CN104084015B

CN104084015B - A kind of system of purifying contaminated air and method of work thereof

Info

Publication number: CN104084015B
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: 2016-01-20
Anticipated expiration: 2034-04-23
Also published as: CN104084015A; WO2015161671A1

Abstract

The invention provides a kind of system and method for work thereof of purifying contaminated air, native system has an advanced filtration system to eliminate the toxic discharge in waste gas.Utilize new process technologies to catch the noxious material gone out from the smoke stack emission of pollution sources or coal-burning boiler, utilize pollutants all in nanometer technology and advanced chemical reaction scavenging, apply the interactional principle of interaction between gas and liquid and gas and solid, finally give off clean air, and reclaim the sulfuric acid and nitric acid that produce 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.

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 for coal, since Reformation and development, the demand incremental change of annual coal is greatly about 8 ~ 12%, and the maximum dirty disease produced with this is exactly serious air pollution.

The China of today is one of country that atmosphere pollution is the most serious in the world (being only second to India).The not long ago theme proposing ' eliminating the trouble of common people's cardiopulmonary ' special in the regular meeting of State Council of the People's Republic of China; Pollution administration is combined with people's state, the people's livelihood, makes a decision to forgo and pollute the cap of big country.It will be also environmentally that country, the people, offspring and even the world make positive contribution that Chinese Government determines not only will soar economically.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 Chinese main kinetic energy energy in long-time.Mean that atmosphere pollution will be more serious along with industrial requirement constantly increases exhibition, effectively alleviating with preventing and remedying pollution will be a heavy problem forever.

As everyone knows, serious atmosphere pollution can bring biologies all on the earth irreversible disaster, and the air polluted is mainly derived from the industrial fumes containing a large amount of poisonous and harmful substance.These noxious fume are the overwhelming majority produced by coal burning process.But, there is no absolute clean coal in the world, only have the coal resources that the levels of toxic substances proportion that produces because of the difference of geological conditions is different.For example, the coal that NORTH CHINA is produced is the low-sulfur coal of high-quality, and sulfur content only has 1% ~ 2%; And its sulfur content of coal that Yunnan, Guizhou and Inner Mongol are produced 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.Have 40 city SO2 emissions to exceed the secondary standard line of country's formulation, 39 cities even are inferior to national grade III Standard line in the city of 113 atmosphere pollution keypoint treatments! The Acid Rain Pollution caused by air pollution has wreaked havoc the territory of China 1/3rd.The faster pollution index of going together with it of industrial process speedup will be higher, and relevant department can be all the more difficult to the control of environment.

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

Except sulfur dioxide, PM2.5 has caused at present the impact of health and has paid close attention to widely.What is particle 2.5 (PM2.5)? they refer to the small pieces of solid or the liquid substance that are combined in diameter in earth atmosphere and are less than 2.5 microns.Particle composition can cause obvious visual effect, and as flue dust, it is made up 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 ₂sulfuric acid can be converted under high humility and low temperature.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 premature death.

Granular material dischargedly all be subject to strict supervision in most industry country.Due to environmental problem, most industries all needs the operation carrying out 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.But, cheap cleaner efficiency is very low, Tong Chang Da is less than 80%; Good equipment such as the right efficiency of electrostatic precipitation ， Although up to 99%, but can also have its fatal defects: (1) equipment is huge, and consumption steel is many, needs high-voltage transforming and rectifying installation, therefore invests high.(2) efficiency of dust collection is by the restriction of dust specific resistance, generally 104 ~ 105 ohm every centimeter or be greater than the dust of 1010 ~ 1011 ohm every centimeter is less than to ratio resistance, 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 run in spite of illness, or can only shutdown maintenance.Generally speaking, any efficient equipment except PM is built with maintenance cost is all very high.

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

	PM10	PM2.5
			Every year	70 micrograms/cubic meter	35 micrograms/cubic meter
Daily (24 hours)	150 micrograms/cubic meter	75 micrograms/cubic meter

Nitre (NOx) is the one 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 and form ozone in the sun.Children and the people working out of doors or move are easy to be subject to the harmful effect of ozone.Ozone causes asthma, destroys lung tissue and reduce PFT etc.Ozone can also be transferred by wind and air-flow, exceedes original nitrogen oxide from far away to the impact of health.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, mixes among the land rain in ground, mist, snow or microparticle.Acid rain damage car, building and cause the deterioration of historical place; Acid rain causes lake and streams to become acid, 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 cause 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, accelerates " eutrophication " of water quality, thus causes oxygen excessively to consume, thus decrease the quantity of fish and shellfish.

According to the report of China Power, 300,000 kilowatts of unit carry out the one-tenth of denitration reform strengthening should approximately at about 6,000 ten thousand yuan.Beijing Longdian Hongtai Environment Technology Co., Ltd. and the official signature of Shangqiu Yu Dong Power Generation Corporation Ltd. of Henan coalification group belonging in September, 2013 electric energy engineering company of China " 2x315MW (310,005 kilowatts) unit denitrating flue gas improvement project EPC general contract ", total Value of Contract 1.2 hundred million yuan.Also this general cost has been confirmed.Except manufacturing cost, the operating cost of denitration also unusual height.According to report: " 300,000 kilowatts of denitration reforming equipments will be implemented denitration electricity price and really want 1.2 points of/kilowatt of ability just to offset cost, and the unit that operating cost is the highest reaches 2.7 points/kilowatt ".In addition, the efficiency of current domestic denitration can only reach 40% ~ 70%.Zhejiang power plant engineer once represented on Zhuan Ye Baos Publications, domesticly at present select excellent fired power generating unit denitration facility to build up, go into operation few, the technology of flue gas monitoring and automatic control aspect is still not mature enough, and correlation technique is still in gropes with in sorption enhanced process.Existing SCR denitration technology, swashs the accuracy of the escaping of ammonia monitoring of penetrating, the problem such as control of ammonia spraying amount and efficiency all need to solve under underload.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.Supply falls short of demand on market at home for current catalyst, and what market was supplied is substantially all external product, and the research and apply of domestic catalyst just starts.So generally, SCR equipment domestic at present and material all must rely on external import, and this also virtually adds it and manufactures and operating cost.

