Process for the preparation and use of a deactivation denitration catalyst wash sol

Abstract

The application discloses a preparation and use method of a cleaning sol for deactivation denitration catalysts, and belongs to the field of regenerated denitration catalysts. The cleaning sol is mainly composed of alginate, a cross-linking agent and an inorganic acid, and is used for cleaning and removing toxic elements such as phosphorus, magnesium, calcium, sodium, potassium, arsenic and lead in the deactivation denitration catalysts while retaining active components. The removed toxic elements such as phosphorus, magnesium, calcium, arsenic and lead are adsorbed by alginate colloid. The use method is suitable for an existing cleaning process. The raw materials required by the application have a wide source and low price, the cleaning sol is environment-friendly, the cleaning process is simple, and the application is easy to be industrialized.

Description

Technical Field

[0001] This invention belongs to the field of environmental catalysts, specifically relating to a cleaning sol for SCR flue gas denitrification catalyst and its preparation method. Background Technology

[0002] As a major energy consumer that relies heavily on thermal power generation, my country emits large amounts of NO during coal combustion. x Selective catalytic reduction (SCR) technology is used to achieve NO reduction. x Ultra-low emissions are an effective means of denitrification. Among numerous denitrification methods, selective catalytic reduction (SCR) is characterized by high denitrification rates (>90%), mature technology, and no harmful byproduct formation, and has become a popular method for controlling NOx emissions both domestically and internationally. x The dominant method (accounting for 96%) is the cleaning of deactivated denitrification catalysts. In SCR systems, the catalyst is a critical component, typically accounting for 30%-50% of the initial investment. Its service life is generally 2-3 years. During this period, due to the complex composition of flue gas, salts and oxides of elements such as phosphorus, lead, and arsenic in the flue gas can easily lead to catalyst poisoning and blockage, resulting in catalyst deactivation during use. For deactivated denitrification catalysts, offline cleaning can remove blockages and heavy metal poisons, restoring the activity to over 80% of that of a fresh catalyst. Researching efficient and environmentally friendly cleaning methods for deactivated denitrification catalysts is of great significance for extending catalyst lifespan, reducing the operating costs of SCR systems, and mitigating environmental burden. Colloids are three-dimensional network structures composed of hydrophilic or amphiphilic polymer chains through physical or chemical cross-linking. They have been widely used in water treatment and solid waste treatment and have great potential in cleaning deactivated denitrification catalysts. Alginic acid colloid is a natural polysaccharide that is non-toxic, has good biocompatibility and biodegradability, is inexpensive and readily available, and possesses many excellent properties, such as good colloidal stability, acid resistance, biocompatibility, high loading capacity, ease of multifunctionalization, and easy capture of heavy metal elements, which promotes its application in many fields.

[0003] Currently, the regeneration and cleaning of poisoned and deactivated catalysts mainly involves processes such as water washing to remove blockages and ash, acid washing to remove alkali metal poisons, alkali washing to remove heavy metal poisons, and water washing again to remove introduced sodium and potassium ions. Existing regeneration and cleaning processes have problems such as long process flow, generation of large amounts of wastewater containing heavy metals, excessive chemical oxygen demand of wastewater, and strong acidity or alkalinity of cleaning agents leading to loss of catalyst active components.

[0004] Patent CN104857998A discloses a kind of high-efficiency regeneration method for As poisoning denitration catalyst, with calcium nitrate or saturated limestone as arsenic removal reagent, wherein the pH value of calcium nitrate and cleaning solution is respectively in the interval of 1-4wt% and 7-11, the pH value of dilute nitric acid is 2;Under the premise of no active implantation step, most of the original catalyst active components (V2O5 and WO3 loss rate <10%) are left. In this method, alkali metal calcium ions that affect catalyst activity are introduced and need to be removed by combining with dilute sulfuric acid cleaning, which increases the cleaning step and reduces the strength of the denitration catalyst carrier, which is not conducive to the regeneration of the catalyst;The cleaning ability of dilute sulfuric acid to calcium ions is limited, and calcium ions are easily left to affect the activity of the catalyst;After acid pickling, it still needs to be washed with water for 3-4 times, which produces a large amount of wastewater containing toxic heavy metals, and the treatment difficulty is increased.

[0005] Patent CN106179529A discloses a kind of cleaning fluid for regeneration of failed denitration catalyst, its preparation method and application. The cleaning fluid includes titanate, silicate, organic acid, organic reducing agent, anhydrous alcohol and water, which removes harmful ions in the failed denitration catalyst, reduces the cleaning frequency of the catalyst and reduces the mass loss of the failed catalyst during cleaning. However, a large amount of organic matter that cannot be degraded by organisms is introduced in this method, and the chemical oxygen demand of the wastewater is large, which is difficult to treat.

[0006] Patent CN106000100A discloses a method for regenerating failed SCR catalyst under negative pressure. The cleaning method first performs alkaline cleaning under negative pressure, and then performs acid cleaning after alkaline cleaning, which improves the leaching rate of phosphorus and arsenic and shortens the cleaning time. In this method, 10wt% and 5wt% hydrofluoric acid mixed acid is used for acid cleaning, which is extremely acidic and has a great impact on the strength of the catalyst carrier; Hydrofluoric acid dissolves a large amount of vanadium and tungsten elements, resulting in a large amount of active component loss, which requires a large amount of active component to be supplemented again; And maintaining negative pressure condition consumes a large amount of energy, which increases the carbon emission of the regeneration process.

[0007] In summary, the existing cleaning agent and cleaning method for deactivated denitration catalyst can achieve high heavy metal removal rate, but the cleaning has a great impact on the strength of the catalyst carrier, the active component is lost, a large amount of wastewater containing toxic heavy metal elements and organic matter is produced, strong alkali and strong acid are used, and the energy consumption is high, which increases the carbon emission of the regeneration process. Therefore, there is an urgent need for a cleaning agent and cleaning method that can effectively remove the toxic elements on the surface of the deactivated denitration catalyst, adsorb toxic heavy metal elements, and reduce the energy consumption of the cleaning process. SUMMARY

[0008] To solve the above problems, improve the cleaning effect of the catalyst, reduce the treatment difficulty of the wastewater, and reduce the loss of activity and mechanical strength caused by catalyst regeneration, the present application proposes the following scheme.

[0009] The present application relates to a kind of for cleaning the preparation method of poisoning denitration catalyst and its application method, and this cleaning sol can efficiently remove the heavy metal ions such as arsenic, lead on the surface of poisoning SCR denitration catalyst.The purpose of the present application is to solve the problems in the related art: reduce the generation of toxic wastewater, adsorb toxic heavy metal elements;Reduce soaking time, avoid using strong acid or base to protect carrier;Improve the cleaning efficiency of micropore and heavy metal;Use environment-friendly alginic acid as main component, reduce environmental pollution;Toxic heavy metal elements are adsorbed by alginic acid colloid, simplify wastewater treatment process and cost.

[0010] To achieve the above object, the present application is realized by the following scheme:

[0011] A kind of preparation method of deactivated denitration catalyst cleaning sol, the cleaning sol is composed of ammonium alginate, fatty alcohol polyoxyethylene ether and crosslinking agent;The crosslinking agent is one or more than one of iron sulfate, ferrous sulfate, calcium sulfate, iron carbonate and calcium carbonate;The pH value of the cleaning sol is adjusted by sulfuric acid.

[0012] Further, the cleaning sol is prepared under the conditions of 20-80 ℃ and 120-450 r / min stirring, and the cleaning sol contains 0.05-2.00 wt.% of ammonium alginate, 0.01-1.000 wt.% of fatty alcohol polyoxyethylene ether and 0.01-1.00 wt.% of crosslinking agent, and the balance is water.

[0013] Further, the preparation method of deactivated denitration catalyst regeneration cleaning sol as described above includes the following specific steps:

[0014] (1) dissolve ammonium alginate in water;

[0015] (2) add fatty alcohol polyoxyethylene ether and crosslinking agent;

[0016] (3) after adjusting the pH to 0.5-5.0 with 0.01-1.00 mol / L dilute sulfuric acid solution, continue stirring for 5-120 min;

[0017] (4) stand for 1-24 h to obtain the cleaning sol.

[0018] Further, in the step (3), when the crosslinking agent contains one or more than one of calcium sulfate, calcium carbonate, iron carbonate and iron oxide, slowly add dilute acid solution, and the crosslinking agent that is insoluble in alginate solution forms colloid with alginate root by crosslinking when the dilute acid solution is added;When the crosslinking agent does not contain any of calcium sulfate, calcium carbonate, iron carbonate and iron oxide, alginate root has been crosslinked with the crosslinking agent to form colloid in step (2) when the crosslinking agent is added, and the viscosity of the sol decreases as the hydrogen bond between some alginate roots is broken with the addition of dilute acid solution.

