CN101108300B - Ozone production processes and its use in industrial processes - Google Patents
Ozone production processes and its use in industrial processes Download PDFInfo
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- CN101108300B CN101108300B CN2007101026992A CN200710102699A CN101108300B CN 101108300 B CN101108300 B CN 101108300B CN 2007101026992 A CN2007101026992 A CN 2007101026992A CN 200710102699 A CN200710102699 A CN 200710102699A CN 101108300 B CN101108300 B CN 101108300B
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Abstract
Contaminants, particularly NO x , are removed from a flue gas stream by reaction with ozone in a suitable reactor. The NO x is converted to N 2 O 5 which can be readily absorbed in an aqueous scrubbing liquid. The ozone is provided in an ozone-containing gas stream which is generated from an oxygen-containing gas stream and subjected to separation to remove oxygen. The so separated oxygen is used to generate further ozone. The concentration of ozone in the ozone-containing gas stream is preferably 6% by weight or less.
Description
Background technology
In recent years, federal with local environmental legislation requires significantly to reduce the discharging of pernicious gas material to atmosphere.That this type of pernicious gas pollutant is main is nitrogen oxide (NO
X).Carry out in strictness under the pressure of these rules, industrial gasses pollutant emission enterprise made a large amount of effort reduce these harmful substances from industry or public utilities pollution sources with the form of gaseous waste to airborne discharge capacity.Effectively reduce NO in the gaseous waste
XThe method of concentration be usually directed to use based on the reducing agent of nitrogen and the NO in the waste gas
XReaction.
The another kind of known NO that from gas flow, removes
XMethod comprise with ozone and NO
XThe contact and they are oxidized to for example N
2O
5Deng nitrogen oxide more at high price, through the water scrubber high oxide is removed from gas flow again.
NO based on ozone
XThe detail of oxidation technology is disclosed in No. 5206002,5316737,5985223 and 6197268, the United States Patent (USP), and they are incorporated into this by reference.
In addition, information that Bureau for Environmental Protection announced shows, the mercury level in the environment has reached the level that possibly have a negative impact to health.Coal-fired power station boiler is one of the largest source of the artificial mercury emissions that is harmful to, but also is NO
XAnd SO
XThe source of discharging.
Because strict air pollution control rules, it is more and more important to eliminate oxidisability air-polluting technology.
Compare with the technology that is adopted in many industrial quarters, because its simplification and the convenience integrated with existing air pollution equipment have a great attraction in industry based on the technology that in flue gas, adds ozone.Adopting the prior art of commercially available ozone generator can only be ozone with 10～12% oxygen conversion, therefore requires 8～10 times oxygen of ozone demand to supply with.When the higher conversion ratio of needs, power consumption and capital cost that generator and water cooling equipment are required improve rapidly.Therefore, when applying as the pollution inorganic agent, the cost of ozone makes us hanging back.
Summary of the invention
The present invention is a kind of through improved oxidation technology, and oxygen source is integrated on its advantage ground, ozone takes place and utilization, and significantly reduces from industrial gasses stream and remove NO
X, Hg, SO
X, all contaminations such as Cl/HCl whole cost.Should can also remove based on the oxidation technology of ozone and be present in the evil of two in flue gas stream compounds, furfuran compound, PCB, VOC and odorant.
This technology comprises with oxygen and generates ozone with low concentration from commercially available ozone generator, but adopts obviously higher flow velocity.Generate the employed power of ozone of aequum required power low 40～60% can be than 10wt% the time with lower concentration (6wt% below).In addition, under lower concentration, the productivity ratio designed capacity of ozone generator exceeds 60～70%.Yet, generate the required oxygen of ozone and also therefore have more many.
The present invention utilizes oxygen recirculation, generates more a large amount of ozone with close or lower concentration from commercially available ozone generating apparatus.One separative element separates ozone from oxygen, and makes oxygen be circulated back to generator.This separation bed can be based on adsorbent, also can be O
3Compare O
2Film that more preferably sees through or opposite film.Under the situation of using adsorbent bed, the ozone quilt is with higher pressure preferential adsorption, and ozone is fully removed from the gas flow that flows out this and can not recycled back generator with the oxygen supply.
Used adsorbent comprises silica gel, high silicon mordenite and sealumination modified Y zeolite.These adsorbents can not destroy ozone in absorption.After the ozone in this is saturated, with like dry air carrier gas such as (CDA) with lower pressure with its desorb.Gas flow ozoniferous under such low concentration and pressure is more stable in essence, and can more effectively be scattered in the process gas air-flow.At this moment be diluted in ozone and the pollutant reaction in the process gas air-flow and they are converted into the optimum compound that can in dry method, semidry method or wet method scrubber, easily be removed or their oxidised form.This reaction and scrubbing preferably carry out in same container.
