CN103433081A - Regeneration method for honeycomb type SCR (Selective Catalytic Reduction) denitration catalyst - Google Patents
Regeneration method for honeycomb type SCR (Selective Catalytic Reduction) denitration catalyst Download PDFInfo
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Abstract
The invention discloses a regeneration method for a honeycomb type SCR (Selective Catalytic Reduction) denitration catalyst, and belongs to the technical field of power environment protection. The regeneration method comprises the following steps: 1) dipping a poisoned honeycomb type SCR catalyst into a diluted sulfuric acid solution, carrying out ultrasonic treatment, then taking out and drying; 2) putting the honeycomb type SCR catalyst treated in the step 1 into a cerous nitrate solution, dipping for 1-3 hours and then taking out; 3) roasting the honeycomb type SCR catalyst treated in the step 2, raising the temperature to be 110 DEG C at the speed of no greater than 3 DEG C/min, subsequently preserving the temperature for 3-5 hours, furthermore, raising the temperature to be 300 DEG C at the speed of no greater than 3 DEG C/min, and preserving the temperature for 8-10 hours to obtain the regenerated honeycomb type SCR denitration catalyst. The active precusor substance cerous nitrate used in the regeneration method is wide in source and good in solvability; the activity of the catalyst subjected to regeneration treatment can be recovered to be more than 80% as compared with the activity of the catalyst which is not poisoned; meanwhile, the regeneration process is simplified, the regeneration cost is lowered, and the regeneration method is simple and convenient to operate, environment-friendly and applicable to large-scale industrial production and application.
Description
Technical field
The invention belongs to the power environment protection technical field, relate to a kind of renovation process of denitrating catalyst, be specifically related to a kind of renovation process of honeycomb type SCR denitrating catalyst.
Background technology
The nitrogen oxide of coal fired power plant (NOx) emission control is the major tasks in energy-conserving and environment-protective field during country " 12 ", and " fossil-fuel power plant atmospheric pollutant emission standard " of up-to-date promulgation (GB13223-2011) formulated control criterion (100mg/m3) the strictest in the world wide especially to the NOx concentration of emission.Along with the appearance of these national policies, discharge how effectively to control NOx has become one of important topic urgently to be resolved hurrily in the current power field of Environment Protection.
At present, the denitrating flue gas of coal fired power plant (DeNOx) mainly adopts SCR (SCR) technology, and this technology be take ammonia as reducing agent, by the SCR catalyst, the NOx in flue gas is reduced into to the N of nonhazardous
2and H
2o, thus reach the purpose of controlling the NOx discharge.The SCR denitrating catalyst, refer to be applied in the SCR(selective catalytic reduction of power plant) catalyst on denitrating system, the SCR catalyst is the core of SCR flue gas denitrification system, its performance directly affects denitration efficiency and denitration cost.Typical commercial SCR catalyst is with TiO
2for carrier, V
2o
5-WO
3or V
2o
5-MoO
3for the honeycomb type catalyst of active material, this kind of catalyst denitration efficiency is high, and technology maturation is reliable, is used widely.
But due to catalyst for a long time in the working environment in high-temperature high dust, and contain alkali (soil) metal in dust as potassium, sodium, calcium etc., very easily cause sintering of catalyst, alkali (soil) metal poisoning and active material to run off, catalyst activity is reduced, shorten service life, for example V
2o
5-WO
3/ TiO
2usually only have 2～3 years the service life of type SCR catalyst.Because the initial investment of SCR catalyst is large, account for 40～60% of whole denitrating system gross investment, after catalyst poisoning, if can cause the denitration cost to increase considerably with the raw catelyst replacement; And if adopt suitable technology to carry out active regeneration to catalyst, can effectively reduce the denitration cost; According to measuring and calculating, to typical 600 megawatt units, if adopt catalyst regeneration technical finesse poisoned catalyst, can save 100～3,000,000 RMB every year.Therefore, the SCR catalyst regeneration technology of research high efficiency, low cost seems particularly necessary and important.
