CN101171070B - Dry simultaneous desulfurization/denitrification apparatus for exhaust gas - Google Patents

Dry simultaneous desulfurization/denitrification apparatus for exhaust gas Download PDF

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CN101171070B
CN101171070B CN2006800152949A CN200680015294A CN101171070B CN 101171070 B CN101171070 B CN 101171070B CN 2006800152949 A CN2006800152949 A CN 2006800152949A CN 200680015294 A CN200680015294 A CN 200680015294A CN 101171070 B CN101171070 B CN 101171070B
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free radical
desulfurization
denitration
raw material
generates
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CN101171070A (en
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神原信志
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Gifu University NUC
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/32—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by electrical effects other than those provided for in group B01D61/00
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B01D2257/302—Sulfur oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/40—Nitrogen compounds
    • B01D2257/404—Nitrogen oxides other than dinitrogen oxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/40—Nitrogen compounds
    • B01D2257/406—Ammonia
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/80—Employing electric, magnetic, electromagnetic or wave energy, or particle radiation
    • B01D2259/818—Employing electrical discharges or the generation of a plasma

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treating Waste Gases (AREA)
  • Exhaust Gas After Treatment (AREA)

Abstract

To provide a dry simultaneous desulfurization/denitrification apparatus for exhaust gas that can remove any sulfur oxides and nitrogen oxides contained in exhaust gas simultaneously with high efficiency and that is compact and inexpensive. There is provided dry simultaneous desulfurization/denitrification apparatus for exhaust gas (30) capable of removing any sulfur oxides and nitrogen oxides contained in exhaust gas (EG) by the use of radical chain reaction, characterized by including not only swirling denitrification radical generation means (22) for converting to radicals a material for denitrification while swirling in plasma reactor (11) composed of a pair of electrodes to thereby produce denitrification radicals (RN) but also desulfurization radical generation means (6) for converting a material for desulfurization to radicals to thereby produce desulfurization radicals, which means (6) is disposed at a position under influence from the swirling denitrification radical generation means (22).

Description

Dry simultaneous desulfurization/denitrification apparatus for exhaust gas
Technical field
The present invention relates to a kind of dry simultaneous desulfurization/denitrification apparatus for exhaust gas; It is used to handle from the waste gas of incinerator or combustion furnace discharge, from the waste gas of engine for boat or the waste gas of diesel power generation etc., removes the oxysulfide (SO in the burnt gas with denitration free radical and desulfurization free radical 2) and nitrogen oxide (NO).
Background technology
If coal combustion or oil, general discarded object, trade waste, wooden biological substance etc. then can generate oxysulfide and nitrogen oxide from sulphur that is contained in the fuel and nitrogen.Because these can impact environment or health, thereby limit its discharge rate.In the past, for processing contains the waste gas of oxysulfide or nitrogen oxide, use ammonia and catalyst catalyst denitration method (SCR), use the wet type desulfurizing method (FGD) of lime stone mainly to be used in power industry with boiler or general industry non-utility power generation boiler.
Yet,, thereby area is set and installation cost is bigger because these device volumes are bigger; Owing to need catalyst or lime stone, thereby operating cost is also bigger, because wet desulfurizer needs water; Thereby its use is confined to make in a large number the region of water; Owing to need the desulfurization drain treatment apparatus, thereby need its installation cost and operating cost, therefore; These devices be not suitable for middle and small scale incinerator, build in the stove on ground, use is not at present installed emission-control equipment or ammonia is blown into the simple and easy denitration method in the stove or is blown into the simple desulfurization method of white lime.The denitration rate of above-mentioned easy method or desulfurization degree are about 30～50%.
Yet, if consider the reinforcement of the restriction of environmental protection from now on, also can receive the restriction same, the therefore urgent exploitation of expecting more small-sized, cheap and high efficiency dry simultaneous desulfurization/denitrification apparatus with large-scale incinerator even can learn the incinerator of middle and small scale.Have again, since at present looser to the restriction of engine for boat or diesel power generation, thereby needn't take the desulphurization denitration countermeasure.Yet because American-European trend, it is strict that the restriction of China in the near future also will become.
In recent years, the new known favourable method of dry simultaneous desulfurization/denitrification apparatus (referenced patent document 1) with electron beam, utilize the method (referenced patent document 2) of corona discharge and utilize the method (referenced patent document 3) of pulsed discharge.Yet, owing to these methods are all directly shone electron beam in large quantity of exhaust gas, or make it pass through discharge tube, thereby the reduction of its power consumption, in other words, energy efficiency (is removed NO or the SO of 1g 2Etc. required electric weight (kWh)) reduction become bigger problem.
To this, the inventor of the application's case had once proposed to generate ammonia free radical with low temperature plasma in the past, and its method of denitration that is blown in the waste gas is used as waste gas processing method (referenced patent document 4) cheap and that high efficiency is carried out denitration.
Fig. 9 (a) is the whole pie graph of concept nature that has possessed the burning complete set of equipments of employed denitrification apparatus in this method, (b) is the figure that conceptually representes the major part formation of this denitrification apparatus.
Shown in Fig. 9 (a); This incinerator 101 possesses: combustion furnace 102, outlet of still 103, catalyst type denitrification apparatus 104, heat exchanger 105, dust arrester 106, desulfurizer 107 and chimney 108, the denitrification apparatus 110 that will have above-mentioned characteristic is arranged at suitable a plurality of positions of combustion furnace 102, outlet of still 103.
Shown in Fig. 9 (b), denitrification apparatus 110 possesses: blender 115, accept from NH respectively 3The NH of supply department 111, Ar supply department 3The supply of gas, Ar gas and generate mist; Discharge tube 112 is made up of the dual pipe of cylinder of negative electrode urceolus 112a and anode inner core 112b; Plasma electrical source 113 is in order to put on ac high voltage this anode inner core 112b; Conduit 122 will be in order to will be fed to discharge tube 112 outlet sides from the mist of blender 115; And be blown into mouth 125, in order to the denitration free radical that is generated in the discharge tube 112 is blown in combustion furnace 102, the outlet of still 103.
In above-mentioned formation, according to this denitrification apparatus 110, from the NH of blender 115 3The mist of gas, Ar gas imports discharge tube 112 entrance sides, and free radicalization expeditiously in the dual pipe of cylinder that is made up of this electrode pair 112a, 112b is blown into the waste gas from being blown into mouthfuls 125, in mixer S, mixes, reacts with NO, generation N 2, H 2O, but high efficiency is carried out denitration.
In addition, same mixture gas is blown into first free radical that is generated from the conduit 122 that is arranged at discharge tube 112 outlet sides, generates the NH that contains high concentration 2Second free radical of free radical and NH free radical thus, is realized its high efficiency.
Yet, this device 110, that is, the invention of being put down in writing in the patent documentation 4 is that oxygen concentration is that the denitration rate is low to moderate about 60% under 5% the condition in the waste gas at usage range, requires further to improve.In addition, do not consider in the waste gas removal with the simultaneously contained oxysulfide of nitrogen oxide fully, that is, and desulfurization.
Patent documentation 1: No. 3361200 communique of japanese
Patent documentation 2: japanese kokai publication hei 10-235137 communique
Patent documentation 3: japanese kokai publication hei 10-118448 communique
Patent documentation 4: TOHKEMY 2004-89752 communique
Summary of the invention
The present invention constitutes in order to address the above problem, its purpose be to provide a kind of can be simultaneously and high efficiency remove oxysulfide and small-sized, the cheap dry simultaneous desulfurization/denitrification apparatus for exhaust gas of nitrogen oxide in the waste gas.