With as for good effect other application of the ozone such as the drinking water that contains streams of ozone or wastewater disinfection of preferred higher concentration different, in off-gas oxidizing technology, ozone is first diluted, again with pollutant reaction.In fact, adopt as carrier gas such as CDA with the ozone of the same amount of low concentration generation at NO
XRemoval in demonstrate better efficient.
Disclosed a kind of technology that generates ozone in the another embodiment of the invention, it comprises through oxygen is recycled to the containing the oxygen supply gas of ozone generating-device from piece-rate system, thereby increases flowing to the oxygen-containing gas of said ozone generating-device.
The concentration of ozone reaches 6 weight % or following.
Said oxygen-containing gas is supplied with air-flow and is selected from oxygen, dry air and air.Said piece-rate system is separated the mixture of ozone and oxygen-containing gas through film separation system or adsorbent piece-rate system.
Said adsorbent piece-rate system comprises a kind of adsorbent that is selected from silica gel, dealuminium Y type beta stone and high silicon mordenite.
In a kind of preferred implementation of the present invention, disclosed a kind of technology that generates ozone, wherein ozone is used to contain in the gas stream of pollutant, and this technology comprises: in ozone generator, supply with the step that contains oxygen supply gas stream; In piece-rate system with oxygen separation steps from gas ozoniferous stream; To lead the step of the said supply gas stream of getting back to said ozone generator from the said oxygen of said piece-rate system; And said ozone imported said flue gas stream, process gas stream or other contains the air-flow of pollutant.
The said gas stream that contains pollutant comes from the process gas of chemical industry, oil and petrochemical industry, metal, semiconductor and glass operation for coming from the flue gas stream in combustion of fossil fuel source, and tail gas stream.
Said oxygen-containing gas is supplied with air-flow and is selected from oxygen, dry air and air.Said pollutant is selected from nitrogen oxide, oxysulfide, mercury, chlorine and hydrochloric acid.
Said piece-rate system is selected from film separation system and adsorbent piece-rate system, and said adsorbent is selected from silica gel, dealuminium Y type beta stone and high silicon mordenite.
Get into the temperature of the ozone of the said gas stream that contains pollutant at about 40 ℉～about 350 ℉.The concentration of ozone is at about 6 weight % or following.
Disclosed a kind of technology of from industrial flue gas stream, removing pollutant in a kind of preferred implementation of the present invention, it may further comprise the steps:
A) in ozone generator, supply with oxygen-containing gas stream, generation contains ozone gas stream thus;
B) the said ozone gas conductance that contains is gone in the gas separation unit, oxygen is separated from contain ozone gas stream;
C) oxygen that said separation is obtained imports the said oxygen-containing gas stream of step a);
D) will come from industrial flue gas stream supplies in the flue gas carrier pipe; And
E) the said ozone gas stream of containing is supplied to the flue gas carrier pipe, said ozone therein with flue gas stream in pollutant reaction.
Perhaps, disclosed a kind of technology of from industrial flue gas stream, removing pollutant, it may further comprise the steps:
A) in ozone generator, supply with oxygen-containing gas stream, generation contains ozone gas stream thus;
B) the said ozone gas conductance that contains is gone in the gas separation unit, oxygen is separated from contain ozone gas stream;
C) oxygen that said separation is obtained imports the said oxygen-containing gas stream of step a);
D) will come from industrial flue gas stream and supply to the flue gas carrier pipe;
E) the said ozone gas stream of containing is supplied to the stack gases carrier pipe, said ozone therein with flue gas stream in pollutant reaction;
F) will be incorporated in the flue gas carrier pipe like reagent liquid such as caustic soda, the reaction product of ozone and pollutant will be converted into HNO
3, H
2SO
3And H
2SO
4Deng diluted acid;
G) diluted acid is absorbed in the liquid water, thus diluted acid is converted into the salt that comprises nitrate, sulphite and sulfate; And
H) from the flue gas carrier pipe, discharge the flue gas stream that has been substantially devoid of pollutant.
Said pollutant is selected from nitrogen oxide, oxysulfide, acid gas and heavy metal, and nitrogen oxide is selected from nitric oxide and nitrogen dioxide.
Description of drawings
Fig. 1 is the block diagram that generates ozone and the application technology of removing pollutant in commercial production thereof.
Fig. 2 is the graph of a relation of power consumption to the ozone amount of ozone generating apparatus generation.
