CN112473752A - High-dust-blockage honeycomb type SCR denitration catalyst cleaning solution and preparation and cleaning methods thereof - Google Patents
High-dust-blockage honeycomb type SCR denitration catalyst cleaning solution and preparation and cleaning methods thereof Download PDFInfo
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- CN112473752A CN112473752A CN202011363786.5A CN202011363786A CN112473752A CN 112473752 A CN112473752 A CN 112473752A CN 202011363786 A CN202011363786 A CN 202011363786A CN 112473752 A CN112473752 A CN 112473752A
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- 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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- 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
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
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- 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
- 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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- 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
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B15/00—Preventing escape of dirt or fumes from the area where they are produced; Collecting or removing dirt or fumes from that area
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
- B08B3/02—Cleaning by the force of jets or sprays
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
- B08B3/04—Cleaning involving contact with liquid
- B08B3/08—Cleaning involving contact with liquid the liquid having chemical or dissolving effect
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
- B08B3/04—Cleaning involving contact with liquid
- B08B3/10—Cleaning involving contact with liquid with additional treatment of the liquid or of the object being cleaned, e.g. by heat, by electricity or by vibration
- B08B3/12—Cleaning involving contact with liquid with additional treatment of the liquid or of the object being cleaned, e.g. by heat, by electricity or by vibration by sonic or ultrasonic vibrations
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B5/00—Cleaning by methods involving the use of air flow or gas flow
- B08B5/04—Cleaning by suction, with or without auxiliary action
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B2203/00—Details of cleaning machines or methods involving the use or presence of liquid or steam
- B08B2203/02—Details of machines or methods for cleaning by the force of jets or sprays
- B08B2203/0288—Ultra or megasonic jets
Abstract
The invention discloses a high-dust-blockage honeycomb type SCR denitration catalyst cleaning solution and preparation and cleaning methods thereof, and relates to the technical field of honeycomb denitration catalysts. The invention can greatly reduce the corrosion to the denitration device and reduce the loss of the surface of the catalyst and the loss of active components while keeping the good cleaning effect on the high-dust-clogging honeycomb type SCR catalyst.
Description
Technical Field
The invention relates to the technical field of honeycomb denitration catalysts, in particular to a high-dust-blockage honeycomb type SCR denitration catalyst cleaning solution and preparation and cleaning methods thereof.
Background
Nitrogen oxide (NOx) is one of the main causes of acid rain, can generate photochemical smog pollution under certain conditions together with other pollutants, can directly damage human bodies and plants, and is the main gas for treating the atmospheric pollution at present. From the selection of the existing domestic denitration process of the large-capacity unit of the coal-fired power plant, the SCR technology has the advantages of mature technology, high denitration efficiency, stable operation, simple maintenance and the like, and occupies 90 percent of market share at present. The cost of the catalyst accounts for 40% or more of the whole SCR system, and meanwhile, the performance of the catalyst directly determines the denitration efficiency of the SCR system, so that the excellent catalyst becomes the key of the SCR denitration technology.
The SCR flue gas denitration device is generally disposed between an economizer and an air preheater and located in a high fly ash section, and catalyst activity is easily reduced due to catalyst blockage and fouling caused by fly ash deposition and alkali metals, alkaline earth metals, precious metal elements and the like contained in fly ash. According to the practical operation experience of coal-fired power plants, the average service life of the catalyst is about 3 years. Therefore, the regeneration of the catalyst has good economic benefit and environmental benefit. According to the difference of carriers, the SCR denitration catalyst can be divided into honeycomb type, flat plate type and corrugated plate type catalysts, wherein the honeycomb type SCR denitration catalyst accounts for the largest proportion of the three. The chemical cleaning solution is an indispensable key technology in the regeneration process of the waste SCR denitration catalyst, and the reaction activity of the catalyst has a great relationship with the external surface area and the pore characteristics of the catalyst. In the cleaning of the high-dust-clogging honeycomb type SCR catalyst, the clogging substances in the pore channels cannot be removed by simple water washing, and the medium-high concentration acid washing can damage the structure of the catalyst and cause certain harm to the environment. Therefore, finding a suitable high dust plugging honeycomb SCR catalyst cleaning solution and adopting a suitable cleaning method are one of the key points of the current work.
