CN104084015A

CN104084015A - Polluted air purifying system and work method thereof

Info

Publication number: CN104084015A
Application number: CN201410166764.8A
Authority: CN
Inventors: 傅国琳
Original assignee: CHE DAOLAN
Current assignee: CHE DAOLAN
Priority date: 2014-04-23
Filing date: 2014-04-23
Publication date: 2014-10-08
Anticipated expiration: 2034-04-23
Also published as: WO2015161671A1; CN104084015B

Abstract

The invention provides a polluted air purifying system and a work method thereof. The system has an advanced filter system to eliminate toxic emissions in exhaust gas. A new technology is used to capture toxic substances emitted from a pollution source or a chimney of a fire coal boiler, a nano-technology and advanced chemical reactions are used to remove pollutants in the exhaust gas, and principles of the interaction between the gas and a liquid and the interaction between the gas and a solid are applied, so a clean gas is finally emitted, and sulfuric acid and nitric acid generated in the above reaction process are recovered to make a filtering recovery system become beneficial circulation. The polluted air purifying system has a low cost, and benefits for popularized use.

Description

A kind of system of purifying contaminated air and method of work thereof

(1) technical field:

The present invention relates to a kind of cleaning system and method for work thereof, particularly a kind of system of purifying contaminated air and method of work thereof.

(2) background technology:

Under the form of China's economic sustained and rapid development, energy resource consumption demand sharply rises; Only take coal as example, and since Reformation and development, the demand incremental change of annual coal is greatly about 8～12%, and the maximum dirt disease producing with this is exactly serious air pollution.

The China of today is one of the most serious country of atmosphere pollution in the world (being only second to India).The theme that not long ago special proposition ' eliminated the trouble of common people's cardiopulmonary ' in the regular meeting of State Council of the People's Republic of China; Administer polluting with people's state, the people's livelihood, combining, making a decision to forgo and polluting the cap of big country.Chinese Government determines not only will soar economically also will be for country, the people, offspring and even the world make positive contribution on environment.On the road of China Reconstructs, new cleaning fuel is subject to the restriction of reserves and International Politics and cannot becomes the main alternative kinetic energy of domestic industry demand.Therefore, coal can be still the main kinetic energy energy of China in long-time.Along with industrial requirement constantly increases exhibition, mean that atmosphere pollution will be more serious, effectively alleviate and prevent and remedy pollution and will be forever a heavy problem.

As everyone knows, serious atmosphere pollution meeting brings biologies all on the earth irreversible disaster, and the air polluting is mainly derived from the industrial fumes that contain a large amount of poisonous and harmful substances.These harmful flue dust overwhelming majority produce in coal burning process.Yet, there is no absolute clean coal in the world, the different coal resources of noxious material content proportion that only have the difference because of geological conditions to produce.For example, the coal that NORTH CHINA is produced is high-quality low-sulfur coal, and sulfur content only has 1%～2%; And its sulfur content of the coal that produce Yunnan, Guizhou and Inner Mongol can reach more than 5%.According to measuring and calculating: the sulfur dioxide annual emissions in Chinese industrial flue dust is up to more than 20,000,000 tons.In the city of 113 atmosphere pollution keypoint treatments, there are 40 city SO2 emissions to surpass the secondary standard line that country formulates, 39 cities even are inferior to national grade III Standard line! The Acid Rain Pollution being caused by air pollution has been wreaked havoc the territory of China 1/3rd.Industrial process speedup is faster, and colleague's pollution index will be higher with it, and relevant department is all the more difficult to the control meeting of environment.

Over nearly 20 years Chinese to flue dust desulfurization carried out continual technical research.The pollution of controlling sulfur dioxide with flue gas desulfurization technique is an important step in Environmental Protection in China application.Just with low-sulfur coal (sulfur content 1%), calculate: fire the sulfur dioxide that one ton of coal can produce 16 kilograms (1600x1%, kilogram).Medium-sized coal-burning boiler every day is the coal of 150～200 tons of burnings approximately; That is to say that can produce the sulfur dioxide of 2.4～3.2 tons every day.Current desulfur technology comprises coal be mixed lime or additive; In stove, directly spray calcium and ebullated bed lime stone dry desulfurization; And the wet desulphurization such as calcium alkaline process, ammonia-soda process, soda method, magnesium alkaline process.Through eliminating of practical proof and market economy technology for many years, only have the technical equipment of minority really to enter coal-fired industry boiler applications.Wherein take the tower device of spiral board as at present main application.The tower device of spiral board is in the nineties of flue gas desulfurization and dedusting for coal-fired industry boiler after technological transformation.The advantage of this device is that the contact area of flue gas and liquid is large, simple in structure, resistance is less, stable be main feature.Its shortcoming is that existing technology desulfuration efficiency on average only reaches 60～80%, and cost is very big.The operating cost of desulfurization is now 0.3 yuan every watt, and the annual operating cost in coal-burning power plant of medium-sized 10,002 m. gigawatt (GW)s is 44,300,000 yuan; And the cost of its desulfurizer is 3.6 hundred million yuan! Huge large Installed puts and transports row Charges with really making medium-sized and small enterprises face the crisis of Zhu Bing factory.

Except sulfur dioxide, PM2.5 is causing widely and is paying close attention at present healthy impact.What is particle 2.5 (PM2.5)? they refer to and are combined in small pieces solid or the liquid substance that in earth atmosphere, diameter is less than 2.5 microns.Particle composition can cause obvious visual effect, and as flue dust, it is comprised of sulfur dioxide, nitrogen oxide, carbon monoxide, Mineral Dusts, organic substance and elemental carbon, is also referred to as black carbon or coal smoke.Due to the existence of sulphur, particle is moisture absorption, and SO ₂can under high humility and low temperature, be converted into sulfuric acid.This by cause visibility reduction, yellow air, ozone, with the suction sense of shouting pain.The impact that the mankind and animal suck particle matter is extensively studied; PM2.5 cause health problem comprise asthma, lung cancer, cardiovascular problems, respiratory disease, birth defect and dead too early.

Granular material dischargedly in most industry country, be all subject to strict supervision.Due to environmental problem, most industries all needs to carry out the operation of certain dust collecting system, granular material discharged to control.These systems comprise centrifugal deduster (cyclone dust), fiber filter deduster (sack cleaner), wet scrubber and electrostatic precipitator.Yet, cheap cleaner efficiency is very low, Tong Chang Da is less than 80%; Good equipment such as the right efficiency of electrostatic precipitation ， Although can be up to 99%, but also have its fatal shortcoming: (1) equipment is huge, and consumption steel is many, needs high-voltage transforming and rectifying installation, therefore invest high.(2) efficiency of dust collection is subject to the restriction of dust specific resistance, general contrast resistance is less than 104～105 ohm every centimeter or be greater than the dust of 1010～1011 ohm every centimeter, if do not take certain measure, efficiency of dust collection will be affected. and (3) do not possess off-line maintenance function, once equipment breaks down, or operation in spite of illness, or can only shutdown maintenance.Generally speaking, any efficient construction of the equipment except PM is all very high with maintenance cost.

China has also proposed the restriction (seeing the following form) to particulate in air discharge, and each factory and enterprise is also all pressed the Regulations cleaner of having Dinged Installed.Yet huge maintenance expense makes medium-sized and small enterprises unable to make ends meet really.Therefore developing an inexpensive and effective dust arrester should be also the task of top priority.

?	PM10	PM2.5
			Every year	70 microgram/cubic meters	35 microgram/cubic meters
Daily (24 hours)	150 microgram/cubic meters	75 microgram/cubic meters

Nitre (NOx) is a kind of common name of nitrogen oxide, and this term refers to NO and NO ₂the total concentration of (nitric oxide and nitrogen dioxide).Nitrogen oxide and volatile organic matter in air (VOCs) can produce chemical reaction in the sun and form ozone.Children and the people who works out of doors or move are easy to be subject to the harmful effect of ozone.Ozone causes asthma, destroys lung tissue and reduces PFT etc.Ozone can also be transferred by wind and air-flow, and healthy impact is surpassed to original nitrogen oxide from far away.Other impact of ozone also comprises and destroys plant growth and cause crop yield to decline.In addition, other substance reaction forms acid rain in nitrogen oxide and sulfur dioxide and air, mix and landing among rain, mist, snow or the microparticle on ground.Acid rain damage car, building and cause the deterioration of historical place; Acid rain causes lake and streams to become acidity, causes the imbalance of natural water area ecology.Acid microparticle is deep into the sensitive part of lung, can cause or increase the weight of respiratory disease, as pulmonary emphysema, bronchitis with increase the weight of original heart disease.Acid microparticle also can stop the transmission of light and lower visibility, and caused the weather of haze, people can't see blue sky all the year round.Even if nitrogen oxide does not become ozone, acid rain or is adsorbed on microparticle, extra nitrogen is dissolved in streams and lake, has accelerated " eutrophication " of water quality, thereby has caused oxygen excessively to consume, thereby reduced the quantity of fish and shellfish.

According to the report of China Power, 300,000 kilowatts of unit carry out one-tenth that denitration transformation builds should be approximately 6,000 ten thousand yuan of left and right.Under in September, 2013 China electric energy engineering company Beijing Long electricity Hong Tai Environmental Protection Technology Co., Ltd and the official signature of Shangqiu Yu Dong Power Generation Corporation Ltd. of Henan coalification group < < 2x315MW (310,005 kilowatts) unit denitrating flue gas improvement project EPC general contract > >, 1.2 hundred million yuan of total Value of Contract.Also confirmed this general cost.Except manufacturing cost, the operating cost of denitration is unusual height also.According to report: " 300,000 kilowatts of denitration reforming equipments will be implemented denitration electricity price and really want 1.2 minutes/kilowatt of ability just to offset cost, and the unit that operating cost is the highest reaches 2.7 minutes/kilowatt ".In addition, the efficiency of current domestic denitration can only reach 40%～70%.Engineer of Zhejiang power plant once represented on Zhuan Ye is Baoed Publications, at present domesticly select few that excellent fired power generating unit denitration facility builds up, goes into operation, the technology of flue gas monitoring and automatically control aspect is still not mature enough, and correlation technique is still in groping and absorbing in conversion process.Existing SCR denitration technology, under the accuracy of sharp the escaping of ammonia monitoring of penetrating, underload, the problems such as control of ammonia spraying amount and efficiency all need to solve.The most ripe and the most widely used technology of current domestic denitration is SCR (SCR), lacks the new technology that other has practical value and application prospect.The key of SCR technology is catalyst.At present supply falls short of demand on market at home for catalyst, and what on market, supply is substantially all external product, and the research of domestic catalyst just starts with application.So generally, domestic SCR equipment and material all must rely on external import at present, and this has also increased its manufacture and operating cost virtually.

Coal-burning power plant is the greatest contamination source of heavy metal in air (as mercury, lead) content, the growth of mercury, lead contamination meeting serious infringement nervous system in children and cause the badly damaged of children's intelligence.The chief of EPA in 2011 signs and has belonged to a about reducing the policy of the law of noxious material in air, and the removal efficiency that is defined in the mercury of all fire coals in 2016 and fuel electric generator must reach 91%.The U.S. approximately has the mercury emission of 117 tons nearly every year; And each coal-burning power plant of the U.S. at least spends 6,000,000～7,000,000 dollars of discharges of eliminating mercury every year, but the U.S. can only reach 40%～70% efficiency for the removal efficiency of mercury so far.Also there is similar problem in equally, plumbous removing.

Up to the present, only have a method with minimizing mercury emissions ability to be affirmed, that injects activated carbon (ACI) exactly.The research of current most green technologies emphasizes that it is the technology reducing discharging as major control mercury that activated carbon injects (ACI).Activated carbon (material that is most commonly used to remove pollutant in peculiar smell and potable water system) has been proved to be on the mercury in absorption fire coal boiler fume has gratifying effect of a few minutes.Mercury adheres to active carbon particle, and then, by the particle control device in downstream, for example electrostatic precipitator or bag hose are removed.Activated carbon (highly processing, the carbon that contains a large amount of micropores) absorbs the mercury of gaseous form, and be converted into can captive particulate form.Yet, report, in flue gas, the appearance of high-load sulphur can significantly damage the performance of activated carbon.In addition, because very low than the relative concentration of other harmful substance of the mercury in flue gas, therefore with the very a large amount of activated carbon of of short duration needs time of contact (being less than 3 seconds) of ACI adsorbent to reach the effect of anticipation.In order to realize the high clearance (>91%) of mercury, carbon and mercury (C/Hg) required ratio in flue gas has been proved to be 3000～20000 to 1 (w/w), specifically depends on process condition.Although the relative low price of activated carbon itself, the cost that operates whole ACI system is very expensive.In addition, be not only the activated carbon that the mercury refuse of removing sufficient amount needs flood tide; Activated carbon itself is also a source of worsening our environment.How to dispose a year mercury activated carbon and become a difficult problem.If contain the mercury that is less than 260ppm in activated carbon, rules allow its stabilized landfill (being for example enclosed in concrete).Yet, the mercury that buried for many years can spill eventually, and pollutes our underground water.Contain the activated carbon that is greater than 260ppm mercury and be considered to belong to high mercury subclass, and be prohibited landfill.The ACI of high mercury content must be stored in warehouse from far-off regions forever.The problem of disposing year mercury activated carbon will become a global predicament.Similarly, the lead in how effectively removing smoke, is also urgent problem.

