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 PDFInfo
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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
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- flue gas
- absorption tower
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- 238000010521 absorption reaction Methods 0.000 claims abstract description 337
- 239000007788 liquid Substances 0.000 claims abstract description 264
- 239000003546 flue gas Substances 0.000 claims abstract description 111
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 89
- 238000000034 method Methods 0.000 claims abstract description 82
- UGFAIRIUMAVXCW-UHFFFAOYSA-N carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 73
- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulfur dioxide Inorganic materials O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 67
- 239000007789 gas Substances 0.000 claims abstract description 64
- 230000003197 catalytic Effects 0.000 claims abstract description 27
- 238000004140 cleaning Methods 0.000 claims abstract description 15
- 230000008929 regeneration Effects 0.000 claims description 139
- 238000011069 regeneration method Methods 0.000 claims description 139
- 239000000243 solution Substances 0.000 claims description 137
- VTLYFUHAOXGGBS-UHFFFAOYSA-N fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 120
- 239000003610 charcoal Substances 0.000 claims description 76
- KCXVZYZYPLLWCC-UHFFFAOYSA-N edta Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 57
- NINIDFKCEFEMDL-UHFFFAOYSA-N sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 50
- 239000005864 Sulphur Substances 0.000 claims description 41
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 38
- CWYNVVGOOAEACU-UHFFFAOYSA-N fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 30
- 239000002994 raw material Substances 0.000 claims description 24
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 23
- 230000003009 desulfurizing Effects 0.000 claims description 19
- 229910052757 nitrogen Inorganic materials 0.000 claims description 19
- 238000006477 desulfuration reaction Methods 0.000 claims description 18
- 230000024881 catalytic activity Effects 0.000 claims description 16
- 238000005516 engineering process Methods 0.000 claims description 15
- KRKNYBCHXYNGOX-UHFFFAOYSA-K 2qpq Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 13
- 230000000694 effects Effects 0.000 claims description 11
- 238000000746 purification Methods 0.000 claims description 11
- 229910052717 sulfur Inorganic materials 0.000 claims description 10
- 239000011593 sulfur Substances 0.000 claims description 10
- 238000002425 crystallisation Methods 0.000 claims description 9
- 230000005712 crystallization Effects 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000001480 isothermal pyrolysis Methods 0.000 claims description 9
- 230000002045 lasting Effects 0.000 claims description 9
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 9
- 239000002028 Biomass Substances 0.000 claims description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L na2so4 Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 8
- 230000001172 regenerating Effects 0.000 claims description 8
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 8
- 235000011152 sodium sulphate Nutrition 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 8
- 230000001502 supplementation Effects 0.000 claims description 8
- 239000010413 mother solution Substances 0.000 claims description 7
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- 238000007873 sieving Methods 0.000 claims description 2
- 235000019504 cigarettes Nutrition 0.000 claims 1
- 239000002250 absorbent Substances 0.000 abstract description 33
- 230000002745 absorbent Effects 0.000 abstract description 33
- 239000003054 catalyst Substances 0.000 abstract description 29
- 239000000126 substance Substances 0.000 abstract description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 5
- 239000003795 chemical substances by application Substances 0.000 abstract description 5
- 229910052742 iron Inorganic materials 0.000 abstract description 5
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- 230000001131 transforming Effects 0.000 abstract 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 310
- 239000012071 phase Substances 0.000 description 20
- 230000001603 reducing Effects 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- 238000006722 reduction reaction Methods 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 11
- 239000003344 environmental pollutant Substances 0.000 description 11
- 231100000719 pollutant Toxicity 0.000 description 11
- 239000007791 liquid phase Substances 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 8
- 239000008139 complexing agent Substances 0.000 description 7
- 230000033116 oxidation-reduction process Effects 0.000 description 7
- 238000000197 pyrolysis Methods 0.000 description 7
- 239000003638 reducing agent Substances 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 238000006479 redox reaction Methods 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 238000007323 disproportionation reaction Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052813 nitrogen oxide Inorganic materials 0.000 description 4
- 230000001590 oxidative Effects 0.000 description 4
- 239000002738 chelating agent Substances 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 241000209149 Zea Species 0.000 description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 2
- 238000006701 autoxidation reaction Methods 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium monoxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 230000000536 complexating Effects 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 235000005822 corn Nutrition 0.000 description 2
- 235000005824 corn Nutrition 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000010907 stover Substances 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N Ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Ammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K Trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 238000005039 chemical industry Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drugs Drugs 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- -1 radical ion Chemical class 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 239000011778 trisodium citrate Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
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
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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| CN111117866A (en) * | 2019-12-03 | 2020-05-08 | 同济大学 | Denitrification equipment for enriching nitrous oxide and recovering energy |
| CN112619392A (en) * | 2020-11-17 | 2021-04-09 | 天津浩创节能环保设备有限公司 | Dust removal, desulfurization and denitrification process for boiler flue gas |
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| CN112619392A (en) * | 2020-11-17 | 2021-04-09 | 天津浩创节能环保设备有限公司 | Dust removal, desulfurization and denitrification process for boiler flue gas |
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