CN110721754B - Regeneration and recovery method of waste SCR denitration catalyst - Google Patents
Regeneration and recovery method of waste SCR denitration catalyst Download PDFInfo
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- B01J2038/005—Regeneration or reactivation of catalysts, in general involving supercritical treatment
Abstract
The invention provides a regeneration and recovery method of a waste SCR denitration catalyst, which comprises the steps of adopting microwave heating to treat an active loaded reversible deactivated SCR denitration catalyst to prepare a regenerated SCR denitration catalyst; wherein the regeneration liquid used in the active load comprises an irreversible deactivated SCR denitration catalystRespectively recovered Ti 4+ 、V 5+ And W is 6+ . According to the method for regenerating and recovering the waste SCR denitration catalyst, provided by the invention, the mechanical strength of the regenerated catalyst can be effectively improved by adopting microwave heating, the catalyst can be regenerated for multiple times, the uniformity of dispersing active components on the surface of the catalyst is improved, and the denitration activity of the regenerated catalyst is improved; and, for Ti respectively 4+ 、V 5+ And W is 6+ Recovering the Ti thus recovered 4+ 、V 5+ And W is 6+ The method can be used as the supplement of regeneration liquid in the regeneration process to form closed loop circular economy, and the surplus product can be used as a product for sale, namely, the resources of the waste denitration catalyst are comprehensively recycled.
Description
Technical Field
The invention relates to the technical field of catalyst regeneration, in particular to a method for regenerating and recycling a waste SCR denitration catalyst.
Background
Nitrogen oxides are the main atmospheric pollution source released by coal-fired power plants, and along with the rapid development of the power industry in China, the release amount of the nitrogen oxides is also more and more, so that the denitration environment-friendly technology is fully developed in the power industry in China.
At present, most coal-fired power plants in China use a Selective Catalytic Reduction (SCR) method for dry flue gas denitration, nitrogen oxides are selectively reduced into harmless nitrogen and water by ammonia or other reducing agents, and SCR catalysts mainly comprise vanadium-tungsten systems, vanadium-molybdenum systems and vanadium-tungsten-molybdenum systems; all three are in V form 2 O 5 And Ti O 2 As a catalytically active body, there is used a vanadium-tungsten catalyst comprising WO 3 As an auxiliary agent, the vanadium-molybdenum system is prepared by MoO 3 As an auxiliary agent, the vanadium-tungsten-molybdenum system is WO 3 And MoO 3 As a common auxiliary agent. In the selective catalytic reduction technique, the investment in the catalyst is a coreIn the core, the activity of the catalyst directly determines the efficiency of denitration.
However, SCR catalysts have a limited service life and require timely replacement after expiration, and the replaced spent catalyst is classified into a reversible deactivated catalyst and an irreversible deactivated catalyst. The former can be regenerated by measures such as back-blowing ash removal, water washing, acid washing and vanadium supplementing, so that the denitration rate of the catalyst is recovered to be more than 90% of the original denitration rate and is reused, and the cost is 20-30% of the total replacement cost; however, a large amount of SCR denitration catalyst is not regenerated or damaged in the regeneration process and needs to be abandoned, wherein the catalyst contains TiO 2 The content is 80% -90%, WO 3 The content is 4-6%, V 2 O 5 The content is 0.4% -1.5%. Because titanium and tungsten have higher economic value, a comprehensive recycling method of the waste SCR denitration catalyst is sought, pollution can be reduced, recycling can be realized, the waste catalyst is utilized to the greatest extent, and higher economic and social benefits are achieved.
At present, the recovery process of the waste SCR denitration catalyst is mainly divided into a dry method and a wet method. The dry method generally uses a heating furnace to heat and melt the waste SCR denitration catalyst, a reducing agent and a fluxing agent together, so that metal components are reduced and melted into metal or alloy for recovery, and the carrier and the fluxing agent form slag for discharge; however, the dry method has the disadvantages of high energy consumption and possible release of sulfur dioxide gas during the melting process. The wet method is to dissolve the waste SCR denitration catalyst by acid and alkali or other solvents, and then to obtain a recovered product after the steps of impurity removal, purification, separation, drying and the like, so that the recovery process of the waste SCR denitration catalyst is generally to recover by the wet method.
For example, chinese patent document CN105709861a discloses a method for regenerating an SCR denitration catalyst, which comprises pretreating a waste and deactivated SCR denitration catalyst, pulverizing the waste SCR denitration catalyst, heating the waste SCR denitration catalyst with alkali liquor, filtering and separating to obtain a recovery solution containing sodium tungstate and sodium vanadate, and adjusting the concentration of vanadium in the recovery solution to 2-10g/L to obtain a regenerated solution; immersing the dried and deactivated SCR denitration catalyst into the prepared concentration regeneration liquid at room temperature for regeneration, taking out, standing at room temperature, and drying, calcining and cooling to obtain a regenerated SCR denitration catalyst; realizes the resource utilization and harmless treatment of the waste SCR denitration catalyst. However, the waste SCR denitration catalyst regenerated by the method is unfavorable for multiple times of regeneration and has poor regeneration capacity; and secondly, the recovery of the mixed salt solution of vanadium and tungsten can only be used for the regeneration liquid in the regeneration process, and titanium is not recovered, so that the waste SCR denitration catalyst is not comprehensively recycled.
Disclosure of Invention
Therefore, the invention aims to overcome the defects that the regenerated waste SCR denitration catalyst is unfavorable for repeated regeneration and has poor regeneration capacity and the waste SCR denitration catalyst is not comprehensively recycled in the prior art, thereby providing a method for regenerating and recycling the waste SCR denitration catalyst.
