CN111185077B - Flue gas denitration device and method based on gaseous oxidizing ions - Google Patents
Flue gas denitration device and method based on gaseous oxidizing ions Download PDFInfo
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- CN111185077B CN111185077B CN202010136738.6A CN202010136738A CN111185077B CN 111185077 B CN111185077 B CN 111185077B CN 202010136738 A CN202010136738 A CN 202010136738A CN 111185077 B CN111185077 B CN 111185077B
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- flue gas
- oxidizing gas
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- 230000001590 oxidative effect Effects 0.000 title claims abstract description 271
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 234
- 239000003546 flue gas Substances 0.000 title claims abstract description 234
- 238000000034 method Methods 0.000 title claims abstract description 28
- 150000002500 ions Chemical class 0.000 title claims abstract description 24
- 239000007789 gas Substances 0.000 claims abstract description 246
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims abstract description 76
- 239000007788 liquid Substances 0.000 claims abstract description 59
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 28
- 230000003647 oxidation Effects 0.000 claims abstract description 27
- 230000003750 conditioning effect Effects 0.000 claims abstract description 12
- 238000007664 blowing Methods 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 173
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 claims description 70
- 239000002994 raw material Substances 0.000 claims description 70
- 238000010521 absorption reaction Methods 0.000 claims description 48
- 239000012452 mother liquor Substances 0.000 claims description 39
- 239000002250 absorbent Substances 0.000 claims description 38
- 230000002745 absorbent Effects 0.000 claims description 38
- 239000004155 Chlorine dioxide Substances 0.000 claims description 35
- 235000019398 chlorine dioxide Nutrition 0.000 claims description 35
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 17
- 239000002002 slurry Substances 0.000 claims description 15
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 13
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 13
- 238000005192 partition Methods 0.000 claims description 13
- 239000011734 sodium Substances 0.000 claims description 13
- 229910052708 sodium Inorganic materials 0.000 claims description 13
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims description 12
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical group [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 10
- 239000000920 calcium hydroxide Substances 0.000 claims description 10
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 10
- 239000012295 chemical reaction liquid Substances 0.000 claims description 10
- 239000010881 fly ash Substances 0.000 claims description 10
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical group O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 150000002736 metal compounds Chemical class 0.000 claims description 8
- 229910000831 Steel Inorganic materials 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000010959 steel Substances 0.000 claims description 7
- 239000007921 spray Substances 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 230000009471 action Effects 0.000 claims description 4
- 238000005507 spraying Methods 0.000 claims description 4
- 238000005273 aeration Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000000428 dust Substances 0.000 description 28
- 229910052783 alkali metal Inorganic materials 0.000 description 24
- -1 alkali metal chlorate Chemical class 0.000 description 24
- 239000006227 byproduct Substances 0.000 description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 239000000779 smoke Substances 0.000 description 17
- 239000006096 absorbing agent Substances 0.000 description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- XTEGARKTQYYJKE-UHFFFAOYSA-M chlorate Inorganic materials [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 12
- 229910001919 chlorite Inorganic materials 0.000 description 12
- 229910052619 chlorite group Inorganic materials 0.000 description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 10
- 239000004202 carbamide Substances 0.000 description 10
- 239000001509 sodium citrate Substances 0.000 description 6
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000012527 feed solution Substances 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000003541 multi-stage reaction Methods 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910000314 transition metal oxide Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 description 1
- 229940005991 chloric acid Drugs 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/75—Multi-step processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/32—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by electrical effects other than those provided for in group B01D61/00
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/54—Nitrogen compounds
- B01D53/56—Nitrogen oxides
-
- 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/76—Gas phase processes, e.g. by using aerosols
-
- 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/80—Semi-solid phase processes, i.e. by using slurries
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/10—Oxidants
- B01D2251/108—Halogens or halogen compounds
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2259/00—Type of treatment
- B01D2259/80—Employing electric, magnetic, electromagnetic or wave energy, or particle radiation
- B01D2259/818—Employing electrical discharges or the generation of a plasma
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Dispersion Chemistry (AREA)
- Treating Waste Gases (AREA)
Abstract
The invention discloses a flue gas denitration device and method based on gaseous oxidizing ions. The apparatus includes an oxidizing gas generating device configured to generate an oxidizing gas by a reaction feed liquid, and provided with a compressed air inlet, an air inlet for adjustment, and an oxidizing gas outlet; an air compressor connected to the compressed air inlet and configured to provide compressed air to the oxidizing gas generating apparatus; a blower connected to the conditioning air inlet and configured to be capable of blowing conditioning air into the oxidizing gas generating apparatus; a plasma generating and flue gas oxidizing device connected to the oxidizing gas outlet and configured to convert the oxidizing gas into gaseous oxidizing ions and oxidize nitrogen oxides in the flue gas to be treated to form oxidized flue gas; and the denitration device is connected with the plasma generation and flue gas oxidation device and is arranged to be capable of carrying out denitration treatment on oxidized flue gas so as to obtain denitration flue gas. The device has high operation safety.
Description
Technical Field
The invention relates to a flue gas denitration device and method, in particular to a flue gas denitration device and method based on gaseous oxidizing ions.
Background
Currently, the main technologies applied to flue gas denitrification are Selective Catalytic Reduction (SCR) and selective non-catalytic reduction (SNCR). SCR denitration efficiency is high, but equipment investment and operation maintenance cost are high, and the catalyst is expensive, easy to inactivate, and ammonia escape caused by incomplete reaction can cause secondary pollution. SNCR has lower investment and operation cost, but has lower denitration efficiency, and does not reach increasingly strict emission standards. The two flue gas denitration methods both require higher temperature and larger occupied area, and the existing power plant equipment is greatly improved.
The chlorine dioxide is used as a green oxidant with strong oxidizing property, has low cost and has better effect when being applied to desulfurization and denitrification in an oxidation absorption method. However, chlorine dioxide is extremely easy to decompose, and has the danger of explosion, which is not beneficial to industrial safety application.
CN105771577a discloses a device for preparing chlorine dioxide for flue gas denitrification. The device comprises a Y-shaped three-way pipeline serving as two feeding ports, a check valve is arranged on the pipeline, the rest third pipeline is used as a mixed reaction generator, a pressure gauge and a distribution spraying device are arranged at the outlet end of the pipeline, the distribution spraying device comprises a safety valve and a plurality of spray heads which are connected in parallel, and the spray heads can directly penetrate into a flue gas pipeline. The device is suitable for the liquid oxidation of chlorine dioxide, and is easy to cause the escape of chlorine dioxide. In addition, the device can not fully react reactants, and the yield of chlorine dioxide is low; the phenomenon of overhigh chlorine dioxide concentration easily occurs in the reaction process, and potential safety hazard is generated.
Disclosure of Invention
In view of the above, the invention provides a flue gas denitration device, the concentration of chlorine dioxide in oxidizing gas can be adjusted, and the operation safety is high. Further, the chlorine dioxide gas yield of the invention is higher. On the other hand, the invention provides a method for flue gas denitration by adopting the device, and the method has high operation safety. The technical aim is achieved by the following technical scheme.
