CN107661693A - A kind of method and combined system of the flue gas denitrification system stable operations of SCR in low- load conditions - Google Patents

A kind of method and combined system of the flue gas denitrification system stable operations of SCR in low- load conditions Download PDF

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Publication number
CN107661693A
CN107661693A CN201610604979.2A CN201610604979A CN107661693A CN 107661693 A CN107661693 A CN 107661693A CN 201610604979 A CN201610604979 A CN 201610604979A CN 107661693 A CN107661693 A CN 107661693A
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China
Prior art keywords
flue gas
adsorbent
scr
gas denitrification
blown
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CN201610604979.2A
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Chinese (zh)
Inventor
单玉华
郭芳芳
高玉新
王宇峰
郝晓鹏
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Harbin Boshen Science & Technology Development Co Ltd
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Harbin Boshen Science & Technology Development Co Ltd
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Priority to CN201610604979.2A priority Critical patent/CN107661693A/en
Publication of CN107661693A publication Critical patent/CN107661693A/en
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86Catalytic processes
    • B01D53/8621Removing nitrogen compounds
    • B01D53/8625Nitrogen oxides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/06Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with moving adsorbents, e.g. rotating beds
    • B01D53/10Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with moving adsorbents, e.g. rotating beds with dispersed adsorbents
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/46Removing components of defined structure
    • B01D53/54Nitrogen compounds
    • B01D53/56Nitrogen oxides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2251/00Reactants
    • B01D2251/20Reductants
    • B01D2251/206Ammonium compounds
    • B01D2251/2062Ammonia
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2253/00Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10Inorganic adsorbents
    • B01D2253/112Metals or metal compounds not provided for in B01D2253/104 or B01D2253/106
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2257/00Components to be removed
    • B01D2257/30Sulfur compounds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2257/00Components to be removed
    • B01D2257/30Sulfur compounds
    • B01D2257/302Sulfur oxides

Abstract

The invention discloses a kind of method of the flue gas denitrification system stable operations of SCR in low- load conditions, it is characterized in that, injection system is respectively arranged before and after SCR flue gas denitrification systems, for being blown nanoscale dry powder alkali formula adsorbent into flue gas, the particle diameter of the absorbent particles is 5 100nm.The invention also discloses a kind of denitrating flue gas combined system of stable operation in low- load conditions.

