CN102059156B - Denitration catalyst regenerating solution and regenerating method thereof - Google Patents

Denitration catalyst regenerating solution and regenerating method thereof Download PDF

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CN102059156B
CN102059156B CN 201010598331 CN201010598331A CN102059156B CN 102059156 B CN102059156 B CN 102059156B CN 201010598331 CN201010598331 CN 201010598331 CN 201010598331 A CN201010598331 A CN 201010598331A CN 102059156 B CN102059156 B CN 102059156B
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China
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catalyst
regenerating
liquid
solution
cleaning fluid
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CN 201010598331
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Chinese (zh)
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CN102059156A (en
Inventor
黄锐
刘伟
刘显彬
成丹
魏丽斯
刘红辉
席文昌
李云涛
袁鹏
黄新竹
王雷
张政科
邓巧莲
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重庆远达催化剂制造有限公司
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Abstract

The invention discloses a cellular denitration catalyst regenerating solution for a coal fired power plant and a regenerating method thereof. The regenerating solution comprises a cleaning solution and an activated replenishing solution, wherein the cleaning solution contains H2SO4 and an emulsifying agent S-185; the activated replenishing solution contains VOSO4 and ammonium paratungstate; and ultrasonic cleaning is adopted in the cleaning method. The regenerated catalyst has relative activity (K/Ko) of 0.95-0.99 and SO2/SO3 conversion rates of both less than 1 percent and meets the requirement on the engineering; and the regenerating process is simple in operation and is suitable for industrialized massive regeneration.

