CN113231080B - Regeneration method of rare earth-based SCR denitration catalyst - Google Patents

Regeneration method of rare earth-based SCR denitration catalyst Download PDF

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CN113231080B
CN113231080B CN202110720536.0A CN202110720536A CN113231080B CN 113231080 B CN113231080 B CN 113231080B CN 202110720536 A CN202110720536 A CN 202110720536A CN 113231080 B CN113231080 B CN 113231080B
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李慧远
杨中原
伊茂广
李亮亮
史元通
王志民
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Shandong Gemsky Environmental Protection Technology Co ltd
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Abstract

The invention belongs to the technical field of denitration catalyst regeneration, and particularly relates to a regeneration method of a rare earth-based SCR denitration catalyst. The method comprises the following steps: (1) removing fly ash and ammonium bisulfate, and cleaning a pore channel: putting the deactivated catalyst into a cleaning kettle, adding water to immerse the catalyst, and adding a cleaning agent; (2) starting steam heating, and controlling the pressure in the kettle; (3) cleaning: cooling, opening a discharge valve at the bottom of the cleaning kettle, and discharging the cleaning solution; pumping pure water to flush the catalyst and immersing the catalyst in the pure water in the kettle; and (4) heavy metal removal: adding a saturated rare earth solution to immerse the catalyst; (5) adding organic acid to react; (6) after the reaction is finished, adding an adsorbent; (7) cleaning: pumping pure water to flush the catalyst; (8) drying: and (5) putting the catalyst into a vacuum drying oven for drying, and finishing the regeneration of the catalyst. The regeneration method of the invention has the advantages of basically no loss of active components, no solid waste, small waste water amount and high denitration efficiency of the regenerated catalyst.

Description

Regeneration method of rare earth-based SCR denitration catalyst
Technical Field
The invention belongs to the technical field of denitration catalyst regeneration, and particularly relates to a regeneration method of a rare earth-based SCR denitration catalyst.
Background
With the promotion of the emission reduction work of nitrogen oxides, the SCR flue gas denitration process is widely applied to domestic thermal power plants. During the nitrogen oxide treatment, a large amount of deactivated denitration catalyst is generated. The catalyst is the core of the SCR flue gas denitration technology, and relevant parameters such as components, surface structures and the like of the catalyst can directly influence the integral denitration effect of the SCR denitration system. At present V 2 O 5 /TiO 2 The base catalyst and the rare earth base catalyst are most widely applied to an SCR denitration system.
The main reasons for the deactivation of the rare earth-based SCR denitration catalyst are: (1) During the use process of the catalyst, ammonia gas reacts with sulfuric acid to generate a large amount of ammonium bisulfate which is deposited on the catalyst to block catalyst pore channels, so that the catalyst is inactivated; (2) Fly ash and other organic matters are carried in the flue gas, so that the pore channel of the catalyst is blocked; (3) In the denitration process, the flue gas contains heavy metal compounds, which causes catalyst poisoning.
The regeneration of the rare earth denitration catalyst realizes the resource reutilization by reactivating the deactivated catalyst with qualified mechanical strength, and reduces the resource waste of the whole SCR industry. The pollution control cost of the waste SCR catalyst is about 2600 yuan/t and about 5.3 percent of the total cost of the SCR catalyst. The method for treating the deactivated catalyst in a burying manner is adopted, so that not only are environmental problems such as underground water pollution easily caused, but also the loss of rare earth elements such as cerium and zirconium in the deactivated catalyst is caused, and the rare earth-based SCR denitration catalyst mainly comprises titanium dioxide and rare earth oxide and is relatively expensive.
The introduction of the domestic SCR technology is late, the research on the regeneration technology of the inactivated rare earth-based SCR denitration catalyst is less, an effective treatment method or a technical route is not found, and the rare earth catalyst is reactivated by nitric acid and hydrochloric acid in some documents, but the loss of active components is large and is about 60-70 percent, so that a regeneration method of the rare earth-based SCR denitration catalyst is urgently needed.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a regeneration method of a rare earth-based SCR denitration catalyst, which basically has no loss of active components, no solid waste, small wastewater amount and high denitration efficiency of the regenerated catalyst.
