CN103433081B - 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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- CN103433081B CN103433081B CN201310345045.8A CN201310345045A CN103433081B CN 103433081 B CN103433081 B CN 103433081B CN 201310345045 A CN201310345045 A CN 201310345045A CN 103433081 B CN103433081 B CN 103433081B
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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 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 denitration.
Background technology
Nitrogen oxide (NOx) emission control of coal fired power plant is the major tasks in country " 12 " period energy-conserving and environment-protective field, and " fossil-fuel power plant atmospheric pollutant emission standard " (GB13223-2011) of up-to-date promulgation has formulated control criterion (100mg/m3) the strictest in world wide especially to NOx emission concentration.Along with the appearance of these national policies, how effectively the discharge of control NOx has become one of important topic urgently to be resolved hurrily in current power field of Environment Protection.
At present, the denitrating flue gas (DeNOx) of coal fired power plant mainly adopts SCR (SCR) technology, and this technology is reducing agent with ammonia, by SCR catalyst, the NOx in flue gas is reduced into the N of nonhazardous
2and H
2o, thus reach the object controlling NOx emission.SCR denitration, refers to be applied in power plant SCR(selective catalytic reduction) catalyst on denitrating system, SCR catalyst is the core of SCR flue gas denitrification system, and 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 because catalyst is in the working environment of high-temperature high dust for a long time, 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, service life shortens, such as V
2o
5-WO
3/ TiO
2the service life of type SCR catalyst only has 2 ~ 3 years usually.Because SCR catalyst initial investment is large, account for 40 ~ 60% of whole denitrating system gross investment, when after catalyst poisoning, if denitration cost can be caused to increase considerably with raw catelyst replacement; And according to suitable technology, active regeneration is carried out to catalyst, then effectively can reduce denitration cost; According to measuring and calculating, to typical 600 megawatt units, according to catalyst regeneration techniques process poisoned catalyst, 100 ~ 3,000,000 RMB can be saved every year.Therefore, the SCR catalyst regeneration techniques studying high efficiency, low cost seems particularly necessary and important.
New discovery is looked into by literature search, common SCR catalyst regeneration thinking is: first purge the dust on catalyst with compressed air, then remove alkali (soil) slaine on catalyst with acid soak and recover sour position, finally using active material presoma (mainly ammonium metavanadate and ammonium metatungstate) solution to soak catalyst with the active material of supplementary 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 conventional very little (5g/L of the solubility of active material presoma ammonium metavanadate in water, 20 DEG C), therefore the load capacity (magnitude of recruitment) regulating it in SCR catalyst by controlling solution concentration is difficult to, and can only be regulated by " dipping-dry " technique repeatedly, this has report on patent CN101574671 and patent CN102114422, this not only adds the triviality of technological operation, and adds regeneration cost; Meanwhile, another kind of conventional active material presoma ammonium metatungstate, price is higher, is the principal element affecting SCR catalyst production cost, if use in catalyst regeneration, increases 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 denitration, the method raw material sources are wide, regeneration cost is low, are beneficial to through engineering approaches application.
The present invention is achieved through the following technical solutions:
A renovation process for honeycomb type SCR denitration, comprises the following steps:
1) poisoning honeycomb type SCR catalyst being impregnated in mass concentration is in the dilution heat of sulfuric acid of 1% ~ 2%, takes out after ultrasonic process 0.5 ~ 1.5h, dries;
2) the honeycomb type SCR catalyst through step 1) process is placed in the cerous nitrate solution of 0.3 ~ 0.9mol/L, takes out after dipping 1 ~ 3h;
3) to through step 2) the honeycomb type SCR catalyst that processes carries out roasting, after being warming up to 110 DEG C with the speed being not more than 3 DEG C/min, insulation 3 ~ 5h, then after being warming up to 300 DEG C with the speed being not more than 3 DEG C/min, insulation 8 ~ 10h, obtains the honeycomb type SCR denitration after regenerating.
Ultrasonic process described in step 1) is carried out under ultrasonic power is 40 ~ 60KHZ.
Oven dry described in step 1) is at 100 ~ 120 DEG C, dry 3 ~ 6h.
Compared with prior art, the present invention has following useful technique effect:
The active material presoma cerous nitrate that the present invention adopts solubility property good, cheap is for the regeneration of SCR catalyst, the low ammonium metavanadate of solubility and the high ammonium metatungstate of price is instead of with cerous nitrate, and its load capacity (magnitude of recruitment) on a catalyst can be regulated by the concentration of regulation and control presoma cerous nitrate solution, thus simplify regeneration technology, reduce regeneration cost.By denitration efficiency testing experiment, demonstrate the honeycomb type SCR catalyst after the inventive method regeneration process, activity can return to more than 80% of poisoning procatalyst activity.
The inventive method is easy and simple to handle, environmental friendliness, is applicable to industrialization large-scale production and application.
Detailed description of the invention
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 certain coal fired power plant domestic has run 30000 hours, and its model is V
2o
5-WO
3/ TiO
2type, wall thickness is 0.7mm, and pitch is 6.8mm.After this SCR catalyst being cut into the fritter of 35mm × 35mm × 90mm, carry out regeneration process.
