Summary of the invention
In view of this, one of purpose of the present invention is to provide a kind of denitrating catalyst regenerated liquid, its hypotoxicity, and regeneration effect is good, and the process time is short.
For achieving the above object, technical scheme of the present invention is:
The denitrating catalyst regenerated liquid is made up of cleaning fluid and the active liquid that replenishes, and contains sulfuric acid and emulsifying agent S-185 in the described cleaning fluid, and described activity is replenished liquid and contained vanadic sulfate and ammonium metatungstate.
Further, described denitrating catalyst regenerated liquid is composed as follows:
Cleaning fluid: emulsifying agent S-185 mass fraction is 0.005~1%, and the sulfuric acid molar concentration is 0.2~0.8mol/L.
The active liquid that replenishes: the vanadic sulfate molar concentration is 0.2~0.8mol/L, and the ammonium metatungstate molar concentration is 0.2~0.8mol/L.
Two of purpose of the present invention is to provide a kind of denitrating catalyst renovation process, and this method only needs to be used simple device, can avoid complicated calcination steps, can comparatively fast finish the regeneration of catalyst.
For achieving the above object, technical scheme of the present invention is:
The denitrating catalyst renovation process, concrete steps are: at first, catalyst to be regenerated is at first used cleaning fluid in service sink, adopt the ultrasonic wave mode to remove the hole inside ash of catalyst; Then, in the activation pond, the catalyst soakage that has cleaned is replenished liquid in activity, carry out active component and replenish; At last, will in drying box, carry out drying with the catalyst that has replenished active component.Finally, just obtain the denitrating catalyst of regenerating.
Wherein, ultrasonic cleaning is 10~30 minutes; The active time of replenishing the liquid dipping is 20~60 minutes; Adopt under 80~150 ℃ of hot-air conditions when dry, dried the denitrating catalyst of to regenerate 2~5 hours.
Beneficial effect of the present invention is: since in the cleaning fluid except sulfuric acid solution and emulsifying agent S-185, cleaning process adopts the ultrasonic wave cleaning way simultaneously, therefore, scavenging period only needs 10~30 minutes, only is 1/2 of existing technology; Adopt vanadic sulfate and ammonium metatungstate that catalyst is carried out active component simultaneously and replenish, promptly avoided the severe toxicity of ammonium metavanadate to cause unsafe factor, avoided the complicated technology of the repeatedly roasting of catalyst again.Adopt the denitrating catalyst after this method is regenerated: activity can return to 95~99% of original activity; SO
2/ SO
3Conversion ratio all satisfies the engineering design requirement less than 1%; Simultaneously, regeneration technology is simple to operate, is applicable to industrial scale regeneration.
The specific embodiment
In order to make the purpose, technical solutions and advantages of the present invention clearer, below the preferred embodiments of the present invention are described in detail.
Embodiment 1
One, the preparation of regenerated liquid
1, the preparation of cleaning fluid
In the ultrasonic wave service sink, configuration emulsifying agent S-185 mass fraction is 0.005%, and the molar concentration of sulfuric acid is the mixed solution of 0.8mol/L.Carry out ultrasonic wave and handled 10 minutes, it is mixed, placed aging 1 hour, amount to 200L.
2, the active preparation that replenishes liquid
In the activation pond, the configuration molar concentration is the mixed solution of the ammonium metatungstate of the vanadic sulfate of 0.8mol/L and 0.8mol/L.Carry out mechanical agitation 5 minutes, it is mixed, placed aging 1 hour, amount to 200L.
Two, denitrating catalyst regeneration technology flow process
Discarded catalyst is immersed in the service sink that cleaning fluid is housed, carried out ultrasonic cleaning 10 minutes; Then, catalyst soakage is replenished liquid in activity, flooded 60 minutes; Take out catalyst and be placed in the drying box, 80 ℃ of dryings 5 hours.Catalyst regeneration finishes.
Embodiment 2
One, the preparation of regenerated liquid
1, the preparation of cleaning fluid
In the ultrasonic wave service sink, configuration emulsifying agent S-185 mass fraction is 1%, H
2SO
4Molar concentration is the mixed solution of 0.2mol/L.Carry out ultrasonic processing 10 minutes, it is mixed, placed aging 1 hour, obtain cleaning fluid, amount to 200L.
2, the active preparation that replenishes liquid
In the activation pond, the configuration molar concentration is the mixed solution of the ammonium metatungstate of the vanadic sulfate of 0.2 mol/L and 0.2mol/L.Carry out mechanical agitation 5 minutes, it is mixed, placed aging 1 hour, obtain the active liquid that replenishes, amount to 200L.
