CN105435634A - Regeneration method for As-poisoned SCR denitration catalyst - Google Patents
Regeneration method for As-poisoned SCR denitration catalyst Download PDFInfo
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- CN105435634A CN105435634A CN201510922285.9A CN201510922285A CN105435634A CN 105435634 A CN105435634 A CN 105435634A CN 201510922285 A CN201510922285 A CN 201510922285A CN 105435634 A CN105435634 A CN 105435634A
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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
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- B01D—SEPARATION
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/54—Nitrogen compounds
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract
The invention relates to a regeneration method for an As-poisoned SCR denitration catalyst, especially to a catalyst cleaning process for high-efficiency arsenic removal by using a neutral cleaning solution. The regeneration method for the As-poisoned SCR denitration catalyst comprises the following steps: step 1, removing ash of the inactivated catalyst by using a negative pressure dust collector, high-pressure water jet and bubbling; step 2, placing the catalyst obtained in the step 1 in a mixed solution having a pH value of 6.0 to 7.5 and containing a reducing agent, a heavy metal chelator and a microporous penetrating agent for ultrasonic cleaning for 5 to 30 min and then rinsing the obtain for 5 to 30 min; and step 3, taking out the catalyst obtained in the step 2, drying the catalyst at 60 to 120 DEG C for 1 to 2 h and then carrying out roasting at 400 to 450 DEG C for 1 to 4 h so as to obtain the catalyst without harmful components like arsenic, calcium and sulfur. As on the surface of the catalyst is removed by using the simple and highly efficient cleaning method under neutral conditions, active components of the cleaned SCR denitration catalyst are remained to a greatest extent, and original mechanical strength of the SCR denitration catalyst is not reduced.
Description
Technical field
The present invention relates to the catalyst wash technique that a kind of As poisoning SCR denitration renovation process, particularly a kind of pH are neutral cleaning fluid effectively removing arsenic.
Background technology
SCR (SCR) denitration technology becomes the gas denitrifying technology that domestic and international power plant is most widely used because of good, the selective advantages of higher of its denitration effect, the core of this technology is catalyst.Current commercial widely used denitrating catalyst is V
2o
5-WO
3/ TiO
2catalyst series, such catalyst is expensive, accounts for 50% of SCR denitration system total price, and because of the impact by ash content, impurity and poisonous and harmful chemical composition in flue gas in the process used, its catalytic activity can constantly decline until thoroughly lose activity.SCR denitration generally uses just to be needed to change for about 3 years, and in order to save the operating cost of SCR denitration system, thermal power plant can carry out regeneration process to inactivation SCR denitration catalyst.In SCR denitration system actual moving process, As is poisoning is one of common cause causing catalysqt deactivation.China's coal As changes of contents is larger, and from 0.5-80ppm not etc., the especially northwestern such as Inner Mongol and the Three Eastern Provinces, the arsenic content in fire coal is higher.As
2o
3can catalyst surface be deposited on after entering SCR reactor with flue gas, thus cause the As of catalyst surface
2o
3content increases, such as, after Siping electricity generating corporation, Ltd SCR denitration runs certain hour, and its surface A s
2o
3content increases to 1.27% by 0.01%.The As brought into by flue gas
2o
3can be adsorbed on the active sites V of catalyst surface
2o
5and TiO
2on, cause the hydroxyl of catalyst surface by As
2o
3substitute, the As of absorption
2o
3with O
2and V
2o
5reaction generates As
2o
5, As
2o
5occupy and destroy the active sites of catalyst; Meanwhile, As
2o
3diffusion is deposited in catalyst pores, and the diffusion of reacting gas in catalyst is restricted.Be irreversible because SCR denitration As is poisoning, easily cause catalyst activity to reduce, therefore invent the method for a kind of effective removal inactivation SCR denitration catalyst surface arsenic compound, the regeneration issues solving the poisoning SCR denitration of As is very necessary.
