CN103949291A - Denitration catalyst regeneration solution and preparation method thereof as well as catalyst regeneration method - Google Patents

Denitration catalyst regeneration solution and preparation method thereof as well as catalyst regeneration method Download PDF

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CN103949291A
CN103949291A CN201410165148.0A CN201410165148A CN103949291A CN 103949291 A CN103949291 A CN 103949291A CN 201410165148 A CN201410165148 A CN 201410165148A CN 103949291 A CN103949291 A CN 103949291A
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parts
nitrate
regenerated liquid
deionized water
denitrating catalyst
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CN201410165148.0A
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CN103949291B (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 denitration catalyst regeneration solution and a preparation method thereof as well as a catalyst regeneration method. The denitration catalyst regeneration solution comprises the following raw material ingredients in parts by weight: 4-6 parts of vanadyl oxalate, 0.08-0.10 part of cerium nitrate, 0.11-0.13 part of lanthanum nitrate, 0.05-0.07 part of copper nitrate, 0.4-0.6 part of silica sol ST-O and 95 parts of deionized water. The catalyst regeneration method comprises the following steps of firstly, evenly mixing vanadyl oxalate and the deionized water; then, feeding cerium nitrate, lanthanum nitrate and copper nitrate into mixed solution, and fully stirring until the mixture is completely dissolved; finally, feeding silica sol ST-O, and continuing to stir until homogeneous phase is obtained; and sequentially carrying out strong scavenging and ultrasonic cleaning on an inactivated denitration catalyst module, soaking the module in cleaning solution for 18-25 minutes, continuing soaking the module in the regeneration solution for 25-40 minutes, taking out the denitration catalyst module and drying. After the denitration catalyst regeneration solution and the catalyst regeneration method are adopted, the activity of the inactivated denitration catalyst can be efficiently recovered, and the temperature range of the catalyst activity is widened.

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 causing highlights day by day.Selective catalytic reduction (Selective Catalytic Reduction, SCR) is the method for nitrogen oxides pollution of eliminating 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 the more than 75% of total equipment for denitrifying flue gas.In China, SCR device accounts for the more than 90% of the total equipment for denitrifying flue gas in coal-burning power plant especially, and these devices are used SCR denitrating catalyst mostly.

SCR denitrating catalyst belongs to running stores, and chemical lifetime is generally 3 years, is generally mechanical life about 6 years, and expensive catalyst change expense is a significant problem of domestic and international SCR systems face.But catalyst has recyclability, its recyclability is both relevant, also relevant with operation operating mode and the actual level of deactivation of catalyst with the original component Constitution Elements of SCR denitrating catalyst, proportioning, structure, specific area etc.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, can greatly save the operating cost of SCR system, but also save the work of disposing decaying catalyst, eliminate the hidden danger of environmental pollution.

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

Summary of the invention

Primary and foremost purpose of the present invention is, overcomes problems of the prior art, and a kind of regenerated liquid of denitrating catalyst is provided, and can recover efficiently the activity of inactivation denitrating catalyst, and expands 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, oxalic acid vanadyl: 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.

With respect to prior art, the present invention has obtained following beneficial effect: 1. the water-soluble of oxalic acid vanadyl better can form homogeneous system in deionized water, and in regenerative process, the aqueous solution of oxalic acid vanadyl can be more even when denitrating catalyst surface attachment; Oxalic acid vanadyl can thermal decomposition generate vanadium dioxide, VOC under high-temperature flue gas 2o 4→ VO 2+ CO ↑+CO 2↑, vanadium dioxide oxidable generation in air 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 physics and chemistry performance, not only itself has catalytic performance, and can be used as additive and co-catalyst carries out modification 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 deoxygenation ability of catalyst, Ce adheres to the remarkable quantity that has increased bronsted (Bronsted) acidic site, improves the catalytic reduction activity of denitrating catalyst; 4. in denitrating catalyst, add transition metal Cu, Cu and CeO 2between cooperative effect can make the activity of denitrating catalyst and stability 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, by adding cerous nitrate, lanthanum nitrate and copper nitrate, utilizes the cooperative effect of transition metal and rare earth oxide, further improves the active 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, therefore the porous place of water can be permeated, and dispersiveness and permeability are all very good and when other material mixes; When Ludox water evaporates, colloidal particle is attached to body surface securely, forms silica combination between particle, can effectively facilitate the moulding of regenerated catalyst; 8. in this denitrating catalyst regenerated liquid, the content of each component maintains within the scope of the invention, can guarantee under the prerequisite of regeneration effect, cost is lower, regeneration expense is less than changing 60% of raw catelyst expense, its mesoxalic acid vanadyl is that main active content is maximum, rare earth element is lower as auxiliary agent content, and Ludox mobility is poor, and content is the lower flowable that is easier to keep regenerated liquid also.