The regeneration method of the rare earth-based SCR denitration catalyst comprises the following steps:
(1) Removing fly ash and ammonium bisulfate, and cleaning the pore channel: putting the deactivated catalyst into a cleaning kettle, adding water to immerse the catalyst, and adding a cleaning agent; the cleaning agent is one or more of hydrogen peroxide, acetonitrile or ethylene glycol dimethyl ether, and the mass ratio of the deactivated catalyst to the cleaning agent is 1000:2 to 5, the pressure in the kettle is 0.2 to 0.4MPa, the temperature is 15 to 20 ℃, and the time is 10 to 20 minutes;
(2) Starting steam to heat to 70-110 ℃, and controlling the pressure in the kettle to be-5 to-9 kPa for 5-15 minutes;
(3) Cleaning: cooling to 15-20 ℃, opening a discharge valve at the bottom of the cleaning kettle, discharging cleaning liquid, and pumping the cleaning liquid into a waste liquid tank; opening a pure water pipeline valve and a pure water pump, pumping pure water to wash the catalyst clean, and immersing the catalyst in the pure water in the kettle;
(4) Removing heavy metals: adding a saturated rare earth solution to immerse the catalyst;
(5) Adding organic acid to react, wherein the reaction pressure is normal pressure, the reaction time is 20-30 minutes, and the reaction temperature is 20-30 ℃;
(6) After the reaction is finished, adding an adsorbent for 20-30 minutes at the temperature of 20-30 ℃;
(7) Cleaning: opening a pure water pipeline valve and a pure water pump, pumping pure water to wash the catalyst completely, opening a discharge valve at the bottom of the kettle, opening a rare earth solution discharge pump, and pumping the unsaturated rare earth solution into a storage tank;
(8) And (3) drying: and (5) putting the catalyst into a vacuum drying oven for drying, and completing the regeneration of the catalyst.
Wherein:
in the step (1), after adding the cleaning agent, introducing nitrogen or air for pressurization.
In the step (3), the cleaning liquid in the waste liquid tank is pumped into a diaphragm filter press, the air permeability of the filter cloth is 1-3%, and the circulation time is not less than 20 minutes in the filter press process; and (3) after the filtrate is transparent and has no particles, beating the filtrate to the step (1) for recycling. After being used for many times, the wastewater is treated.
In the step (4), the saturated rare earth solution is one or more of a cerium nitrate solution, a zirconium nitrate solution, a lanthanum nitrate solution or a neodymium nitrate solution.
In the step (5), the organic acid is one or more of salicylic acid, stearic acid or ethylene diamine tetraacetic acid, and the mass of the added organic acid is 0.1-0.5 per mill of the mass of the catalyst.
In the step (6), the adsorbent is one or more of activated carbon, silicon dioxide or silicon-aluminum spinel, and the mass of the adsorbent is 1-2 per mill of that of the catalyst.
In the step (7), pumping the unsaturated rare earth solution to a membrane filter press for filter pressing, wherein the air permeability of filter cloth is 3-5%, pumping the filtrate into a storage tank after the filtrate is transparent and has no particles, starting steam for heating, concentrating into a saturated solution, and pumping to the step (4) for recycling. Filter cakes subjected to filter pressing by the membrane filter press are mainly used as adsorbents, and the adsorbents are roasted and regenerated and recycled to the step (6); the roasting temperature is 500-600 ℃, and the roasting time is 30-60 minutes.
In the step (8), the drying pressure is-0.92 to-0.98 MPa, the drying temperature is 70 to 80 ℃, and the drying time is 1 hour.
Compared with the prior art, the invention has the following beneficial effects:
(1) The traditional catalyst regeneration is cleaned by pure water, nitrogen or air, and only impurities on the surface layer of the catalyst can be removed. The invention can clean impurities in micropores, mesopores and macropores by adding the cleaning agent, and the cleaning effect is far better than that of water washing or gas washing.
(2) The traditional catalyst regeneration uses nitric acid, hydrochloric acid or sulfuric acid to remove heavy metal oxides, and the rare earth element loss rate is extremely high because the activity of the rare earth oxides is stronger than that of the heavy metal oxides. The invention stops the reaction of acid and rare earth oxide by adding saturated rare earth solution due to salting-out effect, and the loss rate of rare earth elements is extremely low.
(3) The invention forms complex compound by using organic acid to react with heavy metal, and the complex compound is absorbed by the absorbent. The adsorbent can be regenerated by roasting and recycled, and no solid waste is generated in the regeneration process of the deactivated catalyst.