In one aspect, the present invention provides a flue gas denitration device, including:
an oxidizing gas generating device configured to generate an oxidizing gas by a reaction liquid, and provided with a compressed air inlet, an air inlet for adjustment, and an oxidizing gas outlet;
an air compressor connected to the compressed air inlet and configured to provide compressed air to the oxidizing gas generating apparatus;
a blower connected to the conditioning air inlet and configured to be capable of blowing conditioning air into the oxidizing gas generating apparatus;
a plasma generating and flue gas oxidizing device connected to the oxidizing gas outlet configured to convert the oxidizing gas into gaseous oxidizing ions and oxidize nitrogen oxides in the flue gas to be treated to form oxidized flue gas;
And the denitration device is connected with the plasma generation and smoke oxidation device and is arranged to be capable of carrying out denitration treatment on oxidized smoke from the plasma generation and smoke oxidation device so as to obtain denitration smoke.
According to the flue gas denitration device of the present invention, preferably, the oxidizing gas generating apparatus is a horizontal advection reactor; at least one partition provided in the oxidizing gas generating apparatus, the partition being configured to partition an internal space of the oxidizing gas generator into a plurality of compartments; in at least a portion of the cells, a honeycomb catalyst is disposed for catalyzing the reaction feed to obtain an oxidizing gas.
According to the flue gas denitration device of the present invention, preferably, one or both of the following conditions are satisfied:
(1) A deflector pipe is arranged between the compartments, and is used for overflowing the reaction feed liquid in the previous compartment to the next compartment;
(2) The oxidizing gas generating apparatus is further provided with a steam inlet for supplying heating steam to the oxidizing gas generating apparatus.
According to the flue gas denitration device of the present invention, preferably, the flue gas denitration device further includes a mother liquor tank having a mother liquor inlet and a mother liquor outlet;
The oxidizing gas generating equipment is provided with a feed liquid outlet; the feed liquid outlet is connected with the mother liquid inlet so as to lead out at least part of reaction feed liquid to a mother liquid tank;
the oxidizing gas generating device is provided with a feed liquid inlet; the feed liquid inlet is connected with the mother liquid outlet and is arranged to circulate the mother liquid in the mother liquid tank to the oxidizing gas generating device.
According to the flue gas denitration device of the present invention, preferably, the flue gas denitration device further includes a first raw material tank containing a material a, a second raw material tank containing a material C, a third raw material tank containing a material B, and a fourth raw material tank containing a material S;
a plurality of feed inlets are formed in the side wall of the oxidizing gas generating device;
the first raw material tank, the second raw material tank, the third raw material tank and the fourth raw material tank are respectively arranged to be capable of being connected with corresponding feed inlets, so that materials A, C, B and S are supplied to the oxidizing gas generating equipment to form reaction feed liquid.
According to the flue gas denitration device of the present invention, preferably, the flue gas denitration device further includes a first raw material tank containing a material a, a second raw material tank containing a material C, a third raw material tank containing a material B, and a fourth raw material tank containing a material S;
The side wall of the oxidizing gas generating device is provided with a first feed port, a second feed port and a third feed port;
the first raw material tank and the second raw material tank are connected with the first feed port, so that after the materials A and C are mixed, the materials A and C are fed to the oxidizing gas generating equipment through the first feed port;
a third feed tank is arranged to be connectable to the second feed inlet for feeding material B to the oxidizing gas generating apparatus;
the fourth feed tank is arranged to be connectable to the third feed inlet for feeding the material S to the oxidizing gas generating apparatus to form a reaction feed liquid.
According to the flue gas denitrification device of the invention, preferably, the first raw material tank contains slurry containing alkali metal chlorate and/or alkali metal chlorite as a material a;
the second raw material tank contains hydrogen peroxide and/or methanol as a material C;
the third raw material tank contains concentrated hydrochloric acid and/or concentrated sulfuric acid as a material B;
the fourth feed tank contains urea, sodium humate and/or sodium citrate as material S.
According to the flue gas denitration device of the present invention, preferably, the denitration apparatus includes an absorption tower, an absorbent bin, and a water supply apparatus; the absorption tower is a circulating fluidized bed absorption tower;
The absorption tower is provided with a flue gas inlet and a flue gas outlet; the plasma generation and flue gas oxidation device is connected with the flue gas inlet and is arranged to be capable of conveying oxidized flue gas to the absorption tower; the absorbent bin is connected with the absorption tower and is used for supplying powdery absorbent to the absorption tower; the water supply device is arranged to be able to spray water to the absorbent and the oxidized flue gas in the absorption tower.
On the other hand, the invention provides a method for flue gas denitration by adopting the flue gas denitration device, which comprises the following steps:
(1) Placing a material R serving as a honeycomb catalyst in a compartment of an oxidizing gas generating device, and respectively conveying a material A, a material C, a material B and a material S into the oxidizing gas generating device by a first material tank, a second material tank, a third material tank and a fourth material tank to form a reaction material liquid, and conveying compressed air into the oxidizing gas generating device by an air compressor to perform aeration; reacting the feed liquid to generate chlorine dioxide gas, wherein the chlorine dioxide gas and air form mixed gas; the blower conveys air for adjustment to the oxidizing gas generating equipment so as to adjust the concentration of chlorine dioxide in the mixed gas, thereby obtaining oxidizing gas;
(2) Delivering an oxidizing gas to a plasma generating and flue gas oxidizing device; in the plasma generation and flue gas oxidation equipment, oxidizing gas is converted into gaseous oxidizing ions under the action of metal or metal compounds in the flue gas to be treated, and the gaseous oxidizing ions oxidize nitrogen oxides in the flue gas to be treated to form oxidized flue gas;
(3) Denitration is carried out on the oxidized flue gas in denitration equipment;
wherein the material A is slurry containing alkali metal chlorate and/or alkali metal chlorite, the material B is concentrated hydrochloric acid and/or concentrated sulfuric acid, the material C is hydrogen peroxide and/or methanol, the material S is urea, sodium humate and/or sodium citrate, the material R is transition metal oxide, and the flue gas to be treated is flue gas from the steel industry.
According to the flue gas denitration method of the present invention, preferably, the amount of alkali metal chlorate and/or alkali metal chlorite in the material a is 1 to 15 parts by weight, the amount of the material B is 1 to 10 parts by weight, the amount of the material C is 1 to 12 parts by weight, the amount of the material R is 0.002 to 0.006 parts by weight, and the amount of the material S is 0.02 to 0.1 part by weight.
The concentration of the active ingredients of the oxidative gas of the denitration device can be adjusted, and the denitration device is safe in industrial application. Further, the chlorine dioxide yield of the invention is higher. In another aspect, the invention provides a method for flue gas denitration, which is safe in industrial application. Furthermore, the method converts the oxidizing gas into gaseous oxidizing ions, improves the oxidizing property, and can reach higher oxidation rate of the nitrogen oxides in a short time.
Drawings
Fig. 1 is a schematic diagram of a flue gas denitration device according to the present invention.
Fig. 2 is a schematic diagram of another flue gas denitration device according to the present invention.
The reference numerals are explained as follows:
1-a first raw material tank; 2-a second feedstock tank; 3-a third raw material tank; 4-a fourth raw material tank; 5-catalyst; 6-a first feed pump; 7-a second feed pump; 8-a third feed pump; 9-a fourth feed pump; 10-an oxidizing gas generating apparatus; 11-steam inlet; 12-blower; 13-an air compressor; 14-a mother liquor tank; 15-a mother liquor pump; 16-induced draft fan; 17-plasma generation and flue gas oxidation equipment; 18 an absorbent bin; 19-a water supply device; 20-an absorption tower; 21-a dust removal device; 22-a byproduct bin; 23-chimney.
Detailed Description
The present invention will be further described with reference to specific examples, but the scope of the present invention is not limited thereto.