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

Another object of the present invention is, a kind of preparation method of denitrating catalyst regenerated liquid is provided, and the regenerated liquid of the denitrating catalyst being prepared from 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) by following component and weight content, prepare regenerated liquid raw material, oxalic acid vanadyl: 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; (2) will in oxalic acid vanadyl and deionized water input mixer, stir; (3) in mixer, continue to drop into cerous nitrate, lanthanum nitrate and copper nitrate and fully stir until dissolve completely; (4) in mixer, drop into Ludox ST-O continuation stirring until homogeneous phase.

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

With respect to prior art, the beneficial effect of obtaining that manufacture of the present invention forms is as follows: first add the oxalic acid vanadyl that content is the highest, then add the rare earth element that content is very low, after solution evenly mixes, finally add the poor Ludox of mobility, can more effectively make solution mix; The beneficial effect that the denitrating catalyst regenerated liquid that manufacture forms is obtained as mentioned above.

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

For solving above technical problem, the invention provides a kind of renovation process of denitrating catalyst, in turn include the following steps: (1) by following component and weight content, prepare cleaning fluid raw material, AEO: 0.8 ~ 1.2 part; 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 obtain denitrating catalyst cleaning fluid; (2) by following component and weight content, prepare regenerated liquid raw material, oxalic acid vanadyl: 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 will in oxalic acid vanadyl and deionized water input mixer, stir, again to continuing to drop into cerous nitrate, lanthanum nitrate and copper nitrate in mixer and fully stirring until dissolve completely, then to dropping into Ludox ST-O in mixer, continue to stir until homogeneous phase obtains denitrating catalyst regenerated liquid; By inactivation but mechanical life also denitrification catalyst module, through brute force, purge successively and Ultrasonic Cleaning is removed after 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), after 25 minutes ~ 40 minutes, take out; (5) denitrification catalyst module is carried out to bake drying.

With respect to prior art, the beneficial effect of obtaining that manufacture of the present invention forms 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, surface at solution can align, and can reduce the surface tension of water, change the angle of wetting of solid liquid interface, wetability, wetability is all fine again, and there is emulsification and clean result, can improve the cleaning performance of cleaning fluid to denitrating catalyst micropore, also promote better the dipping of regenerated liquid simultaneously.(2) ethanol, as micropore cleaning agent, can clean denitrating catalyst micropore canals effectively, and the active material in regenerated liquid is more easily adhered at catalyst micropore surface, improves the denitration activity of the denitrating catalyst after regeneration.(3) AEO and cithrol content are less, so the volatile content of ethanol is slightly high, but both percentage compositions must be controlled within the scope of the invention, otherwise can affect the interpolation of follow-up active component, so that the use of impact regeneration rear catalyst.(4) the water-soluble of oxalic acid vanadyl better can form homogeneous system in deionized water, and in regenerative process, the aqueous solution of oxalic acid vanadyl can be more even when denitrating catalyst surface attachment; Oxalic acid vanadyl can thermal decomposition generate vanadium dioxide, VOC under high-temperature flue gas 2o 4→ VO 2+ CO ↑+CO 2↑, vanadium dioxide oxidable generation in air 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 physics and chemistry performance, not only itself has catalytic performance, and can be used as additive and co-catalyst carries out modification 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 deoxygenation ability of catalyst, Ce adheres to the remarkable quantity that has increased 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 can make the activity of denitrating catalyst and stability 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, by adding cerous nitrate, lanthanum nitrate and copper nitrate, utilizes the cooperative effect of transition metal and rare earth oxide, further improves the active 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, therefore the porous place of water can be permeated, and dispersiveness and permeability are all very good and when other material mixes; When Ludox water evaporates, colloidal particle is attached to body surface securely, forms silica combination between particle, can effectively facilitate the moulding of regenerated catalyst; (11) in this denitrating catalyst regenerated liquid, the content of each component maintains within the scope of the invention, can guarantee under the prerequisite of regeneration effect, cost is lower, regeneration expense is less than changing 60% of raw catelyst expense, its mesoxalic acid vanadyl is that main active content is maximum, rare earth element is lower as auxiliary agent content, and Ludox mobility is poor, and content is the lower flowable that is easier to keep regenerated liquid also.

As preferred version of the present invention, described step also comprises ammonium metatungstate in the raw material components of regenerated liquid in (2), the weight ratio of described ammonium metatungstate and described deionized water is (6 ~ 8): 95, after described oxalic acid vanadyl and deionized water stir in mixer, described ammonium metatungstate is dropped into mixer and stirs, then continue to drop into described cerous nitrate, lanthanum nitrate and copper nitrate and fully stir until dissolve completely in mixer.SO when denitrating catalyst 2/ SO 3there is being greater than 1% situation in conversion ratio, adding of ammonium metatungstate can effectively 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: oxalic acid vanadyl: 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: oxalic acid vanadyl: 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: oxalic acid vanadyl: 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: oxalic acid vanadyl: 5 parts; 7 parts of ammonium metatungstates; 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.

The specific embodiment

Embodiment mono-

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

(1) following component and weight content are prepared 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 obtain denitrating catalyst cleaning fluid;

(2) by following component and weight content, prepare regenerated liquid raw material, oxalic acid vanadyl: 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; First will in oxalic acid vanadyl and deionized water input mixer, stir, again to continuing to drop into cerous nitrate, lanthanum nitrate and copper nitrate in mixer and fully stirring until dissolve completely, then to dropping into Ludox ST-O in mixer, continue to stir until homogeneous phase obtains denitrating catalyst regenerated liquid;

By inactivation but mechanical life also denitrification catalyst module, through brute force, purge successively and Ultrasonic Cleaning is removed after 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), after 25 minutes, take out;

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

Embodiment bis-

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

(1) following component and weight content are prepared 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 obtain denitrating catalyst cleaning fluid;

(2) following component and weight content are prepared regenerated liquid raw material, oxalic acid vanadyl: 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 will in oxalic acid vanadyl and deionized water input mixer, stir, again to continuing to drop into cerous nitrate, lanthanum nitrate and copper nitrate in mixer and fully stirring until dissolve completely, then to dropping into Ludox ST-O in mixer, continue to stir until homogeneous phase obtains denitrating catalyst regenerated liquid;

Inactivation but mechanical life also denitrification catalyst module, through brute force, purge successively and Ultrasonic Cleaning is removed after 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), after 35 minutes, takes out;

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

Embodiment tri-

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

(1) following component and weight content are prepared 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 obtain denitrating catalyst cleaning fluid;

(2) by following component and weight content, prepare regenerated liquid raw material, oxalic acid vanadyl: 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; First will in oxalic acid vanadyl and deionized water input mixer, stir, again to continuing to drop into cerous nitrate, lanthanum nitrate and copper nitrate in mixer and fully stirring until dissolve completely, then to dropping into Ludox ST-O in mixer, continue to stir until homogeneous phase obtains denitrating catalyst regenerated liquid;

By inactivation but mechanical life also denitrification catalyst module, through brute force, purge successively and Ultrasonic Cleaning is removed after 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), after 40 minutes, take out;

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

Embodiment tetra-

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

(1) following component and weight content are prepared 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 obtain denitrating catalyst cleaning fluid;

(2) by following component and weight content, prepare regenerated liquid raw material, oxalic acid vanadyl: 4 parts; 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 will in oxalic acid vanadyl and deionized water input mixer, stir, again to continuing to drop into cerous nitrate, lanthanum nitrate and copper nitrate in mixer and fully stirring until dissolve completely, then to dropping into Ludox ST-O in mixer, continue to stir until homogeneous phase obtains denitrating catalyst regenerated liquid;

By inactivation but mechanical life also denitrification catalyst module, through brute force, purge successively and Ultrasonic Cleaning is removed after 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), after 30 minutes, takes out;

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

Embodiment five

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

(1) following component and weight content are prepared 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 obtain denitrating catalyst cleaning fluid;

(2) by following component and weight content, prepare regenerated liquid raw material, oxalic acid vanadyl: 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 will in oxalic acid vanadyl and deionized water input mixer, stir, again to continuing to drop into cerous nitrate, lanthanum nitrate and copper nitrate in mixer and fully stirring until dissolve completely, then to dropping into Ludox ST-O in mixer, continue to stir until homogeneous phase obtains denitrating catalyst regenerated liquid;

By inactivation but mechanical life also denitrification catalyst module, through brute force, purge successively and Ultrasonic Cleaning is removed after 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), after 35 minutes, take out;

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

Embodiment six

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

(1) following component and weight content are prepared 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 obtain denitrating catalyst cleaning fluid;

(2) following component and weight content are prepared regenerated liquid raw material, oxalic acid vanadyl: 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 will in oxalic acid vanadyl and deionized water input mixer, stir, again to continuing to drop into cerous nitrate, lanthanum nitrate and copper nitrate in mixer and fully stirring until dissolve completely, then to dropping into Ludox ST-O in mixer, continue to stir until homogeneous phase obtains denitrating catalyst regenerated liquid;

Inactivation but mechanical life also denitrification catalyst module, through brute force, purge successively and Ultrasonic Cleaning is removed after 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), after 36 minutes, takes out;

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

Embodiment seven

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

(1) following component and weight content are prepared 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 obtain denitrating catalyst cleaning fluid;

(2) by following component and weight content, prepare regenerated liquid raw material, oxalic acid vanadyl: 4 parts; 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 will in oxalic acid vanadyl and deionized water input mixer, stir, then ammonium metatungstate dropped into mixer and stir, again to continuing to drop into cerous nitrate, lanthanum nitrate and copper nitrate in mixer and fully stirring until dissolve completely, then to dropping into Ludox ST-O in mixer, continue to stir until homogeneous phase obtains denitrating catalyst regenerated liquid;

By inactivation but mechanical life also denitrification catalyst module, through brute force, purge successively and Ultrasonic Cleaning is removed after 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), after 25 minutes, take out;

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

Embodiment eight

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

(1) following component and weight content are prepared 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 obtain denitrating catalyst cleaning fluid;

(2) following component and weight content are prepared regenerated liquid raw material, oxalic acid vanadyl: 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 will in oxalic acid vanadyl and deionized water input mixer, stir, then ammonium metatungstate dropped into mixer and stir, again to continuing to drop into cerous nitrate, lanthanum nitrate and copper nitrate in mixer and fully stirring until dissolve completely, then to dropping into Ludox ST-O in mixer, continue to stir until homogeneous phase obtains denitrating catalyst regenerated liquid;

Inactivation but mechanical life also denitrification catalyst module, through brute force, purge successively and Ultrasonic Cleaning is removed after 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), after 32 minutes, takes out;

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

Embodiment nine

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

(1) following component and weight content are prepared 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 obtain denitrating catalyst cleaning fluid;

(2) by following component and weight content, prepare regenerated liquid raw material, oxalic acid vanadyl: 6 parts; 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 will in oxalic acid vanadyl and deionized water input mixer, stir, then ammonium metatungstate dropped into mixer and stir, again to continuing to drop into cerous nitrate, lanthanum nitrate and copper nitrate in mixer and fully stirring until dissolve completely, then to dropping into Ludox ST-O in mixer, continue to stir until homogeneous phase obtains denitrating catalyst regenerated liquid;

By inactivation but mechanical life also denitrification catalyst module, through brute force, purge successively and Ultrasonic Cleaning is removed after 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), after 40 minutes, take out;

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

Active ratio K/K0 before and after the denitrification catalyst module regeneration of embodiment mono-to embodiment nine is carried out to test comparison as table 1, and the active ratio K/K0 of described denitrating catalyst is compared and draws with fresh denitrating catalyst active (K0) by surveying denitrating catalyst active (K).Adopt the SCR denitrating system catalyst activity test experience device in the Chinese utility model patent that publication number is 203479784U to detect.

