CN103623682A - HC-LSCR/O-AS engineering system for fume cleaning - Google Patents

HC-LSCR/O-AS engineering system for fume cleaning Download PDF

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CN103623682A
CN103623682A CN201310684139.8A CN201310684139A CN103623682A CN 103623682 A CN103623682 A CN 103623682A CN 201310684139 A CN201310684139 A CN 201310684139A CN 103623682 A CN103623682 A CN 103623682A
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张继惟
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Abstract

The invention provides an HC-LSCR/O-AS engineering system for fume cleaning. The invention relates to a system engineering method and device for reducing NOx in fume by using unburnt hydrocarbons, CO and other reducing gases in boiler fume at low temperature (110-180 DEG C). Compared with the NH3-SCR method, the method provided by the invention has the following advantages: 1. no external reducer, such as ammonia, is needed, so the operating cost is low; 2. the system can be arranged behind the deduster when working at low temperature, so the service life is greatly prolonged; 3. the whole system can satisfy strict emission requirements, such as PM<=10mg/NM3, SO2<=20mg/NM3 and NOx<=50mg/NM3, and can oxidize simple substance mercury, hydrocarbons, dioxin, CO and the like; and 4. the investment for the whole system is lower than that of the combination of the NH3-SCR and spray desulfurizer.