Strong acid (H is adopted in the Chinese patent of publication number CN102814201A
2sO
4) highly basic (NaOH) alternating action cleans inactivation SCR denitration catalyst.This invention utilizes As
2o
3be dissolved in the character of soda acid, thus reach the object of arsenic removal.Adopt strong base-weak acid salt (sodium carbonate, sodium acetate etc.) for removing As reagent in the Chinese patent of publication number CN103878034A.This invention utilizes cleaning fluid to be faintly acid, and arsenic compound is dissolved in the character of acid to reach the object of arsenic removal.To adopt in the Chinese patent of publication number CN104857998A under the condition of pH=7-11 with calcium nitrate or lime stone for except As reagent, and be the calcium ion of the dust technology cleaning introducing of 2 with pH.The know-why of this invention is that the arsenic species of catalyst surface in the basic conditions can be free in the solution with the form of arsenious acid and arsenic acid, again by adding calcium ion in solution, make the arsenious acid in itself and solution and arsenic acid generation precipitation reaction generate calcium arsenite, calcium arsenate, thus reach arsenic removal object.(the DeactivationandregenerationofacommercialSCRcatalyst:Comp arisonwithalkalimetalsandarsenic.AppliedCatalysisB:Envir onmental such as YuePeng, 168-169 (2015) 195 – 202) adopt the hydrogen peroxide of 4% to remove the arsenic on inactivation SCR denitration catalyst surface, the know-why of this invention utilizes H
2o
2the arsenic species of catalyst surface are oxidized to pentavalent arsenic soluble in water, thus reach the object of arsenic removal.But there is following problem in above technology.
The mechanical strength of regenerated catalyst can be caused to sustain damage by strong acid and strong base process inactivation SCR denitration catalyst, reduce the service life of SCR denitration; When adopting sodium salt or calcium nitrate to clean As poisoned catalyst, cleaning fluid introduces new toxic component-sodium ion, calcium ion to catalyst surface, causes producing a large amount of waste liquid in follow-up cleaning, and then adds cost for wastewater treatment; Adopt H
2o
2catalyst surface active component V can be caused while the arsenic on solution cleaning inactivation SCR denitration catalyst surface
2o
5run off, the later stage activity increasing conventional regeneration technology implants cost.
Therefore the poisoning SCR denitration renovation process of development of new As, retains SCR denitration mechanical strength and original V thereof
2o
5active component, and the regeneration cost reduced in regenerative process is very necessary.
Summary of the invention
In order to overcome the shortcoming of prior art with not enough, the object of the present invention is to provide the poisoning SCR denitration renovation process of a kind of As.In neutral conditions, with one succinct cleaning method efficiently removing catalyst surface As, farthest retain the active component of SCR denitration after cleaning, and do not reduce the original mechanical strength of SCR denitration.
Realize technical scheme of the present invention as follows:
The poisoning SCR denitration renovation process of a kind of As, is characterized in that, comprise the following steps:
Step 1: decaying catalyst is utilized negative pressure dust removing device and high-pressure water jet, bubbling carries out deashing;
Step 2: catalyst step 1 obtained is placed in the mixed solution ultrasonic cleaning 5-30min containing reducing agent, heavy metal chelant, micropore permeation agent that pH is 6.0-7.5, then rinsing 5-30min;
Step 3: catalyst step 2 obtained takes out, 60-120 DEG C of dry 1-2h, then 400-450 DEG C of roasting 1-4h, obtains the catalyst removing the harmful constituents such as arsenic, calcium, sulphur.
Further, jet pressure 0.4-1MPa in step 1, flow 10-50l/min; Bubbling pressure 0.4-1MPa, flow 3-10m
3/ min, adopts and limits the pressure of jet flow cleaning and the pressure of flow and pressure pulse cleaning and flow, can ensure the effect of jet flow cleaning and bulge cleaning, makes the floating ash on SCR denitration surface and is easy to the dirt that comes off.
Further, the cleaning fluid that described rinsing adopts is deionized water.
Further, the reducing agent in the mixed solution in described step 2 is one or both in ammonium oxalate, ammonium tartrate, and the concentration of described reducing agent in mixed solution is: 1.0-10g/l.
Further, the poisoning SCR denitration renovation process of a kind of As according to claim 1 or 4 any one, described heavy metal chelant is Unithiol or dimercaprol, and the concentration of heavy metal chelant in mixed solution is 0.01-0.7g/l.