Fig. 3 is the figure of ratio of the relative ozone of the rate of removing and nitrogen oxide of the nitrogen oxide of technology of the present invention and two kinds of already known processes.
Fig. 4 is that the rate of removing of nitrogen oxide of technology of the present invention and already known processes is to the graph of a relation of every pound of power that nitrogen oxide consumed that is removed.
The specific embodiment
Fig. 1 describes a kind of preferred implementation of said improved process.Said improved process can be handled the flue gas stream that comes from the combustion of fossil fuel source; The process gas that comprises bad pollutant that comes from chemical industry, oil and petrochemical industry, metal, semiconductor, glass or any manufacturing process is perhaps from the various tail gas stream that comprise the source of bad pollutant.
Oxygen is supplied to ozone generating-device A through pipeline 1.The equipment that ozone generator normally can be buied on market, these ozone generators may be used to technology of the present invention.The gas flow that contains ozone, oxygen and other trace gas gets into ozone piece-rate system B through pipeline 2 from ozone generating-device A.The system of this ozone piece-rate system for oxygen is separated from ozone or ozone is separated from oxygen, thus oxygen can be recycled back oxygen service 1 through pipeline 12.
This piece-rate system is typically film system or adsorbent bed system.Said film system is a kind of system that optionally allows oxygen through film.The typical film system that can use in the method for the invention comprises the conventional gas diffusion barrier of processing by like polysulfones, Merlon, polyimides, cellulose acetate and their polymer such as modified form.
Said adsorbent bed system uses the bed that contains the adsorbent that is selected from silica gel, high silicon mordenite and dealuminium Y type beta stone.When this adsorbent bed is saturated by ozone, carry out desorb through under low pressure introducing flowing of piece-rate system B like compression drying gas gases such as (CDA) through pipeline 4.
Mixture by ozone generator A generation and the ozone of ozone conduct in desorption gas that from oxygen, separates leaves ozone piece-rate system B through pipeline 3.This gas flows into the pipeline 5 that leads to scrubber device E.
Coal or other fossil fuel get into boiler C through pipeline 13 with the air from pipeline 14.Boiler C is used to produce power, and combustion of fossil fuels and generate flue gas, and flue gas must be removed from boiler.Flue gas gets into the selective absorbent cells D through pipeline 15 from boiler C.This selective absorbent cells D provides regulating step to flue gas, and can be selected from electrostatic precipitator or the bag room that is used for dust, particulate or adsorbent.This selective absorbent cells D also can provide to be preferably in remove before the off-gas flows catalytic oxidation reagent ozone like SO
2Selectivity scrubbing Deng oxysulfide or hydrochloric acid.Water gets into this selective absorbent cells D through pipeline 10.This regulating step also can be used to through using indirect heat exchanger, direct chilling or evaporative cooling the temperature of flue gas stream to be brought down below the temperature of 325 ℉.
Therefore, this selective absorbent cells D can be by the constituting of two or more separate units, thereby adjusted before waste gas contact ozone.Flue gas stream through regulating leaves the selective absorbent cells D through pipeline 5, contact with ozone from pipeline 3, and generation still residues in pollutant and the reaction of ozone in the flue gas stream herein.This reaction also can continue to scrubber unit E as required.
Comprise in the selective absorbent cells D under the situation of quench step, the water that comes from quencher flows out to the storage facility F of storage of water through pipeline 6, and storage facility F also possesses like devices such as pumping installations other position in water distribution to the technology.
Get into scrubber unit E with the flue gas stream behind the ozone reaction through pipeline 5.Scrubber unit in this technology is wet method scrubber unit, and it can be packed column, spray column, sieve-plate tower or bubble tower dish-type scrubber.In other method of the present invention, the scrubber unit can be dry method or semidry method type scrubber.
Water is pumped through pipeline 8 from storage unit F, gets into scrubber unit E through pipeline 8A, 8B and 8C.These pipelines connect can provide various spray patterns to contact the nozzle of the gas flow that gets into the scrubber unit.This scrubbing is removed like pollutant and oxidized pollutants such as particles, and treated flue gas stream leaves scrubber unit E through pipeline 7, gets back to storage facility F.Clean flue gas stream through scrubbing flows out from scrubber E through pipeline 9.
