/L), a sodium phosphate solution (with the concentration of 0.1 mol/L) and a sodium chloride solution (with the concentration of 2 mol/L), wherein the soaking temperature is 80 ℃ for 4 hours each time, and taking out the material c after the completion of the soaking;
(4) Drying and crushing the material c to below 100 meshes to obtain a crushed material d;
(5) Soaking the crushed material d in 10% hydrogen peroxide solution at 70 ℃ for 100min, and adding Na with the concentration of 0.3mol/L into the hydrogen peroxide solution after the soaking 2 S 2 O 3 The aqueous solution is continuously soaked at the soaking temperature of 70 ℃ for 100min; filtering to obtain residue, washing the residue with water, and standing in NaOH solution (OH - Soaking in 0.1 mol/L) at 80 ℃ for 120min, filtering after finishing, washing the obtained filter residue, soaking in oxalic acid solution (with the concentration of 0.05 mol/L) for 4h at 80 ℃, filtering to obtain filter residue, washing the obtained filter residue, sequentially soaking in potassium iodide solution (with the concentration of 0.2 mol/L), EDTA solution (with the concentration of 0.3 g/L), sodium phosphate solution (with the concentration of 0.1 mol/L) and sodium chloride (with the concentration of 2 mol/L) solution, filtering after finishing to obtain a material e, wherein the solid-liquid ratio during soaking is 1g:15 ml;
(6) Uniformly mixing the material e with a surfactant (the mixture of sodium fatty acid and sodium dodecyl sulfonate is 1:2) according to the weight ratio of 0.05:1, then adding ethanol for ball milling for 48 hours, centrifugally filtering after ball milling, washing filter residues with water, and drying and sieving with a 200-mesh sieve to obtain a reclaimed material;
wherein, tiO in the waste denitration catalyst 2 、WO 3 、V 2 O 5 As, heavy metals (Ni, pb, cr, zn and Cu), water-soluble vanadium V 2 O 5 The ammonium salt and sulfate ion contents were 73.22wt%, 3.61wt%, 0.76wt%, 387.26. Mu.g/g, 491.12. Mu.g/g, 0.13wt%, 0.21wt% and 0.57wt% in this order.
Example 2
(1) Purging the waste honeycomb denitration catalyst to remove floating ash on the surface and in the pore canal, then placing the catalyst in a hydrogen peroxide solution with the concentration of 12% for first-stage soaking, wherein the first-stage soaking temperature is 75 ℃, the first-stage soaking time is 100min, and adding Na into the hydrogen peroxide solution after the first-stage soaking is finished 2 S 2 O 3 Soaking in water solution (0.35 mol/L) at 75deg.C for 100min, taking out, and washing with water for 4-5 times to obtain material a;
(2) The material a was placed in NaOH solution (OH - The concentration is 0.1 mol/L), the third stage soaking is carried out, the third stage soaking temperature is 80 ℃, and the third stage soaking time is 120min; taking out the block after finishing, washing for 4-5 times, then placing the block in oxalic acid solution (the concentration is 0.05 mol/L) for soaking in the fourth stage, wherein the soaking temperature in the fourth stage is 80 ℃, the soaking time in the fourth stage is 4 hours, and then taking out and washing with water for 4-5 times to obtain a material b;
(3) Sequentially soaking the material b in a potassium iodide solution (with the concentration of 0.25 mol/L), an EDTA solution (with the concentration of 0.25 g/L), a sodium phosphate solution (with the concentration of 0.15 mol/L) and a sodium chloride solution (with the concentration of 2 mol/L), wherein the soaking temperature is 80 ℃ for 4 hours each time, and taking out and drying after finishing to obtain a material c;
(4) Drying and crushing the material c to below 100 meshes to obtain a crushed material d;
(5) Soaking the crushed material d in 12% concentration hydrogen peroxide solution at 75 deg.cSoaking for 100min, adding Na with concentration of 0.35mol/L into hydrogen peroxide solution after soaking 2 S 2 O 3 The aqueous solution is continuously soaked at the soaking temperature of 75 ℃ for 100min; filtering to obtain residue, washing the residue with water, and standing in NaOH solution (OH - Soaking in 0.1 mol/L) at 80 ℃ for 120min, filtering after finishing, washing the obtained filter residue, soaking in oxalic acid solution (with the concentration of 0.05 mol/L) for 4h at 80 ℃, filtering to obtain filter residue, washing the obtained filter residue, sequentially soaking in potassium iodide solution (with the concentration of 0.25 mol/L), EDTA solution (with the concentration of 0.25 g/L), sodium phosphate solution (with the concentration of 0.1 mol/L) and sodium chloride (with the concentration of 2 mol/L) solution, filtering after finishing to obtain a material e, wherein the solid-liquid ratio during soaking is 1 g/13 ml;
(6) Uniformly mixing the material e with a surfactant (the mixture of sodium fatty acid and sodium dodecyl sulfonate according to the weight ratio of 1:2) according to the weight ratio of 0.06:1, then adding ethanol for ball milling for 48 hours, centrifugally filtering after ball milling, washing filter residues with water, and drying and sieving with a 200-mesh sieve to obtain a reclaimed material;
Wherein, tiO in the waste denitration catalyst 2 、WO 3 、V 2 O 5 As, heavy metals (Ni, pb, cr, zn and Cu), water-soluble vanadium V 2 O 5 The ammonium salt and sulfate ion contents were 69.97wt%, 3.44wt%, 0.92wt%, 197.73. Mu.g/g, 512.31. Mu.g/g, 0.23wt%, 0.16wt% and 0.49wt% in this order.