For realizing this purpose; The dry simultaneous desulfurization/denitrification apparatus for exhaust gas of being put down in writing in the scheme 1 of independent mode; Utilize free radical chain reactions to remove oxysulfide and nitrogen oxide in the waste gas, it is characterized in that possessing: rotary denitration free radical generates mechanism; In the low temperature plasma that the dual pipe of cylinder that is made up of dielectric system electrode pair is generated, make denitration with raw material while rotating free radicalization and generate the denitration free radical; And the desulfurization free radical generates mechanism; Be arranged at and receive the position that this rotary denitration free radical generates mechanism's influence; In the low temperature plasma that the dual pipe of cylinder that is made up of dielectric system electrode pair is generated; Make desulfurization generate the desulfurization free radical with the raw material free radicalization, denitration is the arbitrary mist that is selected from argon and ammonia, argon and ammoniacal liquor, argon and the urea with raw material, and desulfurization is to be selected from the waste gas that contains moisture, steam, the humid air any with raw material.
According to this device (invention), when denitration with raw material through the dual pipe of the cylinder that constitutes by electrode pair in and during free radical, denitration is rotated in dual pipe with raw material.Thus,, can further be blown into waste gas stream, further improve denitration efficiency with the state of expectation control free radical no matter pipe range how, can expect to control the length that free radical generates operation.In addition, through forming eddy current, also can prolong free radical generation operation length even pipe range is short, thereby can realize miniaturization.Again owing to be eddy current, even thereby denitration be single-stage with raw material supply source (raw material supply mechanism is used in denitration), also can generate required sufficient denitration free radical.
In addition; According to this device; Make the raw material free radicalization in the low temperature plasma that in the dual pipe of the cylinder that constitutes by dielectric system electrode pair, is generated, thereby reduce raw material free radical institute energy requirement significantly, and the no equipment which requires cooling of device itself etc.; With compare in the past, reduce desulfurization significantly and consumed energy is used in denitration.
Have again and since free radical generate generate in the mechanism denitration free radical and desulfurization free radical the two, thereby with the mixer of waste gas in the occasion that generated compare, can suppress unexpected reaction (being helpless to the reaction of denitration and desulfurization).
Have again; According to this device; Because desulfurization free radical generation mechanism is arranged on and can receives the position that rotary denitration free radical generates the influence of mechanism, thereby when the desulfurization free radical generates mechanism's generation desulfurization free radical, can use the denitration free radical that generates mechanism's generation through the denitration free radical.Here, " can affected position " be to generate mechanism when desulfurization generates the desulfurization free radical with raw material when the desulfurization free radical, the position of the denitration free radical through the generation of rotary denitration free radical generation mechanism capable of using.Even do not utilize the denitration free radical can generate the desulfurization free radical though the desulfurization free radical generates mechanism yet,, can generate a large amount of denitration free radical NH once more through utilizing the denitration free radical 2, and also generate a large amount of desulfurization free radical OH.
Particularly, denitration is the arbitrary mist that is selected from argon and ammonia, argon and ammoniacal liquor, argon and the urea with raw material, and desulfurization is to be selected from the waste gas that contains moisture, steam, the humid air any with raw material.Therefore; If make denitration then can generate the H free radical,, but pass through the effect of this H free radical as one of denitration free radical with the raw material free radicalization; Compare with the occasion of raw material free radicalization with only in the low temperature plasma ambiance, making desulfurization, can generate a large amount of desulfurization free radicals is the OH free radical.In addition, because denitration contains argon with raw material, thereby low temperature plasma is stable, but high efficiency generates denitration free radical and desulfurization free radical.
In addition, contain the moisture about several % in the waste gas, use raw material as desulfurization, can realize the resources effective application through using this waste gas.
Have, even can consider desulfurization free radical and denitration free radical in electric field, self-generating is longer to the time of eliminating (being the life-span), for about the several seconds again.Therefore, not becoming denitration with denitration radical reduction that nitrogen oxide reacts is amino molecule with raw material, but through this amino molecule (NH 3), through the sulfuric acid (H that reaction generated of OH free radical and oxysulfide 2SO 4) can be transformed into solid constituent.Therefore, dry type ground reclaims the sulphur composition easily.
As above-mentioned, through being arranged on, desulfurization free radical generation mechanism (no matter whether being rotary) can receive the position that rotary denitration free radical generates the influence of mechanism, and can carry out desulphurization denitration with the effect that multiplies each other and handle.
Then, will be blown into waste gas stream like the denitration free radical and the desulfurization free radical of above-mentioned generation.
The scheme of slave mode is that the scheme that the dry simultaneous desulfurization/denitrification apparatus for exhaust gas of putting down in writing (in the scheme 2 to 7 each record) in the scheme 2 to 7 possesses independent mode is the constitutive requirements of the dry simultaneous desulfurization/denitrification apparatus for exhaust gas of record in the scheme 1.Therefore, in the scheme 2 to 7 invention of record have with the subordinate scheme in the identical effect of invention put down in writing.Below, scenarios at length is described.
The dry simultaneous desulfurization/denitrification apparatus for exhaust gas of record is subordinated to scheme 1 in the scheme 2; It is characterized in that; Possesses rotating vane; Be arranged on by rotary denitration free radical and generate denitration free radical and the mixed position, mixer dead ahead of waste gas that mechanism generated, be blown into this mixer in order to the denitration free radical that will form eddy current.
According to this device, owing to can the denitration free radical that generated the eddy current that mechanism was generated by this denitration free radical still be kept delivering to well mixer with rotating vane, thereby mix with exhaust-gas efficient rate ground in mixer, improve denitration efficiency.
The dry simultaneous desulfurization/denitrification apparatus for exhaust gas of record is subordinated to scheme 1 or 2 in the scheme 3; It is characterized in that; The denitration free radical generates mechanism and the desulfurization free radical generates mechanism's formation one, and the denitration free radical organization of supply that the denitration free radical is fed to denitration free radical generation mechanism is arranged at the back segment that the desulfurization free radical is fed to the desulfurization free radical organization of supply of desulfurization free radical generation mechanism.
According to this device; Because the desulfurization free radical generates mechanism and the denitration free radical generates mechanism's formation one; Thereby can be shared free radical generate the dual pipe of cylinder of the main composition assembly of mechanism, do not need to be provided with in addition the dual pipe of cylinder, can reduce cost and realize miniaturization.
In addition, according to this device, owing to generate in the mechanism at the desulfurization free radical, receive rotary denitration free radical and generate mechanism's influence, desulfurization also can be rotated with raw material naturally, thereby can pass out to mixer rapidly.Therefore, the short desulfurization free radical of application life effectively.
Have again,, owing to constitute one, thereby can further reduce consumed energy, and whenever when the desulfurization free radical generates, can improve the expenditure of answering of denitration free radical according to this device.
The dry simultaneous desulfurization/denitrification apparatus for exhaust gas of record is subordinated to scheme 3 in the scheme 4, it is characterized in that desulfurization free radical organization of supply is arranged at the position, dead ahead of rotating vane.
Have again,, because the free base load of desulfurization is taken advantage of in eddy current, pass out to mixer rapidly according to this device, thereby the application life desulfurization free radical of lacking effectively.
The dry simultaneous desulfurization/denitrification apparatus for exhaust gas of record is subordinated to scheme 1 or 2 in the scheme 5; It is characterized in that; The rotary denitration free radical that desulfurization free radical generation mechanism is configured in waste gas stream generates on the allocation position of mechanism; Or on its downstream position, and the desulfurization free radical generates mechanism and this rotary denitration free radical generates mechanism's split setting.
According to this device, because the denitration free radical is generated mechanism and the split setting of desulfurization free radical generation mechanism, thereby can independently carry out the control that the desulfurization free radical generates, improve the independence of control, can only be conceived to desulfurization degree and control.
In addition,,, the desulfurization free radical is arranged at the allocation position that rotary denitration free radical generates mechanism because generating mechanism according to this device, or its downstream position, thereby when generating the desulfurization free radical, denitration free radical capable of using.
The dry simultaneous desulfurization/denitrification apparatus for exhaust gas of scheme 6 records is subordinated to scheme 5; It is characterized in that; Possess desulfurization and use rotating vane; Be arranged on the position, dead ahead (near the position leading portion side) of the mixer of mixing with waste gas, in order to the desulfurization free radical is blown into this mixer by the desulfurization free radical generation desulfurization free radical that mechanism generated.
