CN110142064A - A kind of denitrifying catalyst with selective catalytic reduction regeneration technology - Google Patents
A kind of denitrifying catalyst with selective catalytic reduction regeneration technology Download PDFInfo
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- CN110142064A CN110142064A CN201910367025.8A CN201910367025A CN110142064A CN 110142064 A CN110142064 A CN 110142064A CN 201910367025 A CN201910367025 A CN 201910367025A CN 110142064 A CN110142064 A CN 110142064A
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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
- B01D53/96—Regeneration, reactivation or recycling of reactants
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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
- B01J38/02—Heat treatment
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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
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
- B01J38/12—Treating with free oxygen-containing gas
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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
- B01J38/485—Impregnating or reimpregnating with, or deposition of metal compounds or catalytically active elements
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- 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
- B01J38/60—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using acids
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Abstract
The present invention provides a kind of SCR denitration regeneration technologies, it is characterized in that, include: to carry out catalytic oxidation treatment using SCR denitration of the Catalytic oxidation furnace to inactivation, is carbon dioxide by the oxidation of coal of residual in the catalyst, separates it with catalyst in the form of a vapor；Catalytic oxidation furnace fire box temperature is increased again, and SCR denitration is calcined at this temperature, takes out SCR denitration after being cooled to room temperature；SCR denitration after catalysis oxidation is rinsed with deionized water, is then dried.It recycles vaccum suction tube to be sucked by vacuum it, the substance for adhering to, being blocked in catalyst micropore is pumped；SCR catalyst after vacuum suction is placed in cleaning solution and is impregnated, and washes away catalyst with cleaning solution, sufficiently to wash away the impurity component in catalyst.The present invention has favorable regeneration effect, SO2/SO3The features such as conversion ratio is low, regeneration cost is low, environmental-friendly.
Description
Technical field
The present invention relates to catalyst regeneration techniques fields, and in particular to a kind of new selective catalytic reduction (SCR) denitration
The regeneration technology of catalyst.
Background technique
With China's economy and industrial expansion, the trend of cumulative year after year is presented in primary energy consumption, it is contemplated that 2050
Year, China's non-renewable energy demand is up to 6657.4 ten thousand tons.It is counted according to BP in 2016, China consumes the coal in the whole world about 50%
Charcoal, ranking the first in the world.Unquestionably within following quite long one period, energy supply pattern of the China based on coal
It will not occur to sexually revise at all, coal accounting in total energy is difficult lower than 50%.And 80% or more in coal consumed by China
It is used directly or indirectly in burning, generates a large amount of SO2、 NOx, a variety of flue gas pollutants such as Hg, cause serious atmosphere pollution to ask
Topic.For thermal power plant, the discharge amount of sulfur dioxide and nitrogen oxides account for national industrial pollutants total release about 50% with
On, wherein again with discharged nitrous oxides ratio highest.
SCR denitration technology is a kind of gas denitrifying technology efficiently, reliable, mature, is widely used in coal-burning power plant, China
In boiler flue gas denitration system.Catalyst is the core component of SCR system, and general catalyst just will appear mistake using 3 years or so
Appear vividly as.The reason of causing catalyst inactivation mainly has sintering, arsenic poisoning, calcium intoxication, the alkali metal poisoning, SO of catalyst3In
Poison and the blocking of catalyst void dust stratification etc..It is contemplated that discarding after several years or the SCR catalyst of inactivation will become the puzzlement neck
The great solid waste in domain handles problem, therefore the regeneration for studying SCR catalyst has critically important realistic meaning.
At this stage, SCR catalyst regeneration technology both domestic and external mainly include soot blowing, ultrasonic cleaning, chemical cleaning, activity at
Divide several links such as supplement and roasting.Active constituent supplement mainly uses the regeneration activity liquid comprising ammonium metavanadate or ammonium tungstate,
Pretreated inactivation SCR catalyst is impregnated, surface is obtained by calcining process again after a certain period of time and supplements V2O5
Or WO3SCR catalyst, to restoring its denitration activity to a certain degree.It is dissolved in regeneration activity liquid containing vanadium or tungsten
Compound not only will increase regeneration technology cost, also poisonous metal compound will be made further to pollute environment.
Summary of the invention
The object of the present invention is to provide a kind of low costs, the SCR denitration regeneration technology of environmental protection.