Therefore, the invention provides the following technical scheme:
a method for regenerating and recovering a waste SCR denitration catalyst comprises the steps of adopting microwave heating to treat an active loaded reversible deactivated SCR denitration catalyst to prepare a regenerated SCR denitration catalyst;
wherein the regeneration liquid used in the active load comprises Ti which is respectively recovered from irreversible deactivated SCR denitration catalyst 4+ 、V 5+ And W is 6+ 。
The microwave heating time is 5-15min, the microwave energy is 50-100w/kg, and the frequency is 3000-4000MHz.
The SCR denitration catalyst regeneration step comprises the following steps: the pretreated reversible deactivated SCR denitration catalyst is subjected to chemical cleaning, active loading, drying, microwave heating and cooling.
The method for regenerating and recovering the waste SCR denitration catalyst further comprises Ti 4+ 、V 5+ And W is 6+ The recovery step of (2) comprises: drying, crushing and grinding the pretreated irreversible deactivated SCR denitration catalyst, leaching with alkali liquor to obtain leaching residue and leaching liquid, and concentrating V in the leaching liquid 5+ And W is 6+ The recovery is carried out respectively, and the recovery is carried out,for Ti in leaching slag 4+ And (5) recycling.
The Ti is 4+ 、V 5+ And W is 6+ In the recovery step of (2), alkali liquor leaching refers to reacting the ground irreversible deactivated SCR denitration catalyst in 10-50% sodium hydroxide aqueous solution for 1-1.5h at 40-110 ℃ in a volume-mass ratio of 3:1-15:1 (ml: g); filtering after the reaction is finished to obtain leaching liquid and leaching slag.
Wherein, tungsten and vanadium metal elements are left in the leaching liquid in an ionic form, and the residual filtered leaching residues mainly comprise titanium dioxide and other impurities, and the reaction principle is as follows:
2NaOH+V 2 O 5 ＝2NaVO 3 +H 2 O
2NaOH+WO 3 ＝Na 2 WO 4 +H 2 O
adding water to dilute the leached slag after the reaction with sulfuric acid to obtain a metatitanic acid precipitate, and drying and calcining the obtained metatitanic acid precipitate to obtain titanium dioxide; the reaction principle is as follows:
TiO 2 +H 2 SO 4 ＝TiOSO 4 +H 2 O
TiOSO 4 +2H 2 O＝H 2 SO 4 +H 2 TiO 3 ↓
H 2 TiO 3 ＝TiO 2 +H 2 O
and/or regulating the pH value of the leaching solution to 10.0 by sulfuric acid, regulating the pH value of the filtrate obtained by filtering to 7.0-9.0 again, adding ammonium chloride to react for 1-5 hours at the temperature of 30-80 ℃, and filtering to obtain filtrate and ammonium metavanadate solid; wherein NH is 4 + /V 5+ The molar ratio of (2) to (1) to (20) to (1);
the reaction principle is as follows: naVO (NaVO) 3 +NH 4 Cl＝NH 4 VO 3 ↓+NaCl
And/or mixing the obtained filtrate with dilute sulfuric acid, reacting for 1-5 hours at room temperature, and filtering to obtain tungstic acid;
wherein W is contained in the filtrate 6+ And sulfuric acid in a molar ratio of 1:1 to 1:10.
The reaction principle is as follows:
Na 2 WO 4 +H 2 SO 4 ＝H 2 WO 4 ↓+Na 2 SO 4
(NH 4 ) 2 WO 4 +H 2 SO4＝H 2 WO 4 ↓+(NH 4 ) 2 SO 4
the contents of the metal vanadium and the metal tungsten in the leaching solution are detected by adopting ICP plasma spectrum, namely an inductively coupled plasma spectrometer.
The chemical cleaning is to firstly soak the pretreated reversible deactivated SCR denitration catalyst in dilute sulfuric acid cleaning solution, and then put the pretreated reversible deactivated SCR denitration catalyst in chemical cleaning solution for cleaning;
preferably, the volume ratio of the dilute sulfuric acid cleaning solution to the pretreated reversible deactivated SCR denitration catalyst is 2:1-10:1; the soaking temperature is 50-70deg.C, and the soaking time is 30-60min;
the volume ratio of the chemical cleaning agent to the pretreated reversible deactivated SCR denitration catalyst is 5:1-10:1; the cleaning temperature is 30-60 ℃, and the cleaning time is 20-60min.
The dilute sulfuric acid cleaning solution comprises hydrofluoric acid and EDTA, and the mass ratio of the hydrofluoric acid is 2-10% based on the total weight of the dilute sulfuric acid cleaning solution; the mass ratio of EDTA is 1-4%.
The chemical cleaning agent comprises a surfactant, a penetrating agent, a complexing agent and an auxiliary agent; based on the total weight of the chemical cleaning agent, the mass ratio of the surfactant is 2-5%, the mass ratio of the penetrating agent is 5-8%, the mass ratio of the complexing agent is 2-5%, and the mass ratio of the auxiliary agent is 3-6%.
The surfactant is polyoxyethylene ether, the penetrating agent is fatty alcohol polyoxyethylene ether (JFC), the complexing agent is EDTA, and the auxiliary agent is DTC heavy metal trapping agent.
The volume of the pretreated reversible deactivated SCR denitration catalyst is calculated according to the apparent volume of the catalyst, namely the catalyst is of a three-dimensional structure, and the catalyst is long, wide and high.
After the reversible deactivated SCR denitration catalyst is chemically cleaned, deionized water is further used for cleaning the reversible deactivated SCR denitration catalyst before the active load; preferably, the deionized water is washed 2-3 times.