According to this device, use special use because desulfurization is arranged at desulfurization free radical generation mechanism with rotating vane as desulfurization, thereby the free base load of desulfurization is taken advantage of in eddy current, pass out to mixer rapidly, effectively the short desulfurization free radical of application life.Here, the desulfurization free radical the allocation position preferably position, dead ahead of rotating vane (near the position leading portion side) that generates mechanism.Its reason also is the effectively short desulfurization free radical of application life.
Scheme according to independent mode is the dry simultaneous desulfurization/denitrification apparatus of record in the scheme 1, can simultaneously and remove oxysulfide and the nitrogen oxide in the waste gas expeditiously, and small-sized, cheap device is provided.
Scheme according to slave mode is the dry simultaneous desulfurization/denitrification apparatus for exhaust gas of record in the scheme 2 to 7, possesses the effect of the dry simultaneous desulfurization/denitrification apparatus for exhaust gas of putting down in writing in the scheme 1 of independent mode.
Description of drawings
Fig. 1 is the figure that conceptually representes an example of dry simultaneous desulfurization/denitrification apparatus for exhaust gas of the present invention, (a) is its longitudinal sectional view, (b) is its major part transverse sectional view, (c) is the side view of rotating vane, (d) is the transverse sectional view of rotating vane.
Fig. 2 is a routine whole pie graph of burning (burning) complete set of equipments of the expression dry simultaneous desulfurization/denitrification apparatus for exhaust gas that possessed Fig. 1.
Fig. 3 (a) is illustrated in the performance test result of dry simultaneous desulfurization/denitrification apparatus for exhaust gas of Fig. 1, applies the chart of the relation of oxygen concentration and denitration rate in voltage and the waste gas, (b) is the chart that expression applies the relation of oxygen concentration and desulfurization degree in voltage and the waste gas.
Fig. 4 is illustrated in the performance test result of dry simultaneous desulfurization/denitrification apparatus for exhaust gas of Fig. 1 the chart of the relation of energy density and energy efficiency.
Fig. 5 is another the routine figure that conceptually representes dry simultaneous desulfurization/denitrification apparatus for exhaust gas of the present invention, is its longitudinal sectional view (a), (b) is the AA cutaway view of (a), (c) is the BB cutaway view of (b).
Fig. 6 is a routine whole pie graph of another routine burning (burning) complete set of equipments of the expression dry simultaneous desulfurization/denitrification apparatus for exhaust gas that possessed Fig. 5.
Fig. 7 (a) is the whole pie graph of an example of expression another routine burning (burning) complete set of equipments of having possessed waste gas of the present invention week dry simultaneous desulfurization/denitrification apparatus, (b) is the amplification view partly that is provided with of this complete set of equipments.
Fig. 8 (a) is another the routine figure that conceptually representes dry simultaneous desulfurization/denitrification apparatus for exhaust gas of the present invention; (b) be its longitudinal sectional view, (c) be possessed (a) dry simultaneous desulfurization/denitrification apparatus for exhaust gas burning (burning) complete set of equipments one the example whole pie graph.
Fig. 9 (a) is the whole pie graph of concept nature that has possessed the burning complete set of equipments of existing denitrification apparatus, (b) is the figure that conceptually representes the major part formation of this denitrification apparatus.
Symbol description:
The 1-denitration is rotated supply pipe with raw material; 2,2A-earth electrode (negative electrode); 3-high-voltage electrode (anode); 4-high voltage pulse power supply; 5-ground connection; The 6-desulfurization is with raw material supply tube (the desulfurization free radical generates mechanism); Feedstock supply unit is used in the 6b-desulfurization; The 7-gap; 8,8B-rotating vane (whirlpool blade); The 8A-desulfurization is with rotating vane (whirlpool blade); 9-incinerator or combustion furnace; The 10-thermometer; 11,11A, 11B, 11C-plasma reactor; The raw material storage facility is used in the 12-denitration; Raw material supply tube is used in the 13-denitration; Raw material supply tube is used in the 14-desulfurization; 15A-mixer concentration analysis device; Concentration analysis device before the 15B-chimney; The 16-control device; The 17-dust arrester; The 18-flue; 19-exhaust gas recirculation fan; The 20-chimney; The rotary denitration free radical of 22-generates mechanism; 23-desulfurization free radical generates mechanism; The 30-dry simultaneous desulfurization/denitrification apparatus for exhaust gas; 40-has burning (burning) complete set of equipments of desulfuring and denitrifying apparatus; The 50-dry simultaneous desulfurization/denitrification apparatus for exhaust gas; The S-mixer
The specific embodiment
Below, with reference to the example (embodiment) of description of drawings preferred embodiments of the present invention.Though technical scope of the present invention comprises following embodiment, do not receive any restriction of these embodiment.
(embodiment 1)
Fig. 1 is the figure of an example (embodiment 1) of conceptually representing dry simultaneous desulfurization/denitrification apparatus for exhaust gas of the present invention; (a) be its longitudinal sectional view; (b) being its major part transverse sectional view, (c) being the side view of rotating vane, (d) is the transverse sectional view of rotating vane; Fig. 2 be the expression possessed Fig. 1 dry simultaneous desulfurization/denitrification apparatus for exhaust gas the burning complete set of equipments one the example whole pie graph; Fig. 3 (a) is illustrated in the performance test result of dry simultaneous desulfurization/denitrification apparatus for exhaust gas of Fig. 1, applies the chart of the relation of oxygen concentration and denitration rate in voltage and the waste gas, (b) is the chart that expression applies the relation of oxygen concentration and desulfurization degree in voltage and the waste gas; Fig. 4 is illustrated in the performance test result of dry simultaneous desulfurization/denitrification apparatus for exhaust gas of Fig. 1 the chart of the relation of energy density and energy efficiency.
As shown in Figure 2; This dry simultaneous desulfurization/denitrification apparatus for exhaust gas shown in Figure 1 30; Be used in burning (burning) complete set of equipments 40 of burning or coal combustion or oil, general discarded object, trade waste, wooden biological substance etc., carrying out the desulphurization denitration of waste gas, mainly constitute by plasma reactor 11.This plasma reactor 11 is to have the device that in low temperature plasma, generates the characteristic of free radical, thereby also can be described as low temperature plasma free radical generating apparatus.
Plasma reactor 11 possesses: denitration is with raw material rotation supply opening pipe 1; Earth electrode pipe (negative electrode) 2; High-voltage electrode pipe (anode) 3; Desulfurization is with raw material supply mouth pipe 6; And rotating vane 8 (blade of guiding rotation is also referred to as the rotation guide blade).
Dry simultaneous desulfurization/denitrification apparatus for exhaust gas 30 except plasma reactor 11, also possess high voltage pulse power supply 4, ground connection 5, denitration with raw material storage facility 12, denitration with raw material supply tube 13 and desulfurization with raw material supply tube 14.
Plasma reactor 11 is the cylinder double-sleeve structures as the quartz glass of dielectric, and interior pipe constitutes high-voltage electrode pipe 3, and this high-voltage electrode pipe 3 is connected on the high voltage pulse power supply 4.Outer tube constitutes earth electrode pipe 2, and this earth electrode pipe 2 is connected on the ground connection 5.
Between the outer tube of dual pipe and interior pipe, be provided with gap (space) 7, this gap 7 constitutes free radical streams.Denitration flows in this gap 7 with raw material with raw material and desulfurization, and the free radicalization through the low temperature plasma that in gap 7, produces generates denitration free radical, desulfurization free radical.
Denitration is installed near the inlet of plasma reactor 11 with raw material rotation supply opening pipe 1, constitutes the flow channel of denitration with raw material.This denitration, is installed on the tangential direction of plasma reactor 11 (the dual pipe of cylinder) shown in Fig. 1 (b) with raw material rotation supply opening pipe 1, its result, and denitration forms eddy current with raw material, the gap 7 of flowing through.
(in other words, in the dead ahead of plasma reactor 11 with the link position of flue 18 (being also referred to as flue gas leading)) is provided with desulfurization with raw material supply mouth pipe 6 near the outlet of plasma reactor 11, constitutes the flow channel of desulfurization with raw material.Like this, desulfurization is configured in the back segment of denitration with raw material rotation supply opening pipe 1 with raw material supply mouth pipe 6.