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

Up to the present, only have one to have the method reducing mercury emissions ability and affirmed, that injects activated carbon (ACI) exactly.It is the technology reduced discharging as major control mercury that the research of current most green technology emphasizes that activated carbon injects (ACI).Activated carbon (one is most commonly used to the material removing pollutant in peculiar smell and potable water system) has been proved to be has a few minutes gratifying effect absorbing on the mercury in fire coal boiler fume.Mercury adheres to active carbon particle, and then by the particulate control device in downstream, such as electrostatic precipitator or bag hose remove.Activated carbon (further processing, the carbon containing a large amount of micropore) absorbs the mercury of gaseous form, and is converted into the particulate form that can be captured.But, report, in flue gas, the appearance of high-load sulphur significantly can damage the performance of activated carbon.In addition, because the mercury in flue gas than other harmful substance relative concentration very low, the very a large amount of activated carbon of therefore of short duration with ACI adsorbent time of contact (being less than 3 seconds) needs is to reach the effect of anticipation.In order to realize the high clearance (>91%) of mercury, carbon and mercury (C/Hg) ratio needed 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 operating whole ACI system is very expensive.In addition the mercury refuse, being not only removing sufficient amount needs the activated carbon of 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 containing the mercury being less than 260ppm in activated carbon, regulation allows its stabilized landfill (being such as enclosed in concrete).But, can be spilt eventually by the mercury buried for many years, and pollute our underground water.Be considered to belong to high mercury subclass containing the activated carbon being greater than 260ppm mercury, and be prohibited landfill.The ACI of high mercury content must be stored in the warehouse of remote districts forever.Dispose the problem of carrying mercury activated carbon and will become a global predicament.Similarly, the lead in how effectively removing smoke also is urgent problem.

After current cleaning equipment cost intensive, purification, refuse cannot recycling, easily causes 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 to eliminate the toxic discharge in waste gas.Utilize new process technologies to catch the noxious material gone out from the smoke stack emission of pollution sources or coal-burning boiler, utilize pollutants all in nanometer technology and advanced chemical reaction scavenging, apply the interactional principle of interaction between gas and liquid and gas and solid, finally give off clean air, and reclaim the sulfuric acid and nitric acid that produce 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, it is characterized in that it be take off dirt storehouse by air-introduced machine a, circulating pump, pretreatment storehouse, denitration storehouse, desulfurization, service cover, heavy metal filter, air-introduced machine b, chemical reagent supplement tank a, acid purification treating apparatus, chemical reagent supplement tank b, measuring pump, chemical reagent supplement tank c and formed; 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, desulfurization takes off the input of the output connection heavy metal filter in dirt storehouse, the output of heavy metal filter connects air-introduced machine, and purified gas discharged by air-introduced machine; Described desulfurization takes off and dirt storehouse is connected with chemical reagent supplements tank, the liquid outlet that pretreatment storehouse, denitration storehouse and desulfurization take off dirt storehouse is connected acid purification treating apparatus respectively, pretreatment storehouse is connected chemical reagent with denitration storehouse respectively by pipeline and supplements tank a, pretreatment storehouse, denitration storehouse and desulfurization take off dirt storehouse and are connected chemical reagent by measuring pump and supplement tank b, and storehouse is equipped with circulating pump in pretreatment; Described acid purification treating apparatus is made up of the feeder having 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 storehouse described above 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 above reservoir, 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 storehouse described above spray equipment is the pressurized spray device being arranged on pretreatment warehouse inner top, or is the pressurized spray device being arranged on pretreatment warehouse inner top and the atomizing spray equipment be arranged on pretreatment warehouse inwall.

Denitration storehouse described above 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 input of output bottom denitration storehouse warehouse and 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.

Desulfurization described above takes off dirt storehouse and 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 luminous energy warehouse bottom close to the position at the bottom of storehouse, described luminous energy storehouse suction pump connects the input of output bottom luminous energy warehouse and 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, described purification warehouse places luminous energy warehouse, described luminous energy storehouse liquid outlet stretches in purification warehouse, described fluid flow controls bolt and is arranged on the liquid outlet of luminous energy storehouse, described luminous energy storehouse liquid outlet is positioned at above purification plate, described purification plate is fixed in purification warehouse, and described cleaning position liquid outlet is arranged on bottom purification warehouse.

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

The fibrous matrix being 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 prepares before working well and starts each relevant device, comprising:

Add water in pretreatment storehouse and contain oxidant and use nitric acid adjust ph to the solution being less than or equal to 3;

Add in denitration storehouse containing oxidant and pH value be less than or equal to 3 solution;

Take off in desulfurization in the luminous energy storehouse in dirt storehouse and add containing Fenton reagent and use 'alpha '-hydroxy acids adjust ph to the solution being 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 luminous energy storehouse;

(2) work in pretreatment storehouse: contaminated air enters pretreatment storehouse by air-introduced machine, fully contacts with liquid in storehouse, the solid particle that the diameter in preprocessing process removing 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; Solution containing solid particle and nitric acid is flowed into acid purification treating apparatus by pretreating containers, and purified gas discharges 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 containing nitric acid flows into acid purification treating apparatus by denitration storehouse, and purified gas discharges denitration storehouse;

(4) desulfurization takes off the work in dirt storehouse: the gas that denitration storehouse is discharged enters desulfurization and takes off dirt storehouse, haptoreaction abundant with the Fenton reagent in storehouse, make the hydrocarbons decompose in gas be carbon dioxide and water, Oxidation of Carbon Monoxide is carbon dioxide, and sulfur trioxide is dissolved in solution and generates sulfuric acid; Solution containing sulfuric acid takes off dirt storehouse by desulfurization and flows into acid purification treating apparatus, and purified gas discharges desulfurization storehouse;

(5) work of heavy metal filter: nano material embeds on fibrous matrix by (5.1); (5.2) make the flue gas containing heavy metal by being embedded with the fibrous matrix of nano material; (5.3) heavy metal in nano material and flue gas reacts, and catches the heavy metal in flue gas;

(6) work of acid purification treating apparatus: from pretreatment storehouse, denitration storehouse, desulfurization take off the mixing material containing sulfuric acid and nitric acid flowed out in dirt storehouse and flow in the feeder acid purification treating apparatus, feeder with heating devices heat mixing material nitric acid is gasified, heating-up temperature is more than or equal to 122 DEG C, the method of then refining through distillation purifies, be collected in nitric acid cooling bath after nitric acid cooling after purification medium to be recycled, it is medium to be recycled that sulfuric acid will stay 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) sulfuric acid of being discharged by the system of purifying contaminated air and nitric acid is reclaimed;

(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 the problem of a consideration interface.Under these circumstances, because target substance needs to react through a gas-liquid interface, states of matter conversion ratio must be considered (see Fig. 8).In the invention of our such complication system similar, the Substance Transformation rate between two kinds of different states of matters is the major issue in design.