Further, described micropore permeation agent is JFC, and the concentration of micropore permeation agent in mixed solution is 0.001-2.0g/l.
In sum, the present invention has following beneficial effect:
1, chemical of the present invention is neutral (pH=6.0-7.5) solution, can not destroy the mechanical strength of SCR denitration, overcome the deficiency of existing cleaning agent.
2, chemical of the present invention contains heavy metal chelant, and As clearance is high, and can not introduce new toxic component on SCR denitration surface.
3, while the method for the invention effectively removes SCR denitration surface A s, eliminated the harmful constituent such as calcium, aluminium, sulphur on inactivation SCR denitration catalyst surface by the synergy of microwave and micropore permeation agent JFC, SCR denitration Adsorption is effectively restored.
4, the method for the invention farthest retains original active component V on SCR denitration surface
2o
5.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is further described.
Embodiment one
The poisoning SCR denitration renovation process of a kind of As, it is characterized in that, comprise the following steps: step 1: decaying catalyst is utilized negative pressure dust removing device, negative pressure dust removing device utilizes high pressure draught to purge SCR denitration module, the fouling that the floating ash and being easy to of going out surface comes off, then, carries out high-pressure water jet by SCR denitration module, bubbling carries out deashing, the pressure of described high-pressure spray is 0.4MPa, flow 10l/min; Bubbling pressure 0.4MPa, flow 3m
3/ min;
Step 2: catalyst step 1 obtained is placed in the mixed solution ultrasonic cleaning 5min containing reducing agent, heavy metal chelant, micropore permeation agent that pH is 6.0, described reducing agent is ammonium tartrate, concentration is 1g/l, heavy metal chelant is DMPS, and concentration is 0.01g/l, and micropore permeation agent is JFC, concentration is 0.001g/l, after ultrasonic cleaning, SCR denitration module is carried out rinsing, rinsing time is 5min; The cleaning fluid of rinsing is deionized water;
Step 3: catalyst step 2 obtained takes out, 60 DEG C of dry 2h, then 400 DEG C of roasting 4h, obtains the catalyst removing the harmful constituents such as arsenic, calcium, sulphur.
Embodiment two
The poisoning SCR denitration renovation process of a kind of As, it is characterized in that, comprise the following steps: step 1: decaying catalyst is utilized negative pressure dust removing device, negative pressure dust removing device utilizes high pressure draught to purge SCR denitration module, the fouling that the floating ash and being easy to of going out surface comes off, then, carries out high-pressure water jet by SCR denitration module, bubbling carries out deashing, the pressure of described high-pressure spray is 1MPa, flow 50l/min; Bubbling pressure 1MPa, flow 10m
3/ min;
Step 2: catalyst step 1 obtained is placed in the mixed solution ultrasonic cleaning 30min containing reducing agent, heavy metal chelant, micropore permeation agent that pH is 7.5, described reducing agent is ammonium oxalate, concentration is 10g/l, heavy metal chelant is dimercaprol, and concentration is 0.7g/l, and micropore permeation agent is JFC, concentration is 2g/l, after ultrasonic cleaning, SCR denitration module is carried out rinsing, rinsing time is 5min; The cleaning fluid of rinsing is deionized water;
Step 3: catalyst step 2 obtained takes out, 120 DEG C of dry 1h, then 450 DEG C of roasting 1h, obtains the catalyst removing the harmful constituents such as arsenic, calcium, sulphur.
Embodiment three
The poisoning SCR denitration renovation process of a kind of As, it is characterized in that, comprise the following steps: step 1: decaying catalyst is utilized negative pressure dust removing device, negative pressure dust removing device utilizes high pressure draught to purge SCR denitration module, the fouling that the floating ash and being easy to of going out surface comes off, then, carries out high-pressure water jet by SCR denitration module, bubbling carries out deashing, the pressure of described high-pressure spray is 0.6MPa, flow 20l/min; Bubbling pressure 0.6MPa, flow 6m
3/ min;
Step 2: catalyst step 1 obtained is placed in the mixed solution ultrasonic cleaning 30min containing reducing agent, heavy metal chelant, micropore permeation agent that pH is 7.0, described reducing agent is ammonium tartrate, concentration is 2.5g/l, heavy metal chelant is DMPS, and concentration is 0.54g/l, and micropore permeation agent is JFC, concentration is 0.5g/l, after ultrasonic cleaning, SCR denitration module is carried out rinsing, rinsing time is 20min; The cleaning fluid of rinsing is deionized water;
Step 3: catalyst step 2 obtained takes out, 120 DEG C of dry 1h, then 400 DEG C of roasting 3h, obtains the catalyst removing the harmful constituents such as arsenic, calcium, sulphur.