< flue gas denitration device >
The flue gas denitration device comprises an oxidizing gas generating device, an air compressor, a blower, a plasma generating device, a flue gas oxidizing device and a denitration device. In some embodiments, the flue gas denitrification device of the invention can further comprise a mother liquor tank, a raw material tank, a dust removal device, and/or a byproduct bin. The flue gas denitration device is suitable for large concentration of nitrogen oxides (NOx) 100mg/Nm or less 3 Is used for flue gas denitration. The following is a detailed description.
Oxidizing gas generating apparatus
The oxidizing gas generating apparatus of the present invention is used for generating an oxidizing gas. The oxidizing gas generating apparatus is provided with a plurality of feed ports, a compressed air inlet, a conditioning air inlet, and an oxidizing gas outlet.
The plurality of feed inlets are configured to be connected to a plurality of feedstock tanks for delivering feedstock for the reaction to the oxidizing gas generating apparatus. According to one embodiment of the invention, a plurality of feed inlets are provided in a side wall of the oxidizing gas generating apparatus.
The compressed air inlet is arranged with an air compressor for delivering compressed air to the oxidizing gas generating apparatus. According to one embodiment of the invention, the compressed air inlet is provided in an upper part of a side wall of the oxidizing gas generating apparatus.
The air inlet for adjustment is connected with a blower for blowing air into the oxidizing gas generating device, thereby adjusting the concentration of chlorine dioxide in the oxidizing gas. According to one embodiment of the invention, the conditioning air inlet is provided at the top of the oxidizing gas generating apparatus.
The oxidizing gas outlet is arranged to be connected to the plasma generating and flue gas oxidizing device for delivering the oxidizing gas to the plasma generating and flue gas oxidizing device. According to one embodiment of the invention, the oxidizing gas outlet is provided at the top of the oxidizing gas generating apparatus.
The oxidizing gas generating apparatus may also be provided with a feed liquid outlet and/or a feed liquid inlet. The feed liquid outlet may be provided at an upper portion of the oxidizing gas generating apparatus. The feed liquid inlet may be provided on a side wall of the oxidizing gas generating apparatus. The feed liquid inlet may be shared with the feed inlet.
The oxidizing gas generating apparatus is further provided with a steam inlet for supplying heating steam to the oxidizing gas generating apparatus. Preferably, the steam inlet is arranged at the bottom of the oxidizing gas generating device. Thus, heat exchange is carried out more fully, the reaction temperature is ensured, and the reaction is promoted.
The oxidizing gas generating apparatus of the present invention may be a horizontal advection reactor. At least one separator is disposed within the oxidizing gas generating apparatus. The partition is for partitioning an interior space of the oxidizing gas generating apparatus into a plurality of compartments. According to one embodiment of the invention, a deflector pipe is arranged between the compartments, wherein the deflector pipe is used for overflowing the reaction feed liquid of the previous compartment to the next compartment. This allows the reaction mixture to undergo a multistage reaction. According to another embodiment of the present invention, no deflector is provided between the compartments of the oxidizing gas generating apparatus, and the reaction liquid in the previous compartment overflows to the next compartment through the separator.
In at least a portion of the cells, a honeycomb catalyst is disposed for catalyzing the reaction feed to obtain an oxidizing gas. According to one embodiment of the invention, a honeycomb catalyst for catalyzing the reaction feed solution to obtain an oxidizing gas is disposed within all of the compartments.
According to one embodiment of the invention, the oxidizing gas generating apparatus is a horizontal advection reactor; at least one partition provided in the oxidizing gas generating apparatus, the partition being configured to partition an internal space of the oxidizing gas generating apparatus into a plurality of compartments; in at least a portion of the cells, a honeycomb catalyst is disposed for catalyzing the reaction feed to obtain an oxidizing gas.
Air compressor
The air compressor of the present invention may employ conventional air compression equipment. An air compressor is provided in connection with the compressed air inlet of the oxidizing gas generating apparatus for providing compressed air to the oxidizing gas generating apparatus. Specifically, the air compressor supplies compressed air to the reaction feed liquid of the oxidizing gas generating apparatus. The compressed air is aerated in the oxidizing gas generating equipment to fully stir the reaction feed liquid, thereby being beneficial to the reaction and the escape of the oxidizing gas. The reaction feed liquid generates chlorine dioxide gas, and the chlorine dioxide gas and air form mixed gas.
Blower fan
The blower of the present invention may employ a conventional blower device. The blower is connected with the air inlet for adjusting the oxidizing gas generating equipment and is used for blowing the air for adjusting the oxidizing gas generating equipment to adjust the concentration of chlorine dioxide in the mixed gas so as to obtain the oxidizing gas. Specifically, the blower blows conditioning air to the vicinity of the oxidizing gas outlet of the oxidizing gas generating apparatus to adjust the concentration of chlorine dioxide in the mixed gas, thereby obtaining the oxidizing gas. Thus, the concentration of chlorine dioxide in the mixed gas can be regulated, and the danger caused by the too high concentration of chlorine dioxide is avoided. The oxidizing gas is discharged from an oxidizing gas outlet of the oxidizing gas generating apparatus.
Plasma generation and flue gas oxidation equipment
The plasma generating and flue gas oxidizing device is connected with the oxidizing gas outlet and is used for converting the oxidizing gas into gaseous oxidizing ions and oxidizing nitrogen oxides in the flue gas to be treated to form oxidized flue gas. For example, oxidation of nitrogen oxides of low valence (e.g. NO) in the flue gas to be treated to nitrogen compounds of high valence (e.g. NO) 2 ). According to one embodiment of the invention, the oxidizing gas is converted by the metal or metal compound in the flue gas to be treated into gaseous oxidizing ions which oxidize nitrogen oxides in the flue gas to form oxidized flue gas. Although the principle is not clear, we hypothesize that the flue gas to be treated from the steel industry contains some metals or metal compounds that can promote the conversion of oxidizing gases to gaseous oxidizing ions. The gaseous oxidizing ions mean that an active material such as plasma is present in the gas. The active material may comprise oxygen active ions, active electrons, e.g. ClO 2 ·、HO·、HO 2 ·、O 3 Etc.
In certain embodiments, the plasma generating and flue gas oxidizing apparatus is connected to the oxidizing gas outlet by an induced draft fan. The induced draft fan is capable of extracting the oxidizing gas from the oxidizing gas generating apparatus.
Denitration device
The denitration device is connected with the plasma generation and flue gas oxidation device and is used for carrying out denitration treatment on oxidized flue gas from the plasma generation and flue gas oxidation device so as to obtain denitration flue gas. The denitration treatment of the present invention is preferably a semi-dry or dry denitration.
The denitration device may include an absorption tower, an absorbent bin, and a water supply device. The absorber is preferably a circulating fluidized bed absorber. The absorption tower is provided with a flue gas inlet and a flue gas outlet. And the plasma generating and oxidizing equipment is connected with the flue gas inlet and is used for conveying oxidized flue gas to the absorption tower. The absorbent bin is connected to the absorber tower for feeding the powdery absorbent to the absorber tower. The oxidized flue gas is mixed with an absorbent to form a mixed flue gas. The absorbent may be selected from one or more of calcium oxide, calcium hydroxide, magnesium oxide, magnesium hydroxide, sodium carbonate, sodium bicarbonate, fly ash, etc. Preferably, the absorbent is an absorbent formed from calcium hydroxide and fly ash. The mass ratio of the calcium hydroxide to the fly ash is 1-5:1, preferably 1.2-4.5:1, and more preferably 3:1. The water supply device is used for spraying water to the mixed flue gas formed by the absorbent and the oxidized flue gas in the absorption tower.