Having the thickness of an imaginary static state to be the film of δ between two adjacent states of matter interfaces, must there is molecule conduction by it in various material.Other parts in liquid, can be described as main body, are to keep stable, so the energy relevant to transmission is almost complete in film.If reactant diffusion principle also participates in the chemical reaction in liquid, then reaction can occur in the film, in main body or both all (see Fig. 8).The relation of molecular diffusion system and mass transfer coefficient is

k _L’＝D _A/δ

Here k _l' be mass transfer coefficient, D _abe the diffusion coefficient of reactant, δ is film thickness.Gas liquid reaction is classified by the ratio of reaction rate and material transfer rate:

1, reaction slowly 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

But because not every reaction is all occur in static system, above-mentioned boundary-layer theory, can not cover all gas liquid reactions.Such as, when gaseous molecular enters in the film of a flowing, be a kind of time-dependent behavion.When there being the film of flowing, penetration theory can be used to fill traditional boundary-layer theory, compensates with the vertical flow velocity of gas-liquid interface.When there being flowing film to participate in, main body concentration [A] is negligible:

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

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

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

2NO+O ₂→2NO ₂(1)

2NO ₂+H ₂O ₂→2HNO ₃(2)

3NO ₂+H ₂O→2HNO ₃+NO(3)

2NO+HNO ₃+H ₂O→3HNO ₂(4)

HNO ₂+H ₂O ₂→HNO ₃+H ₂O(5)

Formula 1 and 2 is optimal situations.To come up Talk, if NO molecules all in flue gas is converted into NO completely in pretreatment storehouse from theory ₂(formula 1), it should in denitration storehouse and H ₂o ₂react and produce HNO ₃(formula 2).But the reaction rate of formula one is very slow, the liquid of adding in pretreatment storehouse drops lower Come, makes whole gas liquid reaction system be in unstable state.Therefore, penetration theory (see Fig. 9) must be used when the kinetics calculating pretreatment storehouse.

Denitration storehouse is in a steady-state system, and wherein various variable is all stable, although there is continual process strength to attempt to change them.Because various variable is all stable, just must there is one through the flowing of the whole decorum, occur so equation 3 to 5 is most likely in denitration cabin.The NO that a part is converted in pretreatment storehouse ₂molecule may produce to react with water and form HNO ₃with NO (formula 3).In pretreatment storehouse not by the NO of peroxide oxidation add from formula 3 produce NO 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 ₂very important with water reaction in the film.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 ionized than the acid dissolve 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.Overall solution keeps PH≤3, and absorption process just can be accelerated.Meanwhile, due to low solubility and the conversion NO to NO of NO ₂then to HNO ₃the complexity of kinetics, the design in denitration storehouse is also to guarantee that the time of contact between flue gas and solution is extended down to the longest for the most main.

Fenton's reaction is helped about light:

Except gas-liquid is had a common boundary, we have also used light-assistance reaction to improve invention, and desulfurization employs wideband ultraviolet in storehouse.After adding iron and hydrogen peroxide again, hydroxyl radical free radical can produce, 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 ₂oxygen can be resolved into.Substantially, desirable pH value wants≤3.In order to control the temperature raised in pH value and reaction, be preferably carrying out step by step reaction controlling, 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 is a lot of dispute in theory, for many years, have much different mechanism to be published.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 delivered

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

Device:

As shown in Figure 10-1 ~ 10-4, one has four kinds of gas liquid reaction forms:

Typical reaction slowly and long response time are conversion of nitric oxide gas is nitric acid, and the speed difference of reaction rate and material diffusion is few.The reaction of typical mode 3 and mode 4 is Sulphur Dioxide is sulfuric acid, and kinetically reaction mainly occurs in interface film.When mode 3 or mode 4, reaction rate should be defined on interface.

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

The flow velocity of reactant

Mode of operation and corresponding rate equation

The gas-liquid mixed feature determined by reactor

Table 1 illustrates flow process and Substance Transformation feature in most of general gas-liquid reactor, by table 1, and depend on that reaction occurs in main body or in interfacial film, devise the system of a reaction vessel association and a kind of purifying contaminated air of the present invention thus.(table 1)

Table 1

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

Namely described pretreatment storehouse is mainly Glover tower, because typical waste gas flow velocity is more than 6m/s, and to mix feature be gas and liquid in the cabin in is all laminar flow.Design except oxynitrides of the present invention is between one between bubble column and batch process reactor, and the generation due to nitric acid is quite slow, so the turnover of liquid is not be in a stable state always.So denitration storehouse of the present invention is the combination (see Figure 11-1,11-2) based on laminar flow gas and mixed flow liquid.Desulfurization storehouse of the present invention make use of the efficient of Fenton's reaction, and the process rate producing sulfuric acid is as follows

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

The design in desulfurization storehouse of the present invention completes (see Figure 11-1) by the design of laminar flow gas.