Current cleaning equipment cost is expensive, purify after refuse cannot recycling, easily cause the trouble of secondary pollution.

(3) summary of the invention:

The object of the present invention is to provide a kind of system and method for work thereof of purifying contaminated air, native system has an advanced filtration system and eliminates the toxic discharge in waste gas.The noxious material that utilizes new process technologies to catch to go out from the smoke stack emission of pollution sources or coal-burning boiler, utilize all pollutants in nanometer technology and advanced chemical reaction scavenging, interaction between gas and liquid and the interactional principle of gas and solid have been applied, finally give off clean air, and reclaim sulfuric acid and the nitric acid producing in course of reaction, make filtering recovering system become a benign cycle.Native system is with low cost, is beneficial to and promotes the use of.

Technical scheme of the present invention: a kind of system of purifying contaminated air, is characterized in that it is to be supplemented tank c and formed by air-introduced machine a, circulating pump, pretreatment storehouse, denitration storehouse, the de-dirt of desulfurization storehouse, service cover, heavy metal filter, air-introduced machine b, the supplementary tank a of chemical reagent, acid purification treating apparatus, the supplementary tank b of chemical reagent, measuring pump, chemical reagent; Pollute source of the gas and enter pretreatment storehouse through described air-introduced machine, the output in pretreatment storehouse connects the input in denitration storehouse, the output in denitration storehouse connects the input in desulfurization storehouse, the output in the de-dirt of desulfurization storehouse connects the input of heavy metal filter, the output of heavy metal filter connects air-introduced machine, and air-introduced machine is discharged purified gas; On the de-dirt of described desulfurization storehouse, be connected with chemical reagent and supplement tank, the liquid outlet in the de-dirt of pretreatment storehouse, denitration storehouse and desulfurization storehouse is connected respectively acid purification treating apparatus, pretreatment storehouse is connected respectively chemical reagent with denitration storehouse by pipeline and supplements tank a, the de-dirt of pretreatment storehouse, denitration storehouse and desulfurization storehouse is connected chemical reagent by measuring pump and supplements tank b, and pretreatment is equipped with circulating pump on storehouse; Described acid purification treating apparatus is to consist of the feeder that has heating efficiency, distilling apparatus and nitric acid cooling bath, the output of feeder connects the input of distilling apparatus, the output of distilling apparatus connects the input of nitric acid cooling bath, the output of nitric acid cooling bath flows out the nitric acid after processing, and the output of feeder flows out the sulfuric acid after processing.

Pretreatment described above storehouse comprises pretreatment warehouse, pretreatment storehouse spray equipment, pretreatment storehouse air inlet, pretreatment storehouse suction pump, reservoir, pretreatment storehouse liquid outlet, pretreatment storehouse inlet and gas outlet, pretreatment storehouse, the bottom of described pretreatment warehouse is reservoir, pretreatment storehouse liquid outlet is arranged on reservoir place, described pretreatment storehouse air inlet, pretreatment storehouse inlet and gas outlet, pretreatment storehouse are arranged on the pretreatment warehouse of reservoir top, gas outlet, pretreatment storehouse is above the air inlet of pretreatment storehouse, described pretreatment storehouse spray equipment is arranged in pretreatment warehouse, described pretreatment storehouse suction pump connects the output of reservoir and the input of pretreatment storehouse spray equipment by pipeline.

Pretreatment described above storehouse spray equipment is the pressurization spray equipment that is arranged on pretreatment warehouse inner top, or for being arranged on the pressurization spray equipment of pretreatment warehouse inner top and being arranged on the atomizing spray equipment on pretreatment warehouse inwall.

Denitration described above storehouse comprises denitration storehouse warehouse, gas outlet, denitration storehouse, denitration storehouse spray system, denitration storehouse air inlet, denitration storehouse inlet, gas-liquid mixed passage, denitration storehouse liquid outlet and denitration storehouse suction pump; Described denitration storehouse air inlet and gas outlet, denitration storehouse are arranged on the top of denitration storehouse warehouse; Described denitration storehouse inlet is arranged on the middle part of denitration storehouse warehouse; Described denitration storehouse liquid outlet is arranged on the bottom of denitration storehouse warehouse; Described gas-liquid mixed passage, denitration storehouse spray system are positioned at denitration storehouse warehouse; The input of gas-liquid mixed passage connects denitration storehouse air inlet, and output is placed in the liquid in the warehouse of denitration storehouse; Described denitration storehouse suction pump connects the output of warehouse bottom, denitration storehouse and the input of denitration storehouse spray system by pipeline.

Gas-liquid mixed passage described above comprises 3 medium-sized gas-liquid mixed passages and 3 small-sized gas-liquid mixed passages, or comprises 5 large-scale hybrid channels.

The de-dirt of desulfurization described above storehouse comprises luminous energy storehouse, described luminous energy storehouse comprises luminous energy warehouse, luminous energy storehouse air inlet, gas outlet, luminous energy storehouse, luminous energy storehouse inlet, gas-liquid mixed passage, luminous energy storehouse suction pump, luminous energy storehouse liquid outlet, luminous energy storehouse spray equipment and light irradiation apparatus, described luminous energy storehouse air inlet and gas outlet, luminous energy storehouse are arranged on the top of luminous energy warehouse, described luminous energy storehouse inlet is arranged on the middle part of luminous energy warehouse, described luminous energy storehouse liquid outlet is arranged on the bottom of luminous energy warehouse, described gas-liquid mixed passage, luminous energy storehouse spray equipment and light irradiation apparatus are positioned at luminous energy warehouse, the input of gas-liquid mixed passage connects luminous energy storehouse air inlet, the output of gas-liquid mixed passage is positioned at the position at the bottom of luminous energy warehouse bottom approaches storehouse, described luminous energy storehouse suction pump connects the output of luminous energy warehouse bottom and the input of luminous energy storehouse spray equipment by pipeline.

Cleaning position described above comprises purification warehouse, purification plate, fluid flow control bolt and cleaning position liquid outlet, on described purification warehouse, place luminous energy warehouse, described luminous energy storehouse liquid outlet stretches into and purifies in warehouse, described fluid flow is controlled bolt and is arranged on the liquid outlet of luminous energy storehouse, described luminous energy storehouse liquid outlet is positioned at purification plate top, described purification plate is fixed on and purifies in warehouse, and described cleaning position liquid outlet is arranged on and purifies warehouse bottom.

Heavy metal filter described above comprises the fibrous matrix that is embedded with nano material.

The fibrous matrix that is embedded with nano material described above is attached on the flabellum of centrifugal fan, or is arranged between inclination flabellum; The angle of inclination of described inclination flabellum is 30-45 degree.

A method of work for the system of above-mentioned purifying contaminated air, is characterized in that comprising the following steps:

(1) preparation: each working bin is prepared before working well and started each relevant device, comprising:

In pretreatment storehouse, add water and contain oxidant and use nitre acid for adjusting pH value to the solution that is less than or equal to 3;

In denitration storehouse, add and contain oxidant and pH value is less than or equal to 3 solution;

In luminous energy storehouse in the de-dirt of desulfurization storehouse, add and contain Fenton reagent and use Alpha-hydroxy acid for adjusting pH value to the solution that is less than or equal to 3, described Fenton reagent comprises can there is metal system and the hydrogen peroxide that light helps Fenton's reaction; The mass percent of described solution allocation hydrogen peroxide and water is 3%～5%; Hydrogen peroxide and metal system mol ratio are more than or equal to 10:1; According to the optical absorption peak of metal system, in luminous energy storehouse, illumination system is set;

(2) work in pretreatment storehouse: contaminated air enters pretreatment storehouse by air-introduced machine, fully contacts with liquid in storehouse, and preprocessing process is removed the solid particle that the diameter in gas is greater than 10 microns, and NO is oxidized to NO ₂, carbon granule is oxidized to carbon monoxide, and oxidizing sulfur dioxide is sulfur trioxide; The solution that contains solid particle and nitric acid is flowed into acid purification treating apparatus by pretreating containers, and purified gas is discharged pretreatment storehouse;

(3) work in denitration storehouse: pretreatment storehouse purified gas enters in denitration storehouse, nitrogen oxide and oxidant reaction generate nitric acid, and the solution that contains nitric acid flows into acid purification treating apparatus by denitration storehouse, and purified gas is discharged denitration storehouse;

(4) work in the de-dirt of desulfurization storehouse: the gas that discharge in denitration storehouse enters the de-dirt of desulfurization storehouse, with the abundant haptoreaction of Fenton reagent in storehouse, making the hydrocarbons decompose in gas is carbon dioxide and water, and Oxidation of Carbon Monoxide is carbon dioxide, and sulfur trioxide is dissolved in solution and generates sulfuric acid; The solution that contains sulfuric acid flows into acid purification treating apparatus by the de-dirt of desulfurization storehouse, and purified gas is discharged desulfurization storehouse;

(5) work of heavy metal filter: (5.1) embed nano material on fibrous matrix; (5.2) flue gas that makes to contain heavy metal is by being embedded with the fibrous matrix of nano material; (5.3) nano material is reacted with the heavy metal in flue gas, catches the heavy metal in flue gas;

(6) work of acid purification treating apparatus: in the feeder the mixing material that contains sulfuric acid and the nitric acid inflow acid purification treating apparatus flowing out from pretreatment storehouse, denitration storehouse, the de-dirt of desulfurization storehouse, feeder with heater heating mixing material make nitric acid gasification, heating-up temperature is more than or equal to 122 ℃, the method of then refining through distillation purifies, after nitric acid after purification is cooling, be collected in nitric acid cooling bath medium to be recycled, it is medium to be recycled that sulfuric acid will be stayed feeder;

(7) concentration of the reaction solution in each storehouse of periodic monitor, according to the situation of monitoring, supplements tank by chemical reagent and be filled with corresponding reagent in each corresponding storehouse, makes solution composition keep stable;

(8) reclaim sulfuric acid and the nitric acid of being discharged by the system of purifying contaminated air;

(9) after the purification of being discharged by heavy metal filter, gas is outside air-introduced machine discharge system.

Operation principle of the present invention and technique effect:

Native system utilizes the principle of gas liquid reaction effectively to solve the problem of exhaust gas cleaning.When a chemical reaction comprises more than one states of matter, inevitably need to consider the problem of an interface.Under these circumstances, because target substance need to react through a gas-liquid interface, states of matter conversion ratio must be considered.In the invention of similar our such complication system, the Substance Transformation rate between two kinds of different states of matters is the major issue in design.

The film that the thickness that has an imaginary static state between two adjacent states of matter interfaces is δ, must there is molecule by it and conduct in various materials.Other parts in liquid, can be described as main body, are to keep stable, so the energy relevant to transmission is almost completely in film.If reactant diffusion principle also participates in the chemical reaction in liquid, reaction can occur in film, in main body or both all (accompanying drawings 1).The relation of molecular diffusion system and substance transfer coefficient is

k _L’＝D _A/δ

The k here _l' be substance transfer coefficient, D _abe the diffusion coefficient of reactant, δ is film thickness.Gas liquid reaction is to classify by the ratio of reaction rate and material transfer rate:

1, very slow reaction only occurs in the main body of liquid

2, slow reaction occurs in the main body of film and liquid simultaneously

3, reaction occurs in fluid film fast

4, transient response occurs on gas-liquid interactive interface

Yet because not every reaction is all to occur in static system, above-mentioned boundary-layer theory, can not cover all gas liquid reactions.For example, when gaseous molecular enters in a mobile film (accompanying drawing 2), be a kind of unstable state behavior.When having mobile film, penetration theory can be used to fill traditional boundary-layer theory, to compensating with the vertical flow velocity of gas-liquid interface.When having flowing film to participate in, main body concentration [A] is negligible:

{k_{L}}^{'} = 2 x \sqrt{\frac{DV \max}{πδ}}

The Vmax is here the maximum of laminar flowing film speed from the side, and Vmax/ δ is called contact velocity, k _l' be substance transfer coefficient, D _ait is the diffusion coefficient of reactant.