The first step of this improved process is an adjustments of gas stream.This regulating step can comprise electrostatic precipitator (ESP) or the bag room that uses to dust, particulate or adsorbent.This regulating step can use and be used to remove SO
2Or the selectivity scrubbing of HCl, perhaps being used to remove can't be oxidized or be most the pollutant that is removed before the oxidising agent being exposed to.This regulating step also can be used to through use indirect heat exchanger, directly chilling or evaporative cooling reduce the temperature of flue gas stream, because be the temperature that is lower than 325 ℉ based on the preferable range of the oxidation reaction of ozone.This regulating step can use one or more unit operations to realize one or more purposes.After this gas was by preconditioning, carrier gas air-flow ozoniferous (CDA) was dispersed in the integral body of this gas.Introduce this through the preferred range that contains streams of ozone of the gas regulated 40～350 ℉ preferably.
Carrier gas stream ozoniferous obtains from a sub-systems; Wherein ozone is to generate through the commercially available excessively ozone generator of the Oxygen Flow that makes larger volume with lower weight concentration; Then ozone is adsorbed in as on the adsorbents such as silica gel, high silicon mordenite and dealuminium Y type beta stone, uses like carrier gas such as dry air desorbed ozone.
The ozone of nearly all commercial use is produced through discharge, is also referred to as corona discharge, and lining glass or ceramic dielectric pipe wherein are set in the water-cooled stainless steel tube, between two surfaces, forms annular gap (discharging gap).Oxygen-containing gas is through this gap, and when this gap was applied high voltage, part oxygen was converted into ozone.
O
2+[O]＝O
3
Oxygen is to ozone [O
3] conversion need dissociate or interrupt chemical bond highly stable in the oxygen molecule, and with this oxygen atom or " singlet " oxygen atom [O] and another oxygen molecule [O
2] combine.When discharging gap is applied high voltage, bump between electronics and the oxygen molecule.Few part in these electronics has enough kinetic energy (about 6 or 7eV) dissociates oxygen molecule and forms ozone, and remaining electronics discharges their energy with the form of heat simultaneously.
Because corona discharge, ozone concentration increases along the length direction of pipe.The concentration of the ozone of the effuser in the one way ozone generator is near nominal design concentration.Therefore, for the ozone as 10～12wt% of nominal concentration, there is an ozone molecule in per 10～15 molecular oxygens.Singlet oxygen is powerful oxidising agent, also is reducing agent.Singlet oxygen [O] and ozone [O
3] collision can become ozone molecule again oxygen molecule.The electronics of fast moving also can destroy part ozone with the ozone collision.It below is simple reaction.
The mechanism of ozone partial destruction is very complicated in the ozone generator, and is not to understand to such an extent that be perfectly clear.But the practical experience of operation ozone generating apparatus is that power consumption factor (specific powerconsumption) raises with the rising of the concentration of generation ozone.Fig. 2 shows the obtainable O of prior art
3The typical power consumption factor curve of generator.
Therefore, if ozone with 5 or 6wt% generates rather than 10～12wt%, then can save 40% power, but this needs the oxygen of twice.
The ozone of about commercial use more than 95% is used for drinking water, bleaching, sterilization and wastewater treatment plant.In this all application, ozone is transferred to liquid phase through gas-liquid contact apparatus.If ozone is supplied with the flow velocity of half the concentration and twice, these technologies can lose efficient.On the contrary, for the application of the pollutant in the oxidation gaseous effluent, air-flow ozoniferous evenly distributes in air flow.Mixed ozone concentration is hundreds of ppm, reacts with pollutant then.In fact, because the volume of gas ozoniferous stream doubles, it is mixed better with flue gas stream, so the efficient of this technology improve.
In the technology of this improvement, the oxygen flow ozoniferous that flows out ozone generator is admitted to ozone is transferred to the carrier gas air-flow and most oxygen is recycled back the separator of the supply air-flow of ozone generator.This piece-rate system in a kind of embodiment is made up of adsorbent bed, transfer valve, dashpot and process controller.First's ozone in circulation is adsorbed in adsorbent bed under higher pressure, saturated when this, and ozone desorb under lower pressure is also taken out of container like carrier gas such as dry air.
After desorption cycle, this cleans to remove the nitrogen on the adsorbent with oxygen, repeats the ozone sorption cycle then.Gas stream from this clean cycle is rich in oxygen, can be used to other place, in the burning of the FCC of boiler, kiln or refinery operation, utilizes this oxygen-enriched air, perhaps recycles back oxygen generator and supplies with circulation.Known real convention is that (0.5～3vol%) replenishes pure oxygen supplies to ozone generator with little nitrogen stream.This a spot of nitrogen is asked to periodically or adds constantly to keep the efficient of generator.
