CN107497299A - A kind of MnOx/ PG denitrating catalyst spent regeneration methods - Google Patents
A kind of MnOx/ PG denitrating catalyst spent regeneration methods Download PDFInfo
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- CN107497299A CN107497299A CN201710953984.9A CN201710953984A CN107497299A CN 107497299 A CN107497299 A CN 107497299A CN 201710953984 A CN201710953984 A CN 201710953984A CN 107497299 A CN107497299 A CN 107497299A
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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
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
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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
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/2073—Manganese
Abstract
The present invention relates to catalyst regeneration field, MnO is specifically providedxThe renovation process of/PG denitrating catalysts, this method comprise the following steps：1st, by the MnO of sulfur poisoningx/ PG denitrating catalysts impregnate in deionized water, are placed in water-bath constant temperature oscillator；2nd, the temperature of water-bath constant temperature oscillator is adjusted to 30 DEG C, and frequency of oscillation is set to 120Hz, changes the solid-to-liquid ratio of decaying catalyst and regenerative agent, and the decaying catalyst remained immersed in deionized water shakes 10min in water-bath constant temperature oscillator.3rd, the MnO that will be treated through step (2)xMicrowave drying is carried out after/PG filtering denitration catalysts, 110 DEG C is warming up to the speed no more than 5 DEG C/min, is incubated 3h, the MnO after being regeneratedx/ PG denitrating catalysts.By the catalyst recovery process, resulting regenerated catalyst activity can return to fresh catalyst activity, add the service life of catalyst, and technical process is simple, and regeneration cost is relatively low, environment-friendly, be adapted to industrialized production and application.
Description
Technical field
The present invention relates to the regeneration field of catalyst, and in particular to after a kind of MnOx/PG denitrating catalysts sulfur poisoning again
Generation method.
Background technology
Nitrogen oxides is to cause one of major air pollutants of environmental problem such as acid rain, photochemical fog, and at present
The emphasis and difficult point of atmospheric environment protection.Various countries are to NOxDischarge have strict limitation, and target more and more higher.China is certainly
Start to NO within 2004xCharges for disposing pollutants are collected, are carried out on a large scale from this denitrating flue gas in China.
SCR (Selective catalytic reduction, SCR) denitration is most main in the world at present
The gas denitrifying technology of stream, wherein, catalyst is the core of technology.The domestic and international research and development master about low-temperature SCR catalyst at present
Concentrate on transition metal oxide, using Mn, Co, Cu as the more of active component.Research shows that low-temperature denitration activity is best
Metal be Mn, its carrier mainly has TiO2, molecular sieve, activated carbon, attapulgite etc., as a result find, using attapulgite to carry
Low-temperature catalyzed performance during the denitrating catalyst of body has well.Attapulgite have easy-formation, high temperature resistant, high mechanical strength,
The advantages that specific surface area is big, the process costs of catalyst are greatly reduced, realize that industrialization provides theoretical foundation for catalyst.
In non-electrical industry flue gas low-temperature denitration, MnOx/ PG low-temperature SCR catalysts have been obtained for extensive use, such as burnt
Low temperature SCR denitration in kiln gas.But MnOx/ PG denitrating catalysts are easily gradually inactivated in middle low temperature environment by sulfur poisoning.
The poisoning and deactivation of catalyst reduces its service life, adds out-of-stock cost.Therefore in order to improve the resource secondary of catalyst
Recovery utilization rate, denitration cost is saved, the regeneration of decaying catalyst just seems particularly necessary and important.
Found by pertinent literature, conventional renovation process has：Washing regeneration, gas hot recycling and reducing/regenerating, generally
In the case of, washing regeneration can wash away the material that catalyst surface deposits.The sulphur that hot recycling can adsorb catalyst surface converts
For SO2.The sulfate reduction of formation can be SO by reducing/regenerating2, while SO2H can be converted into after further treatment2SO4Or element
Sulphur.For example, Ma Jianrong etc. in renovation process to V2O5Water is described in the text of influence one of/AC catalyst simultaneous SO_2 and NO removal activity
Wash regeneration, Ar hot recyclings and 5%NH3These three renovation process of -95%Ar reducing/regeneratings are to V2O5The influence of/AC catalyst activities,
As a result find that although washing can wash away the sulphur-containing substance of catalyst surface, can also wash away amount of activated component, while heat
Regeneration and reducing/regenerating also can make the denitration activity of catalyst have certain recovery.Hu Yufeng etc. is in Mn-Ce/TiO2Low temperature
Washing, hot recycling and reducing gas are employed in selective catalytic reduction catalysts sulfur dioxide poisoning and the text of reproducing characteristic one also
Original regenerates these three methods to Mn-Ce/TiO2Catalyst is regenerated, and as a result finds to wash regeneration effect most in three kinds of methods
It is good.