The best example that simultaneously uses penetration theory and boundary-layer theory is our denitrating system, and we change NO by following principle ₂to nitric acid:

Formula 1 and 2 is optimal situations.From the theory Talk that comes up, if all NO molecules (diagram three) in pretreatment storehouse are converted into NO completely in flue gas ₂(formula 1), it should be in denitration storehouse (diagram three) and H ₂o ₂react and produce HNO ₃(formula 2).Yet the reaction rate of formula one is very slow, add liquid in the pretreatment storehouse lower Come that drops, make whole gas liquid reaction system in unstable state.Therefore, in the kinetics of calculating pretreatment storehouse, must use penetration theory.

Denitration storehouse (diagram three) is in a steady-state system, and wherein various variablees are all stable, although there is continual process strength to attempt to change them.Because various variablees are all stable, just must there is one to pass flowing of the whole decorum, so being most likely in denitration cabin, equation 3 to 5 occurs.The NO that a part is converted in pretreatment storehouse ₂molecule may react with water generates and form HNO ₃and NO (formula 3).In pretreatment storehouse not by the NO of peroxide oxidation add from formula 3 NO that produces will with HNO ₃and H ₂o reacts and produces intermediate HNO ₂(formula 4); This intermediate again with H ₂o ₂further reaction, generates end product: HNO ₃add H ₂o (formula 5).

NO ₂reaction with water in film is very important.Some researchs show, equation 6 also likely occurs at gas-liquid interface

2NO ₂+H ₂O→HNO ₂+HNO ₃ (6)

Nitrogen dioxide is 10 by liquid water absorption ^-3to 10 ^-1

HONO (gas) → HONO (solution)

The speed of dissolving ionization than the acid of back reaction is slow

So in order to accelerate nitre absorption dynamics process, the aqueous solution in out of stock storehouse must control pH value.Whole solution keeps PH≤3, and absorption process just can be accelerated.Meanwhile, due to the low solubility of NO and conversion NO to NO ₂then to HNO ₃the complexity of kinetics, the design in denitration storehouse is also to guarantee that be extended down to the longest for the most main time of contact between flue gas and solution.

About light, help Fenton's reaction:

Except gas-liquid, have a common boundary, our light of also having used helps chemical reaction to improve invention, and desulfurization has been used wideband ultraviolet in storehouse.After adding iron and hydrogen peroxide, hydroxyl radical free radical can produce again, and reaction mechanism is as follows:

Fe ²⁺+H ₂O ₂---->Fe ³⁺+.·OH+OH ^- (7)

Fe ³⁺+H ₂O ₂---->Fe ²⁺+·OOH+H ⁺ (8)

FeSO ₄typical case metering be mol ratio>=10 of hydrogen peroxide to iron.What need exactissima diligentia is pH value, if pH value is too high, iron can form Fe (OH) ₃precipitation form, and H ₂o ₂can resolve into oxygen.Substantially, desirable pH value wants≤3.In order to control the temperature raising in pH value and reaction, preferably, reacting the carrying out of controlling as step by step, the iron catalyst of reaction passes through FeSO ₄solution form is added, and then by H ₂o ₂slowly add.

Due to the complexity of Fenton's reaction, there are in theory a lot of disputes, there is much different mechanism to be published in for many years.But an acknowledged fact is the generation of active oxygen and the catalytic action of iron.Wherein Harber-Weiss reaction is the foremost Fenton's reaction mechanism of having delivered

From mechanism above-mentioned, can find out, hydroxyl radical free radical, peroxide radical, hydroxide ion is the main partner of Fenton's reaction.Oxygen also can produce simultaneously, and the product of all Fenton's reactions is that sulfuric acid is all useful to us by oxidizing sulfur dioxide.

Device

As shown in Figure 4, one have four kinds of gas liquid reaction forms:

Typical very slow reaction and long response time is that nitric oxide is converted into nitric acid, and the speed difference of reaction rate and material diffusion is few.The reaction of typical mode 3 and mode 4 is that Sulphur Dioxide is sulfuric acid, and in dynamics, reaction mainly occurs in interface film.The in the situation that of mode 3 or mode 4, reaction rate should be defined on interface.

Design a gas-liquid reactor, the main variable of considering is:

The flow velocity of reactant

Mode of operation and corresponding rate equation

The gas-liquid mixed feature being determined by reactor

Table 1 has been shown flow process and Substance Transformation feature in most of general gas-liquid reactors, by table 1, and depend on that reaction occurs in main body or in interfacial film, designing thus Liao Yige reaction vessel association is the system of a kind of purifying contaminated air of the present invention.(table 1)

Table 1

PF=laminar flow, MF=mixed flow, PMF=horizontal sliding mixed flow

Described pretreatment storehouse is mainly Glover tower, because typical waste gas flow velocity surpasses 6m/s, and in cabin, mixed feature is that gas and liquid are all laminar flows.Design except oxynitrides of the present invention is between a bubble column and batch process reactor, because the generation of nitric acid is quite slow, so the turnover of liquid is not always in a stable state.So denitration of the present invention storehouse is the combination based on laminar flow gas and mixed flow liquid, desulfurization of the present invention storehouse has utilized the efficient of Fenton's reaction, and the process rate that produces sulfuric acid is as follows

[SO in gas ₂clearance]=[SO in liquid ₂reactivity]

The design in desulfurization of the present invention storehouse completes by the design of laminar flow gas.

Separation bin of the present invention is acid purification treating apparatus.

Native system is a kind of automatically working system, and the design object of this system is at sulfuric acid and nitric acid productive rate certain in the situation that, and it is main the volume of reactor being minimized and reduce energy resource consumption.The composition of reactant is to draw on the theory analysis basis of chamber experiment by experiment and coal-burning boiler scene preliminary examination.The 30 tons of coal coal-burning boilers that burn an every day of take are example, have calculated the output of nitric acid and sulfuric acid.

The production of nitric acid:

The nitrogen that the generation of nitric acid starts from air is oxidized in coal-burning boiler

1a)N ₂+O ₂→2NO

1b)2NO+O ₂→2NO ₂

1c)2NO ₂+H ₂O ₂→2HNO ₃

Or

2a)N ₂+O ₂→2NO

2b)2NO+O ₂→2NO ₂

2e)HNO ₂+H ₂O ₂→HNO ₃+H ₂O

Although step 1b and 2b determine in whole process that the step of speed, hydrogen peroxide are main determinant.No matter nitrogen is converted into nitric acid by which step, and it is impossible occur that final step 1c and 2e do not have hydrogen peroxide.We know in air containing nitrogen 78.09% (volume ratio) 75.47% (weight ratio) in other words, and on sea level, 20 ℃ time, under international standard atmosphere, the density of air is approximately 1.204kg/m ³.Namely the quality of every cubic metres of air is 1.204Kg, and nitrogen wherein accounts for (1.204Kg x75.47%) 908.7g, in theory, 1 cubic metres of air enters boiler, the nitrogen that wherein includes 908.7g ÷ 28g/mole=32.454mole, can produce the NO of 973g, needs the H of 1.1Kg ₂o ₂just can be translated into the nitric acid of 2.04Kg (32.454mole x63g/mole).< < During Pollution Emission Declaration registration application manual > > " the 21st chapter the 4th chapters and sections NO writing according to State Environmental Protection Administration _xemission amount calculation ", the NO that coal-burned industrial boiler produces _xcomputing formula as follows: NO _xdischarge capacity (ton)=1.63X coal consumption (ton) X (NO in the content X fire coal of combustion nitrogen content of coal _xconversion ratio %+0.000938)

NO _xdischarge capacity (ton)=1.63X coal consumption (ton) X (the NOX conversion ratio %+0.000938 of 0.015X combustion nitrogen content of coal)

The NO of 1 ton of coal _xdischarge capacity=1.63X1X (0.015X25%+0.000938)=0.00764 ton=7.6Kg

As according to above algorithm, burn the coal of 30 tons every day, can produce the NOx of 7.6x30=228Kg, so need the H of [228/ (30x0.9) is (46x0.1)] x34=242Kg ₂o ₂come is made into the nitric acid of 448Kg.As the hydrogen peroxide ， The by 35% weight ratio concentration needs the consumption of 690Kg every day.But by our Shi Inter experiment repeatedly, water is the important role of performer in the process that produces nitric acid, in the equation 2c of this equation 6 at 2.1.1 joint and 2.2.2.1 joint, all mentioned.3 meters of the diameters (Fig. 3) in our denitration storehouse, fill 0.5 meter of high water (3.5 tons), hydrogen peroxide by measuring pump input 12Kg (35%) per hour, the consumption of one day 35% hydrogen peroxide is about 290 to 300Kg. every seven to eight days denitration storehouses need be with the hydrogen peroxide of 2.8 ton 35% but can produce the nitric acid of 5 ton of 68% concentration.According to business society staple commodities list data, show, in the April, 2014, domestic nitric acid market glided, and price is 1427 yuan per ton, more expensive a little than 35 industrial hydrogen peroxide prices, and institute is so that denitration operating cost is negative basically.

The production of sulfuric acid:

The coal-fired SO of < < During Pollution Emission Declaration registration application manual > > writing according to State Environmental Protection Administration ₂the estimation computing formula of discharge capacity:

In SO2 discharge capacity (ton)=2X0.8X coal consumption (ton) X coal containing sulphur content (%) X (1-desulfuration efficiency %). 1 ton of the coal consumption of take is benchmark, and the sulfur-bearing in coal is divided into 1.5%, the SO of 1 ton of coal ₂if the sulfur-bearing in generation=2X0.8X1X1.5%=0.024 ton=24Kg. coal is divided into 1%, the SO of 1 ton of coal ₂generation=2X0.8X1X1%=0.016 ton=16Kg. is from SO ₂to H ₂sO ₄process as follows:

So if 1 ton of coal of burning (wherein containing 1% sulphur) can produce 16kg sulfur dioxide, that just can produce the H of (16/64) x98=24.5Kg ₂sO ₄.

For the boiler of the 30 tons of coals that burn an every day, can produce the H of 24.5x30=735Kg every day ₂sO ₄, by Fenton's reaction, one mole of H ₂o ₂can produce 2 moles of hydroxyl radical free radicals, so need the H of [(735/98) x34]/2=127Kg every day ₂o ₂(the H of 364kg35% concentration ₂o ₂).Water has been played the part of again important effect in the process of producing sulfuric acid.By us, repeatedly repeat the data that test obtains, the sulfuric acid producing and the hydrogen peroxide ratio of consumption are only 20:1 (mol ratio), this means we except producing the sulfuric acid of 735kg in sulfur dioxide device every day, only need every day the hydrogen peroxide (the 35% concentration hydrogen peroxide of 36Kg) that consumes 12.7Kg.According to business society staple commodities list data, show, domestic sulfuric acid market of in April, 2014 glide be 364 yuan per ton.But to manufacture the sulfuric acid of 735Kg, only need use industry 35% hydrogen peroxide of 36Kg, the operating cost of desulfurization also, as denitration cost, is negative.

About purification process, be the course of work of acid purification treating apparatus:

From nitric acid and the sulfuric acid of denitration storehouse and the outflow of desulfurization storehouse, can directly enter acid purification treating apparatus.Purifier comprises a feeder (10a) with heating efficiency, distilling apparatus, and nitric acid cooling bath (10b).68% nitric acid has 1.51293 density and the boiling point of 121 degrees Celsius.The density of the concentrated sulfuric acid is 1.843, and boiling point is 337 degrees Celsius.Due to the heavy relation of density ratio water, two kinds of acid all can divide other bottom that sinks to denitration storehouse and desulfurization storehouse, then via measuring pump, are introduced into the feeder (10a) that cleanization Installed puts.Purify feeder and can be heated to 122 ℃ of clean nitric acid gasifications, after the method for then refining through distillation is cooling by the nitric acid purifying, be received in nitric acid cooling bath.Sulfuric acid will be stayed in feeder and directly reclaim.

Table 2: the mass transfer characteristic of flow and common gas-liquid reactor

1, about the course of work and the device of desulfurization:

A method for the flue gas that processing contains sulfur dioxide, comprises the following steps:

(1) in pretreating containers, add water;

(2) in reaction vessel, add and contain Fenton reagent and use Alpha-hydroxy acid for adjusting pH value to the solution that is less than or equal to 3, described Fenton reagent comprises can there is metal system and the hydrogen peroxide that light helps Fenton's reaction;

The mass percent of described solution allocation hydrogen peroxide and water is 3%～5%.

