CN102101060B

CN102101060B - Process and device for restoring activity of smoke denitration catalyst

Info

Publication number: CN102101060B
Application number: CN 200910113056
Authority: CN
Inventors: 陈进生; 刘海宁; 赵金平; 张福旺; 商雪松
Original assignee: Institute of Urban Environment of CAS
Current assignee: Zhongke Jiaci Kunshan Environmental Protection Technology Co ltd
Priority date: 2009-12-21
Filing date: 2009-12-21
Publication date: 2013-01-09
Anticipated expiration: 2029-12-21
Also published as: CN102101060A

Abstract

The invention relates to a process and device for restoring activity of a smoke denitration catalyst, belonging to the technical field of environmental engineering air pollution control. The process comprises the steps of: firstly, carrying out soot blowing treatment on a deactivated catalyst, removing sediments on the surface of the catalyst and dredging micropores by using a cooperative cleaning action of ultrasonic, an acidic agent and a micropore penetrating agent, dissolving ammonium metavanadate by using oxalate for repairing active components of the catalyst, and finally, rinsing and drying the catalyst so that the activity of the catalyst is restored. The device realizes integration on restoring links, such as dusting, cleaning, repairing, rinsing, drying and the like of the catalyst. The restoring procedure is operated in a streamline, is suitable for the massive restoring operation of the catalyst, and is convenient for the movement among different power stations. The process effectively fills a gap on the aspect of the smoke denitration catalyst restoring technology in China.

Description

A kind of technique and device for restoring activity of smoke denitration catalyst

Technical field

The invention belongs to environmental project air pollution control technique field, is a kind of technique for restoring activity of smoke denitration catalyst and device.

Background technology

In recent years, the discharge capacity of China's coal fired power plant nitrogen oxide (NOx) constantly rose, and the NOx total emission volumn has increased to 8,400,000 tons before 2008, accounts for 40% of national NOx discharge capacity, and atmospheric environment and the ecological safety of China caused great harm." 12 " in the works, country will be the reduction of discharging of NOx as binding performance assessment criteria, also formulate stricter coal steam-electric plant smoke pollutant (comprising NOx) discharge standard at present.

In the coal-burning power plant of developed area and environmental sensitive area, begun to adopt efficient gas denitrifying technology-selective catalytic reduction (Selective catalytic reduction, SCR) technique.The principle of SCR method denitration is to spray into NH in the boiler emission flue gas ₃Deng reducing agent, under catalyst action with flue gas in NOx generate harmless N ₂And H ₂O.To the end of the year 2008, the denitrating flue gas unit that China has put into operation is 19620MW approximately, accounts for 3.4% of coal group of motors capacity.At the denitrification apparatus of building nearly 100 at present, expected for the end of the year 2010, the denitrating flue gas generating set capacity that China builds up will more than 100,000,000 kW, account for more than 12% of coal-burning power plant.

For guaranteeing the smooth and easy of flue gas circulation, denitrating catalyst all adopts regular bulk catalyst, and pattern mainly contains honeycomb fashion and flat, and Main Ingredients and Appearance can be expressed as V ₂O ₅(WO ₃)/TiO ₂, wherein, V ₂O ₅Active constituent, TiO ₂Catalyst carrier, WO ₃It then is catalyst aid.

The technological core of flue-gas denitration process is catalyst, because more expensive, the manufacturing technology of catalyst primary raw material price also rests in the external fewer companies hand at present, so the price of catalyst is very high, account for whole denitration engineering total price 1/3.Catalyst in use is subjected to flue dust in the flue gas, SO ₂, the chemical analysis such as P, As, alkali metal and alkali earth metal impact, active can decline gradually, only be 2～3 years average life.This is just so that the operation expense of denitrating flue gas is very high.Take 1 600MW unit as example, the denitrating catalyst volume of use is 400m approximately ³, the price of denitrating catalyst is 2,000 ten thousand yuan, according to changing once meter in per 3 years, the renewal cost of catalyst is just up to 7,000,000 yuan.

If but can carry out activation recovering and recycling to decaying catalyst, with the operating cost of saving more than 2/3, also can reduce simultaneously the decaying catalyst disposal costs as solid waste, reduce the use to rare earth metal (vanadium, tungsten, titanium etc.), the resource of saves valuable.

Summary of the invention

The object of the present invention is to provide a kind of operation comparatively simple, the regeneration financial cost is comparatively cheap, can be applicable to technique and the device of coal fired power plant fume denitration catalyst activity industrialization recovery, thus the service life of extending catalyst, the sky high cost of minimizing catalyst change.

Technical scheme of the present invention is made of the recovery technique of catalyst activity soot blower, ultrasonic cleaning pond, chemical activation pond, rinsing bath, drying device etc.Soot blower adopts the dust stratification on compressed air purging and surface, vacuum suction mode Removal of catalyst duct, and ultrasonic cleaning equipment is used for further removing the chemical sediment of the inner obstruction of catalyst microcellular structure, thereby increases the needed specific area of catalytic reaction.The Main Ingredients and Appearance of ultrasonic cleaning liquid is dilute sulfuric acid, and concentration is controlled at 0.1～1.0mol/L; Auxiliary components is micropore permeation agent JFC-1, and concentration is controlled at 0.01～0.5wt%; Hyperacoustic cleaning power is controlled at 100～1000W; Scavenging period is controlled at 10～60min.The chemical activation pond is used for replenishing of catalyst activity component, and the Main Ingredients and Appearance in chemical activation pond is ammonium metavanadate, and concentration is controlled at 0.01～0.1wt%, and auxiliary components is oxalic acid, and concentration is controlled at 0.1～1.0mol/L; Drying device then carries out heated-air drying to the good catalyst of regenerating, and reduces wet part of impact on catalyst quality of regenerative process, and the dry-heat air temperature is controlled at 50～150 ℃.

The structure of apparatus of the present invention is shown in Figure of description 1.Soot blower (1) comprises compressed air line, vavuum pump and detergent line thereof, ultrasonic cleaning equipment (2) is furnished with supersonic generator and comprises acid solution and the chemical mediator pond of micropore permeation agent, ultrasonic cleaning is conducive to further remove the chemical sediment in the structure of catalyst duct, such as CaO, K ₂O etc. are on the larger chemical constituent of catalyst activity impact.Chemical activation pond (3) adopts the medicaments such as ammonium metavanadate that dissolve in the oxalic acid to repair active component according to the front loss of active component situation that detects of catalyst recovery.Rinsing bath (4) is removed the chemical residue in the catalyst activity recovery process, and drying device (5) is introduced hot blast, blows down wet part in the catalyst regeneration process.

Operating process of the present invention is: the catalyst to inactivation blows the ash processing, immersion is equipped with in the ultrasonic cleaning equipment of acid solution and micropore permeation agent, utilize ultrasonic wave, acid solution and micropore permeation agent three's synergy, the catalyst surface harmful chemical is removed, dredged simultaneously blocked small duct.Then catalyst carries out the repairing of active ingredient, and after rinsing and drying, catalyst can come into operation again.

Characteristics of the present invention are mainly as follows:

(1) utilizes ultrasonic wave, diluted acid medicament and micropore permeation agent three's collaborative cleaning action, realize the dredging of the sedimental removal of catalyst surface and microcellular structure, avoid simultaneously the catalyst activity component influenced.

(2) the chemical activation pond is used for replenishing of catalyst activity component, adopts oxalic acid dissolving ammonium metavanadate, reduces and introduces external component or impurity to catalyst.

(3) device waits the realization of recovery link integrated in ash disposal-cleaning-repairing-rinsing-drying, and the recovery operation realizes pipelining, is fit to catalyst mass recovery operation.In addition, device convenient vehicle-mounted, can be mobile flexibly between different power stations.

Description of drawings

The active reanimate device schematic diagram of Figure of description 1 denitrating flue gas decaying catalyst

The specific embodiment

Embodiment 1:

Get the honeycomb type denitrification catalyst monomer of an inactivation, volume is 0.015m approximately ³, remove surperficial laying dust after, placing acid number is that 0.1～1.0mol/L, micropore permeation agent concentration are the chemical solution of 0.01～0.5wt%, adjusts ultrasonic power at 100～1000W, scavenging period is controlled at 10～60min.When chemism was repaired, ammonium metavanadate concentration was 0.01～0.1wt%, and concentration of oxalic acid is 0.1～1.0mol/L, and after rinsing and drying, the temperature of heated drying air is controlled at 50～150 ℃.With compare before the recovery, specific surface area of catalyst increases 2.37 times, the active rising 1.81 times.

Embodiment 2:

Get the flat denitrating catalyst monomer of an inactivation, volume is 0.015m approximately ³After removing surperficial laying dust, placing acid number is that 0.1～1.0mol/L, micropore permeation agent concentration are the chemical solution of 0.01～0.5wt%, adjusts ultrasonic power at 100～1000W, and scavenging period is controlled at 10～60min.When chemism was repaired, ammonium metavanadate concentration was 0.01～0.1wt%, and concentration of oxalic acid is 0.1～1.0mol/L, and after rinsing and drying, the temperature of heated drying air is controlled at 50～150 ℃.With compare before the recovery, specific surface area of catalyst increases 2.01 times, the active rising 1.77 times.

Claims

1. technique that is used for restoring activity of smoke denitration catalyst, comprise the steps: that at first decaying catalyst being blown ash processes, utilize ultrasonic wave, acid medicine and micropore permeation agent three's collaborative cleaning action realizes the dredging of the sedimental removal of catalyst surface and micropore, the Main Ingredients and Appearance of described acid medicine is dilute sulfuric acid, the solution acid number is 0.1～1.0mol/L, the micropore permeation agent is JFC-1, concentration is controlled at 0.01～0.5wt%, ultrasonic power is at 100～1000W, adopt oxalic acid dissolving ammonium metavanadate to repair the catalyst activity component, at last catalyst is carried out rinsing and the wet part of heated-air drying removal, the activity of catalyst is recovered, device is realized integrated in catalyst ash disposal-cleaning-repairing-rinsing-dry recovery link, the recovery operation adopts pipelining, be fit to the catalyst batched operation, in addition, device is convenient vehicle-mounted, can be mobile flexibly between different power stations.

2. a kind of technique for restoring activity of smoke denitration catalyst according to claim 1, it is characterized in that: the concentration of ammonium metavanadate is controlled at 0.01～0.1wt%, and the concentration of oxalic acid is controlled at 0.1～1.0mol/L.

3. a kind of technique for restoring activity of smoke denitration catalyst according to claim 1 is characterized in that: the method that described removal catalyst is wet part is to adopt the hot-air method, and temperature is controlled at 50～150 ℃.