Description

A kind of method and group of the flue gas denitrification system stable operations of SCR in low- load conditions Syzygy is united
Technical field
The present invention relates to a kind of method and combined system of the flue gas denitrification system stable operations of SCR in low- load conditions.
Background technology
In order to remove the nitrogen oxides in combustion product gases, prevent from polluting environment, it is necessary to carry out denitration process to combustion product gases. At present, the denitration technology industrially commonly used is SCR technology (SCR), its restoring function using ammonia to NOx, NOx (mainly NO) is reduced to be not much air the N of influence in the presence of catalyst2And water, reducing agent NH3
It should be noted that in coal-fired flue-gas, sulphur content is contained in fuel, contains substantial amounts of dioxy in caused flue gas Change sulphur and a small amount of sulfur trioxide.It is sulfur trioxide that SCR flue gas denitrification systems, which cause this part sulfur dioxide inverted, in spray ammoniacal liquor After form acid mist, while with the NH of excess3Ammonium sulfate and ammonium hydrogen sulfate are generated, these directly results in the blocking of air preheater with after End equipment is corroded.In addition, ammonium sulfate and the micropore on ammonium hydrogen sulfate meeting blocking catalyst surface, make catalyst failure, reduce SCR The efficiency of flue gas denitrification system, reduce the service life of catalyst.The sulfur trioxide discharged after SCR flue gas denitrification systems can be right Atmospheric environment causes serious pollution.
US7618602, US6126910, US6803025 disclose the solution that alkaline matter is sprayed into flue gas. US6126910 sprays into the solution containing bisulfite into flue gas, and US6803025 sprays into sodium carbonate, bicarbonate into flue gas Sodium, sodium hydroxide, ammonium hydroxide, potassium hydroxide, the solution of potassium carbonate and saleratus, but the content base of sulfur dioxide in flue gas This is not reduced.
CN103055684A discloses a kind of device and technique that sulfur trioxide in flue gas is effectively removed using trona, Nozzle system is set at the flue between SCR reactors afterbody and air preheater, trona slurries are sprayed into flue.
Subject matter existing for the above method of the prior art is drop atomization technique, and the technology realizes condition at present Harshness, technical costs are higher.
This invention address that a kind of method of flue gas denitrification system stable operations of SCR in low- load conditions is provided and is System, the efficiency of SCR flue gas denitrification systems under underload (≤50%) operating mode can be optimized, reduce the pollutant in discharge flue gas.
The content of the invention
The present invention provides a kind of method of the flue gas denitrification system stable operations of SCR in low- load conditions, it is characterised in that Injection system is respectively arranged before and after SCR flue gas denitrification systems, for being blown nanoscale dry powder alkali formula adsorbent into flue gas.
Using the method for the present invention, the SCR flue gas denitrification systems under underload (≤50%) operating mode can be greatly lowered The middle possibility blocked because forming ABS and ammonium hydrogen sulfate, the denitration efficiency of SCR flue gas denitrification systems is improved, is extended The service life of catalyst, it is cost-effective, so as to ensure that the normal operation of SCR flue gas denitrification systems, while prevent The stickum such as ammonium sulfate and ammonium hydrogen sulfate blocks boiler air preheater and rear end equipment, has ensured the steady of overall flue system Fixed operation.
The present invention also provides a kind of denitrating flue gas combined system of stable operation in low- load conditions, and it includes SCR cigarettes Gas denitrating system and injection system, it is characterised in that be respectively arranged before and after SCR flue gas denitrification systems for being sprayed into flue gas Shot blasting footpath is the injection system of 5-100nm nanoscale dry powder alkali formula adsorbent.
Brief description of the drawings
Fig. 1 shows the schematic diagram of the denitrating flue gas combined system of the present invention.
Fig. 2 is shown under different boiler working conditions, using alkali formula adsorbent with being blown without using alkali formula adsorbent, SCR The change of the denitration efficiency of flue gas denitrification system.
Fig. 3 is shown under the conditions of different boiler working conditions, is blown the absorbent particles of different-grain diameter, SCR denitrating flue gas system The contrast of the denitration efficiency of system.