Table 1:

Visible, through regeneration of the present invention, make the active 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 requirement of the present invention.

Claims (10)

1. a regenerated liquid for denitrating catalyst, is characterized in that, raw material components and the weight content of described regenerated liquid are as follows, oxalic acid vanadyl: 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.
2. the regenerated liquid of denitrating catalyst according to claim 1, is characterized in that, also comprises that ammonium metatungstate, the weight ratio of described ammonium metatungstate and described deionized water are (6 ~ 8): 95 in described regenerated liquid.
3. a preparation method for denitrating catalyst regenerated liquid, is characterized in that, the manufacture of described regenerated liquid in turn includes the following steps: (1) by following component and weight content, prepare regenerated liquid raw material, oxalic acid vanadyl: 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; (2) will in oxalic acid vanadyl and deionized water input mixer, stir; (3) in mixer, continue to drop into cerous nitrate, lanthanum nitrate and copper nitrate and fully stir until dissolve completely; (4) in mixer, drop into Ludox ST-O continuation stirring until homogeneous phase.
4. the preparation method of denitrating catalyst regenerated liquid according to claim 3, it is characterized in that, in the raw material components of described regenerated liquid, also comprise ammonium metatungstate, the weight ratio of described ammonium metatungstate and described deionized water is (6 ~ 8): 95, described step (2) and described step increase following steps between (3): described ammonium metatungstate is dropped into mixer and stirs.
5. a renovation process for denitrating catalyst, is characterized in that, in turn includes the following steps: (1) by following component and weight content, prepare cleaning fluid raw material, AEO: 0.8 ~ 1.2 part; 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 obtain denitrating catalyst cleaning fluid; (2) by following component and weight content, prepare regenerated liquid raw material, oxalic acid vanadyl: 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 will in oxalic acid vanadyl and deionized water input mixer, stir, again to continuing to drop into cerous nitrate, lanthanum nitrate and copper nitrate in mixer and fully stirring until dissolve completely, then to dropping into Ludox ST-O in mixer, continue to stir until homogeneous phase obtains denitrating catalyst regenerated liquid; By inactivation but mechanical life also denitrification catalyst module, through brute force, purge successively and Ultrasonic Cleaning is removed after 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), after 25 minutes ~ 40 minutes, take out; (5) denitrification catalyst module is carried out to bake drying.
6. the renovation process of denitrating catalyst according to claim 5, it is characterized in that, described step also comprises ammonium metatungstate in the raw material components of regenerated liquid in (2), the weight ratio of described ammonium metatungstate and described deionized water is (6 ~ 8): 95, after described oxalic acid vanadyl and deionized water stir in mixer, described ammonium metatungstate is dropped into mixer and stirs, then continue to drop into described cerous nitrate, lanthanum nitrate and copper nitrate and fully stir until dissolve completely in mixer.
7. the renovation process of denitrating catalyst according to claim 5, is characterized in that, the raw material components of described regenerated liquid and weight content are: oxalic acid vanadyl: 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.
8. the renovation process of denitrating catalyst according to claim 5, is characterized in that, the raw material components of described regenerated liquid and weight content are: oxalic acid vanadyl: 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.
9. the renovation process of denitrating catalyst according to claim 5, is characterized in that, the raw material components of described regenerated liquid and weight content are: oxalic acid vanadyl: 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.
10. the renovation process of denitrating catalyst according to claim 6, is characterized in that, the raw material components of described regenerated liquid and weight content are: oxalic acid vanadyl: 5 parts; 7 parts of ammonium metatungstates; 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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