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

Native system is a kind of automatically working system, the design object of this system be when sulfuric acid and nitric acid productive rate certain, by the volume minimization of reactor with to reduce energy resource consumption be main.The composition of reactant be room experiment and coal-burning boiler scene preliminary examination by experiment theory analysis basis on draw.For the 30 tons of coal coal-burning boilers that burn an every day, calculate 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

2c)3NO ₂+H ₂O→2HNO ₃+NO

2d)2NO+HNO ₃+H ₂O→3HNO ₂

2e)HNO ₂+H ₂O ₂→HNO ₃+H ₂O

Although step 1b and 2b is the step determining speed in whole process, hydrogen peroxide is main determinant.No matter nitrogen is converted into nitric acid by which step, and final step 1c and 2e does not have hydrogen peroxide not occur.We know that on sea level when 20 DEG C, under international standard atmosphere, the density of air is approximately 1.204kg/m containing nitrogen 78.09% (volume ratio) 75.47% (weight ratio) in other words in air ³.Namely the quality of every cubic metres of air is 1.204Kg, nitrogen wherein accounts for (1.204Kgx75.47%) 908.7g, in theory, 1 cubic metres of air enters boiler, wherein include the nitrogen of 908.7g ÷ 28g/mole=32.454mole, the NO of 973g can be produced, need the H of 1.1Kg ₂o ₂just can be translated into the nitric acid of 2.04Kg (32.454molex63g/mole).According to " Polluting discharge registration application manual " " the 21st chapter the 4th chapters and sections NO that State Environmental Protection Administration writes _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 (0.015X fires the NOX conversion ratio %+0.000938 of 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, the NOx of 7.6x30=228Kg can be produced, so need the H of [228/ (30x0.9) (46x0.1)] x34=242Kg ₂o ₂come is made into the nitric acid of 448Kg.As needed the consumption of 690Kg every day with the hydrogen peroxide ， The of 35% concentrations by weight.But by our Shi Inter experiment repeatedly, the water role that performer is important in the process producing nitric acid, refer in the equation 2c of this equation 6 at 2.1.1 joint and 2.2.2.1 joint.The diameter 3 meters (Fig. 3) in our denitration storehouse, fill the water (3.5 tons) of 0.5 meter high, the hydrogen peroxide being inputted 12Kg (35%) by measuring pump per hour, the consumption of one day 35% hydrogen peroxide is about 290 to 300Kg. every seven to eight days denitration storehouses need can produce the nitric acid of 5 ton of 68% concentration with the hydrogen peroxide of 2.8 ton 35%.According to the staple commodities list data display of business society, 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, so making denitration operating cost is basically negative.

The production of sulfuric acid:

According to " Polluting discharge registration application manual " coal-fired SO that State Environmental Protection Administration writes 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 %). with coal consumption 1 ton for benchmark, the sulfur-bearing in coal is divided into 1.5%, then 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%, then the SO of 1 ton of coal ₂generation=2X0.8X1X1%=0.016 ton=16Kg. is from SO ₂to H ₂sO ₄process as follows:

1.SO ₂+1/2O ₂→SO ₃

2.SO ₃+OH　→HSO ₃ ^-

3.HSO ₃ ^-+H ⁺→H ₂SO ₄

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

For the boiler of 30 tons of coals that burns an every day, the H of 24.5x30=735Kg can be produced every day ₂sO ₄, by Fenton's reaction, one mole of H ₂o ₂2 hydroxy free radicals can be produced, so every day needs the H of [(735/98) x34]/2=127Kg ₂o ₂(the H of 364kg35% concentration ₂o ₂).Water plays again important effect in the process of producing sulfuric acid.By our the repeatedly data that obtain of repeating test, the sulfuric acid produced and the hydrogen peroxide ratio of consumption are only 20:1 (mol ratio), this means at us except the sulfuric acid producing 735kg in sulfur dioxide device every day, only need every day and consume the hydrogen peroxide (35% concentration of hydrogen peroxide of 36Kg) of 12.7Kg.According to the display of business society staple commodities list data, in April, 2014 domestic sulfuric acid market glide be 364 yuan per ton.But only need use industry 35% hydrogen peroxide of 36Kg with the sulfuric acid manufacturing 735Kg, the operating cost of desulfurization, also as denitration cost, is negative.

The course of work about purification process and acid purification treating apparatus:

The nitric acid flowed out from denitration storehouse and desulfurization storehouse and sulfuric acid can directly enter acid purification treating apparatus.Purifier comprises the feeder (10a) that has heating efficiency, distilling apparatus, and nitric acid cooling bath (10b).The nitric acid of 68% has the density of 1.51293 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 relation that density ratio water is heavy, two kinds of acid all can divide and else sink to the bottom in denitration storehouse and desulfurization storehouse, are then introduced into via measuring pump the feeder (10a) that cleanization Installed puts.Purification feeder can be heated to 122 DEG C of clean nitric acid gasifications, is received in nitric acid cooling bath after cleaned nitric acid cools by the method for then refining through distillation.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 of process containing sulfur dioxide, comprises the following steps:

(1) in pretreating containers, water is added;

(2) add in reaction vessel containing Fenton reagent and use 'alpha '-hydroxy acids adjust ph to the solution being 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 making diameter be greater than 10 microns stays in a liquid;

(5) liquid of the solid particle being greater than 10 microns containing diameter is derived pretreating containers;

(6) flue gas after purification is discharged pretreating containers;

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

(8) after reacting, sulfur acid solution is derived, and periodic monitor derives the concentration of Fenton reagent in solution, according to the situation of monitoring, adds the new solution containing Fenton reagent and makes solution composition keep stable;

(9) purified gas is discharged reaction vessel.

Adding step (1 ') after step described above (1) for using below nitric acid adjusted to ph to 3, then adding oxidising agent, making 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 (1 ') described above needs periodic monitor and supplements oxidising agent as required 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, then the ultraviolet light of illumination to be wavelength be 200nm ~ 400nm; When metal system is Cu (I)/Cu (II) system, the visible ray of illumination to be wavelength be 600nm ~ 800nm.

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

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

In step described above (4) mode of fully contact be by liquid by spray equipment to gas shower, to increase area and the time of waste gas and liquid comes into contact.

Flue gas in step described above (4) enters from pretreating containers bottom, direction level be 40 ~ 50 degree of angles with chamber wall, to increase the time with liquid comes into contact.

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

Hydrogen peroxide described above is that diameter is less than after the peromag of 50 nanometers, sodium peroxide or calper calcium peroxide react in described solution and produces.

The consumption of hydrogen peroxide described above passes through periodic collection sample by close monitoring, and uses iodine/potassium permanganate (I/KMnO4) titration to observe the consumption rate of peroxide.

