Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J38/00—Regeneration or reactivation of catalysts, in general
  • B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
• • 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
• • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J38/00—Regeneration or reactivation of catalysts, in general
  • B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
  • B01J38/50—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
  • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL-COMBUSTION ENGINES
  • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
  • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
  • F01N3/0807—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by using absorbents or adsorbents
  • F01N3/0828—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by using absorbents or adsorbents characterised by the absorbed or adsorbed substances
  • F01N3/0842—Nitrogen oxides
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
  • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL-COMBUSTION ENGINES
  • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
  • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
  • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
  • F01N3/18—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control
  • F01N3/20—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control specially adapted for catalytic conversion

Definitions

• the present invention relates to a method for regenerating a denitration catalyst used in a flue gas denitration apparatus such as a thermal power plant.
• flue gas denitrification systems have been installed in boilers of thermal power plants, various large-scale boilers, and other waste incinerators that use oil, coal, gas, etc. as fuel.
• a plurality of denitration catalysts are built in.
• the denitration catalyst generally, T I_ ⁇ 2, etc. as the carrier, using a v 2 o 5 and the like as the active ingredient, which oxides of tungsten and molybdenum is added as a co-catalyst component, VO x - Compound acid forms such as WO y — T i 0 2 and VO x -M b O y — T i 0 2 are used.
• a honeycomb type or a plate type is used as a catalyst shape.
• a honeycomb type a honeycomb shape is manufactured from the base material, and then the catalyst component is coated.
• the kneaded type is formed by kneading the catalyst component into the base material.
• the honeycomb shape base material is impregnated with the catalyst component. And impregnated forms.
• the plate-like material is obtained by coating a metal core or a ceramic with a catalyst component.
• a method of washing with an acid having a pH of 5 or less or an alkali having a pH of 8 or more Japanese Patent Application Laid-Open No. 64444/1984
• washing with water or a dilute inorganic acid aqueous solution followed by 0.1 to 5% by weight oxalic acid aqueous solution
• a method of removing oxalic acid remaining on the catalyst by washing with water JP-A-7-222924
• a method of washing with water at 50 ° C or more and 80 ° C or less and drying JP-A-8-196920.
• the method of physically polishing or the like has a problem that the operation is complicated and the denitration catalyst itself is cracked or destroyed by the regeneration operation.
• the alkali component is generally removed by washing with an alkaline aqueous solution or hot water, and the heavy metal component mainly composed of vanadium is washed with an oxalic acid aqueous solution.
• a denitration catalyst with increased so 3 conversion rate due to the attachment of vanadium In the method of regenerating the activity, a method of washing with an aqueous solution of 0.1 to 30% citric acid and an aqueous solution of 0.1 to 20% sulfuric acid (Japanese Patent Application Laid-Open No.
• a method of washing the catalyst by setting the concentration of hydrofluoric acid in the washing solution to 0.3 to 3% by weight and maintaining the concentration of the washing solution at 20 to 80 ° C Japanese Patent Laid-Open No. 10-235209.
• denitration ratio is decreased by K content adheres also increase S_ ⁇ 3 conversion adheres vanadium component contained in the fuel, in the active regeneration process of the denitration catalyst to regenerate the denitrification catalyst, inorganic alkali
• a method of washing with an aqueous solution and an acid solution Japanese Patent Application Laid-Open No.
• the concentration of sulfuric acid or ammonia in the cleaning solution is set to 0.05 to 20% by weight, the temperature of the cleaning solution is maintained at 10 to 90 ° C, and the denitration catalyst is added to the cleaning solution. Soak It is later, and a method of washing with water (Japanese Patent No. 3059136) is proposed Have been.
• a denitrification catalyst that regenerates its activity by washing a denitration catalyst to which vanadium has adhered with a washing solution containing an organic acid aqueous solution, an inorganic acid aqueous solution, and an alkaline aqueous solution.
• a method of removing the vanadium eluted as ions into the waste liquid after washing by ion exchange to regenerate the waste liquid Japanese Patent Application Laid-Open No.