Shown in Fig. 1 (b); This desulfurization is arranged on the direction with the circumference quadrature of plasma reactor 11 with raw material supply mouth pipe 6; Though the desulfurization of supply is rotated with raw material, desulfurization also can generate rotation along the eddy current of denitration free radical naturally with raw material, and free radicalization expeditiously.
At this moment, desulfurization must not hinder the eddy current of denitration free radical with raw material supply mouth pipe 6.In addition, also can desulfurization be installed on the tangential direction with raw material supply mouth pipe with raw material rotation supply opening pipe 1 identically, thereby become stronger eddy current with denitration.
Rotating vane 8 is installed in outlet (in other words, at the link position of plasma reactor 11 with flue 18) at plasma reactor 11, thus, can apply strong eddy current to free radical, mixes with waste gas.Here, with all air-flows towards the mode of same circumferencial direction set denitration with raw material rotation supply opening pipe 1, desulfurization with raw material supply mouth pipe 6 and rotating vane 8.Therefore, though state after the detailed content, can realize free radical reaction of formation and desulfurization and denitrification reaction expeditiously.
The least significant end that is provided with rotating vane 8 of plasma reactor 11 is arranged on the incinerator of the burning with desulfuring and denitrifying apparatus (burning) complete set of equipments 40 illustrated in fig. 2 or flue 18 that combustion furnace 9 stretches out; Mix with the denitration free radical RN of eddy current ejection, the desulfurization free radical RS waste gas EG before mixer S and processing from here, make it become the waste gas EG of denitration, desulfurization.
Preferably design length or the external diameter of plasma reactor 11, the length in gap 7 (the external diameter difference of the internal diameter of earth electrode pipe 2 and high-voltage electrode pipe 3 half the), denitration and rotate supply opening pipe 1 and desulfurization installation site with raw material supply mouth pipe 6 with raw material with the mode that can generate the free radical that is fit to desulfurization and denitrification reaction at most; And preferred design becomes the flow velocity of the outlet of plasma reactor 11 to surpass the waste gas flow velocity.
But high voltage pulse power supply 4 must and apply the power supply more than tens of kHz for the voltage more than the alternation 4kV.The pulse power of the rise time of voltage weak point is thought with regard to unreasonable.
Here; The plasma reactor 11 that denitration is constituted with raw material rotation supply opening pipe 1, by earth electrode pipe 2 and high-voltage electrode pipe 3 is called rotary denitration free radical altogether and generates mechanism 22, as the mechanism that makes denitration with raw material denitration free radicalization while rotating.In addition; Be arranged on the desulfurization of outlet side that this rotary denitration free radical generates mechanism 22 with raw material supply mouth pipe 6; Cause generates mechanism 22 with rotary denitration free radical and is arranged to one, thereby is also referred to as desulfurization free radical generation mechanism 6, as the mechanism that makes desulfurization with the raw material free radicalization.
In addition, in this embodiment, plasma reactor 11 makes rotary denitration free radical generate mechanism 22 and is arranged to one with desulfurization free radical generation mechanism 6.
Shown in Fig. 1 (c), (d); Rotating vane 8 is to make the dual pipe 21 of cylinder, that is, rotary denitration free radical generates the denitration free radical, desulfurization free radical of the eddy current that mechanism 22 generated still to keep the state of its eddy current; Maybe with after the further rectification of this eddy current; Import the mixer S that mixes with waste gas stream, make the outer shroud 8b of a plurality of guide blade 8a of being arranged on the eddy current direction axial upstream side periphery through being arranged on its eddy current and be arranged on interior all interior ring 8c, keep its ordered state.
Burning with desulfuring and denitrifying apparatus (burning) complete set of equipments 40 shown in Figure 2 is characterised in that the dry simultaneous desulfurization/denitrification apparatus for exhaust gas 30 that has possessed Fig. 1; Its essential part comprises: incinerator or combustion furnace 9, in order to coal combustion or oil, gas, general discarded object and trade waste; Dust collect plant 17 is in order to collect the cigarette ash that burning produces; Flue 18 is in order to exhaust gas routing; And chimney 20, be arranged on flue 18 ends.Here, dust collect plant 17 can be made up of electrostatic (electric dust) precipitator, also can be made up of bag hose.
This complete set of equipments 40 also possesses except above-mentioned essential part: thermometer 10, insert flue 18 to measure the EGT of outlet of still; Concentration analysis device 15B before mixer concentration analysis device 15A, the chimney is the NO and the SO of chimney 20 fronts in order to the mixer and the outlet thereof of measuring flue 18 inlets 2Concentration; Control device 16; And exhaust gas recirculation fan 19, with so that waste gas flows to desulfurization with raw material supply mouth pipe 6 from flue 18 downstream.
In addition, dry simultaneous desulfurization/denitrification apparatus for exhaust gas 30 except part shown in Figure 1, also comprises in order to the exhaust gas recirculation fan 19 of supply desulfurization with raw material.
This exhaust gas recirculation fan 19 is used to make the exhaust gas recirculation behind the desulphurization denitration that contains several % moisture effectively to utilize with raw material supply mouth pipe 6 to desulfurization, constitutes the part of desulfurization with raw material supply mouth pipe 6 (desulfurization free radical generation mechanism).This is owing to originally just contain several % moisture in the waste gas, thereby can be with its effective application, moreover is after desulphurization denitration, even thereby in the occasion that refluxes, also can prevent to produce the outer reaction of expection.
In addition, also can use the desulfurization that generation as following contains the air of given (number %) moisture to substitute this exhaust gas recirculation fan 19 with feedstock supply unit 6b (with reference to Fig. 5 (a)).
Control device 16 is according to the concentration of waste gas sulphur oxide and nitrogen oxide and measured value and the desulfurization degree of expectation and the setting value of denitration rate of EGT; Through the desulfurization of dry simultaneous desulfurization/denitrification apparatus for exhaust gas 30 and the design formula of denitration performance; Decision and control denitration with the concentration of raw material and flow, desulfurization with the concentration and the flow of raw material and the optimum value that applies voltage, with the concrete hardware of computer formation.
Dry simultaneous desulfurization/denitrification apparatus for exhaust gas 30 is set, more precisely, the position of plasma reactor 11 is set, remove NO and SO but be preferably disposed on high efficiency 2The position, i.e. the high as far as possible position of EGT.In addition, from the mix viewpoint that promote of free radical with waste gas, preferably plasma reactor 11 is arranged on flue 18 tops of gravity capable of using.Through utilizing gravity, can be blown in the waste gas by rapidly that the life-span is short free radical.
In addition; In the occasion that plasma reactor 11 is arranged on the horizontal component of the flue 18 that can't utilize gravity; Shown in the imaginary line of double dot dash line among Fig. 1 (a), with the mode of the mixer S of direction of principal axis in flue 18 of generated eddy current denitration is set and rotates supply opening pipe 1 ' get final product with raw material.
Can be according to the NO concentration in exhausted air quantity, the waste gas, the SO in the waste gas 2Concentration, answer denitration NO amount, answer desulfurization SO 2Amount is provided with a plurality of plasma reactors 11.In this occasion, can be according to the temperature of waste gas and the caliber of flue 18, will install 10 or arranged in series, or the parallel connection configuration, or be the configuration of clathrate ground or relatively flue 18 be crisscross and dispose.
The chart of Fig. 3 and Fig. 4 is with 400 ℃ of 30 pairs of EGTs of dry simultaneous desulfurization/denitrification apparatus for exhaust gas of the present invention, NO concentration 300ppm, SO 2Concentration 300ppm, O 2The waste gas 3Nl/min of change in concentration to 0%～5% carries out the result of the performance test of dry simultaneous desulfurization/denitrification.
The graphical presentation denitration rate of Fig. 3 (a) applies the variation of voltage relatively, and the graphical presentation desulfurization degree of Fig. 3 (b) applies the variation of voltage relatively.
