CN112023987A - Recycling method of deactivated denitration catalyst - Google Patents

Recycling method of deactivated denitration catalyst Download PDF

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Publication number
CN112023987A
CN112023987A CN202010965921.7A CN202010965921A CN112023987A CN 112023987 A CN112023987 A CN 112023987A CN 202010965921 A CN202010965921 A CN 202010965921A CN 112023987 A CN112023987 A CN 112023987A
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catalyst
sulfuric acid
cleaning
filtrate
denitration catalyst
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王丽苑
于照阳
边振涛
唐光炜
白继春
郭树东
马普利
马国�
王兴峰
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Northwest Research Institute of Mining and Metallurgy
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Northwest Research Institute of Mining and Metallurgy
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    • B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
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    • B01J38/68—Liquid treating or treating in liquid phase, e.g. dissolved or suspended including substantial dissolution or chemical precipitation of a catalyst component in the ultimate reconstitution of the catalyst
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
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    • C22B34/00—Obtaining refractory metals
    • C22B34/30—Obtaining chromium, molybdenum or tungsten
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    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Abstract

The invention discloses a method for recycling an inactivated denitration catalyst, which comprises the steps of screening the inactivated denitration catalyst, regenerating the catalyst with the active component of more than or equal to 46 percent, and extracting noble metals from the catalyst with the active component of 46 percent; after being cleaned, the catalyst to be regenerated is activated and cleaned by using a sulfuric acid solution containing ammonium metavanadate or ammonium metatungstate, and the denitration activity of the catalyst is recovered after drying; crushing a catalyst to be extracted with noble metals, then carrying out acid leaching, carrying out primary filtration, drying primary filter residues, and collecting mixed powder of tungsten trioxide and silicon dioxide; and cooling and crystallizing the primary filtrate, filtering for the second time, drying the secondary filter residue to obtain powdery vanadium pentoxide, and recycling the filtrate again. The method of the invention classifies the inactivated denitration catalyst, saves raw materials and avoids resource waste.

Description

Recycling method of deactivated denitration catalyst
Technical Field
The invention relates to the technical field of environmental protection treatment, in particular to a recycling method of an inactivated denitration catalyst.
Background
The selective catalytic reduction technology (SCR technology) aims at NO in smoke emissionxBy spraying in under the action of a catalystReducing agent ammonia or urea to remove NO from flue gasxReduction to N2And H2And O. The catalyst used in the technology comprises two types of noble metal and non-noble metal, and the flue gas denitration efficiency can reach 90%. In actual operation of an SCR device, catalyst activity may be reduced and life reduced for a number of reasons. The treatment method of the deactivated denitration catalyst is the regeneration of the catalyst, and if the deactivated denitration catalyst cannot recover the activity thereof by adopting the regeneration method, the catalyst can only be updated. The inactivated denitration catalyst contains a large amount of noble metals, and direct discarding can cause huge waste of resources.
Regeneration of the deactivated denitration catalyst is generally applicable to reversible deactivation, including soot plugging in physical deactivation and various chemical deactivations. According to different inactivation reasons, the regeneration of the inactivated denitration catalyst also adopts different processes, and the processes can be divided into cleaning regeneration, heating regeneration, activating regeneration and other regeneration. The denitration performance of the denitration catalyst is reduced due to physical reasons such as structural collapse, sintering and the like, the denitration catalyst cannot be recycled by using a regeneration technology, and only can be directly recovered, separated and recycled and used as a new denitration catalyst raw material. The method has the disadvantages of complex process, difficult process control, high cost, secondary pollution and potential environmental pollution hidden danger.