• an object of the present invention is to provide a method for regenerating a denitration catalyst which can easily recover the catalytic activity of a denitration catalyst that has deteriorated, is simple in work, and has good work efficiency.
• denitration catalysts especially denitration catalysts used in flue gas denitration equipment of coal-fired boilers, have sufficient catalytic activity simply by being immersed in pure water at normal temperature. It has been found that the treated reclaimed water can be used repeatedly, and that the treated reclaimed water can be treated relatively easily because it does not contain heavy metals.
• the Ca component (alkali component) and the S component (acid component) reduce the denitration performance by coating the surface of the denitration catalyst.
• they have found that they can be easily eluted and removed simply by immersing them in pure water at normal temperature, and that the denitration performance can be sufficiently recovered, thus completing the present invention.
• the first aspect of the present invention relates to a method for regenerating a denitration catalyst of a flue gas denitration apparatus, comprising: immersing in a regeneration at room temperature substantially without containing chlorine and a cleaning component; And dewatering the denitration catalyst.
• the inhibitor that reduces the denitration performance can be easily eluted and removed simply by immersing the denitration catalyst in substantially pure water at normal temperature, and the denitration performance can be recovered. it can.
• a second aspect of the present invention is the method for regenerating a denitration catalyst according to the first aspect, characterized in that the denitration catalyst is immersed in regeneration water until foaming is completed.
• the inhibitor when the denitration catalyst is immersed in water until the foaming is completed, the inhibitor can be easily eluted and removed, and the denitration performance can be restored.
• a third aspect of the present invention is the method for regenerating a denitration catalyst according to the first or second aspect, wherein the denitration catalyst is taken out of the regeneration water and then washed with water.
• foreign substances such as dust adhering to the catalyst surface can be removed by washing the denitration catalyst taken out of the water with water.
• a fourth aspect of the present invention is the method for regenerating a denitration catalyst according to any one of the first to third aspects, wherein regenerated water for immersing the denitration catalyst is repeatedly used a plurality of times. ".
• a fifth aspect of the present invention is the method for regenerating a denitration catalyst according to any one of the first to fourth aspects, wherein the regenerated denitration catalyst is set in the flue gas denitration apparatus without drying. .
• the drying step of drying the denitration catalyst can be eliminated and the apparatus can be set in the flue gas denitration apparatus.
• a sixth aspect of the present invention is the denitration catalyst regenerating method according to any one of the first to fifth aspects, wherein after confirming the catalytic performance of the regenerated denitration catalyst, the catalyst is set in the flue gas denitration apparatus. is there.
• the denitration performance can be reliably maintained by checking the catalytic performance of the regenerated denitration catalyst and confirming and using the regeneration effect.
• the regenerated denitration catalyst according to any of the first to sixth aspects, A method for regenerating a denitration catalyst, characterized in that a medium is set in the flue gas denitration apparatus in the reverse direction so that the direction of flow of exhaust gas is reversed.
• the part that is actually involved in denitration can be changed from the previous use state, and the denitration performance can be maintained even higher. it can.
• the determination as to whether or not the regeneration treatment is performed by the method of the present invention may be made periodically according to the service period of the denitration catalyst.However, it does not mean that the denitration catalyst having a plurality of layers deteriorates uniformly, The order of deterioration, the period of deterioration, etc. differ depending on the condition. Therefore, it is preferable that the state of deterioration of each of the denitration catalysts is accurately grasped, and the above-mentioned regeneration treatment is performed when the degree of deterioration has exceeded a predetermined level.
• the denitration rate 77 may be measured based on the ⁇ ⁇ ⁇ concentration.
• the catalyst may be actually sampled from a part of the denitration catalyst, and the performance of the sampled catalyst may be evaluated. -.
• the denitration catalyst particularly the denitration catalyst used in the flue gas denitration device of a coal-fired poiler, can sufficiently recover its catalytic activity only by immersing it in pure water at normal temperature.