In order to achieve the above object, the present invention provides a kind of SCR denitration regeneration technologies, which is characterized in that packet
It includes:
Step 1: carrying out catalytic oxidation treatment using SCR denitration of the Catalytic oxidation furnace to inactivation, urged remaining in
Oxidation of coal in agent is carbon dioxide, separates it with catalyst in the form of a vapor；Catalytic oxidation furnace burner hearth temperature is increased again
SCR denitration is calcined at this temperature to 500-550 DEG C, takes out SCR denitration after being cooled to room temperature by degree；
Step 2: the SCR denitration after catalysis oxidation being rinsed with deionized water, is then dried.It is sharp again
It is sucked by vacuum with vaccum suction tube, the substance for adhering to, being blocked in catalyst micropore is pumped；
Step 3: the SCR catalyst after vacuum suction is placed in cleaning solution and is impregnated, and washes away catalyst with cleaning solution, with
Wash away the impurity component in catalyst；Then SCR catalyst is dried, finally by SCR denitration in negative pressure
It is purged under state using compressed air, to remove catalyst surface attachment and in duct dust granule.
Preferably, the SCR denitration regeneration technology further include:
Step 4: repeating step 1-3, until reaching the requirement of quality control and denitration effect evaluation.
Preferably, SCR catalyst is placed in cleaning solution the impurity component washed away in catalyst in the step 3, most
SCR catalyst is put into blowing-type drying box afterwards dry.
It is highly preferred that the drying temperature is 60~120 DEG C, dry 2~12 hours, heating rate is 5~10 DEG C/
min。
It is highly preferred that the cleaning solution contain account for cleaning solution gross mass 0.1wt%~5.0wt% bleeding agent and
0.1wt%~5.0wt% surfactant, the acid of 90.0wt%~99.8wt%, sour molar concentration be 0.018mol/L~
2.0mol/L。
It is highly preferred that the preparation method of the cleaning solution includes: to close bleeding agent, surfactant and acid-mixed, stirring
10~60 minutes, it is uniformly mixed it, is configured to cleaning solution, pH value is 2~5.
It is highly preferred that the bleeding agent is Phosphate of Polyoxyethylene Isooctyl Ether, aliphatic amine polyoxyethylene ether or alkyl
Phenol polyethenoxy ether.
It is highly preferred that the surfactant is ammonium lauryl sulfate, polyoxyethylene lauryl ether phosphate ammonium
Salt or ammonium lauryl sulfate.
It is highly preferred that the acid is sulfuric acid.
Compared with prior art, the beneficial effects of the present invention are:
1, present invention incorporates chemically and physically means, carry out reparative regeneration to discarded or inactivation SCR denitration,
With favorable regeneration effect, regeneration cost is low, SO2/SO3The features such as conversion ratio is low, environmental-friendly, process flow is easy to operate.
2, the present invention carries out catalysis oxidation, vacuum suction and purging by being repeated several times, and realizes inactivation SCR de-
The regeneration of denox catalyst is repeated several times and carries out catalysis oxidation, also completes the drying and calcination to catalyst module.
Detailed description of the invention
Fig. 1 is SCR denitration regeneration techniques process route chart；
Fig. 2 is catalyst suction tube structural schematic diagram.
Detailed description of the invention:
Vacuum suction machine port 1 is connected, frame 2, stomata 3, regulating valve 4, tube body 5, connection boiler tube port 6 are held.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
Embodiment 1
As shown in Figure 1, a kind of SCR denitration regeneration technology, specific steps are as follows:
(1) catalysis oxidation: using CO (Catalytic Oxidizer, abbreviation CO) Catalytic oxidation furnace, takes the SCR of inactivation de-
Denox catalyst module (150 × 150 × 1000mm) is placed in Catalytic oxidation furnace, carries out catalytic oxidation treatment.Catalytic oxidation furnace is
The activation energy that organic matter is reduced using the effect of catalyst makes the oxidizing temperature of organic matter be reduced to relatively low temperature (example
Such as 300 DEG C) complete oxidation decomposition occurs, generate CO2And H2O.This process is by carbon oxygen remaining in the SCR denitration of inactivation
Carbon dioxide is turned to, separates it with SCR denitration in the form of a vapor, remains in SCR denitration catalysis to eliminate
Carbon in agent.Catalytic oxidation furnace fire box temperature is then risen to 500 DEG C, catalyst module is calcined at this temperature 1.5 hours,
Catalyst module is taken out after being cooled to room temperature.
