CN107983118A - A kind of collaboration recycling processing method containing nitrogen, oxysulfide exhaust gas at the same time - Google Patents
A kind of collaboration recycling processing method containing nitrogen, oxysulfide exhaust gas at the same time Download PDFInfo
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- CN107983118A CN107983118A CN201711057042.9A CN201711057042A CN107983118A CN 107983118 A CN107983118 A CN 107983118A CN 201711057042 A CN201711057042 A CN 201711057042A CN 107983118 A CN107983118 A CN 107983118A
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- exhaust gas
- oxysulfide
- reaction
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- containing nitrogen
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- 239000007789 gas Substances 0.000 title claims abstract description 53
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 24
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000003672 processing method Methods 0.000 title claims abstract description 20
- 238000004064 recycling Methods 0.000 title claims abstract description 19
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 68
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 49
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000007788 liquid Substances 0.000 claims abstract description 31
- 238000010521 absorption reaction Methods 0.000 claims abstract description 30
- 239000012495 reaction gas Substances 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 16
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 14
- 230000003647 oxidation Effects 0.000 claims abstract description 13
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 13
- 238000012545 processing Methods 0.000 claims abstract description 6
- 238000012958 reprocessing Methods 0.000 claims description 8
- 239000002918 waste heat Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 3
- RXQNKKRGJJRMKD-UHFFFAOYSA-N 5-bromo-2-methylaniline Chemical compound CC1=CC=C(Br)C=C1N RXQNKKRGJJRMKD-UHFFFAOYSA-N 0.000 abstract description 11
- 239000002912 waste gas Substances 0.000 abstract description 5
- 238000000034 method Methods 0.000 description 20
- 238000004519 manufacturing process Methods 0.000 description 11
- APRRQJCCBSJQOQ-UHFFFAOYSA-N 4-amino-5-hydroxynaphthalene-2,7-disulfonic acid Chemical compound OS(=O)(=O)C1=CC(O)=C2C(N)=CC(S(O)(=O)=O)=CC2=C1 APRRQJCCBSJQOQ-UHFFFAOYSA-N 0.000 description 7
- 239000000975 dye Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- -1 Nitryl sulfuric acid Chemical compound 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- KBYMQDYGNRTQBR-UHFFFAOYSA-N [S-][N+]=O Chemical compound [S-][N+]=O KBYMQDYGNRTQBR-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005406 washing 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/60—Simultaneously removing sulfur oxides and 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
- B01D53/77—Liquid phase processes
- B01D53/78—Liquid phase processes with gas-liquid contact
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/62—Methods of preparing sulfites in general
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/74—Preparation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
- C01B21/087—Compounds containing nitrogen and non-metals and optionally metals containing one or more hydrogen atoms
- C01B21/093—Compounds containing nitrogen and non-metals and optionally metals containing one or more hydrogen atoms containing also one or more sulfur atoms
- C01B21/094—Nitrosyl containing acids
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/20—Nitrogen oxides; Oxyacids of nitrogen; Salts thereof
- C01B21/50—Nitrous acid; Salts thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/10—Oxidants
- B01D2251/104—Ozone
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
- B01D2257/302—Sulfur oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/40—Nitrogen compounds
- B01D2257/404—Nitrogen oxides other than dinitrogen oxide
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Biomedical Technology (AREA)
- Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Treating Waste Gases (AREA)
Abstract
The invention discloses a kind of collaboration recycling processing method containing nitrogen, oxysulfide exhaust gas at the same time, belong to technical field of waste gas treatment, include the following steps：1. ozone oxidation：Reaction gas I will be obtained containing the life reaction of nitrogen, the exhaust gas of oxysulfide and ozone hybrid concurrency；2. sulfuric acid absorption：Reaction gas I is passed through sulfuric acid absorption system to be absorbed, be absorbed liquid I and reaction gas II；3. sulfur dioxide is reprocessed：Absorbing liquid I is passed through sulfur dioxide to be reprocessed, be absorbed liquid II and reaction gas III；4. residual gas is handled：Reaction gas II and reaction gas III discharge after processing is up to standard.The present invention uses ozone by NO and SO2It is oxidized to more expensive state, NO2、N2O5Content improves the nitric acid content raising so that in absorbing liquid I, SO2And HNO3Reaction also generates nitrosyl sulfuric acid, and system is more stablized, since nitric acid content is high in absorbing liquid, in follow-up SO2Nitric acid need not be added in absorption.