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

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

Step 8 is added after step described above (8) ' utilize the AmberliteIRC748 ion exchange resin coating adsorbs of commercially available DOWchemical company to reclaim described metal system material, by the solution purification containing 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 is arranged on the pretreatment warehouse 1-13 above reservoir 1-7, 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 is 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 is 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 luminous energy warehouse 2-11 bottom close to the position at the bottom of storehouse, described luminous energy storehouse suction pump 2-5 connects the input of output bottom luminous energy warehouse 2-11 and 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 top described above arranges pretreatment storehouse access cover 1-1, the sidewall of pretreatment warehouse 1-13 is arranged pretreatment storehouse access door 1-11, reservoir 1-7 top arranges infundibulate collecting board 1-3, the sidewall of reservoir 1-7 is arranged pretreatment storehouse liquid level meter 1-9 and thief hatch 1-5.

Pretreatment storehouse spray equipment 1-2 described above is the pressurized spray device being arranged on pretreatment warehouse 1-13 inner top, or is the pressurized spray device being arranged on pretreatment warehouse 1-13 inner top and the atomizing spray equipment be arranged on pretreatment warehouse 1-13 inwall.

The spray droplet of pressurized spray device described above is uniform line; The diameter that every dropping liquid drips is 2 ~ 3 millimeters, 6 ~ 10 millimeters, interval between often dripping.

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

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

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

The sidewall of luminous energy warehouse 2-11 described above arranges luminous energy storehouse liquid level meter 2-7, 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 AmberliteIRC748 ion exchange resin coating of commercially available DOWchemical company, reclaims described metal system material for adsorbing, and by the solution purification containing sulfuric acid.

2, about the course of work and the device of de-dirt:

A method for the flue gas of process containing dust, comprises the following steps:

(1) in pretreating containers, water is added;

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 purification is discharged pretreating containers;

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

(8) 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 containing Fenton reagent and makes solution composition keep stable;

(9) purified gas is discharged reaction vessel.

Step (1 ') is added for using below nitric acid adjusted to ph to 3 after step described above (1), then oxidising agent is added, carbon granule is made to 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 above reservoir, 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 luminous energy warehouse bottom close to the position at the bottom of storehouse, described luminous energy storehouse suction pump connects the input of output bottom luminous energy warehouse and luminous energy storehouse spray equipment by pipeline, gas outlet, described pretreatment storehouse connects luminous energy storehouse air inlet.

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

Pretreatment warehouse described above is made up of stainless steel metal plate.

Pretreatment storehouse described above suction pump is acidproof water pump.

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

The sidewall of luminous energy warehouse described above is arranged luminous energy storehouse liquid level meter, 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:

Remove smoke the method for middle nitrogen oxide, it is characterized in that it comprises the following steps:

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

Add in pretreating containers containing oxidant and pH value be less than or equal to 3 solution;

Passed into by flue gas in pretreating containers, fully contact with liquid, the solid particle making diameter be greater than 10 microns stays in the solution, and NO is oxidized to NO ₂;

Solution containing solid particle is derived pretreating containers;

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

Add in denitration container containing oxidant and pH value be less than or equal to 3 solution;

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

(3) purified gas discharges denitration container.

First use below nitric acid adjusted to ph to 3 in described pretreating containers and denitration container, 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 diameter is less than after the peromag of 50 nanometers, sodium peroxide or calper calcium peroxide react in water and produces.

In described pretreating containers, liquid sprays by spray equipment the area and the time that increase flue gas and liquid comes into contact.

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

In described step (1) when selecting hydrogen peroxide to be oxidant, then by the concentration of liquid outlet periodic monitor oxidant, and supplemental oxidant makes oxidant concentration in solution stablize as required; The consumption of described hydrogen peroxide passes through periodic collection sample by close monitoring, and uses iodine/potassium permanganate (I/KMnO4) titration to observe the consumption rate of hydrogen peroxide.

Enter from lower vessel portion when in described step (1), flue gas enters pretreating containers; Direction level be 40 ~ 50 degree of angles with chamber wall, makes flue gas produce helical effect when moving up, to increase the time with liquid comes into contact.

The liquid of pretreating containers is flowed out after removing is greater than 10 micron particles things, by water pump by the spray equipment of Cemented filling to pretreating containers in described step (1).

After reacting in described step (2), solution is derived, when being oxidant when selecting hydrogen peroxide, then periodic monitor derives the concentration of oxidant in solution, according to the situation of monitoring, adds the new solution containing oxidant and makes solution composition in container keep stable; The consumption of described hydrogen peroxide passes through periodic collection sample by close monitoring, and uses iodine/potassium permanganate (I/KMnO4) titration to observe the consumption rate of hydrogen peroxide.

Solution in described step (2) by water pump by the spray equipment of Cemented filling to denitration container.

A kind of nanometer flue gas denitrification system, is characterized in that it is made up 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 above reservoir, 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 input of output bottom denitration storehouse warehouse and denitration storehouse spray system by pipeline.

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

Described pretreatment storehouse spray system is the pressurized spray device being arranged on pretreatment storehouse warehouse inner top, or is the pressurized spray device being arranged on pretreatment storehouse warehouse inner top and the atomizing spray equipment be arranged on the warehouse inwall of pretreatment storehouse.

The spray droplet of described pressurized spray device is uniform line; The diameter that every dropping liquid drips is 2 ~ 3 millimeters, 6 ~ 10 millimeters, interval between often dripping.

Described pretreatment storehouse warehouse is made up of stainless steel metal plate.

Described pretreatment storehouse suction pump is acidproof water pump.

The sidewall of described denitration storehouse warehouse arranges denitration storehouse liquid level meter, and 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 up of 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 adjusted to ph to following, 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 five ten degree, makes flue gas produce helical effect when moving up;

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

(5) consumption of sample monitoring oxidant is regularly collected by thief hatch, according to the NO content in flue gas, 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 uses iodine/potassium permanganate (I/KMnO4) titration to observe the consumption rate of peroxide by sample collection hourly.

The method of denitration:

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

(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, supplemental oxidant in the warehouse of denitration storehouse.

Described a part of NO in pretreated flue gas ₂molecule can produce to react with water and generate HNO ₃and NO; In pretreatment storehouse, do not have oxidized NO to add NO ₂molecule can with water react 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 the course of work and the device that remove heavy metal:

Remove smoke the method for middle heavy metal, and it comprises the following steps:

(1) nano material is embedded on fibrous matrix;

(2) make the flue gas containing heavy metal by being embedded with the fibrous matrix of nano material;

(3) heavy metal in nano material and flue gas reacts, and catches the heavy metal in flue gas.