Look into new discovery by literature search, common SCR catalyst regeneration thinking is: at first with compressed air, purge the dust on catalyst, then remove alkali (soil) slaine on catalyst and recover the acid position with acid soak, finally using active material presoma (being mainly ammonium metavanadate and ammonium metatungstate) solution to soak catalyst to supplement the active material of loss.Although above-mentioned regeneration thinking can have the denitration activity of efficient recovery poisoned catalyst, but when through engineering approaches is applied, there are the following problems: the very little (5g/L of the solubility of active material presoma ammonium metavanadate in water commonly used, 20 ℃), therefore be difficult to regulate its load capacity (magnitude of recruitment) on the SCR catalyst by controlling solution concentration, and can only regulate by " dipping-drying " technique repeatedly, this has report on patent CN101574671 and patent CN102114422, this has not only increased the triviality of technological operation, and has increased regeneration cost; Simultaneously, another kind of active material presoma ammonium metatungstate commonly used, price is higher, is the principal element that affects SCR Catalyst Production cost, if use in catalyst regeneration, has increased regeneration cost.The problems referred to above all can cause the regeneration cost of catalyst higher in a word, are unfavorable for the through engineering approaches application of regeneration techniques.
Summary of the invention
In order to overcome the defect of above-mentioned prior art, the object of the present invention is to provide a kind of renovation process of honeycomb type SCR denitrating catalyst, the method raw material sources are wide, regeneration cost is low, are beneficial to the through engineering approaches application.
The present invention is achieved through the following technical solutions:
A kind of renovation process of honeycomb type SCR denitrating catalyst comprises the following steps:
1) in the dilution heat of sulfuric acid that is 1%～2% by poisoning honeycomb type SCR catalyst soakage in mass concentration, after ultrasonic processing 0.5～1.5h, take out, dry;
2) the honeycomb type SCR catalyst that will process through step 1) is placed in the cerous nitrate solution of 0.3～0.9mol/L, takes out after flooding 1～3h;
3) to through step 2) the honeycomb type SCR catalyst processed carries out roasting, after being warming up to 110 ℃ with the speed that is not more than 3 ℃/min, be incubated 3～5h, then after being warming up to 300 ℃ with the speed that is not more than 3 ℃/min, insulation 8～10h, the honeycomb type SCR denitrating catalyst after being regenerated.
The described ultrasonic processing of step 1) is to carry out under 40～60KHZ at ultrasonic power.
The described oven dry of step 1) is under 100～120 ℃, dry 3～6h.
Compared with prior art, the present invention has following useful technique effect:
The present invention adopts the regeneration for the SCR catalyst of active material presoma cerous nitrate that solubility property is good, cheap, replaced with cerous nitrate ammonium metavanadate and the high ammonium metatungstate of price that solubility is low, and can regulate its load capacity (magnitude of recruitment) on catalyst by the concentration of regulation and control presoma cerous nitrate solution, thereby simplified regeneration technology, reduced regeneration cost.By the denitration efficiency testing experiment, verified the honeycomb type SCR catalyst after the inventive method regeneration is processed, activity can return to more than 80% of poisoning procatalyst activity.
The inventive method is easy and simple to handle, and environmental friendliness is applicable to the large-scale industrialization production application.
The specific embodiment
Below in conjunction with specific embodiment, the present invention is described in further detail, and the explanation of the invention is not limited.
The poisoning SCR catalyst of honeycomb type that the embodiment of the present invention adopts is the SCR catalyst that domestic certain coal fired power plant has moved 30000 hours, and its model is V
2o
5-WO
3/ TiO
2type, wall thickness is 0.7mm, pitch is 6.8mm.After this SCR catalyst is cut into to the fritter of 35mm * 35mm * 90mm, the processing of regenerating.
Embodiment 1
A kind of renovation process of honeycomb type SCR denitrating catalyst comprises the following steps:
1) in the dilution heat of sulfuric acid that is 1% by poisoning honeycomb type SCR catalyst soakage in the 500ml mass concentration, under the 40KHZ ul-trasonic irradiation, after processing 1.5h, take out, be placed in baking oven, under 110 ℃, dry 4h;
2) the honeycomb type SCR catalyst that will process through step 1) takes out after being placed in the cerous nitrate aqueous solution dipping 3h of 0.3mol/L;
3) will be through step 2) the honeycomb type SCR catalyst processed carries out roasting, after being warming up to 110 ℃ with the speed that is not more than 3 ℃/min, insulation 4h, then after being warming up to 300 ℃ with the speed that is not more than 3 ℃/min, insulation 8h, the honeycomb type SCR denitrating catalyst after being regenerated.
Honeycomb type SCR catalyst after poisoning honeycomb type SCR catalyst and regeneration processing is placed in respectively to SCR denitration activity experimental rig, under simulated flue gas, tests denitration efficiency, experiment condition is as follows: NO:350ppm, NH
3: 350ppm, O
2: 3%, SO
2: 500ppm, N
2for balanced gas, total gas flow rate: 10000ml/min, range of reaction temperature: 280～400 ℃.Gas componant is measured by moral figure flue gas analyzer (testo350-Pro).Estimate the regeneration effect result and show, in 280～400 ℃ of scopes, the denitration efficiency of the honeycomb type SCR catalyst of the regeneration all honeycomb type SCR catalyst than poisoning is high, and its activity can return to 81% of poisoning front activity.
Embodiment 2
A kind of renovation process of honeycomb type SCR denitrating catalyst comprises the following steps:
1) in the dilution heat of sulfuric acid that is 1% by poisoning honeycomb type SCR catalyst soakage in the 500ml mass concentration, under the 50KHZ ul-trasonic irradiation, after processing 1h, take out, be placed in baking oven, under 100 ℃, dry 6h;
2) the honeycomb type SCR catalyst that will process through step 1) takes out after being placed in the cerous nitrate aqueous solution dipping 2h of 0.6mol/L;
3) will be through step 2) the honeycomb type SCR catalyst processed carries out roasting, after being warming up to 110 ℃ with the speed that is not more than 3 ℃/min, insulation 3h, then after being warming up to 300 ℃ with the speed that is not more than 3 ℃/min, insulation 9h, the honeycomb type SCR denitrating catalyst after being regenerated.
Honeycomb type SCR catalyst after poisoning honeycomb type SCR catalyst and regeneration processing is placed in respectively to SCR denitration activity experimental rig, under simulated flue gas, tests denitration efficiency, experiment condition is as follows: NO:350ppm, NH
3: 350ppm, O
2: 3%, SO
2: 500ppm, N
2for balanced gas, total gas flow rate: 10000ml/min, range of reaction temperature: 280～400 ℃.Gas componant is measured by moral figure flue gas analyzer (testo350-Pro).Estimate the regeneration effect result and show, in 280～400 ℃ of scopes, the denitration efficiency of the honeycomb type SCR catalyst of the regeneration all honeycomb type SCR catalyst than poisoning is high, and its activity can return to 91% of poisoning front activity.
Embodiment 3
A kind of renovation process of honeycomb type SCR denitrating catalyst comprises the following steps:
1) in the dilution heat of sulfuric acid that is 2% by poisoning honeycomb type SCR catalyst soakage in the 500ml mass concentration, under the 60KHZ ul-trasonic irradiation, after processing 0.5h, take out, be placed in baking oven, under 120 ℃, dry 3h;
2) the honeycomb type SCR catalyst that will process through step 1) takes out after being placed in the cerous nitrate aqueous solution dipping 1h of 0.9mol/L;
3) will be through step 2) the honeycomb type SCR catalyst processed carries out roasting, after being warming up to 110 ℃ with the speed that is not more than 3 ℃/min, insulation 5h, then after being warming up to 300 ℃ with the speed that is not more than 3 ℃/min, insulation 10h, the honeycomb type SCR denitrating catalyst after being regenerated.
Honeycomb type SCR catalyst after poisoning honeycomb type SCR catalyst and regeneration processing is placed in respectively to SCR denitration activity experimental rig, under simulated flue gas, tests denitration efficiency, experiment condition is as follows: NO:350ppm, NH
3: 350ppm, O
2: 3%, SO
2: 500ppm, N
2for balanced gas, total gas flow rate: 10000ml/min, range of reaction temperature: 280～400 ℃.Gas componant is measured by moral figure flue gas analyzer (testo350-Pro).Estimate the regeneration effect result and show, in 280～400 ℃ of scopes, the denitration efficiency of the honeycomb type SCR catalyst of the regeneration all honeycomb type SCR catalyst than poisoning is high, and its activity can return to 83% of poisoning front activity.
To sum up, the renovation process of honeycomb type SCR denitrating catalyst of the present invention, the active precursor material cerous nitrate raw material sources of selecting are wide, solubility property is good, and the catalyst activity of processing through regeneration can return to more than 80% of poisoning procatalyst activity, has simplified regeneration technology simultaneously, reduced regeneration cost, easy and simple to handle, environmental friendliness, be applicable to the large-scale industrialization production application.
Claims (3)
1. the renovation process of a honeycomb type SCR denitrating catalyst, is characterized in that, comprises the following steps:
1) in the dilution heat of sulfuric acid that is 1%～2% by poisoning honeycomb type SCR catalyst soakage in mass concentration, after ultrasonic processing 0.5～1.5h, take out, dry;
2) the honeycomb type SCR catalyst that will process through step 1) is placed in the cerous nitrate solution of 0.3～0.9mol/L, takes out after flooding 1～3h;
3) to through step 2) the honeycomb type SCR catalyst processed carries out roasting, after being warming up to 110 ℃ with the speed that is not more than 3 ℃/min, be incubated 3～5h, then after being warming up to 300 ℃ with the speed that is not more than 3 ℃/min, insulation 8～10h, the honeycomb type SCR denitrating catalyst after being regenerated.
2. the renovation process of a kind of honeycomb type SCR denitrating catalyst according to claim 1, is characterized in that, the described ultrasonic processing of step 1) is to carry out under 40～60KHZ at ultrasonic power.
3. the renovation process of a kind of honeycomb type SCR denitrating catalyst according to claim 1, is characterized in that, the described oven dry of step 1) is under 100～120 ℃, dry 3～6h.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN104888759A (en) * | 2015-06-01 | 2015-09-09 | 西安交通大学 | Method and device for modifying or regenerating SCR catalyst by utilizing lanthanum salt or cerium salt |
| CN106179526A (en) * | 2016-07-07 | 2016-12-07 | 无锡市华东电力设备有限公司 | A kind of renovation process of honeycomb type SCR denitrating catalyst |
| CN112264002A (en) * | 2020-11-19 | 2021-01-26 | 西安热工研究院有限公司 | SCR catalyst and modification method for zero-valent mercury oxidation capacity thereof |
| CN113457665A (en) * | 2021-06-22 | 2021-10-01 | 苏州西热节能环保技术有限公司 | Efficient low-temperature honeycomb type SCR denitration catalyst and preparation method thereof |
| CN114367196A (en) * | 2021-12-01 | 2022-04-19 | 苏州西热节能环保技术有限公司 | Method for regenerating SCR denitration catalyst by online semidry method |
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| CN102658215A (en) * | 2012-04-09 | 2012-09-12 | 南京工业大学 | SCR (selective catalytic reduction) flue gas denitration catalyst regeneration method |
| CN102974368A (en) * | 2012-11-07 | 2013-03-20 | 广东电网公司电力科学研究院 | Deactivated SCR denitration catalyst regeneration method |
-
2013
- 2013-08-08 CN CN201310345045.8A patent/CN103433081B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102658215A (en) * | 2012-04-09 | 2012-09-12 | 南京工业大学 | SCR (selective catalytic reduction) flue gas denitration catalyst regeneration method |
| CN102974368A (en) * | 2012-11-07 | 2013-03-20 | 广东电网公司电力科学研究院 | Deactivated SCR denitration catalyst regeneration method |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN104815675B (en) * | 2015-04-09 | 2019-11-05 | 北京大学包头创新研究院 | Denitrifying catalyst with selective catalytic reduction and its regeneration method and application |
| CN104888759A (en) * | 2015-06-01 | 2015-09-09 | 西安交通大学 | Method and device for modifying or regenerating SCR catalyst by utilizing lanthanum salt or cerium salt |
| CN106179526A (en) * | 2016-07-07 | 2016-12-07 | 无锡市华东电力设备有限公司 | A kind of renovation process of honeycomb type SCR denitrating catalyst |
| CN112264002A (en) * | 2020-11-19 | 2021-01-26 | 西安热工研究院有限公司 | SCR catalyst and modification method for zero-valent mercury oxidation capacity thereof |
| CN113457665A (en) * | 2021-06-22 | 2021-10-01 | 苏州西热节能环保技术有限公司 | Efficient low-temperature honeycomb type SCR denitration catalyst and preparation method thereof |
| CN114367196A (en) * | 2021-12-01 | 2022-04-19 | 苏州西热节能环保技术有限公司 | Method for regenerating SCR denitration catalyst by online semidry method |
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Effective date of registration: 20170120 Address after: 100031 Beijing city Xicheng District Fuxingmen South Street No. 2 C Patentee after: Huaneng Power Internaitonal Inc. Patentee after: Zhuozhou Xire Environmental Protection Catalysts Co., Ltd. Patentee after: Xi'an Xire Boiler Environmental Protection Engineering Co., Ltd. Patentee after: Xi'an Thermal Power Research Institute Co., Ltd. Address before: 072750 Hebei city of Baoding Province, inside industrial district of Zhuozhou City Road on the west side of the south side of the road, two Patentee before: Zhuozhou Xire Environmental Protection Catalysts Co., Ltd. Patentee before: Xi'an Xire Boiler Environmental Protection Engineering Co., Ltd. Patentee before: Xi'an Thermal Power Research Institute Co., Ltd. |
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Granted publication date: 20150715 Termination date: 20170808 |