Hydrogen peroxide and metal system mol ratio are more than or equal to 10:1;

(3), according to the optical absorption peak of metal system, illumination system is set in reaction vessel;

(4) waste gas is passed into pretreating containers, fully contact with liquid, the solid particle that makes diameter be greater than 10 microns is stayed in liquid;

(5) liquid that contains diameter and be greater than the solid particle of 10 microns is derived to pretreating containers;

(6) flue gas after purifying is discharged to pretreating containers;

(7) flue gas of step (6) being discharged passes into reaction vessel, with the abundant haptoreaction of Fenton reagent, makes the oxidizing sulfur dioxide in flue gas become sulfur trioxide and be dissolved in solution to become sulfuric acid;

(8) will react after sulfur acid solution derive, and periodic monitor derives the concentration of Fenton reagent in solution, according to the situation of monitoring, adds the new solution that contains Fenton reagent and makes solution composition keep stable;

(9) purified gas is discharged to reaction vessel.

After step described above (1), add step (1 ') for using nitric acid to adjust below pH value to 3, then add oxidising agent, make carbon granule be oxidized to carbon monoxide, part SO ₂be oxidized to SO ₃, oxidising agent is hydrogen peroxide, the mixture of molybdenum oxide and tungsten oxide, the mixture of magnesia and magnesium hydroxide or di-iron trioxide, wherein, molybdenum oxide, tungsten oxide, magnesia, the diameter of magnesium hydroxide and di-iron trioxide solid particle is less than 20nm, the volume ratio of hydrogen peroxide and water is 1:18～22, the mol ratio of molybdenum oxide and tungsten oxide is 1:1, the mol ratio of magnesia and magnesium hydroxide is 1:1, the amount ratio of molybdenum oxide and water is more than or equal to 10mol/L, the amount ratio of tungsten oxide and water is more than or equal to 10mol/L, the amount ratio of magnesia and water is more than or equal to 10mol/L, the amount ratio of magnesium hydroxide and water is more than or equal to 10mol/L, the amount ratio of di-iron trioxide and water is more than or equal to 20mol/L.

The concentration of the oxidising agent in step described above (1 ') needs periodic monitor and supplements as required oxidising agent to make oxidising agent concentration stabilize in solution.

Metal system in step described above (2) is Fe (II)/F (III) system or Cu (I)/Cu (II) system; When metal system is Fe (II)/F (III) system, illumination is that wavelength is the ultraviolet light of 200nm～400nm; When metal system is Cu (I)/Cu (II) system, illumination is that wavelength is the visible ray of 600nm～800nm.

Fe described above (II)/F (III) system is less than the FeSO of 20 nanometers by diameter ₄and Fe ₃o ₄particle forms.

Cu described above (I)/Cu (II) system is less than the Cu of 20 nanometers by diameter ₂o and CuSO ₄particle forms.

In step described above (4) fully the mode of contact for liquid is sprayed to gas by spray equipment, the area and the time that to increase waste gas, contact with liquid.

Flue gas in step described above (4) enters from pretreating containers bottom, and direction level is also 40～50 degree angles with chamber wall, to increase the time contacting with liquid.

In step described above (5), derive the liquid of pretreating containers after removing the particle that is greater than 10 microns, by suction pump, by pipeline is defeated, got back in pretreating containers.

Hydrogen peroxide described above is that peromag, sodium peroxide or the calper calcium peroxide that diameter is less than 50 nanometers reacts rear generation in described solution.

The consumption of hydrogen peroxide described above is by regularly collecting sample by close monitoring, and the consumption rate of use iodine/potassium permanganate (I/KMnO4) titration observation peroxide.

'alpha '-hydroxy acids described above is glycolic, pyruvic acid or lactic acid.

In step described above (7) fully the mode of contact for gas is directly passed into liquid or by liquid by spray equipment at least one in gas spray.

Step described above (8) adds step 8 afterwards ' utilize the Amberlite IRC748 ion exchange resin coating absorption of commercially available DOW chemical company to reclaim described metal system material, will contain the solution purification of sulfuric acid

Realize a desulfurizer for method described above, comprise pretreatment storehouse and luminous energy storehouse, described pretreatment storehouse comprises pretreatment warehouse 1-13, pretreatment storehouse spray equipment 1-2, pretreatment storehouse air inlet 1-4, pretreatment storehouse suction pump 1-6, reservoir 1-7, pretreatment storehouse liquid outlet 1-8, pretreatment storehouse inlet 1-10 and pretreatment storehouse gas outlet 1-12, the bottom of described pretreatment warehouse 1-13 is reservoir 1-7, pretreatment storehouse liquid outlet 1-8 is arranged on reservoir 1-7 place, described pretreatment storehouse air inlet 1-4, pretreatment storehouse inlet 1-10 and pretreatment storehouse gas outlet 1-12 are arranged on the pretreatment warehouse 1-13 of reservoir 1-7 top, pretreatment storehouse gas outlet 1-12 is above the air inlet 1-4 of pretreatment storehouse, described pretreatment storehouse spray equipment 1-2 is arranged in pretreatment warehouse 1-13, described pretreatment storehouse suction pump 1-6 connects the output of reservoir 1-7 and the input of pretreatment storehouse spray equipment 1-2 by pipeline, described luminous energy storehouse comprises luminous energy warehouse 2-11, luminous energy storehouse air inlet 2-2, luminous energy storehouse gas outlet 2-1, luminous energy storehouse inlet 2-3, gas-liquid mixed passage 2-4, luminous energy storehouse suction pump 2-5, luminous energy storehouse liquid outlet 2-6, luminous energy storehouse spray equipment 2-8 and light irradiation apparatus 2-10, described luminous energy storehouse air inlet 2-2 and luminous energy storehouse gas outlet 2-1 are arranged on the top of luminous energy warehouse 2-11, described luminous energy storehouse inlet 2-3 is arranged on the middle part of luminous energy warehouse 2-11, described luminous energy storehouse liquid outlet 2-6 is arranged on the bottom of luminous energy warehouse 2-11, described gas-liquid mixed passage 2-4, luminous energy storehouse spray equipment 2-8 and light irradiation apparatus 2-10 are positioned at luminous energy warehouse 2-11, the input of gas-liquid mixed passage 2-4 connects luminous energy storehouse air inlet 2-2, the output of gas-liquid mixed passage 2-4 is positioned at the position at the bottom of luminous energy warehouse 2-11 bottom approaches storehouse, described luminous energy storehouse suction pump 2-5 connects the output of luminous energy warehouse 2-11 bottom and the input of luminous energy storehouse spray equipment 2-8 by pipeline, described pretreatment storehouse gas outlet 1-12 connects luminous energy storehouse air inlet 2-2.

Pretreatment warehouse 1-13 described above top arranges pretreatment storehouse access cover 1-1, pretreatment storehouse access door 1-11 is set on the sidewall of pretreatment warehouse 1-13, reservoir 1-7 top arranges infundibulate collecting board 1-3, and pretreatment storehouse liquid level meter 1-9 and thief hatch 1-5 are set on the sidewall of reservoir 1-7.

Pretreatment described above storehouse spray equipment 1-2 is the pressurization spray equipment that is arranged on pretreatment warehouse 1-13 inner top, or for being arranged on the pressurization spray equipment of pretreatment warehouse 1-13 inner top and being arranged on the atomizing spray equipment on pretreatment warehouse 1-13 inwall.

The spray droplet of pressurization spray equipment described above is uniform line; The diameter that every dropping liquid drips is 2～3 millimeters, and between every, interval is 6～10 millimeters.

Pretreatment warehouse 1-13 described above is made by stainless steel metal plate.

Pretreatment described above storehouse suction pump 1-6 is acidproof water pump.

Luminous energy warehouse 2-11 described above is made by stainless steel metal plate, on luminous energy warehouse 2-11 inwall, scribbles corrosion-inhibiting coating.

Luminous energy storehouse liquid level meter 2-7 is set on the sidewall of luminous energy warehouse 2-11 described above, and luminous energy warehouse 2-11 top arranges luminous energy storehouse access cover 2-9.

Light irradiation apparatus 2-10 described above is quartz ampoule uviol lamp or visible lamp.

The Lower Half in above-mentioned luminous energy storehouse has purification plate, and surface scribbles the Amberlite IRC748 ion exchange resin coating of commercially available DOW chemical company, reclaims described metal system material, and will contain the solution purification of sulfuric acid for adsorbing.

2, about taking off the course of work and the device of dirt:

A method for the flue gas that processing contains dust, comprises the following steps:

(1) in pretreating containers, add water;

The mass percent of described solution allocation hydrogen peroxide and water is 3%～5%;

Hydrogen peroxide and metal system mol ratio are more than or equal to 10:1;

(6) flue gas after purifying is discharged to pretreating containers;

(7) flue gas of step (6) being discharged passes into reaction vessel, and with the abundant haptoreaction of Fenton reagent, making the hydrocarbons decompose in flue gas is carbon dioxide and water, and carbon granule and Oxidation of Carbon Monoxide are carbon dioxide;

(8) will react after solution derive, and periodic monitor derives the concentration of Fenton reagent in solution, according to the situation of monitoring, adds the new solution that contains Fenton reagent and makes solution composition keep stable;

(9) purified gas is discharged to reaction vessel.

After step described above (1), add step (1 ') for using nitric acid to adjust below pH value to 3, then add oxidising agent, make carbon granule be oxidized to carbon monoxide, described oxidising agent is hydrogen peroxide, the mixture of molybdenum oxide and tungsten oxide, the mixture of magnesia and magnesium hydroxide or di-iron trioxide, wherein, molybdenum oxide, tungsten oxide, magnesia, the diameter of magnesium hydroxide and di-iron trioxide solid particle is less than 20nm, the volume ratio of hydrogen peroxide and water is 1:18～22, the mol ratio of molybdenum oxide and tungsten oxide is 1:1, the mol ratio of magnesia and magnesium hydroxide is 1:1, the amount ratio of molybdenum oxide and water is more than or equal to 10mol/L, the amount ratio of tungsten oxide and water is more than or equal to 10mol/L, the amount ratio of magnesia and water is more than or equal to 10mol/L, the amount ratio of magnesium hydroxide and water is more than or equal to 10mol/L, the amount ratio of di-iron trioxide and water is more than or equal to 20mol/L.

Realize a device for method described above, comprise pretreatment storehouse and luminous energy storehouse, described pretreatment storehouse comprises pretreatment warehouse, pretreatment storehouse spray equipment, pretreatment storehouse air inlet, pretreatment storehouse suction pump, reservoir, pretreatment storehouse liquid outlet, pretreatment storehouse inlet and gas outlet, pretreatment storehouse, the bottom of described pretreatment warehouse is reservoir, pretreatment storehouse liquid outlet is arranged on reservoir place, described pretreatment storehouse air inlet, pretreatment storehouse inlet and gas outlet, pretreatment storehouse are arranged on the pretreatment warehouse of reservoir top, gas outlet, pretreatment storehouse is above the air inlet of pretreatment storehouse, described pretreatment storehouse spray equipment is arranged in pretreatment warehouse, described pretreatment storehouse suction pump connects the output of reservoir and the input of pretreatment storehouse spray equipment by pipeline, described luminous energy storehouse comprises luminous energy warehouse, luminous energy storehouse air inlet, gas outlet, luminous energy storehouse, luminous energy storehouse inlet, gas-liquid mixed passage, luminous energy storehouse suction pump, luminous energy storehouse liquid outlet, luminous energy storehouse spray equipment and light irradiation apparatus, described luminous energy storehouse air inlet and gas outlet, luminous energy storehouse are arranged on the top of luminous energy warehouse, described luminous energy storehouse inlet is arranged on the middle part of luminous energy warehouse, described luminous energy storehouse liquid outlet is arranged on the bottom of luminous energy warehouse, described gas-liquid mixed passage, luminous energy storehouse spray equipment and light irradiation apparatus are positioned at luminous energy warehouse, the input of gas-liquid mixed passage connects luminous energy storehouse air inlet, the output of gas-liquid mixed passage is positioned at the position at the bottom of luminous energy warehouse bottom approaches storehouse, described luminous energy storehouse suction pump connects the output of luminous energy warehouse bottom and the input of luminous energy storehouse spray equipment by pipeline, gas outlet, described pretreatment storehouse connects luminous energy storehouse air inlet.