The active load step comprises the steps of drying the washed reversible deactivated SCR denitration catalyst at 100-110 ℃ for 1.5-2.5 hours, and immersing the catalyst in the regeneration liquid for 2-10 hours.
The regeneration liquid comprises, by mass, 1% -5% of sulfuric acid, 0.2% -2.0% of ammonium metavanadate, 1% -10% of ammonium metatungstate, 0.5% -1.5% of silica sol, 2% -10% of titanium dioxide and the balance of deionized water; wherein, the ammonium metavanadate, the ammonium metatungstate and the titanium dioxide are recovered from the irreversible deactivated SCR denitration catalyst.
Before pretreatment of the waste SCR denitration catalyst, the waste SCR denitration catalyst is firstly subjected to regeneration performance judgment according to GBT35209-2017 standard and is divided into a reversible deactivated denitration catalyst and an irreversible deactivated denitration catalyst.
The pretreatment step is to respectively and sequentially carry out physical ash removal and ultrasonic water washing on the reversible inactivation and irreversible inactivation SCR denitration catalyst;
the physical ash removal is to clean the surface of the reversible deactivated SCR denitration catalyst and the irreversible deactivated SCR denitration catalyst for 5-10min respectively by adopting a dust collector or a high-pressure gas blowing mode;
the ultrasonic water washing frequency is 40-80kHz, the ultrasonic time is 1-3h, and the ultrasonic temperature is 30-60 ℃.
The technical scheme of the invention has the following advantages:
1. the invention provides a regeneration and recovery method of a waste SCR denitration catalyst, which comprises the steps of adopting microwave heating to treat an active loaded reversible deactivated SCR denitration catalyst to prepare a regenerated SCR denitration catalyst; the applicant finds that the regenerated SCR denitration catalyst prepared by heating the active load reversible deactivated SCR denitration catalyst in a roasting mode is unfavorable for repeated regeneration and has poor regeneration capacity, and the defects are that the surface of the catalyst is heated unevenly during roasting, so that the mechanical strength is low, the phenomenon of breakage or rupture is easy to generate after repeated regeneration, the regeneration capacity is reduced, and in long-term research, the applicant finds that the microwave heating technology is adopted during the regeneration of the SCR denitration catalyst, the regeneration is rapid and uniformThe defect of poor regeneration capability caused by uneven heating of the surface of the catalyst is avoided, and even the phenomenon of breakage or rupture is generated, so that the mechanical strength of the regenerated catalyst can be effectively improved by adopting microwave heating, the catalyst can be regenerated repeatedly, and the problems of poor regeneration capability and difficult repeated regeneration of the existing regenerated SCR denitration catalyst are solved. Meanwhile, as the microwave heating is rapid and uniform, more active centers can be generated in the phase change process of active components deposited on the surface of the catalyst, the uniformity of the dispersion of the active components on the surface of the catalyst is improved, the denitration activity of the regenerated catalyst is improved, and the waste SCR denitration catalyst is fully recycled; again, for Ti respectively 4+ 、V 5+ And W is 6+ Recovering the Ti thus recovered 4+ 、V 5+ And W is 6+ The method can be used as the supplement of regeneration liquid in the regeneration process to form closed loop circular economy, and the surplus product can be used as a product for sale, so that the resources of the waste denitration catalyst are comprehensively recycled.
2. According to the method for regenerating and recovering the waste SCR denitration catalyst, provided by the invention, when the SCR denitration catalyst is regenerated, the denitration activity and the mechanical property of the regenerated catalyst can be further improved by limiting the heating time and the energy of microwaves.
3. According to the method for regenerating and recovering the waste SCR denitration catalyst, vanadium and tungsten metals are left in the leaching liquid in an ionic form by using an alkaline solution leaching method of the ground irreversible deactivated SCR denitration catalyst, the leaching slag obtained by filtering is mainly titanium dioxide and other impurities, the leaching slag reacts with sulfuric acid, the titanium dioxide reacts with sulfuric acid to generate titanyl sulfate, then the titanyl sulfate is diluted by water to generate a metatitanic acid precipitate, and the metatitanic acid precipitate obtained by filtering is calcined to obtain high-purity titanium dioxide; the leaching solution is adjusted to pH to lead impurities such as aluminum, silicon and the like to generate Al (OH) which is difficult to dissolve in water 3 And H 2 SiO 3 Filtering to remove impurities deeply; regulating pH of the leaching solution after the impurity removal again, adding ammonium chloride for reaction, separating out metal vanadium ions in the leaching solution after the impurity removal in the form of ammonium metavanadate precipitation, and filtering to obtainHigh purity ammonium metavanadate; and (3) reacting the filtrate obtained after the high-purity ammonium metavanadate is obtained by filtering with sulfuric acid to enable tungsten ions in the filtrate to be precipitated in the form of solid tungstic acid, standing and filtering to obtain a high-purity tungstic acid product. The method has the advantages of good leaching effect, simple separation and high metal recovery rate and purity, so that the recovered titanium dioxide, ammonium metavanadate and tungstic acid can be recycled as raw materials in the regeneration liquid, and the surplus products can be sold as products, thereby improving the maximum utilization of the waste SCR denitration catalyst resources.
