CN103878035B - The regenerated liquid of a kind of vanadium, titanium based selective catalytic-reduction denitrified catalyst - Google Patents
The regenerated liquid of a kind of vanadium, titanium based selective catalytic-reduction denitrified catalyst Download PDFInfo
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- CN103878035B CN103878035B CN201410128342.1A CN201410128342A CN103878035B CN 103878035 B CN103878035 B CN 103878035B CN 201410128342 A CN201410128342 A CN 201410128342A CN 103878035 B CN103878035 B CN 103878035B
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Abstract
The present invention discloses the regenerated liquid of a kind of vanadium, titanium based selective catalytic-reduction denitrified catalyst, comprise cleaning fluid and active supplement solution, described cleaning fluid is made up of basic organic salts, surfactant and deionized water, and described active supplement solution is made up of weak acid, ammonium metavanadate, ammonium tungstate, cerous nitrate and deionized water.Cleaning fluid component in denitrating catalyst regenerated liquid of the present invention can get rid of the adverse effect of harmful substance to SCR denitration, recovers its pore passage structure; Active supplement solution component can improve denitrating catalyst activity, increases heat endurance and the service life of catalyst; The denitration rate of the catalyst after regeneration can reach 82 ~ 90%, SO
2/ SO
3conversion ratio is less than 1%, and service life is more than 85% of fresh catalyst.
Description
Technical field
The present invention relates to denitrifying catalyst with selective catalytic reduction field, be specifically related to the regenerated liquid of a kind of vanadium of inactivation, titanium based selective catalytic-reduction denitrified catalyst.
Background technology
Along with country is more and more stricter to the control of discharged nitrous oxides, SCR (SCR) gas denitrifying technology is efficiently widely used in the denitrating system of thermal power plant because of it with reliable denitration performance.The technological core of SCR flue-gas denitration process is vanadium, Ti-base catalyst, there is the problem of activity decrease in running.The reason of catalysqt deactivation is caused to have a lot, the impact of existing operating condition, dust in such as flue gas and temperature fluctuation can cause damage to catalyst macrostructure, also to have in flue gas various poisonous and harmful chemical composition to the toxic action of catalyst surface reaction active site, wherein the toxic action that has of arsenic element, alkali metal, alkaline-earth metal and metal oxide is the most obvious.
Catalyst regeneration has great economic benefit and social environment benefit.Denitrating catalyst is the important component part of coal-burning power plant's SCR denitration system, and cost is higher, and decaying catalyst regeneration expense is only 30 ~ 50% of raw catelyst.If do not regenerated, need inject capital into and carry out useless process of endangering, and will the serious waste of resource be caused and bring the secondary pollution of environment.Can predict thus, the SCR denitration regeneration of inactivation is inexorable trend.
The domestic research to denitrating catalyst regeneration to have had many.Refer to the mode that alkali cleaning and active liquid supplement in the Chinese invention patent application of publication number CN102974366, but its alkali cleaning utilizes ammoniacal liquor to carry out, act on more single, treatment effeciency is lower, easy contaminated environment; Its active supplementary form taking to apply, is difficult to play lasting effect in denitrating flue gas process.The Chinese invention patent application of publication number CN102764675 also using weak acid and surfactant regenerates decaying catalyst, this regenerated liquid for arsenic and phosphorus isogonic acidic materials fouled catalyst treatment effect not good; The EDTA added can produce complexing to alkali and alkaline earth metal ions, but its dispersiveness is poor, and needing to add certain dispersant could use.In a word, the problems referred to above illustrate that the performance of the regenerated liquid of existing vanadium, titanium base SCR denitration has much room for improvement, more thoroughly to remove the total material causing inactivation, and retentive activity component and intensity simultaneously, be applicable to large-scale industrial production, and can prevent from causing environmental pollution.
Summary of the invention
The object of the invention is to for the problems referred to above, the regenerated liquid of a kind of vanadium, titanium based selective catalytic-reduction denitrified catalyst is provided.
For achieving the above object, the technical solution adopted in the present invention is:
The regenerated liquid of a kind of vanadium, titanium based selective catalytic-reduction denitrified catalyst, comprise cleaning fluid and active supplement solution, described cleaning fluid is made up of basic organic salts, surfactant and deionized water, and described active supplement solution is made up of weak acid, ammonium metavanadate, ammonium tungstate, cerous nitrate and deionized water.
Wherein, the basic organic salts in described cleaning fluid is the sodium salt of gluconic acid, citric acid or ethylene diamine tetra methylene phosphonic acid (EDTMPA) or one or more of sylvite, and content is 0.5 ~ 5wt%; Surfactant is one or more of alkali-resistant penetrant AEP98, alkali-resistant penetrant OEP-70 or micropore permeation agent JFC, and content is 0.1 ~ 1wt%; All the other content in described cleaning fluid are deionized water.