(4) The regeneration method of the rare earth-based SCR denitration catalyst has the advantages of basically no loss of active components, small waste water amount and high denitration efficiency of the regenerated catalyst, which is 96-99% of the activity of the original catalyst.
Drawings
FIG. 1 is a process flow diagram of a method of regenerating a rare earth-based SCR denitration catalyst of the present invention.
Detailed Description
The present invention is further illustrated by, but is not limited to, the following examples.
All the starting materials used in the examples are commercially available, except where otherwise indicated.
Example 1
Weighing 400kg of deactivated rare earth-based SCR catalyst, and filling the catalyst into a container with the diameter of 1m 3 Cleaning the kettle. The pure water pump was started, and after adding pure water to immerse the catalyst, 2kg of hydrogen peroxide was added. And opening a nitrogen valve, introducing nitrogen, and closing the valve when the pressure in the kettle is 0.2 MPa. The temperature was 16 ℃ for 10 minutes.
And opening a steam valve, and slowly opening a vacuum valve when the temperature of the materials in the heating kettle is 90 ℃. When the pressure in the autoclave was lowered to-6 kPa, the holding time was 10 minutes. The observation is carried out by cleaning the sight glass of the kettle, no bubble is generated in the kettle, and the circulating cooling water valve is opened to start cooling. And when the temperature in the kettle is 20 ℃, opening a discharge valve at the bottom of the cleaning kettle, discharging the cleaning liquid, and pumping the cleaning liquid into a waste liquid tank. And opening a pure water pipeline valve and a pure water pump, pumping pure water to clean the catalyst, pumping cleaning liquid into a waste liquid tank, and closing a bottom valve of the cleaning kettle.
Adding saturated rare earth solution to make the liquid level of the saturated rare earth solution slightly higher than that of the catalyst. The saturated rare earth solution is a cerous nitrate solution and a zirconium nitrate solution. Adding 60g of ethylenediamine tetraacetic acid, wherein the reaction pressure is normal pressure, the reaction time is 30 minutes, and the reaction temperature is 20 ℃. After the reaction, 0.8kg of powdered activated carbon is added for 30 minutes at 30 ℃.
And (4) opening a pure water pipeline valve and a pure water pump, pumping pure water to flush the catalyst, opening a discharge valve at the bottom of the kettle, opening a rare earth solution discharge pump, and pumping the rare earth solution into a storage tank.
The catalyst is put into a vacuum drying oven, the pressure is-0.95 MPa, the temperature is 75 ℃, the time is 1 hour, and the catalyst regeneration is finished. Pumping the liquid in the waste liquid tank to a membrane filter press for filter pressing, wherein the air permeability of filter cloth is 1%, and pumping the filtrate to a cleaning kettle for recycling after the filtrate is transparent and has no particles. After being used for many times, the wastewater is treated.
Pumping the liquid in the storage tank to a membrane filter press for filter pressing, wherein the air permeability of filter cloth is 3%, heating and concentrating the filtrate into saturated solution by steam after the filtrate is transparent and has no particles, and pumping the saturated solution to a cleaning kettle for recycling. And (3) putting the filter cake into a kiln, roasting at 500 ℃ for 30 minutes, and cooling the adsorbent to normal temperature for recycling.
TABLE 1
Figure GDA0004057412780000031
Figure GDA0004057412780000041
Example 2
Weighing 400kg of deactivated rare earth-based SCR catalyst, and filling the catalyst into a container with the diameter of 1m 3 Cleaning the kettle. The pure water pump was started, and after the catalyst was immersed in pure water, 1kg of acetonitrile was added. And opening an air valve, introducing air, and closing the valve when the pressure in the kettle is 0.3 MPa. The temperature was 16 ℃ for 10 minutes.
And opening a steam valve, and slowly opening a vacuum valve when the temperature of the materials in the heating kettle is 100 ℃. When the pressure in the autoclave decreased to-7 kPa, the holding time was 15 minutes. The observation is carried out by cleaning the sight glass of the kettle, no bubble is generated in the kettle, and the circulating cooling water valve is opened to start cooling. And when the temperature in the kettle is 20 ℃, opening a discharge valve at the bottom of the cleaning kettle, discharging the cleaning liquid, and pumping the cleaning liquid into a waste liquid tank. And opening a pure water pipeline valve and a pure water pump, pumping pure water to clean the catalyst, pumping cleaning liquid into a waste liquid tank, and closing a bottom valve of the cleaning kettle.