4. According to the method for regenerating and recovering the waste SCR denitration catalyst, the pretreated reversible deactivated SCR denitration catalyst is firstly cleaned by dilute sulfuric acid cleaning solution and then cleaned by chemical cleaning solution, so that the activity of the regenerated SCR catalyst can be effectively improved; the cleaning effect of the dilute sulfuric acid cleaning liquid can be used for cleaning toxic substances such as metal elements on one hand, and the number and the stability of acid sites on the surface of the catalyst can be increased on the other hand; the hydrofluoric acid and EDTA aqueous solution in the dilute sulfuric acid cleaning solution is mainly used for removing the blockage of vitreous silica or chemically deposited gypsum and holes; the chemical cleaning agent is prepared by a certain physical infiltration, and is mixed with SO in the catalyst pore diameter ash 3 、Al 2 O 3 Chemical reaction of CaO and other compounds to produce trace amount of gas; simultaneously, the solid matters are expanded and loosened under the action of the surfactant, so that the surface tension is reduced, dirt falls off from the catalyst pores under the action of gravity, and the purposes of cleaning and removing the catalyst ash and dirt are achieved; by step cleaning, poisoning or blocking substances can be removed more specifically, and the activity of the regenerated SCR catalyst can be effectively improved.
5. According to the method for regenerating and recovering the waste SCR denitration catalyst, which is provided by the invention, after the reversible deactivated SCR denitration catalyst is subjected to chemical cleaning, deionized water is further used for cleaning before the active load, so that the waste liquid residues of toxic elements attached to the surface of the regenerated SCR catalyst can be effectively removed, incomplete cleaning caused by the fact that the residual elements are loaded on the surface of the regenerated SCR catalyst can be effectively prevented, and finally, the activity of the regenerated SCR catalyst is reduced.
6. According to the method for regenerating and recovering the waste SCR denitration catalyst, the regeneration performance of the waste SCR denitration catalyst is judged before the waste SCR denitration catalyst is regenerated and recovered, so that the efficiency of regenerating and recovering the waste SCR denitration catalyst can be fundamentally improved; secondly, carrying out pretreatment of physical ash removal and ultrasonic water washing on the waste SCR denitration catalyst, wherein the physical ash removal can absorb dust adhered on the surface of the catalyst and in a pore canal, and remove floating ash on the surface and impurities and dust deposited physically; ultrasonic water washing utilizes cavitation, acceleration and direct current of ultrasonic waves in liquid to disperse, emulsify and strip pollutants, so that the aim of cleaning is achieved; meanwhile, the ultrasonic cleaning can be used for deeply cleaning the inside of the pore canal of the deactivated catalyst, so that not only can the residual fly ash on the catalyst be cleaned, but also part of metal elements in the pore canal can be cleaned; the specific surface area of the deactivated catalyst can be effectively increased by adopting an ultrasonic cleaning technology; thereby improving the regenerated catalytic activity and the purity of the recovered metal.
7. The regeneration and recovery method of the waste SCR denitration catalyst provided by the invention has the advantages that the silica sol in the catalyst regeneration liquid is a colloidal solution formed by dispersing nano-scale silica particles in water, the viscosity is low, and the dispersibility and the permeability are good. When the silica sol is evaporated, colloid particles can be firmly attached to the catalyst, and silicon-oxygen bond combination is formed among the particles, so that the mechanical strength of the regenerated catalyst can be enhanced, and the temperature resistance is good.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a specific process flow diagram of a method for regenerating and recovering a spent SCR denitration catalyst in the present invention.
Detailed Description
The following examples are provided for a better understanding of the present invention and are not limited to the preferred embodiments described herein, but are not intended to limit the scope of the invention, any product which is the same or similar to the present invention, whether in light of the present teachings or in combination with other prior art features, falls within the scope of the present invention.
The specific experimental procedures or conditions are not noted in the examples and may be followed by the operations or conditions of conventional experimental procedures described in the literature in this field. The reagents or apparatus used were conventional reagent products commercially available without the manufacturer's knowledge.
For ease of comparison, the honeycomb waste SCR denitration catalyst was used in each of examples 1 to 3 and comparative example 1.
Example 1
The embodiment provides a method for regenerating and recovering a waste SCR denitration catalyst, as shown in FIG. 1, specifically comprising the following steps:
step one: regeneration performance judgment of waste SCR denitration catalyst
a. Appearance requirements are as follows: the average abrasion depth of the windward end of the honeycomb type waste SCR denitration catalyst is not more than 30mm; the number of the penetrating holes is not more than 5; the wear rate of the non-windward end is less than or equal to 0.3 percent;
b. physical and chemical properties, axial compressive strength is not less than 1MPa, radial compressive strength is not less than 0.2MPa, and specific surface area (BET) is not less than 30m 2 /g；
The reversibly deactivated SCR denitration catalyst meets the requirements, and the irreversibly deactivated SCR denitration catalyst does not meet the requirements.
Step two: pretreatment of
Carrying out physical ash removal on the surface of the reversible deactivated SCR denitration catalyst and the irreversible deactivated SCR denitration catalyst by adopting a gas purging mode, wherein the purging time is 5min, and the pressure is 1MPa; and then ultrasonic washing is respectively carried out to further remove impurities, wherein the frequency of ultrasonic washing is 60kHz, the ultrasonic time is 60min, and the ultrasonic temperature is 60 ℃.
Step three: ti (Ti) 4+ 、V 5+ And W is 6+ Is recovered from (a)
Placing the irreversible deactivated SCR denitration catalyst subjected to ultrasonic water washing in an oven at 105 ℃ for drying for 2 hours, and then sequentially crushing, grinding and sieving with a 100-mesh sieve to obtain irreversible deactivated SCR denitration catalyst powder;
10g of irreversible inactivation SCR denitration catalyst powder is taken and placed in 100ml of 30% sodium hydroxide solution with mass fraction, stirred, heated to 90 ℃, reacted for 1.5 hours, and then leached residues and leachate are obtained through solid-liquid separation; reacting the leaching residue with 20ml of sulfuric acid solution with the mass fraction of 15% for 1h to generate titanyl sulfate, then adding 150ml of water into the reaction solution, hydrolyzing to obtain a metatitanic acid precipitate, filtering to obtain a metatitanic acid precipitate, and calcining at 500 ℃ for 7h to obtain titanium dioxide with the purity of 98%;
measurement of W in leachate using ICP inductively coupled plasma spectrometer 6+ And V 5+ The content of (2) is as follows: 30mg and 3mg.
