CN102814112A - Method and device for desulfurizing and denitrating jointly - Google Patents
Method and device for desulfurizing and denitrating jointly Download PDFInfo
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- CN102814112A CN102814112A CN2012102725054A CN201210272505A CN102814112A CN 102814112 A CN102814112 A CN 102814112A CN 2012102725054 A CN2012102725054 A CN 2012102725054A CN 201210272505 A CN201210272505 A CN 201210272505A CN 102814112 A CN102814112 A CN 102814112A
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- 238000000034 method Methods 0.000 title claims abstract description 40
- 230000003009 desulfurizing effect Effects 0.000 title abstract 5
- 239000002250 absorbent Substances 0.000 claims abstract description 76
- 230000002745 absorbent Effects 0.000 claims abstract description 76
- 239000007789 gas Substances 0.000 claims abstract description 76
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000006096 absorbing agent Substances 0.000 claims abstract description 26
- 238000010521 absorption reaction Methods 0.000 claims abstract description 21
- 230000003068 static effect Effects 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 238000006477 desulfuration reaction Methods 0.000 claims description 36
- 230000023556 desulfurization Effects 0.000 claims description 36
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000002608 ionic liquid Substances 0.000 claims description 15
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 14
- 230000003647 oxidation Effects 0.000 claims description 11
- 238000007254 oxidation reaction Methods 0.000 claims description 11
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 7
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 239000007921 spray Substances 0.000 claims description 3
- 230000000630 rising effect Effects 0.000 claims 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 abstract description 39
- 238000000926 separation method Methods 0.000 abstract description 16
- 230000001590 oxidative effect Effects 0.000 abstract description 12
- 239000003054 catalyst Substances 0.000 abstract description 2
- 238000007599 discharging Methods 0.000 abstract 2
- 150000003568 thioethers Chemical class 0.000 abstract 2
- 239000000243 solution Substances 0.000 description 21
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 12
- 238000002425 crystallisation Methods 0.000 description 7
- 230000008025 crystallization Effects 0.000 description 7
- 150000001412 amines Chemical group 0.000 description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 6
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 5
- 239000012452 mother liquor Substances 0.000 description 5
- 235000011121 sodium hydroxide Nutrition 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- -1 heterocycle compound Chemical group 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 238000003915 air pollution Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 239000003546 flue gas Substances 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 235000010344 sodium nitrate Nutrition 0.000 description 3
- 239000004317 sodium nitrate Substances 0.000 description 3
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- ZWWCURLKEXEFQT-UHFFFAOYSA-N dinitrogen pentaoxide Chemical compound [O-][N+](=O)O[N+]([O-])=O ZWWCURLKEXEFQT-UHFFFAOYSA-N 0.000 description 2
- WFPZPJSADLPSON-UHFFFAOYSA-N dinitrogen tetraoxide Chemical compound [O-][N+](=O)[N+]([O-])=O WFPZPJSADLPSON-UHFFFAOYSA-N 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- WJCNZQLZVWNLKY-UHFFFAOYSA-N thiabendazole Chemical compound S1C=NC(C=2NC3=CC=CC=C3N=2)=C1 WJCNZQLZVWNLKY-UHFFFAOYSA-N 0.000 description 2
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- LZDSILRDTDCIQT-UHFFFAOYSA-N dinitrogen trioxide Chemical compound [O-][N+](=O)N=O LZDSILRDTDCIQT-UHFFFAOYSA-N 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 239000001272 nitrous oxide Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- UMPKMCDVBZFQOK-UHFFFAOYSA-N potassium;iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[K+].[Fe+3] UMPKMCDVBZFQOK-UHFFFAOYSA-N 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Treating Waste Gases (AREA)
Abstract
The invention discloses a method and device for desulfurizing and denitrating jointly. The method comprises the following steps: making a gas containing nitrogen oxides and sulfides contact a sulfide absorbent in an absorber, making a gas-liquid mixture which is discharged from the absorber and the sulfide absorbent which absorbs a sulfide enter an absorption cycle groove on the lower part of a separation absorption tower, making the gas from desulfurizing enter an oxidizing device arranged on the middle part of the separation absorption tower to contact air so as to be oxidized, making the gas from desulfurizing enter an upper denitrating layer on the separation absorption tower to contact a denitrating absorbent so as to be denitrated, discharging the denitrating absorbent which absorbs the NO2 from the separation absorption tower, and discharging the purified gas from the top of the separation absorption tower. The absorber and the oxidizing device are static mixers with internal components or mixers with venturi structures. The desulfurizing and the denitrating are completed in signal tower equipment, the tower is lowered obviously, no catalyst is utilized, the operation cost is low, and more than 85% of nitrogen oxides and more that 98% of sulfides in the tail gas are removed.