Described method nano material embedded on fibrous matrix is:

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

Described adhesive is selected to 80 ( ) organic siliconresin solution, epoxy resin or methyl epoxy. 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 not lose the temperature of to bear in adhering situation up to 650 degree, and provides good corrosion resistance; series becomes dry usually after 200 degree of bakings of a hour.

Described method nano material embedded on fibrous matrix is: directly load nano material on fibrous matrix: nano material be 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 being attached with nano material is carried out in the baking box of 500 degree the heating of 3 to 4 hours; After solution evaporation, nano wire and nano particle will with fleece weave in; After being cooled to 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 the golden nanometer particle be attached on nano-carrier particle, the WS be attached on nano-carrier particle ₂nano particle or CdS nano wire.

The synthetic method of the described golden nanometer particle be attached on nano-carrier particle is:

The HAuCl4 of 2 to 4M/L is dissolved in distilled water; With the TiO of 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 (a period of time that needs are stored, to obtain desired quality) 20 to 40 minutes; Be cooled to 40 degrees Celsius, add 30%NH3; Filter and wash with water, drying at least 12 hours in 100 degree of baking ovens; Then in atmosphere 350 DEG C calcining at least 4 hours; 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, load the technology of (DP) by deposition: prepare the chlorauric acid solution of 0.1 to 0.5M/L with distilled water; That is slowly also stirred with the speed of 10 ml/min by solution joins TiO ₂or r-Al ₂o ₃or SiO ₂in the suspension of nano-carrier; Heat to 65 DEG C and keep at least 1 hour, being then cooled to room temperature; Add the NH4OH of 1M/L, pH is adjusted to 7; Slow stirring at least 2 hours; Filter rear hot wash, in 80 DEG C of baking boxs, dry at least 12 hours; Then in atmosphere 180 DEG C calcining at least 4 hours, 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%.

When heavy with moistures time, Au-TiO ₂gold-titanium dioxide has and compares Au-SiO ₂gold-silica and Au-Al ₂o ₃better catalytic activity.

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

The described WS be 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 (NH4) of the Chelsea than 1:18 ~ 20 that rubs 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 least 0.5 hour is heated at 80 DEG C;

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

With higher than 20 kilo hertzs of (per second 20,000 time) ultrasonic process 10 minutes in ultrasonic generator;

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

Dry in atmosphere, obtain end product WS ₂powder, is WS ₂nano particle;

WS ₂in one the 400 DEG C horses being full of nitrogen not Shanghai, 2 hours functionalization are cured before nano particle uses;

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 more than 400 degree dryings 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:

Toluene is put into, distilled water in picoclave high pressure reactor (autoclave), and 1,12 alkanethiols, mix with volume ratio 20:2:1; Add caddy and the thiocarbamide acid of 1:1 mol ratio; Autoclave is remained on 180 degrees Celsius and carry out reaction 24 hours, then make it be cooled to room temperature; A kind of powder of yellow can precipitate, and washs to remove residual organic solvent after collecting precipitation powder thing with ethanol and distilled water; Final product, vacuum 70 DEG C of dryings at least 6 hours, obtains CdS nano wire; CdS nano wire must ultrasonic process in ethanol before using;

Or, first the cadmium sulfate of 0.16 ~ 0.20M is joined in the 7 ~ 8M/L ammonia spirit under constantly stirring; After this, under the stirring of brute force, add the thiocarbamide acid of 0.6 ~ 0.8M slowly; Solution is heated to 65 DEG C, and pH remains on 9-11, powerful stirring 50-70 minute; Then by the yellow solid collected after centrifugation of precipitation, and dry in an oven, and 65 DEG C keep at least 4 hours, obtain CdS nano wire; CdS nano wire must ultrasonic process in ethanol before using.

Described fibrous matrix is meta-aramid Meta-aramid, polytetrafluoroethylene PTFE, polyphenylene thioether PPS, polybenzimidazoles PBI, polyimides ployimide, RY805 fiber (GEEnergyBHAGroup) and PC102 fiber (GEEnergyBHAGroup), or non-woven fibre, described non-woven fibre is the synthetic fibers such as nylon66 fiber, polyester, polyurethane.These synthetic fibers all have the temperature range from 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; Some performances the most outstanding in these fibers are their tensile strength, operating temperature, limited oxygen index (LOI) and chemical resistance.LOI is the oxygen content supported in air needed for burning; The fiber that LOI is greater than 25 is so-called fire retardant, must have the oxygen of at least 25% that them just can be made to burn.

Described heavy metal is mercury or lead.

In described step (3), nano material is golden nanometer particle, gold (Au) element and heavy metal element mercury (Hg °) and (plumbous Pb °) have high-affinity, can chemical bond be formed, thus heavy metal element is caught; Nano material is WS ₂nano particle or CdS nano wire, catch heavy metal element: WS by MLCT (metal ligand charge transfer) principle ₂with 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, and the performance of the characteristic of nonmetallic inorganic part (S) is just as lewis base; Electronics concentrates on mineral ligand, makes the mineral ligand of part become negative electrical charge; Inorganic coordination knows from experience attraction heavy metal element, WS ₂, CdS can attract in flue gas lead ion, Element Lead and element mercury.

Mercury in the heavy metal that the fibrous matrix being embedded with nano material in described step (3) is caught passes through by mercaptopropionic acid and 2, and the liquid of dipicolimic acid 2 synthesis soaks filter by heavy metal wash-out out; Metallic lead (Pb °) in the heavy metal caught can be converted into lead hydroxide Pb (OH) ₂; Lead hydroxide can wash out easily with spirit of vinegar or dust technology.

Described mercaptopropionic acid and 2, the cheland of dipicolimic acid 2 and mercury have the associativity of quite height, and binding constant is respectively logK10.1 and 20.2; So we can clean this non-woven fibrous filter device and reclaim use; The mercury cleared out can extract and then carry out appropriate disposal from cleaning fluid.