[0019] The method for using the inactivation denitration catalyst cleaning sol to recover the denitration catalyst comprises the following steps:

[0020] (1) First, the inactivation denitration catalyst is subjected to blowing and ash removal treatment, the blowing pressure is 0.1-1.2 MPa, and the blowing time is 5-60 min;

[0021] (2) Then, the inactivation denitration catalyst is immersed in the cleaning sol, and is subjected to ultrasonic cleaning at 30-90 DEG C for 10-150 min;

[0022] (3) Then, the inactivation denitration catalyst is drained for 10-120 min;

[0023] (4) Then, the inactivation denitration catalyst is calcined at 300-500 DEG C for 1-4 h to obtain the recovered denitration catalyst.

[0024] Further, the content of the poisoning elements in the inactivation denitration catalyst after ultrasonic cleaning is converted into oxides, P2O5 is less than or equal to 100 ppm, MgO is less than or equal to 100 ppm, Na2O is less than or equal to 50 ppm, K2O is less than or equal to 50 ppm, As2O3 is less than or equal to 150 ppm, and PbO is less than or equal to 150 ppm, the denitration efficiency is recovered to be greater than or equal to 90.0%, the specific surface area is recovered to be greater than or equal to 85.0%, the V loss rate is less than or equal to 15.0%, and the W loss rate is less than or equal to 10.0%.

[0025] Principle of the present application:

[0026] (1) Principle of the seaweed acid sol adsorbing poisoning elements

[0027] In the cleaning process, the oxides and salts of Ca and Mg on the surface of the poisoned denitration catalyst are dissolved by the sulfuric acid in the cleaning sol, the alginate in the cleaning sol can cross-link with Ca 2+ , Mg 2+ , as shown in formula (1), to form stable chemical bonds. Further, the cross-linking forms a three-dimensional network structure with nanometer scale, and the gel formed by the cross-linking of Ca 2+ , Mg 2+ and the alginate can agglomerate with the gel in the cleaning sol, so that the probability of the poisoning elements desorbing from the cleaning sol and migrating into the catalyst is reduced, and the removal rate of the poisoning elements is improved.

[0028] Meanwhile, the three-dimensional network structure of the alginate formed by the poisoning elements as the cross-linking agent can provide more adsorption sites for the heavy metal ions, and effectively adsorb the ions containing P, As and other heavy metal elements.

[0029] The dissolved P in the cleaning sol mainly exists in the form of PO4 3- , and PO4 3-Alginic acid can be adsorbed by electrostatic attraction to one -OH group on the surface as shown in formula (2), and to two -OH groups on the surface as shown in formula (3), and to two -OH groups on the surface as shown in formula (4).

[0030] Alginic acid can adsorb a variety of heavy metal ions, including toxic elements As, Pb. The dissolved arsenic in the cleaning sol is mainly in the form of H3AsO3 and H2AsO4 - . H3AsO3 and alginic acid and the C=O functional group on the surface of the alginic acid colloid react and are oxidized to H2AsO4 - as shown in formula (5). H2AsO4 2- can bind to the -OH and -COOH functional groups on the surface of alginic acid to form stable chemical bonds.

[0031] The Pb element that poisons the denitration catalyst mainly exists in the form of PbO, [Pb(OH)4] 2- , PbSO4, Pb(HSO4)2, the -COO- functional group on the surface of the alginic acid colloid is ionized in water, exchanges with Pb and forms stable chemical bonds; alginic acid can also form chelates with Pb to cross-link as shown in formula (1) to generate a colloid with a three-dimensional network structure using Pb as a cross-linking agent.

[0032] The alginic acid colloid in the cleaning sol uses Ca, Fe and adsorbed toxic elements Mg, Pb, etc. as cross-linking agents, which improves the attraction of the surface of the alginic acid colloid in the sol to PO4 3- , H3AsO3, H2AsO4 - , thereby improving the adsorption efficiency of the cleaning sol for heavy metal elements such as P and As.

[0033] Because the alginic acid colloid cross-linked with metal ions has strong adsorption capacity for heavy metal ions containing P, As, etc., the surface of the alginic acid colloid is the main site for adsorption, and the size of the alginic acid colloid in the cleaning sol is ≥50 nm, so that the colloid adsorbed with heavy metal elements such as P and As cannot enter the surface micropores, ensuring the migration of toxic elements from the deactivated denitration catalyst to the cleaning sol.

[0034] During the natural cooling process of the cleaning sol, the alginic acid colloid adsorbed with heavy metal ions has a larger electronegativity, and the N-H…N hydrogen bonds agglomerate to form larger colloid particles, which is helpful for the adsorption and subsequent treatment of toxic elements.

[0035] (2) Sol ultrasonic cleaning principle

[0036] The surface micropore of the denitration catalyst provides active sites and attachment points for toxic substances, and the scale is between 7-30 nm. The ultrasound can promote the entry of sulfuric acid, uncrosslinked alginic acid and fatty alcohol polyoxyethylene ether into these small spaces. The ultrasound generates high and low pressure cycles in the micropore; in the low pressure stage, the micropore generates a dense cavity, and the cavity wall is composed of uncrosslinked alginic acid and fatty alcohol polyoxyethylene ether, which has higher strength and smaller scale than the cavity generated in pure water; in the high pressure stage, the above cavity bursts and releases a lot of energy; with the continuous formation and burst of the cavity, the stubborn toxic substances attached in the micropore are detached. The ultrasound also promotes the migration of colloids and toxic substances in the cleaning sol, which helps Na, K and other toxic elements to dissolve in the cleaning sol and diffuse; it is beneficial to the combination of particles containing Ca, Mg, P, As, Pb toxic elements and alginic acid colloids.

[0037] (3) Principle of restoring specific surface area of denitration catalyst

[0038] In the ultrasonic cleaning process, the organic components and sulfuric acid in the cleaning sol enter the surface micropore of the catalyst, and the blockage in the micropore is removed in depth with the aid of ultrasound, and is adsorbed by alginic acid gel which cannot enter the micropore to prevent it from entering the surface micropore again. After the denitration catalyst is cleaned in the cleaning sol and drained, some water, sulfuric acid and organic components remain in the micropore; the remaining sulfuric acid and water decompose in the surface micropore under heat to generate SO2 and H2O vapor; the remaining organic components react with oxygen, burn and generate CO2 and H2O vapor during the calcination process; as the gas is generated in the surface micropore, the surface micropore expands, the blocked micropore opens, and the specific surface area of the denitration catalyst is restored.

[0039] (4) Principle of reducing the loss of V, W active components

[0040] The cleaning solution disclosed in the application has weak acidity, the solubility of V2O5 in the solution with pH≥0.5 is at most 0.027 mol / L, the solubility of WO3 in the solution with pH≥0.5 is at most 0.002 mol / L, and the alginic acid in the cleaning sol does not chelate and crosslink with V2O5 and WO3; also, there is no known surface functional group of alginic acid that can ion exchange with V2O5 and WO3 and form stable chemical bonds; in summary, the cleaning sol has weak solubility and adsorption capacity for V and W, which reduces the loss of active components while efficiently adsorbing toxic elements such as Ca, Mg, P, As and Pb.

[0041] (5) Colloid separation principle of cleaning waste liquid

[0042] The alginic acid used in the application is an environmentally friendly biomaterial, which is cheap and easy to obtain, and the crosslinking agent used does not contain heavy metals and does not cause additional burden to the environment. The colloids in the waste liquid can be separated and cleaned by filtration or centrifugation, realizing the recycling of tail liquid and the enrichment of sol of toxic elements such as P, As and Pb.

[0043]

[0044] Compared with the prior art, the application has the following beneficial effects:

[0045] (1) The cleaning has a wide variety of toxic elements. The cleaning sol prepared by the application can react with Ca, Mg, P, As, Pb and other toxic elements and form stable chemical bonds, so as to remove them from the surface of the deactivated denitration catalyst.

[0046] (2) The micropores can be deeply cleaned. The application combines the prepared ultrasonic wave and the physical properties of the cleaning sol with large viscosity, thereby improving the cleaning efficiency of the toxic elements in the micropores on the surface of the deactivated denitration catalyst.