Pretreatment warehouse described above top arranges pretreatment storehouse access cover, and pretreatment storehouse access door is set on the sidewall of pretreatment warehouse, and reservoir top arranges infundibulate collecting board, and pretreatment storehouse liquid level meter and thief hatch are set on the sidewall of reservoir.

Pretreatment warehouse described above is made by stainless steel metal plate.

Pretreatment described above storehouse suction pump is acidproof water pump.

Luminous energy warehouse described above is made by stainless steel metal plate, on luminous energy warehouse inwall, scribbles corrosion-inhibiting coating.

Luminous energy storehouse liquid level meter is set on the sidewall of luminous energy warehouse described above, and luminous energy warehouse top arranges luminous energy storehouse access cover.

Light irradiation apparatus described above is quartz ampoule uviol lamp or visible lamp.

3, about the course of work and the device of denitration:

The remove smoke method of middle nitrogen oxide, is characterized in that it comprises the following steps:

(1) flue gas of nitrogen-containing oxide carries out pretreatment in pretreating containers, and preprocessing process is removed the solid particle that the diameter in flue gas is greater than 10 microns, and NO is oxidized to NO ₂:

In pretreating containers, add and contain oxidant and pH value is less than or equal to 3 solution;

Flue gas is passed in pretreating containers, fully contact with liquid, the solid particle that makes diameter be greater than 10 microns is stayed in solution, and NO is oxidized to NO ₂;

The solution that contains solid particle is derived to pretreating containers;

(2) pretreated flue gas enters in denitration container, and nitrogen oxide and oxidant reaction generate nitric acid:

In denitration container, add and contain oxidant and pH value is less than or equal to 3 solution;

To enter in denitration container through pretreated flue gas, with the abundant haptoreaction of oxidant, generate nitric acid;

(3) purified gas is discharged denitration container.

In described pretreating containers and denitration container, first use nitric acid to adjust below pH value to 3, then add oxidant.

Oxidant in described pretreating containers and denitration container is hydrogen peroxide, the mixture of molybdenum oxide and tungsten oxide, the mixture of magnesia and magnesium hydroxide or di-iron trioxide, wherein, molybdenum oxide, tungsten oxide, magnesia, the diameter of magnesium hydroxide and di-iron trioxide solid particle is less than 20nm, the volume ratio of hydrogen peroxide and water is 1:18～22, the mol ratio of molybdenum oxide and tungsten oxide is 1:1, the mol ratio of magnesia and magnesium hydroxide is 1:1, the amount ratio of molybdenum oxide and water is more than or equal to 10mol/L, the amount ratio of tungsten oxide and water is more than or equal to 10mol/L, the amount ratio of magnesia and water is more than or equal to 10mol/L, the amount ratio of magnesium hydroxide and water is more than or equal to 10mol/L, the amount ratio of di-iron trioxide and water is more than or equal to 20mol/L.

Described hydrogen peroxide is that peromag, sodium peroxide or the calper calcium peroxide that diameter is less than 50 nanometers reacts rear generation in water.

In described pretreating containers, liquid sprays to increase by spray equipment area and the time that flue gas contacts with liquid.

In described denitration container, gas directly passes into area and the time that liquid contacts with liquid to increase flue gas, or liquid sprays to increase by spray equipment area and the time that flue gas contacts with liquid; Or two kinds of modes are used simultaneously.

In described step (1), when selecting hydrogen peroxide to be oxidant, by the concentration of liquid outlet periodic monitor oxidant, and supplemental oxidant is stablized oxidant concentration in solution as required; The consumption of described hydrogen peroxide is by regularly collecting sample by close monitoring, and the consumption rate of use iodine/potassium permanganate (I/KMnO4) titration observation hydrogen peroxide.

When in described step (1), flue gas enters pretreating containers, from container bottom, enter; Direction level is also 40～50 degree angles with chamber wall, makes flue gas when moving up, produce helical effect, to increase the time contacting with liquid.

The liquid that flows out pretreating containers in described step (1) is greater than after 10 micron particles things removing, and is transported to the spray equipment of pretreating containers by water pump by pipeline.

After reacting in described step (2), solution is derived, and when selecting hydrogen peroxide to be oxidant, periodic monitor is derived the concentration of oxidant in solution, according to the situation of monitoring, adds the new solution that contains oxidant and makes solution composition in container keep stable; The consumption of described hydrogen peroxide is by regularly collecting sample by close monitoring, and the consumption rate of use iodine/potassium permanganate (I/KMnO4) titration observation hydrogen peroxide.

Solution in described step (2) is transported to the spray equipment of denitration container by pipeline by water pump.

A nanometer flue gas denitrification system, is characterized in that it consists of pretreatment storehouse and denitration storehouse; The output in described pretreatment storehouse is connected with the input in denitration storehouse;

Described pretreatment storehouse comprises pretreatment storehouse warehouse, pretreatment storehouse spray system, pretreatment storehouse air inlet, pretreatment storehouse suction pump, reservoir, pretreatment storehouse liquid outlet, pretreatment storehouse inlet and gas outlet, pretreatment storehouse; The bottom of described pretreatment storehouse warehouse is reservoir, pretreatment storehouse liquid outlet is arranged on reservoir place, described pretreatment storehouse air inlet, pretreatment storehouse inlet and gas outlet, pretreatment storehouse are arranged on the pretreatment storehouse warehouse of reservoir top, gas outlet, pretreatment storehouse is above the air inlet of pretreatment storehouse, described pretreatment storehouse spray system is arranged in the warehouse of pretreatment storehouse, and described pretreatment storehouse suction pump connects the output of reservoir and the input of pretreatment storehouse spray system by pipeline;

Described denitration storehouse comprises denitration storehouse warehouse, gas outlet, denitration storehouse, denitration storehouse spray system, denitration storehouse air inlet, denitration storehouse inlet, gas-liquid mixed passage, denitration storehouse liquid outlet and denitration storehouse suction pump; Described denitration storehouse air inlet and gas outlet, denitration storehouse are arranged on the top of denitration storehouse warehouse; Described denitration storehouse inlet is arranged on the middle part of denitration storehouse warehouse; Described denitration storehouse liquid outlet is arranged on the bottom of denitration storehouse warehouse; Described gas-liquid mixed passage, denitration storehouse spray system are positioned at denitration storehouse warehouse; The input of gas-liquid mixed passage connects denitration storehouse air inlet, and output is placed in the liquid in the warehouse of denitration storehouse; Described denitration storehouse suction pump connects the output of warehouse bottom, denitration storehouse and the input of denitration storehouse spray system by pipeline.

Warehouse top, described pretreatment storehouse arranges access cover, on the sidewall of warehouse, access door is set, and reservoir top arranges infundibulate collecting board, and pretreatment storehouse liquid level meter and thief hatch are set on the sidewall of reservoir.

Described pretreatment storehouse spray system is the pressurization spray equipment that is arranged on pretreatment storehouse warehouse inner top, or for being arranged on the pressurization spray equipment of pretreatment storehouse warehouse inner top and being arranged on the atomizing spray equipment on the warehouse inwall of pretreatment storehouse.

The spray droplet of described pressurization spray equipment is uniform line; The diameter that every dropping liquid drips is 2～3 millimeters, and between every, interval is 6～10 millimeters.

Described pretreatment storehouse warehouse is made by stainless steel metal plate.

Described pretreatment storehouse suction pump is acidproof water pump.

On the sidewall of described denitration storehouse warehouse, denitration storehouse liquid level meter is set, warehouse top, denitration storehouse arranges access cover.

Described gas-liquid mixed passage comprises 3 medium-sized gas-liquid mixed passages and 3 small-sized gas-liquid mixed passages, or comprises 5 large-scale hybrid channels.

Described denitration storehouse warehouse is made by stainless steel metal plate.

A kind of method of work of above-mentioned nanometer flue gas denitrification system:

Pretreated method:

(1) to water filling in the warehouse of pretreatment storehouse, use nitric acid adjust pH value extremely below, then add oxidant;

(2) open pretreatment storehouse suction pump, pretreatment storehouse spray system is started working;

(3) flue gas enters in the warehouse of pretreatment storehouse from the direction of pretreatment storehouse air inlet and pretreatment storehouse warehouse inwall angle 40 to 50 degree, makes flue gas when moving up, produce helical effect;

(4) NO in flue gas and oxidant reaction generate NO ₂;

(5) regularly by thief hatch, collect the consumption of sample monitoring oxidant, according to the NO content in flue gas, to supplemental oxidant in the warehouse of pretreatment storehouse.

Described oxidant is hydrogen peroxide, the mixture of molybdenum oxide and tungsten oxide, the mixture of magnesia and magnesium hydroxide or di-iron trioxide, wherein, molybdenum oxide, tungsten oxide, magnesia, the diameter of magnesium hydroxide and di-iron trioxide solid particle is less than 20nm, the volume ratio of hydrogen peroxide and water is 1:18～22, the mol ratio of molybdenum oxide and tungsten oxide is 1:1, the mol ratio of magnesia and magnesium hydroxide is 1:1, the amount ratio of molybdenum oxide and water is more than or equal to 10mol/L, the amount ratio of tungsten oxide and water is more than or equal to 10mol/L, the amount ratio of magnesia and water is more than or equal to 10mol/L, the amount ratio of magnesium hydroxide and water is more than or equal to 10mol/L, the amount ratio of di-iron trioxide and water is more than or equal to 20mol/L.

When described oxidant is hydrogen peroxide, the consumption of hydrogen peroxide by close monitoring, and is used iodine/potassium permanganate (I/KMnO4) titration to observe the consumption rate of peroxide by sample collection hourly.

The method of denitration:

(1) at denitration storehouse warehouse, add oxidizing agent solution, through pretreated flue gas, by air inlet, enter gas-liquid mixed passage;

(2) NO in flue gas ₂react to produce HNO with oxidant ₃;

(3) regularly by collecting the consumption of sample monitoring oxidant, according to the NO content in flue gas, to supplemental oxidant in the warehouse of denitration storehouse.

A part of NO in the pretreated flue gas of described process ₂molecule can react with water generates and generate HNO ₃and NO; In pretreatment storehouse, do not have oxidized NO to add NO ₂molecule can react with water the NO that produces will with HNO ₃and H ₂o reacts and produces intermediate HNO ₂; This intermediate again with H ₂o ₂further reaction, generates end product: HNO ₃add H ₂o.

4, about removing the course of work and the device of heavy metal:

The remove smoke method of middle heavy metal, it comprises the following steps:

(1) nano material is embedded on fibrous matrix;

(2) flue gas that makes to contain heavy metal is by being embedded with the fibrous matrix of nano material;

(3) nano material is reacted with the heavy metal in flue gas, catches the heavy metal in flue gas.

The described method that nano material is embedded on fibrous matrix is:

Adhesive bonding agent on fibrous matrix; Before adhesive dries, nano material is sprayed on fabric by nano-spray device; After nano material is sprayed, be placed under room temperature at least 24 hours, make it to solidify completely.

Described adhesive is selected rEN50 to 80 (watt digests ) organic siliconresin solution, epoxy resin or methyl epoxy. rEN series is an adhesive that can be used for any heat-resisting application, and it has been used in many process industries, as automobile and aircraft industry; It can bear the temperature up to 650 degree not losing in adhering situation, and good corrosion resistance is provided; rEN series becomes dry conventionally after the 200 degree bakings of a hour.

The described method that nano material is embedded on fibrous matrix is: directly load nano material on fibrous matrix: nano material is suspended in volatile solvent; Fibrous matrix is soaked in nano material suspension, or by nano material by atomizers spray on fibrous matrix; The fibrous matrix that is attached with nano material is carried out in the baking box of 500 degree to the heat treated of 3 to 4 hours; After solution evaporation, nano wire and nano particle will with fleece weave in; Be cooled to after room temperature, nano material is by being locked in fibrous matrix by safety.

Described volatile solvent is ethanol or ethyl acetate.

Described nano material is to be attached to golden nanometer particle on nano-carrier particle, to be attached to the WS on nano-carrier particle ₂nano particle or CdS nano wire.