Disclosure of Invention
In order to overcome the defects of related products in the prior art, the invention provides a high-dust-clogging honeycomb type SCR denitration catalyst cleaning solution and a preparation and cleaning method thereof, which can greatly reduce the corrosion to denitration equipment and the loss of the surface of a catalyst and the loss of active components while keeping a good cleaning effect on the high-dust-clogging honeycomb type SCR catalyst.
The invention provides a high-dust-clogging honeycomb type SCR denitration catalyst cleaning solution which comprises the following components: 1-5 wt% of polyethylene glycol octyl phenyl ether; fatty alcohol-polyoxyethylene ether sodium sulfate accounting for 0.1-2 wt% of the total content; anhydrous sodium metasilicate accounting for 0.1-2 wt% of the total content; disodium ethylene diamine tetraacetate accounting for 0.1-0.5 wt% of the total content; a penetrating agent accounting for 0.1-0.5 wt% of the total content; a corrosion inhibitor accounting for 0.1-2 wt% of the total content; acid solution accounting for 0.5-3.5 wt% of the total content; the balance of water. The penetrating agent is peregal and JFC, and the corrosion inhibitor is hexamethylenetetramine; the acid is oxalic acid.
The invention provides a preparation method of a high-dust-clogging honeycomb type SCR denitration catalyst cleaning solution, which comprises the following steps:
(1) preparing an oxalic acid solution;
(2) adding polyethylene glycol octyl phenyl ether, anhydrous sodium metasilicate, ethylene diamine tetraacetic acid disodium, peregal, fatty alcohol-polyoxyethylene ether sodium sulfate, JFC and hexamethylenetetramine into the prepared oxalic acid solution;
(3) and (4) uniformly mixing.
The invention provides a cleaning method of a high-dust-clogging honeycomb type SCR denitration catalyst cleaning solution, which comprises the following steps:
(1) the waste catalyst is subjected to dust absorption and manual dredging, and the surface floating and sinking and the dust deposition in the pore channel are removed, so that about 20% -60% of the dust deposition can be removed.
(2) And (4) carrying out clear water spray washing on the catalyst module subjected to ash removal treatment, stopping spraying after 3-5 min, standing for 2-4 min, spraying again, and repeating for three times.
(3) After washing with clear water is finished, introducing 0.5-3.5 wt% of oxalic acid solution, sequentially adding 1-5 wt% of polyethylene glycol octyl phenyl ether, 0.1-2 wt% of anhydrous sodium metasilicate, 0.1-0.5 wt% of disodium ethylene diamine tetraacetate, 0.1-0.5 wt% of penetrating agent, 0.1-2 wt% of corrosion inhibitor, and finally adding 0.1-2 wt% of sodium fatty alcohol polyoxyethylene ether sulfate; when the pH value of the cleaning acid solution is more than or equal to 2, the acid solution is supplemented in time.
(4) And ultrasonically cleaning for 20-50 min.
(5) And (5) bubbling and cleaning for 20-30 min.
(6) And after the chemical cleaning is finished, rinsing for 2-3 times for 5-10 min by using clear water spray water.
(7) And (6) draining.
Compared with the prior art, the invention has the following advantages:
1. according to the invention, the nonionic surfactant polyethylene glycol octyl phenyl ether and the foaming agent fatty alcohol-polyoxyethylene ether sodium sulfate solution are adopted to be matched with other penetrating agents, so that dust attached to the surface of the catalyst can be penetrated and stripped, and meanwhile, the damage to the surface of the catalyst and the loss of active components are avoided to a certain extent.
2. The invention adopts anhydrous sodium metasilicate as a dispersing agent, has excellent performance in the aspects of removing, dispersing and suspending dirt, and can prevent the redeposition of the dirt.
3. The invention adopts disodium ethylene diamine tetraacetate as a complexing agent, and can generate chelation with divalent metal ions such as Ca2+, Mn2+, Fe2+, Mg2+ and the like for removing.
4. The invention adopts peregal and JFC as penetrant, which has good wetting, emulsifying, dispersing and cleaning performances, and mainly removes SiO2, alumina, calcium sulfate and the like attached to the catalyst in dust.
5. The corrosion inhibitor hexamethylenetetramine adopted by the invention can prevent the corrosion of acid liquor to the catalyst packaging iron shell and reduce the influence of the dissolution of iron element on the performance of the catalyst.
6. The invention improves the removal efficiency of the attachments on the surface of the catalyst by utilizing the ultrasonic technology in the cleaning process and provides a good foundation for the attachment of the subsequent regenerative medicament.
7. The invention adopts the oxalic acid regulating solution with the pH value maintained at about 2 and the oxalic acid with weaker acidity than sulfuric acid, thereby avoiding the possibility that the conventional acidification mode (generally taking dilute sulfuric acid as a pickling agent) can corrode the denitration equipment and the reaction and decomposition of the oxalic acid in the whole production process can generate CO2CO and water vapor, the concentration of CO is lower, the CO can be discharged through the exhaust funnel up to the standard, and CO is discharged2And the water vapor can be directly discharged, and the influence on the environment is small.
8. The invention can furthest reduce the corrosion to the inside of the catalyst and reduce the load of a subsequent wastewater treatment system while ensuring the cleaning effect by controlling the concentration and the contact time of the acid liquor.
Detailed Description
In order to make the technical solutions of the present invention better understood by those skilled in the art, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. This invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein, but rather should be construed as broadly as the present disclosure is set forth in order to provide a more thorough understanding thereof. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. It is explicitly and implicitly understood by one skilled in the art that the embodiments described herein can be combined with other embodiments.
The denitration catalyst in an SCR denitration system of a certain power plant is put into operation for 4 years and is abandoned for 2 years, and the dust carried by the invalid catalyst accounts for about 5 percent of the weight of the catalyst. And (3) taking the catalyst module, and removing about 60% of accumulated dust on the module after mechanical and manual dust removal.
The embodiment of the invention adopts the following steps to clean the catalyst.
Step 1: the catalyst module after ash removal treatment (two blocks are shipped each time for 4m in total)3) Transporting to the cleaning device area, and placing into the cleaning tank (volume 8 m) by hoisting3) And covering and sealing, spraying clear water (2t per batch) on the surface of the catalyst through a spray head, stopping spraying after 5min, standing for 2min, spraying again, repeating for three times, and pumping the slurry into water treatment equipment for treatment.
Step 2: after the washing with clear water is finished, introducing oxalic acid solution (120kg, prepared on site), sequentially adding polyethylene glycol octyl phenyl ether (80kg), anhydrous sodium metasilicate (40kg), disodium ethylene diamine tetraacetate (15kg), penetrating agent (10kg), corrosion inhibitor (20kg) and hexamethylenetetramine (18kg), and finally adding fatty alcohol-polyoxyethylene ether sodium sulfate (8 kg); removing impurities such as dust, alkali metal and the like loaded on the surface, and supplementing a proper amount of fresh acid liquor when the pH value of the cleaning acid liquor is more than or equal to 2.
And step 3: when the pickling solution reaches the set liquid level, the ultrasonic cleaning is started for 40min, the dust particles adhered to the inside of the catalyst are gradually taken out through the micro-bubbles, and then the bubbling cleaning is carried out for 20min (the amount of blown air is 10 m)3Min), washing the seriously blocked catalyst holes.
And 4, step 4: and after the chemical cleaning is finished, cleaning with clear water spray water (2t) to remove acid liquor remained on the surface, cleaning for about 5min, draining the catalyst after secondary clear water washing for a period of time (the water content is 30%) in a cleaning section, and finishing the cleaning. Then the subsequent regeneration process is carried out.
And (4) analyzing results:
after the catalyst is cleaned, the attached particles are obviously reduced, the cleaning effect is good, the catalyst is very little in poison, and the subsequent regeneration and the use of the catalyst are facilitated. In the geometrical characteristics before and after the regeneration of the catalyst, except that the porosity and the specific surface area are improved, the V2O5 is slightly reduced, and other parameters are basically kept unchanged after the subsequent processes are supplemented. The denitration rate of the regenerated catalyst is more than or equal to 90 percent, the conversion rate of SO2/SO3 is less than or equal to 1 percent, the activity reaches 36-40 m/h, the resistance is less than or equal to 180Pa, and the use requirement of the subsequent denitration engineering is met.
Those not described in detail in this specification are within the skill of the art. Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments described in the foregoing detailed description, or equivalent changes may be made in some of the features of the embodiments. All equivalents that can be substituted by the contents of the specification of the present invention and applied directly or indirectly to other related technical fields are within the scope of the present invention.
Claims (10)
1. The utility model provides a high dust blocks up honeycomb formula SCR denitration catalyst washing liquid which characterized in that: the high-dust-blockage honeycomb type SCR denitration catalyst cleaning solution is composed of a nonionic surfactant, a foaming agent, a cleaning auxiliary agent, a penetrating agent, a corrosion inhibitor and acid.
2. The high dust plugging honeycomb SCR denitration catalyst cleaning solution according to claim 1, characterized in that: the nonionic surfactant is 1-5 wt% of polyethylene glycol octyl phenyl ether.
3. The high dust plugging honeycomb SCR denitration catalyst cleaning solution according to claim 1, characterized in that: the foaming agent is 0.1-2 wt% of fatty alcohol-polyoxyethylene ether sodium sulfate.
4. The high dust plugging honeycomb SCR denitration catalyst cleaning solution according to claim 1, characterized in that: the cleaning auxiliary agent is 0.1-2 wt% of anhydrous sodium metasilicate.
5. The high dust plugging honeycomb SCR denitration catalyst cleaning solution according to claim 1, characterized in that: the cleaning auxiliary agent is 0.1-0.5 wt% of disodium ethylene diamine tetraacetate.
6. The high dust plugging honeycomb SCR denitration catalyst cleaning solution according to claim 1, characterized in that: the penetrant is 0.1-0.5 wt% of peregal and JFC; the weight ratio of peregal to JFC in the penetrant is 1: 2-3.
7. The high dust plugging honeycomb SCR denitration catalyst cleaning solution according to claim 1, characterized in that: the corrosion inhibitor is 0.1-2 wt% of hexamethylenetetramine.
8. The high dust plugging honeycomb SCR denitration catalyst cleaning solution according to claim 1, characterized in that: the acid is 0.5-3.5 wt% oxalic acid.
9. The preparation method of the high-dust-clogging honeycomb type SCR catalyst cleaning solution applied to any one of claims 1 to 8 is characterized by comprising the following steps: the method comprises the following steps:
(1) preparing an oxalic acid solution;
(2) adding polyethylene glycol octyl phenyl ether, anhydrous sodium metasilicate, ethylene diamine tetraacetic acid disodium, peregal, fatty alcohol-polyoxyethylene ether sodium sulfate, JFC and hexamethylenetetramine into the prepared oxalic acid solution;
(3) and (4) uniformly mixing.
10. The cleaning method applied to the high-dust-clogging honeycomb type SCR denitration catalyst cleaning solution disclosed by claims 1-8 is characterized by comprising the following steps of: the method comprises the following steps:
(1) and (4) carrying out manual ash removal and clear water spray washing on the deactivated catalyst.
(2) Introducing 0.5-3.5 wt% of oxalic acid solution, sequentially adding 1-5 wt% of polyethylene glycol octyl phenyl ether, 0.1-2 wt% of anhydrous sodium metasilicate, 0.1-0.5 wt% of disodium ethylene diamine tetraacetate, 0.1-0.5 wt% of penetrating agent and 0.1-2 wt% of corrosion inhibitor, and finally adding 0.1-2 wt% of sodium fatty alcohol polyoxyethylene ether sulfate; when the pH value of the cleaning acid solution is more than or equal to 2, the acid solution is supplemented in time.
(3) And ultrasonically cleaning for 20-50 min.
(4) And (5) bubbling and cleaning for 20-30 min.
(5) Rinsing with clear water spray for 2-3 times for about 5-10 min.
(6) And (6) draining.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114214129A (en) * | 2021-12-30 | 2022-03-22 | 陕西环保新能源有限公司 | Cleaning solution for SCR honeycomb denitration catalyst, preparation method and regeneration method |
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