Disclosure of Invention
The invention aims to provide a method for recycling an inactivated denitration catalyst, which is used for regenerating the inactivated denitration catalyst and recycling precious metals in the unrenewable inactivated denitration catalyst through the procedures of cleaning and drying, acid leaching, cooling and crystallizing, evaporation and concentration and drying.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for recycling an inactivated denitration catalyst comprises the following steps:
step one, sorting of the inactivated denitration catalyst: spraying and cleaning the inactivated denitration catalyst by using an automatic cleaning machine to remove impurities attached to the inactivated denitration catalyst, analyzing the content of active components in the inactivated denitration catalyst by using a fluorescence analyzer, regenerating the catalyst with the active components being more than or equal to 46%, and extracting noble metals from the catalyst with the active components being less than 46%;
step two, regeneration operation of the deactivated catalyst: the method comprises the following steps:
s2.1 piling the catalyst to be regenerated in a cleaning tank, soaking and cleaning the catalyst in deionized water for 2-4h, evacuating the deionized water, cleaning the catalyst for 10-20min by using a high-pressure water gun, and cleaning the catalyst for 1-2h by using dilute sulfuric acid with the ultrasonic wave auxiliary mass percentage concentration of 20-30%, wherein the ultrasonic frequency is 28KHZ, the ultrasonic power is 2400W, and the heating power is 8KW, so that CaSO attached to the surface of the catalyst is removed4And SiO2；
S2.2, activating and cleaning the catalyst cleaned in the S2.1 for 2-3h by using a sulfuric acid solution containing ammonium metavanadate or ammonium metatungstate, and recovering the denitration activity of the catalyst; the mass volume concentration of the sulfuric acid solution is 100-150g/L, and the V/W mass ratio of ammonium metavanadate or ammonium metatungstate =1: 5;
s2.3, conveying the activated catalyst into a track drying room, drying and calcining at 60-120 ℃ for 2-3h, and solidifying the active carrier to obtain a regenerated denitration catalyst;
step three, extracting the noble metal in the deactivated catalyst: the method comprises the following steps:
s3.1, drying and crushing the catalyst into powder, then placing the powder into a reaction kettle, adding a sulfuric acid solution with the mass volume concentration of 200-300g/L and a hydrogen peroxide solution with the mass percent content of 30% into the reaction kettle for acid leaching, wherein the mass ratio of the sulfuric acid solution to the hydrogen peroxide solution is 1:0.5, heating to 50-65 ℃, fully stirring for 1h, filtering the solution for the first time, and respectively collecting a first filtrate and a first filter residue; sending the first filter residue into a rail drying room, and drying at 60-120 ℃ for 1-2h to obtain tungsten trioxide and silicon dioxide mixed powder;
s3.2, cooling and crystallizing the first filtrate collected in the step S3.1, filtering for the second time, respectively collecting a second filtrate and a second filter residue, wherein the obtained second filter residue is a mixture of vanadyl sulfate, titanium sulfate and tungsten sulfate, adding sodium hydroxide into the second filtrate to adjust the pH value of the second filtrate to 1.6, then carrying out evaporation concentration on the second filtrate, and evaporating at the heating temperature of 350 ℃ for 2-3 hours to obtain powdery vanadium pentoxide; and collecting sulfuric acid distillate generated in the evaporation concentration process, and recycling the sulfuric acid distillate into a waste acid tank for storage.
Preferably, in the second step, a penetration enhancer and a surfactant are mixed into the deionized water, and the mass ratio of the deionized water to the penetration enhancer to the surfactant is 100:10: 10; wherein the penetration enhancer is 84 disinfectant, and the surfactant is demineralized water.
Preferably, the particle size of the deactivated catalyst powder after pulverization in step S3.1 is 100 mesh.
Preferably, sulfuric acid mist generated in the process of activating and cleaning the catalyst by the sulfuric acid solution in the step S2.2 is collected by the smoke collection system, sent to the alkali liquor absorption tower for treatment and then discharged.
Preferably, an exhaust pipeline of the track drying room is connected with a bag-type dust collector, and dust generated by the track drying room is discharged after being treated by the bag-type dust collector.
Preferably, in the step one, the wastewater generated by spraying and cleaning the deactivated catalyst, the S2.1 high-pressure water gun to wash the catalyst, the wastewater generated by ultrasonic cleaning and the wastewater generated by the alkali liquor absorption tower are collected and then sent to a sewage treatment station for treatment and then discharged.
The main chemical equation in the step three S3.1 is as follows:
Figure DEST_PATH_IMAGE002
（1）
Figure DEST_PATH_IMAGE004
（2）
in step 3.2, only sulfuric acid is separated out at 350 ℃ and vanadium pentoxide is not changed because the solution bears weak acidity, the main component is sulfuric acid, the boiling point of the sulfuric acid is 337 ℃ and the melting point of the vanadium pentoxide is 690 ℃, so that powdery vanadium pentoxide is obtained after evaporation.
Firstly, screening the inactivated denitration catalyst, regenerating the catalyst with the active component of more than or equal to 46 percent, and extracting noble metals from the catalyst with the active component of 46 percent; after being cleaned, the catalyst to be regenerated is activated and cleaned by using a sulfuric acid solution containing ammonium metavanadate or ammonium metatungstate, and the denitration activity of the catalyst is recovered after drying; crushing a catalyst to be extracted with noble metals, then carrying out acid leaching, carrying out primary filtration, drying primary filter residues, and collecting mixed powder of tungsten trioxide and silicon dioxide; and cooling and crystallizing the primary filtrate, filtering for the second time, evaporating and concentrating the secondary filter residue to obtain powdery vanadium pentoxide, and recycling or selling the filtrate again. The method of the invention classifies the inactivated denitration catalyst, saves raw materials and avoids resource waste.
The invention reduces the environmental pollution by collecting and processing the waste water, waste acid and dust generated by each work.
Drawings
FIG. 1 is a flow chart of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and examples.
Example 1
The method for recycling the deactivated denitration catalyst shown in fig. 1 comprises the following steps:
step one, sorting of the inactivated denitration catalyst: spraying and cleaning the inactivated denitration catalyst by using an automatic cleaning machine to remove impurities attached to the inactivated denitration catalyst, analyzing the content of active components in the inactivated denitration catalyst by using a fluorescence analyzer, regenerating the catalyst with the active components being more than or equal to 46%, and extracting noble metals from the catalyst with the active components being less than 46%;
step two, regeneration operation of the deactivated catalyst: the method comprises the following steps:
s2.1 piling the catalyst to be regenerated in a cleaning tank, soaking and cleaning the catalyst in deionized water for 2 hours, emptying the deionized water, cleaning the catalyst for 10 minutes by using a high-pressure water gun, and then cleaning the catalyst for 1 hour by using dilute sulfuric acid with the ultrasonic wave auxiliary mass percentage concentration of 20%, wherein the ultrasonic frequency is 28KHZ, the ultrasonic power is 2400W, and the heating power is 8KW, so that CaSO attached to the surface of the catalyst is removed4And SiO2；
S2.2, activating and cleaning the catalyst cleaned in the S2.1 for 2 hours by using a sulfuric acid solution containing ammonium metavanadate, and recovering the denitration activity of the catalyst; the mass volume concentration of the sulfuric acid solution is 100g/L, and the V/W mass ratio of ammonium metavanadate is =1: 5;
s2.3, conveying the activated catalyst into a track drying room, drying and calcining at 60 ℃ for 2h, and curing the active carrier to obtain a regenerated denitration catalyst;
step three, extracting the noble metal in the deactivated catalyst: the method comprises the following steps:
s3.1, drying and crushing the catalyst into powder with the granularity of 100 meshes, then placing the powder into a reaction kettle, adding a sulfuric acid solution with the mass volume concentration of 200g/L and a hydrogen peroxide solution with the mass percent content of 30% into the reaction kettle for acid leaching, wherein the mass ratio of the sulfuric acid solution to the hydrogen peroxide solution is 1:0.5, heating to 50 ℃, fully stirring for 1h, filtering the solution for the first time, and respectively collecting a first filtrate and a first filter residue; sending the first filter residue into a rail drying room to be dried for 1h at the temperature of 60 ℃ to obtain mixed powder of tungsten trioxide and silicon dioxide;
s3.2, cooling and crystallizing the first filtrate collected in the step S3.1, filtering for the second time, respectively collecting a second filtrate and a second filter residue, wherein the obtained second filter residue is a mixture of vanadyl sulfate, titanium sulfate and tungsten sulfate, adding sodium hydroxide into the second filtrate to adjust the pH value of the second filtrate to 1.6, then carrying out evaporation concentration on the second filtrate, and carrying out evaporation for 2 hours at the concentration heating temperature of 350 ℃ to obtain powdery vanadium pentoxide; and collecting sulfuric acid distillate generated in the evaporation concentration process, and recycling the sulfuric acid distillate into a waste acid tank for storage. Sulfuric acid mist generated in the process of activating and cleaning the catalyst by the sulfuric acid solution is collected by the smoke collection system and then is sent into the alkali liquor absorption tower for treatment and then is discharged.
In the second step, a penetration enhancer and a surfactant are mixed into the deionized water, and the mass ratio of the deionized water to the penetration enhancer to the surfactant is 100:10: 10; wherein the penetration enhancer is 84 disinfectant, and the surfactant is demineralized water.
An exhaust pipeline of the track drying room is connected with a bag-type dust collector, and dust generated by the track drying room is discharged after being treated by the bag-type dust collector.
In the step one, waste water generated by spraying and cleaning the inactivated catalyst, S2.1 high-pressure water guns for washing the catalyst, waste water generated by ultrasonic cleaning and waste water generated by an alkali liquor absorption tower are collected and then sent to a sewage treatment station for treatment and then discharged.
Example 2
The method for recycling the deactivated denitration catalyst shown in fig. 1 comprises the following steps:
step one, sorting of the inactivated denitration catalyst: spraying and cleaning the inactivated denitration catalyst by using an automatic cleaning machine to remove impurities attached to the inactivated denitration catalyst, analyzing the content of active components in the inactivated denitration catalyst by using a fluorescence analyzer, regenerating the catalyst with the active components being more than or equal to 46%, and extracting noble metals from the catalyst with the active components being less than 46%;
step two, regeneration operation of the deactivated catalyst: the method comprises the following steps:
s2.1 piling the catalyst to be regenerated in a cleaning tank, soaking and cleaning the catalyst in deionized water for 4h, emptying the deionized water, cleaning the catalyst for 20min by using a high-pressure water gun, and then cleaning the catalyst for 2h by using dilute sulfuric acid with the ultrasonic-assisted mass percentage concentration of 30%, wherein the ultrasonic frequency is 28KHZ, the ultrasonic power is 2400W and the heating power is 8KW, so that CaSO attached to the surface of the catalyst is removed4And SiO2；
S2.2, activating and cleaning the catalyst cleaned in the S2.1 for 3 hours by using a sulfuric acid solution containing ammonium metatungstate, and recovering the denitration activity of the catalyst; the mass volume concentration of the sulfuric acid solution is 150g/L, and the V/W mass ratio of ammonium metavanadate is =1: 5;
s2.3, conveying the activated catalyst into a track drying room, drying and calcining at 120 ℃ for 3h, and curing the active carrier to obtain a regenerated denitration catalyst;
step three, extracting the noble metal in the deactivated catalyst: the method comprises the following steps:
s3.1, drying and crushing the catalyst into powder with the granularity of 100 meshes, then placing the powder into a reaction kettle, adding a sulfuric acid solution with the mass volume concentration of 300g/L and a hydrogen peroxide solution with the mass percent content of 30% into the reaction kettle for acid leaching, wherein the mass ratio of the sulfuric acid solution to the hydrogen peroxide solution is 1:0.5, heating to 65 ℃, fully stirring for 1h, filtering the solution for the first time, and respectively collecting a first filtrate and a first filter residue; sending the first filter residue into a rail drying room to be dried for 2 hours at 120 ℃ to obtain tungsten trioxide and silicon dioxide mixed powder;
s3.2, cooling and crystallizing the first filtrate collected in the step S3.1, filtering for the second time, respectively collecting a second filtrate and a second filter residue, wherein the obtained second filter residue is a mixture of vanadyl sulfate, titanium sulfate and tungsten sulfate, adding sodium hydroxide into the second filtrate to adjust the pH value of the second filtrate to 1.6, then carrying out evaporation concentration on the second filtrate, and evaporating at the heating temperature of 350 ℃ for 3 hours to obtain powdery vanadium pentoxide; and collecting sulfuric acid distillate generated in the evaporation concentration process, and recycling the sulfuric acid distillate into a waste acid tank for storage.
In the second step, a penetration enhancer and a surfactant are mixed into the deionized water, and the mass ratio of the deionized water to the penetration enhancer to the surfactant is 100:10: 10; wherein the penetration enhancer is 84 disinfectant, and the surfactant is demineralized water.
And 2.2, collecting sulfuric acid mist generated in the process of activating and cleaning the catalyst by using the sulfuric acid solution in the step 2.2 by using a smoke collection system, and then sending the collected sulfuric acid mist into an alkali liquor absorption tower for treatment and discharging.
An exhaust pipeline of the track drying room is connected with a bag-type dust collector, and dust generated by the track drying room is discharged after being treated by the bag-type dust collector.
In the step one, waste water generated by spraying and cleaning the inactivated catalyst, S2.1 high-pressure water guns for washing the catalyst, waste water generated by ultrasonic cleaning and waste water generated by an alkali liquor absorption tower are collected and then sent to a sewage treatment station for treatment and then discharged.
Firstly, screening the inactivated denitration catalyst, regenerating the catalyst with the active component of more than or equal to 46 percent, and extracting noble metals from the catalyst with the active component of 46 percent; after being cleaned, the catalyst to be regenerated is activated and cleaned by using a sulfuric acid solution containing ammonium metavanadate or ammonium metatungstate, and the denitration activity of the catalyst is recovered after drying; crushing a catalyst to be extracted with noble metals, then carrying out acid leaching, carrying out primary filtration, drying primary filter residues, and collecting mixed powder of tungsten trioxide and silicon dioxide; and cooling and crystallizing the primary filtrate, filtering for the second time, evaporating and concentrating the secondary filter residue to obtain powdery vanadium pentoxide, and recycling or selling the filtrate again. The method of the invention classifies the inactivated denitration catalyst, saves raw materials and avoids resource waste.

Claims (6)

1. A method for recycling an inactivated denitration catalyst is characterized by comprising the following steps: it comprises the following steps:
step one, sorting of the inactivated denitration catalyst: spraying and cleaning the inactivated denitration catalyst by using an automatic cleaning machine to remove impurities attached to the inactivated denitration catalyst, analyzing the content of active components in the inactivated denitration catalyst by using a fluorescence analyzer, regenerating the catalyst with the active components being more than or equal to 46%, and extracting noble metals from the catalyst with the active components being less than 46%;
step two, regeneration operation of the deactivated catalyst: the method comprises the following steps:
s2.1 piling the catalyst to be regenerated in a cleaning tank, soaking and cleaning the catalyst in deionized water for 2-4h, evacuating the deionized water, cleaning the catalyst for 10-20min by using a high-pressure water gun, and cleaning the catalyst for 1-2h by using dilute sulfuric acid with the ultrasonic wave auxiliary mass percentage concentration of 20-30%, wherein the ultrasonic frequency is 28KHZ, the ultrasonic power is 2400W, and the heating power is 8KW, so that CaSO attached to the surface of the catalyst is removed4And SiO2；
S2.2, activating and cleaning the catalyst cleaned in the S2.1 for 2-3h by using a sulfuric acid solution containing ammonium metavanadate or ammonium metatungstate, and recovering the denitration activity of the catalyst; the mass volume concentration of the sulfuric acid solution is 100-150g/L, and the V/W mass ratio of ammonium metavanadate or ammonium metatungstate =1: 5;
s2.3, conveying the activated catalyst into a track drying room, drying and calcining at 60-120 ℃ for 2-3h, and solidifying the active carrier to obtain a regenerated denitration catalyst;
step three, extracting the noble metal in the deactivated catalyst: the method comprises the following steps:
s3.1, drying and crushing the catalyst into powder, then placing the powder into a reaction kettle, adding a sulfuric acid solution with the mass volume concentration of 200-300g/L and a hydrogen peroxide solution with the mass percent content of 30% into the reaction kettle for acid leaching, wherein the mass ratio of the sulfuric acid solution to the hydrogen peroxide solution is 1:0.5, heating to 50-65 ℃, fully stirring for 1h, filtering the solution for the first time, and respectively collecting a first filtrate and a first filter residue; sending the first filter residue into a rail drying room, and drying at 60-120 ℃ for 1-2h to obtain tungsten trioxide and silicon dioxide mixed powder;
s3.2, cooling and crystallizing the first filtrate collected in the step S3.1, filtering for the second time, respectively collecting a second filtrate and a second filter residue, wherein the obtained second filter residue is a mixture of vanadyl sulfate, titanium sulfate and tungsten sulfate, adding sodium hydroxide into the second filtrate to adjust the pH value of the second filtrate to 1.6, then carrying out evaporation concentration on the second filtrate, and evaporating at the heating temperature of 350 ℃ for 2-3 hours to obtain powdery vanadium pentoxide; and collecting sulfuric acid distillate generated in the evaporation concentration process, and recycling the sulfuric acid distillate into a waste acid tank for storage.
2. The method for recycling the deactivated denitration catalyst according to claim 1, wherein: in the second step, a penetration enhancer and a surfactant are mixed into the deionized water, and the mass ratio of the deionized water to the penetration enhancer to the surfactant is 100:10: 10; wherein the penetration enhancer is 84 disinfectant, and the surfactant is demineralized water.
3. The method of recycling the deactivated denitration catalyst according to claim 2, wherein: the particle size of the deactivated catalyst powder crushed in step S3.1 is 100 mesh.
4. The method of recycling the deactivated denitration catalyst according to any one of claims 1 to 3, wherein: and 2.2, collecting sulfuric acid mist generated in the process of activating and cleaning the catalyst by using the sulfuric acid solution in the step 2.2 by using a smoke collection system, sending the collected sulfuric acid mist into an alkali liquor absorption tower for treatment, and discharging the treated sulfuric acid mist.
5. The method of recycling the deactivated denitration catalyst according to claim 4, wherein: and an exhaust pipeline of the track drying room is connected with a bag-type dust collector, and dust generated by the track drying room is discharged after being treated by the bag-type dust collector.
6. The method of claim 5, wherein the method comprises the steps of: and in the step one, waste water generated by spraying and cleaning the inactivated catalyst, S2.1 high-pressure water guns for washing the catalyst, waste water generated by ultrasonic cleaning and waste water generated by an alkali liquor absorption tower are collected and then sent to a sewage treatment station for treatment and then discharged.
CN202010965921.7A 2020-09-15 2020-09-15 Recycling method of deactivated denitration catalyst Pending CN112023987A (en)

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