(2) it is sucked by vacuum: the deionized water of the SCR denitration after catalysis oxidation being rinsed into 15min, is then placed in drum
It is dried in wind formula drying box.SCR denitration after drying process is sucked by vacuum again, the vacuum is taken out
It inhales and uses catalyst vaccum suction tube, as shown in Fig. 2, the catalyst suction tube includes tube body 5,5 upper port 1 of tube body is logical
It crosses connecting tube and is connected to vacuum suction machine, 5 lower port 6 of tube body is arranged on tube body 5 for being connected with Catalytic oxidation furnace spout part
Internal stomata 3 is always passed to, stomata 3 controls openings of sizes by a regulating valve 4.By the way that a regulating valve 4 is arranged on tube body 5,
It can adjust at any time into the air capacity in suction tube, conducive to the catalyst in suction catalysis oxidation boiler tube, will adhere to, be blocked in
Substance in catalyst micropore pumps.
(3) it purges: after vacuum suction, SCR catalyst being placed in cleaning solution and impregnates 15min, and washed away and urged with cleaning solution
Agent 20min, sufficiently to wash away the impurity component in catalyst.Then treated SCR catalyst is put into blowing-type
Dry in drying box, the drying temperature is 80 DEG C, 6 hours dry, and heating rate is 10 DEG C/min, removes catalyst surface
With the cleaning solution of internal residual.The cleaning liquid making method are as follows: weigh Phosphate of Polyoxyethylene Isooctyl Ether 0.05Kg, 12
Alkylsurfuric acid ammonium 0.05Kg (0.2%) weighs the sulfuric acid 49.90Kg (99.8%) that sour molar concentration is 0.5mol/L, is mixed
It closes, stirs 15 minutes, be uniformly mixed it, be configured to 50Kg cleaning solution, pH 4.After drying, by SCR denitration
It is purged under negative pressure state using compressed air, to remove catalyst surface attachment and in duct dust granule, i.e.,
Obtain the SCR denitration of regeneration activating.
To the active testing and regeneration effect of regenerated catalyst module: it is anti-that regenerated catalyst little module being placed in fixed tubular type
Device is answered, catalyst denitration activity is tested in the case where simulating operating condition flue gas condition.It is urged with the denitration activity of regenerated catalyst with fresh
Evaluation index of the ratio of the denitration activity of agent as regeneration effect.The result shows that: the denitration activity of regenerated catalyst is obvious
It improves, activity can be restored to poisoning preceding active 93.1%.
Embodiment 2
Process flow and operating condition with embodiment 1, the difference is that: by Catalytic oxidation furnace burner hearth temperature in step (1)
Degree rises to 550 DEG C, catalyst module is calcined at this temperature 1.5 hours.The result shows that: the denitration activity of regenerated catalyst is bright
Aobvious to improve, activity can be restored to poisoning preceding active 94.3%.
Embodiment 3
Process flow and operating condition with embodiment 1, the difference is that: step cleans liquid making method described in (3)
Are as follows: weigh polyoxyethylene lauryl ether phosphoric acid ester ammonium salt 0.05Kg, (concrete model is fatty amine (alkylamine) polyoxyethylene ether
AC-1210) 0.05Kg (0.2%) weighs the sulfuric acid 49.90Kg (99.8%) that sour molar concentration is 0.5mol/L, stirs 15 points
Clock is uniformly mixed it, is configured to 50Kg cleaning solution.The result shows that: the denitration activity of regenerated catalyst significantly improves, activity
Active 91.3% before can restoring to poisoning.
Embodiment 4
Process flow and operating condition with embodiment 3, the difference is that: by Catalytic oxidation furnace burner hearth temperature in step (1)
Degree rises to 550 DEG C, catalyst module is calcined at this temperature 1.5 hours.The result shows that: the denitration activity of regenerated catalyst is bright
Aobvious to improve, activity can be restored to poisoning preceding active 92.4%.
Embodiment 5
Process flow and operating condition with embodiment 1, the difference is that: step cleans liquid making method described in (3)
Are as follows: weigh alkyl phenol polyoxyethylene ether (concrete model is NP-4 (OP-4TX-4)) 0.1Kg and ammonium lauryl sulfate 0.1Kg
(0.4%), the sulfuric acid 49.80Kg (99.8%) that sour molar concentration is 0.5mol/L is weighed, is mixed, stirs 15 minutes, makes
It is uniformly mixed, and is configured to 50Kg cleaning solution.The result shows that: the denitration activity of regenerated catalyst significantly improves, and activity can be extensive
Active 88.4% before multiple extremely poisoning.