The content of the invention
Problem to be solved by this invention is to provide a kind of MnOxRenovation process after/PG denitrating catalyst sulfur poisonings, with
Improve the utilization rate of decaying catalyst.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of MnOx/ PG denitrating catalyst spent regeneration methods, comprise the following steps：
1) by sulfur poisoning MnOx/ PG denitrating catalysts impregnate in deionized water, are placed in water-bath constant temperature oscillator；
2) temperature of water-bath constant temperature oscillator is adjusted to 30 DEG C, and frequency of oscillation is set to 120Hz, changes decaying catalyst and again
The solid-to-liquid ratio of raw agent, the decaying catalyst remained immersed in deionized water shake 10min in water-bath constant temperature oscillator；
3) MnO will be treated to obtain through step (2)xMicrowave drying is carried out after/PG catalyst filtrations, with no more than 5 DEG C/min
Heating rate be warming up to 110 DEG C, be incubated 3h, the MnO after being regeneratedx/ PG denitrating catalysts.
Further, in the step 2) of technical solution of the present invention, described solid-to-liquid ratio is set to 2:1、1:1、1:2、1:4 and 1:
6。
Further, in the step 3) of technical solution of the present invention, described microwave drying is at 110 DEG C, dries 3h.
Beneficial effects of the present invention：The present invention is using easy-formation, high temperature resistant, the attapulgite of high mechanical strength as manganese base
The carrier of denitrating catalyst, obtained MnOxStructure will not be destroyed in the regenerative process of/PG catalyst after sulfur poisoning, be preserved
Original physical arrangement, and regeneration effect can be optimized by the solid-to-liquid ratio of failure of adjustment catalyst and regenerative agent.By de-
The ion titrimetry of liquid and the XRF analysis of Mn elements after the test of nitre activity rating, regeneration, at the inventive method regeneration
MnO after reasonx/ PG denitrating catalysts, the ammonium sulfate of its surface deposition is all washed, and active component Mn does not lose
Lose, thus its denitration activity can return to fresh MnOx/ PG denitrating catalysts are horizontal.
The inventive method is easy to operate, environment-friendly, is adapted to industrialized production and application.
Brief description of the drawings
Fig. 1 is the activity rating figure of regenerated catalyst in regenerated catalyst and comparative example in fresh, sulfur poisoning, example 1-5.
Fig. 2 is the SEM figures of fresh MnOx/PG catalyst.
Fig. 3 is the SEM figures of the MnOx/PG catalyst of sulfur poisoning.
Fig. 4 is the SEM figures of the MnOx/PG catalyst after washing regeneration.
Fig. 5 is the ion titrimetry figure of liquid after washing regeneration.
Embodiment
The present invention is described in further detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1
A kind of MnOx/ PG denitrating catalyst spent regeneration methods, comprise the following steps：
1. by the MnO of 2g sulfur poisoningsx/ PG denitrating catalysts are impregnated in 1ml deionized water, are placed on constant temperature water bath and are shaken
Swing in device.
2. adjusting the temperature of water-bath constant temperature oscillator to 30 DEG C, frequency of oscillation is set to 120Hz, will impregnate in deionized water
Decaying catalyst 10min is shaken in water-bath constant temperature oscillator.
3. MnO will be treated to obtain through step (2)xMicrowave drying is carried out after/PG catalyst filtrations, with no more than 5 DEG C/min
Heating rate be warming up to 110 DEG C, be incubated 3h, the MnO after being regeneratedx/ PG denitrating catalysts.
Embodiment 2
A kind of MnOx/ PG denitrating catalyst spent regeneration methods, comprise the following steps：
1. by the MnO of 2g sulfur poisoningsx/ PG denitrating catalysts are impregnated in 2ml deionized water, are placed on constant temperature water bath and are shaken
Swing in device.
2. adjusting the temperature of water-bath constant temperature oscillator to 30 DEG C, frequency of oscillation is set to 120Hz, will impregnate in deionized water
Decaying catalyst 10min is shaken in water-bath constant temperature oscillator.