Description
Technical field
The present invention relates to technical field of waste gas treatment, in particular to a kind of collaboration containing nitrogen, oxysulfide exhaust gas at the same time
Recycling processing method.
Background technology
Conventional method of denitration mainly has SCR, SNCR, ozone+liquid caustic soda washing, ozone+urea spray etc., above method
It is usually used in the NOx removal of boiler of power plant flue gas etc., there is the of high cost and wasting of resources；
Common sulfur method mainly has with CaCO3（Lime stone）Based on calcium method, the magnesium processes based on MgO, with Na2SO3
Based on sodium method, with NH3Based on ammonia process, organic alkaline process based on organic base, these method generally existing equipment
The shortcomings that seriously corroded, operation and maintenance cost are high and easily cause secondary pollution；
Above method desulphurization denitration operating cost is high in a word and causes the serious wasting of resources, provides no advantage against, and do not have at present
There is a kind of technology being capable of simultaneous SO_2 and NO removal.
NOx and/or SO can be produced in dyestuff and/or wherein mesosome production process2, such as：Produced in H acid production processes
In tail gas, NOx concentration usually accounts for more than the 90% of NOx emission total amount in 200000 more than ppm, wherein NO；Isolate SO in tail gas2
Concentration usually in 200000 more than ppm.Common processing method is by being discharged after alkali cleaning by wherein NOx, but can produce suction
The problems such as receiving the incomplete and wasting of resources；SO2Generally sulfuric acid reuse can be turned in sulfuric acid plant's resource, but for no sulfuric acid plant
For dyestuff enterprise, SO2It cannot be effectively addressed, cause environmental pollution and the wasting of resources.
The Chinese utility model patent of 105536478 A of Publication No. CN《A kind of recycling treatment of H acid production tail gas
Method and processing system》In, denitration exhaust gas is absorbed with sulfuric acid solution, obtained absorbing liquid is used to absorb acid out exhaust gas, obtains Asia
Nitryl sulfuric acid product, excessive NOx or SO2It is final to recycle sodium nitrite or sodium sulfite by Alkali absorption.This method can not
Handle NOx and SO2Mix waste gas.
The content of the invention
In order to overcome the shortcomings of such scheme, this application provides a kind of collaboration containing nitrogen, oxysulfide exhaust gas at the same time
Recycling processing method, is mainly used for containing NO to what is produced in dye industry production processxAnd SO2Exhaust gas carry out collaboration money
Sourceization processing, its absorption efficiency is high, and the nitrogen in exhaust gas, oxysulfide can be converted into nitrosyl sulfuric acid, sulphite, sulphur
Acid etc. has the byproduct of recovery value.
To achieve the above object, a kind of collaboration recycling containing nitrogen, oxysulfide exhaust gas at the same time according to the present invention
Processing method, includes the following steps：
1. ozone oxidation：Reaction gas I will be obtained containing the life reaction of nitrogen, the exhaust gas of oxysulfide and ozone hybrid concurrency, generally adopted
With ozone output be 20kg/h and following ozone generator generates ozone, it is desirable to provide oxygen, the source of oxygen can be pure
Oxygen steel cylinder or oxygenerator；
This step is uniformly mixed as far as possible, reaction is abundant, NO, SO in ozone and exhaust gas2The fully reaction generation in blending tank
NO2、N2O5And SO3；
2. sulfuric acid absorption：Reaction gas I is passed through sulfuric acid absorption system to be absorbed, be absorbed liquid I and reaction gas II, preferably adopts
With mass concentration, the concentrated sulfuric acid is absorbed more than 85%, SO3With the water reaction generation H in the concentrated sulfuric acid2SO4, part NO2、N2O5It is raw
Into nitric acid, and overwhelming majority NO2、N2O5And H2SO4Higher diazo reagent-the nitrosyl sulfuric acid of reaction generation industrial value, together
When remaining SO2Generation nitrosyl sulfuric acid is also reacted with nitric acid；
It can be absorbed by the way of jet pump sprays the concentrated sulfuric acid and reaction gas I is absorbed；
At the end of absorption, the content of nitric acid is at least more than 3% in system, and 2 times of nitric acid content contain plus nitrosyl sulfuric acid
Amount, should account for system quality percentage about 40%；
3. sulfur dioxide is reprocessed：Absorbing liquid I is passed through sulfur dioxide to be reprocessed, be absorbed liquid II and reaction gas III,
Absorbing liquid II passes through SO2It is processed further obtaining finished product nitrosyl sulfuric acid；
4. residual gas is handled：Reaction gas II and reaction gas III discharge after processing is up to standard, in reaction gas II and reaction gas III
Remaining acid gas and residue ozone by two-stage alkali cleaning, one-stage water wash qualified discharge.