• the treated reclaimed water can be used repeatedly, and since it does not contain heavy metals during the treatment, there is an effect that the treated water can be treated relatively easily.
• FIG. 1 is a diagram showing a schematic configuration of a flue gas denitration apparatus using a denitration catalyst to which the method of the present invention is applied.
• FIG. 2 is a diagram illustrating a reproducing method according to one embodiment of the present invention.
• FIG. 3 is a diagram showing the results of Test Example 1 of the present invention.
• FIG. 4 is a diagram showing the results of Test Example 2 of the present invention.
• FIG. 5 is a diagram showing the results of Test Example 3 of the present invention.
• FIG. 6 is a diagram showing the results of Test Example 4 of the present invention.
• FIG. 7 is a diagram showing the results of Test Example 6 of the present invention.
• FIG. 8 is a diagram showing the results of Test Example 7 of the present invention. BEST MODE FOR CARRYING OUT THE INVENTION
• FIG. 1 shows a schematic configuration of a flue gas denitration apparatus provided with a denitrification insect medium to which the method of the present invention is applied.
• this flue gas denitration device is provided in a thermal power plant, the denitration catalyst management device of the present embodiment is not limited to this.
• the flue gas denitration device 10 is connected to an exhaust duct 12 connected to the upstream side of the device main body 11 and communicating with the boiler device of the thermal power plant, and a processing gas duct 1 connected to the downstream side.
• a plurality of layers, in this embodiment, four layers of denitration catalysts 14A to 14D are arranged at predetermined intervals.
• Each of the denitration catalysts 14A to 14D is provided so that the exhaust gas introduced from the exhaust duct 12 sequentially passes therethrough.
• the exhaust ducts 1 and 2 that communicate with the Is the NH 3 is adapted to be implanted in accordance with the amount of exhaust gas from Poira body.
• each denitration catalyst 14A-14D the type and the like are not particularly limited, one general is, T I_ ⁇ 2 as a carrier, V 2 0 5 is used as an active ingredient, honeycomb or plate like There are types.
• each of the denitration catalysts 14A to 14D is configured by using a honeycomb type and arranging and combining a plurality of columnar honeycomb type catalysts.
• gas sampling means 15A to 15E are provided on the inlet side and the outlet side of each of the denitration catalysts 14A to 14D.
• 15A ⁇ 15 E is connected to the concentration of NO x measurement means 16A ⁇ 16E respectively, to the NH 3 concentration measurement means 17 A to 17 E, these measurements, the denitration catalyst 14 A to
• Gas collecting means 1 5A ⁇ 'l 5E is desired a desired amount of sample gas is collected through a sampling tube in the timing, the collected sample gas concentration of NO x measurement means 16A ⁇ 16E and NH 3 concentration measurement means 17 A to 17E.
• the sampling time of the sampling gas by the gas sampling means 15A to 15E is not particularly limited, but is preferably performed during normal operation of the power plant, and preferably at the rated load at which the gas amount is maximized. In addition, even if the interval of gas sampling is up to about 6 months, it is enough to control the performance of the denitration catalysts 14A to 14D.However, if the frequency is increased, the management accuracy will be improved. It is preferable to perform it about once. In particular, in the downstream catalyst layer, since the H 3 concentration decreases and the fluctuation range increases, in order to improve the management evaluation, the number of measurements of 3 degrees is increased and the denitration rate is calculated from the average concentration. It is preferable to do so.
• the denitration rate measuring means 18 obtains the measurement results from the ⁇ concentration measuring means 16 ⁇ to 16 ⁇ and the 3 concentration measuring means.17 ⁇ to 1717, and from these measurement results, the respective denitration catalysts 14 ⁇ to 1414 The denitration rate and denitration burden rate of D are calculated.