The interpolation of place of nitrogen, some gases from clean cycle can be recirculated to generator, thereby save N are provided in addition
2Supply.Substitute circulating current, can be used to another group ozone generator and piece-rate system from the oxygen flow of piece-rate system.In fact, the generator series connection that can adopt size progressively to reduce is provided with 3～4 such systems, thereby can need not to utilize same oxygen to supply with recycling.
Said Purge gas is dry air normally, and the part that it can be used as oxygen evolution system system, Vacuum Pressure Swing Adsorption (VSA) or cryogenic oxygen generator generates, and perhaps in the autonomous system through film or adsorption system dried compressed air, generates.In the cryogenic oxygen generation systems, discarded nitrogen also can be used for the purifying adsorbent bed.
In the flue gas oxidation was used, ozone generates the zone can be away from the place to use.Therefore, it is stable that the ozone that is importantly transported kept before arriving the place to use.Ozone can be done longer distance transportation through pipeline.Ozone decompose be under pressure, the influence of gas type that temperature, concentration and being used to is diluted it.
The reaction equation that decomposes is following:
Wherein, M is the remaining gas molecule beyond the deozonize.Disclosed research shows that ozone is stable in nitrogen than in oxygen.In addition, when ozone partial pressure reduces to a half, in gas phase, lean on enough near lessly with the molecule that bumps.Therefore, with generator pressure be present in O
2In ozone compare, more stable with the ozone that half the dividing potential drop is present in the dry air.Because many industrial process that need exhaust-gas treatment are in being exposed to the container that atmosphere do not add protection, to carry out, so the stable particular importance of ozone.The ozone gas stream that contains that transports at the pipeline that is arranged on the pipe support is exposed under the illumination and the temperature in summer of the stability that has a strong impact on ozone.
When waste gas is introduced in carrier gas ozoniferous, use delivery manifold usually with nozzle.Because the ozone requirement is very little, and the pressure height of ozone generation and conveying (18～25psig), so these nozzles have very little aperture usually.Ozone causes a nozzle selection special material at a high speed usually from nozzle ejection.In the technology of improvement, flow rate of carrier gas is for usually based on O
3The twice of oxidation technology, pressure low (10psig), this requires to select bigger spray orifice.Speed when spray orifice is passed through in this carrier gas throttling is less, and the surplus of gas is not an oxygen, and nozzle does not need special material.In addition, the carrier gas that has big flow velocity can mix in flue gas more easily with equably.The spray orifice of large-size also can reduce the possibility of blocking because of the dirt in the flue gas phase and moisture.
This improved process also has the advantage of another corresponding generation.In the conventional technology based on ozone, when collector ozoniferous was placed in the flue gas carrier pipe, the temperature of collector raise, and a large amount of ozone are destroyed in collector.This is owing to higher weight concentration, higher pressure, low flow velocity, O
2Multiple phenomenon as gas surplus and higher temperature.These five kinds of factors are stable unfavorable to ozone all.The technology of improvement has been got rid of all of these factors taken together, has reduced the destruction of ozone directly or indirectly.
The delivery time that the technology of this improvement also uses CFD (computational fluid dynamics simulation) to improve under the specific holdup time in mixed characteristic and the container distributes.
Importantly use CFD to guarantee in ozone is incorporated in the flue gas, promptly to mix.If carrier gas ozoniferous does not mix with flue gas fully; Then ozone molecule is had no chance with the pollutant collision its oxidation; And mix improperly air communication and cross carrier pipe or container; Can produce the unreacted ozone and the pollutant of higher amount, lose efficient, and can't realize adopting the purpose of high efficiency technical.One of the easiest method of mixing ozone and flue gas is to introduce ozone at the entire cross section employing grid of pipeline.Another selection is with ozone introduction pipe (radially) radially.
In gas preconditioning step, do not reduce at effluent gas temperature, and ozone carry under the temperature that is higher than 200 ℉ and the situation of undercompounding under, a large amount of ozone just are destroyed before oxidize contaminants.In case ozone in pipeline or container in the predetermined holdup time oxidation pollutant, must carry out scrubbing or adsorption treatment to flue gas.N
2O
5Be to the highstrung molecule of temperature, have low stability.Yet it and water, alkali or alkaline matter form the chemical bond of quite stable.Through CFD, the technology of this improvement guarantees that the gas stream that has mixed ozone is transported to scrubber or absorber in the predetermined holdup time, make back-mixing arrive bottom line to the amount in pipeline or the container.This distributes through the delivery time of following the tracks of the gas that flows out oxidation tube road or oxidation volume and is confirmed, and oxidation pipeline or oxidation volume are also claimed conversion zone or oxide regions.