In ozone oxidation step, the additive amount of ozone should be NO in exhaust gas and be fully converted to NO2Required theory ozone amount
60%~200%。
As the preferred of above-mentioned technical proposal, dehumidifying step is further included before the ozone oxidation step：Nitrogen, sulphur will be contained
The exhaust gas of oxide exchanges heat by heat exchanger, then removes moisture removal by moisture trap again, absolute humidity is reduced to
100 g/m3Below.
As the preferred of above-mentioned technical proposal, the reaction temperature of the ozone oxidation step is 30 ~ 80 DEG C.
Ozone aoxidizes SO at normal temperatures2Conversion ratio about 30%, preferably, control oxidizing temperature be 30oC~80oC, SO2
Conversion ratio can be promoted to 80%.
As the preferred of above-mentioned technical proposal, the ozone oxidation step utilizes reaction heat produced by sulfuric acid absorption step
Waste heat is heated, and avoids energy waste.
As the preferred of above-mentioned technical proposal, control absorption temperature is less than 80 DEG C in the sulfuric acid absorption step.
As the preferred of above-mentioned technical proposal, in the sulfuric acid absorption step, control absorbs temperature at 52 ~ 58 DEG C.
As the preferred of above-mentioned technical proposal, the sulfur dioxide is reprocessed in step, the material that sulfur dioxide is passed through
Measure as 1 ~ 1.5 times of nitric acid molal quantity in absorbing liquid I.
As the preferred of above-mentioned technical proposal, in the sulfur dioxide reprocessing step, the temperature of absorbing liquid is controlled to be less than
80℃。
As the preferred of above-mentioned technical proposal, in the sulfur dioxide reprocessing step, the temperature of absorbing liquid is controlled to be less than
60℃。
As the preferred of above-mentioned technical proposal, in the sulfur dioxide reprocessing step, control reaction pressure is less than
0.3Mpa。
As the preferred of above-mentioned technical proposal, in the sulfur dioxide reprocessing step, control reaction pressure is less than
0.1Mpa。
The similarity of the application and documents is：The NOx absorption process of use is the same, principle and this intention one
Cause, be all to absorb NOx using the concentrated sulfuric acid to form absorbing liquid I, be further continued for absorption SO2 and form absorbing liquid II, obtain product nitrosyl
Sulfuric acid.
Difference is：It is not proper that documents do not consider in following four problems：（1）The recycling of NOx is taken into consideration only,
If NOx, SO2Mix waste gas can not then be handled（NOx and SO2Mix waste gas results from the row such as DYE PRODUCTION, power plant, coke-oven plant
Industry, especially dye industry, H acid productions can produce NOx, and resolution process produces SO2If the two handles cause the wasting of resources respectively
And it is with high costs, resource turns to nitrosyl sulfuric acid after merging, available for dyestuff diazotising or sells to colleague）；（2）H acid productions
It is mainly NO, NO in tail gas2Concentration is low to cause that absorption efficiency is low, soak time length；（3）Nitrosyl sulfuric acid is unstable, in environment
Temperature is higher or placement process in can occur to decompose on a small quantity, produce SO2, NO in tail gas2Nitric acid content in the few then absorbing liquid of content
It is few, SO2It can cause product more unstable when excessive, occur to become blue smoke event；（4）NO contents height causes to absorb and imitates in tail gas
Fruit is bad, can increase with the increase solution viscosity of nitrosyl sulfuric acid concentration, a large amount of NO are present in absorbing liquid in the form of minute bubbles
In, cause to circulate pump cavitation.