Example 3
(1) Purging the waste honeycomb denitration catalyst to remove floating ash on the surface and in the pore canal, then placing the catalyst in a 5% hydrogen peroxide solution for first-stage soaking at 90 ℃ for 120min, and adding Na into the hydrogen peroxide solution after the completion of the first-stage soaking 2 S 2 O 3 Soaking in water solution (0.45 mol/L) at 90 deg.C for 120min, taking out, and washing with water for 4-5 times to obtain material a;
(2) The material a was placed in NaOH solution (OH - The concentration is 0.1 mol/L), the third stage soaking is carried out, the third stage soaking temperature is 80 ℃, and the third stage soaking time is 150min; taking out the block after finishing, washing for 4-5 times, then placing the block in a phosphoric acid solution (the concentration is 0.05 mol/L) for soaking in the fourth stage, wherein the soaking temperature in the fourth stage is 80 ℃, the soaking time in the fourth stage is 5 hours, and then taking out and washing with water for 4-5 times to obtain a material b;
(3) Sequentially soaking the material b in a potassium iodide solution (with the concentration of 0.4 mol/L), an EDTA solution (with the concentration of 0.2 g/L), a sodium phosphate solution (with the concentration of 0.1 mol/L) and a sodium chloride solution (with the concentration of 2.5 mol/L), wherein the soaking temperature is 80 ℃ for 5 hours each time, and taking out the material c after the completion of the soaking;
(4) Drying and crushing the material e to below 100 meshes to obtain a crushed material d;
(5) Soaking the crushed material d in 5% concentration hydrogen peroxide solution at 90 deg.c for 120min, and adding Na in 0.45mol/L concentration to the hydrogen peroxide solution after soaking 2 S 2 O 3 The aqueous solution is continuously soaked at 90 ℃ for 120min; filtering to obtain residue, washing the residue with water, and standing in NaOH solution (OH - The concentration is 0.1 mol/L), the soaking temperature is 80 ℃ and the soaking time is 150min, after the completion, the obtained filter residue is washed and then is soaked in phosphoric acid solution (the concentration is 0.05 mol/L), the soaking temperature is 80 ℃ and the soaking time is 5h, then the filter residue is obtained after filtration, then the obtained filter residue is washed and then is sequentially soaked in potassium iodide solution (the concentration is 0.4 mol/L), EDTA solution (the concentration is 0.2 g/L), sodium phosphate solution (the concentration is 0.1 mol/L) and sodium chloride (the concentration is 2.5 mol/L) solution, the solid-liquid ratio during soaking is 1g to 16ml, and the material e is obtained after the completion of filtration;
(6) Uniformly mixing the material e with a surfactant (the mixture of sodium fatty acid and sodium dodecyl sulfonate is 1:2) according to the weight ratio of 0.07:1, then adding ethanol for ball milling for 48 hours, centrifugally filtering after ball milling, washing filter residues with water, and drying and sieving with a 200-mesh sieve to obtain a reclaimed material;
wherein, tiO in the waste denitration catalyst 2 、WO 3 、V 2 O 5 As, heavy metals (Ni, pb, cr, zn and Cu), water-soluble vanadium V 2 O 5 The ammonium salt and sulfate ion contents were 74.15wt%, 5.22wt%, 1.04wt%, 288.42. Mu.g/g, 487.33. Mu.g/g, 0.28wt%, 0.18wt% and 0.25wt% in this order.