The described flue gas containing heavy metal carries out pretreatment by passing in reaction vessel before the fibrous matrix that is embedded with nano material; Add in described reaction vessel containing Fenton reagent and use 'alpha '-hydroxy acids adjust ph to the solution being 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, and haptoreaction abundant with 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 containing Fenton reagent and makes solution composition keep stable; Purified gas is discharged 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, then the ultraviolet light of illumination to be wavelength be 200nm ~ 400nm; When metal system is Cu (I)/Cu (II) system, the visible ray of illumination to be wavelength be 600nm ~ 800nm.

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

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

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

The consumption of described hydrogen peroxide passes through periodic collection sample by close monitoring, and uses iodine/potassium permanganate (I/KMnO4) titration to observe the consumption rate of peroxide.

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

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

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

The described fibrous matrix being 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 (GEEnergyBHAGroup) and PC102 fiber (GEEnergyBHAGroup), or non-woven fibre, described non-woven fibre is the synthetic fibers such as nylon66 fiber, polyester, polyurethane.

Described centrifugal fan is made up of framework and flabellum, and flabellum passes through, and flabellum to be connected with framework by central shaft and axle sleeve and to be connected with framework; Described framework and flabellum are made up of nickel-molybdenum alloy (aluminium alloy, stainless steel), because of its acid resistance at any temperature, such as 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, the replaceable and callable fibrous matrix being embedded with nano material will be installed on the flabellum of fan.This nano material being embedded with the fibrous matrix of nano material is through special design and comes to produce with the heavy metal in flue gas to react, especially mercury.According to different service conditions, if the typical 300,000 more secondary coals of megawatt power plant, approximately also only non-woven fibre need be changed 2 ~ 3 times every year.

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 luminous energy warehouse bottom close to the position at the bottom of storehouse, described luminous energy storehouse suction pump connects the input of output bottom luminous energy warehouse and luminous energy storehouse spray equipment by pipeline, gas outlet, described pretreatment storehouse connects luminous energy storehouse air inlet.

Described luminous energy warehouse is made up of stainless steel metal plate, and luminous energy warehouse inwall scribbles corrosion-inhibiting coating.

The sidewall of described luminous energy warehouse is arranged luminous energy storehouse liquid level meter, 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 present invention can effective purifying exhaust air, and nitrogen oxide is become nitric acid, sulfur dioxide is become sulfuric acid, and reclaimed, therefore, the interests that the present invention reclaims far exceed 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 is 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 easy, and manufacture and operating cost be all less than about 50% of current RSC denitration technology.Under the prerequisite strictly following operational procedure, the present invention can protect continuity, and to use 15 ~ 20 years engineered without the need to carrying out, and synchronously can carry out maintaining with the coal-burning boiler run.

5, the advantage of nano material is that its surface area is large, and between molecule, the mutual transmission of electronic shell is 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 the so fast flue gas of flow velocity 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 the need to often attaching, consumption is few, and economy very.

6, this invention desulfurization benefit can reach 99.99%, and manufactures and run all at about 50% of current desulfur technology, and when without any the removal problem solving PM2.5 when extra charge.Equipment take up an area little, transform simple and easy.The present invention is based upon light and helps in the principle of Fenton's reaction, and at elimination SO ₂immense success is achieved with on flue dust.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 the need to any extra manufacture and operating cost.

Native system clean-up effect detection experiment is reported as follows:

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

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

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

3, the present invention is used for the test report (test site is certain power plant and certain steel mill) of purifying industrial waste gases

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 illustrates:

The overall structure schematic diagram of Fig. 1 a kind of system of purifying contaminated air involved by the present invention.

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

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

In the system of Fig. 4 a kind of purifying contaminated air involved by the present invention, desulfurization takes off the luminous energy chamber structure schematic diagram in dirt storehouse.

In the system of Fig. 5 a kind of purifying contaminated air involved by the present invention, desulfurization takes off luminous energy storehouse in dirt storehouse and cleaning position structural representation.

In the system of Fig. 6 a kind of purifying contaminated air involved by the present invention, desulfurization takes off the huge sum of money filter apparatus configuration schematic diagram in dirt storehouse, 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.

The method of work flow chart of Fig. 7 a kind of system of purifying contaminated air involved by the present invention.

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

Fig. 9 is the Reaction-diffusion terms plane geometry schematic diagram of penetration theory.

Figure 10-1 ~ Figure 10-4 is liquid gas median surface course of reaction figure.(Figure 10-1 shows do not have obstacle between gas and liquid transition, and gas directly transmits and is diffused into liquid, and this reaction is for reflect instantaneously.Figure 10-2 shows once pass the median surface of gas and liquid, and 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 shows that gas molecule cannot 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 shows gas and liquid the most effective interactional mode, and the concentration of gas molecule reduces in median surface, and concentration increases in a liquid.)

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

Figure 11-2 is 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 purification warehouse, 3-2 is purification plate, 3-3 is that fluid flow controls 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 being embedded with nano material, and 1-6 is folder.

In Fig. 8, the mole coefficient of PA=reactant A, [A] int=reacts A initial concentration, and [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, the concentration of [A] *=reactant A in median surface, [A] _b=reactant A in the main body concentration of liquid, the distance that x=reactant A spreads in the film.

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

In Figure 11-1, Gasin is gas feed, and Gasout is gas vent, and Liquidin is liquid-inlet, and Liquidout is liquid outlet, F _lfor the direction of liquid flow, F _gfor the direction of gas flowing, P _a0for the initial concentration of reactant, P _affor reactant final concentration, [B] _b0for the initial concentration of main body of liquid, [B] _bffor the final concentration of main body of liquid.

In Figure 11-2, Gasin is gas feed, and Gasout is gas vent, F _gfor the direction of gas flowing, P _a0for the initial concentration of reactant, P _affor reactant final concentration.

(5) detailed description of the invention:

Embodiment 1: a kind of system of purifying contaminated air (see Fig. 1,2-1,3-1,4,6-1,6-2,6-3), it is characterized in that it be take off dirt storehouse by air-introduced machine a, circulating pump, pretreatment storehouse, denitration storehouse, desulfurization, service cover, heavy metal filter, air-introduced machine b, chemical reagent supplement tank a, acid purification treating apparatus, chemical reagent supplement tank b, measuring pump, chemical reagent supplement tank c and formed; 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, desulfurization takes off the input of the output connection heavy metal filter in dirt storehouse, the output of heavy metal filter connects air-introduced machine, and purified gas discharged by air-introduced machine; Described desulfurization takes off and dirt storehouse is connected with chemical reagent supplements tank, the liquid outlet that pretreatment storehouse, denitration storehouse and desulfurization take off dirt storehouse is connected acid purification treating apparatus respectively, pretreatment storehouse is connected chemical reagent with denitration storehouse respectively by pipeline and supplements tank a, pretreatment storehouse, denitration storehouse and desulfurization take off dirt storehouse and are connected chemical reagent by measuring pump and supplement tank b, and storehouse is equipped with circulating pump in pretreatment; Described acid purification treating apparatus is made up of the feeder having 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 storehouse described above 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 above reservoir, 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 pressurized spray device being arranged on pretreatment warehouse inner top and the atomizing spray equipment (see Fig. 2-1) be arranged on pretreatment warehouse inwall.

Denitration storehouse described above 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 input of output bottom denitration storehouse warehouse and 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 (see Fig. 3-1).

Desulfurization described above takes off dirt storehouse and 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 luminous energy warehouse bottom close to the position at the bottom of storehouse, described luminous energy storehouse suction pump connects the input (see Fig. 4) of output bottom luminous energy warehouse and luminous energy storehouse spray equipment by pipeline.

Heavy metal filter described above comprises the fibrous matrix being embedded with nano material.The described fibrous matrix being 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.(see Fig. 6-1,6-2,6-3).

Embodiment 2: a kind of system of purifying contaminated air (see Fig. 1,2-2,3-2,5,6-4), it is characterized in that it be take off dirt storehouse by air-introduced machine a, circulating pump, pretreatment storehouse, denitration storehouse, desulfurization, service cover, heavy metal filter, air-introduced machine b, chemical reagent supplement tank a, acid purification treating apparatus, chemical reagent supplement tank b, measuring pump, chemical reagent supplement tank c and formed; 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, desulfurization takes off the input of the output connection heavy metal filter in dirt storehouse, the output of heavy metal filter connects air-introduced machine, and purified gas discharged by air-introduced machine; Described desulfurization takes off and dirt storehouse is connected with chemical reagent supplements tank, the liquid outlet that pretreatment storehouse, denitration storehouse and desulfurization take off dirt storehouse is connected acid purification treating apparatus respectively, pretreatment storehouse is connected chemical reagent with denitration storehouse respectively by pipeline and supplements tank a, pretreatment storehouse, denitration storehouse and desulfurization take off dirt storehouse and are connected chemical reagent by measuring pump and supplement tank b, and storehouse is equipped with circulating pump in pretreatment; Described acid purification treating apparatus is made up of the feeder having 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 storehouse described above 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 above reservoir, 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 pressurized spray device (see Fig. 2-2) being arranged on pretreatment warehouse inner top.

Denitration storehouse described above 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 input of output bottom denitration storehouse warehouse and denitration storehouse spray system by pipeline.Described gas-liquid mixed passage comprises 5 large-scale hybrid channels (see 3-2).

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

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

Claims

1. a system for purifying contaminated air, it is characterized in that it be take off dirt storehouse by air-introduced machine a, circulating pump, pretreatment storehouse, denitration storehouse, desulfurization, service cover, heavy metal filter, air-introduced machine b, chemical reagent supplement tank a, acid purification treating apparatus, chemical reagent supplement tank b, measuring pump, chemical reagent supplement tank c and formed; Pollute source of the gas and enter pretreatment storehouse through described air-introduced machine a, the output in pretreatment storehouse connects the input in denitration storehouse, the output in denitration storehouse connects the input in desulfurization storehouse, desulfurization takes off the input of the output connection heavy metal filter in dirt storehouse, the output of heavy metal filter connects air-introduced machine b, and air-introduced machine b discharges purified gas; Described desulfurization takes off and dirt storehouse is connected with chemical reagent supplements tank, the liquid outlet that pretreatment storehouse, denitration storehouse and desulfurization take off dirt storehouse is connected acid purification treating apparatus respectively, pretreatment storehouse is connected chemical reagent with denitration storehouse respectively by pipeline and supplements tank a, pretreatment storehouse, denitration storehouse and desulfurization take off dirt storehouse and are connected chemical reagent by measuring pump and supplement tank b, and storehouse is equipped with circulating pump in pretreatment; Described acid purification treating apparatus is made up of the feeder having 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. the system of a kind 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 above reservoir, 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. the system of a kind of purifying contaminated air according to claim 2, it is characterized in that described pretreatment storehouse spray equipment is the pressurized spray device being arranged on pretreatment warehouse inner top, or be the pressurized spray device being arranged on pretreatment warehouse inner top and the atomizing spray equipment be arranged on pretreatment warehouse inwall.

4. the system of a kind 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 input of output bottom denitration storehouse warehouse and denitration storehouse spray system by pipeline.

5. the system of a kind 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. the system of a kind of purifying contaminated air according to claim 1, it is characterized in that described desulfurization takes off dirt storehouse and 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 luminous energy warehouse bottom close to the position at the bottom of storehouse, described luminous energy storehouse suction pump connects the input of output bottom luminous energy warehouse and luminous energy storehouse spray equipment by pipeline.

7. the system of a kind of purifying contaminated air according to claim 6, it is characterized in that described desulfurization takes off dirt storehouse and also comprises cleaning position, described cleaning position comprises purification warehouse, purification plate, fluid flow control bolt and cleaning position liquid outlet, described purification warehouse places luminous energy warehouse, described luminous energy storehouse liquid outlet stretches in purification warehouse, described fluid flow controls bolt and is arranged on the liquid outlet of luminous energy storehouse, described luminous energy storehouse liquid outlet is positioned at above purification plate, described purification plate is fixed in purification warehouse, and described cleaning position liquid outlet is arranged on bottom purification warehouse.

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

9. the system of a kind of purifying contaminated air according to claim 8, the fibrous matrix being 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:

(2) work in pretreatment storehouse: contaminated air enters pretreatment storehouse by air-introduced machine a, fully contacts with liquid in storehouse, the solid particle that the diameter in preprocessing process removing 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; Solution containing solid particle and nitric acid is flowed into acid purification treating apparatus by pretreating containers, and purified gas discharges pretreatment storehouse;

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