[0047] (3) The specific surface area recovery effect is good. The application deeply cleans the micropores in the cleaning process, removes the toxic elements blocking the micropores and restores the micropore structure on the surface of the poisoned catalyst; and in the calcination process, the combustion, decomposition and evaporation of the residual organic matter, sulfuric acid and water in the micropores further expand the micropores, thereby well restoring the specific surface area of the denitration catalyst.

[0048] (4) The loss of active components such as V and W is small. The cleaning sol of the application has low acidity, and V and W oxides are difficult to dissolve in the cleaning sol; the alginic acid gel does not chelate or crosslink with V and W, and does not destroy the surface active sites.

[0049] (5) The application uses ammonium alginate as the main raw material, and the crosslinking agent is Ca and Fe; the cleaning sol material source is wide, the price is low, and the biological affinity is good; the wastewater contains few toxic elements after filtration and is easy to treat; the cleaning process is simple and easy to industrialize.

[0050] The application has the advantages of simple process, good effect, small influence on the strength of the carrier, low regeneration cost and suitability for industrial scale application. BRIEF DESCRIPTION OF DRAWINGS

[0051] Figure 1 The flow chart for preparing the cleaning sol is shown.

[0052] Figure 2 The schematic diagram of the adsorption mechanism is shown.

[0053] As 5+ Take the representative surface -OH group, H2AsO4 - is adsorbed on the surface of alginic acid; As3+ mainly in the form of H3AsO3, and reacts with surface C=O- groups to be oxidized to H2AsO4 - Adsorbed on the surface of alginic acid afterwards.

[0054] M n+ is a crosslinking agent cation.

[0055] Figure 3 Schematic diagram of removing toxic elements by ultrasonic cleaning of sol.

[0056] (a) before ultrasonic cleaning of sol, (b) during ultrasonic cleaning, (c) after ultrasonic cleaning.

[0057] 1 - toxic substance, 2 - denitration catalyst micropores, 3 - alginic acid colloid, 4 - alginic acid root, 5 - ultrasonic wave, 6 - cavity generated by ultrasonic wave due to sol. DETAILED DESCRIPTION

[0058] In order to make the purpose, technical scheme and advantages of the present application more clear, the present application is further described in detail below in combination with the drawings and examples. It should be understood that the specific examples described herein are only used to explain the present application and do not limit the present application.

[0059] On the contrary, the present application covers any substitution, modification, equivalent method and scheme defined by the claims on the essence and scope of the present application. Further, in order to make the public have a better understanding of the present application, some specific details are described in detail in the following detailed description of the present application. The present application can also be completely understood without the description of these details by those skilled in the art.

[0060] The implementation of the present application is described in detail below in combination with specific examples.

[0061] Example 1

[0062] A solution composed of 0.05% ammonium alginate, 1.000% fatty alcohol polyoxyethylene ether, 0.010% iron sulfate crosslinking agent and water is adjusted to pH 5.0 with 0.01 mol / L sulfuric acid, and after stirring at 20°C and 120 r / min for 5 min, a cleaning sol is obtained after standing for 1 h.

[0063] Firstly, the deactivated denitration catalyst was flushed with air at 0.1 MPa for 60 min, then was placed in the prepared washing sol, and was ultrasonically washed at 30 °C for 150 min, then was drained for 120 min, and then was calcined at 300 °C for 4 h to obtain the revived denitration catalyst, wherein the toxic elements were converted into oxides, P2O5 was 30 ppm, MgO was 30 ppm, Na2O was 10 ppm, K2O was 15 ppm, As2O3 was 120 ppm, and PbO was 130 ppm, the denitration efficiency was restored to 91.7%, the specific surface area was restored to 85.0%, the V loss rate was 1.9%, and the W loss rate was 1.4%.

[0064] Example 2

[0065] A solution composed of 0.05% ammonium alginate, 0.90% fatty alcohol polyoxyethylene ether, 0.010% ferrous sulfate, and water was adjusted to pH 4.0 with 0.05 mol / L sulfuric acid, and was stirred at 30 °C and 180 r / min for 5 min, and then was left to stand for 1 h to obtain the washing sol.

[0066] Firstly, the deactivated denitration catalyst was flushed with air at 0.3 MPa for 50 min, then was placed in the prepared washing sol, and was ultrasonically washed at 60 °C for 10 min, then was drained for 15 min, and then was calcined at 500 °C for 1 h to obtain the revived denitration catalyst, wherein the toxic elements were converted into oxides, P2O5 was 60 ppm, MgO was 40 ppm, Na2O was 15 ppm, K2O was 30 ppm, As2O3 was 50 ppm, and PbO was 40 ppm, the denitration efficiency was restored to 90.4%, the specific surface area was restored to 88.1%, the V loss rate was 15.0%, and the W loss rate was 10.0%.

[0067] Example 3

[0068] A solution composed of 0.05% ammonium alginate, 0.90% fatty alcohol polyoxyethylene ether, 0.010% ferrous sulfate, and water was adjusted to pH 4.0 with 0.05 mol / L sulfuric acid, and was stirred at 30 °C and 180 r / min for 5 min, and then was left to stand for 1 h to obtain the washing sol.

[0069] Firstly, the deactivated denitration catalyst was flushed with air at 0.4 MPa for 45 min, then was placed in the prepared washing sol, and was ultrasonically washed at 40 °C for 10 min, then was drained for 10 min, and then was calcined at 320 °C for 4 h to obtain the revived denitration catalyst, wherein the toxic elements were converted into oxides, P2O5 was 80 ppm, MgO was 10 ppm, Na2O was 5 ppm, K2O was 30 ppm, As2O3 was 70 ppm, and PbO was 20 ppm, the denitration efficiency was restored to 93.6%, the specific surface area was restored to 92.4%, the V loss rate was 5.8%, and the W loss rate was 4.5%.

[0070] Example 4

[0071] A solution composed of 2.00% ammonium alginate, 0.04% fatty alcohol polyoxyethylene ether, 1.000% ferrous sulfate and water was adjusted to pH 1.0 with 0.8 mol / L sulfuric acid, and after stirring at 60 °C and 120 r / min for 120 min, the washing sol was obtained after standing for 24 h.

[0072] Firstly, the deactivated denitration catalyst was flushed with air at 0.6 MPa for 35 min, then was placed in the prepared washing sol, and was ultrasonically washed at 70 °C for 150 min, then was drained for 120 min, and then was calcined at 500 °C for 1 h to obtain the revived denitration catalyst, wherein the toxic elements were converted into oxides, P2O5 was 50 ppm, MgO was 10 ppm, Na2O was 5 ppm, K2O was 35 ppm, As2O3 was 50 ppm, and PbO was 20 ppm, the denitration efficiency was restored to 94.9%, the specific surface area was restored to 86.2%, the V loss rate was 12.9%, and the W loss rate was 8.8%.

[0073] Example 5

[0074] A solution composed of 0.05% ammonium alginate, 0.50% fatty alcohol polyoxyethylene ether, 0.010% calcium sulfate and water was adjusted to pH 5.0 with 0.01 mol / L sulfuric acid, and after stirring at 25 °C and 120 r / min for 5 min, the washing sol was obtained after standing for 1 h.

[0075] Firstly, the deactivated denitration catalyst was flushed with air at 0.7 MPa for 30 min, then was placed in the prepared washing sol, and was ultrasonically washed at 35 °C for 10 min, then was drained for 10 min, and then was calcined at 300 °C for 4 h to obtain the revived denitration catalyst, wherein the toxic elements were converted into oxides, P2O5 was 40 ppm, MgO was 30 ppm, Na2O was 30 ppm, K2O was 15 ppm, As2O3 was 120 ppm, and PbO was 110 ppm, the denitration efficiency was restored to 97.3%, the specific surface area was restored to 89.0%, the V loss rate was 2.1%, and the W loss rate was 2.2%.

[0076] Example 6

[0077] A solution composed of 2.00% ammonium alginate, 0.05% fatty alcohol polyoxyethylene ether, 1.000% calcium sulfate and water was adjusted to pH 0.5 with 1 mol / L sulfuric acid, and after stirring at 50 °C and 300 r / min for 60 min, the washing sol was obtained after standing for 24 h.

[0078] Firstly, the deactivated denitration catalyst was flushed with air at 0.9 MPa for 20 min, then was placed in the prepared washing sol, and was ultrasonically washed at 65 °C for 70 min, then was drained for 75 min, and then was calcined at 500 °C for 1 h to obtain the revived denitration catalyst, wherein the toxic elements were converted into oxides, P2O5 was 40 ppm, MgO was 20 ppm, Na2O was 25 ppm, K2O was 35 ppm, As2O3 was 60 ppm, and PbO was 20 ppm, the denitration efficiency was restored to 93.0%, the specific surface area was restored to 92.8%, the V loss rate was 15.0%, and the W loss rate was 10.0%.