Regulating the pH of the leaching solution to 10 by using a sulfuric acid solution with the mass fraction of 15%, stirring for 5min, filtering to remove impurities, standing the filtrate for 2h, and performing secondary filtering to remove impurities; regulating the pH value of the leaching solution after impurity removal to 8.0 by using a sulfuric acid solution with the mass fraction of 15%, adding 50mg of ammonium chloride, stirring at 60 ℃ for reaction for 3 hours, and filtering to obtain ammonium metavanadate precipitate; adding 0.5ml of 10% dilute sulfuric acid into the filtrate, stirring at room temperature for 2h, standing, and filtering to obtain tungstic acid precipitate.
Step four: reversible deactivation SCR denitration catalyst regeneration
Reversibly deactivated SCR denitration catalyst module (measured to be 2m long, 1m wide, 1m high, and 2m volume) 3 ) First using 5m 3 The diluted sulfuric acid cleaning solution (sulfuric acid in the diluted sulfuric acid cleaning solution accounts for 15wt% of the total mass of the sulfuric acid cleaning solution, hydrofluoric acid accounts for 4wt% of the total mass of the sulfuric acid cleaning solution, EDTA accounts for 0.5wt% of the total mass of the sulfuric acid cleaning solution) is soaked and cleaned for 50min at 60 ℃, and then 10m of the diluted sulfuric acid cleaning solution is used 3 Chemical cleaning agent (the chemical cleaning agent comprises 3 percent of polyoxyethylene ether serving as a surfactant, 5 percent of fatty alcohol polyoxyethylene ether JFC serving as a penetrating agent and 2 percent of EDTA serving as a complexing agent),washing the auxiliary agent sodium Dithiocarbamate (DTC) with water at 40 ℃ for 50min, and then washing the auxiliary agent sodium Dithiocarbamate (DTC) with deionized water twice for 2m each time 3 The method comprises the steps of carrying out a first treatment on the surface of the Drying the reversibly deactivated SCR denitration catalyst washed by deionized water in a dryer at 105 ℃ for 2 hours, then immersing the reversibly deactivated SCR denitration catalyst in a regeneration liquid at room temperature for 10 hours, taking out the reversibly deactivated SCR denitration catalyst, slowly heating the reversibly deactivated SCR denitration catalyst to 100 ℃ for 2 hours, carrying out microwave heating reaction for 10 minutes, enabling the microwave energy to be 50w/kg, enabling the frequency to be 3000MHz, and cooling the reversibly deactivated SCR denitration catalyst to the room temperature to obtain the regenerated SCR denitration catalyst.
Wherein, based on the total mass of the regeneration liquid, the regeneration liquid comprises 3wt% of sulfuric acid; 0.5wt% of ammonium metavanadate; 3wt% of ammonium metatungstate; 1wt% of silica sol; 10wt% of titanium dioxide and the balance of deionized water; wherein, the ammonium metavanadate, the ammonium metatungstate and the titanium dioxide are all recovered in the step two.
Example 2
The embodiment provides a method for regenerating and recovering a waste SCR denitration catalyst, as shown in FIG. 1, specifically comprising the following steps:
step one: regeneration performance judgment of waste SCR denitration catalyst
a. Appearance requirements are as follows: the average abrasion depth of the windward end of the honeycomb type waste SCR denitration catalyst is not more than 30mm; the number of the penetrating holes is not more than 5; the wear rate of the non-windward end is less than or equal to 0.3 percent;
b. physical and chemical properties, namely, axial compressive strength is more than or equal to 1MPa, radial compressive strength is more than or equal to 0.2MPa, and specific surface area (BET) is more than or equal to 30m < 2 >/g;
the reversibly deactivated SCR denitration catalyst meets the requirements, and the irreversibly deactivated SCR denitration catalyst does not meet the requirements.
Step two: pretreatment of
Carrying out physical ash removal on the surface of the reversible deactivated SCR denitration catalyst and the irreversible deactivated SCR denitration catalyst by adopting a gas purging mode, wherein the purging time is 10min, and the pressure is 1MPa; and then ultrasonic washing is respectively carried out to further remove impurities, wherein the frequency of ultrasonic washing is 40kHz, the ultrasonic time is 180min, and the ultrasonic temperature is 30 ℃.
Step three: ti (Ti) 4+ 、V 5+ And W is 6+ Is recovered from (a)
Placing the irreversible deactivated SCR denitration catalyst subjected to ultrasonic water washing in an oven at 105 ℃ for drying for 2 hours, and then sequentially crushing, grinding and sieving with a 100-mesh sieve to obtain irreversible deactivated SCR denitration catalyst powder;
10g of irreversible inactivation SCR denitration catalyst powder is taken and placed in 150ml of 10% sodium hydroxide solution with mass fraction, stirred, heated to 60 ℃, reacted for 2 hours, and then leached residues and leachate are obtained through solid-liquid separation; reacting the leaching residue with 30ml of sulfuric acid solution with the mass fraction of 10% for 1h to generate titanyl sulfate, adding 200ml of water into the reaction solution, hydrolyzing to obtain a metatitanic acid precipitate, filtering to obtain a metatitanic acid precipitate, and calcining at 500 ℃ for 7h to obtain titanium dioxide with the purity of 98%;
measurement of W in leachate using ICP inductively coupled plasma spectrometer 6+ And V 5+ The content of (2) is as follows: 31mg and 2mg.
Regulating the pH of the leaching solution to 10 by using sulfuric acid solution with the mass fraction of 10%, stirring for 5min, filtering to remove impurities, standing the filtrate for 2h, and performing secondary filtering to remove impurities; regulating the pH value of the leaching solution after impurity removal to 7.0 by using a sulfuric acid solution with the mass fraction of 10%, then adding 55mg of ammonium chloride, stirring at 30 ℃ for reaction for 2 hours, and filtering to obtain ammonium metavanadate precipitate; adding 0.6ml of 10% dilute sulfuric acid into the filtrate, stirring at room temperature for reaction for 1h, standing, and filtering to obtain tungstic acid precipitate.
Step four: reversible deactivation SCR denitration catalyst regeneration
Reversibly deactivated SCR denitration catalyst module (measured to be 2m long, 1m wide, 1m high, and 2m volume) 3 ) First using 10m 3 The diluted sulfuric acid cleaning solution (sulfuric acid in the diluted sulfuric acid cleaning solution accounts for 16wt% of the total mass of the sulfuric acid cleaning solution, hydrofluoric acid accounts for 5wt% of the total mass of the sulfuric acid cleaning solution, EDTA accounts for 1.0wt% of the total mass of the sulfuric acid cleaning solution) is soaked and cleaned for 30min at 50 ℃, and then 15m of the diluted sulfuric acid cleaning solution is used 3 Chemical cleaning agent (the chemical cleaning agent comprises 3% of polyoxyethylene ether serving as a surfactant, 5% of polyoxyethylene ether JFC serving as a penetrating agent, 2% of EDTA serving as a complexing agent and 3% of sodium dithiocarbamic acid salt (DTC) serving as an auxiliary agent) is subjected to cleaning at 60 ℃ for 20min, and then is subjected to cleaning twice by deionized water, wherein each time is 2m 3 The method comprises the steps of carrying out a first treatment on the surface of the Deionized waterDrying the washed reversible deactivated SCR denitration catalyst in a dryer at 100 ℃ for 2.5 hours, then immersing the catalyst in a regeneration liquid at room temperature for 2 hours, taking out the catalyst, slowly heating the catalyst to 110 ℃ for drying for 1.5 hours, carrying out microwave heating reaction for 5 minutes, enabling the microwave energy to be 100w/kg, enabling the frequency to be 3500MHz, and cooling the catalyst to the room temperature to obtain the regenerated SCR denitration catalyst.
Wherein, based on the total mass of the regeneration liquid, the regeneration liquid comprises 1wt% of sulfuric acid; 2.0wt% of ammonium metavanadate; 10wt% of ammonium metatungstate; 0.5wt% of silica sol; 2wt% of titanium dioxide and the balance of deionized water; wherein, the ammonium metavanadate, the ammonium metatungstate and the titanium dioxide are all recovered in the step two.
Example 3
The embodiment provides a method for regenerating and recovering a waste SCR denitration catalyst, as shown in FIG. 1, specifically comprising the following steps:
step one: regeneration performance judgment of waste SCR denitration catalyst
a. Appearance requirements are as follows: the average abrasion depth of the windward end of the honeycomb type waste SCR denitration catalyst is not more than 30mm; the number of the penetrating holes is not more than 5; the wear rate of the non-windward end is less than or equal to 0.3 percent;
b. physical and chemical properties, namely, axial compressive strength is more than or equal to 1MPa, radial compressive strength is more than or equal to 0.2MPa, and specific surface area (BET) is more than or equal to 30m < 2 >/g;
the reversibly deactivated SCR denitration catalyst meets the requirements, and the irreversibly deactivated SCR denitration catalyst does not meet the requirements.
Step two: pretreatment of
Carrying out physical ash removal on the surface of the reversible deactivated SCR denitration catalyst and the irreversible deactivated SCR denitration catalyst by adopting a gas purging mode, wherein the purging time is 8min, and the pressure is 1MPa; and then ultrasonic washing is respectively carried out to further remove impurities, wherein the frequency of ultrasonic washing is 80kHz, the ultrasonic time is 120min, and the ultrasonic temperature is 45 ℃.
Step three: ti (Ti) 4+ 、V 5+ And W is 6+ Is recovered from (a)
Placing the irreversible deactivated SCR denitration catalyst subjected to ultrasonic water washing in an oven at 105 ℃ for drying for 2 hours, and then sequentially crushing, grinding and sieving with a 100-mesh sieve to obtain irreversible deactivated SCR denitration catalyst powder;
10g of irreversible inactivation SCR denitration catalyst powder is taken and placed in 30ml of 50% sodium hydroxide solution with mass fraction, stirred, heated to 40 ℃, reacted for 1.0h, and then leached residues and leachate are obtained through solid-liquid separation; reacting the leaching residue with 10ml of sulfuric acid solution with the mass fraction of 20% for 1h to generate titanyl sulfate, adding 100ml of water into the reaction solution, hydrolyzing to obtain a metatitanic acid precipitate, filtering to obtain a metatitanic acid precipitate, and calcining at 500 ℃ for 7h to obtain titanium dioxide with the purity of 98%;
measurement of W in leachate using ICP inductively coupled plasma spectrometer 6+ And V 5+ The content of (2) is as follows: 32mg and 3mg.
Regulating the pH of the leaching solution to 10 by using a sulfuric acid solution with the mass fraction of 20%, stirring for 5min, filtering to remove impurities, standing the filtrate for 2h, and performing secondary filtering to remove impurities; regulating the pH value of the leaching solution after impurity removal to 9.0 by using a sulfuric acid solution with the mass fraction of 20%, adding 60mg of ammonium chloride, stirring at 80 ℃ for reaction for 5 hours, and filtering to obtain ammonium metavanadate precipitate; adding 0.8ml of 10% diluted sulfuric acid into the filtrate, stirring at room temperature for reaction for 5 hours, standing, and filtering to obtain tungstic acid precipitate.
Step four: reversible deactivation SCR denitration catalyst regeneration
Reversibly deactivated SCR denitration catalyst module (measured to be 2m long, 1m wide, 1m high, and 2m volume) 3 ) First using 10m 3 The diluted sulfuric acid cleaning solution (sulfuric acid in the diluted sulfuric acid cleaning solution accounts for 25wt% of the total mass of the sulfuric acid cleaning solution, hydrofluoric acid accounts for 9wt% of the total mass of the sulfuric acid cleaning solution, EDTA accounts for 0.5wt% of the total mass of the sulfuric acid cleaning solution) is soaked and cleaned at 70 ℃ for 60min, and then 16m of the diluted sulfuric acid cleaning solution is used 3 Chemical cleaning agent (the chemical cleaning agent comprises 3% of polyoxyethylene ether serving as a surfactant, 5% of polyoxyethylene ether JFC serving as a penetrating agent, 2% of EDTA serving as a complexing agent and 3% of sodium dithiocarbamic acid salt (DTC) serving as an auxiliary agent) and is cleaned at 30 ℃ for 60min, and then the chemical cleaning agent is cleaned with deionized water for three times, wherein each time is 2m 3 The method comprises the steps of carrying out a first treatment on the surface of the Drying the reversibly deactivated SCR denitration catalyst washed by deionized water in a dryer at 110 ℃ for 1.5 hours, then soaking in a regeneration liquid at room temperature for 6 hours, taking out and slowly heating to the temperatureDrying at 100 ℃ for 2.5h, heating with microwaves for reaction for 15min, wherein the microwave energy is 80w/kg, the frequency is 4000MHz, and cooling to room temperature to obtain the regenerated SCR denitration catalyst.
Wherein, based on the total mass of the regeneration liquid, the regeneration liquid comprises 5wt% of sulfuric acid; 1.5wt% of ammonium metavanadate; 1wt% of ammonium metatungstate; 1.5wt% of silica sol; titanium dioxide 6wt% and deionized water as the rest; wherein, the ammonium metavanadate, the ammonium metatungstate and the titanium dioxide are all recovered in the step two.
Comparative example 1
This comparative example provides a method for regenerating and recovering a waste SCR denitration catalyst, wherein the flow and operation conditions of the treatment are similar to those of example 1, except that the mass fraction of NaOH used in the third step of this comparative example is 5%, the heating temperature after adding sodium hydroxide solution is 30 ℃, and the microwave heating of example 1 is changed to calcination after impregnation with a regenerating solution in the fourth step, wherein the calcination temperature is 500 ℃ and the time is 3 hours.
Experimental example
Taking a newly prepared SCR denitration catalyst, carrying out activity detection on the irreversibly deactivated SCR denitration catalyst and the regenerated SCR denitration catalysts prepared in the examples 1-3 and the comparative example 1, wherein the activity detection is carried out by using the reaction conversion rate of NOx in flue gas, the specific detection results are shown in a table 1, and the recovery rate of each metal in the irreversibly deactivated SCR denitration catalyst in the examples 1-3 is shown in a table 2, and the specific detection method is as follows:
detecting by adopting a catalyst activity evaluation device, simulating that the flue gas comprises nitrogen, oxygen, nitric oxide, sulfur dioxide and the like, reacting by taking ammonia as a reducing agent at 380 ℃, and analyzing the components of the inlet and outlet flue gas by adopting a flue gas online monitor to obtain the NOx conversion rate;
wherein, regenerated catalyst activity recovery = regenerated catalyst NOx conversion/NOx conversion of freshly prepared catalyst x 100%.
The specific surface area is detected by adopting a ZXF-10 automatic adsorption instrument;
the compressive strength is detected by a ZCQT compressive strength tester;
the calculation formula of each metal recovery rate is as follows:
vanadium recovery = vanadium content in recovered ammonium metavanadate/vanadium content in spent catalyst x 100%
Tungsten recovery = vanadium content in recovered tungstic acid/tungsten content in spent catalyst x 100%
Titanium recovery = recovered titanium dioxide content/titanium dioxide content in spent catalyst x 100%
TABLE 1 SCR catalyst regeneration Activity detection results
From the data in the table above, the mechanical strength of the regenerated catalyst can be effectively improved by adopting microwave heating to treat the reversibly deactivated SCR denitration catalyst loaded with the activity, so that the regeneration performance of the regenerated catalyst is improved, the uniformity of the dispersion of the active components on the surface of the catalyst is improved, and the denitration activity of the regenerated catalyst is improved.
TABLE 2 detection results of SCR catalyst Metal recovery
As can be seen from the data in the table, the recovery rate of vanadium and tungsten is obviously higher than that of the comparative example.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.
Claims (11)
1. The method for regenerating and recovering the waste SCR denitration catalyst is characterized by comprising the step of adopting microwave heating to treat the active loaded reversible deactivated SCR denitration catalyst to prepare a regenerated SCR denitration catalyst;
wherein the regeneration liquid used in the active load comprises Ti which is respectively recovered from irreversible deactivated SCR denitration catalyst 4+ 、V 5+ And W is 6+ ；
The regeneration liquid comprises, by mass, 1% -5% of sulfuric acid, 0.2% -2.0% of ammonium metavanadate, 1% -10% of ammonium metatungstate, 0.5% -1.5% of silica sol, 2% -10% of titanium dioxide and the balance of deionized water; wherein, the ammonium metavanadate, the ammonium metatungstate and the titanium dioxide are recovered from the irreversible deactivated SCR denitration catalyst;
Ti 4+ 、V 5+ and W is 6+ The recovery step of (2) comprises: drying, crushing and grinding the pretreated irreversible deactivated SCR denitration catalyst, leaching with alkali liquor to obtain leaching residue and leaching liquid, and concentrating V in the leaching liquid 5+ And W is 6+ Respectively recovering Ti in leaching slag 4+ Recycling;
the alkaline leaching is to react the ground irreversible deactivated SCR denitration catalyst in 10-50% sodium hydroxide aqueous solution for 1-1.5h at 40-110 ℃ in a volume-mass ratio of 3:1-15:1; filtering after the reaction to obtain leaching liquid and leaching slag;
adding water to dilute the leached slag after the reaction with sulfuric acid to obtain a metatitanic acid precipitate, and drying and calcining the obtained metatitanic acid precipitate to obtain titanium dioxide;
the leaching solution is adjusted to pH value to lead aluminum and silicon impurities to generate Al (OH) which is difficult to dissolve in water 3 And H 2 SiO 3 The pH value of the filtrate obtained by filtration is regulated to 7.0-9.0 again, ammonium chloride is added to react for 1-5 hours at the temperature of 30-80 ℃, and the filtrate and ammonium metavanadate solid are obtained by filtration; wherein NH is 4 + / V 5+ The molar ratio of (2) to (1) to (20): 1, a step of;
mixing the obtained filtrate with dilute sulfuric acid, reacting for 1-5h at room temperature, and filtering to obtain tungstenAn acid; wherein W is contained in the filtrate 6+ And sulfuric acid in a molar ratio of 1:1 to 1:10.
2. The method for regenerating and recovering a waste SCR denitration catalyst according to claim 1, wherein the microwave heating time is 5-15min, the microwave energy is 50-100w/kg, and the frequency is 3000-4000MHz.
3. The method for regenerating and recovering a waste SCR denitration catalyst according to claim 1 or 2, wherein the SCR denitration catalyst regenerating step comprises: the pretreated reversible deactivated SCR denitration catalyst is subjected to chemical cleaning, active loading, drying, microwave heating and cooling.
4. The method for regenerating and recovering a waste SCR denitration catalyst according to claim 1 or 2, wherein the pH value of the leaching solution is adjusted to 10.0 by sulfuric acid, so that Al (OH) which is difficult to dissolve in water is generated by aluminum and silicon impurities 3 And H 2 SiO 3 。
5. The method for regenerating and recovering the waste SCR denitration catalyst according to claim 3, wherein the chemical cleaning is to soak the pretreated reversible deactivated SCR denitration catalyst in dilute sulfuric acid cleaning solution, and then to clean the catalyst in chemical cleaning solution; the chemical cleaning agent comprises a surfactant, a penetrating agent, a complexing agent and an auxiliary agent; based on the total weight of the chemical cleaning agent, the mass ratio of the surfactant is 2-5%, the mass ratio of the penetrating agent is 5-8%, the mass ratio of the complexing agent is 2-5%, and the mass ratio of the auxiliary agent is 3-6%.
6. The method for regenerating and recovering a waste SCR denitration catalyst according to claim 5, wherein the volume ratio of the dilute sulfuric acid cleaning solution to the pretreated reversible deactivated SCR denitration catalyst is 2:1-10:1; the soaking temperature is 50-70deg.C, and soaking time is 30-60min.
7. The method for regenerating and recovering a waste SCR denitration catalyst according to claim 5 or 6, wherein the volume ratio of the chemical cleaning agent to the reversibly deactivated SCR denitration catalyst after pretreatment is 5:1 to 10:1; the cleaning temperature is 30-60 ℃, and the cleaning time is 20-60min.
8. A method of regenerating and recovering a spent SCR denitration catalyst as defined in claim 3, further comprising, after chemically cleaning the reversibly deactivated SCR denitration catalyst, deionized water cleaning the reversibly deactivated SCR denitration catalyst prior to the active loading.
9. The method for regenerating and recovering a spent SCR denitration catalyst according to claim 8, wherein the number of washing with deionized water is 2 to 3.
10. The method for regenerating and recovering a waste SCR denitration catalyst according to claim 3, wherein the active loading step comprises immersing the washed reversibly deactivated SCR denitration catalyst in the regenerating solution for 2 to 10 hours after drying the reversibly deactivated SCR denitration catalyst at 100 to 110 ℃ for 1.5 to 2.5 hours.
11. The method for regenerating and recovering the waste SCR denitration catalyst according to claim 1, wherein before the waste SCR denitration catalyst is pretreated, the waste SCR denitration catalyst is firstly subjected to regeneration performance judgment according to GBT35209-2017 standard and is divided into a reversible deactivated denitration catalyst and an irreversible deactivated denitration catalyst;
and/or the pretreatment step is to respectively and sequentially carry out physical ash removal and ultrasonic water washing on the reversible deactivation and irreversible deactivation SCR denitration catalyst.
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| CN114535245B (en) * | 2022-01-17 | 2023-04-07 | 北京科技大学 | Method for comprehensively utilizing all components of waste denitration catalyst module |
| CN114471746B (en) * | 2022-02-15 | 2023-07-04 | 中国科学院山西煤炭化学研究所 | SCR denitration catalyst regeneration method |
| CN115228464B (en) * | 2022-04-22 | 2024-01-19 | 南京市生态环境保护科学研究院 | Resource utilization method of waste denitration catalyst |
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