Description

Denitrating catalyst regenerated liquid and renovation process thereof
Technical field
The present invention relates to the denitrating catalyst field, particularly coal-burning power plant's denitrating catalyst regenerated liquid and renovation process thereof.
Background technology
In the recent period, Chinese Ministry of Environmental Protection has externally announced the exposure draft of " thermal power plant's nitrogen oxide Prevention Technique policy ", the comprehensive preventive health measures that advocate that reasonable use fuel combines with pollution control technology, combustion control technology and denitrating flue gas control technology combines is to reduce the discharging of coal-burning power plant's nitrogen oxide.The suggestion original text proposes especially that " spent catalyst should adopt regeneration techniques as far as possible, and the spent catalyst that can't regenerate can carry out landfill by " hazardous waste security landfill pollute control criterion " requirement (GB18598)." " encourage high performance catalyst raw material, new catalyst, the regeneration of spent catalyst and the development and application of safe disposal technology." under normal circumstances, a 600MW unit, finish " 2+1 " after, the discarded amount of annual is about 100 sides, adopts land-fill method easily to cause environmental pollution.Make catalyst return to 95~100% of original activity by regeneration, catalyst can reuse, and cost only is the 40-50% of catalyst changeout cost more.Therefore, carrying out catalyst regeneration namely reduces SCR denitration cost and meets again national industrial policies.
Use ammonium metatungstate and ammonium paratungstate as the active supplementation material (V of make-up catalyst among the Chinese patent application 200910031206.X and 200510117054.7 2O 5And WO 3).Because ammonium metavanadate is extremely toxic substance, need chemical breakdown reaction generation vanadic anhydride is occuring more than 250-300 ℃; The ammonium paratungstate dissolubility is relatively poor: in the time of 20 ℃, solubility is less than 2% in the water, and desired concn solution is disposed in inconvenience.Therefore, adopt mentioned solution to carry out regenerated catalyst, operation easier is larger.Simultaneously, only point out the denitration rate of catalyst contrast situation before and after the regeneration, not relative activity (K/Ko) and the SO of catalyst before and after the explanation regeneration in the patent 2/ SO 3The conversion ratio situation.It is pointed out that relative activity (K/Ko) is the important indicator of catalyst regeneration, simultaneously in the SCR denitrification process, the SO of catalyst 2/ SO 3The conversion ratio General Requirements is less than 1%.Therefore, above-mentioned patent does not illustrate the catalyst regeneration effect better.
Summary of the invention
In view of this, one of purpose of the present invention is to provide a kind of denitrating catalyst regenerated liquid, its hypotoxicity, and regeneration effect is good, and the process time is short.
For achieving the above object, technical scheme of the present invention is:
The denitrating catalyst regenerated liquid is comprised of cleaning fluid and the active liquid that replenishes, and contains sulfuric acid and emulsifying agent S-185 in the described cleaning fluid, and described activity is replenished liquid and contained vanadic sulfate and ammonium metatungstate.
Further, described denitrating catalyst regenerated liquid is composed as follows:
Cleaning fluid: emulsifying agent S-185 mass fraction is 0.005~1%, and the sulfuric acid molar concentration is 0.2~0.8mol/L.
The active liquid that replenishes: the vanadic sulfate molar concentration is 0.2~0.8mol/L, and the ammonium metatungstate molar concentration is 0.2~0.8mol/L.
Two of purpose of the present invention is to provide a kind of denitrating catalyst renovation process, and the method only needs to be used simple device, can avoid complicated calcination steps, can comparatively fast finish the regeneration of catalyst.
For achieving the above object, technical scheme of the present invention is:
The denitrating catalyst renovation process, concrete steps are: at first, catalyst to be regenerated is at first used cleaning fluid in service sink, adopt the ultrasonic wave mode to remove the hole inside ash of catalyst; Then, in activating tank, the catalyst soakage that has cleaned is replenished liquid in activity, carry out active component and replenish; At last, will in drying box, carry out drying with the catalyst that has replenished active component.Finally, just obtain the denitrating catalyst of regenerating.
Wherein, ultrasonic cleaning is 10~30 minutes; The active time of replenishing the liquid dipping is 20~60 minutes; Adopt under 80~150 ℃ of hot-air conditions when dry, dried 2~5 hours, get the regeneration denitrating catalyst.
Beneficial effect of the present invention is: since in the cleaning fluid except sulfuric acid solution and emulsifying agent S-185, cleaning process adopts the Ultrasonic Cleaning mode simultaneously, therefore, scavenging period only needs 10~30 minutes, only is 1/2 of existing technique; Adopt simultaneously vanadic sulfate and ammonium metatungstate that catalyst is carried out active component and replenish, namely avoided the severe toxicity of ammonium metavanadate to cause unsafe factor, avoided again the complicated technology of the repeatedly roasting of catalyst.Adopt the denitrating catalyst after this method is regenerated: activity can return to 95~99% of original activity; SO 2/ SO 3Conversion ratio all satisfies the engineering design requirement less than 1%; Simultaneously, regeneration technology is simple to operate, is applicable to industrial scale regeneration.
The specific embodiment
In order to make the purpose, technical solutions and advantages of the present invention clearer, the below is described in detail the preferred embodiments of the present invention.
Embodiment 1
One, the preparation of regenerated liquid