Fig. 4 shown under different working conditions, different adsorbents:SO3The denitration of SCR flue gas denitrification systems under mol ratio Efficiency.
Fig. 5 shows boiler under 50% load, Xi Fu Ji ︰ SO3Mol ratio is 8:When 1, adsorbent different time is blown The denitration efficiency of SCR flue gas denitrification systems afterwards.
Embodiment
SCR flue gas denitrification systems used in the method for the present invention can be SCR denitrating flue gas as known in the art System.
Injection system used in the method for the present invention can be injection system as known in the art.
In a preferred embodiment of the invention, adsorbent used is selected from sodium base adsorbent, Ca-base adsorbent, magnesium-based and inhaled Common base adsorbent in this area such as attached dose, it is specially:Sodium carbonate, sodium acid carbonate, calcium hydroxide, magnesium carbonate, bicarbonate The one or more therein such as magnesium, magnesium hydroxide.The adsorbent can be used alone or in combination, as long as not influenceing as absorption The performance of agent.
In a preferred embodiment of the invention, the particle diameter of absorbent particles used is 5-100nm, preferably 10- 50nm, specific surface area 65-90m2/g。
The specific surface area of the absorbent particles of the present invention is big, and aperture is small, adsorption capacity is high, reaction rate is fast, cost is not high, Physico-chemical property is similar with flyash, does not influence continuing with for boiler dust removal system and the original flyash of power plant.
The dry powder alkali formula adsorbent in flue with SO2、SO3、H2SO4Gas-solid reaction occurs rapidly Deng gas, can be in cigarette Reacted rapidly below 300 DEG C of temperature degree, generate sulfate solid, do not produce new harmful side product, can enter with flying dust Subordinate equipment.To SO2、SO3、H2SO4SCR flue gas denitrification systems and pot is greatly lowered up to more than 90% in adsorption rate Deng gas The generation that stove air preheater blocks, improves the denitration efficiency of SCR flue gas denitrification systems and the heat exchange efficiency of air preheater, Extend conventional catalyst service life.
By arranging injection system before SCR flue gas denitrification systems, reduce sulfur dioxide and sulfur trioxide in flue gas, Avoid and produce ammonium sulfate and ammonium hydrogen sulfate in SCR flue gas denitrification systems and damaged to caused by SCR flue gas denitrification systems, carry The high denitration efficiency of SCR flue gas denitrification systems.
Dry powder alkali formula adsorbent is blown before SCR flue gas denitrification systems, adsorbs the SO in flue gas2、SO3Deng sour gas, Avoid this partially acidic gas and NH excessive in flue3Reaction, the adhesive attachment thing of hydrogen sulfate ammonia and ammonium sulfate is formed, it is attached In catalyst surface, blocking catalyst micropore, reduce catalyst denitration efficiency and shorten the service life of catalyst.
By arranging injection system after boiler SCR flue gas denitrification systems, reduce further in SCR flue gas denitrification systems Middle SO2/SO3Conversion ratio, reduce the yield of sulfur trioxide, reduce sour gas and environment is polluted.
The adsorbent is blown in SCR flue gas denitrification systems exit, is adsorbed caused one in SCR flue gas denitrification systems Part SO3Deng sour gas, avoid the sticky products such as ammonium sulfate, hydrogen sulfate ammonia from blocking and corrode air preheater, dust arrester etc. Subordinate equipment, can the subordinate equipment such as exhaust air preheater, dust arrester operating efficiency and service life.
Those skilled in the art can by determining the content of sulfur dioxide and sulfur trioxide in flue gas, concrete decision to The amount of base adsorbent is sprayed into flue gas.
When nanoscale alkali formula adsorbent is blown after SCR flue gas denitrification systems, adsorbent:SO3Mol ratio is 4:1 to 8:1 In the range of.
Due to the seasonal variation of power consumption, power plant's generated energy under different operating modes is different, causes smoke temperature change width Degree is very big, and in SCR flue gas denitrification systems, influence of the flue-gas temperature to catalyst is huge.When boiler at low load operates, cigarette Temperature degree drops to less than 300 DEG C, and the reactivity of denitrating catalyst substantially reduces at this temperature, causes the de- of denitrating catalyst Nitre efficiency degradation, then have impact on boiler of power plant NOx discharge, environment is damaged.Usually need in the prior art Flue gas is heated in favor of SCR flue gas denitrification system normal operations.
The method of the present invention is simultaneously suitable for caused flue gas under power plant's high load capacity operating mode and running on the lower load.
