CN110124451A - SO in wet type substep removing flue gas2With the method for NO - Google Patents

SO in wet type substep removing flue gas2With the method for NO Download PDF

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CN110124451A
CN110124451A CN201910391806.0A CN201910391806A CN110124451A CN 110124451 A CN110124451 A CN 110124451A CN 201910391806 A CN201910391806 A CN 201910391806A CN 110124451 A CN110124451 A CN 110124451A
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liquid
absorption
level
flue gas
absorption tower
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CN110124451B (en
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於柯言
胡甜
刘扬
刘畅
刘强
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University of Shanghai for Science and Technology
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University of Shanghai for Science and Technology
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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
    • B01D53/14—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 absorption
    • B01D53/1425—Regeneration of liquid absorbents
    • 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
    • B01D53/14—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 absorption
    • B01D53/1456—Removing acid components
    • 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
    • B01D53/14—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 absorption
    • B01D53/1456—Removing acid components
    • B01D53/1481—Removing sulfur dioxide or sulfur trioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0283—Flue gases

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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)
  • Gas Separation By Absorption (AREA)

Abstract

The invention discloses SO in a kind of wet type substep removal flue gas2With the method for NO, flue gas to be clean is continuously passed through first grade absorption tower and two-level absorption tower；SO in first grade absorption tower, in flue gas2Removal is absorbed after contacting with first order absorption liquid, in two-level absorption tower, the NO in flue gas is absorbed removal, purified gas discharge after contacting with second level absorbing liquid；First order absorption liquid has absorbed SO2Enter regenerator 1. afterwards, under the catalytic action of biological Pd/carbon catalyst, iron organic complex changes；After second level absorbing liquid complexed absorption NO, 2. into regenerator, the transformation of iron organic complex occurs, regenerated absorbing liquid enters back into first grade absorption tower, is recycled in systems.The method of the present invention realizes SO in flue gas2It is removed with the substep efficient green of NO, absorbent used can be recycled, and removal process is without adding other desulphurization denitration chemical agents.

Description

SO in wet type substep removing flue gas2With the method for NO
Technical field
The present invention relates to a kind of methods of flue gas desulfurization or denitration, more particularly to a kind of flue gas desulfurization and denitrification process one The method of change is applied to waste gas purification, environmental engineering technical field.
Background technique
Oxysulfide (SOX) and nitrogen oxides (NOX) it is the major pollutants for causing atmosphere pollution.The people of these pollutants To discharge the combustion process and chemical production process that mostly come from fossil resources such as coal, fuel oil, there is smoke discharge amount Greatly, the features such as pollutant emission is concentrated, Yi Yinqi Regional Atmospheric Pollution problem.Oxysulfide (the SO discharged in combustion product gasesX) Mainly sulfur dioxide (SO2), nitrogen oxides (NOX) it is mainly then nitric oxide (NO), accounting is more than ninety percent.Therefore, to SO2 Removing with NO is the emphasis of combustion product gases purification.
Currently, commercialized desulphurization denitration process mostly uses wet process lime stone or ammonia process to remove SO2, selective recall original (SCR) group technology of NO is removed；But the process flow is complicated, and removal pollutant needs to consume a large amount of chemicals, such as CaO, NH3Deng, while a large amount of waste is also generated, such as desulfurized gypsum.
Wet process while the advantages such as flue gas desulfurization and denitration technique has process simple, and equipment investment is low, it is little for exhaust gas volumn Desulphurization denitration process still there is certain attraction, researchers also develop the work of a variety of wet desulphurization denitrification integrals Skill and technology.Wet process simultaneous SO_2 and NO removal is broadly divided into oxidizing process and Absorption via Chemical Complexation.Oxidizing process is added by adding oxidant The oxidation rate of fast NO, to improve desulphurization denitration rate.As patent CN109276987A uses the mistake of alkali or alkaline earth metal Oxide, the inorganic salts with oxidisability or organic peroxide form oxidant and by water soluble alkalis or with activation The absorbent that is mixed to get of activator of the salt composition of weak acid radical ion can be generated in aqueous solution to remove in industrial tail gas SO2And NO.Patent CN208436644U proposes a kind of first by the NO in flue gas2It is converted into nitric acid and NO, by blasting air again NO is converted by the NO of generation2, while the sulfur dioxide in flue gas is absorbed by aqueous, the technique for realizing desulphurization denitration.Above two The operation of kind method is all very simple, but deals with improperly and be easy to cause secondary pollution, and reagent higher operating costs.
Absorption via Chemical Complexation is the flue gas and desulfurizing and denitrifying technology for being thought to be expected to realize industrial applications by scholar.The technology It is to add the complexing agent that can be reacted with NO into absorbing liquid, the solubility of NO in water can be significantly increased, realizes NO in flue gas Separation, solving the problems, such as NO, mass transfer rate is low in the liquid phase.Ferrous chelating method be current liquid complexing absorption process research most One of more method.This method is absorbent using Fe (II)-EDTA (or Fe (II)-Cit, ironic citrate), absorbs speed to NO Many advantages, such as rate is fast, high-efficient, generation complexing stablizes and is cheap and easy to get.The principles of chemistry that this method is related to are as follows:
Complex reaction occurs for Fe (II) EDTA (Fe (II)-Cit) solution and NO, so that the very low NO of solubility enters liquid Phase forms ferrous nitrosyl complex, so that NO be made to remove from gas:
NO(g)→NO(aq) (1)
NO(aq)+Fe(II)EDTA→Fe(II)EDTA-NO (2)
Since there are 3%-5% oxygen in flue gas, ferrous chelating agent can be made to be oxidized to Fe (III) EDTA, lost activity, No longer have the ability in conjunction with NO, the NO removal efficiency of absorbing liquid caused to reduce:
4Fe(II)EDTA+O2+4H+→4Fe(III)EDTA+2H2O (3)
Therefore, the highly efficient regeneration of ferrous chelating agent is the key that the technique being capable of continuous service.For this problem, patent CN104084023A proposes that, using ferrous chelating agent complexed absorption NO, absorbing liquid is reduced to ammonia by metallic iron and realizes denitration, then Ammonia is mixed with the ammonium hydroxide of desulfurization section, reacts to obtain ammonium sulfite with sulfur dioxide, and then aoxidize and obtain ammonium sulfate, realize de- Sulphur, the technique is also relatively simple, but needs to consume ammonia and metallic iron, so that the cost of processing increased.
In addition, if there are SO in flue gas2, then the SO in flue gas2It is easy to be only absorbed by the water, reacts life with Fe (II) EDTA-NO At Fe (II) EDTA (SO3 2-) NO, the compound is extremely stable, is difficult to decompose, and causes the loss of absorbent.
SO2(g)+H2O→H++SO3 2- (4)
Fe(II)EDTA-NO+SO3 2-→Fe(II)EDTA(SO3 2-)NO (5)
Therefore, developing efficient, cheap regeneration of absorption solution and recycle utilization and technique seems particularly necessary, becomes Technical problem urgently to be resolved.
Summary of the invention
In order to solve prior art problem, it is an object of the present invention to overcome the deficiencies of the prior art, and to provide one kind SO in wet type substep removing flue gas2With the method for NO, energy efficient absorption removes SO in flue gas2And NO, to reduce chemical drugs as far as possible Agent consumption is target, using ferric iron organic complex as absorbent, using ferric iron organic complex to SO2Efficient absorption, Using ferrous iron organic complex to the specific absorption of NO, substep realizes the removal to two kinds of pollutants；It utilizes simultaneously SO2Accelerate electronics transfer using charcoal as catalyst with the oxidation-reduction quality of NO itself, realizes ferric iron organic complex Efficient Conversion between ferrous iron organic complex, to guarantee the regeneration cycle of absorbent and the integration of desulphurization denitration.
In order to achieve the above objectives, the present invention adopts the following technical scheme:
SO in a kind of wet type substep removing flue gas2With the method for NO, to be clean is contained into SO2Successively connect with the flue gas of NO It is continuous to be passed through first grade absorption tower and two-level absorption tower；
SO in first grade absorption tower, in flue gas2Removal is absorbed after contacting with first order absorption liquid, the flue gas after desulfurization after Continuous to enter two-level absorption tower, the main component of the first order absorption liquid is ferric iron organic complex；
In two-level absorption tower, the NO in flue gas is absorbed removal after contacting with second level absorbing liquid, up to standard after denitration purification Gas discharged；
Be additionally provided with regenerator 1. with regenerator 2., the regeneration of the absorbing liquid in absorption towers at different levels can be carried out respectively；
First order absorption liquid absorbs the SO in flue gas in first grade absorption tower2Afterwards, formed sulphur-containing solution, make sulphur-containing solution into 1. the regenerator for entering absorbing liquid, converts ferrous iron organic complex for the ferric iron organic complex in sulphur-containing solution, thus Second level absorbing liquid is formed after regeneration, and is pumped and regenerated second level absorbing liquid is squeezed into two-level absorption tower progress denitrating technique；
After second level absorbing liquid is completed to the absorption of NO in flue gas in two-level absorption tower, is formed and contain nitrogen solution, made nitrogenous molten 2. liquid enters the regenerator of absorbing liquid, will be converted into ferric iron organic complex containing the ferrous iron organic complex in nitrogen solution, To form first order absorption liquid after regeneration, and first grade absorption tower is squeezed into through other pump, supplements the liquid measure of first order absorption liquid, Carry out sulfur removal technology；To form absorbing liquid circular regeneration and lasting use, the integrated chemical industry of wet type substep desulphurization denitration is realized Skill process.
As currently preferred technical solution, the main component of first order absorption liquid is ironic citrate (Fe (III) Cit, Fe (III) EDTA and Fe (III) NTA) at least one of ferric iron organic complex；Regenerator 1. in, in the catalysis of charcoal Under effect, the ferric iron organic complex in sulphur-containing solution is converted into Fe (II) Cit, Fe (II) EDTA and Fe (II) NTA) in At least one ferrous iron organic complex, control sulphur-containing solution residence time are 0.5~2min, are had what is obtained containing ferrous iron The second level absorption liquid pH of machine complex compound is adjusted to 5.0~6.0, then delivers into two-level absorption tower, carries out denitrating technique；Again Raw tower 2. in, under the catalytic action of charcoal, containing the ferrous iron organic complex in nitrogen solution be converted into Fe (III) Cit, Fe (III) EDTA and Fe (III) NTA) at least one of ferric iron organic complex, control nitrogenous Solution dwell time be 1.2 Then~7.2min delivers into first grade absorption tower, sulfur removal technology is carried out, to form absorbing liquid circular regeneration and persistently make With.
As the further preferred technical solution of the present invention, the charcoal be using biomass as raw material, through break process, Sieving, then in N2Under atmosphere, to be not less than the heating rate of 10 DEG C/min, through 300~800 DEG C of isothermal pyrolysis methods, carry out It is pyrolyzed at least 2h, active bio matter is prepared；After the catalytic activity of the charcoal reduces, by supplementing new biology The catalytic activity of charcoal maintenance charcoal.
As currently preferred technical solution, the regenerator 1. in, formed after regenerative response sulfate radical from Sodium sulfate crystal is precipitated after low temperature crystallization in the solution of son, to separate in absorbing liquid, as industrial raw materials, crystallization Mother liquor is transported into two-level absorption tower and continues to use as second level absorbing liquid is formed after regeneration.
In above-mentioned first grade absorption tower, the pH value of preferably control first order absorption liquid is 4.0~6.0, preferably control liquid-gas ratio For 4.2~12.0L/m3.In above-mentioned first grade absorption tower, the pH value for further preferably controlling first order absorption liquid is 4.5~5.5.
In above-mentioned two-level absorption tower, the pH value of preferably control first order absorption liquid is 5.0~6.0, preferably control liquid-gas ratio For 2.0~6.0L/m3。
The principle of the invention is as follows:
SO in a kind of wet type substep removing flue gas of the present invention2It is that flue gas to be clean is continuously passed through one with the technique of NO Grade absorption tower and two-level absorption tower；Flue gas continuously flows through first grade absorption tower and two-level absorption tower, discharges after purification；Absorbing liquid with For (Fe (III) Cit), by first grade absorption tower, the SO in flue gas is absorbed2Afterwards, 1. into regeneration of absorption solution tower, after regeneration Two-level absorption tower is squeezed into through pump, after completing to the absorption of NO in flue gas, 2. into regeneration of absorption solution tower, is squeezed into after regeneration by pump First grade absorption tower is recycled；Concrete technology flow process is as shown in Figure 1.
A. further, the first grade absorption tower, it is characterised in that using Fe (III) Cit solution as absorbing liquid, pH control exists 4.0~6.0, the main SO absorbed in removal flue gas2, liquid-gas ratio control is in 4.2~12.0L/m3, it is specific that following reaction occurs:
SO2+H2O→HSO3 2-+H+ (6)
H++Cit3+→HCit2+ (7)
H++HCit2+→H2Cit+ (8)
Fe described in above-mentioned steps a (III) Cit absorbing liquid the preparation method comprises the following steps: by Fe2(SO4)31 is pressed with sodium citrate : the molar ratio of (1~3), Fe (III) concentration, which is that 0.01~0.03mol/L is soluble in water, to be made.
B. further, the regeneration of absorption solution tower is 1., it is characterised in that using charcoal as filler, control absorbing liquid is stopped Time is 0.5~2min, specific that following reaction occurs:
Charcoal described in above-mentioned steps b is with biomass (such as corn stover) for raw material, through break process, is sieved, In N2Under atmosphere, with the heating rate of 10 DEG C/min, it is prepared within isothermal pyrolysis 2 hours at 300 DEG C~800 DEG C.
C. further, the two-level absorption tower, using the liquid of regeneration of absorption solution tower 1. as absorbing liquid, pH is controlled 5.0 ~6.0, in 2.0~6.0L/m3 following reaction specifically occurs for the main NO absorbed in removal flue gas, liquid-gas ratio control:
NO(g)→NO(aq) (10)
NO(aq)+Fe(II)Cit→Fe(II)Cit-NO (11)
There are in the case where oxygen in flue gas, it may occur that following reaction
4Fe(II)Cit+O2+4H+→4Fe(III)Cit+2H2O (12)
D. further, the regeneration of absorption solution tower 2. in mixed solution, it is characterised in that using charcoal as filler, control The absorbing liquid residence time processed is 1.2~7.2min, specific that following reaction occurs:
Charcoal described in above-mentioned steps d, preparation method with regeneration of absorption solution tower 1. in charcoal.
E. further, the charcoal in the present invention, catalytic activity can supplement fresh charcoal dimension after reducing Hold catalytic activity.
F. further, due to the continuous progress of sweetening process in the absorbing liquid, the accumulation of sulfate is had, can be carried out It recycles, method particularly includes: absorbing liquid is filtered into removal solid impurity, is crystallized using cold water and generates NaSO4, magma is through being centrifuged Dehydration, the mother liquor after separation can return to absorption tower recycling.
The present invention compared with prior art, has following obvious prominent substantive distinguishing features and remarkable advantage:
1. the method for the present invention is using ferric iron organic complex as absorbing liquid, using ferric iron organic complex salt to H+It is slow Punching acts on, the SO in efficient absorption gas phase2, and with the SO of liquid phase dissolved after absorption3 2-For reducing agent, under the effect of the catalyst, Ferric iron organic complex is reduced to ferrous iron organic complex；Recycle the resulting ferrous iron organic complex of reduction special Property absorb NO in gas phase, form complex compound ferrous iron organic complex-NO；Later, in charcoal catalyst divalent Iron organic complex-NO is decomposed to form ferric iron organic complex and N2, realize the regeneration of absorbing liquid；
2. the method for the present invention had not only realized integrated desulphurization denitration, but also avoided the failure of absorbent, ferrous iron ensure that The regeneration of organic complex with recycle, without other chemicals introduce；Catalysis ferric iron organic complex and ferrous iron have Charcoal needed for machine complex compound circular regeneration has raw material sources extensive, and preparation is simple, reusable feature；
3. the method for the present invention technical process is simple, small investment, operating cost is cheap, and it is convenient to control and operate, easy to spread Using.
Detailed description of the invention
Fig. 1 is SO in one wet type of embodiment of the present invention substep removing flue gas2With the process flow diagram of NO.
Specific embodiment
Above scheme is described further below in conjunction with specific implementation example, the preferred embodiment of the present invention is described in detail such as Under:
Embodiment one:
In the present embodiment, referring to Fig. 1, set up absorbing and purifying device, including first grade absorption tower, regeneration of absorption solution tower 1., Two-level absorption tower, regeneration of absorption solution tower are 2.；SO will be contained2It is drawn with the gas of NO by air-introduced machine, enters first order absorption from tower bottom Tower, regenerable absorbent liquid are the main solution for containing Fe (III) Cit, regenerable absorbent liquid are entered after water pump is pressurized by tower top, gas-liquid Two-phase reverse flow, completes SO in first grade absorption tower2Removing；Purified flue gas enters two-level absorption tower bottom, level-one Absorbing liquid flows into regeneration of absorption solution tower and is 1. regenerated, and after regeneration, the solution for mainly containing Fe (II) Cit is obtained, after regeneration Second level absorbing liquid is squeezed at the top of two-level absorption tower through pump, and the gas in two-level absorption tower containing NO is inversely contacted with absorbing liquid, Complete the removing of NO；The absorbing liquid for having absorbed NO enters regeneration of absorption solution tower and is 2. regenerated, after through pump circulation squeeze into level-one Absorption tower is recycled.
In the present embodiment, referring to Fig. 1,1 part of Fe is weighed2(SO4)3With 2 parts of Na3Cit·2H2O configures to form solution, is used in combination Dilute sulfuric acid adjusts pH to 4.5, as SO in wet process substep removing flue gas2With the absorbing liquid of first grade absorption tower in the technique of NO.
In the present embodiment, referring to Fig. 1, the charcoal is using cornstalk biological matter as raw material, through break process, mistake Sieve, then in N2Under atmosphere, pyrolysis 2h is carried out, is prepared into through 800 DEG C of isothermal pyrolysis methods with the heating rate of 10 DEG C/min To active bio matter；After the catalytic activity of the charcoal reduces, urging for charcoal is maintained by supplementing new charcoal Change activity.Prepare active bio charcoal using corn stover, for regeneration of absorption solution tower 1. with regeneration of absorption solution tower 2. in urged Change redox reaction.
In the present embodiment, referring to Fig. 1, SO in a kind of wet type substep removing flue gas2With the method for NO, to be clean is contained There is SO2First grade absorption tower and two-level absorption tower are successively continuously passed through with the flue gas of NO；
SO in first grade absorption tower, in flue gas2Removal is absorbed after contacting with first order absorption liquid, the flue gas after desulfurization after Continuous to enter two-level absorption tower, the main component of the first order absorption liquid is ironic citrate Fe (III) Cit；Control first order absorption liquid PH value be 4.5, control liquid-gas ratio be 6.0L/m3；
In two-level absorption tower, the NO in flue gas is absorbed removal after contacting with second level absorbing liquid, up to standard after denitration purification Gas discharged；The pH value for controlling second level absorbing liquid is 5.0, and control liquid-gas ratio is 4.0L/m3；
Be additionally provided with regenerator 1. with regenerator 2., the regeneration of the absorbing liquid in absorption towers at different levels can be carried out respectively；
First order absorption liquid absorbs the SO in flue gas in first grade absorption tower2Afterwards, formed sulphur-containing solution, make sulphur-containing solution into Enter the regenerator of absorbing liquid 1., the control sulphur-containing solution residence time is 1.0min, and Fe (III) Cit in sulphur-containing solution is converted Regenerated second level absorption liquid pH is adjusted to 5.0, and pass through to form second level absorbing liquid after regeneration for Fe (III) Cit Regenerated second level absorbing liquid is squeezed into two-level absorption tower and carries out denitrating technique by pump；The regenerator 1. in, by regenerative response Sodium sulfate crystal is precipitated after low temperature crystallization in the solution for forming sulfate ion afterwards, thus separated in absorbing liquid, as Industrial raw materials, crystalline mother solution are transported into two-level absorption tower and continue to use as second level absorbing liquid is formed after regeneration；
After second level absorbing liquid is completed to the absorption of NO in flue gas in two-level absorption tower, is formed and contain nitrogen solution, made nitrogenous molten 2. liquid enters the regenerator of absorbing liquid, the control sulphur-containing solution residence time is 5.0min, will be containing Fe (III) Cit in nitrogen solution It is converted into Fe (III) Cit, to form first order absorption liquid after regeneration, regenerated first order absorption liquid pH is adjusted to 4.5, And first grade absorption tower is squeezed into through other pump, the liquid measure of first order absorption liquid is supplemented, sulfur removal technology is carried out；It is followed to form absorbing liquid Ring regeneration and lasting use, realize the integral process process of wet type substep desulphurization denitration.The present embodiment uses single complexing agent Ironic citrate (Fe (III)-Cit) substep absorbs SO2With the technique of NO, avoids not interfereing with each other, utilize SO2Also with NO autoxidation Originality realizes Fe (III)-Cit regeneration cycle, avoids the chemical cost of desulfurization and denitration, significantly using charcoal as catalyst Reduce operating cost.The present embodiment efficient absorption removes SO in flue gas2And NO, reduction chemical consumption as far as possible is mesh Mark, with ironic citrate (Fe (III) Cit) for absorbent, using citrate to SO2Efficient absorption and-Cit couples of Fe (II) The specific absorption substep of NO realizes the removal to two kinds of pollutants；SO is utilized simultaneously2With the oxidation-reduction quality of NO itself, Using charcoal as catalyst, accelerate electronics transfer, the Efficient Conversion between Fe (III) Cit/Fe (II) Cit is realized, to protect Demonstrate,prove the regeneration cycle of absorbent and the integration of desulphurization denitration.
Experimental test and analysis:
The present embodiment absorbing liquid comes into full contact in two-stage rotating stream tray scrubber with polluted gas, is respectively completed SO2With taking off for NO It removes, through detecting SO2Removal efficiency can achieve the removal efficiency of 90~95%, NO and can achieve 82%~91%.
The present embodiment is using Fe (III) Cit as absorbing liquid, using citrate to H+Buffer function, efficient absorption gas phase In SO2, and with the SO of liquid phase dissolved after absorption3 2-Fe (III) Cit is reduced under the effect of the catalyst for reducing agent Fe(II)Cit；It recycles resulting Fe (II) Cit of reduction specifically to absorb the NO in gas phase, is formed complex compound Fe (II) Cit-NO；Later, Fe (III) Cit and N is decomposed to form in charcoal catalyst Fe (II) Cit-NO2, realize absorbing liquid Regeneration；The present invention had not only realized integrated desulphurization denitration, but also avoided the failure of absorbent, ensure that the regeneration of Fe (II) Cit With recycle, without other chemicals introduce.Charcoal needed for being catalyzed Fe (III) Cit/Fe (II) Cit circular regeneration, tool Have that raw material sources are extensive, preparation is simple, and reusable feature, entire technical process is simple, small investment, and operating cost is low It is honest and clean.
Embodiment two:
The present embodiment is basically the same as the first embodiment, and is particular in that:
In the present embodiment, set up absorbing and purifying device, including first grade absorption tower, regeneration of absorption solution tower 1., second level absorb Tower, regeneration of absorption solution tower are 2.；SO will be contained2It is drawn with the gas of NO by air-introduced machine, enters first grade absorption tower from tower bottom, regeneration is inhaled Receiving liquid is the main solution for containing Fe (III) Cit, regenerable absorbent liquid is entered after water pump is pressurized by tower top, gas-liquid two-phase is reverse Flowing, completes SO in first grade absorption tower2Removing；Purified flue gas enters two-level absorption tower bottom, first order absorption liquid stream Enter regeneration of absorption solution tower 1. to be regenerated, after regeneration, obtains the solution for mainly containing Fe (II) Cit, the second level after regeneration is absorbed Liquid is squeezed at the top of two-level absorption tower through pump, and the gas in two-level absorption tower containing NO is inversely contacted with absorbing liquid, completes NO's Removing；The absorbing liquid for having absorbed NO enters regeneration of absorption solution tower and is 2. regenerated, after squeeze into first grade absorption tower through pump circulation and follow Ring uses.
In the present embodiment, 1 part of Fe is weighed2(SO4)3With 2 parts of Na3Cit·2H2O configures to form solution, and with dilute sulfuric acid tune PH to 5.5 is saved, as SO in wet process substep removing flue gas2With the absorbing liquid of first grade absorption tower in the technique of NO.
In the present embodiment, referring to Fig. 1, the charcoal is using discarded sawdust biomass as raw material, through break process, mistake Sieve, then in N2Under atmosphere, pyrolysis 2h is carried out through 500 DEG C and 800 DEG C of isothermal pyrolysis methods with the heating rate of 10 DEG C/min, Active bio matter is prepared；After the catalytic activity of the charcoal reduces, biology is maintained by supplementing new charcoal The catalytic activity of charcoal.Prepare active bio charcoal using discarded sawdust, for regeneration of absorption solution tower 1. with regeneration of absorption solution tower 2. in Carry out catalytic oxidation-reduction reaction.
In the present embodiment, SO in a kind of wet type substep removing flue gas2With the method for NO, to be clean is contained into SO2And NO Flue gas be successively continuously passed through first grade absorption tower and two-level absorption tower；
SO in first grade absorption tower, in flue gas2Removal is absorbed after contacting with first order absorption liquid, the flue gas after desulfurization after Continuous to enter two-level absorption tower, the main component of the first order absorption liquid is ironic citrate Fe (III) Cit；Control first order absorption liquid PH value be 5.5, control liquid-gas ratio be 6.0L/m3；
In two-level absorption tower, the NO in flue gas is absorbed removal after contacting with second level absorbing liquid, up to standard after denitration purification Gas discharged；The pH value for controlling second level absorbing liquid is 6.0, and control liquid-gas ratio is 4.0L/m3；
Be additionally provided with regenerator 1. with regenerator 2., the regeneration of the absorbing liquid in absorption towers at different levels can be carried out respectively；
First order absorption liquid absorbs the SO in flue gas in first grade absorption tower2Afterwards, formed sulphur-containing solution, make sulphur-containing solution into Enter the regenerator of absorbing liquid 1., the control sulphur-containing solution residence time is 1.0min, and Fe (III) Cit in sulphur-containing solution is converted Regenerated second level absorption liquid pH is adjusted to 6.0, and pass through to form second level absorbing liquid after regeneration for Fe (III) Cit Regenerated second level absorbing liquid is squeezed into two-level absorption tower and carries out denitrating technique by pump；The regenerator 1. in, by regenerative response Sodium sulfate crystal is precipitated after low temperature crystallization in the solution for forming sulfate ion afterwards, thus separated in absorbing liquid, as Industrial raw materials, crystalline mother solution are transported into two-level absorption tower and continue to use as second level absorbing liquid is formed after regeneration；
After second level absorbing liquid is completed to the absorption of NO in flue gas in two-level absorption tower, is formed and contain nitrogen solution, made nitrogenous molten 2. liquid enters the regenerator of absorbing liquid, the control sulphur-containing solution residence time is 5.0min, will be containing Fe (III) Cit in nitrogen solution It is converted into Fe (III) Cit, to form first order absorption liquid after regeneration, regenerated first order absorption liquid pH is adjusted to 5.5, And first grade absorption tower is squeezed into through other pump, the liquid measure of first order absorption liquid is supplemented, sulfur removal technology is carried out；It is followed to form absorbing liquid Ring regeneration and lasting use, realize the integral process process of wet type substep desulphurization denitration.The present embodiment uses single complexing agent Ironic citrate (Fe (III)-Cit) substep absorbs SO2With the technique of NO, avoids not interfereing with each other, utilize SO2Also with NO autoxidation Originality realizes Fe (III)-Cit regeneration cycle, avoids the chemical cost of desulfurization and denitration, significantly using charcoal as catalyst Reduce operating cost.The present embodiment efficient absorption removes SO in flue gas2And NO, reduction chemical consumption as far as possible is mesh Mark, with ironic citrate (Fe (III) Cit) for absorbent, using citrate to SO2Efficient absorption and-Cit couples of Fe (II) The specific absorption substep of NO realizes the removal to two kinds of pollutants；SO is utilized simultaneously2With the oxidation-reduction quality of NO itself, Using charcoal as catalyst, accelerate electronics transfer, the Efficient Conversion between Fe (III) Cit/Fe (II) Cit is realized, to protect Demonstrate,prove the regeneration cycle of absorbent and the integration of desulphurization denitration.
Experimental test and analysis:
The present embodiment absorbing liquid comes into full contact in two-stage rotating stream tray scrubber with polluted gas, is respectively completed SO2With taking off for NO It removes, through detecting SO2Removal efficiency can achieve the removal efficiency of 92~98%, NO and can achieve 73%~84%.
The present embodiment is using Fe (III) Cit as absorbing liquid, using citrate to H+Buffer function, efficient absorption gas phase In SO2, and with the SO of liquid phase dissolved after absorption3 2-Fe (III) Cit is reduced under the effect of the catalyst for reducing agent Fe(II)Cit；It recycles resulting Fe (II) Cit of reduction specifically to absorb the NO in gas phase, is formed complex compound Fe (II) Cit-NO；Later, Fe (III) Cit and N is decomposed to form in charcoal catalyst Fe (II) Cit-NO2, realize absorbing liquid Regeneration；The present invention had not only realized integrated desulphurization denitration, but also avoided the failure of absorbent, ensure that the regeneration of Fe (II) Cit With recycle, without other chemicals introduce.Charcoal needed for being catalyzed Fe (III) Cit/Fe (II) Cit circular regeneration, tool Have that raw material sources are extensive, preparation is simple, and reusable feature, entire technical process is simple, small investment, and operating cost is low It is honest and clean.
Embodiment three:
The present embodiment is substantially the same as in the previous example, and is particular in that:
In the present embodiment, set up absorbing and purifying device, including first grade absorption tower, regeneration of absorption solution tower 1., second level absorb Tower, regeneration of absorption solution tower are 2.；SO will be contained2It is drawn with the gas of NO by air-introduced machine, enters first grade absorption tower from tower bottom, regeneration is inhaled Receiving liquid is the main solution for containing Fe (III) EDTA, regenerable absorbent liquid is entered after water pump is pressurized by tower top, gas-liquid two-phase is reverse Flowing, completes SO in first grade absorption tower2Removing；Purified flue gas enters two-level absorption tower bottom, first order absorption liquid stream Enter regeneration of absorption solution tower 1. to be regenerated, after regeneration, obtains the solution for mainly containing Fe (II) EDTA, the second level after regeneration is absorbed Liquid is squeezed at the top of two-level absorption tower through pump, and the gas in two-level absorption tower containing NO is inversely contacted with absorbing liquid, completes NO's Removing；The absorbing liquid for having absorbed NO enters regeneration of absorption solution tower and is 2. regenerated, after squeeze into first grade absorption tower through pump circulation and follow Ring uses.
In the present embodiment, 1 part of Fe is weighed2(SO4)3With 2 parts of Na3EDTA·2H2O configures to form solution, and uses dilute sulfuric acid PH to 4.5 is adjusted, as SO in wet process substep removing flue gas2With the absorbing liquid of first grade absorption tower in the technique of NO.
In the present embodiment, referring to Fig. 1, the charcoal is using discarded sawdust biomass as raw material, through break process, mistake Sieve, then in N2Under atmosphere, pyrolysis 2h is carried out through 700 DEG C and 800 DEG C of isothermal pyrolysis methods with the heating rate of 10 DEG C/min, Active bio matter is prepared；After the catalytic activity of the charcoal reduces, biology is maintained by supplementing new charcoal The catalytic activity of charcoal.Prepare active bio charcoal using discarded sawdust, for regeneration of absorption solution tower 1. with regeneration of absorption solution tower 2. in Carry out catalytic oxidation-reduction reaction.
In the present embodiment, SO in a kind of wet type substep removing flue gas2With the method for NO, to be clean is contained into SO2And NO Flue gas be successively continuously passed through first grade absorption tower and two-level absorption tower；
SO in first grade absorption tower, in flue gas2Removal is absorbed after contacting with first order absorption liquid, the flue gas after desulfurization after Continuous to enter two-level absorption tower, the main component of the first order absorption liquid is Fe (III) EDTA；Control first order absorption liquid pH value be 4.5, control liquid-gas ratio is 6.0L/m3；
In two-level absorption tower, the NO in flue gas is absorbed removal after contacting with second level absorbing liquid, up to standard after denitration purification Gas discharged；The pH value for controlling second level absorbing liquid is 5.0, and control liquid-gas ratio is 4.0L/m3；
Be additionally provided with regenerator 1. with regenerator 2., the regeneration of the absorbing liquid in absorption towers at different levels can be carried out respectively；
First order absorption liquid absorbs the SO in flue gas in first grade absorption tower2Afterwards, formed sulphur-containing solution, make sulphur-containing solution into Enter the regenerator of absorbing liquid 1., the control sulphur-containing solution residence time is 1.0min, and Fe (III) EDTA in sulphur-containing solution is converted Regenerated second level absorption liquid pH is adjusted to 5.0, and pass through to form second level absorbing liquid after regeneration for Fe (III) EDTA Regenerated second level absorbing liquid is squeezed into two-level absorption tower and carries out denitrating technique by pump；The regenerator 1. in, by regenerative response Sodium sulfate crystal is precipitated after low temperature crystallization in the solution for forming sulfate ion afterwards, thus separated in absorbing liquid, as Industrial raw materials, crystalline mother solution are transported into two-level absorption tower and continue to use as second level absorbing liquid is formed after regeneration；
After second level absorbing liquid is completed to the absorption of NO in flue gas in two-level absorption tower, is formed and contain nitrogen solution, made nitrogenous molten 2. liquid enters the regenerator of absorbing liquid, the control sulphur-containing solution residence time is 5.0min, will be containing Fe (III) EDTA in nitrogen solution It is converted into Fe (III) EDTA, to form first order absorption liquid after regeneration, regenerated first order absorption liquid pH is adjusted to 4.5, And first grade absorption tower is squeezed into through other pump, the liquid measure of first order absorption liquid is supplemented, sulfur removal technology is carried out；It is followed to form absorbing liquid Ring regeneration and lasting use, realize the integral process process of wet type substep desulphurization denitration.The present embodiment uses single complexing agent Fe (III) EDTA substep absorbs SO2With the technique of NO, avoids not interfereing with each other, utilize SO2With NO disproportionation, with biology Charcoal is catalyst, realizes Fe (III)-EDTA regeneration cycle, avoids the chemical cost of desulfurization and denitration, greatly reduce operation Cost.The present embodiment efficient absorption removes SO in flue gas2And NO, reduction chemical consumption as far as possible is target, with Fe (III) EDTA is absorbent, using Fe (III) EDTA to SO2Efficient absorption and Fe (II) EDTA to the specific absorption of NO Substep realizes the removal to two kinds of pollutants；SO is utilized simultaneously2With the oxidation-reduction quality of NO itself, using charcoal as catalysis Electronics transfer is accelerated in agent, the Efficient Conversion between Fe (III) EDTA/Fe (II) EDTA is realized, to guarantee the regeneration of absorbent The integration of circulation and desulphurization denitration.
Experimental test and analysis:
The present embodiment absorbing liquid comes into full contact in two-stage rotating stream tray scrubber with polluted gas, is respectively completed SO2With taking off for NO It removes, through detecting SO2Removal efficiency can achieve the removal efficiency of 91~95%, NO and can achieve 84~93%.
The present embodiment is using Fe (III) EDTA as absorbing liquid, using Fe (III) EDTA to H+Buffer function, efficient absorption SO in gas phase2, and with the SO of liquid phase dissolved after absorption3 2-For reducing agent, under the effect of the catalyst, also by Fe (III) EDTA It originally is Fe (II) EDTA；It recycles resulting Fe (II) EDTA of reduction specifically to absorb the NO in gas phase, forms complex compound Fe (II)EDTA-NO；Later, Fe (III) EDTA and N is decomposed to form in charcoal catalyst Fe (II) EDTA-NO2, realize The regeneration of absorbing liquid；The present invention had not only realized integrated desulphurization denitration, but also avoided the failure of absorbent, ensure that Fe (II) The regeneration of EDTA with recycle, without other chemicals introduce.It is catalyzed Fe (III) EDTA/Fe (II) EDTA circular regeneration institute The charcoal needed has raw material sources extensive, and preparation is simple, and reusable feature, entire technical process is simple, investment Few, operating cost is cheap.
Example IV:
The present embodiment is substantially the same as in the previous example, and is particular in that:
In the present embodiment, set up absorbing and purifying device, including first grade absorption tower, regeneration of absorption solution tower 1., second level absorb Tower, regeneration of absorption solution tower are 2.；SO will be contained2It is drawn with the gas of NO by air-introduced machine, enters first grade absorption tower from tower bottom, regeneration is inhaled Receiving liquid is the main solution for containing Fe (III) EDTA, regenerable absorbent liquid is entered after water pump is pressurized by tower top, gas-liquid two-phase is reverse Flowing, completes SO in first grade absorption tower2Removing；Purified flue gas enters two-level absorption tower bottom, first order absorption liquid stream Enter regeneration of absorption solution tower 1. to be regenerated, after regeneration, obtains the solution for mainly containing Fe (II) EDTA, the second level after regeneration is absorbed Liquid is squeezed at the top of two-level absorption tower through pump, and the gas in two-level absorption tower containing NO is inversely contacted with absorbing liquid, completes NO's Removing；The absorbing liquid for having absorbed NO enters regeneration of absorption solution tower and is 2. regenerated, after squeeze into first grade absorption tower through pump circulation and follow Ring uses.
In the present embodiment, 1 part of Fe is weighed2(SO4)3With 2 parts of Na3EDTA·2H2O configures to form solution, and uses dilute sulfuric acid PH to 5.5 is adjusted, as SO in wet process substep removing flue gas2With the absorbing liquid of first grade absorption tower in the technique of NO.
In the present embodiment, referring to Fig. 1, the charcoal is using discarded sawdust biomass as raw material, through break process, mistake Sieve, then in N2Under atmosphere, pyrolysis 2h is carried out through 700 DEG C and 800 DEG C of isothermal pyrolysis methods with the heating rate of 10 DEG C/min, Active bio matter is prepared；After the catalytic activity of the charcoal reduces, biology is maintained by supplementing new charcoal The catalytic activity of charcoal.Prepare active bio charcoal using discarded sawdust, for regeneration of absorption solution tower 1. with regeneration of absorption solution tower 2. in Carry out catalytic oxidation-reduction reaction.
In the present embodiment, SO in a kind of wet type substep removing flue gas2With the method for NO, to be clean is contained into SO2And NO Flue gas be successively continuously passed through first grade absorption tower and two-level absorption tower；
SO in first grade absorption tower, in flue gas2Removal is absorbed after contacting with first order absorption liquid, the flue gas after desulfurization after Continuous to enter two-level absorption tower, the main component of the first order absorption liquid is Fe (III) EDTA；Control first order absorption liquid pH value be 5.5, control liquid-gas ratio is 6.0L/m3；
In two-level absorption tower, the NO in flue gas is absorbed removal after contacting with second level absorbing liquid, up to standard after denitration purification Gas discharged；The pH value for controlling second level absorbing liquid is 6.0, and control liquid-gas ratio is 4.0L/m3；
Be additionally provided with regenerator 1. with regenerator 2., the regeneration of the absorbing liquid in absorption towers at different levels can be carried out respectively；
First order absorption liquid absorbs the SO in flue gas in first grade absorption tower2Afterwards, formed sulphur-containing solution, make sulphur-containing solution into Enter the regenerator of absorbing liquid 1., the control sulphur-containing solution residence time is 1.0min, and Fe (III) EDTA in sulphur-containing solution is converted Regenerated second level absorption liquid pH is adjusted to 6.0, and pass through to form second level absorbing liquid after regeneration for Fe (III) EDTA Regenerated second level absorbing liquid is squeezed into two-level absorption tower and carries out denitrating technique by pump；The regenerator 1. in, by regenerative response Sodium sulfate crystal is precipitated after low temperature crystallization in the solution for forming sulfate ion afterwards, thus separated in absorbing liquid, as Industrial raw materials, crystalline mother solution are transported into two-level absorption tower and continue to use as second level absorbing liquid is formed after regeneration；
After second level absorbing liquid is completed to the absorption of NO in flue gas in two-level absorption tower, is formed and contain nitrogen solution, made nitrogenous molten 2. liquid enters the regenerator of absorbing liquid, the control sulphur-containing solution residence time is 5.0min, will be containing Fe (III) EDTA in nitrogen solution It is converted into Fe (III) EDTA, to form first order absorption liquid after regeneration, regenerated first order absorption liquid pH is adjusted to 5.5, And first grade absorption tower is squeezed into through other pump, the liquid measure of first order absorption liquid is supplemented, sulfur removal technology is carried out；It is followed to form absorbing liquid Ring regeneration and lasting use, realize the integral process process of wet type substep desulphurization denitration.The present embodiment uses single complexing agent Fe (III) EDTA substep absorbs SO2With the technique of NO, avoids not interfereing with each other, utilize SO2With NO disproportionation, with biology Charcoal is catalyst, realizes Fe (III)-EDTA regeneration cycle, avoids the chemical cost of desulfurization and denitration, greatly reduce operation Cost.The present embodiment efficient absorption removes SO in flue gas2And NO, reduction chemical consumption as far as possible is target, with Fe (III) EDTA is absorbent, using Fe (III) EDTA to SO2Efficient absorption and Fe (II) EDTA to the specific absorption of NO Substep realizes the removal to two kinds of pollutants；SO is utilized simultaneously2With the oxidation-reduction quality of NO itself, using charcoal as catalysis Electronics transfer is accelerated in agent, the Efficient Conversion between Fe (III) EDTA/Fe (II) EDTA is realized, to guarantee the regeneration of absorbent The integration of circulation and desulphurization denitration.
Experimental test and analysis:
The present embodiment absorbing liquid comes into full contact in two-stage rotating stream tray scrubber with polluted gas, is respectively completed SO2With taking off for NO It removes, through detecting SO2Removal efficiency can achieve the removal efficiency of 90~94%, NO and can achieve 79~88%.
The present embodiment is using Fe (III) EDTA as absorbing liquid, using Fe (III) EDTA to H+Buffer function, efficient absorption SO in gas phase2, and with the SO of liquid phase dissolved after absorption3 2-For reducing agent, under the effect of the catalyst, also by Fe (III) EDTA It originally is Fe (II) EDTA；It recycles resulting Fe (II) EDTA of reduction specifically to absorb the NO in gas phase, forms complex compound Fe (II)EDTA-NO；Later, Fe (III) EDTA and N is decomposed to form in charcoal catalyst Fe (II) EDTA-NO2, realize The regeneration of absorbing liquid；The present invention had not only realized integrated desulphurization denitration, but also avoided the failure of absorbent, ensure that Fe (II) The regeneration of EDTA with recycle, without other chemicals introduce.It is catalyzed Fe (III) EDTA/Fe (II) EDTA circular regeneration institute The charcoal needed has raw material sources extensive, and preparation is simple, and reusable feature, entire technical process is simple, investment Few, operating cost is cheap.
Embodiment five: the present embodiment is substantially the same as in the previous example, and is particular in that:
In the present embodiment, set up absorbing and purifying device, including first grade absorption tower, regeneration of absorption solution tower 1., second level absorb Tower, regeneration of absorption solution tower are 2.；SO will be contained2It is drawn with the gas of NO by air-introduced machine, enters first grade absorption tower from tower bottom, regeneration is inhaled Receiving liquid is the main solution for containing Fe (III) NTA, regenerable absorbent liquid is entered after water pump is pressurized by tower top, gas-liquid two-phase is reverse Flowing, completes SO in first grade absorption tower2Removing；Purified flue gas enters two-level absorption tower bottom, first order absorption liquid stream Enter regeneration of absorption solution tower 1. to be regenerated, after regeneration, obtains the solution for mainly containing Fe (II) NTA, the second level after regeneration is absorbed Liquid is squeezed at the top of two-level absorption tower through pump, and the gas in two-level absorption tower containing NO is inversely contacted with absorbing liquid, completes NO's Removing；The absorbing liquid for having absorbed NO enters regeneration of absorption solution tower and is 2. regenerated, after squeeze into first grade absorption tower through pump circulation and follow Ring uses.
In the present embodiment, 1 part of Fe is weighed2(SO4)3With 2 parts of Na3NTA·2H2O configures to form solution, and with dilute sulfuric acid tune PH to 4.5 is saved, as SO in wet process substep removing flue gas2With the absorbing liquid of first grade absorption tower in the technique of NO.
In the present embodiment, referring to Fig. 1, the charcoal is using discarded sawdust biomass as raw material, through break process, mistake Sieve, then in N2Under atmosphere, pyrolysis 2h is carried out through 700 DEG C and 800 DEG C of isothermal pyrolysis methods with the heating rate of 10 DEG C/min, Active bio matter is prepared；After the catalytic activity of the charcoal reduces, biology is maintained by supplementing new charcoal The catalytic activity of charcoal.Prepare active bio charcoal using discarded sawdust, for regeneration of absorption solution tower 1. with regeneration of absorption solution tower 2. in Carry out catalytic oxidation-reduction reaction.
In the present embodiment, SO in a kind of wet type substep removing flue gas2With the method for NO, to be clean is contained into SO2And NO Flue gas be successively continuously passed through first grade absorption tower and two-level absorption tower；
SO in first grade absorption tower, in flue gas2Removal is absorbed after contacting with first order absorption liquid, the flue gas after desulfurization after Continuous to enter two-level absorption tower, the main component of the first order absorption liquid is Fe (III) NTA；Control first order absorption liquid pH value be 4.5, control liquid-gas ratio is 6.0L/m3；
In two-level absorption tower, the NO in flue gas is absorbed removal after contacting with second level absorbing liquid, up to standard after denitration purification Gas discharged；The pH value for controlling second level absorbing liquid is 5.0, and control liquid-gas ratio is 4.0L/m3；
Be additionally provided with regenerator 1. with regenerator 2., the regeneration of the absorbing liquid in absorption towers at different levels can be carried out respectively；
First order absorption liquid absorbs the SO in flue gas in first grade absorption tower2Afterwards, formed sulphur-containing solution, make sulphur-containing solution into Enter the regenerator of absorbing liquid 1., the control sulphur-containing solution residence time is 1.0min, and Fe (III) NTA in sulphur-containing solution is converted Regenerated second level absorption liquid pH is adjusted to 5.0, and pass through to form second level absorbing liquid after regeneration for Fe (III) NTA Regenerated second level absorbing liquid is squeezed into two-level absorption tower and carries out denitrating technique by pump；The regenerator 1. in, by regenerative response Sodium sulfate crystal is precipitated after low temperature crystallization in the solution for forming sulfate ion afterwards, thus separated in absorbing liquid, as Industrial raw materials, crystalline mother solution are transported into two-level absorption tower and continue to use as second level absorbing liquid is formed after regeneration；
After second level absorbing liquid is completed to the absorption of NO in flue gas in two-level absorption tower, is formed and contain nitrogen solution, made nitrogenous molten 2. liquid enters the regenerator of absorbing liquid, the control sulphur-containing solution residence time is 5.0min, will be containing Fe (III) NTA in nitrogen solution It is converted into Fe (III) NTA, to form first order absorption liquid after regeneration, regenerated first order absorption liquid pH is adjusted to 4.5, And first grade absorption tower is squeezed into through other pump, the liquid measure of first order absorption liquid is supplemented, sulfur removal technology is carried out；It is followed to form absorbing liquid Ring regeneration and lasting use, realize the integral process process of wet type substep desulphurization denitration.The present embodiment uses single complexing agent Fe (III) NTA substep absorbs SO2With the technique of NO, avoids not interfereing with each other, utilize SO2With NO disproportionation, with biology Charcoal is catalyst, realize Fe (III) NTA regeneration cycle, avoid the chemical cost of desulfurization and denitration, greatly reduce operation at This.The present embodiment efficient absorption removes SO in flue gas2And NO, reduction chemical consumption as far as possible is target, with Fe (III) NTA is absorbent, using Fe (III) NTA to SO2Efficient absorption and Fe (II) NTA to the specific absorption of NO substep Realize the removal to two kinds of pollutants；SO is utilized simultaneously2Added with the oxidation-reduction quality of NO itself using charcoal as catalyst Fast electronics transfer, realize Fe (III) NTA/Fe (II) NTA between Efficient Conversion, thus guarantee absorbent regeneration cycle and The integration of desulphurization denitration.
Experimental test and analysis:
The present embodiment absorbing liquid comes into full contact in two-stage rotating stream tray scrubber with polluted gas, is respectively completed SO2With taking off for NO It removes, through detecting SO2Removal efficiency can achieve the removal efficiency of 92~97%, NO and can achieve 73~82%.
The present embodiment is using Fe (III) NTA as absorbing liquid, using Fe (III) NTA to H+Buffer function, efficient absorption gas SO in phase2, and with the SO of liquid phase dissolved after absorption3 2-Fe (III) NTA is restored under the effect of the catalyst for reducing agent For Fe (II) NTA；It recycles resulting Fe (II) NTA of reduction specifically to absorb the NO in gas phase, is formed complex compound Fe (II) NTA-NO；Later, Fe (III) NTA and N is decomposed to form in charcoal catalyst Fe (II) NTA-NO2, realize absorbing liquid Regeneration；The present invention had not only realized integrated desulphurization denitration, but also avoided the failure of absorbent, ensure that the regeneration of Fe (II) NTA With recycle, without other chemicals introduce.Charcoal needed for being catalyzed Fe (III) NTA/Fe (II) NTA circular regeneration, tool Have that raw material sources are extensive, preparation is simple, and reusable feature, entire technical process is simple, small investment, and operating cost is low It is honest and clean.
Embodiment six:
The present embodiment is substantially the same as in the previous example, and is particular in that:
In the present embodiment, set up absorbing and purifying device, including first grade absorption tower, regeneration of absorption solution tower 1., second level absorb Tower, regeneration of absorption solution tower are 2.；SO will be contained2It is drawn with the gas of NO by air-introduced machine, enters first grade absorption tower from tower bottom, regeneration is inhaled Receiving liquid is the main solution for containing Fe (III) NTA, regenerable absorbent liquid is entered after water pump is pressurized by tower top, gas-liquid two-phase is reverse Flowing, completes SO in first grade absorption tower2Removing；Purified flue gas enters two-level absorption tower bottom, first order absorption liquid stream Enter regeneration of absorption solution tower 1. to be regenerated, after regeneration, obtains the solution for mainly containing Fe (II) NTA, the second level after regeneration is absorbed Liquid is squeezed at the top of two-level absorption tower through pump, and the gas in two-level absorption tower containing NO is inversely contacted with absorbing liquid, completes NO's Removing；The absorbing liquid for having absorbed NO enters regeneration of absorption solution tower and is 2. regenerated, after squeeze into first grade absorption tower through pump circulation and follow Ring uses.
In the present embodiment, 1 part of Fe is weighed2(SO4)3With 2 parts of Na3NTA·2H2O configures to form solution, and with dilute sulfuric acid tune PH to 5.5 is saved, as SO in wet process substep removing flue gas2With the absorbing liquid of first grade absorption tower in the technique of NO.
In the present embodiment, referring to Fig. 1, the charcoal is using discarded sawdust biomass as raw material, through break process, mistake Sieve, then in N2Under atmosphere, pyrolysis 2h is carried out through 700 DEG C and 800 DEG C of isothermal pyrolysis methods with the heating rate of 10 DEG C/min, Active bio matter is prepared；After the catalytic activity of the charcoal reduces, biology is maintained by supplementing new charcoal The catalytic activity of charcoal.Prepare active bio charcoal using discarded sawdust, for regeneration of absorption solution tower 1. with regeneration of absorption solution tower 2. in Carry out catalytic oxidation-reduction reaction.
In the present embodiment, SO in a kind of wet type substep removing flue gas2With the method for NO, to be clean is contained into SO2And NO Flue gas be successively continuously passed through first grade absorption tower and two-level absorption tower；
SO in first grade absorption tower, in flue gas2Removal is absorbed after contacting with first order absorption liquid, the flue gas after desulfurization after Continuous to enter two-level absorption tower, the main component of the first order absorption liquid is Fe (III) NTA；Control first order absorption liquid pH value be 5.5, control liquid-gas ratio is 6.0L/m3；
In two-level absorption tower, the NO in flue gas is absorbed removal after contacting with second level absorbing liquid, up to standard after denitration purification Gas discharged；The pH value for controlling second level absorbing liquid is 6.0, and control liquid-gas ratio is 4.0L/m3；
Be additionally provided with regenerator 1. with regenerator 2., the regeneration of the absorbing liquid in absorption towers at different levels can be carried out respectively；
First order absorption liquid absorbs the SO in flue gas in first grade absorption tower2Afterwards, formed sulphur-containing solution, make sulphur-containing solution into Enter the regenerator of absorbing liquid 1., the control sulphur-containing solution residence time is 1.0min, and Fe (III) NTA in sulphur-containing solution is converted Regenerated second level absorption liquid pH is adjusted to 6.0, and pass through to form second level absorbing liquid after regeneration for Fe (III) NTA Regenerated second level absorbing liquid is squeezed into two-level absorption tower and carries out denitrating technique by pump；The regenerator 1. in, by regenerative response Sodium sulfate crystal is precipitated after low temperature crystallization in the solution for forming sulfate ion afterwards, thus separated in absorbing liquid, as Industrial raw materials, crystalline mother solution are transported into two-level absorption tower and continue to use as second level absorbing liquid is formed after regeneration；
After second level absorbing liquid is completed to the absorption of NO in flue gas in two-level absorption tower, is formed and contain nitrogen solution, made nitrogenous molten 2. liquid enters the regenerator of absorbing liquid, the control sulphur-containing solution residence time is 5.0min, will be containing Fe (III) NTA in nitrogen solution It is converted into Fe (III) NTA, to form first order absorption liquid after regeneration, regenerated first order absorption liquid pH is adjusted to 5.5, And first grade absorption tower is squeezed into through other pump, the liquid measure of first order absorption liquid is supplemented, sulfur removal technology is carried out；It is followed to form absorbing liquid Ring regeneration and lasting use, realize the integral process process of wet type substep desulphurization denitration.The present embodiment uses single complexing agent Fe (III) NTA substep absorbs SO2With the technique of NO, avoids not interfereing with each other, utilize SO2With NO disproportionation, with biology Charcoal is catalyst, realizes Fe (III)-NTA regeneration cycle, avoids the chemical cost of desulfurization and denitration, greatly reduce operation Cost.The present embodiment efficient absorption removes SO in flue gas2And NO, reduction chemical consumption as far as possible is target, with Fe (III) NTA is absorbent, using Fe (III) NTA to SO2Efficient absorption and Fe (II) NTA to the specific absorption of NO substep Realize the removal to two kinds of pollutants；SO is utilized simultaneously2Added with the oxidation-reduction quality of NO itself using charcoal as catalyst Fast electronics transfer, realize Fe (III) NTA/Fe (II) NTA between Efficient Conversion, thus guarantee absorbent regeneration cycle and The integration of desulphurization denitration.
Experimental test and analysis:
The present embodiment absorbing liquid comes into full contact in two-stage rotating stream tray scrubber with polluted gas, is respectively completed SO2With taking off for NO It removes, through detecting SO2Removal efficiency can achieve the removal efficiency of 91~97%, NO and can achieve 65~76%.
The present embodiment is using Fe (III) NTA as absorbing liquid, using Fe (III) NTA to H+Buffer function, efficient absorption gas SO in phase2, and with the SO of liquid phase dissolved after absorption3 2-Fe (III) NTA is restored under the effect of the catalyst for reducing agent For Fe (II) NTA；It recycles resulting Fe (II) NTA of reduction specifically to absorb the NO in gas phase, is formed complex compound Fe (II) NTA-NO；Later, Fe (III) NTA and N is decomposed to form in charcoal catalyst Fe (II) NTA-NO2, realize absorbing liquid Regeneration；The present invention had not only realized integrated desulphurization denitration, but also avoided the failure of absorbent, ensure that the regeneration of Fe (II) NTA With recycle, without other chemicals introduce.Charcoal needed for being catalyzed Fe (III) NTA/Fe (II) NTA circular regeneration, tool Have that raw material sources are extensive, preparation is simple, and reusable feature, entire technical process is simple, small investment, and operating cost is low It is honest and clean.
The above embodiment of the present invention method wet type substep removing sulfur dioxide in flue gas (SO2) and nitric oxide (NO), it will Flue gas to be clean is continuously passed through first grade absorption tower and two-level absorption tower；SO in first grade absorption tower, in flue gas2It is inhaled with level-one It is absorbed removal after receiving liquid contact, in two-level absorption tower, the NO in flue gas is absorbed removal after contacting with second level absorbing liquid, only Gas discharge after change；The first order absorption liquid is ferric iron organic complex solution, and pH value controls between 4.0~6.0； First order absorption liquid has absorbed SO2Enter regenerator 1. afterwards, under the catalytic action of biological Pd/carbon catalyst, ferric iron organic complex It is converted into ferrous iron organic complex, pH is adjusted 5.0~6.0, enters back into two-level absorption tower and used as second level absorbing liquid； After second level absorbing liquid complexed absorption NO, 2. into regenerator, it is organic to change ferric iron under the catalytic action of biological Pd/carbon catalyst Complex compound, regenerated absorbing liquid enter back into first grade absorption tower, are recycled in systems.The biological Pd/carbon catalyst is by biology Matter is in N2Under atmosphere, 300~800 DEG C of pyrolysis at least 2h are obtained.SO in flue gas may be implemented2It is removed with the substep efficient green of NO, Absorbent Fe (III) Cit used can be recycled, and removal process is without adding other desulphurization denitration chemical agents.
Combination attached drawing of the embodiment of the present invention is illustrated above, but the present invention is not limited to the above embodiments, it can be with The purpose of innovation and creation according to the present invention makes a variety of variations, under the Spirit Essence and principle of all technical solutions according to the present invention Change, modification, substitution, combination or the simplification made, should be equivalent substitute mode, as long as meeting goal of the invention of the invention, Without departing from SO in wet type substep removing flue gas of the present invention2With the technical principle and inventive concept of the method for NO, this is belonged to The protection scope of invention.

Claims (7)

1. SO in a kind of wet type substep removing flue gas2With the method for NO, it is characterised in that: to be clean is contained SO2With the cigarette of NO Gas is successively continuously passed through first grade absorption tower and two-level absorption tower；
SO in first grade absorption tower, in flue gas2Removal is absorbed after contacting with first order absorption liquid, the flue gas after desulfurization continue into Enter two-level absorption tower, the main component of the first order absorption liquid is ferric iron organic complex；
In two-level absorption tower, the NO in flue gas is absorbed removal after contacting with second level absorbing liquid, gas up to standard after denitration purification Body is discharged；
Be additionally provided with regenerator 1. with regenerator 2., the regeneration of the absorbing liquid in absorption towers at different levels can be carried out respectively；
First order absorption liquid absorbs the SO in flue gas in first grade absorption tower2Afterwards, sulphur-containing solution is formed, sulphur-containing solution is made to enter suction 1. the regenerator for receiving liquid, converts ferrous iron organic complex for the ferric iron organic complex in sulphur-containing solution, thus by Second level absorbing liquid is formed after regeneration, and is pumped and regenerated second level absorbing liquid is squeezed into two-level absorption tower progress denitrating technique；
In two-level absorption tower second level absorbing liquid complete to the absorption of NO in flue gas after, formed contain nitrogen solution, make containing nitrogen solution into 2. the regenerator for entering absorbing liquid, will be converted into ferric iron organic complex containing the ferrous iron organic complex in nitrogen solution, thus First order absorption liquid is formed after regeneration, and squeezes into first grade absorption tower through other pump, is supplemented the liquid measure of first order absorption liquid, is carried out Sulfur removal technology；To form absorbing liquid circular regeneration and lasting use, the integral process mistake of wet type substep desulphurization denitration is realized Journey.
2. SO in wet type substep removing flue gas according to claim 12With the method for NO, it is characterised in that:
The main component of first order absorption liquid be ironic citrate (Fe (III) Cit, Fe (III) EDTA and Fe (III) NTA) at least A kind of ferric iron organic complex；
Regenerator 1. in, under the catalytic action of charcoal, the ferric iron organic complex in sulphur-containing solution is converted into Fe (II) Cit, Fe (II) EDTA and Fe (II) NTA) at least one of ferrous iron organic complex, control the sulphur-containing solution residence time For 0.5~2min, the obtained second level absorption liquid pH containing ferrous iron organic complex is adjusted to 5.0~6.0, is then conveyed Into two-level absorption tower, denitrating technique is carried out；
Regenerator 2. in, under the catalytic action of charcoal, be converted into Fe containing the ferrous iron organic complex in nitrogen solution (III) Cit, Fe (III) EDTA and Fe (III) NTA) at least one of ferric iron organic complex, control nitrogenous Solution dwell Time is 1.2~7.2min, then delivers into first grade absorption tower, sulfur removal technology is carried out, to form absorbing liquid circular regeneration With lasting use.
3. SO in wet type substep removing flue gas according to claim 22With the method for NO, it is characterised in that: the charcoal is Using biomass as raw material, through break process, sieving, then in N2Under atmosphere, to be not less than the heating rate of 10 DEG C/min, warp 300~800 DEG C of isothermal pyrolysis methods, are pyrolyzed at least 2h, and active bio matter is prepared；When the catalysis of the charcoal After activity reduces, the catalytic activity of charcoal is maintained by supplementing new charcoal.
4. SO in wet type substep removing flue gas according to claim 12With the method for NO, it is characterised in that: in the regenerator 1. in, the solution of sulfate ion is formed after regenerative response, after low temperature crystallization, sodium sulfate crystal is precipitated, to absorb It is separated in liquid, as industrial raw materials, crystalline mother solution is transported into second level suction as second level absorbing liquid is formed after regeneration Tower is received to continue to use.
5. SO in wet type substep removing flue gas according to claim 12With the method for NO, it is characterised in that: in first grade absorption tower In, the pH value of control first order absorption liquid is 4.0~6.0, and control liquid-gas ratio is 4.2~12.0L/m3。
6. SO in wet type substep removing flue gas according to claim 52With the method for NO, it is characterised in that: in first grade absorption tower In, the pH value of control first order absorption liquid is 4.5~5.5.
7. SO in wet type substep removing flue gas according to claim 12With the method for NO, it is characterised in that: in two-level absorption tower In, the pH value of control first order absorption liquid is 5.0~6.0, and control liquid-gas ratio is 2.0~6.0L/m3。
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