Compared with prior art, the present invention haing the following advantages and beneficial effect：
（1）NO is oxidized to the NO of more expensive state using ozone by the present inventionx, such as NO2、N2O5Deng improving the effect of subsequent absorption
Rate, meanwhile, ozone is by SO2It is oxidized to SO3, H is generated after being only absorbed by the water2SO4, add sulfuric acid content；
（2）Ozone oxidation step is heated using the waste heat of reaction heat produced by sulfuric acid absorption step, avoids energy waste；
（3）NO2、N2O5Content improves the nitric acid content raising so that in absorbing liquid I, SO2And HNO3Reaction also generates nitrosyl sulphur
Acid, and system is more stablized；
（4）Since nitric acid content is high in absorbing liquid, in follow-up SO2Nitric acid need not be added in absorption.
Brief description of the drawings
Fig. 1 is the flow diagram of herein described processing method.
Fig. 2 is the production line schematic diagram of herein described processing method.
In figure：Ozone generator 1, moisture separator 2, blending tank 3, first order absorption groove 4, two level absorb groove 5, three-level absorbs
Groove 6, level-one sulfur dioxide absorption kettle 7, two level sulfur dioxide absorption kettle 8, finished product transfer tank 9, residual Flash Gas Compression Skid System 10.
Embodiment
The present invention is described in further detail with specific embodiment below in conjunction with the accompanying drawings：
1 ~ 3 described method and system of embodiment with reference to figure 1, Fig. 2, wherein, the exhaust gas handled by embodiment 1 is situation：Jiangsu
Chemical enterprise, the H acid production exhaust gas about 300000ppm of concentration containing NO, resolution process exhaust gas contain SO2About 350000ppm, exhaust gas mixing
About 150 m of total blast volume afterwards3/h；
Exhaust gas handled by embodiment 2 is situation：Jiangsu chemical enterprise, the H acid production exhaust gas about 280000ppm of concentration containing NO,
Resolution process exhaust gas contains SO2About 330000ppm, about 135 m of total blast volume after exhaust gas mixing3/h；
Exhaust gas handled by embodiment 3 is situation：Jiangsu chemical enterprise, the H acid production exhaust gas about 320000ppm of concentration containing NO,
Resolution process exhaust gas contains SO2About 355000ppm, about 155 m of total blast volume after exhaust gas mixing3/h。
Processing method is：
Dehumidifying：Exhaust gas containing nitrogen, oxysulfide is exchanged heat by heat exchanger, then goes to remove water by moisture trap again
Point；
Ozone oxidation：React being given birth to containing nitrogen, the exhaust gas of oxysulfide and ozone hybrid concurrency, produced using sulfuric acid absorption step
The waste heat of raw reaction heat is heated, and obtains reaction gas I；
Sulfuric acid absorption：Reaction gas I is passed through sulfuric acid absorption system to be absorbed, be absorbed liquid I and reaction gas II；
Sulfur dioxide is reprocessed：Absorbing liquid I is passed through sulfur dioxide to be reprocessed, be absorbed liquid II and reaction gas III；
Residual gas processing：Reaction gas II and reaction gas III qualified discharge after two-stage alkali cleaning, one-stage water wash.
The ozone oxidation step is heated using the waste heat of reaction heat produced by sulfuric acid absorption step.
The technological parameter of 11 ~ embodiment of embodiment of table, 3 the method
The conversion of 21 ~ embodiment of embodiment of table, 3 the method and content of material parameter
Reaction gas II and reaction gas III respectively obtain the molten of nitrite and sulphite after two-stage alkali cleaning, one-stage water wash
Liquid, available for recycling nitrite and sulphite；
Nitrosyl sulfuric acid content is higher in absorbing liquid II, and nitric acid content ＜ 0.2%, is back to industrial production or sells.
Claims (10)
1. a kind of collaboration recycling processing method containing nitrogen, oxysulfide exhaust gas at the same time, it is characterised in that including following step
Suddenly：
1. ozone oxidation：Reaction gas I will be obtained containing the life reaction of nitrogen, the exhaust gas of oxysulfide and ozone hybrid concurrency；
2. sulfuric acid absorption：Reaction gas I is passed through sulfuric acid absorption system to be absorbed, be absorbed liquid I and reaction gas II；
3. sulfur dioxide is reprocessed：Absorbing liquid I is passed through sulfur dioxide to be reprocessed, be absorbed liquid II and reaction gas III；
4. residual gas is handled：Reaction gas II and reaction gas III discharge after processing is up to standard.
2. a kind of collaboration recycling processing method containing nitrogen, oxysulfide exhaust gas at the same time according to claim 1, it is special
Sign is：Dehumidifying step is further included before the ozone oxidation step：By the exhaust gas containing nitrogen, oxysulfide by heat exchanger into
Row heat exchange, then removes moisture removal by moisture trap again, absolute humidity is reduced to 100 g/m3Below.
3. a kind of collaboration recycling processing method containing nitrogen, oxysulfide exhaust gas at the same time according to claim 1, it is special
Sign is：The reaction temperature of the ozone oxidation step is 30 ~ 80 DEG C.
4. a kind of collaboration recycling processing method containing nitrogen, oxysulfide exhaust gas at the same time according to claim 3, it is special
Sign is：The ozone oxidation step is heated using the waste heat of reaction heat produced by sulfuric acid absorption step.
5. a kind of collaboration recycling processing method containing nitrogen, oxysulfide exhaust gas at the same time according to claim 1, it is special
Sign is：Control absorbs temperature less than 80 DEG C in the sulfuric acid absorption step.
6. a kind of collaboration recycling processing method containing nitrogen, oxysulfide exhaust gas at the same time according to claim 5, it is special
Sign is：In the sulfuric acid absorption step, control absorbs temperature at 52 ~ 58 DEG C.
7. a kind of collaboration recycling processing method containing nitrogen, oxysulfide exhaust gas at the same time according to claim 1, it is special
Sign is：In the sulfur dioxide reprocessing step, the amount for the material that sulfur dioxide is passed through is nitric acid molal quantity in absorbing liquid I
1 ~ 1.5 times.
8. a kind of collaboration recycling processing method containing nitrogen, oxysulfide exhaust gas at the same time according to claim 1, it is special
Sign is：The temperature of absorbing liquid is controlled to be less than 80 DEG C in the sulfur dioxide reprocessing step.
9. a kind of collaboration recycling processing method containing nitrogen, oxysulfide exhaust gas at the same time according to claim 8, it is special
Sign is：In the sulfur dioxide reprocessing step, the temperature of absorbing liquid is controlled to be less than 60 DEG C.
10. a kind of collaboration recycling processing method containing nitrogen, oxysulfide exhaust gas at the same time according to claim 1, its
It is characterized in that：In the sulfur dioxide reprocessing step, control reaction pressure is less than 0.3Mpa.
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Citations (4)
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| JPS522868A (en) * | 1975-06-24 | 1977-01-10 | Kobe Steel Ltd | Nox_rich exhaust gas treatment process |
| CN105536478A (en) * | 2016-01-16 | 2016-05-04 | 浙江奇彩环境科技股份有限公司 | Resourceful treatment method and system for H acid production tail gas |
| CN106422694A (en) * | 2016-08-07 | 2017-02-22 | 黄立维 | Method and device for removing sulfur dioxide and nitrogen oxide from airflow |
| CN106552492A (en) * | 2015-09-30 | 2017-04-05 | 中国石油化工股份有限公司 | A kind of processing method and processing device of caprolactam tail gas |
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2017
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS522868A (en) * | 1975-06-24 | 1977-01-10 | Kobe Steel Ltd | Nox_rich exhaust gas treatment process |
| CN106552492A (en) * | 2015-09-30 | 2017-04-05 | 中国石油化工股份有限公司 | A kind of processing method and processing device of caprolactam tail gas |
| CN105536478A (en) * | 2016-01-16 | 2016-05-04 | 浙江奇彩环境科技股份有限公司 | Resourceful treatment method and system for H acid production tail gas |
| CN106422694A (en) * | 2016-08-07 | 2017-02-22 | 黄立维 | Method and device for removing sulfur dioxide and nitrogen oxide from airflow |
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