CN101947405A - Method for circularly absorbing NOX and SO3 in nitrified tail gas by using sulfuric acid - Google Patents
Method for circularly absorbing NOX and SO3 in nitrified tail gas by using sulfuric acid Download PDFInfo
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- CN101947405A CN101947405A CN2010101866499A CN201010186649A CN101947405A CN 101947405 A CN101947405 A CN 101947405A CN 2010101866499 A CN2010101866499 A CN 2010101866499A CN 201010186649 A CN201010186649 A CN 201010186649A CN 101947405 A CN101947405 A CN 101947405A
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- sulfuric acid
- tail gas
- acid
- nitrated
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims abstract description 162
- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000010521 absorption reaction Methods 0.000 claims abstract description 124
- 239000003513 alkali Substances 0.000 claims abstract description 35
- 230000009102 absorption Effects 0.000 claims description 102
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 102
- 239000002253 acid Substances 0.000 claims description 54
- 239000007788 liquid Substances 0.000 claims description 36
- 230000008569 process Effects 0.000 claims description 5
- 239000006096 absorbing agent Substances 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 abstract description 57
- 238000006396 nitration reaction Methods 0.000 abstract description 31
- 229910017604 nitric acid Inorganic materials 0.000 abstract description 27
- 238000006243 chemical reaction Methods 0.000 abstract description 19
- 239000000463 material Substances 0.000 abstract description 14
- 239000002351 wastewater Substances 0.000 abstract description 11
- 239000002994 raw material Substances 0.000 abstract description 9
- 238000007599 discharging Methods 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 63
- 235000011121 sodium hydroxide Nutrition 0.000 description 44
- 239000012530 fluid Substances 0.000 description 15
- 239000000203 mixture Substances 0.000 description 14
- 238000002360 preparation method Methods 0.000 description 14
- 239000007921 spray Substances 0.000 description 11
- 239000002912 waste gas Substances 0.000 description 9
- 239000000945 filler Substances 0.000 description 8
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- 229910000975 Carbon steel Inorganic materials 0.000 description 5
- 239000010962 carbon steel Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- ZXVONLUNISGICL-UHFFFAOYSA-N 4,6-dinitro-o-cresol Chemical group CC1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1O ZXVONLUNISGICL-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- ZODDGFAZWTZOSI-UHFFFAOYSA-N nitric acid;sulfuric acid Chemical compound O[N+]([O-])=O.OS(O)(=O)=O ZODDGFAZWTZOSI-UHFFFAOYSA-N 0.000 description 1
- 230000001546 nitrifying effect Effects 0.000 description 1
- FWFGVMYFCODZRD-UHFFFAOYSA-N oxidanium;hydrogen sulfate Chemical compound O.OS(O)(=O)=O FWFGVMYFCODZRD-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Treating Waste Gases (AREA)
- Gas Separation By Absorption (AREA)
Abstract
The invention belongs to the technical field of environmental protection and in particular relates to a method for circularly absorbing NOX and SO3 in nitrified tail gas by using sulfuric acid. The method comprises the following steps of: introducing air into the nitrified tail gas and mixing; and discharging the mixed gas after first-class absorption, second-class absorption and third-class absorption, wherein 90 to 98 mass percent sulfuric acid is used as absorption solution in the first-class absorption and the second-class absorption; the sulfuric acid after the first-class absorption is recycled; the sulfuric acid after the second-class absorption is returned to the first-class absorption; and alkali liquor is used in the third-class absorption. The NOX and the SO3 in the tail gas are absorbed to form reaction raw materials, namely nitric acid and the sulfuric acid, and volatile materials are dissolved by the sulfuric acid and are returned to nitration, so the using amount of the raw materials can be reduced under the condition of not increasing the kinds of absorption raw materials, simultaneously the technical problems of low absorption rate, high alkali consumption, a large amount of wastewater, difficult treatment of generated wastewater and the like in the conventional absorption method are solved.
Description
Technical field
The invention belongs to environmental protection technical field, be specifically related to a kind of with the NO in the nitrated tail gas of sulfuric acid circulation absorption
XAnd SO
3Method.
Background technology
As everyone knows, itself have the aromatic ring that causes blunt group and carry out two when nitrated, often using oleum and red fuming nitric acid (RFNA) to be mixed with nitration mixture, to carry out high temperature nitrated.At nitration mixture preparation and nitrifying process, can produce the tail gas of nitrogen oxide, sulfur trioxide.At present, the mode that generally adopts the alkali circulation to absorb is eliminated tail gas, and absorptivity is not high, alkali consumption is big, waste water is many, problems such as the wastewater treatment difficulty of generation but exist.