[0079] Example 7

[0080] A solution composed of 0.05% ammonium alginate, 0.80% fatty alcohol polyoxyethylene ether, 0.010% iron carbonate and water was adjusted to pH 4.0 with 0.05 mol / L sulfuric acid, and after stirring at 30 °C and 180 r / min for 5 min, the washing sol was obtained after standing for 1 h.

[0081] Firstly, the deactivated denitration catalyst was flushed with air at 1.0 MPa for 15 min, then was placed in the prepared washing sol, and was ultrasonically washed at 40°C for 20 min, then was drained for 20 min, and then was calcined at 300°C for 4 h to obtain the revived denitration catalyst, wherein the toxic elements were converted into oxides, P2O5 was 40 ppm, MgO was 30 ppm, Na2O was 30 ppm, K2O was 25 ppm, As2O3 was 120 ppm, and PbO was 90 ppm, the denitration efficiency was restored to 90.0%, the specific surface area was restored to 88.0%, the V loss rate was 4.6%, and the W loss rate was 3.1%.

[0082] Example 8

[0083] 2.00% ammonium alginate, 0.08% fatty alcohol polyoxyethylene ether, 1.000% iron carbonate, and water, and the pH was adjusted to 1.0 with 0.5 mol / L sulfuric acid, and after stirring at 80°C and 360 r / min for 120 min, the washing sol was obtained after standing for 24 h.

[0084] Firstly, the deactivated denitration catalyst was flushed with air at 1.2 MPa for 5 min, then was placed in the prepared washing sol, and was ultrasonically washed at 90°C for 140 min, then was drained for 120 min, and then was calcined at 500°C for 1 h to obtain the revived denitration catalyst, wherein the toxic elements were converted into oxides, P2O5 was 90 ppm, MgO was 10 ppm, Na2O was 5 ppm, K2O was 10 ppm, As2O3 was 90 ppm, and PbO was 30 ppm, the denitration efficiency was restored to 91.8%, the specific surface area was restored to 93.4%, the V loss rate was 13.7%, and the W loss rate was 9.7%.

[0085] Example 9

[0086] 0.05% ammonium alginate, 0.70% fatty alcohol polyoxyethylene ether, 0.010% calcium carbonate, and water, and the pH was adjusted to 5.0 with 0.05 mol / L sulfuric acid, and after stirring at 30°C and 130 r / min for 5 min, the washing sol was obtained after standing for 1 h.

[0087] Firstly, the deactivated denitration catalyst was flushed with air at 0.5 MPa for 40 min, then was placed in the prepared washing sol, and was ultrasonically washed at 40 °C for 30 min, then was drained for 30 min, and then was calcined at 300 °C for 4 h to obtain the revived denitration catalyst, wherein the toxic elements were converted into oxides, P2O5 was 60 ppm, MgO was 10 ppm, Na2O was 25 ppm, K2O was 50 ppm, As2O3 was 120 ppm, and PbO was 90 ppm, the denitration efficiency was restored to 96.5%, the specific surface area was restored to 91.3%, the V loss rate was 2.8%, and the W loss rate was 1.8%.

[0088] Example 10

[0089] 1.00% ammonium alginate, 0.07% fatty alcohol polyoxyethylene ether, 0.520% calcium carbonate and water, the pH was adjusted to 3.0 with 0.6 mol / L sulfuric acid, and after stirring at 50 °C and 450 r / min for 60 min, the washing sol was obtained after standing for 6 h.

[0090] Firstly, the deactivated denitration catalyst was flushed with air at 0.6 MPa for 35 min, then was placed in the prepared washing sol, and was ultrasonically washed at 65 °C for 90 min, then was drained for 90 min, and then was calcined at 400 °C for 3 h to obtain the revived denitration catalyst, wherein the toxic elements were converted into oxides, P2O5 was 40 ppm, MgO was 40 ppm, Na2O was 10 ppm, K2O was 25 ppm, As2O3 was 130 ppm, and PbO was 150 ppm, the denitration efficiency was restored to 97.3%, the specific surface area was restored to 88.0%, the V loss rate was 8.2%, and the W loss rate was 5.8%.

[0091] Example 11

[0092] 2.00% ammonium alginate, 0.07% fatty alcohol polyoxyethylene ether, 1.000% calcium carbonate and water, the pH was adjusted to 0.5 with 1 mol / L sulfuric acid, and after stirring at 80 °C and 300 r / min for 120 min, the washing sol was obtained after standing for 24 h.

[0093] Firstly, the deactivated denitration catalyst was flushed with air at 0.7 MPa for 30 min, then was placed in the prepared washing sol, and was washed ultrasonically at 90 °C for 150 min, and was drained for 120 min, and then was calcined at 500 °C for 1 h to obtain the revived denitration catalyst, wherein the toxic elements were converted into oxides, P2O5 was 70 ppm, MgO was 30 ppm, Na2O was 30 ppm, K2O was 15 ppm, As2O3 was 60 ppm, and PbO was 20 ppm, the denitration efficiency was restored to 91.5%, the specific surface area was restored to 85.0%, the V loss rate was 15.0%, and the W loss rate was 9.7%.

[0094] Example 12

[0095] A solution composed of 0.10% ammonium alginate, 0.73% fatty alcohol polyoxyethylene ether, 0.005% ferrous sulfate, 0.005% ferrous sulfate, and water was adjusted to pH 4.3 with 0.06 mol / L sulfuric acid, and after stirring at 35 °C and 170 r / min for 20 min, the washing sol was obtained after standing for 2 h.

[0096] Firstly, the deactivated denitration catalyst was flushed with air at 0.8 MPa for 25 min, then was placed in the prepared washing sol, and was washed ultrasonically at 50 °C for 30 min, and was drained for 25 min, and then was calcined at 300 °C for 4 h to obtain the revived denitration catalyst, wherein the toxic elements were converted into oxides, P2O5 was 50 ppm, MgO was 30 ppm, Na2O was 25 ppm, K2O was 10 ppm, As2O3 was 120 ppm, and PbO was 90 ppm, the denitration efficiency was restored to 93.8%, the specific surface area was restored to 93.6%, the V loss rate was 4.3%, and the W loss rate was 2.5%.

[0097] Example 13

[0098] A solution composed of 0.20% ammonium alginate, 0.65% fatty alcohol polyoxyethylene ether, 0.005% ferrous sulfate, 0.006% calcium sulfate, and water was adjusted to pH 4.1 with 0.05 mol / L sulfuric acid, and after stirring at 45 °C and 210 r / min for 30 min, the washing sol was obtained after standing for 3 h.

[0099] Firstly, the deactivated denitration catalyst was flushed with air at 0.9 MPa for 20 min, then was placed in the prepared washing sol, and was ultrasonically washed at 60 ℃ for 40 min, and then was drained for 40 min, and then was calcined at 320 ℃ for 4 h to obtain the revived denitration catalyst, wherein the toxic elements were converted into oxides, P2O5 was 50 ppm, MgO was 10 ppm, Na2O was 20 ppm, K2O was 5 ppm, As2O3 was 90 ppm, and PbO was 20 ppm, the denitration efficiency was restored to 90.3%, the specific surface area was restored to 87.9%, the V loss rate was 4.5%, and the W loss rate was 3.6%.

[0100] Example 14

[0101] A solution composed of 0.40% ammonium alginate, 0.49% fatty alcohol polyoxyethylene ether, 0.010% iron carbonate, 0.005% calcium carbonate and water was adjusted to pH 3.7 with 0.1 mol / L sulfuric acid, and after stirring at 55 ℃ and 280 r / min for 50 min, the washing sol was obtained after standing for 5 h.

[0102] Firstly, the deactivated denitration catalyst was flushed with air at 0.8 MPa for 25 min, then was placed in the prepared washing sol, and was ultrasonically washed at 70 ℃ for 70 min, and then was drained for 70 min, and then was calcined at 340 ℃ for 4 h to obtain the revived denitration catalyst, wherein the toxic elements were converted into oxides, P2O5 was 40 ppm, MgO was 30 ppm, Na2O was 15 ppm, K2O was 10 ppm, As2O3 was 100 ppm, and PbO was 80 ppm, the denitration efficiency was restored to 93.6%, the specific surface area was restored to 87.7%, the V loss rate was 5.7%, and the W loss rate was 4.9%.