Embodiment four
The poisoning SCR denitration renovation process of a kind of As, it is characterized in that, comprise the following steps: step 1: decaying catalyst is utilized negative pressure dust removing device, negative pressure dust removing device utilizes high pressure draught to purge SCR denitration module, the fouling that the floating ash and being easy to of going out surface comes off, then, carries out high-pressure water jet by SCR denitration module, bubbling carries out deashing, the pressure of described high-pressure spray is 0.6MPa, flow 20l/min; Bubbling pressure 0.6MPa, flow 6m
3/ min;
Step 2: catalyst step 1 obtained is placed in the mixed solution ultrasonic cleaning 30min containing reducing agent, heavy metal chelant, micropore permeation agent that pH is 7.0, described reducing agent is ammonium tartrate, concentration is 2g/l, heavy metal chelant is dimercaprol, and concentration is 0.65g/l, and micropore permeation agent is JFC, concentration is 0.5g/l, after ultrasonic cleaning, SCR denitration module is carried out rinsing, rinsing time is 20min; The cleaning fluid of rinsing is deionized water;
Step 3: catalyst step 2 obtained takes out, 120 DEG C of dry 1h, then 400 DEG C of roasting 3h, obtains the catalyst removing the harmful constituents such as arsenic, calcium, sulphur.
Embodiment five
The poisoning SCR denitration renovation process of a kind of As, it is characterized in that, comprise the following steps: step 1: decaying catalyst is utilized negative pressure dust removing device, negative pressure dust removing device utilizes high pressure draught to purge SCR denitration module, the fouling that the floating ash and being easy to of going out surface comes off, then, carries out high-pressure water jet by SCR denitration module, bubbling carries out deashing, the pressure of described high-pressure spray is 0.6MPa, flow 20l/min; Bubbling pressure 0.6MPa, flow 6m
3/ min;
Step 2: catalyst step 1 obtained is placed in the mixed solution ultrasonic cleaning 30min containing reducing agent, heavy metal chelant, micropore permeation agent that pH is 7.0, described reducing agent is ammonium tartrate, concentration is 2g/l, heavy metal chelant is DMPS, and concentration is 0.54g/l, and micropore permeation agent is JFC, concentration is 0.5g/l, after ultrasonic cleaning, SCR denitration module is carried out rinsing, rinsing time is 20min; The cleaning fluid of rinsing is deionized water;
Step 3: catalyst step 2 obtained takes out, 120 DEG C of dry 1h, then 400 DEG C of roasting 3h, obtains the catalyst removing the harmful constituents such as arsenic, calcium, sulphur.
Embodiment six
The poisoning SCR denitration renovation process of a kind of As, it is characterized in that, comprise the following steps: step 1: decaying catalyst is utilized negative pressure dust removing device, negative pressure dust removing device utilizes high pressure draught to purge SCR denitration module, the fouling that the floating ash and being easy to of going out surface comes off, then, carries out high-pressure water jet by SCR denitration module, bubbling carries out deashing, the pressure of described high-pressure spray is 0.6MPa, flow 20l/min; Bubbling pressure 0.6MPa, flow 6m
3/ min;
Step 2: catalyst step 1 obtained is placed in the mixed solution ultrasonic cleaning 25min containing reducing agent, heavy metal chelant, micropore permeation agent that pH is 7.0, described reducing agent is ammonium tartrate, concentration is 2.5g/l, heavy metal chelant is dimercaprol, and concentration is 0.5g/l, and micropore permeation agent is JFC, concentration is 0.5g/l, after ultrasonic cleaning, SCR denitration module is carried out rinsing, rinsing time is 15min; The cleaning fluid of rinsing is deionized water;
Step 3: catalyst step 2 obtained takes out, 100 DEG C of dry 1.5h, then 430 DEG C of roasting 3.5h, obtains the catalyst removing the harmful constituents such as arsenic, calcium, sulphur.
Embodiment seven
The poisoning SCR denitration renovation process of a kind of As, is characterized in that, comprise the following steps:
Step 1: decaying catalyst is utilized negative pressure dust removing device, negative pressure dust removing device utilizes high pressure draught to purge SCR denitration module, the fouling that the floating ash and being easy to of going out surface comes off, then, SCR denitration module is carried out high-pressure water jet, bubbling carries out deashing, the pressure of described high-pressure spray is 0.6MPa, flow 20l/min; Bubbling pressure 0.6MPa, flow 6m
3/ min;
Step 2: catalyst step 1 obtained is placed in the mixed solution ultrasonic cleaning 25min containing reducing agent, heavy metal chelant, micropore permeation agent that pH is 7.0, described reducing agent is the mixture of ammonium tartrate and ammonium oxalate, concentration is respectively 2.5g/l and 2g/l, heavy metal chelant is dimercaprol, and concentration is 0.6g/l, and micropore permeation agent is JFC, concentration is 1g/l, after ultrasonic cleaning, SCR denitration module is carried out rinsing, rinsing time is 15min; The cleaning fluid of rinsing is deionized water;
Step 3: catalyst step 2 obtained takes out, 100 DEG C of dry 1.5h, then 430 DEG C of roasting 3.5h, obtains the catalyst removing the harmful constituents such as arsenic, calcium, sulphur.
Use the cleaning catalyst of embodiment 1-7 and decaying catalyst to carry out intensity test, and utilize Xray fluorescence spectrometer (XRF) to detect As clearance, V
2o
5turnover rate and WO
3turnover rate, has carried out active testing to SCR catalyst sample simultaneously.The denitration efficiency of catalyst, SO
2/ SO
3conversion ratio, As
2o
3clearance, V
2o
5turnover rate and WO
3turnover rate is calculated as follows:
Denitration efficiency=(NO
import-NO
outlet)/NO
import× 100%;
SO
2/ SO
3conversion ratio=SO
3 outlets/ SO
2 imports× 100%;
As
2o
3clearance=[(As
2o
3/ TiO
2 inactivations-As
2o
3/ TiO
2 cleanings)]/As
2o
3/ TiO
2 inactivations× 100%;
V
2o
5turnover rate=[(V
2o
5/ TiO
2 inactivations-V
2o
5/ TiO
2 cleanings)]/V
2o
5/ TiO
2 inactivations× 100%;
WO
3turnover rate=[(WO
3/ TiO
2 inactivations-WO
3/ TiO
2 cleanings)]/WO
3/ TiO
2 inactivations× 100%.
Wherein, active testing condition is: reaction temperature 385 DEG C, reaction velocity 18000h
-1, flue gas concentration is 191ppmNO, 480ppmSO
2, 3.0%O
2, ammonia nitrogen ratio is 1; As
2o
3/ TiO
2 inactivationsfor As in decaying catalyst
2o
3, TiO
2relative amount, As
2o
3/ TiO
2 cleaningsfor As in cleaning rear catalyst
2o
3, TiO
2relative amount; V
2o
5/ TiO
2 inactivationsfor V in decaying catalyst
2o
5, TiO
2relative amount, V
2o
5/ TiO
2 cleaningsfor V in cleaning rear catalyst
2o
5, TiO
2relative amount; WO
3/ TiO
2 inactivationsfor WO in decaying catalyst
3, TiO
2relative amount, WO
3/ TiO
2 cleaningsfor WO in cleaning rear catalyst
3, TiO
2relative amount.
(1) SCR catalyst mechanical strength test:
The two SCR denitration sample of column electronic table testing machine to inactivation SCR denitration catalyst and embodiment 1-7 process gained of 3367 types adopting American I nstron company to produce carries out mechanical strength test.Respectively twice compression test is carried out to the axis and radial direction of often organizing catalyst sample, average.Test result is as shown in table 1.