Wherein, the weak acid in described active supplement solution is one or more of oxalic acid, acetic acid or citric acid, and content is 0.5 ~ 4wt%; Ammonium metavanadate content is 0.5 ~ 5wt%, and ammonium tungstate content is 2 ~ 6wt%, and cerous nitrate content is 0.05 ~ 1wt%; All the other content in described active supplement solution are deionized water.
Further, preferred described cleaning fluid is made up of following component: 1 ~ 3wt% gluconic acid sodium salt, 0.2 ~ 0.4wt% micropore permeation agent JFC, 96.6 ~ 98.8wt% deionized water;
Further, preferred described active supplement solution is made up of following component: 1 ~ 3wt% oxalic acid, 2 ~ 4wt% ammonium metavanadate, 3 ~ 5wt% ammonium tungstate, 0.2 ~ 0.4wt% cerous nitrate, 87.6 ~ 93.8wt% deionized water.
Beneficial effect:
The beneficial effect of the regenerated liquid of vanadium of the present invention, titanium based selective catalytic-reduction denitrified catalyst is:
(1) cleaning fluid main component of the present invention is basic organic salts, itself has very strong complexing power, dissolubility, soil release performance, especially for alkaline-earth metal and molysite fouled catalyst treatment effect clearly; Its alkalescence is more weak, can keep intensity and the active component of regenerated catalyst to greatest extent; With the addition of bleeding agent in cleaning fluid, improve the efficiency of cleaning;
(2) weakly acidic active supplement solution can be supplemented impaired active component and active sites, improves denitration rate; The cerous nitrate wherein added can increase heat endurance and the service life of regenerated catalyst;
(3) the denitration rate of passing through the catalyst of regeneration can reach 82 ~ 90%, SO2/SO3 conversion ratio and be less than 1%, and service life is more than 85% of fresh catalyst, all meets engineering design requirements.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is elaborated, can be easier to make advantages and features of the invention be readily appreciated by one skilled in the art, thus more explicit defining is made to protection scope of the present invention.
Embodiment 1
(1) regenerated liquid preparation
Cleaning fluid: 2wt% gluconic acid sodium salt, 0.3wt% micropore permeation agent JFC, surplus is deionized water;
Active supplement solution: 0.8wt% oxalic acid, 1wt% ammonium metavanadate, 3wt% ammonium tungstate, 0.3wt% cerous nitrate, surplus is deionized water.
(2) technological process
Institute's sample thief is vanadium, the titanium base SCR denitration that certain power plant has run 20000 hours, finds that denitration rate is 56%, SO after testing
2/ SO
3conversion ratio be 0.78%.First, utilize dried compressed air to purge 10min to the denitrating catalyst of inactivation, to remove the dust stratification on surface; Secondly, insert ultrasonic wave added cleaning 45min in cleaning fluid by blowing the catalyst that ash is disposed, after put into deionized water rinsed clean; Then, by catalyst soakage 3h in active supplement solution; Finally, the hot-air of 120 DEG C is utilized to carry out dry 2h to catalyst.Regenerative process terminates.
Catalyst after regeneration is tested through denitration activity, and denitration rate returns to 90%, SO by 56%
2/ SO
3conversion ratio be 0.82%.
Embodiment 2
(1) regenerated liquid preparation
Cleaning fluid: 1wt% gluconic acid sodium salt, 0.3wt% micropore permeation agent JFC, surplus is deionized water;
Active supplement solution: 0.8wt% oxalic acid, 1wt% ammonium metavanadate, 3wt% ammonium tungstate, 0.3wt% cerous nitrate, surplus is deionized water.
(2) technological process
Institute's sample thief is vanadium, the titanium base SCR denitration that certain power plant has run 20000 hours, finds that denitration rate is 56%, SO after testing
2/ SO
3conversion ratio be 0.78%.First, utilize dried compressed air to purge 10min to the denitrating catalyst of inactivation, to remove the dust stratification on surface; Secondly, insert ultrasonic wave added cleaning 45min in cleaning fluid by blowing the catalyst that ash is disposed, after put into deionized water rinsed clean; Then, by catalyst soakage 3h in active supplement solution; Finally, the hot-air of 120 DEG C is utilized to carry out dry 2h to catalyst.Regenerative process terminates.
Catalyst after regeneration is tested through denitration activity, and denitration rate returns to 83%, SO by 56%
2/ SO
3conversion ratio be 0.78%.