Description

A kind of HC-LSCR/O-AS engineering system for gas cleaning
Technical field:
The present invention relates to field of Environment Protection, be specifically related to Industrial Boiler, the field of purification of kiln gas
Background technology:
The atmosphere pollution of China is mainly coal smoke type environmental pollution, in burning of coal process, most combustibles can be in stove after-flame, incombustible is mainly ash content, is mingled in high-temperature flue gas the flyash after deduster is collected, institute's discharging waste gas is mainly the flue gas after fuel combustion, major pollutants are particle, i.e. flying dust, the SO of gas state 2, NO x, CO, CO 2, hydro carbons etc., SO 2and NO xdeng also, be to generate the important presoma of second particle thing and the main source of acid mist.The main contents of gas cleaning are: particle, SO 2, NO x, heavy metal (mercury, selenium, arsenic), P op s(dioxin), VOC (dissolved organic matter, as hydro carbons), CO, CO 2(carbon emission reduction)
At present, remove particle PM very ripe in gas cleaning engineering means, the use of sack cleaner and electrostatic fabric filter can make the concentration of PM (particle) in flue gas be down to <100mg/m 3, and at present conventional spray column desulfurizer to exist wall built-up crystallization serious, wearing and tearing, the problems such as obstructions, while aerosol is serious, to SO 2removal efficiency 95% left and right only, be difficult to adapt to SO 2the further raising of discharge standard, and the NO rising at present xremoval methods make again CO in flue gas as the method for low nitrogen burning, the discharge of hydro carbons increases, the outer method of stove has again many problems as SNCR and SCR method; Therefore need a kind of comprehensive engineering system to improve existing flue gas purification system; The denitration technology of take carries out the system of comprehensive purifying as core to pollutant in flue gas.
At present, the whole world can through engineering approaches the denitration technology approximately more than 50 of application plant, sort out as table:
Figure BSA0000098973110000021
In the outer method of stove, the most frequently used method of denitration is NH 3-SCR method (selective catalytic reduction) refers at O 2under the condition existing with heterogeneous catalysis, use reducing agent NH 3nO in flue gas is reduced to harmless N 2with the technique of water, in coal-fired flue-gas, the out of stock reducing agent of SCR is ammonia, and liquefied ammonia or ammoniacal liquor are by spraying into after evaporator evaporation in system, and under the effect of catalyst, ammonia is reduced to N by the NO in flue gas 2and H 2o, its chemical equation is:
4NH 3+4NO+O 2→4N 2+6H 2O
4NH 3+2NO 2+O 2→3N 2+6H 2O
Catalyst plays the effect that reduces reaction activity and accelerate reaction rate, the ammonia of the activated adoption of catalyst and the NO in gas phase in gas solid catalytic reaction in reaction xreact, generate N 2and H 2o, the test of N isotope shows: product N 2in molecule, an atom N comes from NH 3, another is from NO, O 2have a reduction that is beneficial to NO.
The catalyst that can be used for SCR system mainly contains noble metal catalyst, three kinds of base metal catalysts and molecular sieve catalysts, typical noble metal catalyst be Pt or Pd as active component, belong to low temperature catalyst, their reductive NOs xactive fine, but selectively not high, NH 3be easy to be oxidized by airborne oxygen, because some noble metals are at relatively low temperature, reductive NO xhigh with the activity of oxidation CO, noble metal catalyst is mainly studied low-temperature catalyzed and application natural gas boiler at present.Business SCR catalyst, its active component is V 2o 5, the TiO that carrier is Detitanium-ore-type 2, WO 3and MoO 3as co-catalyst.
Major influence factors: (1) reaction temperature: in SCR system, owing to having used catalyst, NO xthe required temperature of reduction reaction is low compared with SNCR system, when temperature is temperature required lower than SCR system, and NO xreaction rate reduces, and ammonia escaped quantity increases, when temperature is during higher than the required temperature of SCR system, and the N of generation 2o measures increase, causes sintering and the inactivation of catalyst simultaneously; (2) time of staying and air speed: generally speaking, reactant time of staying in reactor is longer, denitration rate is higher, reaction temperature is influential to the required time of staying, when operating temperature and optimal reaction temperature approach, the required time of staying reduces, and the time of staying, conventional air speed represented, air speed is larger, and the time of staying is shorter; (3) NH 3/ NO mol ratio, according to reaction equation, removes the ammonia that 1molNO needs 1mol, and reacting gas theoretical chemistry metering is than being 1, and dynamics research shows, when operating chemical metering is when being <1, and NO xremoval efficiency and NH 3concentration becomes linear positive relation, when stoichiometric proportion>=1, and NO xremoval efficiency and NH 3concentration is substantially irrelevant.
Its major defect is:
The defect of 1> technical elements: denitrating catalyst is the core technology of SCR method denitrating flue gas, generally account for 30%～50% of overall apparatus cost of investment, the index of the reactivity worth of evaluate catalysts: active, selective, stability (comprising chemical stability, heat-resistant stability, antitoxin stability and mechanical stability), current SCR catalyst main component is anatase titanium dioxide TiO 2for main carriers, catalyst is V 2o 5-WO 3-MoO 3deng metal oxide with according to the supporting microcomponent of flue gas condition, for guaranteed efficiency and the excessive ammonia of control, reaction temperature is 300～400 ℃, therefore conventionally reactor is arranged between economizer and air preheater, this region is high grey high temperature, brings a series of technical problem:
(1) wearing and tearing of catalyst: have particle in cigarette ash to produce with the shock of flue gas, under SCR method environment at present, particle concentration is generally at 10000～30000mg/m 3;