[0103] Example 15

[0104] A solution composed of 0.50% ammonium alginate, 0.41% fatty alcohol polyoxyethylene ether, 0.005% iron sulfate, 0.008% calcium sulfate and water was adjusted to pH 3.5 with 0.1 mol / L sulfuric acid, and after stirring at 65 ℃ and 310 r / min for 75 min, the washing sol was obtained after standing for 6 h.

[0105] Firstly, the deactivated denitration catalyst was flushed with air at 0.2 MPa for 55 min, then was placed in the prepared washing sol, and was ultrasonically washed at 80 °C for 90 min, then was drained for 90 min, and then was calcined at 340 °C for 4 h to obtain the revived denitration catalyst, wherein the toxic elements were converted into oxides, P2O5 was 40 ppm, MgO was 40 ppm, Na2O was 25 ppm, K2O was 50 ppm, As2O3 was 70 ppm, and PbO was 20 ppm, the denitration efficiency was restored to 91.2%, the specific surface area was restored to 85.0%, the V loss rate was 7.1%, and the W loss rate was 4.9%.

[0106] Example 16

[0107] A solution composed of 0.70% ammonium alginate, 0.29% fatty alcohol polyoxyethylene ether, 0.005% ferrous sulfate, 0.010% calcium carbonate and water was adjusted to pH 3.1 with 0.1 mol / L sulfuric acid, and after stirring at 70 °C and 350 r / min for 120 min, the washing sol was obtained after standing for 8 h.

[0108] Firstly, the deactivated denitration catalyst was flushed with air at 1.0 MPa for 15 min, then was placed in the prepared washing sol, and was ultrasonically washed at 85 °C for 130 min, then was drained for 120 min, and then was calcined at 360 °C for 3 h to obtain the revived denitration catalyst, wherein the toxic elements were converted into oxides, P2O5 was 60 ppm, MgO was 30 ppm, Na2O was 15 ppm, K2O was 15 ppm, As2O3 was 80 ppm, and PbO was 30 ppm, the denitration efficiency was restored to 96.2%, the specific surface area was restored to 88.0%, the V loss rate was 7.9%, and the W loss rate was 6.2%.

[0109] Example 17

[0110] A solution composed of 0.80% ammonium alginate, 0.23% fatty alcohol polyoxyethylene ether, 0.005% ferrous sulfate, 0.006% ferrous carbonate and water was adjusted to pH 2.9 with 0.1 mol / L sulfuric acid, and after stirring at 75 °C and 370 r / min for 120 min, the washing sol was obtained after standing for 9 h.

[0111] Firstly, the deactivated denitration catalyst was flushed with air at 0.1 MPa for 60 min, then was placed in the prepared washing sol, and was washed ultrasonically at 85 °C for 130 min, then was drained for 120 min, and then was calcined at 380 °C for 3 h to obtain the revived denitration catalyst, wherein the toxic elements were converted into oxides, P2O5 was 50 ppm, MgO was 30 ppm, Na2O was 40 ppm, K2O was 50 ppm, As2O3 was 100 ppm, and PbO was 110 ppm, the denitration efficiency was restored to 91.1%, the specific surface area was restored to 90.5%, the V loss rate was 7.5%, and the W loss rate was 6.5%.

[0112] Example 18

[0113] 1.00% ammonium alginate, 0.14% fatty alcohol polyoxyethylene ether, 0.008% calcium sulfate, 0.005% calcium carbonate, and water, and the pH was adjusted to 2.5 with 0.1 mol / L sulfuric acid, and the washing sol was obtained after stirring at 80 °C and 390 r / min for 120 min and standing for 10 h.

[0114] Firstly, the deactivated denitration catalyst was flushed with air at 0.8 MPa for 25 min, then was placed in the prepared washing sol, and was washed ultrasonically at 90 °C for 150 min, then was drained for 120 min, and then was calcined at 400 °C for 2 h to obtain the revived denitration catalyst, wherein the toxic elements were converted into oxides, P2O5 was 100 ppm, MgO was 40 ppm, Na2O was 15 ppm, K2O was 25 ppm, As2O3 was 100 ppm, and PbO was 80 ppm, the denitration efficiency was restored to 92.2%, the specific surface area was restored to 93.0%, the V loss rate was 8.8%, and the W loss rate was 7.1%.

[0115] Example 19

[0116] 1.10% ammonium alginate, 0.10% fatty alcohol polyoxyethylene ether, 0.500% iron sulfate, 0.500% ferrous sulfate, and water, and the pH was adjusted to 2.3 with 0.1 mol / L sulfuric acid, and the washing sol was obtained after stirring at 80 °C and 400 r / min for 120 min and standing for 12 h.

[0117] Firstly, the deactivated denitration catalyst was flushed with air at a pressure of 1.2 MPa for 5 min, then was placed in the prepared washing sol, and was ultrasonically washed at 90°C for 130 min, then was drained for 120 min, and then was calcined at 400°C for 2 h to obtain the revived denitration catalyst, wherein the toxic elements were converted into oxides, P2O5 was 60 ppm, MgO was 30 ppm, Na2O was 15 ppm, K2O was 15 ppm, As2O3 was 150 ppm, and PbO was 130 ppm, the denitration efficiency was restored to 98.8%, the specific surface area was restored to 89.0%, the V loss rate was 8.9%, and the W loss rate was 6.3%.

[0118] Example 20

[0119] 1. A solution composed of 0.20% ammonium alginate, 0.07% fatty alcohol polyoxyethylene ether, 0.300% ferrous sulfate, 0.500% calcium sulfate, and water, which was adjusted to pH 2.1 with 0.1 mol / L sulfuric acid, was stirred at 80°C and 420 r / min for 90 min, and then was allowed to stand for 12 h to obtain a washing sol.

[0120] Firstly, the deactivated denitration catalyst was flushed with air at a pressure of 0.7 MPa for 30 min, then was placed in the prepared washing sol, and was ultrasonically washed at 90°C for 120 min, then was drained for 120 min, and then was calcined at 420°C for 2 h to obtain the revived denitration catalyst, wherein the toxic elements were converted into oxides, P2O5 was 40 ppm, MgO was 10 ppm, Na2O was 25 ppm, K2O was 25 ppm, As2O3 was 40 ppm, and PbO was 30 ppm, the denitration efficiency was restored to 92.0%, the specific surface area was restored to 91.9%, the V loss rate was 10.8%, and the W loss rate was 7.0%.

[0121] Example 21

[0122] 1. A solution composed of 0.30% ammonium alginate, 0.04% fatty alcohol polyoxyethylene ether, 0.400% calcium sulfate, 0.500% iron carbonate, and water, which was adjusted to pH 1.9 with 0.1 mol / L sulfuric acid, was stirred at 80°C and 390 r / min for 90 min, and then was allowed to stand for 12 h to obtain a washing sol.

[0123] Firstly, the deactivated denitration catalyst was flushed with air at 0.9 MPa for 20 min, then was placed in the prepared washing sol, and was washed ultrasonically at 90 °C for 120 min, and then was drained for 120 min, and then was calcined at 420 °C for 2 h to obtain the revived denitration catalyst, wherein the toxic elements were converted into oxides, P2O5 was 50 ppm, MgO was 30 ppm, Na2O was 10 ppm, K2O was 35 ppm, As2O3 was 110 ppm, and PbO was 80 ppm, the denitration efficiency was restored to 94.3%, the specific surface area was restored to 86.4%, the V loss rate was 10.8%, and the W loss rate was 7.5%.

[0124] Example 22

[0125] 1. A solution composed of 0.40% ammonium alginate, 0.02% fatty alcohol polyoxyethylene ether, 0.500% iron carbonate, 0.500% calcium carbonate and water, adjusted to pH 1.7 with 0.15 mol / L sulfuric acid, after stirring at 80 °C and 400 r / min for 90 min, and then standing for 15 h, to obtain the washing sol.

[0126] Firstly, the deactivated denitration catalyst was flushed with air at 0.4 MPa for 45 min, then was placed in the prepared washing sol, and was washed ultrasonically at 90 °C for 110 min, and then was drained for 105 min, and then was calcined at 440 °C for 2 h to obtain the revived denitration catalyst, wherein the toxic elements were converted into oxides, P2O5 was 100 ppm, MgO was 100 ppm, Na2O was 15 ppm, K2O was 25 ppm, As2O3 was 70 ppm, and PbO was 20 ppm, the denitration efficiency was restored to 91.1%, the specific surface area was restored to 85.0%, the V loss rate was 11.2%, and the W loss rate was 7.7%.

[0127] Example 23

[0128] 1. A solution composed of 0.50% ammonium alginate, 0.02% fatty alcohol polyoxyethylene ether, 0.500% iron sulfate, 0.200% calcium sulfate and water, adjusted to pH 1.5 with 0.2 mol / L sulfuric acid, after stirring at 75 °C and 380 r / min for 80 min, and then standing for 15 h, to obtain the washing sol.

[0129] Firstly, the deactivated denitration catalyst was flushed with air at 0.9 MPa for 20 min, then was placed in the prepared washing sol, and was washed ultrasonically at 85°C for 90 min, and then was drained for 90 min, and then was calcined at 440°C for 2 h to obtain the revived denitration catalyst, wherein the toxic elements were converted into oxides, P2O5 was 80 ppm, MgO was 30 ppm, Na2O was 10 ppm, K2O was 35 ppm, As2O3 was 80 ppm, and PbO was 30 ppm, the denitration efficiency was restored to 94.8%, the specific surface area was restored to 87.8%, the V loss rate was 12.0%, and the W loss rate was 8.4%.

[0130] Example 24

[0131] 1. A solution consisting of 0.70% ammonium alginate, 0.04% fatty alcohol polyoxyethylene ether, 0.500% iron sulfate, 0.100% calcium carbonate and water, adjusted to pH 1.1 with 0.2 mol / L sulfuric acid, after stirring at 70°C and 370 r / min for 120 min, and standing for 16 h to obtain the washing sol.

[0132] Firstly, the deactivated denitration catalyst was flushed with air at 0.9 MPa for 20 min, then was placed in the prepared washing sol, and was washed ultrasonically at 80°C for 150 min, and then was drained for 120 min, and then was calcined at 460°C for 1 h to obtain the revived denitration catalyst, wherein the toxic elements were converted into oxides, P2O5 was 20 ppm, MgO was 40 ppm, Na2O was 5 ppm, K2O was 25 ppm, As2O3 was 130 ppm, and PbO was 70 ppm, the denitration efficiency was restored to 94.1%, the specific surface area was restored to 92.9%, the V loss rate was 12.3%, and the W loss rate was 9.1%.

[0133] Example 25

[0134] 1. A solution consisting of 0.80% ammonium alginate, 0.04% fatty alcohol polyoxyethylene ether, 0.500% ferrous sulfate, 0.300% iron carbonate and water, adjusted to pH 0.9 with 0.5 mol / L sulfuric acid, after stirring at 65°C and 360 r / min for 120 min, and standing for 17 h to obtain the washing sol.

[0135] Firstly, the deactivated denitration catalyst was flushed with air at 0.3 MPa for 50 min, then was placed in the prepared washing sol, and was washed ultrasonically at 75 °C for 130 min, then was drained for 120 min, and then was calcined at 470 °C for 1 h to obtain the revived denitration catalyst, wherein the toxic elements were converted into oxides, P2O5 was 70 ppm, MgO was 40 ppm, Na2O was 15 ppm, K2O was 40 ppm, As2O3 was 60 ppm, and PbO was 20 ppm, the denitration efficiency was restored to 90.3%, the specific surface area was restored to 90.5%, the V loss rate was 14.0%, and the W loss rate was 9.9%.

[0136] Example 26

[0137] A solution composed of 0.10% ammonium alginate, 0.73% fatty alcohol polyoxyethylene ether, 0.002% ferric sulfate, 0.004% ferrous sulfate, 0.004% calcium sulfate and water was adjusted to pH 4.3 with 0.08 mol / L sulfuric acid, and was stirred at 20 °C and 160 r / min for 30 min, and then was left to stand for 4 h to obtain the washing sol.

[0138] Firstly, the deactivated denitration catalyst was flushed with air at 1.2 MPa for 5 min, then was placed in the prepared washing sol, and was washed ultrasonically at 65 °C for 100 min, then was drained for 95 min, and then was calcined at 490 °C for 1 h to obtain the revived denitration catalyst, wherein the toxic elements were converted into oxides, P2O5 was 80 ppm, MgO was 100 ppm, Na2O was 10 ppm, K2O was 40 ppm, As2O3 was 100 ppm, and PbO was 20 ppm, the denitration efficiency was restored to 98.7%, the specific surface area was restored to 85.7%, the V loss rate was 15.0%, and the W loss rate was 9.1%.

[0139] Example 27

[0140] A solution composed of 0.10% ammonium alginate, 0.73% fatty alcohol polyoxyethylene ether, 0.002% ferric sulfate, 0.004% ferrous sulfate, 0.004% calcium sulfate and water was adjusted to pH 4.3 with 0.08 mol / L sulfuric acid, and was stirred at 20 °C and 160 r / min for 30 min, and then was left to stand for 4 h to obtain the washing sol.

[0141] Firstly, the deactivated denitration catalyst was flushed with air at 0.9 MPa for 20 min, then was placed in the prepared washing sol, and was ultrasonically washed at 35 °C for 40 min, and then was drained for 45 min, and then was calcined at 310 °C for 3 h to obtain the recovered denitration catalyst, wherein the toxic elements were converted into oxides, P2O5 was 40 ppm, MgO was 10 ppm, Na2O was 20 ppm, K2O was 15 ppm, As2O3 was 100 ppm, and PbO was 20 ppm, the denitration efficiency was recovered to 93.0%, the specific surface area was recovered to 88.2%, the V loss rate was 4.9%, and the W loss rate was 2.4%.

[0142] Example 28

[0143] A solution composed of 0.30% ammonium alginate, 0.56% fatty alcohol polyoxyethylene ether, 0.002% calcium sulfate, 0.004% iron carbonate, 0.004% calcium carbonate and water was adjusted to pH 3.9 with 0.1 mol / L sulfuric acid, and then was stirred at 50 °C and 260 r / min for 25 min, and then was allowed to stand for 5 h to obtain the washing sol.

[0144] Firstly, the deactivated denitration catalyst was flushed with air at 0.5 MPa for 40 min, then was placed in the prepared washing sol, and was ultrasonically washed at 60 °C for 50 min, and then was drained for 50 min, and then was calcined at 330 °C for 3 h to obtain the recovered denitration catalyst, wherein the toxic elements were converted into oxides, P2O5 was 40 ppm, MgO was 40 ppm, Na2O was 40 ppm, K2O was 15 ppm, As2O3 was 140 ppm, and PbO was 20 ppm, the denitration efficiency was recovered to 97.6%, the specific surface area was recovered to 89.0%, the V loss rate was 5.9%, and the W loss rate was 4.4%.

[0145] Example 29

[0146] A solution composed of 0.40% ammonium alginate, 0.49% fatty alcohol polyoxyethylene ether, 0.004% iron sulfate, 0.003% ferrous sulfate, 0.003% iron carbonate and water was adjusted to pH 3.7 with 0.1 mol / L sulfuric acid, and then was stirred at 55 °C and 280 r / min for 45 min, and then was allowed to stand for 6 h to obtain the washing sol.

[0147] Firstly, the deactivated denitration catalyst was flushed with air at a pressure of 1.2 MPa for 5 min, then was placed in the prepared washing sol, and was ultrasonically washed at 65°C for 70 min, and then was drained for 75 min, and then was calcined at 330°C for 3 h to obtain the revived denitration catalyst, wherein the toxic elements were converted into oxides, P2O5 was 60 ppm, MgO was 20 ppm, Na2O was 25 ppm, K2O was 5 ppm, As2O3 was 130 ppm, and PbO was 10 ppm, the denitration efficiency was restored to 91.8%, the specific surface area was restored to 85.0%, the V loss rate was 5.9%, and the W loss rate was 4.4%.

[0148] Example 30

[0149] A solution composed of 0.70% ammonium alginate, 0.29% fatty alcohol polyoxyethylene ether, 0.004% ferric sulfate, 0.003% iron carbonate, 0.003% calcium carbonate and water was adjusted to pH 3.1 with 0.2 mol / L sulfuric acid, and after stirring at 70°C and 380 r / min for 120 min, a washing sol was obtained after standing for 8 h.

[0150] Firstly, the deactivated denitration catalyst was flushed with air at a pressure of 0.8 MPa for 25 min, then was placed in the prepared washing sol, and was ultrasonically washed at 80°C for 130 min, and then was drained for 120 min, and then was calcined at 360°C for 2 h to obtain the revived denitration catalyst, wherein the toxic elements were converted into oxides, P2O5 was 70 ppm, MgO was 30 ppm, Na2O was 50 ppm, K2O was 25 ppm, As2O3 was 80 ppm, and PbO was 30 ppm, the denitration efficiency was restored to 92.6%, the specific surface area was restored to 87.6%, the V loss rate was 7.1%, and the W loss rate was 5.0%.