The described synthetic method that is attached to the golden nanometer particle on nano-carrier particle is:

2 to 4M/L HAuCl4 is dissolved in distilled water; TiO with 100 to 200 micron diameters after sieving ₂or r-Al ₂o ₃or SiO ₂as nano-carrier, join in gold solution; Solution is heated to 70 degrees Celsius, then allows its aging (needing stored a period of time, to obtain desired quality) 20 to 40 minutes; Be cooled to 40 degrees Celsius, add 30%NH3; Filter and wash with water, in 100 degree baking ovens, be dried at least 12 hours; Then 350 ℃ of calcinings at least 4 hours in air; Obtain being attached to nano-carrier TiO ₂or r-Al ₂o ₃or SiO ₂au nano particle on particle, i.e. Au-TiO ₂gold-titanium dioxide, Au-SiO ₂gold-silica or Au-Al ₂o ₃;

Or, with depositing the technology that loads (DP): prepare 0.1 to 0.5M/L chlorauric acid solution with distilled water; By solution with the speed of 10 ml/min slowly and stir join TiO ₂or r-Al ₂o ₃or SiO ₂in the suspension of nano-carrier; Heat to 65 ℃ and keep at least 1 hour, being then cooled to room temperature; The NH4OH that adds 1M/L, pH is adjusted to 7; Slowly stir at least 2 hours; After filtering, with hot wash, in 80 ℃ of baking boxs, dry at least 12 hours; Then 180 ℃ of calcinings at least 4 hours in air, obtain being attached to nano-carrier TiO ₂or r-Al ₂o ₃or SiO ₂au nano particle on particle, i.e. Au-TiO ₂gold-titanium dioxide, Au-SiO ₂gold-silica or Au-Al ₂o ₃.

Described Au-TiO ₂gold-titanium dioxide, Au-SiO ₂gold-silica or Au-Al ₂o ₃the mass percent of middle Au is for being less than 5%.

In the time of heavy with moistures, Au-TiO ₂gold-titanium dioxide has the Au-SiO of ratio ₂gold-silica and Au-Al ₂o ₃better catalytic activity.

Gold at low temperature (being not less than-20 ℃), under moistening (humidity >100%) condition, show high catalytic activity, under show superpower stability; When in addition, gold nano grain form is deposited on transition metal oxide carrier, its catalysis characteristics will be improved.

The described WS being attached on nano-carrier particle ₂the synthetic method of nano particle:

According to the quality of solute and molten drug and volume (W/V) than being greater than 50 ratios, by the Chelsea that rubs than (NH4) of 1:18～20 ₆w ₇o ₂₄4H ₂o and Na ₂s9H ₂in the HCl of the 0.8M/L that O adds to, the solution of vigorous stirring; At 80 ℃, heating is at least 0.5 hour;

Then add and Na ₂s9H ₂the NH of O equimolar amounts ₂oHHCl is in solution, and vigorous stirring is at least 1 hour simultaneously;

In ultrasonic generator, use higher than 20 kilo hertzs of (20,000 times per second) ultrasonic processing 10 minutes;

With deionized water washing, for several times to remove the residue of reactant, by centrifugation, obtain black powder;

At air drying, obtain end product WS ₂powder, is WS ₂nano particle;

WS ₂the horse that is full of nitrogen at a 400oC before nano particle is used is not cured 2 hours functionalization in Shanghai;

By WS ₂nano particle and TiO ₂or r-Al ₂o ₃or SiO ₂nano-carrier in mass ratio 1:20-50 mixes in water, slowly stirs at least 1 hour, and then 400 degree are above dry at least 2 hours, obtain being attached to the WS on nano-carrier particle ₂nano particle.

The synthetic method of described CdS nano wire is:

In picoclave high pressure reactor (autoclave), put into toluene, distilled water, and 1,12 alkanethiol, mix with volume ratio 20:2:1; The caddy and the thiocarbamide acid that add 1:1 mol ratio; Autoclave is remained on to 180 degrees Celsius and react 24 hours, then make it be cooled to room temperature; A kind of powder of yellow can precipitate, and after collecting precipitation powder thing, with ethanol and distilled water, washs to remove residual organic solvent; Final product is dried at least 6 hours in 70 ℃, vacuum, obtains CdS nano wire; Must ultrasonic processing in ethanol before CdS nano wire is used;

Or, first the cadmium sulfate of 0.16～0.20M is joined in the 7～8M/L ammonia spirit under continuous stirring; After this, the thiocarbamide acid that adds slowly 0.6～0.8M under powerful stirring; Solution is heated to 65 ℃, and pH remains on 9-11, powerful stirring 50-70 minute; Then by the centrifugal rear collection of yellow solid of precipitation, and dry in baking oven, 65 ℃ of maintenances at least 4 hours, obtain CdS nano wire; CdS nano wire must ultrasonic processing in ethanol before using.

Described fibrous matrix is meta-aramid Meta-aramid, polytetrafluoroethylene PTFE, polyphenylene thioether PPS, polybenzimidazoles PBI, polyimides ployimide, RY805 fiber (GE Energy BHA Group) and PC102 fiber (GE Energy BHA Group), or non-woven fibre, described non-woven fibre is the synthetic fibers such as nylon 66, polyester, polyurethane.These synthetic fibers all have from the temperature range of 190 °～315 ° of continuous operations; The principal character of high-performance fiber is the technical functionality that the physical property of its uniqueness can reach special chemical reaction; The tensile strength that in these fibers, some the most outstanding performances are them, operating temperature, limited oxygen index (LOI) and chemical resistance.LOI supports the oxygen content that burning is required in atmosphere; It is so-called fire retardant that LOI is greater than 25 fiber, must have at least 25% oxygen just can make their burnings.

Described heavy metal is mercury or lead.

In described step (3), nano material is golden nanometer particle, and gold (Au) element and heavy metal element mercury (Hg °) and (plumbous Pb °) have high-affinity, can form chemical bond, thereby heavy metal element is caught; Nano material is WS ₂nano particle or CdS nano wire, catch heavy metal element: WS by MLCT (transfer of metal ligand electric charge) principle ₂and CdS is between ionic compound and covalent compound in the characteristic of chemical constitution; The characteristic performance of metal (W and Cd) is just as lewis acid, but not the performance of the characteristic of metal inorganic part (S) is just as lewis base; Electronics concentrates on inorganic part, makes the inorganic part of part become negative electrical charge; Inorganic ligand can attract heavy metal element, WS ₂, CdS can attract the lead ion in flue gas, Element Lead and element mercury.

In described step (3), be embedded with mercury in the heavy metal that the fibrous matrix of nano material catches by by mercaptopropionic acid and 2, the synthetic liquid of dipicolimic acid 2 soaks filter by heavy metal wash-out out; Metallic lead (Pb in the heavy metal of catching ⁰) can be converted into lead hydroxide Pb (OH) ₂; Lead hydroxide can wash out easily with spirit of vinegar or rare nitric acid.

Described mercaptopropionic acid and 2, the cheland of dipicolimic acid 2 and mercury have the quite associativity of height, and binding constant is respectively log K10.1 and 20.2; So we can clean and reclaim use to this non-woven fibre filter; The mercury being cleared out can extract and then carry out appropriate disposal from cleaning fluid.

The described flue gas that contains heavy metal carries out pretreatment by being embedded with to pass into before the fibrous matrix of nano material in reaction vessel; In described reaction vessel, add and contain Fenton reagent and use Alpha-hydroxy acid for adjusting pH value to the solution that is less than or equal to 3, described Fenton reagent comprises can there is metal system and the hydrogen peroxide that light helps Fenton's reaction; The mass percent of described solution allocation hydrogen peroxide and water is 3%～5%; Hydrogen peroxide and metal system mol ratio are more than or equal to 10:1;

According to the optical absorption peak of metal system, illumination system is set in reaction vessel;

Flue gas passes into reaction vessel, with the abundant haptoreaction of Fenton reagent, makes mercury element be converted into mercury ion;

After reacting, solution is derived, and periodic monitor derives the concentration of Fenton reagent in solution, according to the situation of monitoring, adds the new solution that contains Fenton reagent and makes solution composition keep stable; Purified gas is discharged to reaction vessel.

Described metal system is Fe (II)/F (III) system or Cu (I)/Cu (II) system; When metal system is Fe (II)/F (III) system, illumination is that wavelength is the ultraviolet light of 200nm～400nm; When metal system is Cu (I)/Cu (II) system, illumination is that wavelength is the visible ray of 600nm～800nm.

Described Fe (II)/F (III) system is less than the FeSO of 20 nanometers by diameter ₄and Fe ₃o ₄particle forms.

Described Cu (I)/Cu (II) system is less than the Cu of 20 nanometers by diameter ₂o and CuSO ₄particle forms.

Described 'alpha '-hydroxy acids is glycolic, pyruvic acid or lactic acid.

The consumption of described hydrogen peroxide is by regularly collecting sample by close monitoring, and the consumption rate of use iodine/potassium permanganate (I/KMnO4) titration observation peroxide.

In described reaction vessel, gas directly passes into area and the time that liquid contacts with liquid to increase flue gas, or liquid sprays to increase by spray equipment area and the time that flue gas contacts with liquid; Or two kinds of modes are used simultaneously.

A nanometer flue gas removing heavy-metal device, is characterized in that it comprises the fibrous matrix that is embedded with nano material.

The described fibrous matrix that is embedded with nano material is arranged on centrifugal fan.

The described fibrous matrix that is embedded with nano material is attached on the flabellum of centrifugal fan, or is arranged between inclination flabellum; The angle of inclination of described inclination flabellum is 30-45 degree.

Described fibrous matrix is meta-aramid Meta-aramid, polytetrafluoroethylene PTFE, polyphenylene thioether PPS, polybenzimidazoles PBI, polyimides ployimide, RY805 fiber (GE Energy BHA Group) and PC102 fiber (GE Energy BHA Group), or non-woven fibre, described non-woven fibre is the synthetic fibers such as nylon 66, polyester, polyurethane.

Described centrifugal fan consists of framework and flabellum, and flabellum passes through, and flabellum is connected with framework and is connected with framework with axle sleeve by central shaft; Described framework and flabellum are to be made by nickel-molybdenum alloy (aluminium alloy, stainless steel), for example, because of its acid resistance at any temperature, alloy (65%Ni, 28.5%Mo, 1.5%Cr, 1.5%Fe, 3%Co, 3%W, 3%Mn, 0.5%Al, 0.2%Ti, 0.1%Si and 0.01%C) is a good choice.Before described, the replaceable and callable fibrous matrix that is embedded with nano material will be installed on the flabellum of fan.This nano material that is embedded with the fibrous matrix of nano material is to react with the heavy metal generation in flue gas through special design, especially mercury.According to different service conditions, if time some coals relatively for a typical 30Wan megawatt power plant approximately also need change non-woven fibre every year inferior.

The input of described a kind of nanometer flue gas removing heavy-metal device connects the output in luminous energy storehouse, luminous energy storehouse comprises luminous energy warehouse, luminous energy storehouse air inlet, gas outlet, luminous energy storehouse, luminous energy storehouse inlet, gas-liquid mixed passage, luminous energy storehouse suction pump, luminous energy storehouse liquid outlet, luminous energy storehouse spray equipment and light irradiation apparatus, described luminous energy storehouse air inlet and gas outlet, luminous energy storehouse are arranged on the top of luminous energy warehouse, described luminous energy storehouse inlet is arranged on the middle part of luminous energy warehouse, described luminous energy storehouse liquid outlet is arranged on the bottom of luminous energy warehouse, described gas-liquid mixed passage, luminous energy storehouse spray equipment and light irradiation apparatus are positioned at luminous energy warehouse, the input of gas-liquid mixed passage connects luminous energy storehouse air inlet, the output of gas-liquid mixed passage is positioned at the position at the bottom of luminous energy warehouse bottom approaches storehouse, described luminous energy storehouse suction pump connects the output of luminous energy warehouse bottom and the input of luminous energy storehouse spray equipment by pipeline, gas outlet, described pretreatment storehouse connects luminous energy storehouse air inlet.

Described luminous energy warehouse is made by stainless steel metal plate, on luminous energy warehouse inwall, scribbles corrosion-inhibiting coating.

Luminous energy storehouse liquid level meter is set on the sidewall of described luminous energy warehouse, and luminous energy warehouse top arranges luminous energy storehouse access cover.

Described light irradiation apparatus is quartz ampoule uviol lamp or visible lamp.

Superiority of the present invention:

1, the effective purifying exhaust air of the present invention, has become nitrogen oxide into nitric acid, sulfur dioxide is become to sulfuric acid, and reclaimed, and therefore, the interests that the present invention reclaims far surpass the operating cost of equipment itself, and user can obtain more profit;

2, the present invention can be included into the existing system in coal-burning power plant and be used for improving its validity, or replaces original old system completely;

3, the applicable industrial market at other of the present invention, comprises cement plant, steel plant, trash burning factory of municipal government, clinical waste combustion plant, chlorine manufactory, paper pulp and paper production factory etc.;

4, the present invention take up an area little, transform simple and easyly, and manufacture and operating cost are all less than 50% left and right of current RSC denitration technology.Strictly following under the prerequisite of operational procedure, the present invention can protect continuity, and to use 15～20 years engineered without carrying out, and can synchronize and maintain with the coal-burning boiler of operation.