Adding saturated rare earth solution to make the liquid level of the saturated rare earth solution be slightly higher than that of the catalyst. The saturated rare earth solution is neodymium nitrate solution and lanthanum nitrate solution. Adding 50g of salicylic acid, wherein the reaction pressure is normal pressure, the reaction time is 20 minutes, and the reaction temperature is 20 ℃. After the reaction, 0.6kg of silicon dioxide is added, the adsorption time is 30 minutes, and the adsorption temperature is 20 ℃.
And (3) opening a pure water pipeline valve and a pure water pump, pumping pure water to wash the catalyst completely, opening a discharge valve at the bottom of the kettle, opening a rare earth solution discharge pump, and pumping the rare earth solution into a storage tank.
The catalyst is put into a vacuum drying oven, the pressure is-0.95 MPa, the temperature is 80 ℃, the time is 1 hour, and the catalyst regeneration is finished. Pumping the liquid in the waste liquid tank to a membrane filter press for filter pressing, wherein the air permeability of filter cloth is 1%, and pumping the filtrate to a cleaning kettle for recycling after the filtrate is transparent and has no particles. After being used for many times, the wastewater is treated by sewage.
Pumping the liquid in the storage tank to a membrane filter press for filter pressing, wherein the air permeability of filter cloth is 4%, heating and concentrating the filtrate into saturated solution by steam after the filtrate is transparent and has no particles, and pumping the saturated solution to a cleaning kettle for recycling. And (3) putting the filter cake into a kiln, roasting at the temperature of 550 ℃ for 45 minutes, and cooling the adsorbent to normal temperature for recycling.
TABLE 2
Figure GDA0004057412780000042
Figure GDA0004057412780000051
Example 3
Weighing 400kg of deactivated rare earth-based SCR catalyst, and filling the catalyst into a container with the diameter of 1m 3 Cleaning the kettle. Starting a pure water pump, adding pure water to immerse the catalyst, and adding the ethylene glycolAlcohol dimethyl ether 1.5kg. And opening a nitrogen valve, introducing nitrogen, and closing the valve when the pressure in the kettle is 0.3 MPa. The temperature was 18 ℃ for 15 minutes.
And opening a steam valve, and slowly opening a vacuum valve when the temperature of the materials in the heating kettle is 105 ℃. When the pressure in the autoclave decreased to-6 kPa, the holding time was 10 minutes. The observation is carried out by cleaning the sight glass of the kettle, no bubble is generated in the kettle, and the circulating cooling water valve is opened to start cooling. And when the temperature in the kettle is 20 ℃, opening a discharge valve at the bottom of the cleaning kettle, discharging the cleaning liquid, and pumping the cleaning liquid into a waste liquid tank. And opening a pure water pipeline valve and a pure water pump, pumping pure water to clean the catalyst, pumping cleaning liquid into a waste liquid tank, and closing a bottom valve of the cleaning kettle.
Adding saturated rare earth solution to make the liquid level of the saturated rare earth solution be slightly higher than that of the catalyst. The saturated rare earth solution is a cerous nitrate solution and a neodymium nitrate solution. 100g of stearic acid is added, the reaction pressure is normal pressure, the reaction time is 30 minutes, and the reaction temperature is 20 ℃. After the reaction is finished, 0.4kg of silicon-aluminum spinel is added for 30 minutes at the temperature of 20 ℃.
And (4) opening a pure water pipeline valve and a pure water pump, pumping pure water to flush the catalyst, opening a discharge valve at the bottom of the kettle, opening a rare earth solution discharge pump, and pumping the rare earth solution into a storage tank.
The catalyst is put into a vacuum drying oven, the pressure is-0.95 MPa, the temperature is 80 ℃, the time is 1 hour, and the catalyst regeneration is finished. Pumping the liquid in the waste liquid tank to a membrane filter press for filter pressing, wherein the air permeability of filter cloth is 1%, and pumping the filtrate to a cleaning kettle for recycling after the filtrate is transparent and has no particles. After being used for many times, the wastewater is treated.
Pumping the liquid in the storage tank to a membrane filter press for filter pressing, wherein the air permeability of filter cloth is 3%, heating and concentrating the filtrate into saturated solution by steam after the filtrate is transparent and has no particles, and pumping the saturated solution to a cleaning kettle for recycling. And (3) putting the filter cake into a kiln, and roasting at 540 ℃ for 60 minutes. The adsorbent is cooled to normal temperature and then recycled.
TABLE 3
Figure GDA0004057412780000052
Figure GDA0004057412780000061
Example 4
Weighing 400kg of deactivated rare earth-based SCR catalyst, and filling the catalyst into a container with the diameter of 1m 3 Cleaning the kettle. And starting a pure water pump, adding pure water to immerse the catalyst, and then adding 0.5kg of acetonitrile and 0.5kg of ethylene glycol dimethyl ether. And opening a nitrogen valve, introducing nitrogen, and closing the valve when the pressure in the kettle is 0.3 MPa. The temperature was 16 ℃ for 10 minutes.
And opening a steam valve, and slowly opening a vacuum valve when the temperature of the materials in the heating kettle is 105 ℃. When the pressure in the autoclave decreased to-8 kPa, the holding time was 10 minutes. The kettle is cleaned, the sight glass is observed, basically no bubbles are generated in the kettle, and the circulating cooling water valve is opened to start cooling. And when the temperature in the kettle is 20 ℃, opening a discharge valve at the bottom of the cleaning kettle, discharging the cleaning liquid, and pumping the cleaning liquid into a waste liquid tank. And opening a pure water pipeline valve and a pure water pump, pumping pure water to clean the catalyst, pumping cleaning liquid into a waste liquid tank, and closing a bottom valve of the cleaning kettle.
Adding saturated rare earth solution to make the liquid level of the saturated rare earth solution be slightly higher than that of the catalyst. The saturated rare earth solution is a cerous nitrate solution, a zirconium nitrate solution and a neodymium nitrate solution. Adding 40g of stearic acid and 40g of ethylene diamine tetraacetic acid, wherein the reaction pressure is normal pressure, the reaction time is 30 minutes, and the reaction temperature is 20 ℃. After the reaction, 0.4kg of powdered activated carbon and 0.2kg of silicon dioxide are added for 30 minutes at the temperature of 30 ℃.
And (3) opening a pure water pipeline valve and a pure water pump, pumping pure water to wash the catalyst completely, opening a discharge valve at the bottom of the kettle, opening a rare earth solution discharge pump, and pumping the rare earth solution into a storage tank.
The catalyst is put into a vacuum drying oven, the pressure is-0.95 MPa, the temperature is 75 ℃, the time is 1 hour, and the catalyst regeneration is completed. Pumping the liquid in the waste liquid tank to a membrane filter press for filter pressing, wherein the air permeability of filter cloth is 1%, and pumping the filtrate to a cleaning kettle for recycling after the filtrate is transparent and has no particles. After being used for many times, the wastewater is treated.
Pumping the liquid in the storage tank to a membrane filter press for filter pressing, wherein the air permeability of filter cloth is 3%, heating and concentrating the filtrate into saturated solution by steam after the filtrate is transparent and has no particles, and pumping the saturated solution to a cleaning kettle for recycling. And (3) putting the filter cake into a kiln, and roasting at the temperature of 600 ℃ for 40 minutes. The adsorbent is cooled to normal temperature and then recycled.
TABLE 4
Figure GDA0004057412780000062
Figure GDA0004057412780000071
Comparative example 1
Weighing 400kg of deactivated rare earth-based SCR catalyst, and filling the catalyst into a container with the diameter of 1m 3 Cleaning the kettle. And starting a pure water pump, and adding pure water to immerse the catalyst. And opening a nitrogen valve, introducing nitrogen, and closing the valve when the pressure in the kettle is 0.2 MPa. The temperature is 20 ℃ and the time is 10 minutes. Unlike example 1, no cleaning agent was used in this step.
And opening a steam valve, and slowly opening a vacuum valve when the temperature of the materials in the heating kettle is 90 ℃. When the pressure in the autoclave decreased to-6 kPa, the holding time was 10 minutes. The kettle is cleaned, the sight glass is observed, basically no bubbles are generated in the kettle, and the circulating cooling water valve is opened to start cooling. And when the temperature in the kettle is 20 ℃, opening a discharge valve at the bottom of the cleaning kettle, discharging the cleaning liquid, and pumping the cleaning liquid into a waste liquid tank. And opening a pure water pipeline valve and a pure water pump, pumping pure water to clean the catalyst, pumping cleaning liquid into a waste liquid tank, and closing a bottom valve of the cleaning kettle.