Denitration is argon and ammonia with raw material, and desulfurization is the humid air that contains 5% moisture with raw material.The concentration that is adjusted to ammonia is 900ppm, and flow is 3Nl/min, makes NH 3/ NO mol ratio is 1.0, NH 3/ SO 2Mol ratio is 2.0, and makes desulfurization use the flow of raw material to be 1Nl/min.
With the length in the gap 7 of plasma reactor 11 is that to use the holdup time of raw material be that to use the holdup time of raw material be that 1 second mode has determined length and the desulfurization of plasma reactor 11 position with raw material supply mouth pipe 6 for 5 seconds and desulfurization for 5mm, denitration.
Can know that by these charts when to apply voltage be 4kV～6kV, denitration rate and desulfurization degree were the highest.Apply voltage then denitration rate and desulfurization degree reduction more than it if make.In addition, work as O 2Concentration is 1% o'clock, and denitration rate and desulfurization degree are the highest, if O 2Concentration increases then denitration rate and desulfurization degree reduces.Therefore, preferably apply the 4kV that voltage is set at low power consumption, reduce oxygen concentration of exhaust gases as far as possible.Under desirable condition, can obtain denitration rate 95%, desulfurization degree 85%.
In the method (TOHKEMY 2004-89752 communique) that the application's case inventor invented in the past, if oxygen concentration becomes 5% desulfurization degree and is reduced to 60%, but the present invention can keep more than 80%.Can consider that this is to be blown into waste gas owing to free radical being applied rotation, thereby prolong the incorporation time of free radical and waste gas, improve the result of reactivity.In fact, oxygen concentration is 3%～6% in the waste gas of combustion furnace or incinerator 9, thinks that the present invention is more suitable for practicability.In addition, subsidiary one carries, and argon in the composition of free radical agent (Ar) is 70%, ammonia (NH 3) be 30% occasion, even being set at lower 80%, the denitration rate comes tentative calculation, free base unit weight required for the present invention is compared with waste gas only needs extremely few amount to get final product (waste gas 0.0014 times).Have again, if come tentative calculation to handle waste gas (50000m from the incinerator of general scale with the present invention according to above-mentioned setting 3/ h) 1 year denitration raw material cost of occasion is then compared with catalyst denitration method (SCR), can be at it below 1/10th.
Fig. 4 is the charts of the gap 7 interior desulphurization denitrations of expression plasma reactor 11 with the energy efficiency of the NO amount of raw material institute received energy density and the removal of per unit energy.In this chart, can obtain energy efficiency 140g-NO/kWh, this has substantially exceeded similar techniques.The more little then energy efficiency of energy density is high more, removes efficient and also improves.The design guideline that this has represented the gap and has applied voltage.That is, this means occasion, apply voltage, make energy density become 0.1J/cm to shorten the length of plasma reactor 11, to increase in the length that will increase gap 7 3Mode design get final product.
(embodiment 2)
Fig. 5 is the figure of another example (embodiment 2) of conceptually representing dry simultaneous desulfurization/denitrification apparatus for exhaust gas of the present invention; (a) be its longitudinal sectional view; (b) be the AA cutaway view of (a); (c) be the BB cutaway view of (b), Fig. 6 be the expression possessed Fig. 5 dry simultaneous desulfurization/denitrification apparatus for exhaust gas burner one the example whole pie graph.
Compare with the dry simultaneous desulfurization/denitrification apparatus for exhaust gas 30 of Fig. 1; The difference of dry simultaneous desulfurization/denitrification apparatus for exhaust gas 30A shown in Figure 5 is; The desulfurization free radical generates mechanism 23 and generates the 22A of mechanism split setting with rotary denitration free radical; Though and be arranged on rotary denitration free radical generates the relative flue 18 of the 22A of mechanism identical position, position is set, setting angle is different.Shown in Fig. 5 (a), 180 degree that seemed above-mentioned two relative deflections of mechanism, but this is for the ease of understanding the present invention, in fact as shown in Figure 6, above-mentioned two mechanisms are installed in flue 18 tops.That is, in Fig. 6, the rotary denitration free radical of overlapping diagram generates the 22A of mechanism and the desulfurization free radical generates mechanism 23.
In addition; Difference is; Its result; Generate on the 22A of mechanism at rotary denitration free radical and desulfurization not to be set, on the other hand, constitute rotating vane (whirlpool blade) 8B and be the mode of denitration free radical of the lateral direction jet-stream whirl of earth electrode (negative electrode) 2A towards the urceolus of the rotary denitration free radical generation 22A of mechanism with raw material supply mouth pipe 6.
In addition, the rotary denitration free radical that these splits is provided with generates the 22A of mechanism and the desulfurization free radical generates mechanism 23 altogether as plasma reactor 11A.
The desulfurization free radical generates mechanism 23 to be possessed by the dual pipe 23d of cylinder that constitutes with earth electrode pipe 2, high-voltage electrode pipe 3 and gap 7 identical earth electrode pipe 23a, high-voltage electrode pipe 23b and the gap 23c of the plasma reactor 11 of Fig. 1, accepts supply and the desulfurization that is blown into gap 23c is arranged at gap 23c with raw material supply mouth pipe 6A the entrance side end of the air of given moisture rate with feedstock supply unit 6b from desulfurization.
Outlet side setting at the dual pipe 23d of cylinder is used rotating vane 8A with the rotating vane 8 identical desulfurization of the plasma reactor that is arranged on Fig. 1 11 outlets, and the desulfurization free radical RS that is generated is mixed with waste gas EG in mixer S while rotating.
Shown in Fig. 5 (b), (c), the rotating vane 8B that is arranged at the outlet side end of the rotary denitration free radical generation 22A of mechanism possesses: guide blade 8a is arranged at the electrode container 2a that constitutes earth electrode (negative electrode) 2A; And joint-cutting 8b, be arranged at the outer tube dielectric 2b of the internal layer that likewise constitutes earth electrode (negative electrode) 2A and constitute this electrode container 2a.
In addition, can know that high-voltage electrode pipe 3 possesses anode portion 3a, cover the interior pipe dielectric 3b of its periphery and cover the end dielectric 3c of the outlet side end of anode portion 3a by these Fig. 5 (b), (c).On the other hand, with the outlet side end of end dielectric closing gap 7.
Shown in Fig. 5 (a) and (b); Rotating vane 8B according to above-mentioned formation; The denitration free radical limit of the eddy current that in gap 7, generates is guided by slit 8b, guide blade 8a and is kept eddy current; The limit reaches the mixer S that mixes with waste gas EG towards earth electrode (negative electrode) 2A and sprays, and S mixes well in this mixer.
Like this, the denitration free radical RN of eddy current, desulfurization free radical RS and the waste gas that in mixer S, mixes are solidified into sulfate of ammoniac (measuring more) and nitric acid ammonia (measuring less) through high efficiency and denitration simultaneously and desulfurization.These solids move towards dust arrester 17, and are collected for it, thereby the waste gas after the denitration, desulfurization, dedusting is discharged from flue 18 terminal chimneys 20 environment is not caused dysgenic state.In addition, owing to roughly become N more than 95% in the nitric acid composition 2(gas), thereby through dust arrester 17.
In addition; The electrode container 2a that is provided with the guide blade 8a of rotating vane 8B rotates with the outer tube dielectric 2b that is provided with slit 8b each other; And constitute the structure that the mutual position of rotation after can keeping rotating concerns, thus, scalable is from the flow of the denitration free radical of guide blade 8a rotary-jet.Therefore, through this Flow-rate adjustment, scalable is controlled the denitration rate towards the flow of the denitration free radical of the eddy current of mixer S injection.In other words, because the relative position of variable guide blade 8a and slit 8b is regulated the size in this gap, thereby utilize restriction effect can change the flow velocity of the desulfurization of inflow flue 18 with raw material.In the more occasion of flow, enlarge the gap, in the less occasion of flow, dwindle the gap.
In addition; In this embodiment 2; Though represented that the desulfurization free radical generates mechanism 23 and is arranged on the situation that identical position, position is set that generates the relative flue 18 of the 22A of mechanism with rotary denitration free radical; But in the scope of the influence that can utilize the rotary denitration free radical generation 22A of mechanism, also can be arranged on from rotary denitration free radical and generate being provided with on the position of position by the downstream of flue 18 of the 22A of mechanism.
(embodiment 3)
Fig. 7 (a) representes to have possessed waste gas of the present invention to be used for the formula whole pie graph of an example of burning (burning) complete set of equipments of another example (embodiment 3) of desulfuring and denitrifying apparatus simultaneously, (b) is the amplification view that part is set of this complete set of equipments.
Compare with burning (burning) complete set of equipments 40 of Fig. 2, difference is that incinerator or the combustion furnace 9A of this burning (burning) complete set of equipments 40B are vertical, near the outlet of this incinerator or combustion furnace 9A itself, also are provided with plasma reactor 11B.Therefore, desulfurization not only is connected in plasma reactor 11 with raw material supply tube 13 and denitration with raw material supply tube 14, also is connected in plasma reactor 11B.
In addition; Compare with the plasma reactor 11 of Fig. 1; Among this plasma reactor 11B; Generate mechanism 6 to be arranged to the one this point identical though rotary denitration free radical is generated mechanism 22 and desulfurization free radical, difference is that the rotating vane 8B (whirlpool blade) that is arranged at its outlet side is identical with the rotating vane 8B that the rotary denitration free radical generation 22A of mechanism of Fig. 5 is possessed.
In addition; In Fig. 7 (a); Though separate flue 18 parts of the outlet of flue 18 parts that are provided with plasma reactor 11 and incinerator or combustion furnace 9A with cutting line; Plasma reactors 11 flue 18 parts that the position is different are not overlapping on drawing but this is just for the ease of expression is arranged at highly identical with the flue 18 that stretches out from incinerator or combustion furnace 9A, and not representing has distance therebetween.
In addition, this dry simultaneous desulfurization/denitrification apparatus for exhaust gas 30B possess be arranged at the plasma reactor 11B on incinerator or the combustion furnace 9A and be arranged on the flue 18 plasma reactor 11 the two.
Shown in Fig. 7 (b); For thermal insulation; Constitute incinerator or combustion furnace 9A with the body of heater 26 in the outside and inboard adiabatic material 27, plasma reactor 11B holds and is arranged in the insulation flange 25 that has thermal insulation and insulation concurrently that is provided with the mode that connects this body of heater 26, heat-insulating material 27.
(embodiment 4)
Fig. 8 (a) is the figure of another example (embodiment 4) of conceptually representing dry simultaneous desulfurization/denitrification apparatus for exhaust gas of the present invention; (b) be its longitudinal sectional view, (c) be possessed (a) dry simultaneous desulfurization/denitrification apparatus for exhaust gas burning (burning) complete set of equipments one the example whole pie graph.
Embodiment 4 is that dry simultaneous desulfurization/denitrification apparatus 50 mainly is made up of plasma reactor 11C, and plasma reactor 11C possesses: denitration is with raw material rotation supply opening pipe 1; Earth electrode pipe 2; High-voltage electrode pipe 3; Desulfurization is with raw material supply mouth pipe 6; And rotating vane 8.
Fig. 8 (a) is the side view of plasma reactor 11C, and Fig. 8 (b) is its front view.
Plasma reactor 11C is the cylinder double-sleeve structure as the quartz glass of dielectric, and interior pipe constitutes high-voltage electrode (below be called the high-voltage electrode pipe) 3, and this high-voltage electrode pipe 3 is connected in high voltage pulse power supply 4.Outer tube constitutes earth electrode (below be called the earth electrode pipe) 2, and this earth electrode pipe 2 is connected in ground connection 5.Between the outer tube of dual pipe and interior pipe, form gap (space) 7, raw material flows into gap 7, in gap 7 through argon plasma with denitration with raw material and desulfurization with the raw material free radicalization.
Denitration is installed near the inlet of plasma reactor 11C with raw material rotation supply opening pipe 1, constitutes the flow channel of denitration with raw material.Shown in Fig. 8 (b), be installed on the tangential direction of cylinder because this denitration is rotated supply opening pipe 1 with raw material, thereby denitration forms eddy current with raw material, the gap 7 of flowing through.Desulfurization is set with raw material supply mouth pipe 6 near the outlet of plasma reactor 11C, constitutes the flow channel of desulfurization with raw material.
Owing to desulfurization also likewise is installed on the tangential direction of cylinder with raw material rotation supply opening pipe 1 with denitration with raw material supply mouth pipe 6, thereby desulfurization forms eddy current with raw material, the gap of flowing through.In the outlet of plasma reactor 11C rotating vane 8 is installed, thus, can is applied strong rotation and mix free radical with waste gas.Here, so that disposing denitration, the mode of all same circumferencial directions of air-flows court rotates supply opening pipe 1, desulfurization with raw material supply mouth pipe 6 and rotating vane 8 with raw material.Therefore, though detailed content will be narrated in the back, can realize free radical reaction of formation, denitration reaction and desulphurization reaction expeditiously.
Preferably with the mode that can generate the free radical that is fit to desulfurization and denitrification reaction at most design plasma reactor 11C length or external diameter, gap length, and denitration with raw material rotation supply opening pipe 1 and desulfurization installation site with raw material supply mouth pipe 6; And preferred design becomes the flow velocity of plasma reactor outlet to surpass the waste gas flow velocity.
But high voltage pulse power supply 4 must and apply the power supply more than tens of kHz for the voltage more than the alternation 4kV.The pulse power of the rise time of voltage weak point is thought with regard to unreasonable.
Then, about the occasion on the burning complete set of equipments that the present invention is arranged on Fig. 8 (c), an example of its embodiment is described.The burning complete set of equipments possesses: incinerator or combustion furnace 9, in order to coal combustion or oil, gas, general discarded object and trade waste; Dust collect plant 17 is in order to collect the cigarette ash that burning generates; And chimney 20.Here, dust collect plant 17 can be made up of electrical precipitator, also can be made up of bag hose.
The present invention also is located at above-mentioned burning complete set of equipments, except plasma reactor 11C, also possesses: thermometer 10, insert flue 18 to measure the EGT of outlet of still; Concentration analysis device 15 is in order to measure the NO and the SO of flue gateway 2Concentration; Control device 16; Denitration is with raw material storage facility 12; Denitration is with raw material supply tube 13; Desulfurization is with raw material supply tube 14, through exhaust gas recirculation fan (exhaust gas recirculation device) 19 supplies; And high voltage pulse power supply 4.
Control device 16 at length is described below.Control device 16 is according to the concentration of waste gas sulphur oxide and nitrogen oxide and measured value and the desulfurization degree of expectation and the setting value of denitration rate of EGT; After obtaining by the design formula of the desulfurization of plasma reactor 11C and denitration performance, decision and control denitration with the concentration of raw material and flow, desulfurization with the concentration and the flow of raw material and the optimum value that applies voltage.Generally speaking, constitute by computer.
The position of plasma reactor 11C is set, is preferably disposed on and removes NO and SO expeditiously 2The position, i.e. the high as far as possible position of EGT.In addition, from the mix viewpoint that promote of free radical with waste gas, preferably plasma reactor 11C is arranged on the flue top of gravity capable of using.
Can be according to the NO concentration in exhausted air quantity, the waste gas, the SO in the waste gas 2Concentration, answer denitration NO amount, answer desulfurization SO 2Amount is provided with a plurality of plasma reactor 11C.A plurality of occasions is being set, can accordinging to the temperature of waste gas and the caliber of flue, or arranged in series, or the configuration of clathrate ground, or flue is configuration crisscross relatively.
No matter owing to constitute plasma reactor 11,11A, 11B, the 11C of the major part of dry simultaneous desulfurization/denitrification apparatus for exhaust gas of the present invention is one-piece type or separation type, all little than existing apparatus, thereby like following explanation; Many of the capacity setting that can cooperate burning (burning) complete set of equipments; In addition, shown in this example, also can be arranged on incinerator or combustion furnace 9A and flue 18 both sides; In this occasion, can multiply each other or the effect of this plasma reactor 11 of addition performance, 11A, 11B, 11C.
In addition, the combustion furnace 102 of existing example as shown in Figure 9 in the occasion with outlet of still 104 and so on, also can be provided with plasma reactor 11,11A, 11B, 11C at this.
Then, come at length to explain the process that generates free radical from raw material from the viewpoint of chemical reaction.Below, though for ease of understanding invention, article on plasma precursor reactant device 11 is explained, and is also identical in plasma reactor 11A, 11B, 11C.
At first, as phase I (the denitration free radical generates operation), the denitration that will be made up of the mist of argon and ammonia, argon and ammoniacal liquor or argon and urea to the argon plasma that atmospheric dielectric barrier discharge generated, can generate NH with raw material supply at once 2Free radical, NH free radical, N free radical and H free radical.
Here, argon plays a part the stable plasma that generates under low-voltage, and ammonia, ammoniacal liquor and urea are NH 2The generation source of free radical, NH free radical, N free radical and H free radical.Though these free radicals of the most suitable generation of ammonia also can use the gas of ammoniacal liquor volatilization or the gas that urea is volatilized.
Then; As second stage (the desulfurization free radical generates operation); Supply is used raw material by the desulfurization that the waste gas that contains moisture, steam or humid air from incinerator or combustion furnace 9 constitute; OH free radical, H free radical can be generated at once,, the dry simultaneous desulfurization/denitrification reaction can be carried out by free radical chain reactions through these are blown into waste gas.This desulfurization is the generation source of OH free radical with raw material.Owing in burnt gas, contain the moisture more than 10% usually, thereby utilize this waste gas to be highly profitable at economic aspect with raw material again as desulfurization.Yet, in waste gas, contain the occasion of volume coal dust, also can use steam or humid air.
The inventor of the application's case thinks and utilizes NH 2The representational reaction of the desulfurization and denitrification reaction of free radical, NH free radical, N free radical, H free radical and OH free radical is carried out to the chemical formula 7 like Chemical formula 1.Here, the unit process of known these reactions reaches more than 300.
Chemical formula 1: e -+ NH 3→ e -+ NH 2+ H
Chemical formula 2: e -+ NH 3→ e -+ NH+H+H
Chemical formula 3:e -+ NH 3→ N+H+H+H
Chemical formula 4:e -+ NH+H 2O → OH+NH 2
Chemical formula 5:e -+ H+H 2O → OH+H+H
Chemical formula 6:NH 2+ NO → N 2+ H 2O
Chemical formula 7:2SO 2+ 4OH → 2H 2SO 4
Chemical formula 8:H 2SO 4+ 2NH 3→ (NH 4) 2SO 4
In Chemical formula 1,2,3, with the NH of plasma reactor 11 generations as the denitration free radical 2Free radical, NH free radical, N free radical.In chemical formula 4,5, with the OH free radical of plasma reactor 11 generations as the desulfurization free radical.Chemical formula 6 is main denitration reactions, chemical formula the 7, the 8th, main desulphurization reaction.
Can know that by above-mentioned reaction important free radical is NH in dry simultaneous desulfurization/denitrification 2Free radical and OH free radical, generating these expeditiously like plasma reactor 11 how is the most important problems of dealing with problems.
Chemical formula 4 is that the denitration free radical generates NH free radical and the desulfurization free radical generation employed H of mechanism that mechanism generated 2O reacts, and not only generates desulfurization free radical OH, also generates denitration free radical NH 2 Reaction.Chemical formula 4 is to obtaining the vital reaction of high desulphurization denitration rate.
Produced the imagination that desulfurization free radical generation mechanism is arranged on the maximum of the position that can receive the influence of denitration free radical generation mechanism according to this point,, the desulfurization free radical has been generated mechanism and denitration free radical generation mechanism formation one preferably like embodiment 1.
Have again, shown in chemical formula 8, because free radicalization or not from the NH of free radical state reduction 3The sulfuric acid composition is solidified into sulfate of ammoniac, thereby is easier to control of dust.
That is,, generate the effective NH of denitration reaction by with eddy current supply argon and ammonia, argon and ammoniacal liquor or argon and urea 2, NH, N, H free radical phase I (operation), with the waste gas that contains moisture, steam or the humid air of eddy current supply from combustion furnace 9; Generation makes the free radical that generates in first and second stage become strong eddy current to the second stage (operation) of the effective OH free radical of desulphurization reaction and with rotating vane, and the phase III (being blown into operation) that is blown into waste gas constitutes the oxysulfide that utilizes free radical chain reactions to remove waste gas and the method for nitrogen oxide.
Make equipment miniaturization through denitration being fed to plasma reactor 11 with raw material (argon and ammonia, argon and ammoniacal liquor or argon and urea) with eddy current, and through generating expeditiously the most effective NH of denitration 2The length in the gap 7 of the method for free radical, increase plasma reactor 11; Double to increase the treating capacity of each table apparatus method, be fed to plasma reactor 11 with the waste gas that contains moisture of eddy current spontaneous combustion in the future stove 9, generate the method for the effective OH free radical of desulfurization and denitrification reaction expeditiously and make the NH of generation 2Free radical and OH free radical form eddy current through rotating vane 8, and it is blown in the waste gas, carry out the method for long free radical chain reactions of incorporation time, can carry out dry simultaneous desulfurization/denitrification expeditiously.
Have, the exhausted air quantity that also proposes with good grounds incinerator or combustion furnace 9 disposes a plurality of plasma reactors 11 again, easily the method for enlargement of scale.
Prior art about desulphurization denitration is the combination that mainly utilizes the large-scale catalyst denitrification apparatus of ammonia and catalyst, utilizes the large-scale wet-type desulfurizer and the desulfurization drain treatment apparatus of lime stone and water, and installation cost and operating cost have to increase.Yet, according to the present invention, owing to be simple mechanism, thereby can reduce installation cost, and owing to be dry type, thereby can reduce operating cost.Have again, although be simple mechanism, can realize denitration and desulfurization the two, and denitration rate and desulfurization degree are equated or higher with prior art.
Through desulfurization being blown into plasma reactor 11 with raw material or denitration with raw material with eddy current; Desulfurization can be accepted the excitation energy from plasma with raw material or denitration with raw material expeditiously; Generate expeditiously the effective free radical of desulphurization denitration; Suppress power consumption, improve the desulphurization denitration rate, and can shorten the length of plasma reactor 11.
According to exhausted air quantity a plurality of plasma reactors 11 are set and get final product, can be applicable to the incinerator or the combustion furnace 9 of any size simply from incinerator or combustion furnace 9.
After the denitration free radical generates operation, be provided with OH (desulfurization) free radical and generate operation.OH free radical reactive high, if generate OH in first operation, then easily with the NH that generates in second operation 2Free radical reacts, at NH 2+ OH → NH+H 2In the reaction of O not only to the effective NH of denitration reaction 2Free radical can disappear, and also can disappear to the effective OH free radical of desulphurization reaction, and in this occasion, desulfurization degree or denitration rate become extremely low.
Make the free radical that in above-mentioned first and second operation, generates become strong eddy current and be blown into the method for waste gas through utilizing with rotating vane 8, form the mixed flow of waste gas and free radical, the prolongation incorporation time can further improve desulfurization degree and denitration rate.
More than, according to embodiment the present invention has been described, but in the scope that does not exceed main idea of the present invention, the foregoing description can be done various improvement distortion, in technical scope of the present invention, also comprises these improvement distortion.
Particularly, it is rotary also can making the desulfurization free radical generation mechanism of split, in addition, and also can be with the rotating vane 8B among the plasma reactor 11A of Fig. 5 as the rotating vane on the plasma reactor that is arranged on Fig. 1 11 8.
In addition,, also can utilize the driving force of motor etc. and rotation forcibly produces eddy current, also can only change the direction of free radical by the setting angle of guide blade though rotating vane 8B plays a part to make free radical rotation.
In addition, the present invention comprises the invention of the category that belongs to following method.In addition, following invention is put down in writing with the mode that is suitable for claim.
A kind of waste gas is with dry-type method for simultaneously desulfurizing and denitrating (a); Utilize free radical chain reactions to remove oxysulfide and nitrogen oxide in the waste gas, it is characterized in that possessing: the denitration free radical generates operation; Use raw material in order to the supply denitration, generate the effective free radical of denitration reaction; The desulfurization free radical generates operation, uses raw material in order to the supply desulfurization, generates the effective free radical of desulphurization reaction; And be blown into operation, in order to denitration free radical generation operation and the desulfurization free radical generation free radical that operation generated are blown into waste gas.
A kind of waste gas is characterized in that with dry-type method for simultaneously desulfurizing and denitrating (b), waste gas with dry-type method for simultaneously desulfurizing and denitrating (a) in, above-mentioned denitration is the arbitrary mist that is selected from argon and ammonia, argon and ammoniacal liquor or argon and the urea with raw material.
A kind of waste gas is with dry-type method for simultaneously desulfurizing and denitrating (c); It is characterized in that; With dry-type method for simultaneously desulfurizing and denitrating (a) or (b), above-mentioned desulfurization is to be selected from from the waste gas that contains moisture, steam or the humid air of combustion furnace any with raw material at waste gas.
A kind of waste gas is characterized in that with dry-type method for simultaneously desulfurizing and denitrating (d), arrives in (c) with dry-type method for simultaneously desulfurizing and denitrating (a) at waste gas, and the effective free radical of desulfurization and denitrification reaction is comprised NH 2In free radical, NH free radical, N free radical, H free radical and the OH free radical at least one.
A kind of waste gas is with dry-type method for simultaneously desulfurizing and denitrating (e); It is characterized in that; Arrive in (d) with dry-type method for simultaneously desulfurizing and denitrating (a) at waste gas; Have control device, it is according to oxysulfide and/or the concentration of nitrogen oxide and the setting of desulfurization degree and denitration rate of EGT, exhaust gas entrance, the decision denitration with the concentration of raw material and flow, desulfurization with the concentration and the flow of raw material and apply the optimum value of voltage.
Have, the present invention comprises following invention again.
A kind of dry simultaneous desulfurization/denitrification apparatus for exhaust gas (f) is characterized in that possessing: free radical generates mechanism, with so that denitration generates denitration free radical and desulfurization free radical with raw material and desulfurization with the raw material free radicalization; Feed mechanism is in order to generate this free radical the waste gas that denitration free radical that mechanism generated and desulfurization free radical are fed into process object; Raw material supply mechanism is used in denitration, in order to denitration is generated mechanism with raw material supply to above-mentioned free radical; And raw material supply mechanism is used in desulfurization; In order to desulfurization is generated mechanism with raw material supply to above-mentioned free radical; This free radical generates mechanism and is made up of one or more pairs of electrodes that are made up of the dual pipe of cylinder; Above-mentioned denitration generates mechanism with raw material supply to above-mentioned free radical with denitration with eddy current with raw material supply mechanism, and above-mentioned desulfurization is arranged at the back segment of above-mentioned denitration with raw material supply mechanism with raw material supply mechanism.This device (f) is that the desulfurization free radical generates mechanism and the denitration free radical generates the device that mechanism constitutes the form (type) of one.
A kind of dry simultaneous desulfurization/denitrification apparatus for exhaust gas (g) is characterized in that, in dry simultaneous desulfurization/denitrification apparatus for exhaust gas (f), desulfurization generates mechanism with raw material supply to free radical with desulfurization with eddy current with raw material supply mechanism.
A kind of dry simultaneous desulfurization/denitrification apparatus for exhaust gas (h) is characterized in that, at dry simultaneous desulfurization/denitrification apparatus for exhaust gas (f) or (g), feed mechanism is made up of the rotating vane that is disposed at free radical generation mechanism back segment.
A kind of dry simultaneous desulfurization/denitrification apparatus for exhaust gas (i); It is characterized in that; At dry simultaneous desulfurization/denitrification apparatus for exhaust gas (f) in (h); It is the dual pipe of cylinder that is made up of dielectric that free radical generates mechanism, and constitutes one or more pairs of electrodes that high-voltage electrode and outer tube constitute earth electrode by interior pipe and constitute.
A kind of dry simultaneous desulfurization/denitrification apparatus for exhaust gas (j) is characterized in that, in (i), uses raw material reaction of formation through denitration free radical and desulfurization at dry simultaneous desulfurization/denitrification apparatus for exhaust gas (f), generates at free radical and generates the desulfurization free radical in the mechanism.
Dry simultaneous desulfurization/denitrification apparatus for exhaust gas of the present invention and method are capable of using in requiring all industrial circles from the exhaust-gas efficient rate that contains oxysulfide and nitrogen oxide of incinerator or combustion furnace discharge, small-sized and cheap ground while desulphurization denitration.

Claims (6)

1. a dry simultaneous desulfurization/denitrification apparatus for exhaust gas utilizes free radical chain reactions to remove oxysulfide and nitrogen oxide in the waste gas, it is characterized in that possessing:
Rotary denitration free radical generates mechanism, in the low temperature plasma that the dual pipe of cylinder that is made up of dielectric system electrode pair is generated, make denitration with raw material while rotating free radicalization and generate the denitration free radical; And the desulfurization free radical generates mechanism; Be arranged at and receive the position that this rotary denitration free radical generates mechanism's influence; The affected position of aforementioned meeting is meant when the desulfurization free radical and generates mechanism when desulfurization generates the desulfurization free radical with raw material, and rotary denitration free radical capable of using generates the position of the denitration free radical that mechanism generates, in the low temperature plasma that the dual pipe of cylinder that is made up of dielectric system electrode pair is generated; Make desulfurization generate the desulfurization free radical with the raw material free radicalization
Denitration is with the arbitrary mist in the raw material gas that to be the gas that is selected from argon and ammonia, argon and ammoniacal liquor volatilization, argon volatilize with urea,
Desulfurization is to be selected from the waste gas that contains moisture, steam, the humid air any with raw material.
2. dry simultaneous desulfurization/denitrification apparatus for exhaust gas according to claim 1 is characterized in that,
Possess rotating vane, be arranged on the position, mixer dead ahead of mixing with waste gas, be blown into this mixer in order to the denitration free radical that will form eddy current by the rotary denitration free radical generation denitration free radical that mechanism generated.
3. dry simultaneous desulfurization/denitrification apparatus for exhaust gas according to claim 1 and 2 is characterized in that,
The denitration free radical generates mechanism and the desulfurization free radical generates mechanism's formation one,
Desulfurization is arranged at the back segment that denitration is generated the denitration free radical raw material supply mechanism of mechanism with raw material supply to the denitration free radical with raw material supply to the desulfurization free radical raw material supply mechanism that the desulfurization free radical generates mechanism.
4. according to the described dry simultaneous desulfurization/denitrification apparatus for exhaust gas of the claim 3 that is subordinated to claim 2, it is characterized in that,
Desulfurization free radical raw material supply mechanism is arranged at the position, dead ahead of rotating vane.
5. dry simultaneous desulfurization/denitrification apparatus for exhaust gas according to claim 1 and 2 is characterized in that,
The desulfurization free radical generates mechanism, and the rotary denitration free radical that is configured in waste gas stream generates on the allocation position of mechanism, or on the downstream position of denitration free radical generation mechanism, generates mechanism's split setting with this rotary denitration free radical.
6. dry simultaneous desulfurization/denitrification apparatus for exhaust gas according to claim 5 is characterized in that,
Possess desulfurization and use rotating vane, be arranged on the position, dead ahead of the mixer of mixing with waste gas, in order to the desulfurization free radical is blown into this mixer by the desulfurization free radical generation desulfurization free radical that mechanism generated.
CN2006800152949A 2005-05-06 2006-04-20 Dry simultaneous desulfurization/denitrification apparatus for exhaust gas Expired - Fee Related CN101171070B (en)

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