Embodiment 1
A renovation process for honeycomb type SCR denitration, comprises the following steps:
1) poisoning honeycomb type SCR catalyst being impregnated in 500ml mass concentration is in the dilution heat of sulfuric acid of 1%, takes out, be placed in baking oven under 40KHZ ul-trasonic irradiation after processing 1.5h, at 110 DEG C, and dry 4h;
2) take out after the cerous nitrate aqueous solution being placed in 0.3mol/L through the honeycomb type SCR catalyst of step 1) process being flooded 3h;
3) by through step 2) the honeycomb type SCR catalyst that processes carries out roasting, after being warming up to 110 DEG C with the speed being not more than 3 DEG C/min, insulation 4h, then after being warming up to 300 DEG C with the speed being not more than 3 DEG C/min, insulation 8h, obtains the honeycomb type SCR denitration after regenerating.
Honeycomb type SCR catalyst after poisoning honeycomb type SCR catalyst and regeneration process is placed in SCR denitration activity test unit respectively, and under simulated flue gas, test 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 DEG C.Gas componant is measured by moral figure flue gas analyzer (testo350-Pro).Evaluate regeneration effect result to show, within the scope of 280 ~ 400 DEG C, the honeycomb type SCR catalyst of denitration efficiency all than poisoning of the honeycomb type SCR catalyst of regeneration is high, and its activity can return to 81% of poisoning front activity.
Embodiment 2
A renovation process for honeycomb type SCR denitration, comprises the following steps:
1) poisoning honeycomb type SCR catalyst being impregnated in 500ml mass concentration is in the dilution heat of sulfuric acid of 1%, takes out, be placed in baking oven under 50KHZ ul-trasonic irradiation after processing 1h, at 100 DEG C, and dry 6h;
2) take out after the cerous nitrate aqueous solution being placed in 0.6mol/L through the honeycomb type SCR catalyst of step 1) process being flooded 2h;
3) by through step 2) the honeycomb type SCR catalyst that processes carries out roasting, after being warming up to 110 DEG C with the speed being not more than 3 DEG C/min, insulation 3h, then after being warming up to 300 DEG C with the speed being not more than 3 DEG C/min, insulation 9h, obtains the honeycomb type SCR denitration after regenerating.
Honeycomb type SCR catalyst after poisoning honeycomb type SCR catalyst and regeneration process is placed in SCR denitration activity test unit respectively, and under simulated flue gas, test 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 DEG C.Gas componant is measured by moral figure flue gas analyzer (testo350-Pro).Evaluate regeneration effect result to show, within the scope of 280 ~ 400 DEG C, the honeycomb type SCR catalyst of denitration efficiency all than poisoning of the honeycomb type SCR catalyst of regeneration is high, and its activity can return to 91% of poisoning front activity.
Embodiment 3
A renovation process for honeycomb type SCR denitration, comprises the following steps:
1) poisoning honeycomb type SCR catalyst being impregnated in 500ml mass concentration is in the dilution heat of sulfuric acid of 2%, takes out, be placed in baking oven under 60KHZ ul-trasonic irradiation after processing 0.5h, at 120 DEG C, and dry 3h;
2) take out after the cerous nitrate aqueous solution being placed in 0.9mol/L through the honeycomb type SCR catalyst of step 1) process being flooded 1h;
3) by through step 2) the honeycomb type SCR catalyst that processes carries out roasting, after being warming up to 110 DEG C with the speed being not more than 3 DEG C/min, insulation 5h, then after being warming up to 300 DEG C with the speed being not more than 3 DEG C/min, insulation 10h, obtains the honeycomb type SCR denitration after regenerating.
Honeycomb type SCR catalyst after poisoning honeycomb type SCR catalyst and regeneration process is placed in SCR denitration activity test unit respectively, and under simulated flue gas, test 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 DEG C.Gas componant is measured by moral figure flue gas analyzer (testo350-Pro).Evaluate regeneration effect result to show, within the scope of 280 ~ 400 DEG C, the honeycomb type SCR catalyst of denitration efficiency all than poisoning of the honeycomb type SCR catalyst of regeneration is high, and its activity can return to 83% of poisoning front activity.
To sum up, the renovation process of honeycomb type SCR denitration of the present invention, the active precursor material cerous nitrate raw material sources selected are wide, solubility property is good, and the catalyst activity through regeneration process can return to more than 80% of poisoning procatalyst activity, simplifies regeneration technology simultaneously, reduce regeneration cost, easy and simple to handle, environmental friendliness, is applicable to industrialization large-scale production and application.
Claims (1)
1. a renovation process for honeycomb type SCR denitration, is characterized in that, comprises the following steps:
1) poisoning honeycomb type SCR catalyst being impregnated in mass concentration is in the dilution heat of sulfuric acid of 1% ~ 2%, takes out after ultrasonic process 0.5 ~ 1.5h, dries; Described ultrasonic process is carried out under ultrasonic power is 40 ~ 60 kHz, and described oven dry is at 100 ~ 120 DEG C, dry 3 ~ 6h;
2) by through step 1) the honeycomb type SCR catalyst that processes is placed in the cerous nitrate solution of 0.3 ~ 0.9mol/L, takes out after dipping 1 ~ 3h;
3) to through step 2) the honeycomb type SCR catalyst that processes carries out roasting, after being warming up to 110 DEG C with the speed being not more than 3 DEG C/min, insulation 3 ~ 5h, then after being warming up to 300 DEG C with the speed being not more than 3 DEG C/min, insulation 8 ~ 10h, obtains the honeycomb type SCR denitration after regenerating.
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| 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 |
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 |
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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 |
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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 |