Two, denitrating catalyst regeneration technology flow process
Discarded catalyst is immersed in the service sink that cleaning fluid is housed, carried out ultrasonic cleaning 30 minutes; Then, catalyst soakage is replenished liquid in activity, flooded 20 minutes; Take out catalyst and be placed in the drying box, 150 ℃ of dryings 2 hours.Catalyst regeneration finishes.
Embodiment 3
One, the preparation of regenerated liquid
1, the preparation of cleaning fluid
In the ultrasonic wave service sink, configuration emulsifying agent S-185 mass fraction is 0.5%, H
2SO
4Molar concentration is the mixed solution of 0.4mol/L.Carry out ultrasonic processing 10 minutes, it is mixed, placed aging 1 hour, amount to 200L.
2, the active preparation that replenishes liquid
In the activation pond, the configuration molar concentration is the VOSO of 0.8 mol/L
4Mixed solution solution with the ammonium metatungstate of 0.8mol/L.Carry out mechanical agitation 5 minutes, it is mixed, placed aging 1 hour, amount to 200L.
Two, denitrating catalyst regeneration technology
Discarded catalyst is immersed in the service sink that cleaning fluid is housed, carried out ultrasonic cleaning 20 minutes; Then, catalyst soakage is replenished liquid in activity, flooded 30 minutes; Take out catalyst and be placed in the drying box, 120 ℃ of dryings 3 hours.Catalyst regeneration finishes.
Embodiment 4
One, the preparation of regenerated liquid
1, the preparation of cleaning fluid
In the ultrasonic wave service sink, configuration emulsifying agent S-185 mass fraction is 0.25%, H
2SO
4Molar concentration is the mixed solution of 0.6mol/L.Carry out ultrasonic processing 10 minutes, it is mixed, placed aging 1 hour, amount to 200L.
2, the active preparation that replenishes liquid
In the activation pond, the configuration molar concentration is the VOSO of 0.6 mol/L
4Mixed solution with the ammonium metatungstate of 0.8mol/L.Carry out mechanical agitation 5 minutes, it is mixed, placed aging 1 hour, obtain the active liquid that replenishes, amount to 200L.
Two, denitrating catalyst regeneration technology
Discarded catalyst is immersed in the service sink that cleaning fluid is housed, carried out ultrasonic cleaning 15 minutes; Then, catalyst soakage is replenished liquid in activity, flooded 40 minutes; Take out catalyst and be placed in the drying box, 100 ℃ of dryings 4 hours.Catalyst regeneration finishes.
Embodiment 5
Use the regenerated catalyst and the fresh catalyst of experimental example 1~4 to carry out the catalyst activity contrast, and the SO of test regenerated catalyst
2/ SO
3Conversion ratio.Activity of such catalysts, denitration rate and SO
2/ SO
3Conversion formula is as follows:
Active K=-AV * ln(1-η);
Denitration rate η=(φ
i(NOx)-φ
0(NOx))/φ
i(NOx);
Wherein: φ
i(NOx), φ
0(NOx) be respectively catalyst inlet and exit NOx concentration (ppm)
SO
2/ SO
3Conversion ratio
In the formula:
-SO
2/ SO
3Conversion ratio, %;
The SO of-reactor outlet
3Concentration, μ L/L;
The SO of-reactor inlet
3Concentration, μ L/L butt;
The SO of-reactor inlet
2Concentration, μ L/L butt.
Experiment condition:
The catalyst hole count: 22 * 22, length: 665mm
The catalyst number of plies: 2, catalyst cross section: 150 * 150mm
The engineering Gas Parameters:
Reaction temperature: 380 ℃, flue gas face velocity (AV): 10.55 Nm
3/ (m
2H)
NOx=292ppm,NH
3=292,
SO
2=500ppm, O
2=6%, H
2O=6%。
The The performance test results of table 1 regenerated catalyst
Catalyst sample |
Denitration rate (%) |
Relative activity (K/Ko) |
SO
2/SO
3Conversion ratio (%)
|
Fresh catalyst |
92.5 |
— |
— |
Embodiment 1 |
91.5 |
0.95 |
0.81 |
Embodiment 2 |
91.7 |
0.96 |
0.84 |
Embodiment 3 |
92.1 |
0.98 |
0.85 |
Embodiment 4 |
92.3 |
0.99 |
0.87 |
Result according to embodiment 5 can know that the relative activity of the catalyst after the regeneration (k/Ko) is 0.95-0.99, simultaneously SO
2/ SO
3Conversion ratio (%) is all less than 1%, engineering demands.Wherein, the catalyst regeneration best results of embodiment 4.
Explanation is at last, above embodiment is only unrestricted in order to technical scheme of the present invention to be described, although by invention has been described with reference to the preferred embodiments of the present invention, but those of ordinary skill in the art is to be understood that, can make various changes to it in the form and details, and the spirit and scope of the present invention that do not depart from appended claims and limited.