(2) adopt NH 3as reducing agent, and there is water to generate with NOx reduction reaction product, add in flue gas because coal itself is containing wet, be easy to generate ammonium sulfurous that viscosity is stronger etc. and come adsorption catalyst surperficial with one of flying dust, cause passivation and the obstruction of catalyst;
(3) arsenic poisoning: the arsenic oxide arsenoxide in flue gas diffuses into catalyst, and in this temperature, the region (370 ℃ of left and right) of one Activity and inactivity is solidified;
(4) alkali metal is poisoning: the active sites of alkali metal and catalyst surface contacts, and causes inactivation, due to coal difference (Na, K, Mg, S, the constituent content such as Cl is different for As, Ca) thereby want specific aim to design component and the structure of catalyst.
These reasons cause the life-span of catalyst short, and only 2～3 years, thereby need the soot blower system under the high grey condition of high temperature specially to coordinate with it, simultaneously to NH 3also need special accurate control and flow mixing device with mixing of flue gas.
The defect of 2> environmental protection aspect:
(1) owing to often containing V in SCR special-purpose catalyst 2o 5, MoO 5etc. micro-poisonous substance matter, simultaneously may be in catalyst in long-term use the element such as aggregating heavy metal and arsenic, for avoiding the impact on soil and water, the catalyst of inefficacy, mainly as dangerous solid waste special disposal, is generally and crushes rear landfill and have strict landfill requirement.
(2) reducing agent adopts liquefied ammonia, stores, and uses in the use procedure that all has strict requirement, the ammonia explosive incident of Dehui, Jilin to make liquefied ammonia and has potential safety hazard, if adopt urea to make reducing agent simultaneously, need increase investment.
(3) adopt ammonia as reducing agent, to exist the possibility that forms HCN violent in toxicity.
The defect of 3> economical operation aspect:
The SCR denitrification apparatus of general large power plant >30 ten thousand kw units equilibration device is several years ago about 238 yuan/kw left and right, in recent years due to the production domesticization of catalyst, has been reduced to the level of 145 yuan/kw.
The price of catalyst is at present about 2.5 ten thousand yuan/m 3～3.5 ten thousand yuan/m 3level, the SCR system investment of 300,000 kw units is about: 4,350 ten thousand yuan, catalyst is about 400m 3approximately 1000～1,400 ten thousand yuan/cover, life-span is 3 years, year depreciation is 333～4,670,000 yuan/year, and operating cost is by 75 yuan/kw, and (according to denitration subsidy electricity price, 0.008 yuan/kwh calculates) is about 2,250 ten thousand yuan/year, average Boiler Steam tonnage is approximately: invest 4.15 ten thousand yuan/ty, wherein catalyst is 1～1.4 ten thousand yuan/ty, the depreciation of catalyst year: 0.33～0.467 ten thousand yuan/ty, operating cost is about 2～2.14 ten thousand yuan/ty.
1. main improvement direction develops low dirt low temperature after deduster, and catalyst can increase service life greatly efficiently, reduces investment;
2. avoid as far as possible making reducing agent to avoid catalysqt deactivation and ammonia hidden danger with ammonia;
3. avoid adopting V, the expensive material of micro-poison such as Mo is made catalyst, and useless disposal cost reduces costs and endanger;
Summary of the invention:
HC-LSCR／O-AS(Hydrocarbon-Low-Temperature?Selectine?Catalytic?Reducation／Oxidation-Assimilating?System)
The present invention for (being generally 110 ℃-180 ℃) and utilizing reducibility gas in boiler smoke as hydro carbons under cryogenic conditions, and CO selects the NO in former cigarette under catalyst action x, or utilize the oxygen in flue gas to be oxidized NO-NO 2, in absorption tower, remove NO xmethod, actual is the systems technology method of a kind of comprehensive regulation flue gas pollutant of forming in conjunction with method in stove and SCR method, and NH 3the feature of-SCR method comparison is:
1> is with external reducing substances such as Ammonias, and directly uses unburnt CO in flue gas, H 2, the materials such as hydro carbons, its advantage is to have given up to control uselessly, is removing NO xtime remove hydro carbons and the CO in flue gas, meet later discharge standard.Avoid using unsafe factor in ease ammonia that Ammonia material exists, storage ammonia simultaneously, and the generation of the cyanide that may occur in ammonia reduction; Thereby save a large amount of ammonia resources, energy-saving and emission-reduction, realize recycling economy;
2> is used low temperature catalyst, can denitrating system be installed after deduster, avoids the environment of high temperature, high ash, has avoided catalyst obstruction, inefficacy and heavy metal accumulation, has reduced expensive blow device, and the life-span of catalyst is compared NH 3-SCR method within 3 years, extend to 10-15, significantly energy-saving and cost-reducing;
3>HC-LSCR/O-AS denitrating system cost is lower than NH 3the about 20%-25% of-SCR method denitrating system.
Total system HC-LSCR/O-AS removes NO xefficiency be divided into two parts, i.e. solid catalyst reduction removes NO x, and part NO through catalyst surface by the O in boiler smoke 2be oxidized to water-soluble NO 2, can remove by the interior secondary of reabsorber.If be to be used in combination liquid-phase catalyst in absorption liquid or liquid-phase reduction catalyst can further remove NO x, solid catalyst and use liquid-phase catalyst, in the interception reaction of spraying layer, bubble absorption layer and three levels of interception face formation on absorption tower, remove the polluter in flue gas to greatest extent again.Comprise: to take HC compound, bioxin, PM, the SO of CO as characterizing 2, NO x, Elemental Mercury oxidation etc., the removal efficiency of this system maximum is: institute's power consumption, water are 2/3 of traditional spray column, energy-saving and cost-reducing.
PM:((entrance <100mg) final dusting), catalytic tower dedusting, spraying and dedusting, water bath dust-removing, foam dust-removing add and block dedusting etc., final PM concentration of emission <10mg/Nm 3.
SO 2: through spraying desulfurization, water bath desulfurization, blocking the final desulfurization degree 99.7% of desulfurization.
NO x: through catalyst denitration, water-bath, absorbing the highest denitration rates such as denitration, liquid phase oxidation denitration is 99%, can be combined at present the highest engineering system that removes level both at home and abroad.
technical scheme:
Technical scheme of the present invention is comprised of three parts: comprise catalytic tower, absorption tower and accessory substance treatment system etc., catalytic tower is by flue, current equalizer, acoustic wave ash ejector (or rake purging device), catalyst, housing, ash buckets etc. partly form, can be with regulating one for low-NO_x burner, secondary air flow is controlled furnace reduction gas concentration and is regulated denitration efficiency, for reducibility gas concentration not or the boiler of the lower occasion of flue-gas temperature, can regulate catalytic reactor reducing gas concentration and flue-gas temperature by the mode of the supplementary burner of external natural gas (alkanes) increase.
The major function of catalytic tower is: reproducibility removes the NO in flue gas x, HC compound, the Elemental Mercury of oxidation in flue gas, oxidation removal PoPs, CO etc., part removes the particle PM in flue gas, NO in oxidation flue gas so that in absorption tower secondary remove.
Absorption tower is partly comprised of flue, spray thrower, flue gas bubbling pipe, absorption liquid, inner flue, interception dividing plate, V-type cover, upper spray return channel, demister, rotation demist air-introduced machine, housing etc., absorption tower mainly regulates pH value and the liquid level of absorption liquid, liquid level does not increase 1mm, vapour lock increases 10Pa, removes accordingly SO 2also increase with the ability of PM, absorption liquid can be CaCO 3aqueous solution NaOH, ammoniacal liquor or the spent lye etc. of suspension, MgO, absorption liquid can be used in combination with liquid-phase reduction catalyst or liquid-phase oxidation catalyst, to improve, removes NO xand HC, the ability of CO and other materials, interception dividing plate and V-type cover form flue gas and block layer, are used for blocking the ammonia ease in ammonia absorption process, also can enable the PM, the SO that are used in further purifying smoke 2remove NO with combination liquid-phase oxidation catalyst x.
The function on absorption tower mainly contains:
1> desulfurization;
2> utilizes desulfurizing byproduct most NO as not de-in sulphite reduction x, utilize alkaline matter in absorption liquid to remove and absorb NO x;
3> has spray, water-bath, foam, blocks and carry out repeatedly dedusting, is that PM value minimizes;
4> combination liquid-phase catalyst further removes the pollutant in flue gas;
5> utilizes temperature loss in rotation demist wine guide compensation flue gas, improves the uplift force of flue gas.
Accessory substance treatment system:
The accessory substance of different absorption liquid outputs is different, and system for use in carrying is also variant, and its major function is water and accessory substance to be carried out separated, and liquid-phase catalyst dewaters and is back in new absorption liquid and uses after separation with accessory substance.
Accompanying drawing explanation:
Fig. 1: HC-LSCR/O-AS smoke comprehensive purifying technological system
1-deduster, 2-gas approach, 3-current equalizer, 4-catalytic tower, 5-low temperature catalyst, 6-ash bucket, 7-heat exchanger, 8-absorption tower middle deck, 9-fountain bubble absorbing tower, 10-rotation demist wine guide, 11-demister, 12-V type cover-sieve aperture net locking device, 13-fills with containing the absorption liquid of liquid-phase catalyst, 14-bubbling pipe, 15-absorption liquid, 16-hydrocyclone, 17-crystallizing evaporator, 18-drier, 19-solution pool
Fig. 2: the relation of flue-gas temperature and denitration rate
Fig. 3: be the hydrocarbons interdiction capability characterizing to CO in HC-LSCR/O-AS system
Fig. 4: the reducing substances that the CO of take is sign is to NO xthe relation of removal efficiency
Fig. 5: the relation of import cigarette temperature and denitration rate
The specific embodiment:
In Fig. 1, boiler smoke enters in catalytic tower 4 after deduster 1 is by flue 2, current equalizer 3, through low temperature catalyst 5, and the reducibility gas in flue gas and NO xreaction, the unreacted reducing gas of part and part NO are oxidized, in flue gas, part particle is reunited and is fallen under gravity in ash bucket 6 through catalyst surface friction, flue gas enters in absorption tower middle deck 8 after chimney heat exchanger 7, absorption liquid 15 reactions in middle deck enters lower cabin and cabin through absorption liquid spraying cooling by flue gas bubbling pipe 14, part PM stays in absorption liquid after spray, water-bath, the SO of about 95%-98% 2and the material of oxidized NO and solubility is as HC class, is all reacted in absorption liquid or holds, flue gas is through bubble absorption by flue, and the absorption liquid of locking layer 12 purifies again, after demister 11 and 10 acceleration of demist wine guide, by chimney, enters atmosphere.The absorption liquid of flue gas locking layer 12 (or adding liquid-phase oxidation catalyst) is provided by corresponding system 13.In Fig. 1, accessory substance treatment system is the accessory substance treatment system that ammonia absorption liquid produces, after absorption liquid 15 is oxidized in tower, sulphite becomes neutral sulfatase, solution is after crystallizing evaporator 17 is concentrated, and the part moisture in solution becomes distilled water and flows out, and concentrate is separated with the aqueous solution through hydrocyclone 16 crystallizations, the aqueous solution enters in 19 times towers of liquor box to use, after 18 separation of crystalline solid drying device, the aqueous solution enters liquor box and returns in tower, and dried crystalline solid is sulphate crystal.