Chinese invention patent ZL02138494.0 discloses the method that the rare nitric acid single-stage circulation of a kind of usefulness absorbs nitrogen oxide in the tail gas, this method adopts nitric acid to make absorption liquid, and water is made additional solvent, atmospheric operation, blast air with air blast in tower, the gaseous contaminant of processing is NO
XThis method is only applicable to nitric acid when making catalyst, oxidant, because of the treating tail gas that nitric acid decomposes, reaction produces.Compare with the present invention, the present invention is applicable to the treating tail gas that produces with oleum, red fuming nitric acid (RFNA) preparation nitration mixture, nitration reaction, feed sump tidal air etc., tail gas is carried out the comprehensive regulation, recycle, solved nitrated treating tail gas difficulty, consumption is big when adopting alkali lye to absorb, and absorptivity is not high, and the waste water of generation easily causes secondary pollution problem.
Summary of the invention
The present invention mainly be at existing not high with the existing absorptivity of alkali absorption techniques, alkali consumption is many, waste water is many, the technical problem of the waste water treatment difficulty that produces etc., provides a kind of with circulate NO in the nitrated tail gas of absorption of sulfuric acid
X, SO
3Method.
Above-mentioned technical problem of the present invention is mainly solved by following technical proposals:
A kind of with the NO in the nitrated tail gas of sulfuric acid circulation absorption
XAnd SO
3Method, this method is an entrained air in nitrated tail gas, mixed gas discharges after one-level absorption, secondary absorption and three grades of absorptions respectively, one-level absorbs and the secondary absorption all to adopt mass concentration be that 90～98% sulfuric acid is made absorption liquid, sulfuric acid recycling after one-level absorbs, sulfuric acid after secondary absorbs is back to one-level and absorbs, and three grades absorb employing alkali lye.When adopting the mixed acid nitrification of oleum, red fuming nitric acid (RFNA) preparation, oleum and red fuming nitric acid (RFNA) are delivered to production unit by tank car, respectively put to feed sump, because of containing 20% free SO in the oleum
3, SO
3Volatile escaping, red fuming nitric acid (RFNA) are easily decomposed generation NO
X, these volatile gases are sour gas should absorb elimination.Drop into oleum as nitration reaction is last earlier, drip red fuming nitric acid (RFNA) again and carry out the nitration mixture preparation, drip nitrated raw material again after preparation is finished, carry out nitration reaction then at a certain temperature, reaction finishes the concentration of thin up reaction sulfuric acid, and product is separated with reaction sulfuric acid.When oleum and red fuming nitric acid (RFNA) preparation nitration mixture, because of being strong heat release, nitric acid can hot-spot decompose generation NO
X, during nitration reaction, because of the reaction temperature height, part nitric acid takes place decomposes and generation NO
X, the oleum SO that dissociates
3Volatilely produce nitrated emptying end gas thus, be nitrated tail gas of the present invention.The present invention is that a kind of the circulation absorbs the tail gas method that comprehensive utilization is used for administering nitrated generation, specifically is to use the concentrated sulfuric acid as absorbing medium, and the packed tower circulation absorption tail gas with the Pall ring that tetrafluoro or plastic material are housed utilizes NO
X, SO
3The characteristic that certain solubility is arranged in the concentrated sulfuric acid, carrying out the circulation of secondary sulfuric acid absorbs, secondary absorbs and adopts new sulfuric acid, sulfuric acid after secondary absorbs is back to one-level and absorbs, the recyclable sulfuric acid of sulfuric acid after one-level absorbs as nitration reaction, after the secondary sulfuric acid absorption, eliminate the tail gas more than 90% substantially, after alkali lye absorbs the back discharging.
As preferred version, the nitrated tail gas of described nitrated tail gas during from the mixed acid nitrification that adopts the preparation of oleum and red fuming nitric acid (RFNA).As preferred version, described absorption liquid: preceding secondary is that mass concentration 90～98% sulfuric acid are made circulating absorption solution, and third level alkali lye is that mass concentration is 10% sodium hydrate aqueous solution.