Description
Technical field
The present invention relates to a kind of method and device thereof of desulphurization denitration.
Background technology
Nitrogen oxide and sulfide are one of major pollutants of atmosphere pollution, mainly come the tail gas etc. of flue gas, smelting furnace or the kiln of spontaneous combustion, thermal power plant.Because the desulphurization denitration technology exists complex equipments, floor space big respectively; Operation and shortcoming such as investment cost height, development technique is simple, operating cost is low, the desulphurization denitration technology is the technological important development direction of present coal-fired flue-gas improvement when having good runnability.
The technology of desulphurization denitration mainly contains wet method desulphurization denitration technology and dry method while desulphurization denitration technology simultaneously simultaneously at present.
Wet method desulphurization denitration technology simultaneously can be divided into metal complex method, NaClO
2Oxidizing process, H
2O
2Oxidizing process etc.Adopt the metal chelating agent desulphurization denitration to exist absorption liquid to be difficult for recycle, cost height, to reach problems such as producing other industrial wastes.Zhao Yi etc. utilize jet bubbling method with NaClO
2For oxidant absorbs NO and SO in the flue gas
2CN102274681 discloses employing H
2O
2The method of while desulphurization denitration; CN102350208 discloses and has adopted potassium ferrate or Na2Fe04 to carry out the method for desulphurization denitration as oxidant; This several method is owing to used oxidant; Still there is the cost problem of higher, and, makes the salt purifying and recovering that produces behind the desulphurization denitration comparatively difficult because desulphurization denitration carries out simultaneously.
Dry method desulphurization denitration technology simultaneously mainly contains SNRB technology, SNOX technology, activated carbon method, electron beam irradiation method at present, and nucleus equipment power is big, cost is expensive, equipment dependability is not high more but exist.
Summary of the invention
The technical issues that need to address of the present invention provide a kind of method and apparatus of combined desulfurization and denitration, to overcome the above-mentioned defective that prior art exists.
The method of combined desulfurization and denitration of the present invention comprises the steps:
The gas of nitrogen-containing oxide and sulfide is contacted in absorber with the sulfide absorbent; The sulfide absorbent absorbs sulfide; From the gas-liquid mixture that absorber is discharged, get into the lower floor of separate absorbent tower, gas-liquid separation; Absorb the sulfide absorbent (being also referred to as rich solution) of sulfide, got into the absorption circulating slot of separate absorbent tower bottom;
Said rich solution through peroxidating, concentrate, after Crystallization Separation handles, obtain SO
2Or sulfate product, mother liquor can be recycled;
Implement separation, oxidation, concentrated, Crystallization Separation, be the apparatus and method of routine;
Said nitrogen oxide is nitrous oxide (N
2O), nitric oxide (NO), nitrogen dioxide (NO
2), nitrogen trioxide (N
2O
3), dinitrogen tetroxide (N
2O
4) or dinitrogen pentoxide (N
2O
5) or the like; Said gaseous sulphide is SO
2, SO
3Or H
2S or the like.
In the gas of described nitrogen-containing oxide and gaseous sulphide, the content of nitrogen oxide is 100 ~ 20000mg/m
3The content of sulfide is 100 ~ 35000mg/m
3
It is that 3 ~ 35% sodium hydroxide solution or ammoniacal liquor, weight concentration are 3 ~ 20% sodium carbonate liquor that said sulfide absorbent is selected from weight concentration, and weight concentration is 1 ~ 60% ionic liquid;
Said ionic liquid consist of guanidinesalt class, alcamines, quaternary amine or amine and heterocycle compound, and other auxiliary compounds specifically can be referring to the application study [J] of Zhang Miaomiao plasma liquid in Air Pollution Control. Hebei industrial technology .2011.28 (4)
The ratio of the gas of sulfide absorbent and nitrogen-containing oxide and gaseous sulphide is: 0.1 ~ 10L/m
3(G)
Be absorbed under the normal pressure and carry out, the temperature that is absorbed gas is 1 ~ 150 ℃, preferred 15 ~ 110 ℃;
Described absorber is selected from the static mixer that is provided with inner member, and said inner member is conventional, is among SV, SL, SK, SX or the SH etc. more than one like model; Or the blender of Venturi tube structure;
Said model is the structure of the inner member of SV, SL, SK, SX or SH, and relevant parameter, can be referring to Fan Cunliang. the type selecting of static mixer and progress of application [J]. and chemical equipment technological .1997.18 (6);
The blender of various Venturi tube structures all can use;
Gas after the desulfurization rises and gets into the oxidator at separate absorbent tower middle part, and in oxidator, gas after the desulfurization and air catalytic oxidation are oxidized to NO to NO
2, rise getting into the denitration layer on separate absorbent tower upper strata then, the denitration absorbent under with top spray contacts absorption of N O
2, accomplish denitrification process; Be absorbed under the normal pressure and carry out, the temperature that is absorbed gas is 1 ~ 130 ℃;
The oxidizing temperature of gas is 1 ~ 150 ℃, preferred 1 ~ 99 ℃, and preferred especially 25～70 ℃;
The gas after the desulfurization and the volume ratio of air are: the gas after the desulfurization: air=1.00: 0.01 ~ 1.05, preferred 1.00: 0.15;
The denitration absorbent with the ratio of the gas that gets into the denitration layer is: 0.1 ~ 10L/m
3(G);
Absorbed NO
2Denitration absorbent (being also referred to as the denitration rich solution), from the separate absorbent tower on oxidator top, discharge, oxidative purification, Crystallization Separation then obtain ammonium nitrate products, mother liquor can be recycled;
After the oxidative purification of said denitration rich solution, the Crystallization Separation, the apparatus and method that obtain the nitrate product are conventional, handle the back mother liquor and recycle, and purified gas is discharged by described separate absorbent top of tower;
Described oxidator is selected from the static mixer that is provided with inner member, and said inner member is conventional, is among SV, SL, SK, SX or the SH etc. more than one like model;
Or the blender of Venturi tube structure;
Said model is the structure of the inner member of SV, SL, SK, SX or SH, and relevant parameter, can be referring to Fan Cunliang. the type selecting of static mixer and progress of application [J]. and chemical equipment technological .1997.18 (6);
It is that 3 ~ 35% sodium hydroxide solution or ammoniacal liquor, weight concentration are 3 ~ 20% sodium carbonate liquor that said denitration absorbent is selected from weight concentration, and weight concentration is 1 ~ 60% ionic liquid;
Said ionic liquid consists of guanidinesalt class, alcamines, quaternary amine or amine and heterocycle compound, and its auxiliary compounds; Specifically can be referring to Zhang Miaomiao etc. the application study [J] of ionic liquid in Air Pollution Control. Hebei industrial technology .2011.28 (4);
The invention has the advantages that:
1) described combined desulfurization and denitration is accomplished in a single tower; Single tower adopt the efficient absorption device combine knockout tower, again with the mode of oxidator, absorption tower reasonable combination; Total tower height degree is compared with the double tower simple superposition mode of prior art and is significantly reduced, and can be used for the vent gas treatment of sulfur compound such as factory, thermal power plant and nitrogen oxide.
2). the equipment of employing is simple and easy to, and also is suitable for existing wet desulphurization equipment is carried out corresponding transformation.Compared with prior art, floor space is little, and fixed investment and operating cost significantly reduce.
3). sulfide and nitrogen oxide obtain corresponding product respectively after absorption liquid absorbs, can directly recycle, and have compared with prior art reduced secondary separation, and economic worth is high.
4). nitrogen oxide adopts the air direct oxidation to absorb, and does not need catalyst, has reduced operating cost.
5). this law purification efficiency is high, and the corresponding removal efficiency of nitrogen oxide and sulfide has surpassed 85% and 98% respectively in the tail gas.
Description of drawings
Fig. 1 is the structural representation of while desulfuring and denitrifying apparatus.
Fig. 2 is the venturi mixer structural representation.
Fig. 3 is the venturi mixer structural representation of multitube structure.
Fig. 4 is the another kind of structure of the blender of Venturi tube structure.
Fig. 5 is the venturi mixer structural representation of another kind of multitube structure.
The specific embodiment
Referring to Fig. 1, be used to realize the device of method of the present invention, comprising:
Said separate absorbent tower 2 comprises tower body 205, oxidator 202, absorbs circulating slot 201, denitration layer 203, desulfurization layer 204 and dividing plate 207;
Said absorption circulating slot 201 is arranged on the bottom in the said tower body 205, and said desulfurization layer 204 is arranged on the top that absorbs circulating slot 201, and said dividing plate 207 is arranged on the top of desulfurization layer 204; Said oxidator 202 is fixed on the said dividing plate 207; The oxidator inlet is connected with desulfurization layer 204, and said denitration layer 203 is arranged on dividing plate 207 tops, and the oxidator outlet is connected with denitration layer 203; On the tower body 205 of the bottom of dividing plate 207; Be provided with air intake 209, said air intake 209 is connected with oxidator, and clean gas outlet is arranged on the top of separate absorbent tower 2; The bottom of separate absorbent tower 2 is provided with rich solution outlet 206, and the tower body 205 of the top of said dividing plate 207 is provided with denitration absorbent outlet 208;
The outlet 101 of said absorber 1 is inserted in the tower body 205, and is positioned at desulfurization layer 204 place;
Described absorber 1 is for being provided with the static mixer of inner member, and said inner member be a routine, is among SV, SL, SK, SX or the SH etc. more than one like model; Or the blender of Venturi tube structure;
Described oxidator 202 is for being provided with the static mixer of inner member, and said inner member be a routine, is among SV, SL, SK, SX or the SH etc. more than one like model; Or the blender of Venturi tube structure;
Referring to Fig. 2～Fig. 5, the typical structure in the blender of the said Venturi tube structure of Fig. 2～Fig. 5 comprises the power gas inlet tube 10, trunnion 11 and the enlarged tube 13 that connect successively, and the air or the sulfide absorbent inlet 14 that are arranged on trunnion 11 places;
The diameter proportion of power gas inlet tube 10, trunnion 11 and enlarged tube 13 is:
Power gas inlet tube 10: trunnion 11=1: 0.01 ~ 1;
Trunnion 11: enlarged tube 13=1: 1 ~ 100;
Wherein: the diameter of said enlarged tube 13 refers to the diameter of said enlarged tube 13 maximums;
Said absorber 1 and oxidator 202, can by single or a plurality of described venturi or conventional static mixer separately or parallel connection constitute;
Referring to Fig. 1, adopt the device of Fig. 1, realize the method for described combined desulfurization and denitration, comprise the steps:
The gas of nitrogen-containing oxide and sulfide is contacted in absorber 1 with the sulfide absorbent; The sulfide absorbent absorbs gaseous sulphide, from the gas-liquid mixture that absorber 1 is discharged, gets into the lower floor of separate absorbent tower 2; Gas-liquid separation; Absorb the sulfide absorbent (being also referred to as rich solution) of sulfide, got into the absorption circulating slot 201 of separate absorbent tower 2 bottoms
Said saliferous rich solution through peroxidating, concentrate, after the Crystallization Separation, obtain sulfate product, mother liquor can be recycled, oxidation, concentrate, Crystallization Separation selects conventional apparatus and method for use; Said ionic liquid rich solution is collected SO through the high temperature desorption and regeneration
2Be used for selling or system sulfuric acid, Recycling Mother Solution is used, and separates and selects conventional apparatus and method for use;
It is that 3 ~ 35% sodium hydroxide solution or ammoniacal liquor, weight concentration are 3 ~ 20% sodium carbonate liquor that said sulfide absorbent is selected from weight concentration, and weight concentration is 1 ~ 60% ionic liquid;
Said ionic liquid consist of guanidinesalt class, alcamines, quaternary amine or amine and heterocycle compound and other auxiliary compounds; Specifically can be referring to Zhang Miaomiao etc. the application study [J] of ionic liquid in Air Pollution Control. Hebei industrial technology .2011.28 (4)
The ratio of the gas of sulfide absorbent and nitrogen-containing oxide and gaseous sulphide is: 0.1 ~ 10L/m
3(G)
Be absorbed under the normal pressure and carry out, the temperature that is absorbed gas is 1 ~ 150 ℃, preferred 15 ~ 110 ℃;
Gas after the desulfurization rises and gets into the oxidator 202 at separate absorbent tower 2 middle parts, and in oxidator 202, gas after the desulfurization and air catalytic oxidation are oxidized to NO to NO
2, rise getting into the denitration layer 203 on separate absorbent tower 2 upper stratas then, the denitration absorbent under with top spray contacts absorption of N O
2, accomplish denitrification process;
The gas after the desulfurization and the volume ratio of air are: the gas after the desulfurization: air=1.00: 0.01 ~ 1.05;
Denitration absorbent solution with the ratio of the gas that gets into denitration layer 203 is: 0.1 ~ 10L/m
3(G);
Absorbed NO
2Denitration absorbent (being also referred to as the denitration rich solution), from the separate absorbent tower 2 on oxidator 202 tops, discharge, oxidative purification, Crystallization Separation obtain ammonium nitrate products then, mother liquor can be recycled;
Purified gas is discharged by described separate absorbent tower 2 tops;
It is that 3 ~ 35% sodium hydroxide solution or ammoniacal liquor, weight concentration are 3 ~ 20% sodium carbonate liquor that said denitration absorbent is selected from weight concentration, and weight concentration is 1 ~ 60% ionic liquid.
Operating parameter:
Gas flow 200Nm
3/ h, wherein: oxysulfide content 1100mg/Nm
3, amount of nitrogen oxides 800mg/Nm
3, other is an air;
The sulfide absorbent is the ammoniacal liquor of weight concentration 15%;
The ratio of the gas of sulfide absorbent solution and nitrogen-containing oxide and gaseous sulphide is: 2L/m
3
Be absorbed under the normal pressure and carry out, absorption temperature is 25 ℃;
The denitration absorbent is the ammoniacal liquor of weight concentration 15%;
The gas after the desulfurization and the volume ratio of air are: the gas after the desulfurization: air=1: 0.1; Oxidizing temperature is 25 ℃;
The denitration absorbent with the ratio of the gas that gets into denitration layer 203 is: 3L/m
3, being absorbed under the normal pressure and carrying out, absorption temperature is 25 ℃;
Adopt the device of Fig. 1.
The apparatus structure parameter:
Tower diameter DN200mm, tower height 16m takes the tower outer circular slot;
Power gas inlet tube 10: trunnion 11=1: 0.8;
Trunnion 11: enlarged tube 13=1: 1.3;
The ammonium sulfite solution that absorbs completion obtains ammonium sulfate product behind the oxidation condensing crystallizing;
The ammonium nitrate solution that contains the part ammonium nilrite that absorbs completion finally obtains ammonium nitrate products through air oxidation purifying, condensing crystallizing.
Detect with testo 350XL gas-detecting device, gas discharges sulfide concentration≤50mg/Nm after combined purifying is handled
3, nitrous oxides concentration≤120mg/Nm
3
Operating parameter:
Gas flow 3000m
3/ h, wherein: oxysulfide content 900mg/Nm
3, amount of nitrogen oxides 800mg/Nm
3
The sulfide absorbent is the ionic liquid of weight concentration 1.9% ethylenediamine+1.7% tetramethylethylenediamine/phosphoric acid;
The ratio of the gas of sulfide absorbent and nitrogen-containing oxide and gaseous sulphide is: 1L/m
3
Be absorbed under the normal pressure and carry out, the temperature that is absorbed gas is 60 ℃;
The denitration absorbent is the caustic soda of weight concentration 15%;
The gas after the desulfurization and the volume ratio of air are: the gas after the desulfurization: air=1: 0.08; Oxidizing temperature is 53 ℃;
The denitration absorbent with the ratio of the gas that gets into denitration layer 203 is: 3L/m
3Be absorbed under the normal pressure and carry out, absorption temperature is 53 ℃;
Adopt the device of Fig. 1 and the venturi mixer of Fig. 3,
Apparatus structure parameter: tower diameter DN800mm, tower height 18m;
Oxidator adopts multitube venturi oxidator shown in Figure 3, four pipe parallel connections;
Power gas inlet tube 10: trunnion 11=1: 0.6;
Trunnion 11: enlarged tube 13=1: 1.5;
Absorb the ionic liquid rich solution deionization liquid treating system of accomplishing, 95 ℃ of high temperature desorbs, the SO that emits
2Be used to make sulfuric acid, poor ionic liquid reuse after the desorb.
The sodium nitrate solution that contains the part natrium nitrosum that absorbs completion finally obtains ammonium nitrate products through air oxidation purifying, condensing crystallizing.
Detect with the testo350XL gas-detecting device, gas discharges sulfide concentration≤50mg/Nm after combined purifying is handled
3, nitrous oxides concentration≤150mg/Nm
3
Embodiment 3
Operating parameter:
Gas flow 6000m
3/ h, wherein: oxysulfide content 1000mg/Nm
3, amount of nitrogen oxides 600mg/Nm
3
The sulfide absorbent is the ammonia spirit of weight concentration 15%;
The ratio of the gas of sulfide absorbent and nitrogen-containing oxide and gaseous sulphide is: 2L/m
3
Be absorbed under the normal pressure and carry out, the temperature that is absorbed gas is 110 ℃;
The denitration absorbent is the sodium carbonate liquor of weight concentration 15%;
The gas after the desulfurization and the volume ratio of air are: the gas after the desulfurization: air=1: 0.15; Oxidizing temperature is 70 ℃;
The denitration absorbent with the ratio of the gas that gets into denitration layer 203 is: 3L/m
3Be absorbed under the normal pressure and carry out, absorption temperature is 70 ℃;
Adopt the device of Fig. 1.
Apparatus structure parameter: tower diameter DN1000mm, tower height 20m;
Oxidator adopts multitube venturi oxidator shown in Figure 5, four pipe parallel connections;
The venturi mixer parameter:
Power gas inlet tube 10: trunnion 11=1: 0.55;
Trunnion 11: enlarged tube 13=1: 1.7;
The ammonium sulfite solution that absorbs completion obtains ammonium sulfate product behind the oxidation condensing crystallizing;
The sodium nitrate solution that contains the part natrium nitrosum that absorbs completion finally obtains the sodium nitrate product through air oxidation purifying, condensing crystallizing.
Detect through testo 350XL gas-detecting device, after the gas combined purifying was handled, concentration of emission was: sulfide concentration≤50mg/Nm
3, nitrous oxides concentration≤150mg/Nm
3
Claims (12)
1. the method for combined desulfurization and denitration; It is characterized in that; Comprise the steps: the gas of nitrogen-containing oxide and sulfide is contacted in absorber (1) with the sulfide absorbent,, get into the lower floor of separate absorbent tower (2) from the gas-liquid mixture that absorber (1) is discharged; Absorb the sulfide absorbent of sulfide, got into the absorption circulating slot (201) of separate absorbent tower (2) bottom;
Gas after the desulfurization rises and gets into the oxidator (202) at separate absorbent tower (2) middle part, and with the air catalytic oxidation, rising then gets into the denitration layer (203) on separate absorbent tower (2) upper strata, and following denitration absorbent contacts the completion denitration with top spray;
Absorbed NO
2The denitration absorbent, from the separate absorbent tower (2) on oxidator (202) top, discharge;
Purified gas is discharged by described separate absorbent tower (2) top;
Described absorber (1) and oxidator (202) are for being provided with the static mixer of inner member or the blender of Venturi tube structure.
2. method according to claim 1 is characterized in that, it is that 3 ~ 35% sodium hydroxide solution or ammoniacal liquor, weight concentration are that 3 ~ 20% sodium carbonate liquor or weight concentration are 5 ~ 60% ionic liquid that said sulfide absorbent is selected from weight concentration.
3. method according to claim 2 is characterized in that the ratio of the gas of sulfide absorbent and nitrogen-containing oxide and gaseous sulphide is: 0.1 ~ 10L/m
3
4. method according to claim 1 is characterized in that, is absorbed under the normal pressure and carries out, and the temperature that is absorbed gas is 1 ~ 150 ℃.
5. method according to claim 1 is characterized in that, the gas after the desulfurization and the volume ratio of air are: the gas after the desulfurization: air=1.00: 0.01 ~ 1.05.
6. method according to claim 1 is characterized in that, denitration absorbent solution with the ratio of the gas that gets into denitration layer (203) is: 0.1 ~ 10L/m
3(G).
7. method according to claim 1; It is characterized in that; Method according to claim 1; It is characterized in that it is that 3 ~ 35% sodium hydroxide solution or ammoniacal liquor, weight concentration are that 3 ~ 20% sodium carbonate liquor or weight concentration are 1 ~ 60% ionic liquid that said denitration absorbent is selected from weight concentration.
8. according to each described method of claim 1～7; It is characterized in that; The blender of said Venturi tube structure comprises power gas inlet tube (10), trunnion (11) and the enlarged tube (13) that connects successively, and is arranged on air or sulfide absorbent inlet (14) that trunnion (11) is located;
The diameter proportion of power gas inlet tube (10), trunnion (11) and enlarged tube (13) is:
Power gas inlet tube (10): trunnion (11)=1: 0.01 ~ 1;
Trunnion (11): enlarged tube (13)=1: 1 ~ 100.
9. method according to claim 8 is characterized in that, trunnion (11) is located, and the linear velocity of power gas is 10 ~ 200 meter per seconds.
10. be used to realize the device of each said method of claim 1～9, it is characterized in that, comprise absorber (1) and separate absorbent tower (2);
Said separate absorbent tower (2) comprises tower body (205), oxidator (202), absorbs circulating slot (201), denitration layer (203), desulfurization layer (204) and dividing plate (207);
Said absorption circulating slot (201) is arranged on the bottom in the said tower body (205); Said desulfurization layer (204) is arranged on the top that absorbs circulating slot (201); Said dividing plate (207) is arranged on the top of desulfurization layer (204), and said oxidator (202) is fixed on the said dividing plate (207), and the oxidator inlet is connected with desulfurization layer (204); Said denitration layer (203) is arranged on dividing plate (207) top; The oxidator outlet is connected with denitration layer (203), on the tower body (205) of the bottom of dividing plate (207), is provided with air intake (209); Said air intake (209) is connected with oxidator (202); Clean gas outlet is arranged on the top of separate absorbent tower (2), and the bottom of separate absorbent tower (2) is provided with rich solution outlet (206), and the tower body (205) of the top of said dividing plate (207) is provided with denitration absorbent outlet (208);
The outlet (101) of said absorber (1) is inserted in the tower body (205), and is positioned at desulfurization layer (204) and locates;
Described absorber (1) and described oxidator (202) are for being provided with the static mixer of inner member or the blender of Venturi tube structure.
11. device according to claim 10; It is characterized in that; The blender of said Venturi tube structure comprises power gas inlet tube (10), trunnion (11) and the enlarged tube (13) that connects successively, and is arranged on air or sulfide absorbent inlet (14) that trunnion (11) is located;
The diameter proportion of power gas inlet tube (10), trunnion (11) and enlarged tube (13) is:
Power gas inlet tube (10): trunnion (11)=1: 0.01 ~ 1;
Trunnion (11): enlarged tube (13)=1: 1 ~ 100.
12. according to claim 10 or 11 described devices, it is characterized in that, said absorber (1) and oxidator (202), by single or a plurality of described venturi or conventional static mixer separately or parallel connection constitute.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103768911A (en) * | 2014-02-11 | 2014-05-07 | 汤宁 | Flue gas purification device and method capable of realizing desulfurization, denitrification and respective recovery |
| CN103801178A (en) * | 2014-03-06 | 2014-05-21 | 汤宁 | Smoke purification device and method with integration of desulfuration, denitration, dust removal and mercury removal |
| CN103894047A (en) * | 2014-03-14 | 2014-07-02 | 成都华西堂投资有限公司 | Flue gas pollutant control integrated purifying and recycling process |
| CN104437084A (en) * | 2014-12-10 | 2015-03-25 | 上海亨远船舶设备有限公司 | Method for desulfurization and denitration of tail gas of internal combustion engine of ship |
| CN106890544A (en) * | 2017-02-27 | 2017-06-27 | 湖南云平环保科技有限公司 | Sodium base desulphurization denitration absorbent and preparation method thereof |
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| CN101879404A (en) * | 2010-07-12 | 2010-11-10 | 华东理工大学 | A resource-based flue gas desulfurization and denitrification method |
| CN102350197A (en) * | 2011-07-11 | 2012-02-15 | 华东理工大学 | Fume desulfurizing and denitrifying device based on magnesia and method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101879404A (en) * | 2010-07-12 | 2010-11-10 | 华东理工大学 | A resource-based flue gas desulfurization and denitrification method |
| CN102350197A (en) * | 2011-07-11 | 2012-02-15 | 华东理工大学 | Fume desulfurizing and denitrifying device based on magnesia and method |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103768911A (en) * | 2014-02-11 | 2014-05-07 | 汤宁 | Flue gas purification device and method capable of realizing desulfurization, denitrification and respective recovery |
| CN103801178A (en) * | 2014-03-06 | 2014-05-21 | 汤宁 | Smoke purification device and method with integration of desulfuration, denitration, dust removal and mercury removal |
| CN103894047A (en) * | 2014-03-14 | 2014-07-02 | 成都华西堂投资有限公司 | Flue gas pollutant control integrated purifying and recycling process |
| CN104437084A (en) * | 2014-12-10 | 2015-03-25 | 上海亨远船舶设备有限公司 | Method for desulfurization and denitration of tail gas of internal combustion engine of ship |
| CN104437084B (en) * | 2014-12-10 | 2023-10-31 | 上海亨远船舶设备有限公司 | Desulfurization and denitrification method for tail gas of marine internal combustion engine |
| CN106890544A (en) * | 2017-02-27 | 2017-06-27 | 湖南云平环保科技有限公司 | Sodium base desulphurization denitration absorbent and preparation method thereof |
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Application publication date: 20121212 |