The flue gas inlet is preferably arranged at the bottom of the absorption tower. The absorbent bin is connected with a flue gas pipeline arranged between the flue gas inlet and the Venturi section of the absorption tower. The water supply device is connected with a venturi section positioned at the lower part of the absorption tower so as to spray water to the absorption tower to humidify the mixed flue gas formed by the absorbent and the oxidized flue gas. And (5) continuously rising the mixed flue gas, and finishing denitration in the absorption tower to obtain the denitration flue gas.
The flue gas outlet is positioned at the top or the upper part of the absorption tower; preferably the top. The dust removing device is connected with a flue gas outlet of the absorption tower.
Dust removing equipment
The flue gas denitration device of the invention can also comprise dust removal equipment. The dust removing device is connected with the flue gas outlet of the absorption tower. The dedusting equipment performs dedusting treatment on the denitration flue gas to form clean flue gas and denitration byproducts. The dust removal device is provided with a clean flue gas outlet and a by-product outlet. The clean flue gas is discharged from the clean flue gas outlet. According to one embodiment of the invention, the dust removal device is a bag-type dust collector.
Byproduct bin
The flue gas denitration device of the invention can also comprise a byproduct bin. The byproduct bin is connected with a byproduct outlet of the dust removal device and is used for receiving denitration byproducts.
Mother liquor tank
The flue gas denitration device also comprises a mother liquid tank. The mother liquor tank is provided with a mother liquor inlet and a mother liquor outlet. The oxidizing gas generating equipment is provided with a feed liquid outlet; the feed liquid outlet is connected with the mother liquid inlet so as to lead out at least part of reaction feed liquid to the mother liquid tank; the oxidizing gas generating device is provided with a feed liquid inlet; the feed liquid inlet is connected with the mother liquid outlet and is used for circulating the mother liquid in the mother liquid tank to the oxidizing gas generating equipment.
According to one embodiment of the invention, the mother liquor inlet is connected to the liquor outlet of the oxidizing gas generating apparatus for conducting a portion of the reaction liquor out to the mother liquor tank. The mother liquor outlet is connected with a feed liquor inlet of the oxidizing gas generating device and is used for circulating the mother liquor in the mother liquor tank to the oxidizing gas generating device.
The mother liquor in the mother liquor tank can be directly conveyed back to the oxidizing gas generating equipment, or can be firstly mixed with the raw materials and then conveyed back to the oxidizing gas generating equipment. According to one embodiment of the invention, the mother liquor outlet is connected to the feed liquor inlet of the oxidizing gas generating apparatus by a mother liquor pump.
Material tank
The flue gas denitration device also comprises a plurality of raw material tanks. The raw material tank is connected with a corresponding feed inlet of the oxidizing gas generating equipment and is used for supplying raw materials to the oxidizing gas generating equipment. The raw materials from the different raw material tanks may be mixed first and then supplied to the oxidizing gas generating apparatus.
In certain embodiments, the flue gas denitrification device comprises a first feed tank containing material a, a second feed tank containing material C, a third feed tank containing material B, and a fourth feed tank containing material S; a plurality of feed inlets are formed in the side wall of the oxidizing gas generating device; the first, second, third and fourth feedstock tanks are connected to respective feed inlets, respectively, to supply materials a, C, B and S to the oxidizing gas generating apparatus. Specifically, the first feedstock tank contains as material a slurry containing alkali metal chlorate and/or alkali metal chlorite. The second raw material tank contains hydrogen peroxide and/or methanol as a material C. The third feed tank contains concentrated hydrochloric acid and/or concentrated sulfuric acid as material B. The fourth feed tank contains urea, sodium humate and/or sodium citrate as material S. According to one embodiment of the invention, the flue gas denitrification device comprises a first feed tank containing material A, a second feed tank containing material C, a third feed tank containing material B and a fourth feed tank containing material S. The oxidizing gas generating device is provided with a first feed port, a second feed port, a third feed port and a fourth feed port. The first raw material tank is connected with the first feed port through the first feed pump, thereby supplying the material a to the oxidizing gas generating apparatus. The second raw material tank is connected with the second feed port through the second feed pump, thereby supplying the material C to the oxidizing gas generating apparatus. The third raw material tank is connected with a third feed port through a third feed pump, thereby supplying the material B to the oxidizing gas generating apparatus. The fourth raw material tank is connected to the fourth feed port by a fourth feed pump so as to supply the material S to the oxidizing gas generating apparatus.
In other embodiments, the flue gas denitrification device comprises a first feed tank containing material a, a second feed tank containing material C, a third feed tank containing material B, and a fourth feed tank containing material S; the side wall of the oxidizing gas generating device is provided with a first feed port, a second feed port and a third feed port; the first raw material tank and the second raw material tank are connected with the first feed port, so that after the materials A and C are mixed, the materials A and C are fed to the oxidizing gas generating equipment through the first feed port; a third feed tank is arranged to be connectable to the second feed inlet for feeding material B to the oxidizing gas generating apparatus; the fourth feed tank is arranged to be connectable to the third feed inlet for feeding the material S to the oxidizing gas generating apparatus. Specifically, the first feedstock tank contains as material a slurry containing alkali metal chlorate and/or alkali metal chlorite. The second raw material tank contains hydrogen peroxide and/or methanol as a material C. The third feed tank contains concentrated hydrochloric acid and/or concentrated sulfuric acid as material B. The fourth feed tank contains urea, sodium humate and/or sodium citrate as material S. According to one embodiment of the invention, the flue gas denitrification device comprises a first feed tank containing material A, a second feed tank containing material C, a third feed tank containing material B and a fourth feed tank containing material S. The oxidizing gas generating device is provided with a first feed port, a second feed port and a third feed port. The first raw material tank and the second raw material tank are respectively supplied with a material A and a material C through the first feed pump and the second feed pump. The material A and the material C are mixed and then supplied to the oxidizing gas generating equipment through the first feed inlet. The third raw material tank is connected with the second feed port through a third feed pump, thereby supplying the material B to the oxidizing gas generating apparatus. The fourth raw material tank is connected with the third feed port through a fourth feed pump so as to supply the material S to the oxidizing gas generating equipment.
< flue gas denitration method >
The flue gas denitration method provided by the invention comprises the following steps: (1) a step of preparing an oxidizing gas; (2) Generating gaseous oxidizing ions and oxidizing smoke; (3) flue gas denitration step. Optionally, the flue gas denitration method of the present invention further comprises (4) a step of dust removal. The method has higher denitration efficiency and is suitable for the concentration of nitrogen oxides (NOx) of more than or equal to 100mg/Nm 3 Is used for flue gas denitration. The following is a detailed description.
Step of preparing oxidizing gas
Placing a material R serving as a honeycomb catalyst in a compartment of an oxidizing gas generating device, and respectively conveying a material A, a material C, a material B and a material S into the oxidizing gas generating device by a first material tank, a second material tank, a third material tank and a fourth material tank to form a reaction material liquid, and conveying compressed air into the oxidizing gas generating device by an air compressor to perform aeration; reacting the feed liquid to generate chlorine dioxide gas, wherein the chlorine dioxide gas and air form mixed gas; the blower delivers air for adjustment to the oxidizing gas generating apparatus to adjust the concentration of chlorine dioxide in the mixed gas, thereby obtaining an oxidizing gas.
