CN103949291B - Denitrating catalyst regenerated liquid, regenerated liquid preparation method and catalyst recovery process - Google Patents

Denitrating catalyst regenerated liquid, regenerated liquid preparation method and catalyst recovery process Download PDF

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CN103949291B
CN103949291B CN201410165148.0A CN201410165148A CN103949291B CN 103949291 B CN103949291 B CN 103949291B CN 201410165148 A CN201410165148 A CN 201410165148A CN 103949291 B CN103949291 B CN 103949291B
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parts
nitrate
regenerated liquid
denitrating catalyst
catalyst
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CN201410165148.0A
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CN103949291A (en
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王文选
曹璐
华杰
李守信
许峰
于光喜
华攀龙
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江苏万德环保科技有限公司
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Abstract

The invention discloses a kind of denitrating catalyst regenerated liquid, regenerated liquid preparation method and catalyst recovery process.Raw material components and the weight content of regenerated liquid are as follows, vanadyl oxalate: 4 ~ 6 parts; Cerous nitrate: 0.08 ~ 0.10 part; Lanthanum nitrate: 0.11 ~ 0.13 part; Copper nitrate: 0.05 ~ 0.07 part; Ludox ST-O:0.4 ~ 0.6 part; Deionized water: 95 parts; First that vanadyl oxalate and deionized water and stirring is even, then drop into cerous nitrate, lanthanum nitrate and copper nitrate and fully stir until dissolve completely, finally drop into Ludox ST-O and continue to stir until homogeneous phase; Inactivation denitrification catalyst module is purged and Ultrasonic Cleaning through powerful successively, to be soaked in cleaning fluid 18 minutes ~ 25 minutes, then to continue to be soaked in regenerated liquid 25 minutes ~ 40 minutes, then take out oven dry.This denitrating catalyst regenerated liquid and catalyst recovery process, can recover the activity of inactivation denitrating catalyst efficiently, and expand the temperature range of catalyst activity.

Description

Denitrating catalyst regenerated liquid, regenerated liquid preparation method and catalyst recovery process

Technical field

The present invention relates to the regenerated liquid of denitrating catalyst, also relate to a kind of preparation method of denitrating catalyst regenerated liquid and the renovation process of denitrating catalyst.

Background technology

Nitrogen oxide is one of Air Pollutant Discharge, is one of important root of the series of environmental problems such as photochemical pollution, city haze weather, Atmospheric Acid Deposition.Because nitrogen oxide can be carried at atmosphere middle and long distance, the even global pollution problem of its regionality caused highlights day by day.Selective catalytic reduction (SelectiveCatalyticReduction, SCR) is the method eliminating nitrogen oxides pollution under special catalyst effect, is specially and adopts ammonia or other reducing agent optionally nitrogen oxide NOx to be reduced to N2 and H2O.

Because SCR method has high efficiency and practicality, now become the study hotspot in flue-gas denitrification field, in developed country, SCR device accounts for more than 75% of total equipment for denitrifying flue gas.In China, SCR device accounts for more than 90% of the total equipment for denitrifying flue gas in coal-burning power plant especially, and these devices use SCR denitration mostly.

SCR denitration belongs to running stores, and chemical lifetime is generally 3 years, is generally about 6 years mechanical life, and expensive catalyst change expense is the significant problem that domestic and international SCR system faces.But catalyst has recyclability, its recyclability both component constitution element original in SCR denitration, proportioning, structure, specific area etc. is relevant, also relevant with the operation operating mode of catalyst and actual level of deactivation.Therefore, denitrating catalyst regeneration techniques arises at the historic moment, and passes through regeneration techniques, make the denitrating catalyst activity recovery of inactivation and selective, greatly can save the operating cost of SCR system, but also eliminate the work disposing decaying catalyst, eliminate the hidden danger of environmental pollution.

Existing regeneration step generally comprises carries out dust removal with machine, ultrasonic cleaning, impregnating active and bake drying etc. to inactivation denitrating catalyst, wherein impregnating active is the committed step of regeneration flow process, is related to the performances such as the catalyst activity of regeneration and whether achieves regeneration object.

Summary of the invention

Primary and foremost purpose of the present invention is, overcomes problems of the prior art, provides a kind of regenerated liquid of denitrating catalyst, can recover the activity of inactivation denitrating catalyst efficiently, and expand the temperature range of catalyst activity.

For solving above technical problem, the regenerated liquid of a kind of denitrating catalyst provided by the invention, raw material components and the weight content of described regenerated liquid are as follows, vanadyl oxalate: 4 ~ 6 parts; Cerous nitrate: 0.08 ~ 0.10 part; Lanthanum nitrate: 0.11 ~ 0.13 part; Copper nitrate: 0.05 ~ 0.07 part; Ludox ST-O:0.4 ~ 0.6 part; Deionized water: 95 parts.

Relative to prior art, the present invention achieves following beneficial effect: 1. vanadyl oxalate is better water-soluble, can form homogeneous system in deionized water, and in regenerative process, the aqueous solution of vanadyl oxalate can be more even when denitrating catalyst surface attachment; Vanadyl oxalate thermal decomposition can generate vanadium dioxide, VOC under high-temperature flue gas 2o 4→ VO 2+ CO ↑+CO 2↑, vanadium dioxide in atmosphere oxidable generation has the V of catalytic activity 2o 5, and then reach catalytic action.2. Ce elements and lanthanum element have abundant energy level and special 4f outer shell structure, there is special process based prediction model, not only itself has catalytic performance, and can carry out modification as additive and co-catalyst to denitrating catalyst, improves the catalytic performance of denitrating catalyst; 3. cerous nitrate and lanthanum nitrate in water with CeO 2and La 2o 3form occur, CeO 2have oxygen vacancy and high oxygen mobility, can improve the oxygen scavenging ability of catalyst, the attachment of Ce significantly increases the quantity of bronsted (Bronsted) acidic site, improves the catalytic reduction activity of denitrating catalyst; 4. in denitrating catalyst, transition metal Cu is added, Cu and CeO 2between cooperative effect the activity of denitrating catalyst and stability can be made to be significantly improved; 5. La 2o 3and CeO 2one pack system rare earth oxide, CeO 2-La 2o 3composite oxides all show good catalytic performance in synchronized desulfuring denitrogenation; 6. the present invention is by adding cerous nitrate, lanthanum nitrate and copper nitrate, utilizes the cooperative effect of transition metal and rare earth oxide, improves further the activity of catalyst and expands the temperature range of catalyst activity.7. Ludox ST-O is the dispersion liquid of nano level silica dioxide granule in water or solvent, because the particle diameter of colloidal particle only has 10-20nm, specific area is large, the water white transparency of particle own, viscosity is lower, the porous place of water can be permeated, dispersed and permeability is all very good when therefore mixing with other material; When Ludox water evaporates, colloidal particle is attached to body surface securely, forms silica and combines, can effectively facilitate the shaping of regenerated catalyst between particle; 8. in this denitrating catalyst regenerated liquid, the content of each component maintains within the scope of the invention, can under the prerequisite ensureing regeneration effect, cost is lower, regeneration expense is less than changing 60% of raw catelyst expense, wherein vanadyl oxalate is that main active content is maximum, rare earth element is lower as auxiliary agent content, and Ludox mobility is poor, and content is also lower is easier to the flowable keeping regenerated liquid.

As preferred version of the present invention, also comprise ammonium metatungstate in described regenerated liquid, the weight ratio of described ammonium metatungstate and described deionized water is (6 ~ 8): 95.As the SO of denitrating catalyst 2/ SO 3there is the situation being greater than 1% in conversion ratio, adding of ammonium metatungstate effectively can suppress SO 2/ SO 3conversion ratio.

Another object of the present invention is, provides a kind of preparation method of denitrating catalyst regenerated liquid, the regenerated liquid of the denitrating catalyst be prepared from, and can recover the activity of inactivation denitrating catalyst efficiently.

For solving above technical problem, the invention provides a kind of preparation method of denitrating catalyst regenerated liquid, the manufacture of described regenerated liquid in turn includes the following steps: (1) prepare regenerated liquid raw material, vanadyl oxalate: 4 ~ 6 parts by following component and weight content; Cerous nitrate: 0.08 ~ 0.10 part; Lanthanum nitrate: 0.11 ~ 0.13 part; Copper nitrate: 0.05 ~ 0.07 part; Ludox ST-O:0.4 ~ 0.6 part; Deionized water: 95 parts; (2) vanadyl oxalate and deionized water are dropped in mixer and stir; (3) continue drop into cerous nitrate, lanthanum nitrate and copper nitrate and fully stir until dissolve completely in mixer; (4) in mixer, drop into Ludox ST-O continue to stir until homogeneous phase.

As preferred version of the present invention, also ammonium metatungstate is comprised in the raw material components of described regenerated liquid, the weight ratio of described ammonium metatungstate and described deionized water is (6 ~ 8): 95, described step (2) and described step (3) between increase following steps: described ammonium metatungstate is dropped into mixer and stirs.

Relative to prior art, the beneficial effect obtained of manufacture of the present invention is as follows: first add the highest vanadyl oxalate of content, then adds the very low rare earth element of content, after dissolution homogeneity mixing, finally add the poor Ludox of mobility, can more effectively make solution mix; The beneficial effect that the denitrating catalyst regenerated liquid manufactured obtains is described above.

Another object of the present invention is, provides a kind of renovation process of denitrating catalyst, can recover the activity of inactivation denitrating catalyst efficiently.

For solving above technical problem, the invention provides a kind of renovation process of denitrating catalyst, in turn including the following steps: (1) prepare cleaning fluid raw material, AEO: 0.8 ~ 1.2 part by following component and weight content; Cithrol: 0.8 ~ 1.2 part; Ethanol: 9 ~ 11 parts; Deionized water: 88 parts; Above cleaning fluid raw material is mixed and is stirred in rinse bath and evenly obtains denitrating catalyst cleaning fluid; (2) prepare regenerated liquid raw material, vanadyl oxalate: 4 ~ 6 parts by following component and weight content; Cerous nitrate: 0.08 ~ 0.10 part; Lanthanum nitrate: 0.11 ~ 0.13 part; Copper nitrate: 0.05 ~ 0.07 part; Ludox ST-O:0.4 ~ 0.6 part; Deionized water: 95 parts; First vanadyl oxalate and deionized water are dropped in mixer and stir, continue again drop into cerous nitrate, lanthanum nitrate and copper nitrate and fully stir until dissolve completely in mixer, in mixer, then drop into Ludox ST-O continue to stir until homogeneous phase obtains denitrating catalyst regenerated liquid; By inactivation but mechanical life also denitrification catalyst module, successively after brute force purges and Ultrasonic Cleaning removes dust and adsorption thing, be soaked in taking-up after 18 minutes ~ 25 minutes in step denitrating catalyst cleaning fluid (1); (4) denitrification catalyst module is continued to be soaked in step denitrating catalyst regenerated liquid (2), take out after 25 minutes ~ 40 minutes; (5) bake drying is carried out to denitrification catalyst module.

Relative to prior art, the beneficial effect obtained of manufacture of the present invention is as follows: (1) AEO and cithrol are non-ionic surface active agent, all belong to bleeding agent, there is fixing hydrophilic and oleophilic group, align in the surface energy of solution, and the surface tension of water can be reduced, change the angle of wetting of solid liquid interface, wetability, again wetability are all fine, and there is emulsification and clean result, the cleaning performance of cleaning fluid to denitrating catalyst micropore can be improved, also facilitate the dipping of regenerated liquid simultaneously better.(2) ethanol is as micropore cleaning agent, can effectively clean denitrating catalyst micropore canals, makes the active material in regenerated liquid easier in the attachment of catalyst micropore surface, improves the denitration activity of the denitrating catalyst after regeneration.AEO and cithrol content less, ethanol is volatile so content is slightly high, but both percentage compositions must control within the scope of the invention, otherwise the interpolation of consequent activities composition can be affected, so that affect the use of regenerated catalyst.(4) vanadyl oxalate is better water-soluble, can form homogeneous system in deionized water, and in regenerative process, the aqueous solution of vanadyl oxalate can be more even when denitrating catalyst surface attachment; Vanadyl oxalate thermal decomposition can generate vanadium dioxide, VOC under high-temperature flue gas 2o 4→ VO 2+ CO ↑+CO 2↑, vanadium dioxide in atmosphere oxidable generation has the V of catalytic activity 2o 5, and then reach catalytic action.(5) Ce elements and lanthanum element have abundant energy level and special 4f outer shell structure, there is special process based prediction model, not only itself has catalytic performance, and can carry out modification as additive and co-catalyst to denitrating catalyst, improves the catalytic performance of denitrating catalyst; Cerous nitrate and lanthanum nitrate in water with CeO 2and La 2o 3form occur, CeO 2have oxygen vacancy and high oxygen mobility, can improve the oxygen scavenging ability of catalyst, the attachment of Ce significantly increases the quantity of bronsted (Bronsted) acidic site, improves the catalytic reduction activity of denitrating catalyst; (7) in denitrating catalyst, add transition metal Cu, Cu and CeO 2between cooperative effect the activity of denitrating catalyst and stability can be made to be significantly improved; (8) La 2o 3and CeO 2one pack system rare earth oxide, CeO 2-La 2o 3composite oxides all show good catalytic performance in synchronized desulfuring denitrogenation; (9) the present invention is by adding cerous nitrate, lanthanum nitrate and copper nitrate, utilizes the cooperative effect of transition metal and rare earth oxide, improves further the activity of catalyst and expands the temperature range of catalyst activity.(10) Ludox ST-O is the dispersion liquid of nano level silica dioxide granule in water or solvent, because the particle diameter of colloidal particle only has 10-20nm, specific area is large, the water white transparency of particle own, viscosity is lower, the porous place of water can be permeated, dispersed and permeability is all very good when therefore mixing with other material; When Ludox water evaporates, colloidal particle is attached to body surface securely, forms silica and combines, can effectively facilitate the shaping of regenerated catalyst between particle; (11) in this denitrating catalyst regenerated liquid, the content of each component maintains within the scope of the invention, can under the prerequisite ensureing regeneration effect, cost is lower, regeneration expense is less than changing 60% of raw catelyst expense, wherein vanadyl oxalate is that main active content is maximum, rare earth element is lower as auxiliary agent content, and Ludox mobility is poor, and content is also lower is easier to the flowable keeping regenerated liquid.

As preferred version of the present invention, described step (2) in regenerated liquid raw material components in also comprise ammonium metatungstate, the weight ratio of described ammonium metatungstate and described deionized water is (6 ~ 8): 95, after described vanadyl oxalate and deionized water stir in mixer, described ammonium metatungstate dropped into mixer and stirs, then continuing drop into described cerous nitrate, lanthanum nitrate and copper nitrate and fully stir until dissolve completely in mixer.As the SO of denitrating catalyst 2/ SO 3there is the situation being greater than 1% in conversion ratio, adding of ammonium metatungstate effectively can suppress SO 2/ SO 3conversion ratio.

As preferred version of the present invention, the raw material components of described regenerated liquid and weight content are: vanadyl oxalate: 4 parts; Cerous nitrate: 0.08 part; Lanthanum nitrate: 0.11 part; Copper nitrate: 0.05 part; Ludox ST-O:0.4 part; Deionized water: 95 parts.

As preferred version of the present invention, the raw material components of described regenerated liquid and weight content are: vanadyl oxalate: 5 parts; Cerous nitrate: 0.09 part; Lanthanum nitrate: 0.12 part; Copper nitrate: 0.06 part; Ludox ST-O:0.5 part; Deionized water: 95 parts.

As preferred version of the present invention, the raw material components of described regenerated liquid and weight content are: vanadyl oxalate: 6 parts; Cerous nitrate: 0.10 part; Lanthanum nitrate: 0.13 part; Copper nitrate: 0.07 part; Ludox ST-O:0.6 part; Deionized water: 95 parts.

As preferred version of the present invention, the raw material components of described regenerated liquid and weight content are: vanadyl oxalate: 5 parts; Ammonium metatungstate 7 parts; Cerous nitrate: 0.09 part; Lanthanum nitrate: 0.12 part; Copper nitrate: 0.06 part; Ludox ST-O:0.5 part; Deionized water: 95 parts.

Detailed description of the invention

Embodiment one

For inactivation but mechanical life also and SO 2/ SO 3conversion ratio is the denitrating catalyst of 0.53%, takes following steps to regenerate:

(1) following component and weight content prepare cleaning fluid raw material, AEO: 0.8 part; Cithrol: 0.8 part; Ethanol: 9 parts; Deionized water: 88 parts; Above cleaning fluid raw material is mixed and is stirred in rinse bath and evenly obtains denitrating catalyst cleaning fluid;

(2) prepare regenerated liquid raw material, vanadyl oxalate: 4 parts by following component and weight content; Cerous nitrate: 0.08 part; Lanthanum nitrate: 0.11 part; Copper nitrate: 0.05 part; Ludox ST-O:0.4 part; Deionized water: 95 parts; First vanadyl oxalate and deionized water are dropped in mixer and stir, continue again drop into cerous nitrate, lanthanum nitrate and copper nitrate and fully stir until dissolve completely in mixer, in mixer, then drop into Ludox ST-O continue to stir until homogeneous phase obtains denitrating catalyst regenerated liquid;

By inactivation but mechanical life also denitrification catalyst module, successively after brute force purges and Ultrasonic Cleaning removes dust and adsorption thing, be soaked in taking-up after 18 minutes in step denitrating catalyst cleaning fluid (1);

(4) denitrification catalyst module is continued to be soaked in step denitrating catalyst regenerated liquid (2), take out after 25 minutes;

(5) bake drying is carried out to denitrification catalyst module.

Embodiment two

For inactivation but mechanical life also and SO 2/ SO 3conversion ratio is the denitrating catalyst of 0.62%, takes following steps to regenerate:

(1) following component and weight content prepare cleaning fluid raw material, AEO: 1.0 parts; Cithrol: 1.0 parts; Ethanol: 10 parts; Deionized water: 88 parts; Above cleaning fluid raw material is mixed and is stirred in rinse bath and evenly obtains denitrating catalyst cleaning fluid;

(2) following component and weight content prepare regenerated liquid raw material, vanadyl oxalate: 5 parts; Cerous nitrate: 0.09 part; Lanthanum nitrate: 0.12 part; Copper nitrate: 0.06 part; Ludox ST-O:0.5 part; Deionized water: 95 parts; First vanadyl oxalate and deionized water are dropped in mixer and stir, continue again drop into cerous nitrate, lanthanum nitrate and copper nitrate and fully stir until dissolve completely in mixer, in mixer, then drop into Ludox ST-O continue to stir until homogeneous phase obtains denitrating catalyst regenerated liquid;

Inactivation but mechanical life also denitrification catalyst module, successively after brute force purges and Ultrasonic Cleaning removes dust and adsorption thing, be soaked in taking-up after 22 minutes in step denitrating catalyst cleaning fluid (1);

(4) denitrification catalyst module continues to be soaked in step denitrating catalyst regenerated liquid (2), takes out after 35 minutes;

(5) bake drying is carried out to denitrification catalyst module.

Embodiment three

For inactivation but mechanical life also and SO 2/ SO 3conversion ratio is the denitrating catalyst of 0.67%, takes following steps to regenerate:

(1) following component and weight content prepare cleaning fluid raw material, AEO: 1.2 parts; Cithrol: 1.2 parts; Ethanol: 11 parts; Deionized water: 88 parts; Above cleaning fluid raw material is mixed and is stirred in rinse bath and evenly obtains denitrating catalyst cleaning fluid;

(2) prepare regenerated liquid raw material, vanadyl oxalate: 6 parts by following component and weight content; Cerous nitrate: 0.10 part; Lanthanum nitrate: 0.13 part; Copper nitrate: 0.07 part; Ludox ST-O:0.6 part; Deionized water: 95 parts; First vanadyl oxalate and deionized water are dropped in mixer and stir, continue again drop into cerous nitrate, lanthanum nitrate and copper nitrate and fully stir until dissolve completely in mixer, in mixer, then drop into Ludox ST-O continue to stir until homogeneous phase obtains denitrating catalyst regenerated liquid;

By inactivation but mechanical life also denitrification catalyst module, successively after brute force purges and Ultrasonic Cleaning removes dust and adsorption thing, be soaked in taking-up after 25 minutes in step denitrating catalyst cleaning fluid (1);

(4) denitrification catalyst module is continued to be soaked in step denitrating catalyst regenerated liquid (2), take out after 40 minutes;

(5) bake drying is carried out to denitrification catalyst module.

Embodiment four

For inactivation but mechanical life also and SO 2/ SO 3conversion ratio is the denitrating catalyst of 0.69%, takes following steps to regenerate:

(1) following component and weight content prepare cleaning fluid raw material, AEO: 0.8 part; Cithrol: 1.2 parts; Ethanol: 9 parts; Deionized water: 88 parts; Above cleaning fluid raw material is mixed and is stirred in rinse bath and evenly obtains denitrating catalyst cleaning fluid;

(2) prepare regenerated liquid raw material, vanadyl oxalate: 4 parts by following component and weight content; Cerous nitrate: 0.10 part; Lanthanum nitrate: 0.11 part; Copper nitrate: 0.05 part; Ludox ST-O:0.6 part; Deionized water: 95 parts; First vanadyl oxalate and deionized water are dropped in mixer and stir, continue again drop into cerous nitrate, lanthanum nitrate and copper nitrate and fully stir until dissolve completely in mixer, in mixer, then drop into Ludox ST-O continue to stir until homogeneous phase obtains denitrating catalyst regenerated liquid;

By inactivation but mechanical life also denitrification catalyst module, successively after brute force purges and Ultrasonic Cleaning removes dust and adsorption thing, be soaked in taking-up after 20 minutes in step denitrating catalyst cleaning fluid (1);

(5) denitrification catalyst module continues to be soaked in step denitrating catalyst regenerated liquid (2), takes out after 30 minutes;

(5) bake drying is carried out to denitrification catalyst module.

Embodiment five

For inactivation but mechanical life also and SO 2/ SO 3conversion ratio is the denitrating catalyst of 0.68%, takes following steps to regenerate:

(1) following component and weight content prepare cleaning fluid raw material, AEO: 1.2 parts; Cithrol: 0.8 part; Ethanol: 11 parts; Deionized water: 88 parts; Above cleaning fluid raw material is mixed and is stirred in rinse bath and evenly obtains denitrating catalyst cleaning fluid;

(2) prepare regenerated liquid raw material, vanadyl oxalate: 6 parts by following component and weight content; Cerous nitrate: 0.08 part; Lanthanum nitrate: 0.11 part; Copper nitrate: 0.05 part; Ludox ST-O:0.4 part; Deionized water: 95 parts; First vanadyl oxalate and deionized water are dropped in mixer and stir, continue again drop into cerous nitrate, lanthanum nitrate and copper nitrate and fully stir until dissolve completely in mixer, in mixer, then drop into Ludox ST-O continue to stir until homogeneous phase obtains denitrating catalyst regenerated liquid;

By inactivation but mechanical life also denitrification catalyst module, successively after brute force purges and Ultrasonic Cleaning removes dust and adsorption thing, be soaked in taking-up after 23 minutes in step denitrating catalyst cleaning fluid (1);

(4) denitrification catalyst module is continued to be soaked in step denitrating catalyst regenerated liquid (2), take out after 35 minutes;

(5) bake drying is carried out to denitrification catalyst module.

Embodiment six

For inactivation but mechanical life also and SO 2/ SO 3conversion ratio is the denitrating catalyst of 0.65%, takes following steps to regenerate:

(1) following component and weight content prepare cleaning fluid raw material, AEO: 0.9 part; Cithrol: 0.9 part; Ethanol: 11 parts; Deionized water: 88 parts; Above cleaning fluid raw material is mixed and is stirred in rinse bath and evenly obtains denitrating catalyst cleaning fluid;

(2) following component and weight content prepare regenerated liquid raw material, vanadyl oxalate: 6 parts; Cerous nitrate: 0.09 part; Lanthanum nitrate: 0.11 part; Copper nitrate: 0.07 part; Ludox ST-O:0.4 part; Deionized water: 95 parts; First vanadyl oxalate and deionized water are dropped in mixer and stir, continue again drop into cerous nitrate, lanthanum nitrate and copper nitrate and fully stir until dissolve completely in mixer, in mixer, then drop into Ludox ST-O continue to stir until homogeneous phase obtains denitrating catalyst regenerated liquid;

Inactivation but mechanical life also denitrification catalyst module, successively after brute force purges and Ultrasonic Cleaning removes dust and adsorption thing, be soaked in taking-up after 24 minutes in step denitrating catalyst cleaning fluid (1);

(4) denitrification catalyst module continues to be soaked in step denitrating catalyst regenerated liquid (2), takes out after 36 minutes;

(5) bake drying is carried out to denitrification catalyst module.

Embodiment seven

For inactivation but mechanical life also and SO 2/ SO 3conversion ratio is the denitrating catalyst of 1.01%, takes following steps to regenerate:

(1) following component and weight content prepare cleaning fluid raw material, AEO: 0.8 part; Cithrol: 0.8 part; Ethanol: 9 parts; Deionized water: 88 parts; Above cleaning fluid raw material is mixed and is stirred in rinse bath and evenly obtains denitrating catalyst cleaning fluid;

(2) prepare regenerated liquid raw material, vanadyl oxalate: 4 parts by following component and weight content; Ammonium metatungstate: 6 parts; Cerous nitrate: 0.08 part; Lanthanum nitrate: 0.11 part; Copper nitrate: 0.05 part; Ludox ST-O:0.4 part; Deionized water: 95 parts; First vanadyl oxalate and deionized water are dropped in mixer and stir, then ammonium metatungstate dropped into mixer and stir, continue again drop into cerous nitrate, lanthanum nitrate and copper nitrate and fully stir until dissolve completely in mixer, in mixer, then drop into Ludox ST-O continue to stir until homogeneous phase obtains denitrating catalyst regenerated liquid;

By inactivation but mechanical life also denitrification catalyst module, successively after brute force purges and Ultrasonic Cleaning removes dust and adsorption thing, be soaked in taking-up after 18 minutes in step denitrating catalyst cleaning fluid (1);

(4) denitrification catalyst module is continued to be soaked in step denitrating catalyst regenerated liquid (2), take out after 25 minutes;

(5) bake drying is carried out to denitrification catalyst module.

Embodiment eight

For inactivation but mechanical life also and SO 2/ SO 3conversion ratio is the denitrating catalyst of 1.03%, takes following steps to regenerate:

(1) following component and weight content prepare cleaning fluid raw material, AEO: 1.0 parts; Cithrol: 1.1 parts; Ethanol: 10 parts; Deionized water: 88 parts; Above cleaning fluid raw material is mixed and is stirred in rinse bath and evenly obtains denitrating catalyst cleaning fluid;

(2) following component and weight content prepare regenerated liquid raw material, vanadyl oxalate: 5 parts; Ammonium metatungstate: 7 parts; Cerous nitrate: 0.09 part; Lanthanum nitrate: 0.12 part; Copper nitrate: 0.06 part; Ludox ST-O:0.5 part; Deionized water: 95 parts; First vanadyl oxalate and deionized water are dropped in mixer and stir, then ammonium metatungstate dropped into mixer and stir, continue again drop into cerous nitrate, lanthanum nitrate and copper nitrate and fully stir until dissolve completely in mixer, in mixer, then drop into Ludox ST-O continue to stir until homogeneous phase obtains denitrating catalyst regenerated liquid;

Inactivation but mechanical life also denitrification catalyst module, successively after brute force purges and Ultrasonic Cleaning removes dust and adsorption thing, be soaked in taking-up after 22 minutes in step denitrating catalyst cleaning fluid (1);

(4) denitrification catalyst module continues to be soaked in step denitrating catalyst regenerated liquid (2), takes out after 32 minutes;

(5) bake drying is carried out to denitrification catalyst module.

Embodiment nine

For inactivation but mechanical life also and SO 2/ SO 3conversion ratio is the denitrating catalyst of 1.02%, takes following steps to regenerate:

(1) following component and weight content prepare cleaning fluid raw material, AEO: 1.2 parts; Cithrol: 1.2 parts; Ethanol: 11 parts; Deionized water: 88 parts; Above cleaning fluid raw material is mixed and is stirred in rinse bath and evenly obtains denitrating catalyst cleaning fluid;

(2) prepare regenerated liquid raw material, vanadyl oxalate: 6 parts by following component and weight content; Ammonium metatungstate: 8 parts; Cerous nitrate: 0.10 part; Lanthanum nitrate: 0.13 part; Copper nitrate: 0.07 part; Ludox ST-O:0.6 part; Deionized water: 95 parts; First vanadyl oxalate and deionized water are dropped in mixer and stir, then ammonium metatungstate dropped into mixer and stir, continue again drop into cerous nitrate, lanthanum nitrate and copper nitrate and fully stir until dissolve completely in mixer, in mixer, then drop into Ludox ST-O continue to stir until homogeneous phase obtains denitrating catalyst regenerated liquid;

By inactivation but mechanical life also denitrification catalyst module, successively after brute force purges and Ultrasonic Cleaning removes dust and adsorption thing, be soaked in taking-up after 25 minutes in step denitrating catalyst cleaning fluid (1);

(4) denitrification catalyst module is continued to be soaked in step denitrating catalyst regenerated liquid (2), take out after 40 minutes;

(5) bake drying is carried out to denitrification catalyst module.

Carry out test comparison as table 1 to the activity ratio K/K0 before and after the regeneration of the denitrification catalyst module of embodiment one to embodiment nine, the activity ratio K/K0 of described denitrating catalyst is compared draw for surveying denitrating catalyst activity (K) and fresh denitrating catalyst activity (K0).Employing publication number is that the SCR denitration system catalyst activity test experience device in the Chinese utility model patent of 203479784U detects.

Table 1:

Visible, through regeneration of the present invention, make the activity ratio of denitrating catalyst return to 0.91 ~ 1.02 from 0.64 ~ 0.79.

Ludox ST-O can select the daily output Ludox ST-O of Shanghai Zhu Tian Chemical Industry Science Co., Ltd.

In addition to the implementation, the present invention can also have other embodiments.All employings are equal to the technical scheme of replacement or equivalent transformation formation, all drop on the protection domain of application claims.

Claims (6)

1. a renovation process for denitrating catalyst, is characterized in that, in turn includes the following steps: (1) prepare cleaning fluid raw material, AEO: 0.8 ~ 1.2 part by following component and weight content; Cithrol: 0.8 ~ 1.2 part; Ethanol: 9 ~ 11 parts; Deionized water: 88 parts; Above cleaning fluid raw material is mixed and is stirred in rinse bath and evenly obtains denitrating catalyst cleaning fluid; (2) prepare regenerated liquid raw material, vanadyl oxalate: 4 ~ 6 parts by following component and weight content; Cerous nitrate: 0.08 ~ 0.10 part; Lanthanum nitrate: 0.11 ~ 0.13 part; Copper nitrate: 0.05 ~ 0.07 part; Ludox ST-O:0.4 ~ 0.6 part; Deionized water: 95 parts; First vanadyl oxalate and deionized water are dropped in mixer and stir, continue again drop into cerous nitrate, lanthanum nitrate and copper nitrate and fully stir until dissolve completely in mixer, in mixer, then drop into Ludox ST-O continue to stir until homogeneous phase obtains denitrating catalyst regenerated liquid; By inactivation but mechanical life also denitrification catalyst module, successively after brute force purges and Ultrasonic Cleaning removes dust and adsorption thing, be soaked in taking-up after 18 minutes ~ 25 minutes in step denitrating catalyst cleaning fluid (1); (4) denitrification catalyst module is continued to be soaked in step denitrating catalyst regenerated liquid (2), take out after 25 minutes ~ 40 minutes; (5) bake drying is carried out to denitrification catalyst module.
2. the renovation process of denitrating catalyst according to claim 1, it is characterized in that, described step (2) in regenerated liquid raw material components in also comprise ammonium metatungstate, the weight ratio of described ammonium metatungstate and described deionized water is (6 ~ 8): 95, after described vanadyl oxalate and deionized water stir in mixer, described ammonium metatungstate dropped into mixer and stirs, then continuing drop into described cerous nitrate, lanthanum nitrate and copper nitrate and fully stir until dissolve completely in mixer.
3. the renovation process of denitrating catalyst according to claim 1, is characterized in that, the raw material components of described regenerated liquid and weight content are: vanadyl oxalate: 4 parts; Cerous nitrate: 0.08 part; Lanthanum nitrate: 0.11 part; Copper nitrate: 0.05 part; Ludox ST-O:0.4 part; Deionized water: 95 parts.
4. the renovation process of denitrating catalyst according to claim 1, is characterized in that, the raw material components of described regenerated liquid and weight content are: vanadyl oxalate: 5 parts; Cerous nitrate: 0.09 part; Lanthanum nitrate: 0.12 part; Copper nitrate: 0.06 part; Ludox ST-O:0.5 part; Deionized water: 95 parts.
5. the renovation process of denitrating catalyst according to claim 1, is characterized in that, the raw material components of described regenerated liquid and weight content are: vanadyl oxalate: 6 parts; Cerous nitrate: 0.10 part; Lanthanum nitrate: 0.13 part; Copper nitrate: 0.07 part; Ludox ST-O:0.6 part; Deionized water: 95 parts.
6. the renovation process of denitrating catalyst according to claim 2, is characterized in that, the raw material components of described regenerated liquid and weight content are: vanadyl oxalate: 5 parts; Ammonium metatungstate 7 parts; Cerous nitrate: 0.09 part; Lanthanum nitrate: 0.12 part; Copper nitrate: 0.06 part; Ludox ST-O:0.5 part; Deionized water: 95 parts.
CN201410165148.0A 2014-04-23 2014-04-23 Denitrating catalyst regenerated liquid, regenerated liquid preparation method and catalyst recovery process CN103949291B (en)

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Publication number Priority date Publication date Assignee Title
CN105709861B (en) * 2014-12-05 2018-07-03 中国石油化工股份有限公司 A kind of regeneration method of SCR denitration
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CN106179529B (en) * 2016-06-30 2018-09-28 大唐南京环保科技有限责任公司 One kind is for the regenerated cleaning solution of denitrating catalyst and its preparation method and application that fails
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6025292A (en) * 1997-02-27 2000-02-15 Mitsubishi Heavy Industries Ltd. Method for the regeneration of a denitration catalyst
CN101574671A (en) * 2009-04-29 2009-11-11 常州市肯创环境工程技术有限公司 Regeneration fluid for SCR denitration catalyst
CN102059156A (en) * 2010-12-21 2011-05-18 重庆远达催化剂制造有限公司 Denitration catalyst regenerating solution and regenerating method thereof
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
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
CN102974366A (en) * 2011-09-05 2013-03-20 内诺株式会社 Method for catalyst reactivation

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6025292A (en) * 1997-02-27 2000-02-15 Mitsubishi Heavy Industries Ltd. Method for the regeneration of a denitration catalyst
CN101574671A (en) * 2009-04-29 2009-11-11 常州市肯创环境工程技术有限公司 Regeneration fluid for SCR denitration catalyst
CN102059156A (en) * 2010-12-21 2011-05-18 重庆远达催化剂制造有限公司 Denitration catalyst regenerating solution and regenerating method thereof
CN102974366A (en) * 2011-09-05 2013-03-20 内诺株式会社 Method for catalyst reactivation
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
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

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