CN112718778B - Method for deep dearsenization in waste SCR catalyst acidic system - Google Patents
Method for deep dearsenization in waste SCR catalyst acidic system Download PDFInfo
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- CN112718778B CN112718778B CN201910973414.5A CN201910973414A CN112718778B CN 112718778 B CN112718778 B CN 112718778B CN 201910973414 A CN201910973414 A CN 201910973414A CN 112718778 B CN112718778 B CN 112718778B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B5/00—Operations not covered by a single other subclass or by a single other group in this subclass
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- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- 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 relates to a method for deep dearsenification in an acid system of a waste SCR catalyst, which comprises the following steps: (1) grinding the ash-removed waste SCR catalyst, then adding the waste SCR catalyst powder into a cleaning solution containing an acidic substance and an auxiliary agent, reacting, and filtering; (2) and washing and drying the solid phase obtained by filtering to obtain the product. The method provided by the invention realizes the synchronous removal of toxic components such as arsenic, potassium, sodium, iron and the like by adopting the cleaning solution containing the acidic substance and the auxiliary agent, the removal rate can reach more than 95 percent, and the content of the toxic components in the product is less than 200 ppm; the method has simple process flow and easy operation, avoids the alternative use of acid and alkali and the generation of waste brine, reduces the production cost and the environmental protection pressure, and conforms to the development trend of environmental protection.
Description
Technical Field
The invention relates to the field of solid waste resource utilization, in particular to a method for deep dearsenification in an acid system of a waste SCR catalyst.
Background
Selective Catalytic Reduction (SCR) is the most important method for controlling nitrogen oxide emission in coal-fired power plants in China, wherein a catalyst is the key of the SCR method. At present, the waste SCR denitration catalyst is huge in production amount, is brought into hazardous waste for management, needs to be recycled, changes waste into valuables and saves resources. Aiming at the resource recycling of the waste SCR catalyst, at present, two routes are mainly used, wherein the two routes are that titanium, tungsten and vanadium are distributed, separated and recycled to prepare corresponding metal oxides, and the purified titanium and tungsten powder is recycled for the production of a new SCR catalyst. The recycling route is an important utilization mode in the field of waste catalyst recycling at present due to the fact that the process is relatively simple and easy to implement.
The impurity removal and purification of the waste SCR catalyst are important prerequisites and key steps for recycling. In the using process of the catalyst, a certain amount of catalytic toxic components such as arsenic, potassium, sodium, iron and the like are accumulated and react with the active sites of the catalyst, so that the number of active sites participating in denitration reaction is reduced, the denitration efficiency of the catalyst is reduced, the catalytic toxic components need to be deeply cleaned before recycling, and otherwise, the using effect of a new catalyst is influenced. At present, the common method for removing impurities and purifying the waste SCR catalyst is to remove arsenic by alkali elution and then remove impurities such as potassium, sodium, iron and the like by acid washing. CN105618162A discloses a method for recycling waste vanadium tungsten titanium-based denitration catalysts, which comprises the steps of sequentially adopting a first cleaning solution and a second cleaning solution to clean the waste vanadium tungsten titanium-based denitration catalysts until the contents of ferric oxide, arsenic oxide, sodium oxide and potassium oxide in the catalysts are all lower than 0.001 wt%, and then drying and roasting. Wherein the first cleaning solution comprises sodium hydroxide and/or potassium hydroxide, sodium carbonate, sodium ethylene diamine tetracetate, sodium diethylenetriamine pentaacetate, sodium nitrilotriacetate, sodium citrate, JFC, OP-10, peregal and sodium pyrophosphate; the second cleaning solution comprises sulfuric acid, citric acid, oxalic acid, tartaric acid, ethylene diamine tetraacetic acid, nitrilotriacetic acid, diethylene triamine pentaacetic acid, JFC, OP-10 and peregal. Although the method can deeply remove the impurities such as arsenic, potassium, sodium, iron and the like, the method involves two sections of cleaning and filtering steps and is complicated; meanwhile, the alternative use of acid and alkali inevitably leads to the loss of medicament and the generation of waste saline, resulting in the increase of production cost and environmental protection pressure.
CN106140325A discloses an ultrasonic cleaning solution for waste denitration catalysts, a preparation method and a cleaning method, wherein the cleaning solution comprises deionized water and a heavy metal chelating agent; then adding oxalic acid, wherein the heavy metal chelating agent is at least one of sodium dimethyldithiocarbamate and methylglycine diacetic acid. The heavy metal chelating agent in the cleaning solution can effectively remove Cu 2+ 、Fe 2+ And As and other toxic substances, effectively improve the regeneration effect. However, the removal of arsenic is only partially carried out, and the removal effect of arsenic is not clearly reported.
CN105797790A discloses an acid washing solution for recycling waste denitration catalyst and a method thereof, wherein the method selects proper sulfuric acid or nitric acid concentration, and also adds JFC-1 or TX-10 nonionic surfactant with osmosis, so that alkali metal and alkaline earth metal on the surface and in the waste denitration catalyst can be effectively removed, but Fe can not be removed by the method 2+ As, poisoning substances affecting the cleaningThe denitration activity of the catalyst in the SCR reaction.
Based on the research of the prior art, how to develop a method for efficiently removing arsenic from a waste SCR catalyst under an acidic condition, which realizes the synchronous removal of arsenic, potassium, sodium and iron in an acidic system, obviously simplifies the process flow and avoids the generation of waste brine becomes a problem to be solved urgently at present.
Disclosure of Invention
In view of the problems in the prior art, the invention provides a method for deeply removing arsenic in an acid system of a waste SCR catalyst, which solves the problem of low arsenic removal efficiency in the acid system of the waste SCR catalyst by adopting a cleaning solution containing an acidic substance and an auxiliary agent to react with waste SCR catalyst powder, realizes the synchronous removal of toxic components of arsenic, potassium, sodium and iron, has short process flow and almost no waste saline water, effectively reduces the investment and operation cost, and accords with the development trend of green and environmental protection.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a method for deep dearsenification in an acid system of a waste SCR catalyst, which comprises the following steps:
(1) grinding the ash-removed waste SCR catalyst, then adding the waste SCR catalyst powder into a cleaning solution containing an acidic substance and an auxiliary agent, reacting, and filtering;
(2) and washing and drying the solid phase obtained by filtering to obtain the product.
According to the method provided by the invention, the cleaning solution containing the acidic substance and the auxiliary agent is added, so that the catalytic toxic components of arsenic, potassium, sodium and iron on the surface of the waste SCR catalyst powder and in the micropores are effectively dissolved; compared with the conventional acid washing, the use of the auxiliary agent increases the dissolution of arsenic, has the effect of strengthening arsenic removal, achieves the aim of deep arsenic removal, and effectively improves the impurity removal and purification effects.
Preferably, the acidic substance in step (1) comprises any one or a combination of at least two of sulfuric acid, hydrochloric acid, nitric acid, oxalic acid or acetic acid, preferably any one or a combination of at least two of sulfuric acid, hydrochloric acid or oxalic acid; typical but non-limiting combinations thereof: sulfuric acid and hydrochloric acid, sulfuric acid and oxalic acid, hydrochloric acid, oxalic acid and sulfuric acid. The acidic substance can dissolve catalytic toxic components such as arsenic, potassium, sodium, iron and the like on the surface of the waste SCR catalyst and in the micropores.
Preferably, in the step (1), the auxiliary agent comprises any one or a mixture of at least two of sodium borohydride, sodium thiosulfate, sodium sulfite, sodium bisulfite, sodium bisulfide, potassium thiosulfate, potassium sulfite, potassium bisulfite, potassium sulfide, potassium bisulfide, ammonium thiosulfate, ammonium sulfite, ammonium bisulfite, ammonium sulfide or ammonium bisulfide, preferably any one or a mixture of at least two of sodium sulfide, sodium bisulfide, potassium thiosulfate, potassium sulfite, potassium bisulfite, potassium sulfide, potassium bisulfide, ammonium thiosulfate, ammonium sulfite, ammonium bisulfite, ammonium sulfide or ammonium bisulfide, and further preferably any one or a combination of at least two of sodium sulfide, potassium thiosulfate or sodium sulfite; typical but non-limiting combinations thereof: sodium sulfide and potassium thiosulfate, sodium sulfide and sodium sulfite, sodium sulfide, potassium thiosulfate and sodium sulfite. The auxiliary agent can promote the leaching of arsenic on the surface of the waste SCR catalyst and in the micropores, and has the function of strengthening arsenic removal.
Preferably, the mass concentration of the acidic substance in the cleaning solution in the step (1) is 1-15%, for example, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14% and 15%, and when the mass concentration is less than 1%, the dissolution speed is slow and the reaction time is long; when the mass concentration is more than 15%, the process cost is increased, and preferably 5 to 15%.
Preferably, the mass concentration of the auxiliary agent in the cleaning solution in the step (1) is 0.1-3%, for example, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.8%, 1%, 1.2%, 1.5%, 1.7%, 2%, 2.3%, 2.5%, 2.8% and 3%, and when the mass concentration is less than 0.1%, the amount of arsenic removed is small; when the mass concentration is more than 3%, the process cost is increased, and preferably 0.5 to 3%.
Preferably, the spent SCR catalyst in step (1) comprises any one of a corrugated catalyst, a plate catalyst or a honeycomb catalyst.
Preferably, the mass ratio of the cleaning solution to the waste SCR catalyst in the step (1) is 2-10:1, for example, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1 and 10:1, and if the mass ratio of the cleaning solution to the waste SCR catalyst is 1:1, the diffusion effect is poor, and the removal effect on arsenic, potassium, sodium and iron is poor; if the mass ratio of the cleaning solution to the spent SCR catalyst is greater than 10:1, it will result in an increase in the size of the reaction equipment and an increase in the cost, preferably 2 to 8: 1.
Preferably, the reaction temperature in the step (1) is 20 to 100 ℃, and for example, 20 ℃, 25 ℃, 30 ℃, 32 ℃, 35 ℃, 37 ℃, 40 ℃, 42 ℃, 45 ℃, 48 ℃, 50 ℃, 55 ℃, 60 ℃, 62 ℃, 65 ℃, 67 ℃, 70 ℃, 75 ℃, 80 ℃, 82 ℃, 85 ℃, 88 ℃, 90 ℃, 95 ℃, 98 ℃ and 100 ℃ may be used, the reaction temperature enables the cleaning solution to smoothly react with the waste SCR catalyst powder, the high temperature is favorable for promoting the leaching of impurities, but the excessive temperature increases the cost and equipment investment, and is preferably 30 to 100 ℃.
Preferably, the reaction time in step (1) is 1 to 10 hours, for example, 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours, 6.5 hours, 6.6 hours, 7 hours, 7.5 hours, 8 hours, 8.5 hours, 9 hours, 9.5 hours and 10 hours, and the reaction time is adapted to the reaction temperature, so that the cleaning solution and the waste SCR catalyst powder completely react, preferably 3 to 8 hours.
Preferably, the method comprises the steps of:
(1) grinding the ash-removed waste SCR catalyst, adding the waste SCR catalyst powder into a cleaning solution containing an acidic substance and an auxiliary agent, wherein the mass ratio of the cleaning solution to the waste SCR catalyst is 2-10:1, reacting for 2.5-10h at 20-100 ℃, and filtering.
The acidic substance includes any one or a combination of at least two of sulfuric acid, hydrochloric acid, nitric acid, oxalic acid, or acetic acid, and the mass concentration of the acidic substance in the cleaning solution is 1 to 15%, and may be, for example, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, and 15%.
The auxiliary agent comprises any one or a mixture of at least two of sodium borohydride, sodium thiosulfate, sodium sulfite, sodium bisulfite, sodium sulfide, potassium thiosulfate, potassium sulfite, potassium bisulfite, potassium sulfide, ammonium thiosulfate, ammonium sulfite, ammonium bisulfite, ammonium sulfide or ammonium bisulfide, and the mass concentration of the auxiliary agent in the cleaning solution is 0.1-3%, for example, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.8%, 1%, 1.2%, 1.5%, 1.7%, 2%, 2.3%, 2.5%, 2.8% and 3%.
(2) And washing and drying the solid phase obtained by filtering to obtain the product.
According to the method, the liquid phase obtained by separation can react and separate the waste SCR catalyst powder again, and the steps are repeated, so that unreacted acidic substances and auxiliaries in the liquid phase are fully utilized, meanwhile, the concentration of alum in the liquid phase is enriched, and alum products can be extracted from the liquid phase subsequently, so that the full utilization of resources is realized, and the generation of waste brine is avoided.
In the invention, the concrete mode of dedusting and grinding the waste SCR catalyst is not specially limited, and all the methods commonly used by the technicians in the field are suitable for the invention.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) the method for deeply removing arsenic from the waste SCR catalyst in an acid system realizes synchronous removal of toxic components such as arsenic, potassium, sodium, iron and the like from the waste SCR catalyst by adopting the cleaning solution containing the auxiliary agent of an acid substance, the removal rate can reach more than 95 percent, and the content of the toxic components in the product is less than 200 ppm.
(2) The method for deeply removing arsenic from the waste SCR catalyst in the acid system has the advantages of simple process flow and easy operation, avoids the alternate use of acid and alkali and the generation of waste brine, reduces the production cost and the environmental protection pressure, and conforms to the development trend of green and environmental protection.
Drawings
FIG. 1 is a flow diagram of a process for deep dearsenification of a spent SCR catalyst in an acidic system according to the present invention.
Detailed Description
The following further describes the technical means of the present invention to achieve the predetermined technical effects by means of embodiments with reference to the accompanying drawings, and the embodiments of the present invention are described in detail as follows.
The invention provides a method for deep dearsenification in a waste SCR catalyst acidic system, wherein the flow of the method is shown in figure 1, the method specifically comprises the steps of reacting waste SCR catalyst powder with cleaning solution containing acidic substances and auxiliaries, filtering, washing and drying a solid phase obtained by filtering to obtain a product; and continuously reacting the liquid phase obtained by filtering with the waste SCR catalyst powder, filtering, and concentrating the concentration of vanadium in the liquid phase after a plurality of cycles, so that a vanadium product can be extracted from the liquid phase.
Example 1
The embodiment provides a method for deep dearsenification in an acid system of a waste SCR catalyst, which comprises the following steps:
(1) grinding the ash-removed waste SCR catalyst powder, then adding the waste SCR catalyst powder into a cleaning solution containing 10% of sulfuric acid and 1% of sodium sulfide, wherein the mass ratio of the cleaning solution to the waste SCR catalyst powder is 2:1, reacting for 3 hours at 30 ℃, and filtering;
(2) and washing and drying the solid phase obtained by filtering to obtain the product.
Example 2
The embodiment provides a method for deep dearsenification in an acid system of a waste SCR catalyst, which comprises the following steps:
(1) grinding the ash-removed waste SCR catalyst powder, then adding the waste SCR catalyst powder into a cleaning solution containing 15% of hydrochloric acid and 0.5% of potassium thiosulfate, wherein the mass ratio of the cleaning solution to the waste SCR catalyst powder is 10:1, reacting for 6 hours at 60 ℃, and filtering;
(2) and washing and drying the solid phase obtained by filtering to obtain the product.
Example 3
The embodiment provides a method for deep dearsenification in an acid system of a waste SCR catalyst, which comprises the following steps:
(1) grinding the ash-removed waste SCR catalyst powder, then adding the waste SCR catalyst powder into a cleaning solution containing 11% of oxalic acid and 2% of sodium sulfite, wherein the mass ratio of the cleaning solution to the waste SCR catalyst powder is 8:1, reacting for 8 hours at 100 ℃, and filtering;
(2) and washing and drying the solid phase obtained by filtering to obtain the product.
Example 4
Compared with the embodiment 1, the mass ratio of the cleaning liquid to the waste SCR catalyst powder in the step (1) is replaced by 1:1, and the method specifically comprises the following steps:
(1) grinding the ash-removed waste SCR catalyst powder, then adding the waste SCR catalyst powder into a cleaning solution containing 10% of sulfuric acid and 1% of sodium sulfide, wherein the mass ratio of the cleaning solution to the waste SCR catalyst powder is 1:1, reacting for 3 hours at 30 ℃, and filtering;
(2) and washing and drying the solid phase obtained by filtering to obtain the product.
Example 5
Compared with the embodiment 1, the method has the advantages that the mass concentration of the sulfuric acid in the cleaning liquid in the step (1) is replaced by 0.8 percent, and the method specifically comprises the following steps:
(1) grinding the ash-removed waste SCR catalyst powder, then adding the waste SCR catalyst powder into a cleaning solution containing 4% of sulfuric acid and 1% of sodium sulfide, wherein the mass ratio of the cleaning solution to the waste SCR catalyst powder is 2:1, reacting for 3 hours at 30 ℃, and filtering;
(2) and washing and drying the solid phase obtained by filtering to obtain the product.
Example 6
Compared with the embodiment 1, the method replaces the sodium sulfide used in the step (1) with a mixture of sodium sulfide and potassium thiosulfate, and specifically comprises the following steps:
(1) grinding the ash-removed waste SCR catalyst powder, adding the waste SCR catalyst powder into a cleaning solution containing 10% of sulfuric acid and 1% of a mixture of sodium sulfide and potassium thiosulfate, wherein the mass ratio of the cleaning solution to the waste SCR catalyst powder is 2:1, reacting for 3 hours at 30 ℃, and filtering;
(2) and washing and drying the solid phase obtained by filtering to obtain the product.
Comparative example 1
Compared with the example 1, the difference is that the cleaning solution in the step (1) does not contain sodium sulfide, and the method specifically comprises the following steps:
(1) grinding the ash-removed waste SCR catalyst powder, then adding the waste SCR catalyst powder into a cleaning solution containing 10% of sulfuric acid, wherein the mass ratio of the cleaning solution to the waste SCR catalyst powder is 2:1, reacting for 3 hours at 30 ℃, and filtering;
(2) and washing and drying the solid phase obtained by filtering to obtain the product.
Evaluating the removal effect of arsenic, potassium, sodium and iron in the waste SCR catalyst:
the products obtained by removing arsenic, potassium, sodium and iron using the cleaning solutions in examples 1 to 9 and comparative example 1 described above were subjected to arsenic, potassium, sodium and iron content tests. The test method is as follows: taking a sample with 0.1g of action from the raw material or the obtained product, adding mixed acid of nitric acid and hydrofluoric acid, heating until the solid is completely dissolved, and diluting to 100ml to obtain a solution to be detected. And (4) adopting ICP-OES to test the concentration of each element in the solution, and calculating to obtain the content of each impurity element in the solid.
The test results are shown in tables 1-2, where table 1 shows the arsenic, potassium, sodium and iron contents in the raw materials and products, and table 2 shows the removal rates of arsenic, potassium, sodium and iron.
TABLE 1
TABLE 2
As can be seen from Table 1, the raw materials of the waste SCR catalyst powder used in examples 1-3 and 6 contain high toxic components of arsenic, potassium, sodium and iron, and the products obtained by the reaction of the method of the present invention contain low toxic components of arsenic, potassium, sodium and iron, less than 200 ppm; in example 4, the amount of the cleaning solution was reduced, and the contents of toxic components of arsenic, potassium, sodium and iron in the product after the reaction were respectively 450ppm, 220ppm, 180ppm and 450ppm, which is mainly because the cleaning solution did not react sufficiently with the waste SCR catalyst powder, resulting in incomplete removal of toxic components of arsenic, potassium, sodium and iron; the content of sulfuric acid in the cleaning solution used in example 5 was reduced, and the contents of toxic components of arsenic, potassium, sodium and iron in the product after the reaction were 800ppm, 350ppm, 280ppm and 750ppm, respectively, which indicates that the content of acidic substances in the cleaning solution was too low, the capability of removing toxic components of arsenic, potassium, sodium and iron was weak, and the effect of deep arsenic removal was not achieved.
In comparative example 1, no auxiliary agent is added, and the contents of toxic components of arsenic, potassium, sodium and iron in the product after reaction are respectively 600ppm, 25ppm, 15ppm and 65ppm, which shows that the arsenic removal capability of the cleaning solution without the addition of the auxiliary agent is poor, compared with example 1, the content of arsenic in the product after reaction in example 1 is 50ppm and is obviously lower than that of arsenic in the product after reaction in comparative example 1, which shows that the cleaning solution containing the auxiliary agent can leach more arsenic, and further shows that the auxiliary agent has the effect of strengthening arsenic removal.
As can be seen from Table 2, in examples 1-3 and 6, the cleaning solution containing the acidic substance and the auxiliary agent is adopted to react with the waste SCR catalyst powder to synchronously remove the toxic components of arsenic, potassium, sodium and iron, the removal rate is over 95 percent, the removal effect is good, in comparative example 1, the cleaning solution containing no auxiliary agent sodium sulfide is adopted to react with the waste SCR catalyst to synchronously remove the toxic components of arsenic, potassium, sodium and iron, but the removal rate of arsenic is 47.8 percent and is far lower than 95 percent, and the removal rate of the rest toxic components is close to 95 percent; data analysis shows that the dearsenization effect of the cleaning solution without the auxiliary agent is greatly reduced in an acidic system.
Compared with the example 1, the mass ratio of the cleaning liquid to the waste SCR catalyst powder in the example 4 is 1:1, the dosage of the cleaning liquid is reduced, and the removal rate of the toxic components of arsenic, potassium, sodium and iron is obviously reduced under the same condition, which shows that the mass ratio of the cleaning liquid used by the invention to the waste SCR catalyst powder has a proper range, and the toxic components of arsenic, potassium, sodium and iron below the range can not achieve the expected removal effect.
Compared with the example 1, the content of the sulfuric acid in the cleaning solution used in the example 5 is 0.8%, the content of the sulfuric acid is reduced, and the removal rate of the toxic components of arsenic, potassium, sodium and iron is remarkably reduced under the same conditions, which indicates that the mass ratio of the acidic substance to the auxiliary agent in the cleaning solution adopted by the invention has a proper range, and the toxic components of arsenic, potassium, sodium and iron can not achieve the expected removal effect below the range.
Compared with the example 1, the auxiliary agent in the cleaning solution used in the example 6 is a mixture of sodium sulfide and potassium thiosulfate, and under the same conditions, the removal effect of toxic components of arsenic, potassium, sodium and iron is slightly better than that of the example 1, which shows that the deep arsenic removal effect can be achieved by using the combined auxiliary agent.
The applicant declares that the present invention illustrates the detailed structural features of the present invention through the above embodiments, but the present invention is not limited to the above detailed structural features, that is, it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, additions of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (8)
1. The method for deeply removing arsenic in the acid system of the waste SCR catalyst is characterized by comprising the following steps of:
(1) grinding the ash-removed waste SCR catalyst, then adding the waste SCR catalyst powder into a cleaning solution containing an acidic substance and an auxiliary agent, reacting, and filtering; the mass concentration of acidic substances in the cleaning solution is 5-15%; the mass ratio of the cleaning liquid to the waste SCR catalyst powder is 2-10: 1; the acidic substance comprises any one of or the combination of at least two of sulfuric acid, hydrochloric acid, nitric acid, oxalic acid or acetic acid; the auxiliary agent is any one or mixture of at least two of sodium sulfide, sodium hydrosulfide, potassium thiosulfate, potassium sulfite, potassium bisulfite, potassium sulfide, potassium hydrosulfide, ammonium thiosulfate, ammonium sulfite, ammonium bisulfite, ammonium sulfide or ammonium hydrosulfide; the mass concentration of the auxiliary agent in the cleaning liquid is 0.5-3%; the reaction temperature is 20-100 ℃;
(2) washing and drying the solid phase obtained by filtering to obtain a product;
toxic components such as arsenic, potassium, sodium and iron are synchronously removed from the waste SCR catalyst, and the removal rate reaches over 95 percent.
2. The method according to claim 1, wherein the acidic substance in step (1) is any one or a combination of at least two of sulfuric acid, hydrochloric acid or oxalic acid.
3. The method according to claim 1, wherein the auxiliary in step (1) is sodium sulfide and/or potassium thiosulfate.
4. The method of claim 1, wherein the spent SCR catalyst in step (1) comprises any one of a corrugated catalyst, a plate catalyst, or a honeycomb catalyst.
5. The method according to claim 1, wherein the mass ratio of the cleaning solution to the waste SCR catalyst powder in the step (1) is 2-8: 1.
6. The process according to claim 1, wherein the temperature of the reaction in step (1) is 30 to 100 ℃.
7. The process according to claim 1, wherein the reaction time in step (1) is 1 to 10 hours.
8. The process according to claim 7, wherein the reaction time in step (1) is 3 to 8 hours.
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| CN113430381A (en) * | 2021-06-25 | 2021-09-24 | 郑州大学 | Harmless treatment method for arsenic-containing waste SCR denitration catalyst |
| CN113413925A (en) * | 2021-06-25 | 2021-09-21 | 郑州大学 | Method for recovering As and compounds thereof in waste SCR denitration catalyst |
| CN114558625A (en) * | 2022-03-14 | 2022-05-31 | 龙净科杰环保技术（上海）有限公司 | SCR denitration catalyst regeneration process in steel industry |
| CN115874057B (en) * | 2023-03-08 | 2023-05-05 | 国能龙源环保有限公司 | Method for simultaneously removing cadmium, zinc, lead and copper in waste denitration catalyst by chemical leaching method |
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