Using the method for the present invention, the normal operation of SCR flue gas denitrification systems can be ensured under power plant's full working scope, made The denitration rate of SCR flue gas denitrification systems reaches newest national requirements for environmental protection, SO2/SO3<1%, SO3Discharge capacity Deng gas reduces To below 3ppm.
Embodiment
The present invention is further described below in conjunction with accompanying drawing.
Fig. 1 shows the schematic diagram of the denitrating flue gas combined system of the present invention.According to Fig. 1, before SCR flue gas denitrification systems Nozzle is set respectively with rear, for spraying into dry powder base adsorbent into flue gas.
Analog flue gas experiment is carried out in laboratory, and with blowing into certain flyash.In SCR flue gas denitrification systems With NO concentration detection apparatus, SO are set respectively before air preheater3Gas concentration detection apparatus, SO2Gas concentration detection apparatus, According to NO, SO of disengaging SCR flue gas denitrification systems3、SO2Gas concentration calculates the SO of catalyst2/SO3Conversion ratio and denitration effect Rate.
The composition of analog flue gas is as follows:
NO contents:500mg/Nm3 O2Content:5%
SO3Content:6mg/Nm3 SO2Content:650mg/Nm3
H2O content:10%
Catalyst experiment monomer parameter list is as shown in table 1 below.
Catalyst monomer specification is used in the experiment of table 1
Using 0.3-0.6MPa compressed air spraying nanoscale (5-100nm) base adsorbent, sprayed through bimetal wear resistant Mouth is blown into flue.It is blown the base adsorbent of different-grain diameter respectively under different operating modes.Contrived experiment is as follows:
Embodiment 1:Under boiler difference working condition, SCR flue gas denitrification systems before and after 10nm particle diameter alkali formula adsorbents are blown Denitration efficiency contrast.
Nanoscale alkali formula absorbent particles with compressed air enter flue in, rapidly with the SO in flue gas2、SO3、H2SO4Deng Gas-solid reaction occurs for sour gas, generation sulfate, the solid granule of sulphite, enters subordinate equipment with cigarette ash.
Fig. 2 is shown under different boiler working conditions (entering cigarette temperature), is blown alkali formula adsorbent and is not blown alkali formula adsorbent, The change of the denitration efficiency of SCR flue gas denitrification systems.
It can be observed from fig. 2 that the base absorbent particles of the present invention have substantially to the denitration efficiency of SCR flue gas denitrification systems Under facilitation, particularly boiler at low load operating mode, when flue-gas temperature is below 300 DEG C, raising efficiency becomes apparent.
Embodiment 2:Under boiler difference working condition, different-grain diameter 10nm, 30nm, 50nm absorbent particles are blown.
Fig. 3 is shown under the conditions of different boiler working conditions, is blown the absorbent particles of different-grain diameter, SCR denitrating flue gas system The contrast of the denitration efficiency of system.
As seen from Figure 3, the base absorbent particles of 15nm, 30nm and 50nm particle diameter are to lifting SCR denitrating flue gas system The denitration efficiency of system has a positive effect, and enhancing rate difference is less big.
Embodiment 3:Under different working conditions, nanoscale alkali formula adsorbent, difference absorption are blown after SCR flue gas denitrification systems Agent:SO3Mol ratio.
Fig. 4 is shown under different working conditions, and nanoscale alkali formula adsorbent, absorption are blown after SCR flue gas denitrification systems Agent:SO3Mol ratio is respectively 4:1、6:1、8:When 1, the denitration efficiency of SCR flue gas denitrification systems.
From fig. 4 it can be seen that mol ratio is 8:When 1, the effect for being blown absorbent particles is best.
Embodiment 4:Under the loading condiction of boiler 50%, adsorbent:SO3Mol ratio is 8:When 1, adsorbent is blown 1 minute- 140 minutes.
Fig. 5 shows boiler under 50% loading condiction, adsorbent:SO3Mol ratio is 8:When 1, injection adsorbent is different The change of the denitration efficiency of SCR flue gas denitrification systems after time.
Fig. 5 shown after adsorbent is blown, the effect of SCR flue gas denitrification systems out of 1 minute -140 minutes continuous times The change of rate.Fig. 5 shows that the efficiency of SCR flue gas denitrification systems can be stablized adsorbent in 1 hour after flue is entered.
The embodiment of the present invention is described above in association with accompanying drawing, but the present invention is not limited thereto.Not In the range of the purport of the present invention, those skilled in the art can enter to specific embodiments of the present invention described here Row changes and equivalent transformation, but these should be considered as within claimed the scope of the present invention.

Claims (10)

  1. A kind of 1. method of the flue gas denitrification system stable operations of SCR in low- load conditions, it is characterised in that taken off in SCR flue gases Injection system is respectively arranged before and after nitre system, for being blown nanoscale dry powder alkali formula adsorbent, the adsorbent into flue gas The particle diameter of particle is 5-100nm.
  2. 2. the method as described in claim 1, it is characterised in that the running on the lower load is the temperature of flue gas below 300 DEG C Operating mode.
  3. 3. method as claimed in claim 1 or 2, it is characterised in that the adsorbent is selected from sodium carbonate, sodium acid carbonate, hydrogen-oxygen Change the one or more in calcium, magnesium carbonate, magnesium bicarbonate and magnesium hydroxide.
  4. 4. method as claimed in claim 1 or 2, it is characterised in that be blown adsorbent after SCR flue gas denitrification systems:SO3Rub That ratio is 4:1 to 8:Nanoscale dry powder alkali formula adsorbent in the range of 1.
  5. 5. method as claimed in claim 1 or 2, it is characterised in that the particle diameter of the adsorbent is 10-50nm.
  6. 6. a kind of denitrating flue gas combined system of stable operation in low- load conditions, it includes SCR flue gas denitrification systems and spray Blow system, it is characterised in that it is 5-100nm to be respectively arranged before and after SCR flue gas denitrification systems for being blown particle diameter into flue gas Nanoscale dry powder alkali formula adsorbent injection system.
  7. 7. combined system as claimed in claim 6, it is characterised in that the running on the lower load is the temperature of flue gas at 300 DEG C Following operating mode.
  8. 8. combined system as claimed in claims 6 or 7, it is characterised in that the adsorbent be selected from sodium carbonate, sodium acid carbonate, One or more in calcium hydroxide, magnesium carbonate, magnesium bicarbonate and magnesium hydroxide.
  9. 9. combined system as claimed in claims 6 or 7, it is characterised in that be blown adsorbent after SCR flue gas denitrification systems: SO3Mol ratio is 4:1 to 8:Nanoscale dry powder alkali formula adsorbent in the range of 1.
  10. 10. combined system as claimed in claims 6 or 7, it is characterised in that the particle diameter of the adsorbent is 10-50nm.
CN201610604979.2A 2016-07-28 2016-07-28 A kind of method and combined system of the flue gas denitrification system stable operations of SCR in low- load conditions Withdrawn CN107661693A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023040132A1 (en) * 2021-09-15 2023-03-23 黄庆华 System for reducing blockages of ammonium bisulfate in air preheater of coal-fired power station

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WO2007053786A1 (en) * 2005-11-05 2007-05-10 Radway Jerrold E Control of combustion system emissions
CN102908883A (en) * 2012-09-27 2013-02-06 北京大学 Method for simultaneously desulfurizing and denitrating flue gas
CN104474897A (en) * 2014-12-02 2015-04-01 中国大唐集团科学技术研究院有限公司 Method for removing sulfur trioxide from coal-fired flue gas
CN104857841A (en) * 2015-06-03 2015-08-26 北京国电龙源环保工程有限公司 Device and method for removing sulfur trioxide from smoke
CN205007831U (en) * 2015-08-11 2016-02-03 南京中电环保科技有限公司 Coal fired boiler SCR deNOx systems
CN206184252U (en) * 2016-07-28 2017-05-24 哈尔滨博深科技发展有限公司 Flue gas denitration combined system of steady operation under low load condition

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Publication number Priority date Publication date Assignee Title
CN1537668A (en) * 2003-10-23 2004-10-20 武汉凯迪电力股份有限公司 Multiple reaction integrated process for desulfuizing from fume by dry method and its system
WO2007053786A1 (en) * 2005-11-05 2007-05-10 Radway Jerrold E Control of combustion system emissions
CN102908883A (en) * 2012-09-27 2013-02-06 北京大学 Method for simultaneously desulfurizing and denitrating flue gas
CN104474897A (en) * 2014-12-02 2015-04-01 中国大唐集团科学技术研究院有限公司 Method for removing sulfur trioxide from coal-fired flue gas
CN104857841A (en) * 2015-06-03 2015-08-26 北京国电龙源环保工程有限公司 Device and method for removing sulfur trioxide from smoke
CN205007831U (en) * 2015-08-11 2016-02-03 南京中电环保科技有限公司 Coal fired boiler SCR deNOx systems
CN206184252U (en) * 2016-07-28 2017-05-24 哈尔滨博深科技发展有限公司 Flue gas denitration combined system of steady operation under low load condition

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023040132A1 (en) * 2021-09-15 2023-03-23 黄庆华 System for reducing blockages of ammonium bisulfate in air preheater of coal-fired power station

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Application publication date: 20180206