1, the preparation of cleaning fluid
In the Ultrasonic Cleaning pond, configuration emulsifying agent S-185 mass fraction is 0.005%, and the molar concentration of sulfuric acid is the mixed solution of 0.8mol/L.Carry out ultrasonic wave and processed 10 minutes, it is mixed, placed aging 1 hour, amount to 200L.
2, the active preparation that replenishes liquid
In activating tank, the configuration molar concentration is the mixed solution of the ammonium metatungstate of the vanadic sulfate of 0.8mol/L and 0.8mol/L.Carry out mechanical agitation 5 minutes, it is mixed, placed aging 1 hour, amount to 200L.
Two, denitrating catalyst regeneration technology flow process
Discarded catalyst is immersed in the service sink that cleaning fluid is housed, carried out ultrasonic cleaning 10 minutes; Then, catalyst soakage is replenished liquid in activity, flooded 60 minutes; Take out catalyst and be placed in the drying box, 80 ℃ of dryings 5 hours.Catalyst regeneration finishes.
Embodiment 2
One, the preparation of regenerated liquid
1, the preparation of cleaning fluid
In the Ultrasonic Cleaning pond, configuration emulsifying agent S-185 mass fraction is 1%, H 2SO 4Molar concentration is the mixed solution of 0.2mol/L.Carry out ultrasonic processing 10 minutes, it is mixed, placed aging 1 hour, obtain cleaning fluid, amount to 200L.
2, the active preparation that replenishes liquid
In activating tank, the configuration molar concentration is the mixed solution of the ammonium metatungstate of the vanadic sulfate of 0.2 mol/L and 0.2mol/L.Carry out mechanical agitation 5 minutes, it is mixed, placed aging 1 hour, obtain the active liquid that replenishes, amount to 200L.
Two, denitrating catalyst regeneration technology flow process
Discarded catalyst is immersed in the service sink that cleaning fluid is housed, carried out ultrasonic cleaning 30 minutes; Then, catalyst soakage is replenished liquid in activity, flooded 20 minutes; Take out catalyst and be placed in the drying box, 150 ℃ of dryings 2 hours.Catalyst regeneration finishes.
Embodiment 3
One, the preparation of regenerated liquid
1, the preparation of cleaning fluid
In the Ultrasonic Cleaning pond, configuration emulsifying agent S-185 mass fraction is 0.5%, H 2SO 4Molar concentration is the mixed solution of 0.4mol/L.Carry out ultrasonic processing 10 minutes, it is mixed, placed aging 1 hour, amount to 200L.
2, the active preparation that replenishes liquid
In activating tank, the configuration molar concentration is the VOSO of 0.8 mol/L 4Mixed solution solution with the ammonium metatungstate of 0.8mol/L.Carry out mechanical agitation 5 minutes, it is mixed, placed aging 1 hour, amount to 200L.
Two, denitrating catalyst regeneration technology
Discarded catalyst is immersed in the service sink that cleaning fluid is housed, carried out ultrasonic cleaning 20 minutes; Then, catalyst soakage is replenished liquid in activity, flooded 30 minutes; Take out catalyst and be placed in the drying box, 120 ℃ of dryings 3 hours.Catalyst regeneration finishes.
Embodiment 4
One, the preparation of regenerated liquid
1, the preparation of cleaning fluid
In the Ultrasonic Cleaning pond, configuration emulsifying agent S-185 mass fraction is 0.25%, H 2SO 4Molar concentration is the mixed solution of 0.6mol/L.Carry out ultrasonic processing 10 minutes, it is mixed, placed aging 1 hour, amount to 200L.
2, the active preparation that replenishes liquid
In activating tank, the configuration molar concentration is the VOSO of 0.6 mol/L 4Mixed solution with the ammonium metatungstate of 0.8mol/L.Carry out mechanical agitation 5 minutes, it is mixed, placed aging 1 hour, obtain the active liquid that replenishes, amount to 200L.
Two, denitrating catalyst regeneration technology
Discarded catalyst is immersed in the service sink that cleaning fluid is housed, carried out ultrasonic cleaning 15 minutes; Then, catalyst soakage is replenished liquid in activity, flooded 40 minutes; Take out catalyst and be placed in the drying box, 100 ℃ of dryings 4 hours.Catalyst regeneration finishes.
Embodiment 5
Use regenerated catalyst and the fresh catalyst of experimental example 1~4 to carry out the catalyst activity contrast, and the SO of test regenerated catalyst 2/ SO 3Conversion ratio.The activity of catalyst, denitration rate and SO 2/ SO 3Conversion formula is as follows:
Active K=-AV * ln(1-η);
Denitration rate η=(φ i(NOx)-φ 0(NOx))/φ i(NOx);
Wherein: φ i(NOx), φ 0(NOx) be respectively catalyst inlet and exit NOx concentration (ppm)
SO 2/ SO 3Conversion ratio
In the formula: -SO 2/ SO 3Conversion ratio, %;
The SO of-reactor outlet 3Concentration, μ L/L;
The SO of-reactor inlet 3Concentration, μ L/L butt;
The SO of-reactor inlet 2Concentration, μ L/L butt.
Experiment condition:
The catalyst hole count: 22 * 22, length: 665mm
The catalyst number of plies: 2, catalyst cross section: 150 * 150mm
The engineering Gas Parameters:
Reaction temperature: 380 ℃, flue gas face velocity (AV): 10.55 Nm 3/ (m 2H)
NOx=292ppm,NH 3=292,
SO 2=500ppm,??O 2=6%,??H 2O=6%。
The performance test results of table 1 regenerated catalyst
Catalyst sample Denitration rate (%) Relative activity (K/Ko) SO 2/SO 3Conversion ratio (%)
Fresh catalyst ? 92.5 ???? — ??? —
Embodiment 1 ? 91.5 ???? 0.95 ??? 0.81
Embodiment 2 ? 91.7 0.96 ??? 0.84
Embodiment 3 ? 92.1 0.98 ??? 0.85
Embodiment 4 ? 92.3 0.99 ??? 0.87
Result according to embodiment 5 can know that the relative activity of the catalyst after the regeneration (k/Ko) is 0.95-0.99, simultaneously SO 2/ SO 3Conversion ratio (%) is all less than 1%, engineering demands.Wherein, the catalyst regeneration best results of embodiment 4.
Explanation is at last, above embodiment is only unrestricted in order to technical scheme of the present invention to be described, although by invention has been described with reference to the preferred embodiments of the present invention, but those of ordinary skill in the art is to be understood that, can make various changes to it in the form and details, and not depart from the spirit and scope of the present invention that appended claims limits.