5, the advantage of nano material is that its surface area is large, between molecule the mutual transmission of electronic shell very fast, can make to accelerate as chemical reaction velocity index; Especially in optical field, activity and the momentum of the less luminous energy of diameter of nanometer are larger.So want to make flow velocity fast flue gas like this to produce any chemical reaction, the advantage of nanometer technology is not deniable.The redox reaction of self is spontaneous, has the characteristic of catalyst, so without often attaching, consumption is few, and economy very.

6, this invention desulfurization benefit can reach 99.99%, and manufactures and move all in 50% left and right of desulfur technology at present, and without any extra charge in the situation that, has solved the removal problem of PM2.5.That equipment takes up an area is little, it is simple and easy to transform.The present invention is based upon in the principle that light helps Fenton's reaction, and is eliminating SO ₂with on flue dust, obtained immense success.Equipment of the present invention is principle based on AOPs ?Fenton's reaction and successful industrialized unit.The method of the invention be one more economical, control air-polluting mode more efficiently, without any extra manufacture and operating cost.

It is as follows that native system clean-up effect detects test report:

1, the present invention is used for the test report of purifying automobile tail gas:

Examination criteria (method) and use instrument

Testing result

2, the present invention is used for the test report (test site is certain boiler room) of purification boiler waste gas:

Examination criteria (method) and use instrument

Testing result

Remarks: standard value is according to < < thermoelectricity field atmosphere pollutants emission standards > > (GB13223-2011)

3, the present invention is for the test report (He Mou steel mill of test site Wei Mou power plant) of purifying industrial waste gases

Examination criteria (method) and use instrument

Testing result

4, the present invention is for purifying the test report of sulfur dioxide

5, the present invention is for eliminating the technique effect of mercury:

The present invention is for eliminating plumbous technique effect:

(4) accompanying drawing explanation:

Fig. 1 is the overall structure schematic diagram of the system of the related a kind of purifying contaminated air of the present invention.

Fig. 2 is the pretreatment chamber structure schematic diagram in the system of the related a kind of purifying contaminated air of the present invention, and wherein Fig. 2-1 is the first example structure schematic diagram, and Fig. 2-2 are the second example structure schematic diagram.

Fig. 3 is the denitration chamber structure schematic diagram in the system of the related a kind of purifying contaminated air of the present invention, and wherein, Fig. 3-1 is the first example structure schematic diagram, and Fig. 3-2 are the second example structure schematic diagram.

Fig. 4 is the luminous energy chamber structure schematic diagram in the de-dirt of desulfurization storehouse in the system of the related a kind of purifying contaminated air of the present invention.

Fig. 5 is luminous energy storehouse and the cleaning position structural representation in the de-dirt of desulfurization storehouse in the system of the related a kind of purifying contaminated air of the present invention.

Fig. 6 is the huge sum of money filter apparatus configuration schematic diagram in the de-dirt of desulfurization storehouse in the system of the related a kind of purifying contaminated air of the present invention, wherein 6-1 is the first example structure schematic diagram, 6-2 is the first embodiment perspective view, 6-3 is the first embodiment decomposing schematic representation, and 6-4 is the second example structure schematic diagram.

Fig. 7 is the method for work flow chart of the system of the related a kind of purifying contaminated air of the present invention.

Fig. 8 is the theoretical schematic diagram of substance transfer.

Fig. 9 is the reaction diffusion plane geometrical principle figure of penetration theory.

Figure 10-1～Figure 10-4 are liquid gas median surface course of reaction figure.(Figure 10-1 shows there is no obstacle between gas and liquid transition, and gas directly transmits and be diffused into liquid, and this reaction is moment reflection.Once Figure 10-2 show the median surface through gas and liquid, gas reactant can reduce by initial concentration in gas, and reaction rate depends on that gas transfer arrives the diffusion time of liquid.Figure 10-3 show that gas molecule cannot and be diffused into liquid by gas and liquid median surface, and by this process, reactant is zero in the concentration of liquid.Figure 10-4 show gas and liquid the most effective interactional mode, and the concentration of gas molecule reduces in median surface, and in liquid, concentration increases.)

Figure 11-1 is the design drawing of laminar flow gas-mixed flow liquid.

Figure 11-2 are the design drawing of mixed flow gas-batch processing reaction liquid.

Wherein, in Fig. 1, label is: 1. air-introduced machine a; 2. circulating pump; 3. pretreatment storehouse; 4. denitration storehouse; 5. luminous energy storehouse; 6 service cover; 7. heavy metal filter; 8. air-introduced machine b; 9a-9b. chemical reagent supplements tank a; 10a & 10b. acid purification treating apparatus; 10c. distilling apparatus; 11. chemical reagent supplement tank b; 12. measuring pumps; 13. chemical reagent supplement tank c.

Fig. 2-1, 2-2, 4, in 5, label is: 1-1 is pretreatment storehouse access cover, 1-2 is pretreatment storehouse spray equipment, 1-3 is infundibulate collecting board, 1-4 is pretreatment storehouse air inlet, 1-5 is thief hatch, 1-6 is pretreatment storehouse suction pump, 1-7 is reservoir, 1-8 is pretreatment storehouse liquid outlet, 1-9 is pretreatment storehouse liquid level meter, 1-10 is pretreatment storehouse inlet, 1-11 is pretreatment storehouse access door, 1-12 is gas outlet, pretreatment storehouse, 1-13 is pretreatment warehouse, 2-1 is gas outlet, luminous energy storehouse, 2-2 is luminous energy storehouse air inlet, 2-3 is luminous energy storehouse inlet, 2-4 is gas-liquid mixed passage, 2-5 is luminous energy storehouse suction pump, 2-6 is luminous energy storehouse liquid outlet, 2-7 is luminous energy storehouse liquid level meter, 2-8 is luminous energy storehouse spray equipment, 2-9 is luminous energy storehouse access cover, 2-10 light irradiation apparatus, 2-11 is luminous energy warehouse, 3-1 is for purifying warehouse, 3-2 is purification plate, 3-3 is that fluid flow is controlled bolt, 3-4 is cleaning position liquid outlet.

In Fig. 3, label is: 1-1 is access cover, 1-2 is pretreatment storehouse spray system, 1-3 is infundibulate collecting board, 1-4 is pretreatment storehouse air inlet, 1-5 is thief hatch, 1-6 is pretreatment storehouse suction pump, 1-7 is reservoir, 1-8 is pretreatment storehouse liquid outlet, 1-9 is pretreatment storehouse liquid level meter, 1-10 is pretreatment storehouse inlet, 1-11 is access door, 1-12 is gas outlet, pretreatment storehouse, 1-13 is pretreatment storehouse warehouse, 2-1 is gas outlet, denitration storehouse, 2-2 is denitration storehouse spray system, 2-3 is denitration storehouse air inlet, 2-4 is denitration storehouse inlet, 2-5 is gas-liquid mixed passage, 2-6 is denitration storehouse liquid level meter, 2-7 is denitration storehouse liquid outlet, 2-8 is denitration storehouse suction pump, 2-9 is access cover, 2-10 is denitration storehouse warehouse.

Label in Fig. 6-1,6-2,6-3,6-4 is: 1-1 is framework, and 1-2 is flabellum, axle centered by 1-3, and 1-4 is axle sleeve, and 1-5 is the fibrous matrix that is embedded with nano material, and 1-6 is folder.

In Fig. 8, the mole coefficient of PA=reactant A, [A] int=reaction A initial concentration, [A] bulk=reactant A is in the main body concentration of liquid.

In Fig. 9, the mole coefficient of PA=reactant A, the mole coefficient that PAi=reactant A is initial, [A] *=reactant A is at the concentration of median surface, [A] _b=reactant A is in the main body concentration of liquid, the distance that x=reactant A spreads in film.

In Figure 10-1～10-4, [A] *=reactant A is in the concentration of median surface, and [A] 0=reactant A is in the initial concentration of the main body of liquid, the initial concentration of main body of [B] 0=liquid, δ=median surface thickness.

In Figure 11-1, Gas in is gas feed, and Gas out is gas vent, and Liquid in is liquid-inlet, and Liquid out is liquid outlet, F _lfor the direction of liquid flow, F _gfor the direction of gas flow, P _a0for the initial concentration of reactant, P _affor reactant final concentration, [B] _b0for the initial concentration of main body of liquid, [B] _bffinal concentration for main body of liquid.

In Figure 11-2, Gas in is gas feed, and Gas out is gas vent, F _gfor the direction of gas flow, P _a0for the initial concentration of reactant, P _affor reactant final concentration.

(5) specific embodiment:

Embodiment 1: a kind of system of purifying contaminated air (seeing Fig. 1,2-1,3-1,4,6-1,6-2,6-3), is characterized in that it is to be supplemented tank c and formed by air-introduced machine a, circulating pump, pretreatment storehouse, denitration storehouse, the de-dirt of desulfurization storehouse, service cover, heavy metal filter, air-introduced machine b, the supplementary tank a of chemical reagent, acid purification treating apparatus, the supplementary tank b of chemical reagent, measuring pump, chemical reagent; Pollute source of the gas and enter pretreatment storehouse 3 through described air-introduced machine 1, the output in pretreatment storehouse connects the input in denitration storehouse, the output in denitration storehouse connects the input in desulfurization storehouse, the output in the de-dirt of desulfurization storehouse connects the input of heavy metal filter, the output of heavy metal filter connects air-introduced machine, and air-introduced machine is discharged purified gas; On the de-dirt of described desulfurization storehouse, be connected with chemical reagent and supplement tank, the liquid outlet in the de-dirt of pretreatment storehouse, denitration storehouse and desulfurization storehouse is connected respectively acid purification treating apparatus, pretreatment storehouse is connected respectively chemical reagent with denitration storehouse by pipeline and supplements tank a, the de-dirt of pretreatment storehouse, denitration storehouse and desulfurization storehouse is connected chemical reagent by measuring pump and supplements tank b, and pretreatment is equipped with circulating pump on storehouse; Described acid purification treating apparatus is to consist of the feeder that has heating efficiency, distilling apparatus and nitric acid cooling bath, the output of feeder connects the input of distilling apparatus, the output of distilling apparatus connects the input of nitric acid cooling bath, the output of nitric acid cooling bath flows out the nitric acid after processing, and the output of feeder flows out the sulfuric acid after processing.

Pretreatment described above storehouse comprises pretreatment warehouse, pretreatment storehouse spray equipment, pretreatment storehouse air inlet, pretreatment storehouse suction pump, reservoir, pretreatment storehouse liquid outlet, pretreatment storehouse inlet and gas outlet, pretreatment storehouse, the bottom of described pretreatment warehouse is reservoir, pretreatment storehouse liquid outlet is arranged on reservoir place, described pretreatment storehouse air inlet, pretreatment storehouse inlet and gas outlet, pretreatment storehouse are arranged on the pretreatment warehouse of reservoir top, gas outlet, pretreatment storehouse is above the air inlet of pretreatment storehouse, described pretreatment storehouse spray equipment is arranged in pretreatment warehouse, described pretreatment storehouse suction pump connects the output of reservoir and the input of pretreatment storehouse spray equipment by pipeline, described pretreatment storehouse spray equipment is be arranged on the pressurization spray equipment of pretreatment warehouse inner top and be arranged on the atomizing spray equipment (seeing Fig. 2-1) on pretreatment warehouse inwall.

Denitration described above storehouse comprises denitration storehouse warehouse, gas outlet, denitration storehouse, denitration storehouse spray system, denitration storehouse air inlet, denitration storehouse inlet, gas-liquid mixed passage, denitration storehouse liquid outlet and denitration storehouse suction pump; Described denitration storehouse air inlet and gas outlet, denitration storehouse are arranged on the top of denitration storehouse warehouse; Described denitration storehouse inlet is arranged on the middle part of denitration storehouse warehouse; Described denitration storehouse liquid outlet is arranged on the bottom of denitration storehouse warehouse; Described gas-liquid mixed passage, denitration storehouse spray system are positioned at denitration storehouse warehouse; The input of gas-liquid mixed passage connects denitration storehouse air inlet, and output is placed in the liquid in the warehouse of denitration storehouse; Described denitration storehouse suction pump connects the output of warehouse bottom, denitration storehouse and the input of denitration storehouse spray system by pipeline.Described gas-liquid mixed passage comprises 3 medium-sized gas-liquid mixed passages and 3 small-sized gas-liquid mixed passages (seeing Fig. 3-1).