Claims (3)

1. HC-LSCR/O-AS engineering system of using low temperature catalyst to be used for boiler smoke high-efficient purification, utilize unburnt CO in low-NO_x burner, kiln, the NO that HC class material reduces in flue gas under low temperature (110 ℃-180 ℃) and catalyst condition xfor N 2, and partial oxidation NO makes it further to remove in absorption tower, and simultaneously to Elemental Mercury, hydro carbons, CO etc. all have good low-temperature oxidation effect.
Native system comprises: with the catalytic tower of low temperature catalyst and ash bucket, with regulating wind of boiler and secondary air flow and improving reducibility gas concentration in flue gas by the method for atomized water spray or steam in flue gas recirculation and stove, with the bubble absorbing tower combination of band spray, and with V-type cover and locking screen cloth, with liquid-phase oxidation catalyst and absorbent combination, carry out the de-NO of liquid phase at bubble absorbing tower upper-deck cabin xand gas cleaning, can obtain the effect best to fume cleaning.
2. according to above-mentioned (1) described system, it is characterized by: by regulating the oxygen feeding amount of low-NO_x burner to regulate reducibility gas (CO, HC, H in flue gas 2deng), make the NO in flue gas xon low-temp reaction catalyst, react reduction with these reducibility gas, be enhanced NO in the residue flue gas of oxidizability xin bubble absorbing tower, further remove the treatment of wastes with processes of wastes against one another.
3. according to above-mentioned (1) described system, it is characterized by: under bubble absorbing tower, absorption liquid and liquid-phase reduction catalyst combination can be used in cabin, the upper-deck cabin V-type cover available absorption liquid of locking layer and liquid-phase oxidation catalyst combination, the gas cleaning effect of formation plural serial stage.
CN201310684139.8A 2013-12-16 2013-12-16 HC-LSCR/O-AS engineering system for fume cleaning Pending CN103623682A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105617858A (en) * 2016-01-15 2016-06-01 环境保护部华南环境科学研究所 Combined synergetic deep purification process for multiple pollutants in flue gas
CN105833682A (en) * 2016-04-21 2016-08-10 成都华西堂环保科技有限公司 Boiler air graded low-nitrogen combustion and denitration process
WO2017012557A1 (en) * 2015-07-21 2017-01-26 华能国际电力股份有限公司 High-efficiency gradient hierarchy complex desulfurizing tower
CN111495136A (en) * 2020-04-23 2020-08-07 生态环境部华南环境科学研究所 Full-flow low-temperature dry-method deep treatment system for waste heat treatment flue gas

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CN101680332A (en) * 2007-06-26 2010-03-24 五十铃自动车株式会社 NOX purification system, and method for control of nox purification system
CN101961603A (en) * 2010-09-29 2011-02-02 清华大学 Technique for removing NOx in high-temperature flue gas by reduction of carbon monoxide, and reactor

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101680332A (en) * 2007-06-26 2010-03-24 五十铃自动车株式会社 NOX purification system, and method for control of nox purification system
CN101961603A (en) * 2010-09-29 2011-02-02 清华大学 Technique for removing NOx in high-temperature flue gas by reduction of carbon monoxide, and reactor

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017012557A1 (en) * 2015-07-21 2017-01-26 华能国际电力股份有限公司 High-efficiency gradient hierarchy complex desulfurizing tower
CN105617858A (en) * 2016-01-15 2016-06-01 环境保护部华南环境科学研究所 Combined synergetic deep purification process for multiple pollutants in flue gas
CN105617858B (en) * 2016-01-15 2018-10-30 环境保护部华南环境科学研究所 A kind of assembled smoke gas multi-pollutant collaboration advanced purification process
CN105833682A (en) * 2016-04-21 2016-08-10 成都华西堂环保科技有限公司 Boiler air graded low-nitrogen combustion and denitration process
CN105833682B (en) * 2016-04-21 2018-07-27 成都华西堂环保科技有限公司 A kind of boiler air classification low nitrogen burning and denitrating technique
CN111495136A (en) * 2020-04-23 2020-08-07 生态环境部华南环境科学研究所 Full-flow low-temperature dry-method deep treatment system for waste heat treatment flue gas
CN111495136B (en) * 2020-04-23 2022-01-28 生态环境部华南环境科学研究所 Full-flow low-temperature dry-method deep treatment system for waste heat treatment flue gas

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