• the inlet molar ratio of the denitration catalyst 14 A to L 4D considering the inlet ⁇ 3 / inlet vo chi, is calculated based on the NOx removal rate 77 based on Nyuita 3 concentration to the following equation (1). (Inlet NH — Outlet ⁇ ) 1 ⁇ ⁇ evaluation molar ratio, ⁇
• the evaluation molar ratio is a molar ratio that is set to evaluate the denitration catalyst, and any molar ratio can be set. For example, it may be set to about the operating molar ratio of the power plant, for example, 0.8.
• the respective denitrifying media 14 A to 14 are respectively denitrifying media 14 A to 14
• the denitration rate ⁇ of D is determined, and the performance of each catalyst is controlled based on the magnitude of the denitration rate. If the denitration rate 77 falls below a predetermined value, the regeneration method according to the present invention is used to recover the performance of the deteriorated catalyst. carry out.
• FIG. 2 shows an embodiment of the method of the present invention according to one embodiment.
• the denitration catalyst 14 to be subjected to the regeneration treatment is a row of honeycomb type columnar denitration catalysts 14 ′, and a regeneration tank 30 large enough to be immersed is prepared.
• the regeneration layer 30 stores reclaimed water 31 substantially free of chlorine, in this case, pure water. The fact that chlorine is not substantially contained is because chlorine inhibits the catalytic activity.
• Reclaimed water 31 is substantially neutral and does not contain acids, alkalis, and other additives conventionally used for cleaning.
• the temperature is room temperature, and no special heating is required.
• the normal temperature means a so-called environmental temperature, for example, 5
• the regenerated water 31 can be used repeatedly, and it goes without saying that the second and subsequent regenerated ice 31 will contain components eluted in the first regeneration process.
• the denitration catalyst 14 is suspended by a crane '35 or the like (FIG. 2 (a)) and immersed in the regeneration water 31 of the regeneration tank 30 (FIG. 2 ( b) to (c)).
• the immersion time is several minutes or more, and as a guide, until the foaming from the denitration catalyst 14 is eliminated, for example, about 1 to 30 minutes, preferably about 5 to 15 minutes It is enough.
• the amount of the regenerated water 31 may be an amount in which the denitration catalyst 14 is immersed, but it is preferable to use 2 to 3 times or more the volume of the denitration catalyst 14.
• the denitration catalyst 14 After immersion, the denitration catalyst 14 may be taken out and drained, and there is no need to provide a drying step.
• the denitration catalyst 14 from which water has been drained can be set in the flue gas denitration device and the device can be operated, for example, because it is sufficiently dried with warm air when starting up with light oil. is there.
• it may be dried, for example, dried in the sun and then set in the device.
• the denitration catalyst 14 After removing the denitration catalyst 14 from the reclaimed water 31, it may be washed with a shower. Also in this case, water containing substantially no chlorine is used. This is necessary especially when the regenerated water 31 is used repeatedly, and the purpose is to wash and remove foreign substances such as dust attached to the surface of the denitration catalyst 14.
• the regenerated denitration catalyst may be installed in the flue gas denitration apparatus in the same manner as in the original state, but may be arranged in the reverse direction so that the direction of exhaust gas flow is reversed. Since it was confirmed that the degree of deterioration of the denitration catalyst was large on the upstream side in the transport direction, after regenerating it, use it in the opposite direction to make the use area of the denitration catalyst uniform. Can be. It is based on the applicant's new knowledge that only the upstream side in the exhaust gas transmission direction has a large effect on the denitration reaction.
• the regenerated denitration catalyst has the catalyst activity revived as if it were new, a sample of a part of the regenerated denitration catalyst was sampled to make sure, and the performance of the sampling catalyst was evaluated. It may be returned to the smoke denitration device. For example, cut out a 5 Omm X 5 Omm X 10 Omm (length) from the entrance side of the catalyst layer, set it in a performance test device, and adjust the gas conditions to match the design values of the actual machine to supply the test gas. flow, evaluated denitration performance by measuring the denitrification rate by measuring the concentration of NO x and NH 3 concentration at the outlet side, it is possible to determine the reproduction has been performed completely assimilated.
• the reclaimed water used in the method of the present invention can be repeatedly used up to about 30 times.However, unlike the conventional oxalic acid washing, the reclaimed water used contains heavy metal components. It can be treated with ordinary wastewater treatment facilities such as thermal power plants without going through heavy metal treatment processes. There are advantages.
• a conventional polishing treatment may be performed prior to carrying out the regeneration treatment method of the present invention.
• an inhibitor which is insufficiently removed by the polishing treatment can be surely removed.
• the regeneration effect of the present invention can be obtained in a short time by immersing the denitration catalyst in the regeneration water, and the regeneration water can be repeatedly used up to about 30 times. Comparing this point with shower cleaning, shower cleaning takes more time than immersion, and repeated use of cleaning water in shower cleaning requires a large pump, and the problem of nozzle clogging is also reduced. Come out. 'Therefore, it is necessary to use a large amount of fresh water in the shower cleaning.
• Example 1 The denitration catalyst regenerated in Example 1 was set in a flue gas denitration apparatus, and was further used for about 280,000 hours (total use: about 910,000 hours), and then regenerated in the same manner as in Example 1. did.
• the denitration catalyst used for about 930 hours was divided into 30 parts, and the same regeneration treatment as in Example 1 was repeated 30 times using pure water at room temperature repeatedly.
• the regeneration treatment was performed in the same manner as in Example 1 except that hot water (pure water) at 80 ° C was used instead of normal temperature water.
• the polishing amount was controlled by the time of micro-vibration, and the polishing was performed to a thickness of about 40 m on average.
• Example 6 The denitration catalyst polished in Comparative Example 2 was subjected to the same regeneration treatment as in Example 1.
• the regeneration treatment was performed in the same manner as in Example 1, except that the immersion time in pure water was changed to 1 minute, 10 minutes, 30 minutes, and 60 minutes.
• Example 2 As a result, as in Examples 1 and 2, it was recognized that the catalyst activity was restored to a state close to a new product only by immersion in pure water. In Example 2, the denitration rate did not decrease significantly even before the regeneration, but it was confirmed that the denitration rate was restored to the same level as in Example 1.
• the denitration rate was measured for a new product and that before washing with water (before regeneration) as comparative products.
• Test Example 3 (Test Example 3)-For Examples 4 and 5, the denitration rates before and after regeneration were measured in the same manner as in Test Example 1. The denitration rate was also measured for a new product as a control. The results are shown in FIG. ..-As a result, it was confirmed that the regeneration effect can be expected for the denitration catalyst of the heavy oil-fired power plant as well.
• Example 1 For Example 1 and Comparative Examples 1 and 2, the denitration rate was measured at a molar ratio of 0.82 and 1.0 in the same manner as in Test Example 1, and calculated based on the following equations (2) and (3). Play rate And the recovery rates were compared. The results are shown in Tables 2 and 3. The denitration rate of a new product is shown as a comparative product.
• Example 1 ⁇ Pi 6 and Comparative Example 2 the element concentration in the concentration of inhibitory substances on the surface of the catalyst after regeneration before ⁇ Pi playback (C a O ⁇ Pi S0 3), measured Ri by the X-ray microanalyzer The results are shown in FIG. In addition, the result showed the average value and dispersion
• FIG. 8 shows the results obtained by measuring the component concentrations on the catalyst surface before and after regeneration in Example 7 using an X-ray microphone mouth analyzer.
• Example 2 The components eluted in the regenerating solution used in Example 1 were analyzed. For comparison, the results of treating 0.1N oxalic acid, 1N hydrochloric acid, 0.1N nitric acid, 1N nitric acid, 0.3% EDTA, 3% EDTA, and 5% hydrogen peroxide water instead of pure water were used. See Table 4. In addition, all are the results processed at normal temperature.
• Example 1 As a result, it was found that in the case of pure water treatment, no heavy metals such as Ti, W, and V as catalyst components were eluted at all. As for Example 1, it was confirmed that a inhibitory components CaO, S0 3 and N a O is eluted.

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