The de-dirt of desulfurization described above storehouse comprises luminous energy storehouse, described luminous energy storehouse comprises luminous energy warehouse, luminous energy storehouse air inlet, gas outlet, luminous energy storehouse, luminous energy storehouse inlet, gas-liquid mixed passage, luminous energy storehouse suction pump, luminous energy storehouse liquid outlet, luminous energy storehouse spray equipment and light irradiation apparatus, described luminous energy storehouse air inlet and gas outlet, luminous energy storehouse are arranged on the top of luminous energy warehouse, described luminous energy storehouse inlet is arranged on the middle part of luminous energy warehouse, described luminous energy storehouse liquid outlet is arranged on the bottom of luminous energy warehouse, described gas-liquid mixed passage, luminous energy storehouse spray equipment and light irradiation apparatus are positioned at luminous energy warehouse, the input of gas-liquid mixed passage connects luminous energy storehouse air inlet, the output of gas-liquid mixed passage is positioned at the position at the bottom of luminous energy warehouse bottom approaches storehouse, described luminous energy storehouse suction pump connects the output of luminous energy warehouse bottom and the input (seeing Fig. 4) of luminous energy storehouse spray equipment by pipeline.

Heavy metal filter described above comprises the fibrous matrix that is embedded with nano material.The described fibrous matrix that is embedded with nano material is attached on the flabellum of centrifugal fan, and the angle of inclination of described inclination flabellum is 30-45 degree.(seeing Fig. 6-1,6-2,6-3).

Embodiment 2: a kind of system of purifying contaminated air (seeing Fig. 1,2-2,3-2,5,6-4), is characterized in that it is to be supplemented tank c and formed by air-introduced machine a, circulating pump, pretreatment storehouse, denitration storehouse, the de-dirt of desulfurization storehouse, service cover, heavy metal filter, air-introduced machine b, the supplementary tank a of chemical reagent, acid purification treating apparatus, the supplementary tank b of chemical reagent, measuring pump, chemical reagent; Pollute source of the gas and enter pretreatment storehouse 3 through described air-introduced machine 1, the output in pretreatment storehouse connects the input in denitration storehouse, the output in denitration storehouse connects the input in desulfurization storehouse, the output in the de-dirt of desulfurization storehouse connects the input of heavy metal filter, the output of heavy metal filter connects air-introduced machine, and air-introduced machine is discharged purified gas; On the de-dirt of described desulfurization storehouse, be connected with chemical reagent and supplement tank, the liquid outlet in the de-dirt of pretreatment storehouse, denitration storehouse and desulfurization storehouse is connected respectively acid purification treating apparatus, pretreatment storehouse is connected respectively chemical reagent with denitration storehouse by pipeline and supplements tank a, the de-dirt of pretreatment storehouse, denitration storehouse and desulfurization storehouse is connected chemical reagent by measuring pump and supplements tank b, and pretreatment is equipped with circulating pump on storehouse; Described acid purification treating apparatus is to consist of the feeder that has heating efficiency, distilling apparatus and nitric acid cooling bath, the output of feeder connects the input of distilling apparatus, the output of distilling apparatus connects the input of nitric acid cooling bath, the output of nitric acid cooling bath flows out the nitric acid after processing, and the output of feeder flows out the sulfuric acid after processing.

Pretreatment described above storehouse comprises pretreatment warehouse, pretreatment storehouse spray equipment, pretreatment storehouse air inlet, pretreatment storehouse suction pump, reservoir, pretreatment storehouse liquid outlet, pretreatment storehouse inlet and gas outlet, pretreatment storehouse, the bottom of described pretreatment warehouse is reservoir, pretreatment storehouse liquid outlet is arranged on reservoir place, described pretreatment storehouse air inlet, pretreatment storehouse inlet and gas outlet, pretreatment storehouse are arranged on the pretreatment warehouse of reservoir top, gas outlet, pretreatment storehouse is above the air inlet of pretreatment storehouse, described pretreatment storehouse spray equipment is arranged in pretreatment warehouse, described pretreatment storehouse suction pump connects the output of reservoir and the input of pretreatment storehouse spray equipment by pipeline, described pretreatment storehouse spray equipment is the pressurization spray equipment (seeing Fig. 2-2) that is arranged on pretreatment warehouse inner top.

Denitration described above storehouse comprises denitration storehouse warehouse, gas outlet, denitration storehouse, denitration storehouse spray system, denitration storehouse air inlet, denitration storehouse inlet, gas-liquid mixed passage, denitration storehouse liquid outlet and denitration storehouse suction pump; Described denitration storehouse air inlet and gas outlet, denitration storehouse are arranged on the top of denitration storehouse warehouse; Described denitration storehouse inlet is arranged on the middle part of denitration storehouse warehouse; Described denitration storehouse liquid outlet is arranged on the bottom of denitration storehouse warehouse; Described gas-liquid mixed passage, denitration storehouse spray system are positioned at denitration storehouse warehouse; The input of gas-liquid mixed passage connects denitration storehouse air inlet, and output is placed in the liquid in the warehouse of denitration storehouse; Described denitration storehouse suction pump connects the output of warehouse bottom, denitration storehouse and the input of denitration storehouse spray system by pipeline.Described gas-liquid mixed passage comprises 5 large-scale hybrid channels (seeing 3-2).

Cleaning position described above comprises purification warehouse, purification plate, fluid flow control bolt and cleaning position liquid outlet, on described purification warehouse, place luminous energy warehouse, described luminous energy storehouse liquid outlet stretches into and purifies in warehouse, described fluid flow is controlled bolt and is arranged on the liquid outlet of luminous energy storehouse, described luminous energy storehouse liquid outlet is positioned at purification plate top, described purification plate is fixed on and purifies in warehouse, and described cleaning position liquid outlet is arranged on and purifies warehouse bottom.(seeing Fig. 5)

Heavy metal filter described above comprises the fibrous matrix that is embedded with nano material.The described fibrous matrix that is embedded with nano material is arranged between inclination flabellum, and the angle of inclination of described inclination flabellum is 30-45 degree.(seeing 6-4)

Claims

1. a system for purifying contaminated air, is characterized in that it is to be supplemented tank c and formed by air-introduced machine a, circulating pump, pretreatment storehouse, denitration storehouse, the de-dirt of desulfurization storehouse, service cover, heavy metal filter, air-introduced machine b, the supplementary tank a of chemical reagent, acid purification treating apparatus, the supplementary tank b of chemical reagent, measuring pump, chemical reagent; Pollute source of the gas and enter pretreatment storehouse 3 through described air-introduced machine 1, the output in pretreatment storehouse connects the input in denitration storehouse, the output in denitration storehouse connects the input in desulfurization storehouse, the output in the de-dirt of desulfurization storehouse connects the input of heavy metal filter, the output of heavy metal filter connects air-introduced machine, and air-introduced machine is discharged purified gas; On the de-dirt of described desulfurization storehouse, be connected with chemical reagent and supplement tank, the liquid outlet in the de-dirt of pretreatment storehouse, denitration storehouse and desulfurization storehouse is connected respectively acid purification treating apparatus, pretreatment storehouse is connected respectively chemical reagent with denitration storehouse by pipeline and supplements tank a, the de-dirt of pretreatment storehouse, denitration storehouse and desulfurization storehouse is connected chemical reagent by measuring pump and supplements tank b, and pretreatment is equipped with circulating pump on storehouse; Described acid purification treating apparatus is to consist of the feeder that has heating efficiency, distilling apparatus and nitric acid cooling bath, the output of feeder connects the input of distilling apparatus, the output of distilling apparatus connects the input of nitric acid cooling bath, the output of nitric acid cooling bath flows out the nitric acid after processing, and the output of feeder flows out the sulfuric acid after processing.

2. a kind of system of purifying contaminated air according to claim 1, it is characterized in that described pretreatment storehouse comprises pretreatment warehouse, pretreatment storehouse spray equipment, pretreatment storehouse air inlet, pretreatment storehouse suction pump, reservoir, pretreatment storehouse liquid outlet, pretreatment storehouse inlet and gas outlet, pretreatment storehouse, the bottom of described pretreatment warehouse is reservoir, pretreatment storehouse liquid outlet is arranged on reservoir place, described pretreatment storehouse air inlet, pretreatment storehouse inlet and gas outlet, pretreatment storehouse are arranged on the pretreatment warehouse of reservoir top, gas outlet, pretreatment storehouse is above the air inlet of pretreatment storehouse, described pretreatment storehouse spray equipment is arranged in pretreatment warehouse, described pretreatment storehouse suction pump connects the output of reservoir and the input of pretreatment storehouse spray equipment by pipeline.

3. a kind of system of purifying contaminated air according to claim 2, it is characterized in that described pretreatment storehouse spray equipment is the pressurization spray equipment that is arranged on pretreatment warehouse inner top, or for being arranged on the pressurization spray equipment of pretreatment warehouse inner top and being arranged on the atomizing spray equipment on pretreatment warehouse inwall.

4. a kind of system of purifying contaminated air according to claim 1, is characterized in that described denitration storehouse comprises denitration storehouse warehouse, gas outlet, denitration storehouse, denitration storehouse spray system, denitration storehouse air inlet, denitration storehouse inlet, gas-liquid mixed passage, denitration storehouse liquid outlet and denitration storehouse suction pump; Described denitration storehouse air inlet and gas outlet, denitration storehouse are arranged on the top of denitration storehouse warehouse; Described denitration storehouse inlet is arranged on the middle part of denitration storehouse warehouse; Described denitration storehouse liquid outlet is arranged on the bottom of denitration storehouse warehouse; Described gas-liquid mixed passage, denitration storehouse spray system are positioned at denitration storehouse warehouse; The input of gas-liquid mixed passage connects denitration storehouse air inlet, and output is placed in the liquid in the warehouse of denitration storehouse; Described denitration storehouse suction pump connects the output of warehouse bottom, denitration storehouse and the input of denitration storehouse spray system by pipeline.

5. a kind of system of purifying contaminated air according to claim 4, is characterized in that described gas-liquid mixed passage comprises 3 medium-sized gas-liquid mixed passages and 3 small-sized gas-liquid mixed passages, or comprises 5 large-scale hybrid channels.

6. a kind of system of purifying contaminated air according to claim 1, it is characterized in that the de-dirt of described desulfurization storehouse comprises luminous energy storehouse, described luminous energy storehouse comprises luminous energy warehouse, luminous energy storehouse air inlet, gas outlet, luminous energy storehouse, luminous energy storehouse inlet, gas-liquid mixed passage, luminous energy storehouse suction pump, luminous energy storehouse liquid outlet, luminous energy storehouse spray equipment and light irradiation apparatus, described luminous energy storehouse air inlet and gas outlet, luminous energy storehouse are arranged on the top of luminous energy warehouse, described luminous energy storehouse inlet is arranged on the middle part of luminous energy warehouse, described luminous energy storehouse liquid outlet is arranged on the bottom of luminous energy warehouse, described gas-liquid mixed passage, luminous energy storehouse spray equipment and light irradiation apparatus are positioned at luminous energy warehouse, the input of gas-liquid mixed passage connects luminous energy storehouse air inlet, the output of gas-liquid mixed passage is positioned at the position at the bottom of luminous energy warehouse bottom approaches storehouse, described luminous energy storehouse suction pump connects the output of luminous energy warehouse bottom and the input of luminous energy storehouse spray equipment by pipeline.

7. a kind of system of purifying contaminated air according to claim 6, it is characterized in that the de-dirt of described desulfurization storehouse also comprises cleaning position, described cleaning position comprises purification warehouse, purification plate, fluid flow control bolt and cleaning position liquid outlet, on described purification warehouse, place luminous energy warehouse, described luminous energy storehouse liquid outlet stretches into and purifies in warehouse, described fluid flow is controlled bolt and is arranged on the liquid outlet of luminous energy storehouse, described luminous energy storehouse liquid outlet is positioned at purification plate top, described purification plate is fixed on and purifies in warehouse, and described cleaning position liquid outlet is arranged on and purifies warehouse bottom.

8. a kind of system of purifying contaminated air according to claim 1, is characterized in that described heavy metal filter comprises the fibrous matrix that is embedded with nano material.

9. a kind of system of purifying contaminated air according to claim 8, the fibrous matrix that is embedded with nano material described in it is characterized in that is attached on the flabellum of centrifugal fan, or is arranged between inclination flabellum; The angle of inclination of described inclination flabellum is 30-45 degree.

10. a method of work for the system of purifying contaminated air described in claim 1, is characterized in that comprising the following steps: