CN101428195B - System for treating flue gas nitrogen oxide and recycling nitrite with sodium chloride - Google Patents
System for treating flue gas nitrogen oxide and recycling nitrite with sodium chloride Download PDFInfo
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- CN101428195B CN101428195B CN2008101223196A CN200810122319A CN101428195B CN 101428195 B CN101428195 B CN 101428195B CN 2008101223196 A CN2008101223196 A CN 2008101223196A CN 200810122319 A CN200810122319 A CN 200810122319A CN 101428195 B CN101428195 B CN 101428195B
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- nitrite
- flue gas
- electrolysis
- oxidation
- absorption
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- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title claims abstract description 43
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 title claims abstract description 39
- 239000003546 flue gas Substances 0.000 title claims abstract description 38
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 36
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 title claims abstract description 24
- 239000011780 sodium chloride Substances 0.000 title claims abstract description 19
- 238000004064 recycling Methods 0.000 title abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 66
- 238000010521 absorption reaction Methods 0.000 claims abstract description 38
- 230000003647 oxidation Effects 0.000 claims abstract description 35
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 35
- 239000007788 liquid Substances 0.000 claims abstract description 25
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000000460 chlorine Substances 0.000 claims abstract description 16
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 13
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000011084 recovery Methods 0.000 claims abstract description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- 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 abstract description 3
- -1 flue gas nitrogen oxides Chemical class 0.000 claims abstract description 3
- 239000011734 sodium Substances 0.000 claims abstract description 3
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 3
- 230000001590 oxidative effect Effects 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 10
- 238000006477 desulfuration reaction Methods 0.000 claims description 8
- 230000023556 desulfurization Effects 0.000 claims description 7
- 239000003014 ion exchange membrane Substances 0.000 claims description 2
- 239000000779 smoke Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 abstract 2
- 239000005708 Sodium hypochlorite Substances 0.000 abstract 1
- 239000007844 bleaching agent Substances 0.000 abstract 1
- 239000000428 dust Substances 0.000 abstract 1
- 239000007800 oxidant agent Substances 0.000 description 7
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 235000010344 sodium nitrate Nutrition 0.000 description 3
- 239000004317 sodium nitrate Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 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
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005363 electrowinning Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 238000005373 pervaporation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a system for treating flue gas nitrogen oxides by using sodium chloride and recycling nitrite, which comprises an oxidation system, an absorption system, an electrolysis system and a nitrite recovery system; chlorine bleach liquor is taken as oxidation liquid; a sodium hydroxide solution is taken as absorption liquid; flue gas after being subjected to dust removal and desulphurization is oxidized in the oxidation system, then input into the absorption system to react therein, and is emitted after reaching standards; the absorption liquid which is rich in nitrite after reacting with the flue gas is input into the nitrite reclaiming system for nitrite recovery; the oxidation liquid restored by the flue gas in the oxidation system is input into the electrolysis systemfor electrolysis; when necessary, the electrolysis system is supplemented with sodium chloride to produce sodium hydroxide, hydrogen and chlorine gas; some of sodium hydroxide is recycled to the absorption system, and some of sodium hydroxide reacts with chlorine gas to produce sodium hypochlorite which is recycled to the oxidation system. The method provided by the invention uses sodium chloridewhich is relatively cheap as the raw material for denitration, thereby not only effectively removing NOx, but also recycling nitrite.
Description
Technical field
The present invention relates to the air pollution control technique field, be specially and a kind ofly utilize sodium chloride to administer flue gas nitrogen oxide and reclaim the system of nitrite, be applicable to the denitration of gases such as flue gas that boiler produces, nitric acid production tail gas, flue gas during smelting.
Background technology
Present a kind of improvement method to nitrogen oxide in the flue gas is generally utilizes oxidant with the NO oxidation in the flue gas earlier, utilizes absorbent to absorb again, such as:
Publication number is that the Chinese invention patent of CN1768902 and CN1923341 has proposed a kind of ozone oxidation and denitration method of boiler flue gas and coal-burning boiler fume ozone oxidation and simultaneous desulfurization denitrification apparatus and method thereof respectively, and employing sprays into ozone NO is oxidized to high valence state nitrogen oxide NO soluble in water
2, NO
3Or N
2O
5, and then with the NO of alkali lye after with oxidation
xAbsorb, generate the mixture of nitrate and nitrite in the absorption process.
Publication number is wet ammonia flue gas cleaning technology and the system thereof that the Chinese invention patent of CN101053747 discloses a kind of while desulphurization denitration, its adopt hydrogen peroxide or ozone as oxidant with the NO oxidation, and then with ammoniacal liquor with NO
xAbsorb.
Publication number is that the Chinese invention patent of CN100366325 discloses a kind of wet method combined process for desulfurization and denitration for chlorine-containing strong oxidizer absorption liquid, and pending flue gas is entered absorption reactor thermally, fully contacts the SO in the flue gas with the absorption liquid that contains chloric strong oxidant
2, NO
xBe absorbed the after-purification discharging.The present invention is simple in structure, and is easy to operate, can reach denitration efficiency and the 90% above desulfuration efficiency of 60-95%.
Above prior art has following characteristics: 1, adopt oxidation-absorption process denitration can reach higher removal efficient; 2, especially the gaseous oxidizing agent dosage is big for Chang Yong oxidant, and it is limited to originate, the cost height; 3, the liquid phase oxidation agent also can be well with the NO oxidation and remove; 4, present wet method method of denitration is considered less to the recycling of product.
This shows,, realize the recycling of nitrogen element in the flue gas, need a kind of more economically viable method of denitration in order to satisfy following denitration requirement.
Summary of the invention
At the system after the wet desulphurization, the present invention proposes a kind of method of utilizing sodium chloride improvement flue gas nitrogen oxide and reclaiming nitrite.This technology can utilize the lower sodium chloride of price to carry out denitration as raw material, can not only effectively remove NO
x, can also effectively reclaim nitrite, have broad prospect for its application.
A kind of method of utilizing sodium chloride improvement flue gas nitrogen oxide and reclaiming nitrite comprises oxidative system, absorption system, electrolysis system and nitrite recovery system; Described oxidative system hypochlorous sodium solution is as oxidation liquid, the oxidation in oxidative system of the flue gas after dedusting, the desulfurization; Described absorption system, feeds absorption system through the flue gas of oxidative system oxidation and absorbs the flue gas qualified discharge as absorption liquid with sodium hydroxide solution; The oxidation liquid that is reduced by flue gas in the oxidative system feeds the electrolysis system electrolysis, in electrolysis system, replenish sodium chloride in case of necessity, electrolysis produces NaOH, hydrogen and chlorine, the part sodium hydroxide reuse is to absorption system, generate clorox behind part sodium hydroxide and the chlorine reaction, reuse is to oxidative system; Feed nitrite recovery system recovery nitrite with the absorption liquid of enrichment nitrite anions behind the smoke reaction.
The specific implementation method comprises:
1, oxidation operation
Flue gas enters nitric oxide NO oxidizing tower through after the dedusting, desulfurization, with the liquor natrii hypochloritis of 0.01%～20% (mass percentage concentration) 30～85 ℃ of following oxidations, NO in the flue gas after the oxidation
2The ratio that volume accounts for total nitrogen oxide is about 30%～75%, if control NO
2Volume accounts for 40% of total nitrogen oxide～60% o'clock, can effectively reduce the ratio of nitrate in the subsequent recovery nitrite operation product.React as follows:
NO+HClO→NO
2+HCl
NO+NaClO→NO
2+NaCl
Liquid gas volume ratio is 1～10L/m in tower
3, gas-operated speed 0.6～2m/s in the oxidizing tower, oxidation liquid pH is controlled at 6 optimums.
2, absorb operation
Flue gas after the oxidation enters the absorption tower, absorbs down at 30～50 ℃ as absorption liquid with the sodium hydroxide solution of 0.5%～35% (mass percentage concentration), and qualified discharge, absorption efficiency can reach 50～80%.Following reaction takes place in NaOH in the absorption liquid and nitrogen oxide:
NO
2+NO+2NaOH→2NaNO
2
2NO
2+2NaOH→NaNO
2+NaNO
3+H
2O
Liquid gas volume ratio is 1～10L/m in tower
3, gas-operated speed 0.6～2m/s in the absorption tower.
3, electrowinning process
Sodium chloride solution behind the oxidation operation is adopted diaphragm process or ion exchange membrane electrolysis, and electrolysis temperature is 70～95 ℃, and following reaction takes place in the electrolytic cell:
2NaCl+H
2O → 2NaOH+Cl
2Individual+H
2Individual
The Cl that produces
2Reaction generates clorox NaClO and sodium chloride nacl with NaOH:
Cl
2+2NaOH→NaClO+NaCl+H
2O
Need consume NaOH owing to absorb operation, therefore reaction back hydrogen and chlorine volume ratio are 2～2.2, recover hydrogen and chlorine.
4, sulphite reclaims technology
Along with the raising of absorption liquid Central Asia nitrate ion concentration, reclaim sodium nitrate and natrium nitrosum behind the bigger nitrite solution evaporative crystallization of concentration.The nitrogen dioxide volume accounts for 40% of total nitrogen oxide～60% o'clock after the oxidation, can reduce the ratio of nitrate in the product, and farthest selectivity generates the nitrite of high economic worth, helps the recovery and the recycling of accessory substance.
The present invention is applicable to various type of furnace denitrating flue gas, NO in the flue gas
xContent 500ppm to 5% (volume) all can handle, and tail gas reaches environmental requirement easily, does not produce secondary pollution; Nitrogen resource in the flue gas can be fully recycled, and produces to be worth the raw material of industry product high, that purposes is wide; Technology can continous-stable operation, do not exist such as fouling, obstruction and short period factor such as conversion materials and equipment more; Have good and economic, be fit to the national conditions of current China, utilization is worthy to be popularized.
Description of drawings
Fig. 1 is a kind of feasible flow chart of the inventive method.
The specific embodiment
Adopt technological process as shown in Figure 1, the flue gas behind the desulfurization and dedusting is sent into oxidizing tower 2 by blower fan 1, and the NO in the flue gas partly is oxidized to NO
2, the oxidant liquor natrii hypochloritis in the circulatory pool 3 is delivered to oxidizing tower by circulating pump 4, generates sodium chloride behind clorox and the reaction of nitrogen oxides, passes to carry out electrolysis in the electrolytic cell 8; The flue gas that oxidizing tower 2 is discharged enters absorption tower 5, the NO after the oxidation
xAbsorbed by NaOH in absorption tower 2, purify the back qualified discharge, the absorption liquid of circulatory pool 6 is delivered to the absorption tower by circulating pump 7; Sodium chloride joins and carries out electrolysis in the electrolytic cell 8, and the hydrogen of generation reclaims, and part chlorine feeds reactor 9, and remaining chlorine reclaims, and the NaOH part that electrolysis produces is delivered to circulatory pool 6 and is used for NO after the oxidation
xRemove, another part feeds reactor 9 and generates clorox with chlorine reaction; Along with the raising of absorption liquid Central Asia nitrate ion concentration, the nitrite solution that concentration is bigger is sent into evaporation and crystallization system by circulatory pool 6 bottoms and is reclaimed sodium nitrate and natrium nitrosum.