Embodiment 3
(1) regenerated liquid preparation
Cleaning fluid: 4wt% K-IAO, 0.3wt% micropore permeation agent JFC, surplus is deionized water;
Active supplement solution: 0.8wt% oxalic acid, 1wt% ammonium metavanadate, 3wt% ammonium tungstate, 0.3wt% cerous nitrate, surplus is deionized water.
(2) technological process
Institute's sample thief is vanadium, the titanium base SCR denitration that certain power plant has run 20000 hours, finds that denitration rate is 56%, SO after testing
2/ SO
3conversion ratio be 0.78%.First, utilize dried compressed air to purge 10min to the denitrating catalyst of inactivation, to remove the dust stratification on surface; Secondly, insert ultrasonic wave added cleaning 45min in cleaning fluid by blowing the catalyst that ash is disposed, after put into deionized water rinsed clean; Then, by catalyst soakage 3h in active supplement solution; Finally, the hot-air of 120 DEG C is utilized to carry out dry 2h to catalyst.Regenerative process terminates.
Catalyst after regeneration is tested through denitration activity, and denitration rate is 0.85% by the conversion ratio that 56% returns to 90%, SO2/SO3.
Embodiment 4
(1) regenerated liquid preparation
Cleaning fluid: 2wt% K-IAO, 0.3wt% alkali-resistant penetrant OEP-70, surplus is deionized water;
Active supplement solution: 0.8wt% oxalic acid, 1wt% ammonium metavanadate, 3wt% ammonium tungstate, 0.3wt% cerous nitrate, surplus is deionized water.
(2) technological process
Institute's sample thief is vanadium, the titanium base SCR denitration that certain power plant has run 20000 hours, finds that denitration rate is 56%, SO after testing
2/ SO
3conversion ratio be 0.78%.First, utilize dried compressed air to purge 10min to the denitrating catalyst of inactivation, to remove the dust stratification on surface; Secondly, insert ultrasonic wave added cleaning 45min in cleaning fluid by blowing the catalyst that ash is disposed, after put into deionized water rinsed clean; Then, by catalyst soakage 3h in active supplement solution; Finally, the hot-air of 120 DEG C is utilized to carry out dry 2h to catalyst.Regenerative process terminates.
Catalyst after regeneration is tested through denitration activity, and nitre rate is 0.81% by the conversion ratio that 56% returns to 87%, SO2/SO3.
Embodiment 5
(1) regenerated liquid preparation
Cleaning fluid: 2wt% natrium citricum, 0.3wt% micropore permeation agent JFC, surplus is deionized water;
Active supplement solution: 0.8wt% oxalic acid, 1wt% ammonium metavanadate, 3wt% ammonium tungstate, 0.3wt% cerous nitrate, surplus is deionized water.
(2) technological process
Institute's sample thief is vanadium, the titanium base SCR denitration that certain power plant has run 20000 hours, finds that denitration rate is 56%, SO after testing
2/ SO
3conversion ratio be 0.78%.First, utilize dried compressed air to purge 10min to the denitrating catalyst of inactivation, to remove the dust stratification on surface; Secondly, insert ultrasonic wave added cleaning 45min in cleaning fluid by blowing the catalyst that ash is disposed, after put into deionized water rinsed clean; Then, by catalyst soakage 3h in active supplement solution; Finally, the hot-air of 120 DEG C is utilized to carry out dry 2h to catalyst.Regenerative process terminates.
Catalyst after regeneration is tested through denitration activity, and denitration rate returns to 85%, SO by 56%
2/ SO
3conversion ratio be 0.86%.
Embodiment 6
(1) regenerated liquid preparation
Cleaning fluid: 2wt% ethylene diamine tetra methylene phosphonic acid sodium, 0.5wt% alkali-resistant penetrant AEP98, surplus is deionized water;
Active supplement solution: 0.8wt% citric acid, 1wt% ammonium metavanadate, 3wt% ammonium tungstate, 0.3wt% cerous nitrate, surplus is deionized water.
(2) technological process
Institute's sample thief is vanadium, the titanium base SCR denitration that certain power plant has run 20000 hours, finds that denitration rate is 56%, SO after testing
2/ SO
3conversion ratio be 0.78%.First, utilize dried compressed air to purge 10min to the denitrating catalyst of inactivation, to remove the dust stratification on surface; Secondly, insert ultrasonic wave added cleaning 45min in cleaning fluid by blowing the catalyst that ash is disposed, after put into deionized water rinsed clean; Then, by catalyst soakage 3h in active supplement solution; Finally, the hot-air of 120 DEG C is utilized to carry out dry 2h to catalyst.Regenerative process terminates.
Catalyst after regeneration is tested through denitration activity, and denitration rate returns to 82%, SO by 56%
2/ SO
3conversion ratio be 0.83%.