Adding saturated rare earth solution to make the liquid level of the saturated rare earth solution slightly higher than that of the catalyst. The saturated rare earth solution is cerous nitrate and zirconium nitrate. Adding 60g of ethylenediamine tetraacetic acid, wherein the reaction pressure is normal pressure, the reaction time is 30 minutes, and the reaction temperature is 20 ℃. After the reaction, 0.8kg of powdered activated carbon is added for 30 minutes at 30 ℃.
And (3) opening a pure water pipeline valve and a pure water pump, pumping pure water to wash the catalyst completely, opening a discharge valve at the bottom of the kettle, opening a rare earth solution discharge pump, and pumping the rare earth solution into a storage tank.
The catalyst is put into a vacuum drying oven, the pressure is-0.95 MPa, the temperature is 75 ℃, the time is 1 hour, and the catalyst regeneration is finished. Pumping the liquid in the waste liquid tank to a membrane filter press for filter pressing, wherein the air permeability of filter cloth is 1%, and pumping the filtrate to a cleaning kettle for recycling after the filtrate is transparent and has no particles. After being used for many times, the wastewater is treated.
Pumping the liquid in the storage tank to a membrane filter press for filter pressing, wherein the air permeability of filter cloth is 3%, heating and concentrating the filtrate into saturated solution by steam after the filtrate is transparent and has no particles, and pumping the saturated solution to a cleaning kettle for recycling. And (3) putting the filter cake into a kiln, roasting at 500 ℃ for 30 minutes, and cooling the adsorbent to normal temperature for recycling.
TABLE 5
Figure GDA0004057412780000072
Figure GDA0004057412780000081
Comparative example 2
Weighing 400kg of deactivated rare earth-based SCR catalyst, and filling the catalyst into a container with the diameter of 1m 3 Cleaning the kettle. The pure water pump was started, and after adding pure water to immerse the catalyst, 1kg of hydrogen peroxide was added. And opening a nitrogen valve, introducing nitrogen, and closing the valve when the pressure in the kettle is 0.2 MPa. The temperature was 16 ℃ for 10 minutes.
And opening a steam valve, and slowly opening a vacuum valve when the temperature of the materials in the heating kettle is 90 ℃. When the pressure in the autoclave decreased to-6 kPa, the holding time was 10 minutes. The observation is carried out by cleaning the sight glass of the kettle, no bubble is generated in the kettle, and the circulating cooling water valve is opened to start cooling. And when the temperature in the kettle is 20 ℃, opening a discharge valve at the bottom of the cleaning kettle, discharging the cleaning liquid, and pumping the cleaning liquid into a waste liquid tank. And opening a pure water pipeline valve and a pure water pump, pumping pure water to clean the catalyst, pumping cleaning liquid into a waste liquid tank, and closing a bottom valve of the cleaning kettle.
Adding unsaturated rare earth solution to make the liquid level of the unsaturated rare earth solution slightly higher than that of the catalyst. The unsaturated rare earth solution is cerium nitrate and zirconium nitrate. 100g of concentrated nitric acid is added, the reaction pressure is normal pressure, the reaction time is 30 minutes, and the reaction temperature is 20 ℃. After the reaction, 0.8kg of powdered activated carbon is added for 30 minutes at 30 ℃. Unlike example 1, this step employs concentrated nitric acid.
And (3) opening a pure water pipeline valve and a pure water pump, pumping pure water to wash the catalyst completely, opening a discharge valve at the bottom of the kettle, opening a rare earth solution discharge pump, and pumping the rare earth solution into a storage tank.
The catalyst is put into a vacuum drying oven, the pressure is-0.95 MPa, the temperature is 75 ℃, the time is 1 hour, and the catalyst regeneration is finished. Pumping the liquid in the waste liquid tank to a membrane filter press for filter pressing, wherein the air permeability of filter cloth is 1%, and pumping the filtrate to a cleaning kettle for recycling after the filtrate is transparent and has no particles. After being used for many times, the wastewater is treated.