3. MnO will be treated to obtain through step (2)xMicrowave drying is carried out after/PG catalyst filtrations, with no more than 5 DEG C/min
Heating rate be warming up to 110 DEG C, be incubated 3h, the MnO after being regeneratedx/ PG denitrating catalysts.
Embodiment 3
A kind of MnOx/ PG denitrating catalyst spent regeneration methods, comprise the following steps：
1. by the MnO of 2g sulfur poisoningsx/ PG denitrating catalysts are impregnated in 4ml deionized water, are placed on constant temperature water bath and are shaken
Swing in device.
2. adjusting the temperature of water-bath constant temperature oscillator to 30 DEG C, frequency of oscillation is set to 120Hz, will impregnate in deionized water
Decaying catalyst 10min is shaken in water-bath constant temperature oscillator.
3. MnO will be treated to obtain through step (2)xMicrowave drying is carried out after/PG catalyst filtrations, with no more than 5 DEG C/min
Heating rate be warming up to 110 DEG C, be incubated 3h, the MnO after being regeneratedx/ PG denitrating catalysts.
Embodiment 4
A kind of MnOx/ PG denitrating catalyst spent regeneration methods, comprise the following steps：
1. by the MnO of 2g sulfur poisoningsx/ PG denitrating catalysts are impregnated in 8ml deionized water, are placed on constant temperature water bath and are shaken
Swing in device.
2. adjusting the temperature of water-bath constant temperature oscillator to 30 DEG C, frequency of oscillation is set to 120Hz, will impregnate in deionized water
Decaying catalyst 10min is shaken in water-bath constant temperature oscillator.
3. MnO will be treated to obtain through step (2)xMicrowave drying is carried out after/PG catalyst filtrations, with no more than 5 DEG C/min
Heating rate be warming up to 110 DEG C, be incubated 3h, the MnO after being regeneratedx/ PG denitrating catalysts.
Embodiment 5
A kind of MnOx/ PG denitrating catalyst spent regeneration methods, comprise the following steps：
1. by the MnO of 2g sulfur poisoningsx/ PG denitrating catalysts are impregnated in 12ml deionized water, are placed on constant temperature water bath
In oscillator.
2. adjusting the temperature of water-bath constant temperature oscillator to 30 DEG C, frequency of oscillation is set to 120Hz, will impregnate in deionized water
Decaying catalyst 10min is shaken in water-bath constant temperature oscillator.
3. MnO will be treated to obtain through step (2)xMicrowave drying is carried out after/PG catalyst filtrations, with no more than 5 DEG C/min
Heating rate be warming up to 110 DEG C, be incubated 3h, the MnO after being regeneratedx/ PG denitrating catalysts.
Comparative example
A kind of MnOx/ PG denitrating catalyst spent regeneration methods：2g decaying catalyst is put into tube furnace, with 5 DEG C/
Min heating rate is warming up to 450 DEG C, lasting 3h, in heating process, uses air as protection gas.
By fresh MnOx/ PG catalyst, sulfur poisoning MnOxThe obtained regeneration MnO of/PG catalyst, embodiment 1-5x/ PG is catalyzed
Agent and the obtained regeneration MnO of comparative examplex/ PG catalyst carries out denitration activity test, and method of testing is as follows：Catalyst denitration is lived
Property evaluation carried out in atmospheric fixed bed reactor, heated by electric tube furnace.Simulated flue gas composition is 600ppmNH3、
600ppmNO, 3%O2, Ar be Balance Air and 400ppm SO2, overall flow rate 350mL/min, air speed 6500h-1.Reaction temperature area
Between be 100 DEG C -300 DEG C.Inlet and outlet NO concentration is measured by Testo350 type flue gas analyzers.The denitration activity of catalyst uses NO
Conversion ratio represent：
In formula,The NO of inlet and outlet concentration is represented respectively
Known by Fig. 1, fresh regeneration MnOx/ PG catalyst agent is by SO2Poison after, its denitration activity is notable
Reduce, drop to 11% by 42% at 150 DEG C, drop to 24% by 86% at 200 DEG C；Sulfur poisoning catalyst is through overheating again
After life, its denitration can only partly recover, and after washing regenerates, its denitration activity can return to fresh level, and inactivate
The solid-to-liquid ratio of catalyst and regenerative agent is not above 1:4.Fig. 2,3 and 4 are fresh catalyst, sulfur poisoning catalyst and regeneration respectively
The SEM figures of catalyst, it can be seen that fresh MnOx/ PG catalyst agent surface smoother, disperse also than more uniform；
After being poisoned in sulfur-bearing atmosphere, catalyst surface will become apparent from being wrapped in one layer " whiteness ", and catalyst occurs aggregation, divided
Dissipate obvious not as good as fresh catalyst；" whiteness " of catalyst surface can effectively be removed through washing by poisoning catalyst, and be recovered
The club shaped structure of catalyst, surface also smoother.Fig. 5 is the ion titrimetry figure of liquid after washing regeneration, wherein solid-liquid
Than for 1:6,1-6 represent 20 DEG C -70 DEG C of temperature (temperature range be 10 DEG C) respectively, it can be seen that are the reason for catalyst sulfur poisoning
The ammonium sulfate of generation is deposited on catalyst surface, and washes regeneration and can all wash away ammonium sulfate.Table 1 is catalyst sulphur
XRF before and after poisoning and washing regeneration, it can be seen that after washing regenerates, the active component of catalyst is not washed away,
Thus activity can return to fresh sample.