Last it is noted that obviously, above-described embodiment is only for example of the present invention is clearly described, and the restriction not to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without the need to also giving all embodiments.And thus the apparent change of amplifying out or variation be still among protection scope of the present invention.
Claims (3)
1. the regenerated liquid of a vanadium, titanium based selective catalytic-reduction denitrified catalyst, it is characterized in that: described regenerated liquid comprises cleaning fluid and active supplement solution, described cleaning fluid is made up of basic organic salts, surfactant and deionized water, and described active supplement solution is made up of weak acid, ammonium metavanadate, ammonium tungstate, cerous nitrate and deionized water; Basic organic salts in described cleaning fluid is the sodium salt of gluconic acid, citric acid or ethylene diamine tetra methylene phosphonic acid or one or more of sylvite, and content is 0.5 ~ 5wt%; Surfactant is one or more of alkali-resistant penetrant AEP98, alkali-resistant penetrant OEP-70 or micropore permeation agent JFC, and content is 0.1 ~ 1wt%; All the other content in described cleaning fluid are deionized water; Weak acid in described active supplement solution is one or more of oxalic acid, acetic acid or citric acid, and content is 0.5 ~ 4wt%; Ammonium metavanadate content is 0.5 ~ 5wt%, and ammonium tungstate content is 2 ~ 6wt%, and cerous nitrate content is 0.05 ~ 1wt%; All the other content in described active supplement solution are deionized water.
2. the regenerated liquid of the vanadium according to claims 1, titanium based selective catalytic-reduction denitrified catalyst, is characterized in that: described cleaning fluid is made up of following component: 1 ~ 3wt% gluconic acid sodium salt, 0.2 ~ 0.4wt% micropore permeation agent JFC, 96.6 ~ 98.8wt% deionized water.
3. the regenerated liquid of the vanadium according to claims 1, titanium based selective catalytic-reduction denitrified catalyst, is characterized in that: described active supplement solution is made up of following component: 1 ~ 3wt% oxalic acid, 2 ~ 4wt% ammonium metavanadate, 3 ~ 5wt% ammonium tungstate, 0.2 ~ 0.4wt% cerous nitrate, 87.6 ~ 93.8wt% deionized water.
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| CN105413760B (en) * | 2014-09-12 | 2018-04-13 | 神华集团有限责任公司 | The method for activation recovering of the composition of cleaning solution and its SCR catalyst of application and failure |
| CN104549568A (en) * | 2014-12-19 | 2015-04-29 | 河南合众电力技术有限公司 | Method for washing SCR denitration catalyst of coal-fired boiler of thermal power plant |
| CN104549572A (en) * | 2014-12-30 | 2015-04-29 | 安徽省元琛环保科技有限公司 | Impregnation solution for regeneration of SCR (selective catalytic reduction) denitrification catalyst and preparation method of impregnation solution |
| CN104826669B (en) * | 2015-04-26 | 2017-05-17 | 重庆大学 | Alkali washing liquid for regenerating SCR denitration catalysts and application thereof |
| CN104815674A (en) * | 2015-05-07 | 2015-08-05 | 中国华能集团清洁能源技术研究院有限公司 | Inactivated vanadium-titanium-based honeycomb-like denitration catalyst combined denitration-demercuration modifying regeneration liquid and preparation method thereof |
| CN105289758A (en) * | 2015-10-20 | 2016-02-03 | 清华大学 | Efficient chelating regeneration method for calcium-poisoned denitration catalyst |
| CN105618162B (en) * | 2016-01-04 | 2018-11-06 | 大唐国际化工技术研究院有限公司 | A kind of recycling method of discarded vanadium tungsten titanium-based denitrating catalyst |
| CN107159318A (en) * | 2017-05-24 | 2017-09-15 | 清华大学 | A kind of neutral complexing cleaning liquid and renovation process for calcium intoxication denitrating catalyst |
| CN112371109A (en) * | 2020-11-26 | 2021-02-19 | 西安建筑科技大学 | Preparation method of aged vanadium-based catalyst and rare earth regenerated denitration catalyst |
| CN114471745A (en) * | 2022-04-06 | 2022-05-13 | 山东万达环保科技有限公司 | Regeneration method of SCR denitration catalyst and application of SCR denitration catalyst in denitration |
| CN116809125A (en) * | 2023-06-19 | 2023-09-29 | 陈爱平 | Denitration catalyst regeneration device and process |
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| US6395665B2 (en) * | 1998-07-24 | 2002-05-28 | Mitsubishi Heavy Industries, Ltd. | Methods for the regeneration of a denitration catalyst |
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