In order to improve the delivery time distribution, normally used method is that moving blade changes its direction when flue gas stream is introduced into container.For the reaction of ozone and pollutant, the delivery time distribution that discovery is similar to plug flow reactor is best.Modification method of the present invention utilizes the delivery time to distribute and realizes suitable design, rather than residence time or holdup time.
With ozone oxidation NO
XGas phase in reaction be summarized as follows:
NO+O
3---------->NO
2+O
2
NO
2+O
3---------->NO
3+O
2
NO
3+NO
2<＝＝＝＝＝>N
2O
5
2NO
2<＝＝＝＝＝>N
2O
4
NO+NO
2<＝＝＝＝＝>N
2O
3
20
3---------->30
2
SO
2+O
3---------->SO
3
CO+O
3---------->CO
2
Like also oxidations in oxidant of other pollutant such as simple substance mercury.
Hg
0+O
3---------->Hg
-2+O
2
Reactor can be the autonomous container at pipeline, scrubbing container itself or the scrubbing container upper reaches at the scrubbing container upper reaches.Importantly most of oxidation occurs in and imports before the scrubber medium.When the scrubbing container bottom partly is used as oxidized portion, must add to note reducing as best one can the contact of scrubber medium.
Find SO
2To SO
3Oxidation in reactor, can ignore.Tool dissolubility and reactive be the high oxide of nitrogen, N particularly
2O
5Therefore, in gas volume, take place before the oxidation of aequum, should avoid contacting of any and scrubber medium.
Scrubber can be dry method or semidry method type, wherein uses alkali metal or alkaline earth metal carbonate, bicarbonate, oxide or hydroxide as adsorbent.The wet method scrubber can be packed column, spray column, sieve-plate tower or ancient gas tower tray type scrubber.Filling can be at random or structurized.Spraying can be adopted the nozzle that water curtain is provided, for example flat blade, conulite or solid conical.Scrubber can have wetting wall and defend dirt and erosion.Can reconfigure arbitrarily wet method or dry method scrubber and wash pollutant through oxidation.Said oxidation volume can be in single container, wherein at first uses spraying or playpipe (venture) to come preconditioning gas, and the volume that does not and then have spraying provides the space of oxidize contaminants.
It is effective that single container scheme is considered to cost usually.Yet it is very difficult to design.Bad design causes in the oxidation volume, mixing scrubber liquid.In the exemplary system that text open and that grant patent is offered, be easy to find claim in the claim not have adsorbent liquid in the oxidation volume, but in fact be not like this.The simplest determination methods is check NO
XThe rate of removing is to O
3/ NO
XThe relation curve of ratio or NO
XThe rate of removing is to kilowatt hour power/every pound of NO that removes
XRelation.Import NO for 50～5000PPMV
XIf 70～90% to remove the slope of curve of rate precipitous, then there is not the adsorbent drop in the oxidation volume.Suppose all import NO
XBe NO, second observed result is along with O
3/ NO
XIncrease, NO
XThe rate of removing almost reaches 100%, on the contrary, if curve slope between 70～90% is smooth, then representes ozone and NO
2In oxidation reactor, be washed, because ozone is exhausted NO in reactor
XOxidation can only proceed to NO
2Till.
Fig. 3 has represented three examples.Precipitous continuous line is represented NO
XOxidation almost can be with all NO as betiding in the reactor with envisioning
XBe converted into the high oxide that can in scrubber, be removed.Second example is the situation of vertical absorber, and wherein the chamber of below is an oxidized portion, and introduce the oxidation volume top that adsorbent is sprayed in the circular cylindrical shell.Spraying in the absorber part of container is penetrated from the inside wall of central authorities, and the reagent adsorbent flows along the inwall of this circular cylindrical shell.Be sure of not have drop to fall into the oxidation volume.On the contrary, smooth dotted line representes that oxidation reaction receives the interference that partly falls into the adsorbent drop of reaction volume from scrubbing.As a result, part ozone is washed in reactor and removes, and the increase ozone supply causes that the pettiness of removing efficient improves.The 3rd example is the situation with horizontal scrubber of flat blade type spray nozzle.Ozone is introduced in the downstream of the first chilling spray nozzle.There are not enough reaction volumes at twice spray booth.Yet because the chamber is a level, twice spray booth at first do not have too many adsorbent drop.As a result, present precipitous slope before the rate of removing reaches 87～90%, this is illustrated in twice spray booth does not have the zone of drop that oxidation takes place.When oxidized air-flow contacts NO with the adsorbent spraying
XOxidised form and unreacted ozone be washed and remove, slowed down speed with ozone oxidation.