Example 4
(1) 13.4g of ammonium metatungstate was dissolved in 25mL of an aqueous ammonia solution (concentration 5%) and mixed to obtain a mixed solution A, followed by mixing the mixed solution A with 650g of a titanium source (recovered material prepared from 25% of example 1 and 75% of TiO) 2 Mixing to obtain) and then ball-milling for 20-30min at a ball-milling speed of 800r/min to obtain a titanium-tungsten powder mixture;
(2) Dissolving 4.5g of ammonium metavanadate in 50mL of ammonia water solution (concentration of 5%), adding 50mL of monoethanolamine, uniformly mixing to obtain a mixed solution B, and then mixing the mixed solution B with the titanium tungsten powder mixture obtained in the step (1) to obtain a mixture C;
(3) Mixing the mixture C with 38g of lubricant (triethanolamine), 42g of binder (polyvinyl alcohol), 50g of plasticizer (phthalic acid), 80g of glass fiber and 160g of water, mixing at 200 ℃ for 5 hours, aging at 25 ℃ and standing for 36 hours;
(4) Extruding and molding the stale material to obtain a honeycomb catalyst blank, drying the honeycomb catalyst blank at 80 ℃ for 10 hours, and then calcining twice, wherein the first calcining temperature is 350 ℃, the first calcining time is 1.5 hours, the second calcining temperature is 650 ℃, the second calcining time is 4.5 hours, and cutting after calcining is finished to obtain a denitration catalyst (9 multiplied by 9 holes, and the aperture is 6.4 mm);
wherein the content of the tungsten source is 1.8wt% based on 100wt% of the total weight of the tungsten source and the titanium source, and the content of the vanadium source is 0.53wt% based on 100wt% of the weight of the vanadium source and the titanium source, wherein the tungsten source is WO 3 Calculated by V as the vanadium source 2 O 5 Counting; the tungsten source is ammonium metatungstate, theThe vanadium source is ammonium metavanadate.
Example 5
(1) 15g of ammonium metatungstate was dissolved in 25mL of an aqueous ammonia solution (concentration 5%) and mixed to obtain a mixed solution A, followed by mixing the mixed solution A with 650g of a titanium source (30% of the reclaimed material prepared in example 2 and 75% of TiO) 2 Mixing to obtain) and then ball-milling for 20-30min at a ball-milling speed of 800r/min to obtain a titanium-tungsten powder mixture;
(2) Dissolving 6g of ammonium metavanadate in 50mL of ammonia water solution (with the concentration of 5%), adding 30mL of monoethanolamine, uniformly mixing to obtain a mixed solution B, and then mixing the mixed solution B with the titanium tungsten powder mixture obtained in the step (1) to obtain a mixture C;
(3) Mixing the mixture C with 38g of lubricant (triethanolamine), 42g of binder (polyvinyl alcohol), 50g of plasticizer (phthalic acid), 80g of glass fiber and 160g of water, mixing at 200 ℃ for 5 hours, aging at 25 ℃ and standing for 36 hours;
(4) Extruding and molding the stale material to obtain a honeycomb catalyst blank, drying the honeycomb catalyst blank at 80 ℃ for 10 hours, and then calcining twice, wherein the first calcining temperature is 300 ℃, the first calcining time is 2 hours, the second calcining temperature is 650 ℃, the second calcining time is 4 hours, and cutting after calcining is finished to obtain a denitration catalyst (9 multiplied by 9 holes, and the aperture is 6.4 mm);
wherein the content of the tungsten source is 2.1wt% based on 100wt% of the total weight of the tungsten source and the titanium source, and the content of the vanadium source is 0.65wt% based on 100wt% of the weight of the vanadium source and the titanium source, wherein the tungsten source is WO 3 Calculated by V as the vanadium source 2 O 5 Counting; the tungsten source is ammonium metatungstate, and the vanadium source is ammonium metavanadate.
Example 6
(1) 13.4g of ammonium metatungstate was dissolved in 25mL of an aqueous ammonia solution (concentration 5%) and mixed to obtain a mixed solution A, followed by mixing the mixed solution A with 650g of a titanium source (recovered material prepared in example 3 at 20% and TiO at 75%) 2 Mixing to obtain) and then ball-milling for 20-30min at a ball-milling speed of 800r/min to obtain a titanium-tungsten powder mixture;
(2) Dissolving 4.5g of ammonium metavanadate in 50mL of ammonia water solution (concentration of 5%), adding 50mL of monoethanolamine, uniformly mixing to obtain a mixed solution B, and then mixing the mixed solution B with the titanium tungsten powder mixture obtained in the step (1) to obtain a mixture C;
(3) Mixing the mixture C with 38g of lubricant (triethanolamine), 42g of binder (polyvinyl alcohol), 50g of plasticizer (phthalic acid), 80g of glass fiber and 160g of water, mixing at 200 ℃ for 5 hours, aging at 25 ℃ and standing for 36 hours;
(4) Extruding and molding the stale material to obtain a honeycomb catalyst blank, drying the honeycomb catalyst blank at 80 ℃ for 10 hours, and then calcining twice, wherein the first calcining temperature is 350 ℃, the first calcining time is 2 hours, the second calcining temperature is 600 ℃, the second calcining time is 3.5 hours, and cutting after calcining is finished to obtain a denitration catalyst (9 multiplied by 9 holes, and the aperture is 6.4 mm);
Wherein the content of the tungsten source is 1.8wt% based on 100wt% of the total weight of the tungsten source and the titanium source, and the content of the vanadium source is 0.53wt% based on 100wt% of the weight of the vanadium source and the titanium source, wherein the tungsten source is WO 3 Calculated by V as the vanadium source 2 O 5 Counting; the tungsten source is ammonium metatungstate, and the vanadium source is ammonium metavanadate.
Comparative example 1
The procedure of example 1 was followed, except that the third soaking in NaOH solution in step (1) and step (2) was not performed, and the soaking in NaOH solution in step (1) and step (2) was not repeated for the crushed material c in step (4).
Comparative example 2
The procedure of example 1 was followed, except that the fourth soaking in oxalic acid solution in step (2) was not performed, and the soaking in oxalic acid solution in step (2) was not repeated for the crushed material c in step (4).
Comparative example 3
The procedure of example 1 was followed, except that step (3) was not performed, and that in step (4), the pulverized material c was not repeated in step (3) as well.
Comparative example 4
The procedure of example 1 was followed, except that step (5) was not performed.
Comparative example 5
The procedure of example 4 was followed, except that the recycle of the titanium source was the recycle prepared in comparative example 1.
Comparative example 6
The procedure of example 4 was followed, except that the recycle from the titanium source was the recycle from comparative example 2.
Comparative example 7
The procedure of example 4 was followed, except that the recycle from the titanium source was the recycle prepared in comparative example 3.
Comparative example 8
The procedure of example 4 was followed, except that the recycle from the titanium source was the recycle from comparative example 4.
Comparative example 9
The procedure of example 4 was followed, except that the content of the reclaimed material produced in example 1 in the titanium source was 50%.
Comparative example 10
The procedure of example 4 was followed, except that the content of the tungsten source was 3.5% by weight based on 100% by weight of the total weight of the tungsten source and the titanium source, and the content of the vanadium source was 1.2% by weight based on 100% by weight of the vanadium source and the titanium source, wherein the tungsten source was as defined in WO 3 Calculated by V as the vanadium source 2 O 5 Counting; the tungsten source is ammonium metatungstate, the vanadium source is ammonium metavanadate, and the titanium sources are all commercially available TiO 2 。
Comparative example 11
The procedure of example 4 was followed, except that no recycle was added to the titanium source and commercially available TiO was used 2 The preparation is carried out.
Test case
Test example 1
The titanium white powders recovered in examples 1 to 3 were tested and the products obtained in comparative examples 1 to 4 were tested for properties.
Specific surface area test: testing was performed according to the method of Standard GB/T19587-2004, with the test results shown in Table 1;
TiO in waste denitration catalyst 2 Is used for the recovery rate test of (2): testing the waste denitration catalyst and the TiO in the corresponding reclaimed material by adopting X-ray fluorescence spectrum analysis 2 And calculates the content of TiO 2 The results are shown in Table 1. TiO in waste denitration catalyst 2 The calculation method of the recovery rate of (2) is as follows: (TiO in reclaimed materials) 2 Content of (2) x weight of recovered material)/(TiO in spent denitration catalyst) 2 X the weight of the spent denitration catalyst);
sulfate removal rate test: the waste denitration catalyst and the content of sulfate in the corresponding reclaimed materials were tested by using an X-ray fluorescence spectrum, and the sulfate removal rate was calculated, and the results are shown in Table 1. The sulfate removal rate was calculated by: (content of sulfate in reclaimed material x weight of reclaimed material)/(content of sulfate in waste denitration catalyst x weight of waste denitration catalyst);
And (3) testing the removal rate of As elements: the content of As element in the waste denitration catalyst and the corresponding reclaimed materials was tested by ICP-OES, and the removal rate of As element was calculated, and the results are shown in Table 1. The calculation method of the As element removal rate comprises the following steps: the content of As element in the reclaimed material/the content of As element in the waste denitration catalyst;
heavy metal (Ni, pb, cr, zn, cu) removal test: the content of the heavy metal element (Ni, pb, cr, zn, cu) in the waste denitration catalyst and the corresponding reclaimed materials is tested by ICP-OES, and the removal rate of the heavy metal element (Ni, pb, cr, zn, cu) is calculated, and the result is shown in Table 1. The method for calculating the removal rate of the heavy metal element (Ni, pb, cr, zn, cu) comprises the following steps: the content of heavy metal elements in the reclaimed materials/the content of heavy metal elements in the waste denitration catalyst;
ammonium salt removal rate test: the waste denitration catalyst and the corresponding reclaimed materials are crushed to 200 meshes, then stirred in an aqueous solution at 60 ℃ for 60min, then the content of ammonium ions in the solution is tested by adopting ion chromatography (ICS-2500) for suction filtration and constant volume, and the removal rate of ammonium salts is calculated, and the results are shown in table 1. The method for calculating the ammonium salt removal rate comprises the following steps: the content of ammonium salt in the reclaimed material/the content of ammonium salt in the waste denitration catalyst;
Water-soluble vanadium removal rate test: after the waste denitration catalyst and the corresponding reclaimed materials are crushed and pass through 200 meshes, stirring is carried out in an aqueous solution at room temperature for 30 minutes, then the content of vanadium in the solution is tested by adopting ICP-OES (inductively coupled plasma-optical emission spectrometry) for volume measurement, the content of water-soluble vanadium in the catalyst is calculated according to the volume of the solution, and the removal rate of the water-soluble vanadium is calculated, wherein the result is shown in a table 1. The method for calculating the water-soluble vanadium removal rate comprises the following steps: the content of water-soluble vanadium in the reclaimed materials/the content of water-soluble vanadium in the waste denitration catalyst;
material grain size test: the XRD is adopted to test the waste denitration catalyst and the corresponding reclaimed materials, a corresponding spectrogram is collected, the grain size of the material is calculated according to a Shelle formula, and the result is shown in table 1.
The thank you formula: d=kγ/Bcos θ (k is Scherrer constant, D is grain size, B is measured sample diffraction peak half-peak width or integral width, θ is bragg angle, γ is X-ray wavelength, γ= 1.54056 a).
TABLE 1
As can be seen from the results in Table 1, the sulfate, as element, heavy metal element, ammonium salt and water-soluble vanadium in the waste denitration catalyst can be removed by adopting the method disclosed by the invention, and a very high removal rate can be achieved.
Test example 2
The denitration catalysts prepared in examples 4 to 6 and comparative examples 5 to 11 were tested for physical and mechanical properties and removal rate of nitrogen oxides.
Axial compressive strength: the axial compressive strength and the radial compressive strength of the denitration catalyst are tested by adopting a TYE-300 type pressure testing machine, and the test results are shown in table 2;
specific surface area: the specific surface areas of the denitration catalyst and the product are tested by adopting a full-automatic nitrogen adsorption and desorption instrument (microphone 2020), and the test results are shown in table 2;
and testing the denitration rate of the denitration catalyst at different temperatures: the test method is to take a small sample of the denitration catalyst and a small sample of the product, put the small sample into a catalyst performance evaluation reaction device, and introduce simulated gas to evaluate the activity of the denitration catalyst obtained in examples 4-6 and the product obtained in comparative examples 5-11. The simulated gas composition was similar to the industrial boiler tail gas composition, which was as follows: 500ppm NO, 400ppm NH 3 10.00% O 2 12% of water and the balance of nitrogen. Introducing the simulated gas into a denitration reactor for reaction, wherein the reaction temperature is 210 ℃, the concentration of nitrogen oxides in the flue gas before and after the reaction is analyzed by adopting a 42i-HL flue gas analyzer, and then calculating to obtain the denitration rate of the denitration catalyst when the reaction temperature is 210 ℃, wherein the test result is shown in Table 2;
The denitration rate of the denitration catalyst at 270 ℃ can be obtained by adjusting the reaction temperature in the denitration reactor to 270 ℃, and the test result is shown in table 2;
the method for calculating the denitration rate of the denitration catalyst comprises the following steps: η= (a-b)/a×100%, wherein the concentration of nitrogen oxides in the flue gas before the reaction is a, the concentration of nitrogen oxides in the flue gas after the reaction is b, and the denitration rate of the denitration catalyst is η.
Testing the performance stability of the denitration catalyst: the reaction temperature in the denitration reactor was set to 270 ℃, and the denitration rate of the denitration catalyst after 24 hours of operation of the denitration catalyst was measured, and the results are shown in table 2.
TABLE 2
As can be seen from table 2, the reclaimed materials recovered by the method of the present invention can be successfully used for preparing the denitration catalyst, and the prepared denitration catalyst still has excellent denitration rate, which indicates that the performance of the prepared denitration catalyst is not adversely affected by the method of the present invention. Therefore, the method of the invention can successfully recycle the waste denitration catalyst, and simultaneously reduce the preparation cost of the denitration catalyst, thereby having a large application market.
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 treating a waste denitration catalyst, comprising the steps of:
(1) Placing the waste denitration catalyst into hydrogen peroxide solution for first-stage soaking, and then adding Na into the hydrogen peroxide solution 2 S 2 O 3 Soaking the aqueous solution in the second stage, and performing solid-liquid separation after the soaking is finished to obtain a material a;
(2) Placing the material a in an alkaline solution for a third stage of soaking, then performing solid-liquid separation, placing the obtained solid phase in an acidic solution for a fourth stage of soaking, and then performing solid-liquid separation to obtain a material b;
(3) Sequentially soaking the material b in a potassium iodide solution, an EDTA solution, a phosphate solution and a hydrochloride solution, and then carrying out solid-liquid separation to obtain a material c;
(4) Drying and crushing the material c to obtain a crushed material d;
(5) Subjecting the crushed material d to the operations from step (1) to step (3) to obtain a treated material e;
(6) Mixing the material e, the surfactant and the ethanol, performing ball milling, filtering, washing filter residues, and drying to obtain a reclaimed material.
2. The method for treating a waste denitration catalyst according to claim 1, wherein the mass concentration of the hydrogen peroxide solution is 5-20%;
And/or, the Na 2 S 2 O 3 Na in aqueous solution 2 S 2 O 3 The concentration of (C) is 0.2-0.5mol/L.
3. The method for treating a waste denitration catalyst according to claim 1, characterized in that the conditions for the first stage immersion include: the temperature is 60-90 ℃ and the time is 60-120min;
and/or, the conditions of the second stage soaking include: the temperature is 60-90deg.C, and the time is 60-120min.
4. The method for treating a waste denitration catalyst according to claim 1, wherein the alkaline solution is a NaOH solution and/or a KOH solution; the acidic solution is selected from one or more than two of sulfuric acid solution, oxalic acid solution, hydrochloric acid solution and phosphoric acid solution;
and/or OH in the alkaline solution - The concentration of (2) is 0.02-0.2mol/L;
and/or the concentration of the solute in the acidic solution is 0.01-0.1mol/L;
and/or, the conditions of the third stage soaking include: the temperature is 60-90 ℃ and the time is 60-200min;
and/or, the conditions of the fourth stage soaking include: the temperature is 60-90 ℃ and the time is 1-5h.
5. The method for treating a waste denitration catalyst according to claim 1, wherein the concentration of potassium iodide in the potassium iodide solution is 0.05 to 0.5mol/L, the concentration of EDTA in the EDTA solution is 0.1 to 0.3g/L, the concentration of phosphate in the phosphate solution is 0.02 to 0.2mol/L, and the concentration of hydrochloride in the hydrochloride solution is 0.05 to 5mol/L;
And/or soaking in potassium iodide solution, EDTA solution, phosphate solution and hydrochloride solution at 60-90deg.C for 1-10 hr.
6. The method for treating a waste denitration catalyst according to claim 1, wherein the surfactant is one or more selected from the group consisting of sodium hard fatty acid, sodium dodecyl sulfate and cetyltrimethylammonium bromide;
and/or the weight ratio of the surfactant to the amount of the material e is 0.03-0.1:1.
7. The method for treating a waste denitration catalyst according to claim 1, wherein the solid-to-liquid ratio at the time of immersing in step (5) is 1g:5-30mL.
8. Use of the reclaimed material obtained by the treatment method of the waste denitration catalyst according to any one of claims 1 to 7 in the preparation of a denitration catalyst.
9. A method for preparing a denitration catalyst, which is characterized by comprising the following steps:
(1) Mixing a tungsten source with an ammonia water solution to obtain a mixed solution A, and then mixing the mixed solution A with a titanium source to obtain a titanium-tungsten mixture;
(2) Mixing a vanadium source, an ammonia water solution and monoethanolamine to obtain a mixed solution B, and then mixing the mixed solution B with the titanium-tungsten mixture to obtain a mixture C;
(3) Mixing the mixture C, a lubricant, a binder, a plasticizer and glass fibers, and then mixing and ageing;
(4) Extruding and molding the stale material, and then drying and calcining;
the tungsten source is ammonium metatungstate, and the vanadium source is ammonium metavanadate;
with the tungsten source and the tungsten sourceThe total weight of the titanium source is 100wt%, the content of the tungsten source is 1.8-2.6wt%, the content of the vanadium source is 0.5-0.9wt%, based on the total weight of the vanadium source and the titanium source is 100wt%, wherein the tungsten source is WO 3 Calculated by V as the vanadium source 2 O 5 Counting;
the titanium source is TiO 2 And a reclaimed material obtained by the treatment method according to any one of claims 1 to 7;
the content of the reclaimed materials is 10-30 wt% based on the total weight of the titanium source as 100 wt%.
10. Use of a denitration catalyst obtained by the preparation method of the denitration catalyst as claimed in claim 9 for removing nitrogen oxides in tail gas of an industrial boiler.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310214591.1A CN115869938B (en) | 2023-03-08 | 2023-03-08 | Treatment method of waste denitration catalyst, preparation method of denitration catalyst and application of denitration catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310214591.1A CN115869938B (en) | 2023-03-08 | 2023-03-08 | Treatment method of waste denitration catalyst, preparation method of denitration catalyst and application of denitration catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115869938A CN115869938A (en) | 2023-03-31 |
| CN115869938B true CN115869938B (en) | 2023-04-28 |
Family
ID=85762036
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310214591.1A Active CN115869938B (en) | 2023-03-08 | 2023-03-08 | Treatment method of waste denitration catalyst, preparation method of denitration catalyst and application of denitration catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115869938B (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103436704A (en) * | 2013-09-11 | 2013-12-11 | 北京化工大学 | Method for recovering vanadium and tungsten from tungsten containing vanadium-titanium based waste denitration catalyst |
| CN103981369A (en) * | 2014-05-07 | 2014-08-13 | 西北矿冶研究院 | Comprehensive recovery process for multiple metals in arsenic-containing soot |
| JP2015086119A (en) * | 2013-10-31 | 2015-05-07 | 三菱日立パワーシステムズ株式会社 | Method for producing crystalline titanium oxide and method for regenerating denitration catalyst |
| CN110385044A (en) * | 2019-07-24 | 2019-10-29 | 中国科学院过程工程研究所 | A kind of method of useless SCR catalyst dearsenification desiliconization |
| CN111054451A (en) * | 2019-12-02 | 2020-04-24 | 中节能清洁技术发展有限公司 | Arsenic removal method of waste SCR denitration catalyst and preparation method of regenerated powder of waste SCR denitration catalyst |
| WO2022007450A1 (en) * | 2020-07-09 | 2022-01-13 | 江苏龙净科杰环保技术有限公司 | Method for regenerating thallium poisoning scr denitration catalyst of cement kiln |
| CN115445604A (en) * | 2022-09-02 | 2022-12-09 | 国能龙源内蒙古环保有限公司 | Resource recycling method of waste denitration catalyst |
| CN115612846A (en) * | 2022-10-14 | 2023-01-17 | 北京科技大学 | Method for recycling and preparing titanium-tungsten powder and vanadium products from waste SCR denitration catalyst |
| CN115624968A (en) * | 2022-11-14 | 2023-01-20 | 国能龙源环保有限公司 | Method for preparing denitration catalyst by utilizing waste wind power blades and application |
-
2023
- 2023-03-08 CN CN202310214591.1A patent/CN115869938B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103436704A (en) * | 2013-09-11 | 2013-12-11 | 北京化工大学 | Method for recovering vanadium and tungsten from tungsten containing vanadium-titanium based waste denitration catalyst |
| JP2015086119A (en) * | 2013-10-31 | 2015-05-07 | 三菱日立パワーシステムズ株式会社 | Method for producing crystalline titanium oxide and method for regenerating denitration catalyst |
| CN103981369A (en) * | 2014-05-07 | 2014-08-13 | 西北矿冶研究院 | Comprehensive recovery process for multiple metals in arsenic-containing soot |
| CN110385044A (en) * | 2019-07-24 | 2019-10-29 | 中国科学院过程工程研究所 | A kind of method of useless SCR catalyst dearsenification desiliconization |
| CN111054451A (en) * | 2019-12-02 | 2020-04-24 | 中节能清洁技术发展有限公司 | Arsenic removal method of waste SCR denitration catalyst and preparation method of regenerated powder of waste SCR denitration catalyst |
| WO2022007450A1 (en) * | 2020-07-09 | 2022-01-13 | 江苏龙净科杰环保技术有限公司 | Method for regenerating thallium poisoning scr denitration catalyst of cement kiln |
| CN115445604A (en) * | 2022-09-02 | 2022-12-09 | 国能龙源内蒙古环保有限公司 | Resource recycling method of waste denitration catalyst |
| CN115612846A (en) * | 2022-10-14 | 2023-01-17 | 北京科技大学 | Method for recycling and preparing titanium-tungsten powder and vanadium products from waste SCR denitration catalyst |
| CN115624968A (en) * | 2022-11-14 | 2023-01-20 | 国能龙源环保有限公司 | Method for preparing denitration catalyst by utilizing waste wind power blades and application |
Non-Patent Citations (3)
| Title |
|---|
| Tomoki Yabutani."E ect of leaching conditions on the elution of metals from denitration catalyst wastes".《International Journal of Modern Physics B》.2018,第32卷(第19期),第1-5页. * |
| 戚春萍等."燃煤电厂废旧SCR 脱硝催化剂中TiO2 载体的回收与再利用".《化工学报》.2017,第68卷(第11期),第4239-4248页. * |
| 毕冬雪等."废SCR脱硝催化剂再生与金属回收及载体回用技术".《电力科技与环保》.2022,第38卷(第3期),第232-237页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115869938A (en) | 2023-03-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111485106A (en) | Method for recovering titanium, vanadium and tungsten in waste denitration catalyst | |
| CN110385044A (en) | A kind of method of useless SCR catalyst dearsenification desiliconization | |
| CN111974378B (en) | Denitration catalyst and preparation method thereof | |
| CN114058851A (en) | Method for recycling tungsten, molybdenum and titanium from waste denitration catalyst | |
| CN106607106A (en) | Activity regenerating and performance optimizing method of SCR catalyst for sulfur, arsenic and phosphorus poisoning | |
| CN115463653B (en) | Method for preparing denitration catalyst by utilizing waste wind power blades and application | |
| CN111778398A (en) | Method for extracting vanadium and tungsten from waste SCR denitration catalyst | |
| CN105112672B (en) | A kind of recovery method of the denitrating catalyst of sulphur aging | |
| CN115869938B (en) | Treatment method of waste denitration catalyst, preparation method of denitration catalyst and application of denitration catalyst | |
| DE112022002558T5 (en) | Method for recovering lithium battery waste material | |
| CN106807401A (en) | A kind of renovation process of denitrating catalyst and a kind of regeneration denitrating catalyst and its application | |
| CN111167489B (en) | Honeycomb anti-poison low-temperature SCR denitration catalyst and preparation method thereof | |
| CN110846510B (en) | Method for efficiently and selectively adsorbing and recovering rhenium and mercury from copper smelting multi-element mixed waste acid | |
| US11261101B2 (en) | Method for preparing vanadium battery electrolyte by using waste vanadium catalyst | |
| CN114887587B (en) | Porous adsorbent for heavy metals in wastewater prepared from lithium mine waste residues as raw materials and preparation method thereof | |
| CN110747339A (en) | Treatment process of ship tail gas denitration waste catalyst | |
| CN114733579B (en) | Method for recovering vanadium from waste denitration catalyst, catalyst regeneration agent and preparation method thereof, denitration catalyst and preparation method thereof | |
| CN114682307B (en) | Treatment method of waste denitration catalyst, titanium tungsten powder, denitration catalyst and preparation method of denitration catalyst | |
| CN113528834A (en) | Method for recovering vanadium, tungsten and titanium from waste vanadium-titanium-based SCR catalyst | |
| CN113996311A (en) | Flue gas denitration catalyst and preparation method thereof | |
| CN115869940B (en) | Method for preparing low-temperature denitration catalyst by utilizing titanium-based waste denitration catalyst and low-temperature denitration catalyst | |
| CN115924967B (en) | Method for preparing titanium dioxide by using titanium slag and titanium dioxide | |
| CN115874057B (en) | Method for simultaneously removing cadmium, zinc, lead and copper in waste denitration catalyst by chemical leaching method | |
| CN112156816B (en) | Composite material and preparation method and application thereof | |
| CN115927882B (en) | Method for separating vanadium and nickel |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |