CN115475516A - Recovery method of waste plate type catalyst - Google Patents

Recovery method of waste plate type catalyst Download PDF

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Publication number
CN115475516A
CN115475516A CN202110665905.0A CN202110665905A CN115475516A CN 115475516 A CN115475516 A CN 115475516A CN 202110665905 A CN202110665905 A CN 202110665905A CN 115475516 A CN115475516 A CN 115475516A
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catalyst
plate type
softening
waste plate
waste
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CN115475516B (en
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林德海
刘子林
王宝冬
曹子雄
马少丹
张珑慧
刘伟
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China Energy Investment Corp Ltd
National Institute of Clean and Low Carbon Energy
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China Energy Investment Corp Ltd
National Institute of Clean and Low Carbon Energy
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    • B01D53/34—Chemical or biological purification of waste gases
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    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8877—Vanadium, tantalum, niobium or polonium
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/90—Regeneration or reactivation
    • B01J23/94—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the iron group metals or copper
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    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/613—10-100 m2/g
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/g
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J38/00—Regeneration or reactivation of catalysts, in general
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
    • B01J38/50—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids
    • B01J38/52—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids oxygen-containing
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    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
    • B01J38/64—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using alkaline material; using salts
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    • Y02P20/00—Technologies relating to chemical industry
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    • Y02P20/584—Recycling of catalysts

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Abstract

The invention provides a method for recovering a waste plate type catalyst, which comprises the following steps: s1, contacting a waste plate type catalyst with softening liquid so as to carry out chemical softening treatment on the waste plate type catalyst; s2, carrying out ultrasonic treatment on the waste plate type catalyst subjected to chemical softening treatment, so that the catalyst component falls off from the substrate, and obtaining slurry containing the catalyst component; the softening liquid is a solution containing alkaline substances. The invention classifies and retreats the waste catalysts in the power plant, and can separate and recycle the catalyst components and the stainless substrate of the waste plate type catalysts. The reaction condition is mild, compared with the traditional method, the method omits the crushing and iron removal process, has simple process flow, small waste water amount and low energy consumption, and has high economic benefit, social benefit and environmental benefit. The invention can solve the problems of high iron content and difficult recycling of the waste plate type catalyst powder.

Description

Recovery method of waste plate type catalyst
Technical Field
The invention belongs to the technical field of waste catalyst recovery, and mainly relates to a method for recovering a waste plate type catalyst.
Background
Coal is used as a main energy structure in China, and a large amount of Nitrogen Oxides (NO) are discharged by combustion of coal x )，NO x Is one of the most main atmospheric pollutants in China. The core of the flue gas denitration device of the thermal power plant is a denitration catalyst, which generally accounts for 30-40% of the initial investment. The installed capacity of thermal power is large in China, and reaches 9.33 hundred million kilowatts as long as 2015, and the unit for flue gas denitration in operation accounts for more than 90% of the capacity of coal-electricity units in China. The service life of the denitration catalyst is about 3 years generally, a large amount of waste catalysts are replaced every year from 2015 to 2018, and the amount of the waste SCR denitration catalysts replaced every year reaches 25 million cubic meters. Spent denitration catalysts have been classified as "hazardous waste" in 2014, and if not properly disposed of, not only are significant wastes created, but they also severely pollute the environment.
The catalyst is reversibly inactivated and regenerated by means of ash removal, cleaning and other measures, so that the denitration rate of the catalyst is recovered to over 90 percent of the original denitration rate and reused, and the regeneration cost of the catalyst is 20 to 30 percent of the total replacement cost of the catalyst. The waste denitration catalyst contains a large amount of TiO 2 Vanadium and tungsten, and the consumption of the denitration catalyst is huge, and the denitration catalyst is a type of TiO which is not negligible 2 Or secondary sources of titanate and rare earth metals.
The waste plate type denitration catalyst has the advantages that the carrier is a stainless steel plate, and the active components and the carrier need to be separated and then are respectively disposed. The common method for treating the waste plate type denitration catalyst at present comprises the following steps: the catalyst and the stainless steel screen plate are crushed together by a jaw crusher, and then the carrier is separated from the stainless steel screen plate by magnetic separation. The method has the defects of complex equipment, high energy consumption and two defects: firstly, the broken stainless steel mesh plate is not completely separated from the catalyst carrier; secondly, the iron in the catalyst carrier is difficult to remove completely, and because the simple substance iron is introduced in the physical crushing process and the iron oxide in the fly ash of the power plant is added, the shapes of the iron in the recovered powder are different and the content of the iron is high, the subsequent iron removal aims at removing the simple substance iron and the iron oxide respectively, and the subsequent iron removal of the powder can cause the dissolution of valuable metals such as vanadium and the like in the powder, thereby causing the recovery difficulty of the vanadium, SO the iron content in the physically recovered powder is high, and the existence of the iron can cause SO 2 /SO 3 The conversion rate is increased, thereby affecting the recovery and reuse of the catalyst carrier and the catalyst active components.
Disclosure of Invention
In view of the problems of the prior art, it is an object of the present invention to provide a method for recovering a waste plate-type catalyst, which can completely separate a stainless steel plate from active components by a synergistic effect of a chemical method and a physical method. The process has the advantages of low cost, short flow, low energy consumption, high efficiency, high recovery rate, good performance and high practical value.
The second purpose of the present invention is to provide the application of the above recovery method in the recovery of waste plate catalyst.
In order to achieve one of the purposes, the technical scheme adopted by the invention is as follows:
a method for recovering a spent plate catalyst, comprising:
s1, contacting a waste plate type catalyst with softening liquid so as to carry out chemical softening treatment on the waste plate type catalyst to obtain the waste plate type catalyst subjected to chemical softening treatment, wherein the waste plate type catalyst comprises a catalyst component and a substrate for fixing the catalyst component;
s2, carrying out ultrasonic treatment on the waste plate type catalyst subjected to chemical softening treatment, so that the catalyst component falls off from the substrate, and obtaining slurry containing the catalyst component;
in step S1, the softening liquid is a solution containing an alkaline substance, wherein the concentration of the alkaline substance in the softening liquid is 5wt% to 30wt%, preferably 20wt% to 30wt%.
The inventors of the present application have found in their research that when the waste plate catalyst is chemically softened with the alkali substance of the above specific concentration as a softening liquid, components such as glass fibers in the waste plate catalyst can be effectively dissolved, so that the binding force between the catalyst and the substrate is reduced and the catalyst is more likely to fall off.
According to the present invention, the concentration of the basic substance may be 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%, 11wt%, 12wt%, 13wt%, 14wt%, 15wt%, 16wt%, 17wt%, 18wt%, 19wt%, 20wt%, 21wt%, 22wt%, 23wt%, 24wt%, 25wt%, 26wt%, 27wt%, 28wt%, 29wt%, 30wt%, and any value therebetween.
In some preferred embodiments of the present invention, in step S1, the softening liquid further comprises a deflocculant and/or an osmotic agent.
In some preferred embodiments of the present invention, the concentration of the deflocculant in the softening liquid is 0.25wt% to 1wt%, preferably 0.5wt% to 0.8wt%; the concentration of the penetrant in the softening liquid is 0.025wt% to 0.25wt%, preferably 0.05wt% to 0.1wt%.
According to the invention, the concentration of the deflocculant is between 0.25wt% and 1wt%, and may be 0.25wt%, 0.5wt%, 0.75wt%, 1wt% and any value in between.
According to the present invention, the concentration of the penetrant is 0.025wt% to 0.25wt%, and may be 0.025wt%, 0.05wt%, 0.075wt%, 0.1wt%, 0.125wt%, 0.15wt%, 0.175wt%, 0.2wt%,0.225wt%,0.25wt%, and any value therebetween.
The reaction rate of alkaline matter and glass fiber is slow, and the main reason is that the mass transfer rate is slow due to the high viscosity of sodium silicate, so that the reaction rate of alkaline matter and glass fiber can be increased by adding a proper amount of deflocculant and dispersant into the softening liquid.
In some preferred embodiments of the present invention, the mass ratio of the deflocculant to the basic substance is (2.0 to 7.5): 100.
In some preferred embodiments of the present invention, the mass ratio of the penetrating agent to the basic substance is (0.2 to 0.5): 100.
According to the invention, on one hand, if the concentration of the deflocculant is too high, the phosphate radical and sodium ion content is high, the water consumption for cleaning the powder is large, and if the concentration of the deflocculant is too low, the deflocculant effect of the sodium silicate is poor, and the reaction time is long; too high concentration of penetrant will result in high COD content in the solution and severe foaming, and too low concentration will result in poor penetration effect and low reaction rate of the softening solution.
In some preferred embodiments of the present invention, the alkaline substance is selected from one or more of sodium hydroxide, potassium hydroxide and sodium carbonate.
In some preferred embodiments of the present invention, the deflocculant is selected from sodium tripolyphosphate and/or sodium hexametaphosphate.
In some preferred embodiments of the present invention, the penetrant is selected from at least one of the group consisting of fast penetrant T, alkali-resistant penetrant OEP-70, alkali-resistant penetrant AEP, and penetrant JFC-M.
In some preferred embodiments of the present invention, the softening liquid is used in an amount of 0.5 to 10L, preferably 1 to 5L, and more preferably 1 to 3L, per kg of the waste plate-type catalyst.
According to the invention, on the one hand, when the dosage of the softening liquid is too small, the soaking is insufficient, and the plate-type catalyst is not contacted with the softening liquid completely, so that the softening is incomplete; on the other hand, when the dosage of the softening liquid is too much, the softening liquid can react with titanium dioxide and the like in the plate-type catalyst, so that the sodium ions are difficult to clean, and the three wastes are large and the material consumption is large. Therefore, the amount of the softening liquid used is limited to the above-specified range in order to balance the softening reaction completely with no excess reaction.
In some preferred embodiments of the present invention, the catalyst component comprises glass fibers, a titanium dioxide carrier, vanadium pentoxide, molybdenum trioxide and/or tungsten trioxide, wherein the glass fibers have a major component of silicon dioxide and further comprise a minor amount of alumina. Through the treatment of the softening liquid, structural substances which are easily dissolved in alkaline solution in the catalyst, such as glass fiber, are dissolved, so that the binding force between the catalyst and the stainless steel substrate is reduced.
In some preferred embodiments of the present invention, the substrate may be a stainless steel plate.
In some preferred embodiments of the present invention, in step S1, the conditions of the chemical softening treatment include: the temperature is 20-90 ℃, and the time is 15-45 min; preferably, the temperature is 65-90 ℃ and the time is 30-45 min.
According to the present invention, the temperature of the chemical softening treatment may be 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃ and any value therebetween.
According to the present invention, the time of the chemical softening treatment may be 15min, 20min, 25min, 30min, 35min, 40min, 45min, and any value therebetween.
In some preferred embodiments of the present invention, further comprising S3, performing solid-liquid separation on the slurry to obtain a filter cake, and optionally washing and drying the filter cake; preferably, the water content of the dried filter cake is not higher than 3%.
In some preferred embodiments of the present invention, S4 is further included, and step S2 is repeated one or more times until the residual amount of the catalyst component on the substrate reaches 10% or less, preferably 5% or less, and more preferably 1% or less.
According to the present invention, step S1 or S3 may be repeated one or more times, if desired.
According to the present invention, the residual amount means the mass of the catalyst component remaining on the substrate/the mass of the catalyst component existing on the substrate × 100%.