Improved process described here develops efficiency through the power requirement that reduces in 5～20% the scope, or promotes handling property through less ozone-depleting.
In the wet method scrubber, remove NO in washing
X, SO
XIn the time of with other pollutant, be dissolved in scrubbing liquid from the oxygen of flue gas.Though slower than adopting ozone through dioxygen oxidation sulphite and bisulfites, this can exhaust the amount of free sulphite and bisulfites.The technology of improvement has reduced the amount of the oxygen that need add with ozone, has therefore reduced the consumption of sulphite and bisulfites.
For example, has 750～800PPMv SO
XWith 220PPMv NO
X1000000 Pounds Per Hours flue gas stream radially carry out preparatory scrubbing in the scrubber in advance at the intracanalicular type of the cylindrical shape scrubber that is attached to vertical placement.Under 165 ℉ near saturated flue gas through preparatory scrubbing with after the streams of ozone in the carrier gas (dry air) is mixed, be introduced in main scrubber.The bottom cylindrical shape of scrubber container partly has liquid cell.Flue gas stream in the base section turns to, and upwards flows to the scrubbing part.The air-flow deflecting plate helps to reduce back-mixing, a large amount of NO
XOxidized at this base section.Then, oxidized gas contacts with the scrubbing solution that contains alkali metal hydroxide, carbonate, bicarbonate, sulphite, bisulfites, and it is positioned at the top part of scrubber in the scrubbing part.Inwall cleans to reduce the formation of erosion and particulate through scrubbing liquid.The treated gas stream that flows out scrubber has the NO that is less than 10PPMv
XFig. 4 has gathered CFD and has analyzed the power save that the improvement described in the technology of benefit and improvement in the airflow design of oxidized portion brings.
Though the embodiment with concrete describes the present invention, obviously numerous other forms of invention are apparent to one skilled in the art with modification.The appended claim of the present invention is interpreted as comprising such conspicuous form and the modification in all true spirit of the present invention and the scope usually.
Claims (13)
1. a method of from industrial flue gas stream, removing pollutant is characterized in that, may further comprise the steps:
A) in ozone generator, supply with oxygen-containing gas stream, what generate ozone concentration thus and be 5-6 weight % contains ozone gas stream;
B) the said ozone gas conductance that contains is gone in the gas separation system, oxygen was separated from said containing the ozone gas stream;
C) oxygen that said separation is obtained imports the said oxygen-containing gas stream of step a);
D) supply to the flue gas carrier pipe with said from industrial flue gas stream; And
E) the ozone gas stream that contains behind the oxygen separation that (b) step is obtained supplies to said flue gas carrier pipe, ozone therein with said flue gas stream in pollutant reaction.
2. the method for claim 1 is characterized in that, said oxygen-containing gas stream is selected from oxygen and air.
3. the method for claim 1 is characterized in that, said gas separation system is selected from film separation system and adsorbent piece-rate system.
4. method as claimed in claim 3 is characterized in that, said adsorbent piece-rate system comprises the adsorbent that is selected from silica gel, dealuminium Y type beta stone and high silicon mordenite.
5. the method for claim 1; It is characterized in that said flue gas stream is selected from off-gas flows, the process gas that comes from chemical industry, oil and petrochemical industry, metal, semiconductor and glass operation and the tail gas air-flow that comes from the combustion of fossil fuel source.
6. the method for claim 1 is characterized in that, the temperature that contains ozone gas stream that gets into said flue gas stream is 40 ° of F～350 ° F.
7. the method for claim 1 is characterized in that, and is further comprising the steps of:
F) liquid water is incorporated in the said flue gas carrier pipe, the reaction product of ozone and said pollutant is converted into diluted acid;
G) said diluted acid is absorbed in the reagent liquid, thus said diluted acid is converted into salt; And
H) discharge the said flue gas stream that has not contained pollutant from said flue gas carrier pipe.
8. method as claimed in claim 7 is characterized in that, the reagent of said reagent liquid is caustic soda, the carbonate of calcium, magnesium, potassium or ammonia, bicarbonate or hydroxide.
9. method as claimed in claim 7 is characterized in that said diluted acid is selected from HNO
3, H
2SO
3And H
2SO
4
10. method as claimed in claim 7 is characterized in that said salt is selected from nitrate, sulphite and sulfate.
11. method as claimed in claim 7 is characterized in that, said flue gas carrier pipe reaction or oxide regions are used the delivery time to distribute and are designed.
12. method as claimed in claim 7 is characterized in that, (b) the said ozone gas stream that contains of step is radially introduced the flue gas carrier pipe perhaps is incorporated into the flue gas carrier pipe equably through grid entire cross section.