Embodiment 6
Process flow and operating condition with embodiment 5, the difference is that: by Catalytic oxidation furnace burner hearth temperature in step (1)
Degree rises to 550 DEG C, catalyst module is calcined at this temperature 1.5 hours.The result shows that: the denitration activity of regenerated catalyst is bright
Aobvious to improve, activity can be restored to poisoning preceding active 90.1%.
Claims (8)
1. a kind of SCR denitration regeneration technology characterized by comprising
Step 1: carrying out catalytic oxidation treatment using SCR denitration of the Catalytic oxidation furnace to inactivation, catalyst will be remained in
In oxidation of coal be carbon dioxide, separate it with catalyst in the form of a vapor；Catalytic oxidation furnace fire box temperature is increased again extremely
500-550 DEG C, SCR denitration is calcined at this temperature, takes out SCR denitration after being cooled to room temperature；
Step 2: the SCR denitration after catalysis oxidation being rinsed with deionized water, is then dried, is recycled true
Empty pump suction pipe is sucked by vacuum it, and the substance for adhering to, being blocked in catalyst micropore is pumped；
Step 3: the SCR catalyst after vacuum suction being placed in cleaning solution and is impregnated, and washes away catalyst with cleaning solution, to wash away
Impurity component in catalyst；Then SCR catalyst is dried, finally by SCR denitration in negative pressure state
It is lower to be purged using compressed air, to remove catalyst surface attachment and in duct dust granule.
2. SCR denitration regeneration technology as described in claim 1, which is characterized in that the SCR denitration is again
Raw technique further include:
Step 4: repeating step 1-3, until reaching the requirement of quality control and denitration effect evaluation.
3. SCR denitration regeneration technology as described in claim 1, which is characterized in that the drying temperature be 60~
120 DEG C, 2~12 hours dry, heating rate is 5~10 DEG C/min.
4. SCR denitration regeneration technology as described in claim 1, which is characterized in that the cleaning solution, which contains, to be accounted for clearly
The bleeding agent and 0.1wt%~5.0wt% surfactant of washing lotion gross mass 0.1wt%~5.0wt%, 90.0wt%~
The acid of 99.8wt%, sour molar concentration are 0.018mol/L~2.0mol/L.
5. SCR denitration regeneration technology as described in claim 1, which is characterized in that the preparation side of the cleaning solution
Method includes: to close bleeding agent, surfactant and acid-mixed, and adjusting pH value is 2~5, is stirred 10~60 minutes, keeps its mixing equal
It is even, it is configured to cleaning solution.
6. SCR denitration regeneration technology as described in claim 1, which is characterized in that the bleeding agent is isooctanol
Polyoxyethylene ether phosphate.
7. SCR denitration regeneration technology as described in claim 1, which is characterized in that the surfactant is ten
Dialkyl group ammonium sulfate.
8. SCR denitration regeneration technology as described in claim 1, which is characterized in that the acid is sulfuric acid.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114471745A (en) * | 2022-04-06 | 2022-05-13 | 山东万达环保科技有限公司 | Regeneration method of SCR denitration catalyst and application of SCR denitration catalyst in denitration |
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| CN106311287A (en) * | 2016-07-29 | 2017-01-11 | 河北省电力建设调整试验所 | Regeneration method for alkali-metal-poisoning denitration catalyst |
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2019
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| CN102527234A (en) * | 2012-01-29 | 2012-07-04 | 上海电力学院 | Selective catalytic reduction device for flue gas denitrification and application method thereof |
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| CN106311287A (en) * | 2016-07-29 | 2017-01-11 | 河北省电力建设调整试验所 | Regeneration method for alkali-metal-poisoning denitration catalyst |
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| 黄显兵 等: "火电厂SCR烟气脱硝催化剂再生方法进展", 《内蒙古石油化工》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114471745A (en) * | 2022-04-06 | 2022-05-13 | 山东万达环保科技有限公司 | Regeneration method of SCR denitration catalyst and application of SCR denitration catalyst in denitration |
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Application publication date: 20190820 |