In some preferred embodiments of the present invention, the sonication conditions include: the ultrasonic frequency is 35 kHz-100 kHz; the ultrasonic power is 30W/L-50W/L; the total ultrasonic time is 15-60 min.
In some preferred embodiments of the present invention, the ultrasonic frequency is 45kHz to 80kHz; preferably 50kHz to 75kHz.
According to the present invention, the ultrasonic frequency may be 35kHz, 40kHz, 45kHz, 50kHz, 55kHz, 60kHz, 65kHz, 70kHz, 75kHz, 80kHz, 85kHz, 90kHz, 95kHz, 100kHz and any value therebetween.
According to the invention, the ultrasonic power may be 30W/L, 35W/L, 40W/L, 45W/L, 50W/L and any value in between.
According to the invention, the ultrasound time may be 15min, 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min, 60min and any value in between.
In some preferred embodiments of the invention, the sparging is performed intermittently during the sonication; preferably, the pressure of the bubbled compressed gas is 0.2 to 0.4MPa; the bubbling time is 10 to 60min, more preferably 10 to 20min.
In some preferred embodiments of the present invention, the pressure of the sparged compressed gas is 0.3MPa; bubbling time was 15min.
The waste plate type catalyst is separated from the stainless steel substrate by adding the oscillation function to the waste plate type catalyst in a mode of combining ultrasonic and intermittent bubbling, and the stainless steel substrate stripped of catalyst components can be used for iron recovery after being cleaned.
According to the invention, said intermittent bubbling during said sonication can be carried out in an ultrasonic bubbling device.
In some preferred embodiments of the present invention, the drying conditions include: the drying time is 3-6 h, and the drying temperature is 80-150 ℃.
According to the present invention, the solid-liquid separation can be carried out according to conventional means in the art, for example by means of pressure filtration.
According to the invention, the solid-liquid separation means separating a solid rich in the catalyst component from a liquid rich in the softening liquid.
According to the present invention, the filter cake may be water washed in a manner commonly employed in the art, including but not limited to: and washing the filter cake for 1-3 times by adopting water.
In order to achieve the second purpose, the invention adopts the following technical scheme:
the application of the recovery method in the recovery of the waste plate catalyst.
The invention has the advantages that at least the following aspects are realized:
firstly, the invention classifies and then treats the waste catalysts in the power plant, and can separate and recycle the catalyst components and the stainless substrate of the waste plate type catalysts.
Secondly, the method has mild reaction conditions, saves the crushing and iron removal process compared with the traditional method, has simple process flow, small waste water amount and low energy consumption, and has very high economic benefit, social benefit and environmental benefit.
Thirdly, the invention can solve the problems of high iron content and difficult recycling of the waste plate type catalyst powder.
Drawings
FIG. 1 is a process flow diagram of a method for recovering a spent plate catalyst according to example 1 of the present invention.
FIG. 2 is a diagram showing the recovery effect of the plate catalyst of example 1 of the present invention, wherein FIG. 2a is a photograph of an original sample of a used plate catalyst to be recovered; FIG. 2b is a photograph of the waste plate catalyst after being chemically softened by the softening liquid for 30 min; FIG. 2c is a photograph of a first sonicated spent plate catalyst; FIG. 2d is a photograph of a second sonicated spent slab catalyst.
Detailed Description
The present invention will be described in detail below with reference to examples, but the scope of the present invention is not limited to the following description.
In the following embodiments, unless otherwise specified, the used waste plate catalyst is a Selective Catalytic Reduction (SCR) denitration catalyst comprising a catalyst component and a stainless substrate for fixing the catalyst component, wherein the deactivated active component is vanadium pentoxide, the catalyst carrier is titanium dioxide, and the auxiliary agent is molybdenum trioxide (tungsten). Based on the total weight of the catalyst, in the sample of the experiment, the weight of the stainless steel substrate is about 51wt%, the weight of the vanadium pentoxide is 1.2wt%, the weight of the titanium dioxide is 38.3wt%, the weight of the molybdenum trioxide is 1.6wt%, and the weight of the glass fiber is 5.4wt%.
In the present invention, the expression of the porosity is as follows:
Figure BDA0003117395180000061
in formula (I):
a.
n 0 A sample initial loading hole number;
n i a reaction rate of the reaction is higher than that of the sample.
In the present invention, the number of supported pores means the number of pores on which the catalyst is supported.
According to the present invention, the through-hole ratio is used to characterize the degree of exfoliation of the catalyst component, and the higher the through-hole ratio, the higher the degree of exfoliation of the catalyst component.
And (3) solid index detection: the powder obtained by recovering the waste plate type catalyst is tested by XRF to show the carrier stripping reaction and the impurity removal reaction.
Testing powder indexes: the specific surface performance of the powder obtained by recovering the waste plate type catalyst is tested by a static adsorption method to show that the performance of the catalyst carrier after the carrier stripping reaction is close to the performance of commercial carrier powder.
Example 1
Step 1, soaking 68.27g of waste plate type catalyst (the appearance is shown in figure 2 a) in 0.5L of softening liquid for chemical softening treatment. The softening liquid contains 25wt% of sodium hydroxide, 0.8wt% of sodium hexametaphosphate, 0.075wt% of alkali-resistant penetrating agent AEP and the balance of water. The temperature of the chemical softening treatment was 75 ℃ and the time of the chemical softening treatment was 30min.
And 2, carrying out first ultrasonic treatment on the waste plate type catalyst (the shape is shown in figure 2 b) subjected to the chemical softening treatment to enable the catalyst component to fall off from the stainless steel substrate, so as to obtain first slurry containing the catalyst component, wherein the ultrasonic frequency is 100kHz, the ultrasonic power is 50W/L, and the ultrasonic time is 40min.
And 3, carrying out secondary ultrasonic treatment on the waste plate type catalyst (the shape is shown in figure 2 c) subjected to the primary ultrasonic treatment to enable the catalyst component to fall off from the stainless steel substrate, so as to obtain second slurry containing the catalyst component, wherein the ultrasonic frequency is 100kHz, the ultrasonic power is 50W/L, and the ultrasonic time is 20min.
As shown in fig. 2d, the through-hole ratio in this example is 100%. It should be noted that, although a white object appears in fig. 2d, it is a powder adhered to the water film, not the supported catalyst component. In fact, the stainless steel plate treated in example 1 was almost all-pass.
Example 2
Example 2 the process of example 1 is essentially followed except that the weight concentration of sodium hydroxide in the softening liquor is 15wt%.
The results showed that the through-hole ratio was 100%.
Example 3
Example 3 the process of example 1 is essentially followed except that the weight concentration of sodium hydroxide in the softening solution is 35wt%.
The results showed that the through-hole ratio was 100%.
Although example 3 can also achieve higher catalyst component stripping effect, but, because of the high sodium hydroxide, the recovered carrier harmful impurity Na 2 The O is too high, so that the quality of the recovered carrier is influenced; and the material consumption and the three wastes are high.
Example 4
Example 4 proceeds substantially as in example 1, except that the weight concentration of sodium hydroxide in the softening solution is 10wt%.
The results showed that the through-hole ratio was 50%.
Example 5
Example 5 the process of example 1 is essentially followed except that no sodium hexametaphosphate and alkali resistant osmotic agent AEP are added to the softener and the weight concentration of sodium hydroxide in the softener is 25wt%.
The results showed a through-hole ratio of 75%.
Example 6
Example 6 the procedure of example 1 was essentially followed except that the temperature of the chemical softening treatment was 90 ℃.
The results showed that the through-hole ratio was 100%.
Example 7
Example 7 was carried out essentially as in example 1, except that the temperature of the chemical softening treatment was 25 ℃.
The results showed that the through-hole ratio was 50%.
Example 8
Example 8 the procedure of example 1 is essentially followed except that the sodium hexametaphosphate concentration in the softener is 1wt%.
The results showed that the through-hole ratio was 100%.
Example 9
Example 9 proceeds substantially as in example 1, except that the sodium hexametaphosphate concentration in the softening solution was 0.25wt%.
The results showed that the through-hole ratio was 92%.
Example 10
Example 10 is carried out essentially as in example 1 except that the sodium hexametaphosphate concentration in the softener is 1.5wt%.
The results showed that the through-hole ratio was 100%.
According to the present invention, although example 10 can achieve a high effect of stripping the catalyst component, the softening liquid contains sodium hexametaphosphate in an excessively high concentration by weight, which results in a high content of sodium oxide and phosphorus pentoxide in the recovered carrier, and affects the quality of the product after the reaction.
Example 11
Example 11 proceeds substantially as in example 1, except that the sodium hexametaphosphate concentration in the softening solution was 0.2wt%.
The results showed that the through-hole ratio was 88%.
Example 12
Example 12 proceeds substantially as in example 1, except that the weight concentration of AEP in the softening solution is 0.025wt%.
The results showed that the through-hole ratio was 92%.
Example 13
Example 13 was conducted essentially as in example 1 except that the weight concentration of AEP in the softener was 0.25wt%.
The results showed that the through-hole ratio was 100%.
According to the invention, although example 13 can also achieve higher stripping effect of the catalyst component, the high AEP weight concentration in the softening liquid affects the recovery of vanadium and molybdenum in the solution on one hand and causes difficulty in subsequent wastewater treatment on the other hand.
Example 14
Example 14 was conducted essentially as in example 1 except that the temperature of the chemical softening treatment was 60 ℃.
The results showed that the through-hole ratio was 89%.
Example 15
Example 15 the procedure of example 1 was followed except that the temperature of the chemical softening treatment was 45 ℃.
The results showed that the through-hole ratio was 73%.
Example 16
Example 16 was conducted substantially as in example 1 except that the time of the chemical softening treatment was 50min.
The results showed that the through-hole ratio was 100%.
Example 17
Example 17 was carried out essentially as in example 1, except that the time for the chemical softening treatment was 10min.
The results showed a through-hole ratio of 72%.
Example 18
Example 18 was conducted substantially in the same manner as in example 1 except that the ultrasonic treatment was conducted only once, to finally obtain a slurry containing a catalyst component, wherein the ultrasonic frequency was 100kHz, the ultrasonic power was 50W/L, and the ultrasonic time was 60min.
The results showed that the through-hole ratio was 80%.
Comparative example 1
Comparative example 1 the same waste plate catalyst as in example 1 was selected, subjected to mechanical crushing, screen separation to remove an iron frame, magnetic separation, and then subjected to component analysis, yielding a carrier recovery of 53%. The method comprises the following specific steps:
1. mechanical crushing: the material is crushed by a hammer crusher, the grain size of the discharged material is 0-10mm, the rotating speed of an eccentric shaft can be set to 290r/min, and the crushing ratio is set to 40.
2. Screening and separating: the crushed material obtained in step 1 was sieved using a sieve having a sieve diameter of 180mm and a sieve gap of 0.5 mm.
3. Magnetic separation: magnetic separation is carried out by using magnetic separation equipment, strong neodymium equipment is adopted, and the magnetic field intensity is set to be 100mT.
Comparative example 2
Comparative example 2 was conducted substantially in the same manner as in example 1 except that the used plate catalyst was softened with water.
The results showed a through-hole ratio of 10%.
Comparative example 3
Comparative example 3 was conducted essentially as in example 1, except that: the softening treatment is carried out on the waste plate type catalyst by using the softening liquid, and the ultrasonic treatment is not carried out. Wherein the temperature of the chemical softening treatment is 75 ℃, and the time of the chemical softening treatment is 30min.
The results showed a porosity of 52%.
Test example
Taking the catalyst powder recovered in the above examples 1 to 18 and comparative examples 1 to 3, and performing a solid index test, wherein the test items include the comparative area, pore volume and pore diameter of the catalyst powder, and the results are shown in table 1; performing powder index test, wherein the test item comprises Na 2 O、SiO 2 、SO 3 、TiO 2 、MoO 3 、V 2 O 5 、Fe 2 O 3 And Al 2 O 3 The results are shown in Table 2. In addition, for convenience of comparison and analysis, the test results of the through-hole ratio are shown in table 3.
TABLE 1 solid index test results
Figure BDA0003117395180000111
Figure BDA0003117395180000121
TABLE 2 powder index test
Unit: is based on
Figure BDA0003117395180000122
Figure BDA0003117395180000131
TABLE 3 through-hole Rate test results
Item n 0 n 1 η(％)
Example 1 418 0 100.00
Example 2 396 0 100.00
Example 3 418 0 100.00
Example 4 399 199 49.87
Example 5 418 105 74.99
Example 6 396 395 100.00
Example 7 399 199 50.12
Example 8 408 408 100.00
Example 9 411 379 92.21
Example 10 409 409 100.00
Example 11 396 348 87.88
Example 12 403 371 92.06
Example 13 408 408 100.00
Example 14 413 368 89.11
Example 15 411 300 72.99
Example 16 406 406 100
Example 17 408 294 72.06
Example 18 396 317 80.05
Comparative example 1 399 80 79.95
Comparative example 2 418 376 10.05
Comparative example 3 411 214 52.07
The embodiment shows that the plate-type catalyst carrier is stripped by a chemical method, so that on one hand, the carrier and the metal mesh can be nondestructively separated, and the metal mesh can be continuously used after separation; on the other hand, the performance of the carrier is greatly improved due to the chemical reaction, and the carrier can be continuously used as a carrier for preparing the catalyst, so that the waste-plate type catalyst is recycled without waste.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined within the scope of the claims and modifications may be made without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.

Claims (10)

1. A method for recovering a spent plate catalyst, comprising:
s1, contacting a waste plate type catalyst with softening liquid so as to carry out chemical softening treatment on the waste plate type catalyst to obtain the waste plate type catalyst subjected to chemical softening treatment, wherein the waste plate type catalyst comprises a catalyst component and a substrate for fixing the catalyst component;
s2, carrying out ultrasonic treatment on the waste plate type catalyst subjected to chemical softening treatment, so that the catalyst component falls off from the substrate, and obtaining slurry containing the catalyst component;
in step S1, the softening liquid is a solution containing an alkaline substance, wherein the concentration of the alkaline substance in the softening liquid is 5wt% to 30wt%.
2. The recycling method according to claim 1, wherein in step S1, the softening liquid further comprises a deflocculant and/or a penetrant;
preferably, in the softening liquid, the concentration of the deflocculant in the softening liquid is 0.25-1 wt%; the concentration of the penetrant in the softening liquid is 0.025wt% -0.25 wt%;
more preferably, the mass ratio of the deflocculant to the basic substance is (2.0-7.5): 100, and/or the mass ratio of the penetrant to the basic substance is (0.2-0.5): 100.
3. The recovery method according to claim 1 or 2, wherein the alkaline substance is selected from one or more of sodium hydroxide, potassium hydroxide, and sodium carbonate; and/or the presence of a gas in the gas,
the deflocculant is selected from sodium tripolyphosphate and/or sodium hexametaphosphate; and/or the presence of a gas in the gas,
the penetrant is selected from at least one of a rapid penetrant T, an alkali-resistant penetrant OEP-70, an alkali-resistant penetrant AEP and a penetrant JFC-M.
4. The recovery method according to any one of claims 1 to 3, wherein the softening liquid is used in an amount of 0.5L to 10L, preferably 1L to 5L, more preferably 1L to 3L, per kg of the spent plate catalyst.
5. The recovery method according to any one of claims 1 to 4, characterized in that the catalyst component comprises glass fibers, titanium dioxide support, vanadium pentoxide, molybdenum trioxide and/or tungsten trioxide, wherein the glass fibers comprise silica and alumina.
6. A recycling method according to any one of claims 1 to 5, characterized in that in step S1, the conditions of said chemical softening treatment comprise: the temperature is 20-90 ℃, and the time is 15-45 min; preferably, the temperature is 65-90 ℃ and the time is 30-45 min.
7. The recycling method according to any one of claims 1 to 6, further comprising:
s3, carrying out solid-liquid separation on the slurry to obtain a filter cake, and optionally washing and drying the filter cake; preferably, the water content of the dried filter cake is not higher than 3%.
8. A recycling method according to any one of claims 1-7, characterized in that the recycling method further comprises:
s4, repeating the step S2 one or more times until the residual amount of the catalyst component on the substrate reaches 10% or less, preferably 5% or less, and more preferably 1% or less.
9. The recovery process of any one of claims 1 to 7, wherein the conditions of the sonication include: the ultrasonic frequency is 35 kHz-100 kHz; the ultrasonic power is 30W/L-50W/L; the total ultrasonic time is 15 min-60 min;
preferably, the bubbling is carried out intermittently while the ultrasonication is carried out;
more preferably, the pressure of the compressed gas to be bubbled is 0.2 to 0.4MPa; the total bubbling time is 10 to 60min, and more preferably 10 to 20min.
10. Use of a recovery process according to any one of claims 1-9 in the recovery of spent plate catalyst.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1697704A (en) * 2003-03-10 2005-11-16 松下电器产业株式会社 Method for recovering catalyst material, catalyst material recovered by said recovering method, method for recovering substrate, substrate recovered by said recovering method
CN105854956A (en) * 2016-04-08 2016-08-17 天河（保定）环境工程有限公司 Recovery and reuse method of waste titanium-based vanadium-series plate type SCR catalyst
CN107419104A (en) * 2017-07-24 2017-12-01 航天龙源(北京)环保科技发展有限公司 The comprehensive recovering process of useless SCR denitration
KR20180076390A (en) * 2016-12-27 2018-07-06 대영씨엔이(주) Method for Rematerializing Waste De-NOx Catalyst Using Inorganic Acid
CN110499427A (en) * 2019-08-30 2019-11-26 云南省环境科学研究院(中国昆明高原湖泊国际研究中心) A method of recycling noble metal from the wire mesh integral catalyzer of waste and old carried noble metal
CN112547135A (en) * 2020-11-13 2021-03-26 南京碧林环保科技有限公司 Method for separating recycled aggregate of waste flat plate type denitration catalyst

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1697704A (en) * 2003-03-10 2005-11-16 松下电器产业株式会社 Method for recovering catalyst material, catalyst material recovered by said recovering method, method for recovering substrate, substrate recovered by said recovering method
CN105854956A (en) * 2016-04-08 2016-08-17 天河（保定）环境工程有限公司 Recovery and reuse method of waste titanium-based vanadium-series plate type SCR catalyst
KR20180076390A (en) * 2016-12-27 2018-07-06 대영씨엔이(주) Method for Rematerializing Waste De-NOx Catalyst Using Inorganic Acid
CN107419104A (en) * 2017-07-24 2017-12-01 航天龙源(北京)环保科技发展有限公司 The comprehensive recovering process of useless SCR denitration
CN110499427A (en) * 2019-08-30 2019-11-26 云南省环境科学研究院(中国昆明高原湖泊国际研究中心) A method of recycling noble metal from the wire mesh integral catalyzer of waste and old carried noble metal
CN112547135A (en) * 2020-11-13 2021-03-26 南京碧林环保科技有限公司 Method for separating recycled aggregate of waste flat plate type denitration catalyst

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