Claims (2)

1. the denitrating catalyst regenerated liquid is comprised of cleaning fluid and the active liquid that replenishes, and it is characterized in that: contain H in the described cleaning fluid 2SO 4With emulsifying agent S-185, the active liquid that replenishes contains vanadic sulfate and ammonium metatungstate; Contained H in the cleaning fluid 2SO 4Molar concentration be 0.2~0.8mol/L, the mass fraction of emulsifying agent S-185 is 0.005~1%; Contained vanadic sulfate molar concentration is 0.2~0.8mol/L in the active additional liquid; The ammonium metatungstate molar concentration is 0.2~0.8mol/L.
2. use denitrating catalyst regenerated liquid claimed in claim 1 to prepare the method for the denitrating catalyst of regenerating, it is characterized in that concrete steps are: denitrating catalyst that will be to be regenerated was with described denitrating catalyst cleaning fluid ultrasonic cleaning 10~30 minutes; Adopt again the active liquid that replenishes to flood 20~60 minutes; At last, adopt under 80~150 ℃ of hot-air conditions, dried 2~5 hours, get the regeneration denitrating catalyst.
CN 201010598331 2010-12-21 2010-12-21 Denitration catalyst regenerating solution and regenerating method thereof CN102059156B (en)

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CN102658170B (en) * 2012-04-11 2014-09-03 西安交通大学 Regeneration technology of V-Ti-based honeycomb SCR denitration catalyst, and apparatus thereof
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
CN103623876B (en) * 2013-05-08 2016-06-15 苏州华乐大气污染控制科技发展有限公司 A kind of fluffy powder for SCR denitration regenerative process and preparation method thereof
CN103418446A (en) * 2013-07-25 2013-12-04 苏州华乐大气污染控制科技发展有限公司 Pore recovery agent used in SCR (Selective Catalytic Reduction) denitration catalyst regeneration process and pore recovery agent preparation method
CN103816946A (en) * 2014-02-12 2014-05-28 无锡华光新动力环保科技股份有限公司 Cleaning liquid for regenerated SCR (silicon controlled rectifier) denitration catalyst and method for regenerating SCR denitration catalyst
CN103878034B (en) * 2014-04-01 2015-10-21 李灏呈 The renovation process of a kind of arsenic and phosphorism denitrifying catalyst with selective catalytic reduction
CN103949291B (en) * 2014-04-23 2016-01-13 江苏万德环保科技有限公司 Denitrating catalyst regenerated liquid, regenerated liquid preparation method and catalyst recovery process
CN104307577A (en) * 2014-10-08 2015-01-28 天河(保定)环境工程有限公司 Active impregnation solution and preparation method thereof
CN104707482B (en) * 2015-03-19 2017-01-18 南京宇行环保科技有限公司 Regeneration method of deactivated catalyst
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CN107126977B (en) * 2016-02-29 2020-04-17 神华集团有限责任公司 Cleaning agent composition and method for regenerating deactivated denitration catalyst
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Address after: 401336 Chongqing City, South Bank of the Yangtze River Road, No. 11

Patentee after: State Power Investment Group Yuanda environmental protection catalyst Co., Ltd.

Address before: 401336 Chongqing City, South Bank of the Yangtze River Road, No. 11

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Patentee after: Chongqing Yuanda catalyst comprehensive utilization Co., Ltd.

Address before: 401336 Chongqing City, South Bank of the Yangtze River Road, No. 11

Patentee before: State Power Investment Group Yuanda environmental protection catalyst Co., Ltd.