The mechanical strength test result of table 1SCR catalyst sample
Inactivation in table is the SCR denitration of inactivation, and real 1 is that embodiment one processes the SCR denitration obtained, the like.
As shown in Table 1, the SCR denitration of embodiment 1 ~ 5 process gained maintains the mechanical strength of original catalyst.Require in commercial Application that the axial compression strength of SCR catalyst need be greater than 2.0MPa, radial crushing strength need be greater than 1.0MPa.From table 1 data, the compression strength of the SCR denitration after the method for the invention process is adopted to meet commercial Application requirement.
(2) SCR catalyst XRF detects:
Adopt the surface chemistries composition of Xray fluorescence spectrometer (XRF) to the SCR denitration sample of inactivation SCR denitration catalyst and embodiment 1-7 process gained to analyze, XRF testing result is as shown in table 2.
Table 2SCR catalyst sample XRF test result
| Test item | Unit | Real 1 | Real 2 | Real 3 | Real 4 | Real 5 | Real 6 | Real 7 | Inactivation |
| V 2O 5 | ％ | 0.47 | 0.48 | 0.49 | 0.48 | 0.48 | 0.47 | 0.48 | 0.49 |
| WO 3 | ％ | 5.53 | 5.63 | 5.89 | 5.80 | 5.82 | 5.84 | 5.8 | 5.18 |
| As 2O 3 | ％ | 0.41 | 0.38 | 0.39 | 0.40 | 0.06 | 0.05 | 0.21 | 1.27 |
| TiO 2 | ％ | 86.84 | 86.54 | 86.27 | 86.42 | 86.66 | 86.77 | 85.78 | 84.75 |
| SiO 2 | ％ | 5.32 | 5.18 | 5.49 | 5.39 | 5.20 | 5.15 | 5.02 | 4.32 |
| Na 2O | ％ | 0.03 | 0.03 | 0.02 | 0.03 | 0.03 | 0.03 | 0.02 | 0.03 |
| K 2O | ％ | 0.05 | 0.05 | 0.05 | 0.04 | 0.04 | 0.04 | 0.05 | 0.07 |
| Fe 2O 3 | ％ | 0.05 | 0.05 | 0.04 | 0.06 | 0.03 | 0.05 | 0.03 | 0.17 |
| SO 3 | ％ | 0.34 | 0.43 | 0.38 | 0.36 | 0.26 | 0.30 | 0.19 | 1.08 |
| CaO | ％ | 0.05 | 0.04 | 0.08 | 0.05 | 0.02 | 0.04 | 0.03 | 1.09 |
| Al 2O 3 | ％ | 0.03 | 0.05 | 0.04 | 0.05 | 0.03 | 0.04 | 0.03 | 1.17 |
| P 2O 5 | ％ | 0.03 | - | 0.04 | 0.06 | 0.01 | 0.02 | 0.01 | 0.05 |
| ZrO 2 | ％ | 0.05 | 0.05 | 0.05 | 0.05 | 0.05 | 0.05 | 0.05 | 0.06 |
| Nb 2O 5 | ％ | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 |
| MoO 3 | ％ | 0.07 | 0.08 | 0.08 | 0.07 | 0.05 | 0.05 | 0.05 | 0.13 |
| As 2O 3/TiO 2 | ％ | 0.47 | 0.44 | 0.45 | 0.46 | 0.07 | 0.07 | 0.07 | 1.50 |
| As 2O 3Clearance | ％ | 68.67 | 70.67 | 70.00 | 69.33 | 95.33 | 85.33 | 90.35 | / |
| V 2O 5/TiO 2 | ％ | 0.54 | 0.55 | 0.57 | 0.55 | 0.55 | 0.56 | 0.57 | 0.58 |
| V 2O 5Turnover rate | ％ | 6.90 | 5.17 | 5.72 | 5.17 | 5.17 | 5.32 | 5.20 | / |
| WO 3/TiO 2 | ％ | 6.37 | 6.51 | 6.83 | 6.71 | 6.72 | 6.77 | 6.74 | 6.11 |
| WO 3Turnover rate | ％ | 0 | 0 | 0 | 0 | 0 | 0 | 0 | / |
From table 2 data: adopt the method for the invention effectively except other harmful constituents (calcium, aluminium, sulphur) etc. also eliminating SCR denitration surface while As (arsenic removal efficiency is 68 ~ 96%).In embodiment 1 ~ 7, the V on SCR denitration surface
2o
5turnover rate only has 1.0 ~ 7.0%, and WO
3turnover rate is 0.More than analyze and show: it is very feasible that the method for the invention realizes regeneration to inactivation SCR denitration catalyst.
(3) SCR catalyst denitration activity and SO thereof
2/ SO
3conversion ratio is tested
The SCR denitration sample of fixed-bed tube reactor to inactivation SCR denitration catalyst and embodiment 1-7 process gained of normal pressure continuous-flow is adopted to carry out active testing.The denitration efficiency of SCR denitration and SO
2/ SO
3conversion ratio test result is as shown in table 3, table 4:
The denitration efficiency (385 DEG C) of table 3SCR catalyst sample
| Project | Unit | Inactivation | Real 1 | Real 2 | Real 3 | Real 4 | Real 5 | Real 6 | Real 7 |
| Entrance NO | ppm | 191 | 191 | 191 | 191 | 191 | 191 | 191 | 191 |
| Outlet NO | ppm | 87 | 29 | 30 | 25 | 53 | 23 | 35 | 40 |
| Denitration efficiency | ％ | 54.45 | 84.82 | 84.29 | 86.91 | 84.29 | 87.96 | 81.68 | 79.06 |
From table 3 data, the denitration efficiency of the SCR denitration of embodiment 1-7 process gained is obviously better than the denitration efficiency of inactivation SCR denitration catalyst, and the denitration efficiency of the SCR denitration of embodiment 1-7 process gained is about 85%.This shows, adopts the denitration activity of the inactivation SCR denitration catalyst after the inventive method process to be effectively restored.
The SO of table 4SCR catalyst sample
2oxygenation efficiency (385 DEG C)
From table 4 data, the SO of the SCR denitration of embodiment 1-7 process gained
2oxygenation efficiency is only 0.27% ~ 0.29%, much smaller than the SO of inactivation SCR denitration catalyst
2oxygenation efficiency, and the SO of the SCR denitration of embodiment 1-7 process gained
2oxygenation efficiency meets commercial Application requirement.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from Spirit Essence of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (6)
1. the poisoning SCR denitration renovation process of As, is characterized in that, comprise the following steps:
Step 1: decaying catalyst is utilized negative pressure dust removing device and high-pressure water jet, bubbling carries out deashing;
Step 2: catalyst step 1 obtained is placed in the mixed solution ultrasonic cleaning 5-30min containing reducing agent, heavy metal chelant, micropore permeation agent that pH is 6.0-7.5, then rinsing 5-30min;
Step 3: catalyst step 2 obtained takes out, 60-120 DEG C of dry 1-2h, then 400-450 DEG C of roasting 1-4h, obtains the catalyst removing the harmful constituents such as arsenic, calcium, sulphur.
2. the poisoning SCR denitration renovation process of a kind of As according to claim 1, is characterized in that: jet pressure 0.4-1MPa in step 1, flow 10-50l/min; Bubbling pressure 0.4-1MPa, flow 3-10m3/min.
3. the poisoning SCR denitration renovation process of a kind of As according to claim 1, is characterized in that: the cleaning fluid that described rinsing adopts is deionized water.
4. the poisoning SCR denitration renovation process of a kind of As according to claim 1, it is characterized in that: the reducing agent in the mixed solution in described step 2 is one or both in ammonium oxalate, ammonium tartrate, and the concentration of described reducing agent in mixed solution is: 1.0-10g/l.
5. the poisoning SCR denitration renovation process of a kind of As according to claim 1 or 4 any one, it is characterized in that: described heavy metal chelant is 2,3-DMPS or dimercaprol, the concentration of heavy metal chelant in mixed solution is 0.01-0.7g/l.
6. the poisoning SCR denitration renovation process of a kind of As according to claim 5, it is characterized in that: described micropore permeation agent is JFC, the concentration of micropore permeation agent in mixed solution is 0.001-2.0g/l.
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