[0151] Example 31

[0152] A solution composed of 0.80% ammonium alginate, 0.23% fatty alcohol polyoxyethylene ether, 0.004% ferrous sulfate, 0.004% calcium sulfate, 0.002% calcium carbonate and water was adjusted to pH 2.9 with 0.3 mol / L sulfuric acid, and after stirring at 75°C and 380 r / min for 120 min, a washing sol was obtained after standing for 9 h.

[0153] Firstly, the deactivated denitration catalyst was flushed with air at 0.1 MPa for 60 min, then was placed in the prepared washing sol, and was washed ultrasonically at 90 °C for 130 min, and was drained for 120 min, and then was calcined at 370 °C for 2 h to obtain the revived denitration catalyst, wherein the toxic elements were converted into oxides, P2O5 was 60 ppm, MgO was 10 ppm, Na2O was 30 ppm, K2O was 10 ppm, As2O3 was 70 ppm, and PbO was 80 ppm, the denitration efficiency was restored to 92.2%, the specific surface area was restored to 87.5%, the V loss rate was 8.9%, and the W loss rate was 6.4%.

[0154] Example 32

[0155] A solution composed of 0.90% ammonium alginate, 0.18% fatty alcohol polyoxyethylene ether, 0.002% ferrous sulfate, 0.004% iron carbonate, 0.004% calcium carbonate and water was adjusted to pH 2.7 with 0.3 mol / L sulfuric acid, and after stirring at 80 °C and 400 r / min for 120 min, the washing sol was obtained after standing for 10 h.

[0156] Firstly, the deactivated denitration catalyst was flushed with air at 0.7 MPa for 30 min, then was placed in the prepared washing sol, and was washed ultrasonically at 90 °C for 150 min, and was drained for 120 min, and then was calcined at 380 °C for 2 h to obtain the revived denitration catalyst, wherein the toxic elements were converted into oxides, P2O5 was 80 ppm, MgO was 30 ppm, Na2O was 25 ppm, K2O was 25 ppm, As2O3 was 70 ppm, and PbO was 20 ppm, the denitration efficiency was restored to 95.0%, the specific surface area was restored to 89.2%, the V loss rate was 7.7%, and the W loss rate was 5.9%.

[0157] Example 33

[0158] A solution composed of 1.10% ammonium alginate, 0.10% fatty alcohol polyoxyethylene ether, 0.300% iron sulfate, 0.300% ferrous sulfate, 0.400% calcium sulfate and water was adjusted to pH 2.3 with 0.3 mol / L sulfuric acid, and after stirring at 80 °C and 410 r / min for 120 min, the washing sol was obtained after standing for 14 h.

[0159] Firstly, the deactivated denitration catalyst was flushed with air at 0.5 MPa for 40 min, then was placed in the prepared washing sol, and was washed ultrasonically at 90 °C for 130 min, then was drained for 120 min, and then was calcined at 400 °C for 2 h to obtain the revived denitration catalyst, wherein the toxic elements were converted into oxides, P2O5 was 60 ppm, MgO was 40 ppm, Na2O was 15 ppm, K2O was 35 ppm, As2O3 was 80 ppm, and PbO was 10 ppm, the denitration efficiency was restored to 91.4%, the specific surface area was restored to 89.8%, the V loss rate was 9.7%, and the W loss rate was 5.9%.

[0160] Example 34

[0161] 1. A solution composed of 0.30% calcium sulfate, 0.300% iron carbonate, 0.300% calcium carbonate and water, and adjusted to pH 1.9 with 0.5 mol / L sulfuric acid, was stirred at 80 °C and 380 r / min for 120 min, and then was allowed to stand for 14 h to obtain the washing sol.

[0162] Firstly, the deactivated denitration catalyst was flushed with air at 0.8 MPa for 25 min, then was placed in the prepared washing sol, and was washed ultrasonically at 90 °C for 130 min, then was drained for 120 min, and then was calcined at 420 °C for 2 h to obtain the revived denitration catalyst, wherein the toxic elements were converted into oxides, P2O5 was 60 ppm, MgO was 30 ppm, Na2O was 25 ppm, K2O was 5 ppm, As2O3 was 80 ppm, and PbO was 10 ppm, the denitration efficiency was restored to 94.3%, the specific surface area was restored to 85.0%, the V loss rate was 10.3%, and the W loss rate was 8.2%.

[0163] Example 35

[0164] 1. A solution composed of 0.30% calcium sulfate, 0.300% iron carbonate, 0.300% calcium carbonate and water, and adjusted to pH 1.9 with 0.5 mol / L sulfuric acid, was stirred at 80 °C and 380 r / min for 120 min, and then was allowed to stand for 14 h to obtain the washing sol.

[0165] Firstly, the deactivated denitration catalyst was flushed with air at 0.1 MPa for 60 min, then was placed in the prepared washing sol, and was ultrasonically washed at 90 °C for 130 min, and was drained for 120 min, and then was calcined at 440 °C for 2 h to obtain the revived denitration catalyst, wherein the toxic elements were converted into oxides, P2O5 was 60 ppm, MgO was 30 ppm, Na2O was 40 ppm, K2O was 50 ppm, As2O3 was 30 ppm, and PbO was 30 ppm, the denitration efficiency was restored to 90.5%, the specific surface area was restored to 86.5%, the V loss rate was 11.3%, and the W loss rate was 8.4%.

[0166] Example 36

[0167] 1. A solution consisting of 0.70% ammonium alginate, 0.04% fatty alcohol polyoxyethylene ether, 0.300% ferric sulfate, 0.100% iron carbonate, 0.400% calcium carbonate and water, and adjusted to pH 1.1 with 0.7 mol / L sulfuric acid, was stirred at 70 °C and 350 r / min for 120 min, and was then left to stand for 17 h to obtain a washing sol.

[0168] Firstly, the deactivated denitration catalyst was flushed with air at 0.5 MPa for 40 min, then was placed in the prepared washing sol, and was ultrasonically washed at 80 °C for 130 min, and was drained for 120 min, and then was calcined at 460 °C for 1 h to obtain the revived denitration catalyst, wherein the toxic elements were converted into oxides, P2O5 was 40 ppm, MgO was 30 ppm, Na2O was 10 ppm, K2O was 40 ppm, As2O3 was 60 ppm, and PbO was 20 ppm, the denitration efficiency was restored to 97.8%, the specific surface area was restored to 85.9%, the V loss rate was 12.6%, and the W loss rate was 8.1%.

[0169] Example 37

[0170] 1. A solution consisting of 0.80% ammonium alginate, 0.04% fatty alcohol polyoxyethylene ether, 0.300% ferrous sulfate, 0.200% iron carbonate, 0.400% calcium carbonate and water, and adjusted to pH 0.9 with 0.8 mol / L sulfuric acid, was stirred at 65 °C and 350 r / min for 120 min, and was then left to stand for 20 h to obtain a washing sol.

[0171] Firstly, the deactivated denitration catalyst was flushed with air at 0.5 MPa for 40 min, then was placed in the prepared washing sol, and was ultrasonically washed at 80 °C for 140 min, and then was drained for 120 min, and then was calcined at 470 °C for 1 h to obtain the revived denitration catalyst, wherein the toxic elements were converted into oxides, P2O5 was 30 ppm, MgO was 20 ppm, Na2O was 15 ppm, K2O was 10 ppm, As2O3 was 130 ppm, and PbO was 40 ppm, the denitration efficiency was restored to 93.9%, the specific surface area was restored to 92.0%, the V loss rate was 14.5%, and the W loss rate was 10.0%.

[0172] Example 38

[0173] A solution composed of 0.20% ammonium alginate, 0.65% fatty alcohol polyoxyethylene ether, 0.004% ferric sulfate, 0.002% ferrous sulfate, 0.002% calcium sulfate, 0.002% iron carbonate, and water was adjusted to pH 4.1 with 0.05 mol / L sulfuric acid, and after stirring at 45 °C and 230 r / min for 30 min, the washing sol was obtained after standing for 5 h.

[0174] Firstly, the deactivated denitration catalyst was flushed with air at 0.1 MPa for 60 min, then was placed in the prepared washing sol, and was ultrasonically washed at 55 °C for 50 min, and then was drained for 45 min, and then was calcined at 320 °C for 4 h to obtain the revived denitration catalyst, wherein the toxic elements were converted into oxides, P2O5 was 80 ppm, MgO was 10 ppm, Na2O was 10 ppm, K2O was 10 ppm, As2O3 was 50 ppm, and PbO was 30 ppm, the denitration efficiency was restored to 95.5%, the specific surface area was restored to 88.5%, the V loss rate was 4.1%, and the W loss rate was 4.4%.

[0175] Example 39

[0176] A solution composed of 0.50% ammonium alginate, 0.41% fatty alcohol polyoxyethylene ether, 0.004% ferric sulfate, 0.002% calcium sulfate, 0.006% iron carbonate, 0.002% calcium carbonate, and water was adjusted to pH 3.5 with 0.15 mol / L sulfuric acid, and after stirring at 65 °C and 320 r / min for 85 min, the washing sol was obtained after standing for 6 h.

[0177] Firstly, the deactivated denitration catalyst was flushed with air at 0.6 MPa for 35 min, then was placed in the prepared washing sol, and was ultrasonically washed at 75 °C for 110 min, then was drained for 110 min, and then was calcined at 340 °C for 3 h to obtain the revived denitration catalyst, wherein the toxic elements were converted into oxides, P2O5 was 70 ppm, MgO was 30 ppm, Na2O was 5 ppm, K2O was 10 ppm, As2O3 was 50 ppm, and PbO was 65 ppm, the denitration efficiency was restored to 93.4%, the specific surface area was restored to 86.8%, the V loss rate was 6.9%, and the W loss rate was 4.0%.

[0178] Example 40

[0179] A solution composed of 0.60% ammonium alginate, 0.35% fatty alcohol polyoxyethylene ether, 0.004% ferrous sulfate, 0.003% calcium sulfate, 0.002% iron carbonate, 0.002% calcium carbonate, and water was adjusted to pH 3.3 with 0.2 mol / L sulfuric acid, and after stirring at 70 °C and 350 r / min for 120 min, the washing sol was obtained after standing for 7 h.

[0180] Firstly, the deactivated denitration catalyst was flushed with air at 0.5 MPa for 40 min, then was placed in the prepared washing sol, and was ultrasonically washed at 80 °C for 130 min, then was drained for 120 min, and then was calcined at 350 °C for 3 h to obtain the revived denitration catalyst, wherein the toxic elements were converted into oxides, P2O5 was 50 ppm, MgO was 40 ppm, Na2O was 25 ppm, K2O was 35 ppm, As2O3 was 140 ppm, and PbO was 145 ppm, the denitration efficiency was restored to 92.9%, the specific surface area was restored to 91.0%, the V loss rate was 6.8%, and the W loss rate was 5.0%.

[0181] Example 41

[0182] A solution composed of 1.30% ammonium alginate, 0.04% fatty alcohol polyoxyethylene ether, 0.400% iron sulfate, 0.200% ferrous sulfate, 0.050% calcium sulfate, 0.200% calcium carbonate, and water was adjusted to pH 1.9 with 0.4 mol / L sulfuric acid, and after stirring at 80 °C and 430 r / min for 120 min, the washing sol was obtained after standing for 15 h.

[0183] Firstly, the deactivated denitration catalyst was flushed with air at 0.4 MPa for 45 min, then was placed in the prepared washing sol, and was ultrasonically washed at 90 °C for 140 min, and was drained for 120 min, and then was calcined at 420 °C for 2 h to obtain the revived denitration catalyst, wherein the toxic elements were converted into oxides, P2O5 was 60 ppm, MgO was 10 ppm, Na2O was 10 ppm, K2O was 5 ppm, As2O3 was 140 ppm, and PbO was 150 ppm, the denitration efficiency was restored to 94.3%, the specific surface area was restored to 86.2%, the V loss rate was 11.8%, and the W loss rate was 8.3%.

[0184] Example 42

[0185] 1. A solution consisting of 0.50% ammonium alginate, 0.02% fatty alcohol polyoxyethylene ether, 0.400% ferric sulfate, 0.120% calcium sulfate, 0.200% iron carbonate, 0.002% calcium carbonate and water, adjusted to pH 1.5 with 0.6 mol / L sulfuric acid, after stirring at 75 °C and 420 r / min for 120 min, and standing for 15 h, to obtain a washing sol.

[0186] Firstly, the deactivated denitration catalyst was flushed with air at 0.2 MPa for 55 min, then was placed in the prepared washing sol, and was ultrasonically washed at 90 °C for 140 min, and was drained for 120 min, and then was calcined at 440 °C for 2 h to obtain the revived denitration catalyst, wherein the toxic elements were converted into oxides, P2O5 was 60 ppm, MgO was 10 ppm, Na2O was 15 ppm, K2O was 5 ppm, As2O3 was 130 ppm, and PbO was 20 ppm, the denitration efficiency was restored to 92.1%, the specific surface area was restored to 87.0%, the V loss rate was 11.1%, and the W loss rate was 8.8%.

[0187] Example 43

[0188] 2. A solution consisting of 0.50% ammonium alginate, 0.02% fatty alcohol polyoxyethylene ether, 0.400% ferric sulfate, 0.120% calcium sulfate, 0.200% iron carbonate, 0.002% calcium carbonate and water, adjusted to pH 1.5 with 0.6 mol / L sulfuric acid, after stirring at 75 °C and 420 r / min for 120 min, and standing for 15 h, to obtain a washing sol.

[0189] First, the deactivated denitration catalyst was flushed with air at 0.2 MPa for 55 min, then placed in the prepared cleaning sol, and ultrasonically cleaned at 65 ℃ for 110 min. After draining for 110 min, the revived denitration catalyst was obtained by calcination at 490 ℃ for 1 h. The toxic elements in the catalyst were converted into oxides, P2O5 was 70 ppm, MgO was 60 ppm, Na2O was 10 ppm, K2O was 10 ppm, As2O3 was 130 ppm, and PbO was 30 ppm. The denitration efficiency was restored to 96.7%, the specific surface area was restored to 91.2%, the V loss rate was 15.0%, and the W loss rate was 9.4%.

Claims

1. A method for preparing a deactivation denitration catalyst cleaning sol, characterized by, The specific preparation steps include: (1) dissolving ammonium alginate in water; (2) adding a fatty alcohol polyoxyethylene ether and a crosslinking agent; (3) adjusting the pH to 0.5-5.0 with a 0.01-1.00 mol / L dilute sulfuric acid solution and continuing to stir for 5-120 min; (4) standing for 1-24 h to obtain a cleaning sol; The crosslinking agent is one or more of iron sulfate, ferrous sulfate, calcium sulfate, iron carbonate and calcium carbonate.

2. The method of claim 1, wherein the deactivated de-NOx catalyst cleaning sol is prepared by the steps of: In step (3), when the crosslinking agent contains one or more of calcium sulfate, iron carbonate and calcium carbonate, the dilute sulfuric acid solution is slowly added, and the crosslinking agent that is insoluble in the alginate solution is crosslinked with alginate to form a colloid as the dilute sulfuric acid solution is added; when the crosslinking agent does not contain any of calcium sulfate, iron carbonate and calcium carbonate, the alginate is crosslinked with the crosslinking agent to form a colloid in step (2), and as the dilute sulfuric acid solution is added, some of the hydrogen bonds between alginate in the sol are broken, and the viscosity of the sol decreases.

3. The method of using the cleaning sol of the deactivated denitration catalyst prepared according to claim 1, characterized in that, The steps include: (1) first, the deactivated denitration catalyst is treated by blowing and cleaning, the blowing pressure is 0.1-1.2 MPa, and the blowing time is 5-60 min; (2) then, the deactivated denitration catalyst is immersed in the cleaning sol and ultrasonically cleaned at 30-90℃ for 10-150 min; (3) then, draining for 10-120 min; (4) finally, calcining at 300-500℃ for 1-4 h to obtain a revived denitration catalyst.

4. The method of using a deactivation de-NOx catalyst cleaning sol according to claim 3, wherein The content of the poisoning elements in the ultrasonically cleaned denitration catalyst, converted into oxides, is P2O5≤100 ppm, MgO≤100 ppm, Na2O≤50 ppm, K2O≤50 ppm, As2O3≤150 ppm and PbO≤150 ppm, the denitration efficiency is restored to ≥90.0%, the specific surface area is restored to ≥85.0%, the V loss rate is ≤15.0%, and the W loss rate is ≤10.0%.

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