Pumping the liquid in the storage tank to a membrane filter press for filter pressing, wherein the air permeability of filter cloth is 3%, heating and concentrating the filtrate into saturated solution by steam after the filtrate is transparent and has no particles, and pumping the saturated solution to a cleaning kettle for recycling. And (3) putting the filter cake into a kiln, roasting at 500 ℃ for 30 minutes, and cooling the adsorbent to normal temperature for recycling.
TABLE 6
Figure GDA0004057412780000082
Figure GDA0004057412780000091
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Claims (6)

1. A regeneration method of a rare earth-based SCR denitration catalyst is characterized by comprising the following steps: the method comprises the following steps:
(1) Removing fly ash and ammonium bisulfate, and cleaning the pore channel: putting the deactivated catalyst into a cleaning kettle, adding water to immerse the catalyst, and adding a cleaning agent; the cleaning agent is one or more of hydrogen peroxide, acetonitrile or ethylene glycol dimethyl ether, and the mass ratio of the deactivated catalyst to the cleaning agent is 1000:2 to 5, the pressure in the kettle is 0.2 to 0.4MPa, the temperature is 15 to 20 ℃, and the time is 10 to 20 minutes;
(2) Starting steam to heat to 70-110 ℃, and controlling the pressure in the kettle to be-5 to-9 kPa for 5-15 minutes;
(3) Cleaning: cooling to 15-20 ℃, opening a discharge valve at the bottom of the cleaning kettle, discharging cleaning liquid, and pumping the cleaning liquid into a waste liquid tank; opening a pure water pipeline valve and a pure water pump, pumping pure water to wash the catalyst clean, and immersing the catalyst in the pure water in the kettle;
(4) Removing heavy metals: adding a saturated rare earth solution to immerse the catalyst;
(5) Adding organic acid to react under normal pressure for 20-30 min at 20-30 deg.c;
(6) After the reaction is finished, adding an adsorbent for 20-30 minutes at the temperature of 20-30 ℃;
(7) Cleaning: opening a pure water pipeline valve and a pure water pump, pumping pure water to wash the catalyst completely, opening a discharge valve at the bottom of the kettle, opening a rare earth solution discharge pump, and pumping the unsaturated rare earth solution into a storage tank;
(8) And (3) drying: putting the catalyst into a vacuum drying oven for drying, and finishing the regeneration of the catalyst;
in the step (1), adding a cleaning agent, and introducing nitrogen or air for pressurization;
in the step (5), the organic acid is one or more of salicylic acid, stearic acid or ethylene diamine tetraacetic acid, and the mass of the added organic acid is 0.1-0.3 per mill of the mass of the catalyst;
in the step (6), the adsorbent is one or more of activated carbon, silicon dioxide or silicon-aluminum spinel, and the mass of the adsorbent is 1-2 per mill of that of the catalyst.
2. The method for regenerating a rare earth-based SCR denitration catalyst according to claim 1, wherein: in the step (3), the cleaning fluid in the waste fluid tank is pumped into a membrane filter press, the air permeability of filter cloth is 1-3%, and the circulation time is not less than 20 minutes in the filter press process; and (3) after the filtrate is transparent and has no particles, beating the filtrate to the step (1) for recycling.
3. The method for regenerating a rare earth-based SCR denitration catalyst according to claim 1, wherein: in the step (4), the saturated rare earth solution is one or more of a cerium nitrate solution, a zirconium nitrate solution, a lanthanum nitrate solution or a neodymium nitrate solution.
4. The method for regenerating a rare earth-based SCR denitration catalyst according to claim 1, wherein: and (7) pumping the unsaturated rare earth solution to a membrane filter press for filter pressing, wherein the air permeability of filter cloth is 3-5%, pumping the filtrate into a storage tank after the filtrate is transparent and has no particles, starting steam for heating, concentrating into a saturated solution, and pumping to the step (4) for recycling.
5. The method for regenerating a rare earth-based SCR denitration catalyst according to claim 4, wherein: filter cakes subjected to filter pressing by the membrane filter press are mainly used as adsorbents, and the adsorbents are roasted and regenerated and recycled to the step (6); the roasting temperature is 500-600 ℃, and the roasting time is 30-60 minutes.
6. The method for regenerating a rare earth-based SCR denitration catalyst according to claim 1, wherein: in the step (8), the drying pressure is-0.92 to-0.98 MPa, the drying temperature is 70 to 80 ℃, and the drying time is 1 hour.
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