The material A of the present invention is a slurry containing alkali metal chlorate and/or alkali metal chlorite. The solute may be selected from one or more of alkali metal chlorate or alkali metal chlorite. Preferably, material a is a sodium chloride-containing slurry. The concentration of alkali metal chlorate and/or alkali metal chlorite in the slurry containing alkali metal chlorate and/or alkali metal chlorite may be 200 to 800g/L, preferably 300 to 600g/L, more preferably 350 to 500g/L.
The material B of the invention can be selected from one or more of concentrated hydrochloric acid or concentrated sulfuric acid. Preferably, the material B is concentrated sulfuric acid. The concentration of the concentrated sulfuric acid may be 80 to 99.9wt%, preferably 98wt% or more.
The material C of the invention can be selected from one or more of hydrogen peroxide and methanol. Preferably, the material C is hydrogen peroxide.
The material S is a stabilizer and can be selected from one or more of urea, sodium humate and sodium citrate. Preferably, the material S is selected from one of urea or sodium humate.
Preferably, the material R may be a transition metal oxide. The material R may be selected from one or more of iron oxide, manganese oxide or cerium oxide. Preferably, R is ferric oxide.
According to one embodiment of the invention, the material a is sodium chlorate, the material B is concentrated sulfuric acid, the material C is hydrogen peroxide, R is ferric oxide, and the material S is urea or sodium humate. According to one embodiment of the invention, the material A is sodium chlorate, the material B is concentrated sulfuric acid, the material C is hydrogen peroxide, R is ferric oxide, and the material S is sodium humate.
In the invention, the amount of alkali metal chlorate and/or alkali metal chlorite in the material A is 1-15 parts by weight, the amount of the material B is 1-10 parts by weight, the amount of the material C is 1-12 parts by weight, the amount of the material R is 0.002-0.006 parts by weight, and the amount of the material S is 0.02-0.1 part by weight. Preferably, the amount of alkali metal chlorate and/or alkali metal chlorite in the material A is 8-11 parts by weight, the amount of the material B is 5-8 parts by weight, the amount of the material C is 5-10 parts by weight, the amount of the material R is 0.002-0.004 parts by weight, and the amount of the material S is 0.04-0.06 parts by weight.
The reaction time of the materials A, B, C, S and R can be 2-8 h; preferably 3 to 6 hours; more preferably 4 to 5 hours. The reaction temperature can be 45-85 ℃; preferably 50 to 75 ℃; more preferably 55 to 60 ℃. And conveying the steam for heating to the oxidizing gas generating equipment through a steam inlet, and heating the raw materials in a heat exchange mode.
In certain embodiments, feed a, feed B are added to an oxidizing gas generating apparatus. When the acidity of the reaction feed solution in the oxidizing gas generating apparatus reaches 4 to 9N, preferably 5 to 8N, more preferably 6 to 7N, and the concentration of A reaches 200 to 800g/L, preferably 300 to 600g/L, more preferably 350 to 500g/L, the materials C and S are fed into the oxidizing gas generating apparatus. This is advantageous for smooth reaction.
The oxidizing gas generating apparatus of the present invention has a plurality of cells therein, and a material R as a honeycomb catalyst is disposed in at least a part of the cells. The reaction feed liquid in the previous compartment overflows to the next compartment, thereby completing the multistage reaction. The material R is preferably arranged in all compartments.
In some embodiments, the reaction feed solution from the oxidizing gas generating apparatus is directed to a mother liquor tank, and the mother liquor in the mother liquor tank is recycled to the oxidizing gas generating apparatus. For example, the mother liquor in the mother liquor tank is mixed with the material B from the third raw material tank and recycled to the oxidizing gas generating apparatus. Thus, the reaction progress can be controlled, and the excessive concentration of chlorine dioxide in the oxidizing gas is avoided.
The concentration of chlorine dioxide in the oxidizing gas may be 1 to 10vol%; preferably 1 to 7vol%; more preferably 2 to 5vol%. Thus, the oxidation effect can be ensured, and the operation safety is improved.
Generating gaseous oxidizing ions and oxidizing the flue gas
Delivering an oxidizing gas to a plasma generating and flue gas oxidizing device; in the plasma generation and flue gas oxidation apparatus, the oxidizing gas is converted into gaseous oxidizing ions under the action of a metal or metal compound in the flue gas to be treated, and the gaseous oxidizing ions oxidize nitrogen oxides in the flue gas to be treated to form oxidized flue gas. The metal or metal compound is the residual impurity in the flue gas to be treated. The present invention surprisingly utilizes these impurities to convert oxidizing gases to gaseous oxidizing ions, thereby facilitating the oxidation reaction of nitrogen oxides. The flue gas to be treated in the invention is preferably flue gas from the steel industry; for example, fumes from a steel pelletizing process or a steel sintering process.
The oxidizing gas can be conveyed to the plasma generation and flue gas oxidation equipment by an induced draft fan. The induced draft fan makes the inside of the oxidizing gas generating equipment form negative pressure. The pressure in the oxidizing gas generating apparatus may be-1.0 to-5 kPa; preferably-1.2 to-3.5 kPa; more preferably, -1.5 to-3.0 kPa.
The temperature of the flue gas in the flue gas to be treated can be 80-200 ℃; preferably 80 to 150 ℃; more preferably 100 to 130 ℃. The sulfur dioxide content can be 700-2000 mg/Nm 3 The method comprises the steps of carrying out a first treatment on the surface of the Preferably 1000 to 1800mg/Nm 3 The method comprises the steps of carrying out a first treatment on the surface of the More preferably 1000 to 1500mg/Nm 3 . The content of nitrogen oxides can be 100-500 mg/Nm 3 The method comprises the steps of carrying out a first treatment on the surface of the Preferably 100 to 400mg/Nm 3 The method comprises the steps of carrying out a first treatment on the surface of the More preferably 100 to 300mg/Nm 3 。
The contact time of the oxidizing gas and the flue gas to be treated in the plasma generation and flue gas oxidation equipment can be 0.3-5 s; preferably 0.5 to 2s; more preferably 1 to 1.5s. This is advantageous in terms of both the oxidation rate of nitrogen oxides and the treatment efficiency.
Flue gasDenitration step
And (3) denitration is carried out on the oxidized flue gas in denitration equipment. And conveying the oxidized flue gas to an absorption tower, conveying an absorbent from a powdery absorbent bin to a flue gas pipeline arranged between a flue gas inlet of the absorption tower and the Venturi section, and mixing the oxidized flue gas and the absorbent to form mixed flue gas. Water is sprayed to a venturi section positioned at the lower part of the absorption tower through water supply equipment, so that the mixed flue gas is humidified. And (5) continuously rising the mixed flue gas, and finishing denitration in the absorption tower to obtain the denitration flue gas.
The absorbent may be selected from one or more of calcium oxide, calcium hydroxide, magnesium oxide, magnesium hydroxide, sodium carbonate, sodium bicarbonate, fly ash, etc. Preferably, the absorbent is an absorbent formed from calcium hydroxide and fly ash. The mass ratio of the calcium hydroxide to the fly ash is 1-5:1, preferably 1.2-4.5:1, and more preferably 3:1.
Dust removal step
And conveying the denitration flue gas from the absorption tower to dust removal equipment to form clean flue gas and denitration byproducts. The clean flue gas is discharged from the chimney. And conveying one part of denitration byproducts to a byproduct bin, and conveying the other part of denitration byproducts to an absorption tower for recycling.
The following examples are described as follows:
an absorbent: the absorbent is formed by calcium hydroxide and fly ash, and the mass ratio of the calcium hydroxide to the fly ash is 3:1.
Concentrated sulfuric acid: 98wt%.
Sodium chlorate slurry: formed from a solid of sodium chlorate dispersed in water at a concentration of 500g/L.
Example 1
Fig. 1 is a schematic diagram of a flue gas denitration device according to the present invention. The flue gas denitration device of the present embodiment includes a first raw material tank 1, a second raw material tank 2, a third raw material tank 3, a fourth raw material tank 4, an oxidizing gas generating apparatus 10, a blower 12, an air compressor 13, a mother liquid tank 14, a plasma generating and flue gas oxidizing apparatus 17, an absorbent bin 18, an absorption tower 20, a dust removing apparatus 21, a by-product bin 22, and a chimney 23.
The oxidizing gas generating apparatus 10 is a horizontal advection reactor. The inside of the oxidizing gas generating apparatus 10 is partitioned into a plurality of compartments by a partition member. A baffle is arranged between the compartments. The reaction liquid in the previous compartment overflows to the next compartment through the deflector pipe. At least a portion of the cells are provided with a honeycomb catalyst 5. The bottom of the oxidizing gas generating apparatus 10 is provided with a steam inlet 11 for supplying steam for heating to the oxidizing gas generating apparatus 10.
The side wall of the oxidizing gas generating apparatus 10 is provided with a plurality of feed inlets, which are a first feed inlet, a second feed inlet, a third feed inlet, and a fourth feed inlet, respectively. The first raw material tank 1, the second raw material tank 2 are connected with respective feed ports (first feed port, second feed port) through a first feed pump 6, a second feed pump 7, respectively, to supply the material a and the material C to the oxidizing gas generating apparatus 10, respectively. The third and fourth raw material tanks 3, 4 are connected to the respective feed ports (third and fourth feed ports) by third and fourth feed pumps 8, 9, respectively, to supply the materials B and S to the oxidizing gas generating apparatus 10, respectively. Thus, a reaction solution was formed.
The side wall upper portion of the oxidizing gas generating apparatus 10 is provided with a compressed air inlet (not shown). An air compressor 13 is connected to the compressed air inlet to supply compressed air to the reaction feed liquid of the oxidizing gas generating apparatus 10. The compressed air is aerated in the oxidizing gas generating apparatus 10 to sufficiently agitate the reaction feed solution. The chlorine dioxide gas generated by the reaction is mixed with air to form mixed gas.
The top of the oxidizing gas generating apparatus 10 is also provided with a conditioning air inlet (not shown). The blower 12 is connected to the conditioning air inlet to blow air into the vicinity of the oxidizing gas outlet of the oxidizing gas generating apparatus 10, thereby adjusting the concentration of chlorine dioxide in the mixed gas to obtain the oxidizing gas.
The oxidizing gas generating apparatus 10 is provided at an upper portion thereof with a feed liquid outlet for discharging the reaction feed liquid to the mother liquor tank 14. The mother liquor tank 14 is provided with a mother liquor inlet and a mother liquor outlet. The mother liquor inlet is connected with the feed liquor outlet. The mother liquor outlet is connected to the oxidizing gas generating apparatus 10 through a mother liquor pump 15. The material B from the third feed tank 3 is mixed with the mother liquor and then recycled to the oxidizing gas generating apparatus 10.
The top of the oxidizing gas generating apparatus 10 is provided with an oxidizing gas outlet (not shown). The plasma generation and flue gas oxidation device 17 is connected to the oxidizing gas outlet via a draught fan 16. The oxidizing gas from the oxidizing gas generating apparatus 10 enters the plasma generating and flue gas oxidizing apparatus 17 by the induced draft fan 16. In the plasma generating and flue gas oxidizing apparatus 17, the oxidizing gas from the oxidizing gas generating apparatus 10 is converted into gaseous oxidizing ions by the metal or metal compound in the flue gas to be treated, and nitrogen oxides in low valence states in the flue gas to be treated are oxidized into nitrogen-containing compounds in high valence states, thereby obtaining oxidized flue gas.
The absorber 20 of the present embodiment is a circulating fluidized bed absorber. The bottom of the absorber 20 has a flue gas inlet (not shown). The plasma generating and flue gas oxidizing device 17 is connected to the flue gas inlet so as to deliver oxidized flue gas to the absorber 20. The absorbent bin 18 is connected to a flue gas duct provided between the flue gas inlet and the venturi section of the absorber 20 for feeding powdery absorbent thereto. The oxidized flue gas is mixed with an absorbent in the flue gas duct to form a mixed flue gas. The water supply device 19 is connected to a venturi section located at the lower part of the absorption tower 20 so as to spray water to the absorption tower 20 to humidify the mixed flue gas. The mixed flue gas continues to rise, and denitration is completed in the absorption tower 20, so that denitration flue gas is obtained.
The top or upper portion of the absorber 20 has a flue gas outlet (not shown). The dust removing device 21 is a bag-type dust remover, which is connected with the flue gas outlet of the absorption tower 20. The upper part of the dust removing device 21 is connected to a chimney 23. The lower part of the dust removing device 21 is connected with a byproduct bin 22. The denitration flue gas is discharged from a flue gas outlet and enters the dust removal device 21. The dust removing device 21 removes dust from the denitration flue gas. The obtained clean flue gas is discharged from a chimney 23; the resulting denitration by-product is transported to the by-product bin 22.
In a specific implementation process, the material A is a slurry containing alkali metal chlorate or a slurry containing alkali metal chlorite. The material B is concentrated hydrochloric acid or concentrated sulfuric acid. The material C is hydrogen peroxide or methanol. The material S is a stabilizer selected from urea, sodium humate or sodium citrate. The material R as honeycomb catalyst 5 is a transition metal oxide catalyst selected from the group consisting of iron oxide, manganese oxide and cerium oxide. The flue gas to be treated is sintering flue gas or pellet flue gas in the steel industry.
Example 2
The rest is the same as in example 1 except for the following settings:
as shown in fig. 2, a first feed port, a second feed port, and a third feed port (not shown) are provided on the side wall of the oxidizing gas generating apparatus 10. The first raw material tank 1 and the second raw material tank 2 are respectively supplied with the materials A and C through the first feed pump 6 and the second feed pump 7. Material a and material C are mixed and then supplied to the oxidizing gas generating apparatus 10 through the first feed port. The third raw material tank 3 is connected to the second feed port by a third feed pump 8, thereby supplying the material B to the oxidizing gas generating apparatus 10. The fourth raw material tank 4 is connected to the third feed port by a fourth feed pump 9, thereby supplying the material S to the oxidizing gas generating apparatus 10. Thus, a reaction solution was formed.
Example 3
The rest is the same as in example 1 except for the following settings:
no deflector tube is provided between the compartments of the oxidizing gas generating apparatus 10. The reaction liquid in the previous compartment overflows to the next compartment through the partition.
Example 4
The rest is the same as in example 1 except for the following settings:
a honeycomb catalyst 5 is disposed in all the cells.
Example 5
The rest is the same as in example 2 except for the following settings:
no deflector tube is provided between the compartments of the oxidizing gas generating apparatus 10. The reaction liquid in the previous compartment overflows to the next compartment through the partition.
Example 6
The rest is the same as in example 2 except for the following settings:
a honeycomb catalyst 5 is disposed in all the cells.
Example 7
The flue gas denitration is carried out by adopting the denitration device of the embodiment 2, and the specific steps are as follows:
the sodium chlorate slurry (material a) from the first material tank 1, the concentrated sulfuric acid (material B) from the third material tank 3, the hydrogen peroxide solution (material C) from the second material tank 2 and the urea (material S) from the fourth material tank 4 are fed to the oxidizing gas generating apparatus 10 to form a reaction liquid.
The reaction mixture reacts with a honeycomb catalyst 5 (honeycomb-shaped ferric oxide R) disposed in the cells. The reaction liquid in the previous compartment overflows to the next compartment through the deflector pipe, thereby completing the multistage reaction. The heating steam is supplied to the oxidizing gas generating apparatus 10 through the steam inlet 11, and the raw material is heated by heat exchange. Compressed air from an air compressor 13 is supplied to the reaction liquid of the oxidizing gas generating apparatus 10 to be aerated, and chlorine dioxide generated by the reaction and air form a mixed gas. The conditioning air was sent to the vicinity of the oxidizing gas outlet of the oxidizing gas generating apparatus 10 by the blower 12 to adjust the chlorine dioxide concentration of the mixed gas to 3vol%, and the resultant oxidizing gas was discharged from the oxidizing gas generating apparatus 10.
The reaction liquid from the oxidizing gas generating apparatus 10 is led out to the mother liquor tank 14, and the mother liquor in the mother liquor tank 14 is mixed with concentrated sulfuric acid (material B) from the third raw material tank by the mother liquor pump 15 and then fed back to the oxidizing gas generating apparatus 10. The oxidizing gas from the oxidizing gas generating apparatus 10 is sent to the plasma generating and flue gas oxidizing apparatus 17 by the induced draft fan 16. In the plasma generating and flue gas oxidizing device 17, the oxidizing gas is converted into gaseous oxidizing ions under the action of the metal or metal compound in the flue gas to be treated, and the nitrogen oxides in the flue gas to be treated are oxidized to obtain oxidized flue gas.
The oxidized flue gas is delivered to an absorber 20. The powdered absorbent (formed from calcium hydroxide and fly ash) from the absorbent bin 18 is fed into a flue gas duct disposed between the flue gas inlet of the absorber 20 and the venturi section, and the oxidized flue gas is mixed with the absorbent to form a mixed flue gas. The water is sprayed through the water supply device 19 to the venturi section located at the lower portion of the absorption tower 20, thereby humidifying the mixed flue gas. The mixed flue gas continues to rise, and denitration is completed in the absorption tower 20, so that denitration flue gas is obtained.
The denitration flue gas from the absorber 20 is sent to a dust removal device 21, forming clean flue gas and denitration byproducts. The clean flue gas is discharged from the stack 23. A portion of the denitration byproducts are conveyed to the byproduct bin 22, and another portion of the denitration byproducts are conveyed to the absorption tower 20 for recycling.
The raw materials and the amounts thereof are shown in Table 1, and the yield of chlorine dioxide is 1.5t/d.
The flue gas to be treated comes from the 150 ten thousand t/a pellet project, and specific parameters are shown in table 2.
The time for the oxidizing gas to contact the flue gas to be treated in the plasma generating and flue gas oxidizing apparatus 17 is 0.8s. By analyzing the components of different nitrogen oxides in oxidized flue gas, the oxidation rate of NO is 89%, and NO is mainly oxidized 2 And HNO 3 ，HNO 3 In the form of nitric acid vapor.
The parameters of the clean flue gas are shown in table 3. The operation is carried out for 6 months, and the operation safety is high.
TABLE 1
| Raw materials | Dosage (weight portions) |
| Chloric acid in sodium chlorate slurry (A)Sodium salt | 2.8 |
| Concentrated sulfuric acid (B) | 1.9 |
| Hydrogen peroxide (C) | 1.9 |
| Ferric oxide (R) | 0.003 |
| Urea (S) | 0.05 |
TABLE 2
| Parameters (parameters) | Unit (B) | Numerical value |
| Smoke volume (working condition) | m 3 /h | 900000 |
| Standard state smoke quantity | Nm 3 /h | 640000 |
| NOx concentration | mg/Nm 3 | 150 |
| Dust content | mg/Nm 3 | 48 |
| Temperature (temperature) | ℃ | 110 |
| Moisture content | ％ | 17.6 |
TABLE 3 Table 3
| Parameters (parameters) | Unit (B) | Numerical value |
| Smoke volume (working condition) | m 3 /h | 920000 |
| Standard state smoke quantity | Nm 3 /h | 680000 |
| NOx concentration | mg/Nm 3 | 20 |
| Dust | mg/Nm 3 | 1.5 |
| Temperature (temperature) | ℃ | 97 |
| Denitration efficiency | ％ | 86 |
Example 8
Example 7 is the same as example 7 except for the following parameters:
the raw materials and the amounts thereof are shown in Table 4, and the yield of chlorine dioxide was 3t/d.
The flue gas to be treated comes from 132m 2 In the sintering machine project, specific parameters are shown in table 5.
The time for the oxidizing gas to contact the flue gas to be treated in the plasma generating and flue gas oxidizing apparatus 17 is 1s. By analyzing the components of different nitrogen oxides in oxidized flue gas, the oxidation rate of NO is 90 percent, and NO is mainly oxidized 2 And HNO 3 ，HNO 3 In the form of nitric acid vapor.
The parameters of the clean flue gas are shown in table 6. The operation is carried out for 6 months, and the operation safety is high.
TABLE 4 Table 4
| Raw materials | Dosage (weight portions) |
| Sodium chlorate in sodium chlorate slurry (A) | 5.2 |
| Concentrated sulfuric acid (B) | 3.7 |
| Hydrogen peroxide (C) | 3.9 |
| Ferric oxide (R) | 0.004 |
| Sodium humate (S) | 0.06 |
TABLE 5
| Parameters (parameters) | Unit (B) | Numerical value |
| Smoke volume (working condition) | m 3 /h | 780000 |
| Standard state smoke quantity | Nm 3 /h | 680000 |
| NOx concentration | mg/Nm 3 | 250 |
| Dust content | mg/Nm 3 | 48 |
| Temperature (temperature) | ℃ | 130 |
| Moisture content | ％ | 16.6 |
TABLE 6
| Parameters (parameters) | Unit (B) | Numerical value |
| Smoke volume (working condition) | m 3 /h | 815000 |
| Standard state smoke quantity | Nm 3 /h | 711000 |
| NOx concentration | mg/Nm 3 | 30 |
| Dust | mg/Nm 3 | 1.5 |
| Temperature (temperature) | ℃ | 97 |
| Denitration efficiency | ％ | 88 |
Example 9
Example 7 is the same as example 7 except for the following parameters:
the raw materials and the amounts thereof are shown in Table 7, and the yield of chlorine dioxide is 5.5t/d.
The flue gas to be treated comes from 180m 2 In the sintering machine project, specific parameters are shown in table 8.
The time for the oxidizing gas to contact the flue gas to be treated in the plasma generating and flue gas oxidizing apparatus 17 is 1.2s. By analyzing the components of different nitrogen oxides in oxidized flue gas, the oxidation rate of NO is 91 percent, and the NO is mainly oxidized into NO 2 And HNO 3 ，HNO 3 In the form of nitric acid vapor.
The parameters of the clean flue gas are shown in table 9. The operation is carried out for 6 months, and the operation safety is high.
TABLE 7
| Raw materials | Dosage (weight)Parts by weight of |
| Sodium chlorate in sodium chlorate slurry (A) | 9.5 |
| Concentrated sulfuric acid (B) | 6.9 |
| Hydrogen peroxide (C) | 7.1 |
| Ferric oxide (R) | 0.004 |
| Sodium humate (S) | 0.06 |
TABLE 8
| Parameters (parameters) | Unit (B) | Numerical value |
| Smoke volume (working condition) | m 3 /h | 1080000 |
| Standard state smoke quantity | Nm 3 /h | 720000 |
| NOx concentration | mg/Nm 3 | 300 |
| Dust content | mg/Nm 3 | 48 |
| Temperature (temperature) | ℃ | 130 |
| Moisture content | ％ | 16.6 |
TABLE 9
| Parameters (parameters) | Unit (B) | Numerical value |
| Smoke volume (working condition) | m 3 /h | 110000 |
| Standard state smoke quantity | Nm 3 /h | 76000 |
| NOx concentration | mg/Nm 3 | 30 |
| Dust | mg/Nm 3 | 1.5 |
| Temperature (temperature) | ℃ | 97 |
| Denitration efficiency | ％ | 90 |
The present invention is not limited to the above-described embodiments, and any modifications, improvements, substitutions, and the like, which may occur to those skilled in the art, fall within the scope of the present invention without departing from the spirit of the invention.
Claims (3)
1. A flue gas denitration method is characterized in that,
the flue gas denitrification device used comprises:
an oxidizing gas generating device configured to generate an oxidizing gas by a reaction liquid, and provided with a compressed air inlet, an air inlet for adjustment, and an oxidizing gas outlet;
the oxidizing gas generating device is a horizontal advection reactor; at least one partition provided in the oxidizing gas generating apparatus, the partition being configured to partition an internal space of the oxidizing gas generator into a plurality of compartments; in each of these compartments is disposed a honeycomb catalyst for catalyzing the reaction feed to obtain an oxidizing gas;
the oxidizing gas generating apparatus is further provided with a steam inlet for supplying heating steam to the oxidizing gas generating apparatus;
The flue gas denitration device further comprises a first raw material tank containing a material A, a second raw material tank containing a material C, a third raw material tank containing a material B and a fourth raw material tank containing a material S;
a plurality of feed inlets are formed in the side wall of the oxidizing gas generating device; the first raw material tank, the second raw material tank, the third raw material tank and the fourth raw material tank are respectively arranged to be capable of being connected with corresponding feed inlets, so that materials A, C, B and S are supplied to the oxidizing gas generating equipment to form reaction feed liquid; or (b)
The side wall of the oxidizing gas generating device is provided with a first feed port, a second feed port and a third feed port; the first raw material tank and the second raw material tank are connected with the first feed port, so that after the materials A and C are mixed, the materials A and C are fed to the oxidizing gas generating equipment through the first feed port; a third feed tank is arranged to be connectable to the second feed inlet for feeding material B to the oxidizing gas generating apparatus; a fourth feed tank is arranged to be connectable to the third feed inlet so as to supply the material S to the oxidizing gas generating apparatus to form a reaction feed liquid;
an air compressor connected to the compressed air inlet and configured to provide compressed air to the oxidizing gas generating apparatus;
A blower connected to the conditioning air inlet and configured to be capable of blowing conditioning air into the oxidizing gas generating apparatus;
a plasma generating and flue gas oxidizing device connected to the oxidizing gas outlet configured to convert the oxidizing gas into gaseous oxidizing ions and oxidize nitrogen oxides in the flue gas to be treated to form oxidized flue gas;
a denitration device connected with the plasma generation and flue gas oxidation device and configured to be capable of performing denitration treatment on oxidized flue gas from the plasma generation and flue gas oxidation device to obtain denitration flue gas;
the denitration device comprises an absorption tower, an absorbent bin and water supply equipment; the absorption tower is a circulating fluidized bed absorption tower;
the absorption tower is provided with a flue gas inlet and a flue gas outlet; the plasma generation and flue gas oxidation device is connected with the flue gas inlet and is arranged to be capable of conveying oxidized flue gas to the absorption tower; the absorbent bin is connected with the absorption tower and is used for supplying powdery absorbent to the absorption tower; the water supply device is arranged to spray water to the absorbent and the oxidized flue gas in the absorption tower;
The method comprises the following steps:
(1) Placing a material R serving as a honeycomb catalyst in a compartment of an oxidizing gas generating device, and respectively conveying a material A, a material C, a material B and a material S into the oxidizing gas generating device by a first material tank, a second material tank, a third material tank and a fourth material tank to form a reaction material liquid, and conveying compressed air into the oxidizing gas generating device by an air compressor to perform aeration; reacting the feed liquid to generate chlorine dioxide gas, wherein the chlorine dioxide gas and air form mixed gas; the blower conveys air for adjustment to the oxidizing gas generating equipment so as to adjust the concentration of chlorine dioxide in the mixed gas, thereby obtaining oxidizing gas; wherein the reaction time of the material A, the material B, the material C, the material S and the material R is 2-8 h, and the reaction temperature is 55-60 ℃;
(2) Delivering an oxidizing gas to a plasma generating and flue gas oxidizing device; in the plasma generation and flue gas oxidation equipment, oxidizing gas is converted into gaseous oxidizing ions under the action of metal or metal compounds in the flue gas to be treated, and the gaseous oxidizing ions oxidize nitrogen oxides in the flue gas to be treated to form oxidized flue gas; the contact time of the oxidizing gas and the flue gas to be treated in the plasma generation and flue gas oxidation equipment is 1 to 1.5s;
(3) Conveying the oxidized flue gas to an absorption tower, conveying a powdery absorbent from an absorbent bin to a flue gas pipeline arranged between a flue gas inlet of the absorption tower and a Venturi section, and mixing the oxidized flue gas and the absorbent to form mixed flue gas; spraying water to a venturi section positioned at the lower part of the absorption tower through water supply equipment so as to humidify the mixed flue gas; the mixed flue gas continuously rises, and denitration is completed in an absorption tower, so that denitration flue gas is obtained; the absorbent is calcium hydroxide and fly ash with the mass ratio of 3:1;
wherein the material A is sodium chlorate slurry, the material B is concentrated sulfuric acid, the material C is hydrogen peroxide, the material S is sodium humate, the material R is ferric oxide, and the flue gas to be treated is flue gas from the steel industry;
wherein, the dosage of sodium chlorate in the material A is 8-11 weight parts, the dosage of concentrated sulfuric acid is 5-8 weight parts, the dosage of hydrogen peroxide is 5-10 weight parts, the dosage of ferric oxide is 0.002-0.004 weight parts, and the dosage of sodium humate is 0.04-0.06 weight parts;
NO in the flue gas to be treated x The concentration of (C) is 100-300 mg/Nm 3 The temperature of the flue gas to be treated is 100-130 ℃.
2. The method according to claim 1, wherein a baffle is provided between the compartments of the horizontal advection reactor, the baffle being used to overflow the reaction feed liquid from the previous compartment to the next compartment.
3. The method of claim 1, wherein the flue gas denitrification device further comprises a mother liquor tank having a mother liquor inlet and a mother liquor outlet;
the oxidizing gas generating equipment is provided with a feed liquid outlet; the feed liquid outlet is connected with the mother liquid inlet so as to lead out at least part of reaction feed liquid to a mother liquid tank;
the oxidizing gas generating device is provided with a feed liquid inlet; the feed liquid inlet is connected with the mother liquid outlet and is arranged to circulate the mother liquid in the mother liquid tank to the oxidizing gas generating device.
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