13. method as claimed in claim 2 is characterized in that said air is a dry air.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US79637306P | 2006-05-01 | 2006-05-01 | |
| US60/796,373 | 2006-05-01 | ||
| US11/784,855 US7766995B2 (en) | 2006-05-01 | 2007-04-10 | Ozone production processes and its use in industrial processes |
| US11/784,855 | 2007-04-10 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101108300A CN101108300A (en) | 2008-01-23 |
| CN101108300B true CN101108300B (en) | 2012-08-22 |
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|---|---|---|---|
| CN2007101026992A Expired - Fee Related CN101108300B (en) | 2006-05-01 | 2007-04-29 | Ozone production processes and its use in industrial processes |
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| Country | Link |
|---|---|
| CN (1) | CN101108300B (en) |
| NZ (1) | NZ554881A (en) |
| ZA (1) | ZA200703388B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8840705B2 (en) * | 2011-07-07 | 2014-09-23 | Linde Aktiengesellschaft | Methods for the ozonolysis of organic compounds |
| CN103663384B (en) * | 2012-09-14 | 2015-07-01 | 福建新大陆环保科技有限公司 | Method for separating mixed gas of oxygen and ozone and ozone generating system using method |
| PL2719440T3 (en) * | 2012-10-15 | 2017-09-29 | Linde Aktiengesellschaft | Method for removing contaminants from exhaust gases by adding ozone |
| CN105148700B (en) * | 2015-08-27 | 2018-05-08 | 北京市环境保护科学研究院 | The method and device of pollutant in a kind of oxidative absorption processing natural gas boiler flue gas |
| CN106731526A (en) * | 2016-12-05 | 2017-05-31 | 山西北极熊环境科技有限公司 | One kind separation and recovery O2And O3Method and device |
| WO2020083098A1 (en) * | 2018-10-22 | 2020-04-30 | 上海必修福企业管理有限公司 | Engine emission treatment system and method |
| CN112194323B (en) * | 2020-10-16 | 2023-04-18 | 中交天航港湾建设工程有限公司 | Municipal sewage treatment system based on internet of things |
| CN113582139B (en) * | 2021-07-01 | 2023-11-21 | 光大水务科技发展（南京）有限公司 | Air-oxygen alternate purging type ozone separation pressure swing adsorption system and method thereof |
| TWI809531B (en) * | 2021-10-15 | 2023-07-21 | 李德隆 | A steam injection device that fully mixes ozone and exhaust gas in the flue |
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|---|---|---|---|---|
| EP1036758A1 (en) * | 1999-03-05 | 2000-09-20 | The Boc Group, Inc. | Ozone purification |
| EP1036759A1 (en) * | 1999-03-05 | 2000-09-20 | The Boc Group, Inc. | Ozone purification |
| US6136284A (en) * | 1999-12-09 | 2000-10-24 | The Boc Group, Inc. | Process for the removal of nitrogen oxides from gas streams |
| CN1490242A (en) * | 2002-04-25 | 2004-04-21 | 波克股份有限公司 | Ozone producing method |
| CN1768904A (en) * | 2005-10-14 | 2006-05-10 | 浙江大学 | Method for removing hydrargyrum from coal burning boiler flue gas by ozone oxidation |
-
2007
- 2007-04-25 ZA ZA200703388A patent/ZA200703388B/en unknown
- 2007-04-29 CN CN2007101026992A patent/CN101108300B/en not_active Expired - Fee Related
- 2007-05-01 NZ NZ554881A patent/NZ554881A/en unknown
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1036758A1 (en) * | 1999-03-05 | 2000-09-20 | The Boc Group, Inc. | Ozone purification |
| EP1036759A1 (en) * | 1999-03-05 | 2000-09-20 | The Boc Group, Inc. | Ozone purification |
| US6136284A (en) * | 1999-12-09 | 2000-10-24 | The Boc Group, Inc. | Process for the removal of nitrogen oxides from gas streams |
| CN1490242A (en) * | 2002-04-25 | 2004-04-21 | 波克股份有限公司 | Ozone producing method |
| CN1768904A (en) * | 2005-10-14 | 2006-05-10 | 浙江大学 | Method for removing hydrargyrum from coal burning boiler flue gas by ozone oxidation |
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| Title |
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| JP特開平7-247102A 1995.09.26 |
Also Published As
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|---|---|
| CN101108300A (en) | 2008-01-23 |
| NZ554881A (en) | 2010-02-26 |
| ZA200703388B (en) | 2009-08-26 |
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