Table 1
The foregoing is only a specific embodiment of the invention, but protection scope of the present invention is not limited thereto, affiliated
Those skilled in the art make various modifications or supplement to described specific embodiment or use similar side
Formula substitutes, and method without departing from invention or surmounts scope defined in the claims, all should belong to the present invention's
Protection domain.
Claims (3)
- A kind of 1. MnOx/PG denitrating catalysts spent regeneration method, it is characterised in that comprise the following steps：(1) by sulfur poisoning MnOx/PG denitrating catalysts dipping in deionized water, it is placed in water-bath constant temperature oscillator；(2) temperature of water-bath constant temperature oscillator is adjusted to 30 DEG C, and frequency of oscillation is set to 120, changes decaying catalyst and regenerative agent Solid-to-liquid ratio, the decaying catalyst remained immersed in deionized water shakes 10min in water-bath constant temperature oscillator；(3) will be so treated that to carry out microwave drying after MnOx/PG catalyst filtrations through step (2), with the liter no more than 5 DEG C/min Warm speed is warming up to 110 DEG C, is incubated 3h, the MnOx/PG denitrating catalysts after being regenerated.
- A kind of 2. MnOx/PG denitrating catalysts spent regeneration method according to claim 1, it is characterised in that step (2) Described solid-to-liquid ratio is set to 2:1、1:1、1:2、1:4 and 1:6.
- A kind of 3. MnOx/PG denitrating catalysts spent regeneration method according to claim 2, it is characterised in that step (3) Described microwave drying is at 110 DEG C, dries 3h.
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| CN201710953984.9A CN107497299B (en) | 2017-10-13 | 2017-10-13 | MnO (MnO)xRegeneration method for failure of PG denitration catalyst |
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| CN201710953984.9A CN107497299B (en) | 2017-10-13 | 2017-10-13 | MnO (MnO)xRegeneration method for failure of PG denitration catalyst |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102974405A (en) * | 2012-12-04 | 2013-03-20 | 成都东方凯特瑞环保催化剂有限责任公司 | SCR (selective catalytic reduction) denitration catalyst regenerated liquid and preparation and regeneration methods thereof |
| CN104028315A (en) * | 2014-06-03 | 2014-09-10 | 陈凯 | Regeneration method of sulfur-poisoned selective catalytic reduction (SCR) denitrification catalyst |
| CN104815675A (en) * | 2015-04-09 | 2015-08-05 | 北京大学包头创新研究院 | Selective catalytic reduction denitration catalyst and regeneration method and application thereof |
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- 2017-10-13 CN CN201710953984.9A patent/CN107497299B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102974405A (en) * | 2012-12-04 | 2013-03-20 | 成都东方凯特瑞环保催化剂有限责任公司 | SCR (selective catalytic reduction) denitration catalyst regenerated liquid and preparation and regeneration methods thereof |
| CN104028315A (en) * | 2014-06-03 | 2014-09-10 | 陈凯 | Regeneration method of sulfur-poisoned selective catalytic reduction (SCR) denitrification catalyst |
| CN104815675A (en) * | 2015-04-09 | 2015-08-05 | 北京大学包头创新研究院 | Selective catalytic reduction denitration catalyst and regeneration method and application thereof |
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