Application examples:
Contain NO behind the desulfurization and dedusting
xFlue gas, NO
xConcentration 1200ppm, tolerance 100,000 Nm
3/ h, gas is sent into oxidizing tower 2 by blower fan 1, and carrying mass fractions 5%, pH value with circulating pump 4 circulation is that 6 liquor natrii hypochloritis carries out oxidation, and the conveying capacity of circulating pump is 200m
3Gas-operated speed is 1m/s, liquid-gas ratio 3L/m in the/h, oxidizing tower
3, oxidizing temperature is 70 ℃, NO in the flue gas after the oxidation
xMiddle NO
2Volume accounts for total NO
x49%; The NO that oxidizing tower is discharged
xSend into absorption tower 5, circulating pump 7 is carried 10% sodium hydroxide solution 100m
3/ h absorbs, and absorption tower gas-operated speed is 1.5m/s, liquid-gas ratio 5L/m
3, absorbing temperature is 40 ℃, the NO after the absorption
x≤ 200ppm, qualified discharge.Generate sodium chloride behind the hypochlorite oxidation NO, be delivered to electrolytic cell 8 recyclings from circulating slot 3; NaOH absorbs the NO after the oxidation
xThe back generates sodium nitrate and natrium nitrosum, reclaims after pervaporation, crystallization, filtration; Sodium chloride replenishes and adds to electrolytic cell 8, and electrolysis temperature is 80 ℃; The hydrogen that electrolysis generates reclaims, and the chlorine of generation partly is used to generate clorox, and remaining chlorine reclaims, and the NaOH of generation partly is used to prepare clorox, and another part removes NO after the oxidation as absorption liquid
x
Claims (4)
1. a system that utilizes sodium chloride improvement flue gas nitrogen oxide and reclaim nitrite comprises oxidative system, absorption system, electrolysis system and nitrite recovery system; Described oxidative system hypochlorous sodium solution is as oxidation liquid, the oxidation in oxidative system of the flue gas after dedusting, the desulfurization; Described absorption system, feeds absorption system through the flue gas of oxidative system oxidation and absorbs the flue gas qualified discharge as absorption liquid with sodium hydroxide solution; The oxidation liquid that is reduced by flue gas in the oxidative system feeds the electrolysis system electrolysis, replenish sodium chloride in electrolysis system, electrolysis produces NaOH, hydrogen and chlorine, and the part sodium hydroxide reuse is to absorption system, generate clorox behind part sodium hydroxide and the chlorine reaction, reuse is to oxidative system; Feed nitrite recovery system recovery nitrite with the absorption liquid of enrichment nitrite anions behind the smoke reaction.
2. the system as claimed in claim 1, it is characterized in that: the oxidizing condition of described oxidative system is: liquor natrii hypochloritis's mass percentage concentration is 0.01%～20%, 30～85 ℃ of oxidizing temperatures, liquid gas volume ratio is 1～10L/m
3, gas-operated speed 0.6～2m/s.
3. the system as claimed in claim 1, it is characterized in that: the acceptance condition of described absorption system is: the mass percentage concentration of sodium hydroxide solution is 0.5%～35%, absorbs 30～50 ℃ of temperature, liquid gas volume ratio is 1～10L/m
3, gas-operated speed 0.6～2m/s.
4. the system as claimed in claim 1 is characterized in that: described electrolysis system adopts diaphragm process or ion exchange membrane electrolysis, and electrolysis temperature is 70～95 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101223196A CN101428195B (en) | 2008-11-10 | 2008-11-10 | System for treating flue gas nitrogen oxide and recycling nitrite with sodium chloride |
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|---|---|---|---|
| CN2008101223196A CN101428195B (en) | 2008-11-10 | 2008-11-10 | System for treating flue gas nitrogen oxide and recycling nitrite with sodium chloride |
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| Publication Number | Publication Date |
|---|---|
| CN101428195A CN101428195A (en) | 2009-05-13 |
| CN101428195B true CN101428195B (en) | 2011-10-19 |
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| CN104014230A (en) * | 2014-06-20 | 2014-09-03 | 北京中冶隆生环保科技发展有限公司 | Wet flue gas denitration process |
| CN104028096A (en) * | 2014-06-20 | 2014-09-10 | 北京中冶隆生环保科技发展有限公司 | Technology for pressurized turbulent wet-process flue gas denitration and denitration waste liquid reuse |
| CN105536532A (en) * | 2016-02-26 | 2016-05-04 | 中国电力工程顾问集团东北电力设计院有限公司 | Electrically-catalytic low-temperature wet method full-load denitration system |
| CN109173637A (en) * | 2018-10-30 | 2019-01-11 | 攀钢集团攀枝花钢铁研究院有限公司 | The method of low-temperature flue gas liquid phase oxidation denitration |
| CN111135692A (en) * | 2018-11-05 | 2020-05-12 | 新疆硅基新材料创新中心有限公司 | Method and system for recycling waste slurry obtained by power plant boiler flue gas desulfurization and denitrating power plant boiler flue gas |
| CN109647144A (en) * | 2018-12-25 | 2019-04-19 | 湖北蔚天环保科技有限公司 | A kind of liquid-phase catalyst, preparation and application |
| CN110681252A (en) * | 2019-10-22 | 2020-01-14 | 江苏绿塔环境工程有限公司 | Solid waste incineration waste gas treatment process |
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2008
- 2008-11-10 CN CN2008101223196A patent/CN101428195B/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| CN101428195A (en) | 2009-05-13 |
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