As preferred version, the temperature that keeps sulfuric acid in one-level absorption and the secondary absorption process is in 10～60 ℃ of scopes, and optimum is 20～40 ℃.Because of NO
X, SO
3Absorption reaction be strong exothermal reaction, if in the untimely transfer of heat of carrying out of each stage, operating temperature will raise, the too high meeting of temperature is unfavorable for NO
XAbsorption, reduced absorptivity.Each stage absorption liquid internal circulating load also is important operating parameter in addition, and spray flux is few, and gas and absorption liquid contact area are just few, and assimilation effect will descend.Liquid at different levels internal circulating load in the absorption tower, the control sprinkle density is at 30～100m
3/ m
2H can do suitably to adjust according to assimilation effect.
As preferred version, the volume ratio of air and nitrated tail gas is 4～7:1.NO in the described nitrated tail gas of absorption that circulates with absorption liquid
XAnd SO
3Method in, the definite method that contains air and nitrated tail gas mixed proportion is as follows, according to following reaction equation
Above-mentioned NO
XReaction be reversible reaction, the nitric acid and the sulfuric acid that utilize to generate dissolve each other, and have component between nitric acid and sulfuric acid molecule, hydrogen bond action is arranged again, thereby improved the stability of nitric acid, are beneficial to balance and move to right.Blast air, oxygen and moisture content can be provided, general airborne water content easily makes NO more than 40% in the presence of strong oxidizers such as sulfuric acid, nitric acid
XGenerate nitric acid, be dissolved in the sulfuric acid, reach the effect of absorption reaction.The ratio of airborne oxygen and moisture content is: 1 volume NO consumes 0.75 volume O
2, 1 volume NO
2Consume 0.25 volume O
2, contain 0.2 volume O in 1 volumes of air
2, according to NO in the tail gas
XAnd SO
3Content, ratio and flow, and the humidity size of air determines that as calculated the volume ratio of air and nitrated tail gas is 4～7:1.
As preferred version, adopt packed absorber to increase the area of gas and absorption liquid, the height on absorption tower is 3～6M, adopt single-stage or twin-stage tower to absorb, the concrete device of every grade of absorption comprises filler and fixture thereof, the gas-liquid separator of the liquid distribution trough of filler top and filler below, liquid flows into circulating slot, and the outside chuck of installing of circulating slot carries out heat exchange, and the operating temperature that guarantees to absorb is at 10～60 ℃.
As preferred version, adopt half spent acid to replace sulfuric acid as the firsts and seconds absorption liquid.Adopt 98% red fuming nitric acid (RFNA), the nitration mixture of 105% oleum preparation is produced fragrant two itrated compounds, production process is that nitrated and a dinitro divides out reaction, red fuming nitric acid (RFNA) with 98%, it is two nitrated that the nitration mixture of 105% oleum preparation carries out, it is half spent acid (h 2 so 4 concentration is about 95-98%) that the waste mixed acid of two nitrated generations is commonly called as, after half spent acid drips nitric acid, as a nitrated usefulness acid.
Therefore, the present invention has the following advantages:
1, be main absorption equipment with the absorption tower, air-introduced machine is for blasting system air, absorbs after sodium hydrate aqueous solution absorbs through the acid circulation again, and the discharging of each pollutant reaches and is lower than country's " discharge standard of air pollutants ".
2, NO in the tail gas
X, SO
3By raw material nitric acid and sulfuric acid that sulfuric acid absorption becomes to react, the material of volatilization is back to nitration reaction by sulfuric acid dissolution, is not increasing under the situation that absorbs raw material type, can reduce the consumption of raw material.
3, use high-concentration sulfuric acid as circulating absorption solution, little to corrosion of Carbon Steel, equipment is simple, and reduced investment is stable.
4, through sulfuric acid circulation absorption of N O
X, SO
3After, the liquid caustic soda consumption of three grades of absorption usefulness of minimizing, the waste water of generation can be used as the Dilution of sulphuric acid water after the nitrated end and does not produce contaminated wastewater.
5, the present invention is specially adapted to nitration mixture preparation, mixed acid nitrification, administers with the recovery of nitric acid sulfuric acid storage tank tidal air.
Description of drawings
Fig. 1 is a kind of schematic flow sheet of the present invention.
Fig. 2 is the apparatus structure schematic diagram of the embodiment of the invention 4.
Among the figure: 1, tail gas inlet pipe 2, air inlet pipe 3-1, first grade absorption tower 3-2, two-level absorption tower 4-1, sulfuric acid circulating slot 4-2, sulfuric acid circulating slot 5-1, sulfuric acid circulating pump 5-2, sulfuric acid circulating pump 6, flowmeter 7, three grades of absorption towers 8, alkali lye circulating slot 9, NaOH solution circulating pump 10, gas phase pipe 11, exhaust outlet pipe 12, air-introduced machine.
The specific embodiment
Below by embodiment, and in conjunction with the accompanying drawings, technical scheme of the present invention is described in further detail.
Embodiment 1:
Adopt 98% red fuming nitric acid (RFNA), the nitration mixture of 105% oleum preparation is produced fragrant two itrated compounds, production process is that nitrated and a dinitro divides out reaction, red fuming nitric acid (RFNA) with 98%, it is two nitrated that the nitration mixture of 105% oleum preparation carries out, it is half spent acid (h 2 so 4 concentration is about 95-98%) that the waste mixed acid of two nitrated generations is commonly called as, after half spent acid drips nitric acid, as a nitrated usefulness acid.For utilizing half spent acid, available half spent acid replaces the sulfuric acid circulation to absorb, and half spent acid goes a nitration reaction again after circulation absorbs.Consequent NO
XAnd SO
3Waste gas, flow 80.6m
3/ h, NO
XVolumetric concentration be about 85%, wherein NO and NO
2Ratio be about 1:1, SO
3Volumetric concentration be about 6%, enter absorption section after by volume ratio 1:6 mixes with air with waste gas, preceding secondary adopts half waste acid column to absorb, and back one-level adopts washing tower to absorb, liquid distribution trough and tetrafluoro material filler, liquid circulating slot and other annex all are equipped with in every grade of absorption tower.The absorption liquid internal circulating load is 10 m
3/ h, the tower diameter on absorption tower are 0.5M, tower height 3M.Half spent acid absorbs and annex adopts carbon steel, and alkali lye absorbs and annex adopts plastic material.With circulating pump half spent acid is delivered to the first grade absorption tower top spray and flow down, circulating fluid flow rate is 10m
3/ h, nitrated emptying waste gas enters from the first grade absorption tower bottom, with the 500m that replenishes
3/ h air mixes.SO in the nitrated tail gas
3Reaction generates H with half spent acid circulation fluid counter current contacting
2SO
4, NO
XReaction generates nitric acid and NO with half spent acid circulation fluid counter current contacting, and oxidation reaction takes place in air NO, continues mutual absorption reaction.First grade absorption tower ejects the gas that comes and enters the two-level absorption tower bottom, proceed the gas-liquid counter current haptoreaction with the half spent acid circulation fluid that flows down from the two-level absorption tower top spray, eject the gas that comes from two-level absorption tower and enter bottom, three grades of absorption towers, advance three grades of absorption tower its SO of nitrated tail gas
3Substantially all absorbed NO
XConcentration is 6m
3/ h, one-level half spent acid circulating slot concentration of nitric acid is 12.5%, and secondary half spent acid circulating slot concentration of nitric acid is 8.2%, and circulation fluid half spent acid temperature is 52 ℃.Carry out the gas-liquid counter current haptoreaction with the sodium hydrate aqueous solution that flows down from three grades of absorption tower top sprays, reacted gas is through high altitude discharge behind the air-introduced machine.Alkali lye circulating slot temperature is a normal temperature, NO in the emptying end gas
XConcentration of emission be 11mg/kg.Half spent acid behind absorption reaction one batch materials is made the raw material of a nitration reaction, and half spent acid of secondary absorption reaction is back to one-level half spent acid circulating slot, and secondary half spent acid circulating slot adds fresh half spent acid, continues circulation and absorbs.When the approaching neutrality of the liquid caustic soda in the alkali lye circulating slot, with lye pump to nitration waste water measuring tank, make thinned water, the alkali lye circulating slot adds new alkali lye, continues the circulation absorption.
Embodiment 2:
The red fuming nitric acid (RFNA) of the sulfuric acid absorption 98% of employing 98%, the tidal air of 105% oleum storage tank, the NO of generation
XAnd SO
3Waste gas, flow 1.6m
3/ h, NO
XVolumetric concentration be about 60%, wherein NO and NO
2Ratio be about 2:1, SO
3Volumetric concentration be about 12%, enter absorption section after by volume ratio 1:5 mixes with air with waste gas, previous stage adopts 98% sulfuric acid tower to absorb, and back one-level adopts washing tower to absorb, every grade of tower is equipped with liquid distribution trough and tetrafluoro material filler, liquid circulating slot and other annex.The absorption liquid internal circulating load is 5 m
3/ h, the absorption tower tower diameter is 0.4M, tower height 3M.Sulfuric acid absorption and annex thereof adopt carbon steel, and alkali lye absorbs and annex adopts plastic material.With circulating pump sulfuric acid is delivered to the first grade absorption tower top spray and flow down, circulating fluid flow rate is 5m
3/ h, nitrated emptying waste gas enters from the first grade absorption tower bottom, with the 8m that replenishes
3/ h air mixes.SO in the nitrated tail gas
3Reaction generates H with sulfuric acid circulation fluid counter current contacting
2SO
4, NO
XReaction generates nitric acid and NO with sulfuric acid circulation fluid counter current contacting, and oxidation reaction takes place in air NO, continues mutual absorption reaction.First grade absorption tower ejects the gas that comes and enters the two-level absorption tower bottom, advances its SO of the nitrated tail gas of two-level absorption tower
3Substantially all absorbed NO
XConcentration is 0.45m
3/ h, circulation fluid sulfuric acid temperature is a normal temperature.Sulfuric acid circulating slot concentration of nitric acid increases to 10%, and pump is done the nitrated acid of using to the nitration reaction still, and circulating slot adds fresh sulfuric acid, continues circulation and absorbs.Advance the nitrated tail gas of two-level absorption tower and carry out the gas-liquid counter current haptoreaction with the sodium hydrate aqueous solution that flows down from the two-level absorption tower top spray, reacted gas is through high altitude discharge behind the air-introduced machine.Alkali lye circulating slot temperature is a normal temperature, NO in the emptying end gas
XConcentration of emission be 7mg/kg.When the approaching neutrality of the liquid caustic soda in the alkali lye circulating slot, lye pump to the nitration waste water measuring tank, is made thinned water, the alkali lye circulating slot adds new alkali lye, continues the circulation absorption.
Embodiment 3:
Adopt in 98% the sulfuric acid absorption itrated compound and the time NO that produces
XTail gas, nitration reaction through standing demix, obtains containing the itrated compound of nitration mixture after finishing, and the washing that need neutralize is to remove nitration mixture, the NO of generation
XExhaust flow 30m
3/ h, NO
XVolumetric concentration be about 20%, wherein NO and NO
2Ratio be about 1:1, enter absorption section after by volume ratio 1:3 mixes with air with waste gas and adopt double-column in series, previous stage adopts 98% sulfuric acid tower to absorb, and back one-level adopts washing tower to absorb, every grade of tower is equipped with liquid distribution trough and tetrafluoro material filler, liquid circulating slot and other annex.The absorption liquid internal circulating load is 10 m
3/ h, the absorption tower tower diameter is 0.5M, tower height 3M.Sulfuric acid absorption and annex thereof adopt carbon steel, and alkali lye absorbs and annex adopts plastic material.With circulating pump sulfuric acid is delivered to the first grade absorption tower top spray and flow down, circulating fluid flow rate is 10m
3/ h, nitrated emptying waste gas enters from the first grade absorption tower bottom, with the 100m that replenishes
3/ h air mixes.NO in the nitrated tail gas
XReaction generates nitric acid and NO with sulfuric acid circulation fluid counter current contacting, and oxidation reaction takes place in air NO, continues mutual absorption reaction.First grade absorption tower ejects the gas that comes and enters two-level absorption tower bottom, its NO
XConcentration is 0.25m
3/ h, circulation fluid sulfuric acid temperature is a normal temperature.Sulfuric acid circulating slot concentration of nitric acid increases to 10%, and pump is done the nitrated acid of using to the nitration reaction still, and circulating slot adds fresh sulfuric acid, continues circulation and absorbs.Advance the nitrated tail gas of two-level absorption tower and carry out the gas-liquid counter current haptoreaction with the sodium hydrate aqueous solution that flows down from the two-level absorption tower top spray, reacted gas is through high altitude discharge behind the air-introduced machine.Alkali lye circulating slot temperature is a normal temperature, NO in the emptying end gas
XConcentration of emission be 8mg/kg.When the approaching neutrality of the liquid caustic soda in the alkali lye circulating slot, lye pump is pending to wastewater trough, and the alkali lye circulating slot adds new alkali lye, continues the circulation absorption.
Embodiment 4:
The present invention adopts 98% red fuming nitric acid (RFNA), the nitration mixture of 105% oleum preparation is produced fragrant two itrated compounds, production process is Fan Ying not nitrated dividing with dinitro, red fuming nitric acid (RFNA) with 98%, it is two nitrated that the nitration mixture of 105% oleum preparation carries out, and it is half spent acid (h 2 so 4 concentration is about 95%, and the nitric acid mass concentration is about 3%) that the waste mixed acid of two nitrated generations is commonly called as, after half spent acid drips nitric acid, as a nitrated usefulness acid.For effectively utilizing half spent acid, available half spent acid replaces the sulfuric acid circulation to absorb, and half spent acid goes a nitration reaction again after circulation absorbs.Consequent NO
XAnd SO
3Waste gas, flow 80.6m
3/ h, NO
XVolumetric concentration be about 60%, wherein NO and NO
2Ratio be about 1:1, rate of discharge is 19Kg/h, SO
3Volumetric concentration be about 6%, rate of discharge is 7Kg/h.Shown in Figure of description 2, nitrated tail gas enters absorption section by tail gas inlet pipe 1, about 500 m of bubbling air from first grade absorption tower 3-1 bottom
3/ h(tail gas and Air mixing ratio are about 1:6) enter sulfuric acid circulating slot 4-1 by air inlet pipe 2.It is that carbon steel, tail gas inlet pipe select for use stainless steel, filler with 20 * 20 tetrafluoro material Pall rings that the tower diameter of first grade absorption tower 3-1 and two-level absorption tower 3-2 is 0.5M, tower height 3M, circulating slot and tower and annex material.Sulfuric acid circulating slot 4-1 and sulfuric acid circulating slot 4-2 are equipped with chuck respectively and carry out heat exchange, half spent acid flow to sulfuric acid circulating pump 5-1 from sulfuric acid circulating slot 4-1 by valve, control valve is equipped with in sulfuric acid circulating pump 5-1 outlet, regulate the flow of half spent acid to flowmeter 6, with sulfuric acid circulating pump 5-1 half spent acid is delivered to first grade absorption tower 3-1 top again and flow down the SO in the nitrated tail gas by the liquid distribution trough spray
3Reaction generates H with half spent acid circulation fluid counter current contacting
2SO
4, NO
XReaction generates nitric acid and NO with half spent acid circulation fluid counter current contacting, and oxidation reaction takes place in air NO, continues mutual absorption reaction.The gas that first grade absorption tower 3-1 comes out at the top enters two-level absorption tower 3-2 tower bottom, proceed the gas-liquid counter current haptoreaction with the half spent acid circulation fluid that flows down from two-level absorption tower 3-2 top of tower spray, half spent acid flow to sulfuric acid circulating pump 5-2 from sulfuric acid circulating slot 4-2 by valve, and the amount of half spent acid circulation is 10 m
3/ h.The gas that comes out from two-level absorption tower 3-2 cat head enters three grades of absorption tower 7 tower bottoms, the NO in its tail gas by gas phase pipe 10
XRate of discharge is 1.5Kg/h, NO
XAbsorptivity be 92%, SO
3Basic all absorptions in the sixth of the twelve Earthly Branches.Concentration of nitric acid is 8.5% among the sulfuric acid circulating slot 4-1 of absorption back, and concentration of nitric acid is 4.2% in the sulfuric acid circulating slot 4-2.At this moment half spent acid of sulfuric acid circulating slot 4-1 is recyclable utilizes again, and promptly pump to nitre still is made the raw material of a nitration reaction, and the half spent acid pump of sulfuric acid circulating slot 4-2 to sulfuric acid circulating slot 4-1, is added fresh half spent acid to sulfuric acid circulating slot 4-2, continues circulation and absorbs.The tower diameter on three grades of absorption towers 7 is that 0.5M, tower height 3M, circulating slot and tower and annex material are polypropylene plastics, tail gas inlet pipe polypropylene plastics, filler with 20 * 20 tetrafluoro material Pall rings.Tail gas after half spent acid absorbs enters the tower bottom on three grades of absorption towers 7 by gas phase pipe 10, carry out the gas-liquid counter current haptoreaction with the sodium hydrate aqueous solution that flows down from three grades of absorption tower 7 tops of tower sprays, alkali lye flow to NaOH solution circulating pump 9 from alkali lye circulating slot 8 by valve, and the alkali lye internal circulating load also is 10 m
3/ h.Reacted gas process exhaust outlet pipe 11 is to air-introduced machine 12 back high altitude discharges.NO in the emptying end gas
XRate of discharge be 0.08Kg/h, concentration of emission is 110mg/Kg.(available timing is measured the pH value or with online survey pH, autoalarm arranged) with lye pump to nitration waste water measuring tank, makes thinned water when the approaching neutrality of the liquid caustic soda in the alkali lye circulating slot, and the alkali lye circulating slot adds new alkali lye, continues the absorption that circulates.Half spent acid temperature is about 40 ℃ in the present embodiment, and alkali lye is normal temperature.Half spent acid in the present embodiment can be 90～98% sulfuric acid replacement by mass concentration.
Should be understood that this embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Claims (7)
1. one kind absorbs NO in the nitrated tail gas with sulfuric acid circulation
XAnd SO
3Method, it is characterized in that: entrained air in nitrated tail gas, mixed gas discharges after one-level absorption, secondary absorption and three grades of absorptions respectively, one-level absorbs and the secondary absorption all to adopt mass concentration be that 90～98% sulfuric acid is made absorption liquid, sulfuric acid recycling after one-level absorbs, sulfuric acid after secondary absorbs is back to one-level and absorbs, and three grades absorb employing alkali lye.
2. method according to claim 1 is characterized in that: described alkali lye is that mass concentration is 10% sodium hydroxide solution.
3. method according to claim 1 and 2 is characterized in that: keep the temperature of sulfuric acid in 10～60 ℃ of scopes in one-level absorption and the secondary absorption process.
4. method according to claim 1 and 2 is characterized in that: keep the temperature of sulfuric acid in 20～40 ℃ of scopes in one-level absorption and the secondary absorption process.
5. method according to claim 1 and 2 is characterized in that: the volume ratio of air and nitrated tail gas is 4～7:1.
6. method according to claim 1 and 2 is characterized in that: adopt packed absorber to increase the area of gas and absorption liquid, the height on absorption tower is 3～6m, adopts single-stage or twin-stage tower to absorb.
7. method according to claim 1 and 2 is characterized in that: adopt half spent acid to replace sulfuric acid as the firsts and seconds absorption liquid.
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| CN103566733A (en) * | 2012-07-31 | 2014-02-12 | 苏州仕净环保设备有限公司 | High-concentration nitrogen oxide three-level tail gas purifying tower system device |
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| CN104984649A (en) * | 2015-06-14 | 2015-10-21 | 黄志强 | Purification system suitable for waste gas treatment and control method thereof |
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| CN113019070A (en) * | 2021-03-02 | 2021-06-25 | 华侨大学 | Resource treatment method for sulfonated waste gas and nitrated waste gas generated in dye production |
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| CN104607025A (en) * | 2014-12-25 | 2015-05-13 | 甘肃银光化学工业集团有限公司 | Device and method for reducing concentration of nitrogen oxide in discharged tail gas of explosive powder production line |
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| CN104984649A (en) * | 2015-06-14 | 2015-10-21 | 黄志强 | Purification system suitable for waste gas treatment and control method thereof |
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| CN113184815A (en) * | 2020-10-29 | 2021-07-30 | 江苏方圆芳纶研究院有限公司 | Method for preparing nitrated mixed acid by using nitrogen oxide |
| CN113184815B (en) * | 2020-10-29 | 2023-08-15 | 江苏方圆芳纶研究院有限公司 | Method for preparing nitrified mixed acid by using nitrogen oxides |
| CN113019070A (en) * | 2021-03-02 | 2021-06-25 | 华侨大学 | Resource treatment method for sulfonated waste gas and nitrated waste gas generated in dye production |
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Effective date of registration: 20231017 Address after: 354000 Xingling Platform, Phase III, Jintang Industrial Park, Shaowu City, Nanping City, Fujian Province Patentee after: Fujian Kangfeng New Materials Co.,Ltd. Address before: 322104 Bachelor's Mansion Industrial Zone, Weishan Town, Dongyang City, Jinhua City, Zhejiang Province Patentee before: ZHEJIANG KANGFENG CHEMICALS Co.,Ltd. |